Interface Vol. 25, No. 3, Fall 2016 by The Electrochemical Society

VOL. 25, NO.3 Fall 2016

IN THIS ISSUE 3 From the Editor:

Electrochemistry and the Olympics

7 Pennington Corner:

Digital Media to Promote the Importance of Our Research

31 Special Section:

PRiME 2016 Honolulu, Hawaii

PMS motor DC/AC inverter battery

50 ECS Classicsâ&#x20AC;&#x201C;Historical Origins of the Rotating Ring-Disk Electrode

63 Tech Highlights 65 Lithium-Ion Batteriesâ&#x20AC;&#x201D; The 25th Anniversary of Commercialization

67 Batteries and a Sustainable Modern Society

71 The Dawn

of Lithium-Ion Batteries

75 Importance of Coulombic

Efficiency Measurements in R&D Efforts to Obtain Long-Lived Li-Ion Batteries

79 The Li-Ion Battery:

25 Years of Exciting and Enriching Experiences

85 Lithium and Lithium-Ion

Batteries: Challenges and Prospects

INTERFACE

ECS Institutional Members The Electrochemical Society values the support of our institutional members. Institutional members help ECS support scientific education, sustainability, and innovation. Through ongoing partnership, ECS will continue to lead as the advocate, guardian, and facilitator of electrochemical and solid state science and technology.

Visionary

AMETEK – Scientific Instruments (35) USA

Metrohm USA (10) USA

Benefactor Asahi Kasei Corporation (8) Japan Bio-Logic USA (8) USA Duracell (59) USA Gamry Instruments (9) USA Gelest Inc. (7) USA Hydro-Québec (9) Canada

Industrie De Nora S.p.A. (33) Italy Pine Research Instrumentation (10) USA Saft Batteries, Specialty Battery Group (34) USA Scribner Associates Inc. (20) USA Zahner-elektrik (1) Germany

Patron El-Cell (2) Germany Energizer (71) USA Faraday Technology, Inc. (10) USA IBM Corporation (59) USA

Lawrence Berkeley National Lab (12) USA Panasonic Corporation (22) Japan Toyota Research Institute of North America (8) USA

Sponsoring Axiall Corporation (21) USA BASi (1) USA Central Electrochemical Research Institute (23) India Electrosynthesis Company, Inc. (20) USA Ford Motor Company (2) USA GS-Yuasa International Ltd. (36) Japan Honda R&D Co., Ltd. (9) Japan IMERYS Graphite & Carbon (29) Switzerland Medtronic, Inc. (36) USA Molecular Rebar Design (1) USA

Next Energy EWE – Forschungszentrum (8) Germany Nissan Motor Co., Ltd. (9) Japan Permascand AB (13) Sweden TDK Corporation, Device Development Center (23) Japan Technic, Inc. (20) USA Teledyne Energy Systems, Inc. (17) USA Tianjin Battery Joint-Stock Co., Ltd (2) China Toyota Central R&D Labs., Inc. (36) Japan Yeager Center for Electrochemical Sciences (18) USA ZSW (12) Germany

Sustaining 3M Company (27) USA General Motors Research Laboratories (64) USA Giner, Inc./GES (30) USA International Lead Zinc Research Organization (37) USA Kanto Chemical Co., Inc., (4) Japan Leclanche SA (31) Switzerland

Los Alamos National Laboratory (8) USA Occidental Chemical Corporation (74) USA Quallion, LLC (16) USA Sandia National Labs (40) USA SanDisk (2) Japan Western Digital (1) USA

Please help us continue the vital work of ECS by joining as an institutional member today. To join or discuss institutional membership options please contact Beth Fisher, Director of Membership Services at 609.737.1902 ext. 103 or beth.fisher@electrochem.org. (Number in parentheses indicates years of membership)

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FROM THE EDITOR

Electrochemistry and the Olympics

eing in the midst of transition this summer, the Olympics were well underway when I began writing this column. Given the ubiquitous nature of electrochemistry and its applications, I was not particularly surprised to find some rather interesting applications wherein electrochemistry, specifically (wearable) electrochemical sensors, could aid in the performance of athletes and help them recover from their exertions. Those of us who have participated in endurance sports are well aware of the term “hitting the wall,” that sinking feeling you get when the body simply gives up and refuses to obey the mind. The mechanism behind this phenomenon is quite well understood—briefly, as the energy needed by the body to function exceeds the energy available by usual aerobic means, anaerobic metabolism kicks in, with lactic acid and lactate being the by-products. Unfortunately, the lactate thus generated is not readily dissipated and builds up within the body, resulting, among other things, in extreme fatigue that causes the muscles to shut down. Lactate can be readily detected using sensors that have either lactate oxidase or lactate dehydrogenase as the active element. These electrochemical biosensors can accurately measure lactate levels in sweat. It is easy to see how these devices can aid in training by allowing athletes to understand their lactate buildup profile and to optimize their training and performance plans accordingly. One could point out that it would be cumbersome to carry around and utilize such devices during periods of intense activity, but it turns out that these sensors can simply be printed onto your skin1 and can provide real time data! Maintaining optimal hydration levels is another issue of critical importance to all athletes. Once again, electrochemistry comes to the rescue with electrochemical sensors that detect the concentration of relevant ions present in sweat. For example, by using an ion selective electrode proximal to the body, accurate measures of the sodium ion concentration can be obtained.2 It is not difficult to imagine that this data could be conveyed to the athlete without interrupting his/her activity, allowing them to take suitable preventive measures at the very onset of dehydration. On the flip side, much of the conversation surrounding the Rio games has centered around performance enhancing drugs and the difficulty in assuring compliance. This provides another domain of opportunity, wherein wearable electrochemical sensors could be designed to detect traces of PED by-products both during and out of competition. On another note, this issue commemorates the 25th anniversary of the commercialization of the lithium-ion battery. We have an outstanding set of articles from stalwarts in the field that provide both technical and historical perspectives of the development of this most impactful of technologies. As always, we welcome your input and feedback, and we look forward to seeing you at the PRiME meeting in October!

References 1. Wenzhao Jia, Amay J. Bandodkar, Gabriela Valdés-Ramírez, Joshua R. Windmiller, Zhanjun Yang, Julian Ramírez, Garrett Chan, and Joseph Wang, “Electrochemical Tattoo Biosensors for Real-Time Noninvasive Lactate Monitoring in Human Perspiration,” Anal. Chem., 85, 6553 (2013). DOI: 10.1021/ac401573r. 2. Benjamin Schazmann, Deirdre Morris, Conor Slater, Stephen Beirne, Cormac Fay, Ronen Reuveny, Niall Moyna, and Dermot Diamond, “A Wearable Electrochemical Sensor for the Real-Time Measurement of Sweat Sodium Concentration,” Anal. Methods, 2, 342 (2010). DOI: 10.1039/B9AY00184K.

Vijay Ramani, Interface Co-Editor http://orcid.org/0000-0002-6132-8144

Published by: The Electrochemical Society (ECS) 65 South Main Street Pennington, NJ 08534-2839, USA Tel 609.737.1902, Fax 609.737.2743 www.electrochem.org Co-Editors: ramani@wustl.edu; Petr Vanýsek, pvanysek@ gmail.com Guest Editors: Zempachi Ogumi, ogumi@scl.kyoto-u. ac.jp; Robert Kostecki, r_kostecki@lbl.gov; Dominique Guyomard, dominique.guyomard@cnrs-imn.fr; and Minoru Inaba, minaba@mail.doshisha.ac.jp Contributing Editor: Donald Pile, donald.pile@gmail.com Managing Editor: Annie Goedkoop, annie.goedkoop@electrochem.org Interface Production Manager: Dinia Agrawala, interface@electrochem.org Advertising Manager: Casey Emilius, casey.emilius@electrochem.org Advisory Board: Robert Kostecki (Battery), Sanna Virtanen (Corrosion), Durga Misra (Dielectric Science and Technology), Elizabeth PodlahaMurphy (Electrodeposition), Jerzy Ruzyllo (Electronics and Photonics), A. Manivannan (Energy Technology), Paul Gannon (High Temperature Materials), John Staser (Industrial Electrochemistry and Electrochemical Engineering), Uwe Happek (Luminescence and Display Materials), Slava Rotkin (Nanocarbons), Jim Burgess (Organic and Biological Electrochemistry), Andrew C. Hillier (Physical and Analytical Electrochemistry), Nick Wu (Sensor) Publisher: Mary Yess, mary.yess@electrochem.org Publications Subcommittee Chair: Yue Kuo Society Officers: Krishnan Rajeshwar, President; Johna Leddy, Senior Vice President; Yue Kuo, 2nd Vice President; Christina Bock, 3rd Vice President; James Fenton, Secretary; E. Jennings Taylor, Treasurer; Roque J. Calvo, Executive Director Statements and opinions given in The Electrochemical Society Interface are those of the contributors, and ECS assumes no responsibility for them. Authorization to photocopy any article for internal or personal use beyond the fair use provisions of the Copyright Act of 1976 is granted by The Electrochemical Society to libraries and other users registered with the Copyright Clearance Center (CCC). Copying for other than internal or personal use without express permission of ECS is prohibited. The CCC Code for The Electrochemical Society Interface is 1064-8208/92. Canada Post: Publications Mail Agreement #40612608 Canada Returns to be sent to: Pitney Bowes International, P.O. Box 25542, London, ON N6C 6B2 ISSN : Print: 1064-8208

Online: 1944-8783

The Electrochemical Society Interface is published quarterly by The Electrochemical Society (ECS), at 65 South Main Street, Pennington, NJ 08534-2839 USA. Subscription to members as part of membership service; subscription to nonmembers is available; see the ECS website. Single copies $10.00 to members; $19.00 to nonmembers. © Copyright 2016 by The Electrochemical Society. Periodicals postage paid at Pennington, New Jersey, and at additional mailing offices. POSTMASTER: Send address changes to The Electrochemical Society, 65 South Main Street, Pennington, NJ 08534-2839. The Electrochemical Society is an educational, nonprofit 501(c)(3) organization with more than 8000 scientists and engineers in over 70 countries worldwide who hold individual membership. Founded in 1902, the Society has a long tradition in advancing the theory and practice of electrochemical and solid-state science by dissemination of information through its publications and international meetings.

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org All recycled paper. Printed in USA.

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Lithium-Ion Batteries— The 25th Anniversary of Commercialization

Vol. 25, No.3 Fall 2016

by Zempachi Ogumi, Robert Kostecki, Dominique Guyomard, and Minoru Inaba

Batteries and a Sustainable Modern Society

the Editor: 3 From Electrochemistry

by John B. Goodenough

Corner: 7 Pennington Digital Media to Promote

The Dawn of Lithium-Ion Batteries by Yoshio Nishi

Importance of Coulombic Efficiency Measurements in R&D Efforts to Obtain Long-Lived Li-Ion Batteries by J. R. Dahn, J. C. Burns, and D. A. Stevens

The Li-Ion Battery: 25 Years of Exciting and Enriching Experiences by J. M. Tarascon

Lithium and Lithium-Ion Batteries: Challenges and Prospects by Stefano Passerini and Bruno Scrosati

and the Olympics the Importance of Our Research

8 Society News Section: 31 Special PRiME 2016

Honolulu, Hawaii

Lithium 47 Chalkboard: Batteries as Electrochemical Sources of Energy

Classics–Historical 50 ECS Origins of the Rotating Ring-Disk Electrode

61 People News 63 Tech Highlights 88 Awards Program 90 New Members 94 Student News Orleans, Louisiana 101 New Call for Papers 105 SOFC-XV Hollywood, Florida Call for Papers

On the cover . . .

Sony developed a Li-ion battery in 1991 to power the Sony camcorder. As a result, competing battery manufacturers also began to produce Li-ion batteries and the use spread into countless other devices. The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Cover design by Constance M. Wynn-Smith.

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Pennington Corner

Digital Media to Promote the Importance of Our Research “What is electrochemistry?” The oldest video series we have posted was produced in That was the title of an educational the early 1980s by the Case Western Reserve University brochure that ECS used for many Alumni Foundation and sponsored by the Eltech Systems years to explain the science and Lectureship in Electrochemistry Endowment Fund. This engineering disciplines in our technical domain. It was a lecture series captures four of the all-time greatest teachers and wonderfully descriptive tool for our many technical interest investigators of electrochemistry (A. J. Arvia, Allen J. Bard, areas and it provided me with a basic understanding of the Heinz Gerischer, and Charles W. Tobias), all of whom have important research areas within the Society. Yet after over 35 left a tremendous legacy in their body of work and extended years of electrochemistry repartee with family, friends, and it through dozens of former students now making significant business associates, most are still pretty clueless about what is contributions of their own. electrochemistry. In a little over a year But I am happy to we created 38 episodes of report that this has recently the ECS Podcasts, a way to changed because our Free connect the dots between our “Our members have made some of the Science initiative science and your everyday the world’s greatest discoveries, we (www.freethescience.org) lives. The ECS Masters just needed more tools to educate is creating new interest in, Video Series has so far and connection to, how our featured talks with 10 of people about the importance of the science solves worldwide today’s most important research we disseminate.” problems in energy, water, figures in electrochemistry health care, and generally and solid state science the sustainability of our and technology. These planet. It turns out the interviews are exclusive question is not what is opportunities to hear from electrochemistry, but rather why is electrochemical and solidaccomplished scientists and engineers who share their life state science and technology critical to the sustainability of our stories, experiences, and achievements. These are real stories planet and quality of our lives? about people whose scientific ingenuity created incredible new Now when I talk about ECS, family and friends do not innovations and through their stories we hear the secrets of get that glazed look or change the subject, they ask how they their successes—integrity, fortitude, resilience—and for these can help to Free the Science. The why question has become scientists, a determination to use their knowledge to advance increasingly important as we progress toward complete discoveries that benefit humankind. open access or availability of our Digital Library because Why Free the Science… listen to them and no other Free the Science is ultimately about increasing discovery explanation is necessary. Watch and listen to ECS digital and advancement of the essential technical interest areas of media at www.electrochem.org/digital-media. our science. During the Society’s 114 years of publishing and meetings, our members have made some of the world’s greatest discoveries, and so we have answered why in spades, but we just needed more tools and the means to educate people about the importance of the research we disseminate. A few years ago, we embarked on a strategic plan to Roque J. Calvo capture and share more information about the importance of ECS Executive Director our science.We determined that the case for supporting Free the Science would best be articulated by the Society’s great Special thanks to: leaders, so we have been producing podcasts and video series Rob Gerth, ECS Director of Marketing & Communications, who has and making them available for free on the ECS website. These led the strategic plan for these series. digital media series (see page 6) are growing in popularity and David J. Caruso, PhD, Director, Center for Oral History at the thus are becoming powerful advocates for our science and the Chemical Heritage Foundation Oral History Project. Free the Science initiative. Daniel Scherson, Director of the Ernest B. Yeager Center for Actually, ECS first started documenting stories about the Electrochemical Sciences and curator of the Eltech Systems great men and women in our science in oral histories produced Lectureships, and Ernest B. Yeager who hosted the series. by the Chemical Heritage Foundation in the early 1990s. These oral histories were captured as audio recordings, then transcribed into a series of bound volumes, which we have recently begun to repurpose so you will be able to listen to the stories of these great scientists as told by them.

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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Highlights from IMLB 2016 The 18th International Meeting on Lithium Batteries (IMLB 2016) was held at the Hyatt Regency in downtown Chicago, Illinois from June 19-24th. IMLB is the premier international conference on the state of lithium battery science and technology as well as current and future applications in transportation, commercial, aerospace, biomedical, and other promising sectors. The conference drew over 1,300 attendees from 33 different countries. The technical program included 76 keynote speakers and 1,108 poster presentations. IMLB provided an exciting forum to discuss recent progress in advanced lithium batteries for energy storage and conversion. The meeting was focused on both basic and applied research findings that have led to improved Li battery materials, and to the understanding of the fundamental processes that determine and control electrochemical performance. A major, but not exclusive, theme of the meeting was

recent advances in beyond lithium-ion technologies. In addition, the meeting covered a wide range of topics relating to lithium battery science and technology including, but not limited to, issues related to sources and availability of materials for Li batteries; Li battery recycling, and manufacturing and formation techniques. The IMLB 2016 conference proceedings have been published in a volume of ECS Transactions and are available now in the ECS Digital Library. There will also be a special focus issue of the Journal of The Electrochemical Society published with papers from this meeting. The IMLB organizers and ECS would like to thank all the sponsors and technical exhibitors whose support helped make this meeting a success. The next IMLB will take place in 2018 in Kyoto, Japan, and Germany was selected as the host country for 2020. To stay up to date on what IMLB has coming up next, please visit: www.IMLB.org

Scenes from IMLB 2016

The Electrochemical Society Interface â&#x20AC;˘ Fall 2016 â&#x20AC;˘ www.electrochem.org

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Focus on Focus Issues ECS publishes special focus issues of the Journal of The Electrochemical Society (JES) and ECS Journal of Solid State Science and Technology (JSS) that highlight scientific and technological areas of current interest and future promise. The issues are handled by a prestigious group of ECS Technical Editors and guest editors, and all submissions undergo the same rigorous peer review process as papers in the regular issues. Many articles in the focus issues are open access and can be read for free.

most advanced analytical techniques, so that device-based analysis, relying on DC and AC characteristics and supported by TCAD becomes more and more relevant. In addition, the atomic cluster sizes considered in today’s ab initio calculations of defect properties and based among others on the Density Functional Theory approach come closer to the size of ultimately scaled nanostructures, so that the outcome becomes more and more quantitative and certainly provides a good qualitative insight.

Recent Issues …

Issue: JSS, http://jss.ecsdl.org/content/5/4.toc Guest Editor: Eddy Simoen JSS Technical Editor: Stefan De Gendt

Defect Characterization in Semiconductor Materials and Devices This focus issue was inspired by a rapidly growing interest and concern that have developed within the microelectronics industry and research community with respect to defect characterization in hetero-epitaxial layers and nano-structures for CMOS and photonic applications. A typical example is the integration of highmobility semiconductors (Ge, III-V, GaN, ...) on a silicon platform for high-performance, photonics or high-power devices, where the lattice mismatch with the substrate can result in the creation of threading and misfit dislocations. The control and assessment of (extended) defects is crucial in the successful development of these novel technologies. Moreover, scaling of the feature sizes makes the device performance sensitive to single-defect fluctuations or Random Telegraph Noise, which contribute to the process variability and reliability. Defect control on such a level requires novel epitaxial-growth strategies and optimized processing conditions. At the same time, defect analysis in thin epitaxial layers and nano-structures is very challenging and requires continuous innovations in well-known structural, chemical and electrical characterization techniques, where high spatial resolution is key. It turns out that devices are sometimes more sensitive to the effect of point and extended defects than can be revealed by the

Schematic demonstrating the operating principle of the AFM-IR technique incorporating an illumination from a tunable infrared laser at an angle from above the cantilever tip. An AFM tip is in contact with the sample surface and infrared pulses from a tunable laser source impinge and excite the surface. When absorbed, rapid thermal expansion impacts the cantilever lever and amplitude of the ringing motions are detected and sequenced into absorption-like spectra. [From JSS Focus Issue on Defect Characterization in Semiconductor Materials and Devices, 5(4) P3018.]

Nanocarbons in Sensing Applications This special issue focuses on nanocarbons such as single- and multi-wall carbon nanotubes, graphene, graphene oxide, and their composites for sensing applications. The issues provides in-depth papers on topics of interest to a diverse and multidisciplinary community working in both nanocarbons materials and sensing areas. The papers included in the issue present information on a variety of subjects and cover topics including the latest DNA-SWCNTbased sensing platforms and the design of nanocarbons-based multifunctional devices for biomedical, environmental and energy applications, multiple CNT-based electrodes for real-time monitoring of analytes, different semiconductors based on carbon nanotubes, sensing technology based on optical properties of single-walled carbon nanotubes, carbon fiber electrodes based biofuel cell, and the wearable biofuel-powered sensor system based on silver ink coated carbon yarn. Issue: JSS, http://jss.ecsdl.org/content/5/8.toc Guest Editor: Aleksandr Simonian JSS Technical Editor: Francis D’Souza (continued on next page)

To make a strain-sensing smart skin (S4), nanotubes (SWCNTs) are added to a toluene solution of PFO polymer, ultrasonically dispersed, and centrifuged to remove aggregates before mixing with urethane host polymer. Application gives a thin film that changes SWCNT emission wavelengths when strained, allowing non-contact monitoring. [From JSS Focus Issue on Nanocarbons in Sensing Applications, 5(8) M3012.]

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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Electrolysis for Increased Renewable Energy Penetration Renewable energy sources, particularly wind and solar, are growing in their abundance and point toward a more sustainable energy future. Unfortunately, wind and solar both come with intermittency challenges and have limitations in their abilities to impact sectors such as industrial and transportation where energy carriers based on chemical bonds have provided the basis for much of the energy needs. Electrolysis offers the potential to meet the multi-GW demand for both grid-balancing and input into the industrial and transportation sectors. Therefore interest in this area has increased significantly with focus on several different technological approaches, each with its own unique challenges. Examples include, cost challenges for PEM water electrolysis, and thermal and durability challenges for high-temperature, solid-oxide electrolysis. Alkaline water electrolysis offers potentially lower cost stacks, but with still demanding R&D on improving its performance and operational characteristics or the pursuit of alkaline membrane technology that avoids issues of liquid electrolytes. This focus issue presents articles that address these challenges.

Electrochemical Deposition as Surface Controlled Phenomenon: Fundamentals and Applications Technological advances in microelectronic, optical, magnetic and energy conversion devices depend in large part on an ever increasing accuracy of material synthesis and ultra-thin film fabrication methods. Electro/electroless deposition plays an important role in this pursuit. In particular, the deposition concepts where the energetics of the surface/ deposit and solution species are exploited and manipulated to achieve unprecedented control over the deposit thickness, nucleation, growth, and microstructure. The focus of this issue is on electrochemical deposition as phenomenon which is fundamentally a function of surface energetics and chemical activity. Issue: JES, http://jes.ecsdl.org/content/163/12.toc Guest Editor: Stanko Brankovic JES Technical Editor: Charles Hussey

Issue: JES, http://jes.ecsdl.org/content/163/11.toc Guest Editors: Bryan Pivovar, Kathy Ayers, Marcelo Carmo, Jim O’Brien, and Xiaoyu Zhang JES Technical Editor: Thomas Fuller

Artistic view of the submonolayer deposit morphology on a facet of a nanoparticle. [See JES Focus Issue on Electrochemical Deposition as Surface Controlled Phenomenon: Fundamentals and Applications, 163(12).]

Electrolysis as part of the energy system. Illustration by Al Hicks, National Renewable Energy Laboratory. [See JES Focus Issue on Electrolysis for Increased Renewable Energy Penetration, 163(11).]

Upcoming Focus Issues … • JSS Focus Issue on Properties, Devices, and Applications Based on 2D Layered Materials • JES Focus Issue of Selected Papers from IMLB 2016 with Invited Papers Celebrating 25 Years of Lithium Ion Batteries • JSS Focus Issue on Ultrawide Bandgap Materials and Devices • JSS Focus Issue on Thermoelectric Materials and Devices • JES Focus Issue on Biological Fuel Cells • JSS Focus Issue Honoring Sir Harold “Harry” W. Kroto • JES Focus Issue on Biosensors and Micro-Nano Fabricated Electrochemical Systems There may still be time to submit to these issues. To see the Calls for Papers and the submission deadlines, check the following page: 10

www.electrochem.org/focus

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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Taking Electrochemistry to the U.S. House of Representatives In a push for more basic research funding for electrochemical science, past ECS President Daniel Scherson testified before the U.S. House Committee on Science, Space, and Technology’s Subcommittee on Energy to discuss innovations in solar fuels, electricity storage, and advanced materials. “I want them to understand where electrochemistry fits in many aspects of our lives,” Scherson, the Frank Hovorka Professor of Chemistry at Case Western Reserve University, said prior to the hearing. During the hearing, Scherson emphasized to the subcommittee that in order to solve some of society’s most pressing problems, more federal funding to basic electrochemistry research is critical. He further explained that without efforts in electrochemistry, nearly all aspects of energy storage and conversion—including batteries, fuels cells, EVs, and wind and solar energy—would cease to be viable. “Electrochemistry is a two century old discipline that has reemerged in recent years as a key to achieve sustainability and improve human welfare,” Scherson told the subcommittee. In recent years, budget cuts in federal spending have adversely affected scientific research. In April of this year, Sen. Jeff Flake (R-Ariz.) launched an attack on federal research dollars in the form of the Wastebook—a report detailing specific studies that the senator believes to be wasteful spending. Many of these accusations of wasteful spending are often derived from the misunderstanding of basic research. Basic research, in any discipline, is critical for the long term success of a product. Because the money invested doesn’t immediately yield a commercially viable product, does not mean those dollars are wasted. Take, for instance, the cellphone. The technology behind the first radio telephone service for motorists emerged in 1959, but it wasn’t until 1983 that the first cellphone was approved for commercial use. Additionally, the cellphone of 1983 is much different than the cellphone of today due to basic research in fields such as battery, materials science, display technology, sensor technology, and many more. Now, focus on the pace of innovation in basic research has seen a great shift toward energy storage technology. Scherson’s message

to the U.S. House Subcommittee was that if we want to see practical devices in energy storage and a shift in the energy landscape, there must be more basic research funding for the field. “Electrochemistry has become a central way to generate, store, and manage electricity derived from such intermittent energy sources as wind,” Scherson said in the testimony. Advances in energy storage could make a huge impact in the future of the electrical grid, widespread implementation of electric vehicles, and mitigating the effects of climate change. The grid and transportation sectors currently account for two-thirds of all energy used in the U.S. Additionally, these changes, according to Scherson, could help bolster a global economy. “Technological advances in these areas will bring about a reduction in operating costs, spur economic growth, create new jobs, and promote new assimilation in the global marketplace,” Scherson said.

Interface @ 25 Education in the Pages of Interface In this 25th year of Interface we are looking through some memorable articles that enriched the pages of the magazine in the past. The spring 2012 issue was dedicated to education and among the authors were such notable leaders of educational institutions as Marye Anne Fox and Larry R. Faulkner. Altogether, five articles on the topics of education were published in that issue. Quite interesting was “Physical Electrochemistry in the Undergraduate Curriculum: A Critical Assessment” by Ann Abraham, Nikola Matic, Denis Martins de Godoi, Jing Xu, Zhange Feng, Imre Treufeld, Doe Kunsa, Adriel Jebaraj, and Daniel Scherson (p. 73). The study in this article took a look at eleven textbooks of physical chemistry used in the undergraduate courses—taught in English and for the most part, primarily offered in the U.S. textbook market. The authors analyzed twenty-one representative topics relevant to electrochemistry education and assessed the absence or presence of the topic in the particular text and also looked at any pattern in the way the topic was presented. Among other comments that the authors made was one on teaching about batteries: “Also long overdue is the use of lithium ion batteries as examples that should replace the Weston or Daniell’s voltaic pile...” While it may be a while before the copper-zinc Daniell cell (1836), which sight unseen still provides an example of useful calculation based on the Nernst equation, disappears from the physical chemistry textbooks, the Interface authors made an attempt in this issue to introduce lithium batteries to undergraduates in the Chalkboard column (see p. 47). INTERFACE

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Meet the New ECS Board Members What our newly elected board members have to say about the Society’s Free the Science initiative.

Krishnan Rajeshwar ECS President

Christian Bock Vice President

James Fenton Secretary

Distinguished Professor, University of Texas at Arlington; working in fuel cells, capacitors, toxic waste treatment, and sensing of pollutants

Senior Research Scientist, National Research Council; working in waste water treatment, fuel cells, and water splitting reactions

Director of the University of Central Florida’s Florida Solar Energy Center; working in fuel cells, pollution prevention, and sustainable energy

“Ultimately what are we doing this for? We are doing this to improve the quality of life, to leave a better world for the succeeding generations. I’m proud to be part of Free the Science.”

“The effect of not having to pay for open access charges means that the money goes directly into science, where it is, in the first place, intended for.”

“By freeing this information, we have the chance to affect a lot more people, and in a lot of cases deliver solutions to the grand challenges of the world to places that many not get that information.”

Upcoming ECS Sponsored Meetings In addition to the ECS biannual meetings and ECS satellite conferences, ECS, its divisions, and sections, sponsor meetings and sympoisa of interest to the technical audience ECS serves. The following is a partial list of upcoming sponsored meetings. Please visit the ECS website for a list of all sponsored meetings.

2016 Sponsored Meetings • 5th International Conference on Metal-Organic Frameworks & Open Framework Compounds (MOF 2016), September 16-19, 2016 — Long Beach, CA, USA • 11th European Space Power Conference (ESPC 2016), October 3-7, 2016 — Thessaloniki, Greece

2017 Sponsored Meetings • 68th Annual Meeting of the International Society of Electrochemistry, August 27-September 1, 2017 — Providence, RI, USA • Sixth International Conference on Electrophoretic Deposition: Fundamentals and Applications (EPD-2017), October 1-6, 2017 — Gyeongju, South Korea To learn more about what an ECS sponsorship could do for your meeting, including information on publishing proceeding volumes for sponsored meetings, or to request an ECS sponsorship of your technical event, please contact ecs@electrochem.org.

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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Division News 25 Years of Excellence In October 1991, a few dozen chemists and physicists gathered in Phoenix at the ECS meeting to share their research findings on a new class of molecules—the carbon cage structures known as fullerenes. The beautifully symmetric soccer ball structure of C60, the central compound in this class, had captured the public imagination and ignited great excitement in the scientific community. Although the Buckminsterfullerene C60 molecule. fullerenes had been discovered as gas phase species at Rice University in 1985 by Richard Smalley, Robert Curl, and Harry Kroto (in work later recognized by the Nobel Prize), no bulk samples existed until 1990, when Wolfgang Kratschmer and Donald Huffman reported a simple preparation method involving carbon arc synthesis and soot extraction. Suddenly, all of the tools of modern chemistry could be applied to study fullerenes. Activity in the field exploded. ECS members S. I. Raider and Barry Miller foresaw that fullerenes properties would be of interest to the Society, and they organized the first topical symposium for the Phoenix meeting. Although that small 1991 program included only 22 speakers, the list included such luminaries as Richard Smalley, Donald Huffman, Robert Haddon, Karl Kadish, and Allen Bard. From that modest-sized start, symposia on carbon nanostructure research grew into a regular and substantial fixture at ECS spring meetings. Distinguished Barry Miller addressing the ECS members Barry Miller anniversary reception. and Karl Kadish guided the formation of a Fullerenes interest group within the Society in 1993. The Group’s symposia grew rapidly in attendance, scope, and importance as fullerenes research blossomed. ECS meetings quickly gained international recognition for defining the emerging field as the number of fullerene publications grew exponentially in the mid1990s; starting from 87 fullerene papers in 1991, it tripled the next year and increased 10-fold over the Karl Kadish, wearing commemorative next 5 years. During that baseball cap while addressing the period, the Fullerenes Group anniversary reception.

Display of ECS proceedings volumes from Nanocarbons Division symposia.

A graph showing the explosive growth in nanocarbons research publications, including those on fullerenes, nanotubes and other carbon nanostructures.

published a famous series of ECS proceedings volumes containing research papers presented at the annual symposia. These ECS symposia became recognized as the leading international forum for fullerenes investigators and the ECS Fullerenes Group was promoted to full division status in the Society. Since then, the Division has played an increasing role in the Society. Five distinguished nanocarbon researchers—S. Iijima, Ph. Avouris, R. Haddon, N. Martin and D. Guldi, have been honored with Richard E. Smalley Research Awards from the Division, and outstanding young researchers have received SES Research Young Investigator Awards. The most recent of these, presented in San Diego, was to J. Luo. As the field of carbon nanostructures expanded from fullerenes to carbon nanotubes and eventually to graphene and related nanomaterials, the symposium topics continually adjusted to capture the latest research developments. The Division’s name reflected these changes, evolving from “Fullerenes” to “Fullerenes, Nanotubes, and Carbon Nanostructures,” and finally to its current name,

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“Nanocarbons.” As basic research on nanocarbons has advanced and matured over the years, the Division’s focus has also broadened to include applications of carbon nanostructures in several areas of traditional importance in ECS. A unique role of the Nanocarbons Division has been to bring together scientists, engineers, and industrial researchers from all disciplines related to Daniel Scherson, ECS President, made nanocarbons—chemistry, welcoming remarks at the anniversary materials science, electrical reception. and chemical engineering, physics, and biology. At recent meetings, its symposia have attracted more than 300 papers from researchers around the world. The 229th ECS Meeting in San Diego marked a significant milestone: 25 years of nanocarbons in the Society. To celebrate this anniversary, a special reception was organized for the evening of May 31. More than 140 attendees mingled and socialized while enjoying drinks and gourmet desserts. Many wore their custom commemorative baseball caps given out at the door. A program moderated by Division Chair Bruce Weisman provided commentary and a slide show with images from the past quarter-century’s activities. ECS President Daniel Scherson conveyed congratulations for the Nanocarbons Division’s

Bruce Weisman (left), the outgoing Nanocarbons Division Chair, welcoming his successor, Slava V. Rotkin (right), at the anniversary reception.

contributions to the Society over these years, and several long-time participants, including Barry Miller, Karl Kadish, David Schuster, and Luis Echegoyen, shared fascinating recollections of the wilder incidents at the group’s early get-togethers. Another historical touch was provided by a special display of the full set of symposium proceedings volumes published by the Division. The Nanocarbons community looks forward to many more years of mutually beneficial activities in the ECS.

High Temperature Materials Division Members Receive Awards Harlan Anderson, professor emeritus of the University of Missouri at Rolla, was chosen to receive the 2016 High Temperature Materials (HTM) Division Outstanding Achievement Award for his seminal work in elucidating the defect chemistry and transport properties of mixed conducting perovskites, which are investigated intensely for catalytic electrodes in solid oxide fuel cells, and developed also for other catalytic and membrane processes. This prestigious award scroll and prize will be presented to Prof. Anderson during the PRiME meeting in Honolulu, Hawaii, where he will also present his award talk at the Solid State Ionic Devices 11 symposium. Sean Bishop received the HTM Division J. B. Wagner, Jr., Harlan Anderson Young Investigator Award and made his award presentation at the Mechano-Electro-Chemical Coupling in Energy Related Materials and Devices 2 symposium at the ECS 229th meeting in San Diego in June 2016. The HTM Division is sponsoring several symposia at the upcoming PRiME meeting in Honolulu, Hawaii in October 2016, namely, Solid State Ionic Devices 11, Electrosynthesis of Fuels 4, and Membrane-Based Electrochemical Separations 2. Sean Bishop delivered his award presentation at the San Diego meeting.

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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New Division Officer Slates New officers for the fall 2016–fall 2018 term have been nominated for the following Divisions. All election results will be reported in the winter 2016 issue of Interface.

Battery Division

Sensor Division

Chair Christopher Johnson, Argonne National Laboratory Vice Chair Marca Doeff, Lawrence Berkeley National Laboratory Secretary Y. Shirley Meng, University of California, San Diego Treasurer Brett Lucht, University of Rhode Island Members-at-Large Khalil Amine, Argonne National Laboratory Thomas Barrera, The Boeing Company Yi Cui, Stanford University Dominique Guyomard, CNRS IEMN Minoru Inaba, Doshisha University Richard Jow, US Army Research Laboratory Prashant N. Kumta, University of Pittsburgh Bor Yann Liaw, Idaho National Laboratory Bryan McCloskey, Lawrence Berkeley National Laboratory John Muldoon, Toyota Research Institute of North America Chao-Yang Wang, Pennsylvania State University Martin Winter, Westfälische Wilhelms-Universität Münster Jie Xiao, Pacific Northwest National Laboratory Marina Yakovleva, FMC Corporation

Chair Nianqiang (Nick) Wu, West Virginia University Vice Chair Ajit Khosla, Lab177 Inc. Secretary Jessica Koehne, NASA Ames Research Center Treasurer Praveen Sekhar, Washington State University Raluca-Ioana Stefan Van Staden, Institute of Research for Electrochemistry and Condensed Matter Larry Nagahara, Johns Hopkins University Members-at-Large Sheikh Akbar, Ohio State University Michael Carter, KWJ Engineering, Inc. Jay Grate, Pacific Northwest National Laboratory Peter Hesketh, Georgia Institute of Technology A. Robert Hillman, University of Leicester Gary Hunter, NASA Glenn Research Center Tatsumi Ishihara, Kyushu University Sangmin Jeon, POSTECH Mira Josowicz, Georgia Institute of Technology Pawel Kulesza, University of Warsaw Jing Li, NASA Ames Research Center Chung-Chiun Liu, Case Western Reserve University Vadim Lvovich, NASA Glenn Research Center Sushanta Mitra, University of Alberta Rangachary Mukundan, Los Alamos National Laboratory Larry Nagahara, National Cancer Institute Milad Navaei, Georgia Tech Antonio Ricco, Stanford University Christopher Salthouse, Draper Labs Michael Sailor, University of California, San Diego Praveen Kumar Sekhar, Washington State University Yasuhiro Shimizu, Nagasaki University Aleksandr Simonian, Auburn University Thomas Thundat, University of Alberta Petr Vanýsek, Northern Illinois University

ECS Redcat Blog The blog was established to keep members and nonmembers alike informed on the latest scientific research and innovations pertaining to electrochemistry and solid state science and technology. With a constant flow of information, blog visitors are able to stay on the cutting-edge of science and interface with a like-minded community.

www.electrochem.org/redcat-blog The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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ECS Division Contacts High Temperature Materials

Battery Robert Kostecki, Chair Lawrence Berkeley National Laboratory r_kostecki@lbl.gov • 510.486.6002 (U.S.)

Turgut Gür, Chair Stanford University turgut@stanford.edu • 650.725.0107 (U.S.)

Christopher Johnson, Vice-Chair Marca Doeff, Secretary Shirley Meng, Treasurer Doron Aurbach, Journals Editorial Board Representative

Gregory Jackson, Sr. Vice-Chair Paul Gannon, Jr. Vice-Chair Sean Bishop, Secretary/Treasurer Raymond Gorte, Journals Editorial Board Representative

Corrosion

Industrial Electrochemistry and Electrochemical Engineering

Rudolph Buchheit, Chair Ohio State University buchheit.8@osu.edu • 614.292.6085 (U.S.)

Douglas Riemer, Chair Hutchinson Technology Inc. riemerdp@hotmail.com • 952.442.9781 (U.S.)

Sannakaisa Virtanen, Vice-Chair Masayuki Itagaki, Secretary/Treasurer Gerald Frankel, Journals Editorial Board Representative

John Staser, Vice-Chair Shrisudersan (Sudha) Jayaraman, Secretary/Treasurer Venkat Subramanian, Journals Editorial Board Representative

Dielectric Science and Technology

Luminescence and Display Materials

Yaw Obeng, Chair National Institute of Standards and Technology yaw.obeng@nist.gov

Madis Raukas, Chair Osram Sylvania madis.raukas@sylvania.com • 978.750.1506 (U.S.)

Vimal Chaitanya, Vice-Chair Gangadhara Mathad, Secretary Puroshothaman Srinivasan, Treasurer Stefan De Gendt, Journals Editorial Board Representative

Mikhail Brik, Vice-Chair/Secretary/Treasurer Kailash Mishra, Journals Editorial Board Representative

Electrodeposition Elizabeth Podlaha-Murphy, Chair Northeastern University e.podlaha-murphy@neu.edu • 617.373.3769 (U.S.) Stanko Brankovic, Vice-Chair Philippe Vereecken, Secretary Natasa Vasiljevic, Treasurer Charles Hussey, Journals Editorial Board Representative Electronics and Photonics Mark Overberg, Chair Sandia National Laboratories meoverb@sandia.gov • 505.284.8180 (U.S.) Colm O’Dwyer, Vice-Chair Junichi Murota, 2nd Vice-Chair Soohwan Jang, Secretary Yu-Lin Wang, Treasurer Fan Ren, Journals Editorial Board Representative

Nanocarbons Slava Rotkin, Chair Lehigh University rotkin@lehigh.edu • 610.758.3931 (U.S.) Hiroshi Imahori, Vice-Chair Olga Boltalina, Secretary R. Bruce Weisman, Treasurer Francis D’Souza, Journals Editorial Board Representative Organic and Biological Electrochemistry Mekki Bayachou, Chair Cleveland State University m.bayachou@csuohio.edu • 216.875.9716 (U.S.) Graham Cheek, Vice-Chair Diane Smith, Secretary/Treasurer Dennis Peters, Journals Editorial Board Representative Physical and Analytical Electrochemistry

Energy Technology Scott Calabrese Barton, Chair Michigan State University scb@msu.edu • 517.355.0222 (U.S.) Andy Herring, Vice-Chair Vaidyanathan Subramanian, Secretary William Mustain, Treasurer Thomas Fuller, Journals Editorial Board Representative

Pawel Kulesza, Chair University of Warsaw pkulesza@chem.uw.edu.pl • +482.282.20211 (PL) Alice Suroviec, Vice-Chair Petr Vanýsek, Secretary Robert Calhoun, Treasurer David Cliffel, Journals Editorial Board Representative Sensor Bryan Chin Auburn University chinbry@auburn.edu • 334.844.3322 (U.S.) Nianqiang Wu, Vice-Chair Ajit Khosla, Secretary Jessica Koehne, Treasurer Rangachary Mukundan, Journals Editorial Board Representative

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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websites of note by Petr Vanýsek

Big Data Mining—Words and Phrases

The Google Ngram Viewer is an online search engine that charts frequencies of any set of commadelimited search strings using a yearly count of n-grams found in sources printed between 1500 and 2008. The program can search for a single word or a phrase existing in the Google’s Text corpora. Unlike the search in science databases, this search reveals relative frequency of the word or a phrase in the whole corpora. Thus, for example from the lead topic in this issue “lithium” as a word appears to have already peaked, while research papers on the subject keep increasing. The specific phrase “rotating disk electrode” highlighted in this issue’s Classics has its own interesting trend history. • Michel, Jean-Baptiste et al.: Quantitative Analysis of Culture Using Millions of Digitized Books, Science 331 (2011) 176-182. https://books.google.com/ngrams/

Electrochemistry Dictionary and Encyclopedia

Zoltan Nagy was instrumental in starting (in 1995) a website “Electrochemical Science and Technology Information Resource (ESTIR)” which was for a short time hosted on the Argonne National Labs’ computer, it was later moved to the Ernest B. Yeager Center for Electrochemical Sciences (YCES) at Case Western Reserve University, and finally the contents found its home with The Electrochemical Society. • http://knowledge.electrochem.org/encycl/

About the Guest Author

Petr Vanýsek is a co-editor of Interface and substituted for Zoltan Nagy for this installment of websites of note. An emeritus professor of chemistry and biochemistry at Northern Illinois University, Prof. Vanýsek is presently on leave of absence researching electrochemical energy storage while visiting in the Central European Institute of Technology in Brno, Czech Republic.

Zoltan Nagy—websites of note INTERFACE This year we are looking back at the first twenty-five years in which Interface was bringing electrochemistry information to its readers. Some of its features remain since its inception, but new columns were introduced over the years. A new column, websites of note, was introduced in the summer 2009 issue of Interface. The contributing author, or indeed, the contributing editor of this column was Zoltan Nagy. He was well-qualified for this task as he started electrochemistry USENET group (sci.chem.electrochem) in 1994, and later the Electrochemistry Source Portal. Through the years of publishing the websites of note he was able to bring to attention a number of sites interesting to electrochemists that might be sometimes buried in casual internet searchers. The About the Author section of the websites of note column described Dr. Nagy: “Zoltan Nagy is a semi-retired electrochemist. After 15 years in a variety of electrochemical industrial research, he spent 30 years at Argonne National Laboratory carrying out research on electrode kinetics and surface electrochemistry. Presently he is at the Chemistry Department of the University of North Carolina at Chapel Hill.” At Argonne he was interested in high-temperature electrochemistry and in using synchrotron x-ray scattering methods and contributed several articles on the subject to the Journal of The Electrochemical Society. He was also actively involved for many years in the executive committee of the ECS Chicago Section. After seven year of involvement in the websites of note, Dr. Nagy decided to retire from its editorship. On behalf of Interface I thank Zoltan for all his hard and sustained work for our magazine and for electrochemistry in general. While Dr. Nagy may be retiring from the column editorship, the column will not be retired. In the interim, I was happy to fill in with a few internet discoveries I found interesting. We expect to see original work from a new contributing editor in the next issue.

—Petr Vanýsek Interface Co-Editor

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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Institutional Member spotlight 2016 Leadership Circle Awards It is with tremendous pride and immense gratitude that ECS recognizes the recipients of the 2016 Institutional Membership Leadership Circle Awards. The following organizations celebrate milestones in institutional ECS membership this year:

Silver Level (10 years): Faraday Technology, Inc., Metrohm USA, and Pine Research Instrumentation

Gold Level (35 years): Princeton Applied Research/Solartron Analytical

• Faraday Technology, Inc. provides its government and commercial clients with applied electrochemical engineering technology development from bench-scale through pilot or preproduction levels. www.faradaytechnology.com/ • Metrohm USA provides precise measurement solutions for diverse fields. Metrohm’s expertise ranges from traditional electro-analysis methods such as polarography to hyphenated modern technologies. www.metrohm.com/en • Pine Research Instrumentation manufactures and supplies Superpave and Marshall asphalt testing equipment, three models of Superpave Gyratory Compactor, and electrochemistry research equipment. www.pineinstrument.com/

• Princeton Applied Research is a leading manufacturer of laboratory instruments utilized for investigations in the field of electrochemistry, which includes batteries, fuel cells, corrosion, sensors and general physical chemistry. www.princetonappliedresearch.com/ • Solartron Analytical is the global leader in Electrochemical Impedance Spectroscopy, providing more than 60 years of instrumentation development expertise for materials and electrochemical research. www.solartronanalytical.com/

Want to learn more about ECS membership and its many benefits for your company, institution, or organization? Visit www.electrochem.org or contact Beth Fisher, Director of Membership Services, at customerservice@electrochem.org.

In the

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The winter 2016 issue of Interface will feature the ECS Sensor Division. The issue will be guest edited by Peter Hesketh from Georgia Tech. It is scheduled to include the following technical articles: “Sensors Based upon Cell Phones,” by Nick Wu; “Portable Breath Monitoring: A New Frontier in Personalized Health Care,” by Gary W. Hunger, Raed A. Dweik, and Darby B. Makel; “Wearable Environmental Gas Sensors,” by Joe Stetter and Peter Hesketh; “Point of Care Diagnosis with Electrochemical Sensors,” by Reluca Stefan-van Staden; “Water Quality Sensors,” by Sushanta K. Mitra; and “Rapid Water Quality Monitoring,” by Naga Siva Kumar Gunda and Sushanta K. Mitra.

issue of

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Highlights from PRiME 2016. News and photos from this most significant research conference that includes the 6th International ECS Electrochemical Energy Summit (E2S). Biographical sketches and candidacy statements of the nominated candidates for the annual election of ECS officers. Tech Highlights continuing to provide readers with summaries of some of the most interesting papers published in the ECS journals. As always, the papers mentioned are free online. The 2016 ECS Summer Fellowship Reports from the recipients of the 2016 Weston Summer Fellowship, the 2016 Fink Summer Fellowship, the 2016 Richards Summer Fellowship, the 2015 Becket Summer Fellowship, and the 2015 Uhlig Summer Fellowship. (See page 94 of this issue for the names and bios of the 2016 Summer Fellowship Winners.)

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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Next Generation Electrochemistry (NGenE) Launched The inaugural edition of Next Generation Electrochemistry (NGenE), a weeklong summer research institute on the frontiers of electrochemistry, took place at the University of Illinois at Chicago (UIC), June 13-17, 2016. The program welcomed 22 advanced graduate students and postdocs and 13 world-renowned experts to address the research frontiers of electrochemistry and the application of innovative strategies to address them. The institute was presented by University of Illinois at Chicago (Jordi Cabana, Director, and George Crabtree, Supporting Director) in partnership with Argonne National Laboratory, Northwestern University, and University of Chicago, sponsored by Bio-Logic USA and endorsed by The Electrochemical Society (ECS) and by Materials Research Society (MRS). The inaugural program focused on concepts for the generation, conversion, Inaugural NGenE lecture by Dan Scherson (standing at right) of Case Western Reserve University. and storage of energy. Experts presented high-level lectures related to the current body of knowledge, highlighting critical gaps in the frontier that need to be explored and surpassed for transformative advances. Vigorous student-driven discussions followed each lecture. The lectures were complemented with demonstrations of cutting-edge tools such as UICâ&#x20AC;&#x2122;s in situ electron microscopy, and visits to large scale user facilities at ANL, such as the Advanced Photon Source. Participants were challenged to identify a frontier fundamental question in electrochemistry and to develop a proposal to resolve their chosen frontier issue using the most modern and upcoming methods. They worked in teams of four or five to develop their own critical and original thinking, with faculty providing mentoring during hour-long sessions of project discussion. They presented their innovative solutions to their peers and the faculty, who acted as reviewers. The lively discussions and stimulating atmosphere of the workshop produced NGenE 2016 students during a discussion session, preparing their research projects: (left to right) Adam many creative and engaging proposals. Tornheim (ANL), Yu Kambe (U. of Chicago) and Soo Kim (Northwestern U.). As hoped for, after the conclusion of the program, continuing interactions between faculty and students have materialized. maintain an overlapping roster of faculty from year to year as it builds Plans for NGenE 2017 are underway. The organizing team seeks a continuity of challenges and opportunities in electrochemistry. The input from key players in the community to shape the critical features research projects will be refined to target fundamental challenges at of our program, focusing on fundamental aspects of electrochemical the frontier of electrochemistry and original, innovative approaches to science. While the scientific emphasis will evolve, NGenE will overcoming them.

The Electrochemical Society Interface â&#x20AC;˘ Fall 2016 â&#x20AC;˘ www.electrochem.org

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Staff News Paul Cooper Celebrates 25th Anniversary with ECS Paul Cooper celebrated 25 years with The Electrochemical Society on July 15, 2016. A recent graduate from St. Joseph’s University in Philadelphia, PA, Paul joined the Society as a Publications Assistant in 1991, working as a copy-editor on Journal manuscripts and doing production work on the ECS Proceedings Series. One year later, when the decision was made to launch Interface magazine, he took on the production work for that publication as well, in the process moving the Society into desktop publishing and the in-house production of publications and materials. Always interested in learning new skills, Paul gradually took on responsibility for the entire journal production process, which ultimately led to his being named Journals Production Manager in 1998 and being tasked with the in-house production of the Society’s new letters-style journal, Electrochemical and Solid-State Letters, until that journal had grown sufficiently to require an outside production vendor due to the increase in submissions and acceptances. In 2002 Paul was promoted to Assistant Director of Publications and became responsible for the day-to-day operation of the Publications Department. He held this position until June of 2004, when fate and family obligations stepped in and required relocation to the Washington DC area. Rather than leave the organization which had become very much like another family, Paul accepted the offer of a part-time, remote position working with the ECS Editorial Board on the peer-review process and serving as the administrator for the Society’s on-line submission system, ExP. At this time he also took the opportunity to continue his education and earned a MA in Liberal Arts from St. John’s College in Annapolis, MD in 2006. In 2010 Paul was asked to come back full-time as the Editorial Manager, continuing to work with the authors, reviewers, and editors on all aspects of the review process, and also serving as the Senior Copy-Editor for the ECS Journals program. “During his 20 years of service, Paul has done it all for ECS publications—copyediting, production, layout and design, manuscript submission, and for past six years he has been our editorial manager. His function in this area is to work with members of our Journals Editorial Board to maintain a diligent and efficient peer review process, which is critical to the success and stewardship of our journals” said Roque Calvo, ECS Executive Director. “I’m certain that the authors, reviewers, editors, and staff who have worked with Paul have benefited from his experience and would join me in expressing appreciate for his great service and congratulations on reaching this milestone.”

Interface @25 Journal Lagtimes: How Times Have Changed INTERFACE

Back in the summer 1994 issue of Interface, ECS touted improved JES lagtimes. Here is a quick comparison of where we were then to where we are now:

Submission to Publication: • 1994: 8 months on average • 2016: 70 days (2.3 months) Submission to Acceptance: • 1994: 70% of acceptances are completed in 6 months or less • 2016: median is 60 days (2 months) Acceptance to Publication: • 1994: 4 months • 2016: 10 days

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The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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The Electrochemical Society and Toyota North America Announce 2016-2017 Fellowship Winners for Projects in Green Energy Technology

The ECS Toyota Young Investigator Fellowship Selection Committee has selected three recipients who will receive a minimum of $50,000 each for fellowships for projects in green energy technology. The winners are Elizabeth Biddinger, City College of New York; Joaquin Rodriguez Lopez, University of Illinois at Urbana-Champaign; and Joshua Snyder, Drexel University. The ECS Toyota Young Investigator Fellowship, a partnership between The Electrochemical Society and Toyota Research Institute of North America (TRINA), a division of Toyota Motor Engineering & Manufacturing North America, Inc. (TEMA), is in its second year. A diverse applicant pool of more than 100 young professors and scholars pursuing innovative electrochemical research in green energy technology responded to ECS’s request for proposals. “Scientists and engineers seek to unveil what is possible and to exploit that knowledge to provide solutions to the myriad of problems facing our world,” says ECS Executive Director Roque Calvo. “We are proud to have the continued support of Toyota in this never ending endeavor to uncover new frontiers and face new challenges.” The ECS Toyota Young Investigator Fellowship aims to encourage young professors and scholars to pursue research in green energy technology that may promote the development of next-generation vehicles capable of utilizing alternative fuels. Global development of industry and technology in the 20th century increased production of vehicles and the growing population have resulted in massive consumption of fossil fuels. Today, the automotive industry faces three challenges regarding environmental and energy issues: (1) Finding a viable alternative energy source as a replacement for oil (2) Reducing CO2 emissions (3) Preventing air pollution Although the demand for oil alternatives—such as natural gas, electricity and hydrogen—may grow, each alternative energy source has its disadvantages. Currently, oil remains the main source of automotive fuel; however, further research and development of alternative energies may bring change. Electrochemical research has already informed the development and improvement of innovative batteries, electrocatalysts, photovoltaics and fuel cells. Through this fellowship, ECS and TRINA hope to see further innovative and unconventional technologies borne from electrochemical research. “With this year’s winners, we were able to further expand on the number of interesting and innovative technologies covered by this Fellowship,” says Fellowship Chair and manager of Toyota’s North American Research Strategy Office, Paul Fanson. “While the new projects this year focus on traditional applications such as Li-ion batteries and fuel cells, each project proposes unique solutions to known challenges which may also be instructive in other areas. That is the beauty of research. You plant seeds and sometimes unexpected things grow, especially when you are fortunate enough to work with a group of energetic and diverse young faculty such as this year’s winners.”

The selected fellows will receive restricted grants of a minimum of $50,000 to conduct the research outlined in their proposals within one year. They will also receive a one-year complimentary ECS membership as well as the opportunity to present and/or publish their research with ECS.

2016-2017 ECS Toyota Young Investigator Fellows Elizabeth Biddinger, City College of New York Industrial Electrochemistry and Electrochemial Engineering Division of ECS Electrochemical Safety Switch Using Switchable Electrolytes: To examine the use of silylamine reversible ionic liquids that have the ability to have conductivity turned off or on reversibly using carbon dioxide as a trigger for application as a reversible safety switch in high energy density batteries, and the impact of silylamine chemical structure on electrochemical switching properties. Joaquin Rodriguez Lopez, University of Illinois at Urbana-Champaign Physical and Analytical Electrochemistry Division of ECS Achieving the Ultimate Performance of Fuel Cell Electrocatalysts via Programmable Electronic Control of Surface Reactivity: To explore the reactive modulation of cathodes for the oxygen reduction reaction using a dynamic surface on which complex perturbations are created during operation and evaluated using advanced electroanalytical tools. Joshua Snyder, Drexel University Physical and Analytical Electrochemistry Division of ECS Electrocatalytic Interface Engineering to Address Scaling Relations in Multi-Intermediate Electrochemical Reactions: To control the interaction of water with electrocatalytic surfaces through the development of metal/ionic liquid composite interfaces and their role in breaking intermediate scaling relations. The ECS Toyota Young Investigator Fellowship is an annual program, and the 2017-2018 request for proposals will be released in the fall of 2016. Special thanks to the 2016-2017 selection committee: • Paul Fanson, Toyota, Chair • Scott Calabrese Barton, Michigan State University, ECS Energy Technology Division • Robert Hillman, University of Leicester, ECS Physical and Analytical Electrochemistry Division • Hongfei Jia, Toyota • Brett Lucht, University of Rhode Island, ECS Battery Division • Rana Mohtadi, Toyota • Kensuke Takechi, Toyota The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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Advancement News Battery Division Receives Gift from K. M. Abraham ECS and the Battery Division are pleased to announce the K. M. Abraham Travel Awards, established with a $50,000 endowed gift from Kuzhikalail M. Abraham. The annual awards, made from proceeds of the gift, recognize promising students in the science and engineering areas of electrochemical energy storage and conversion, and are intended to help defray the costs of travel, lodging, registration, and subsistence for students to present a paper at an Electrochemical Society meeting, in a symposium sponsored by the Battery Division. “It is important that we support students and encourage them to go to ECS meetings,” Dr. Abraham said. “When I was young and just starting my career, I greatly benefitted from traveling to the meetings and I am happy to help others at the beginning of their careers. I hope by supporting this travel grant program that I will influence others to also give back to ECS.” Dr. Abraham has been a member of ECS for almost 40 years and he served as the Battery Division Chair, and thus on the ECS Board of Directors, 2006 to 2008. He held various other positions within the division and Society and has published almost 100 papers in ECS journals and proceeding volumes. Dr. Abraham is the principal of E-KEM Sciences, a battery consulting company in Needham, Mass. and a professor at the Center for Renewable Energy Technology (NUCRET), Northeastern

University, Boston, Mass. He was previously president of Covalent Associates, Inc, Woburn, Mass., and senior scientist, group leader, vice president and director of battery research and development at EIC Laboratories, Inc., Norwood, Mass. Over his illustrious career he has conducted pioneering research on rechargeable lithium, lithium-ion, lithium-polysulfide, and lithium-air batteries. It is fitting that ECS will be able to announce this gift during the Battery Division’s celebrations of the 25th anniversary of the Li-ion battery at PRiME in October. Shirley Meng, treasurer of the Battery Division, oversees the administration of the division’s travel grant programs. “This exceptionally generous gift from K.M. is greatly needed and will make a big impact on our ability to support students,” she remarked. “The requests we receive for travel grants is increasing every year and we hope that we can identify more donors to support this important program which provides great networking and experience for our next generation of scientists.” Dr. Abraham’s gift along with the newly established Battery Division Postdoctoral Associate Research Award sponsored by MTI Corporation and the Jiang Family Foundation, give the Battery Division a great boost for their programming. This kind of support also helps ECS’s overall goal of building the Free the Science Fund. When divisions identify outside revenue for their programmatic activities, ECS can contribute more operational funds to building this important fund over the next decade that will ultimately provide free and complete open access to our Digital Library for authors and readers.

Giving to ECS

New

Have you received an award from ECS for your outstanding contributions and research? Have you forged valuable connections with friends, research collaborators, business partners, or individuals in your field at our meetings? Now we need your help! There are so many ways you can give back to the Society to help continue to disseminate valuable research in the field: • Donate online or send us a check in the mail. • Give a gift of securities. • Make a gift through your estate. • Give through your donor advised fund • If you’re 70½ or older you can arrange an IRA charitable rollover And don’t forget, no matter how you donate, please check if your company has a matching gifts program— this can double the impact of your gift!

For more resources on giving visit: www.electrochem.org/give

Annual Report Available Our financial statements reflect our dedication to our mission, to advance electrochemical and solid state science and technology by disseminating technical content. In order to meet these objectives, the society produces high quality meetings, publishes high quality research in the ECS Digital Library, and creates strategic grant and award programs, all while maintaining a balance of conservative pricing and the maximization of our resources. Annual Report

Providing Solutions

You can learn more in our 2015 Annual Report— click the “About ECS” tab on our website or go directly to www.electrochem.org/finances.

www.electrochem.org/finances

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

societ y news

Free the Science News Free the Science Launch in San Diego Although complete open access and the Free the Science initiative were approved in 2014 after the Committee for the Free Dissemination of Research (CFDR) released its report making these bold recommendations, the more visible launch and unveiling of the new logo and messaging took place in San Diego in May 2016. The vision for Free the Science is that by 2024 the ECS Digital Library will be completely open access and ECS will not charge authors to publish or readers to download articles, meeting abstracts, or proceedings. Currently, ECS is the only nonprofit publisher making the transition to completely free open access. Many publishers (commercial and nonprofit) have launched spin-off open access journals or offer author choice open access but ECS is the only organization that will make all of its publishing open access. Not only does Free the Science respond to the recommendations by the CFDR, it also responds to our societal needs to create and store renewable energy, detect and cure illness, create a more sustainable environment, among other important technologies. Free the Science also responds to the growing trend by governments to require that publicly funded research is freely available to everyone. We are also seeing this trend more and more in the private foundation community. And at ECS we know it’s the right thing to do. The Internet has afforded so many people access to information and services that are helping them improve their standard of living and we believe with open access to research we can have more minds working together to solve problems.

Most important, Free the Science directly relates to our mission to disseminate and advance electrochemistry and solid state science and technology. It is comforting when faced with so much disruption in the publishing industry that we can adhere to our mission from 1902 and respond to these changes. Free the Science truly is a mission-based initiative with a social imperative. For Free the Science to succeed we need to raise a significant fund, attract the best content in our field for our journals, and promote the widest possible distribution of our Digital Library as possible. Here’s how you can help between now and when we fully realize Free the Science in approximately 8 years: • Publish your research with ECS • Donate to the Free the Science Fund at www.freethescience.org • Be an advocate for open access and share your networks with ECS—perhaps you have a funding connection or ideas to further expand dissemination of our Digital Library • Encourage your organization to subscribe to ECS Plus during this interim transition period. Please share our new librarians resource: https://ecslibblog.wordpress.com/ Last, we hope you will visit our new website www.freethescience.org and share the video that we made about our sciences and this initiative. The video is intended to also be a tool for you to use to generally explain the type of work that you do. The more people who understand the impacts of electrochemistry and solid state science and technology, the more traction we will get with Free the Science.

Scientific research is crucial to solving our world’s most pressing problems. Today, this research is not freely available: there are huge costs to publish and to access knowledge. Through Free the Science, ECS will remove publishing barriers to ensure that the sciences of sustainability and progress are free and open to everyone.

www.freethescience.org

Visit the Free the Science booth in the Exhibit Hall at PRiME 2016 to learn more or text "ECS" on your U.S. phone to 41444 to donate.

socie t y ne ws Advisory Board Created to Guide Campaign

The ECS Board of Directors has appointed a special advisory board to oversee the Free the Science campaign. The Advisory Board will offer advice and expertise, and forge connections with potential funders and advocates of open access. The group, comprised of both ECS representatives and outside interested parties, is expected to grow in size as the campaign progresses and new partnerships are established.

Free the Science in Hawaii ECS will continue to promote Free the Science at the PRiME meeting in Hawaii. Please visit our special booth in the Exhibit Hall to learn more and be eligible for special prizes, including free meeting registration and two hotel nights in New Orleans, lifetime membership, and more!

The board is co-chaired by Tetsuya Osaka and E. J. Taylor. The members are Craig Arnold, Cor Claeys, Lili Deligianni, Fernando Garzon, Robert Kostecki, Matt Spitzer, Brian Stoner, Stuart Swirson, Esther Takeuchi, and Martin Winter. The ex officio members are Roque Calvo, Karla Cosgriff, Dennis Hess, Tim Gamberzky, Krishnan Rajeshwar, Robert Savinell, Dan Scherson, and Mary Yess.

And, join us for the 5K race on Monday, Oct 3 at 6:30am on beautiful Waikiki Beach or on Friday, October 7 at 5:45am for a sunrise hike up Diamond Head, the world’s most famous volcanic crater.

The Advisory Board gathered for a preliminary meeting in San Diego and had a kick-off call in July. Three subcommittees were formed: Finance and Forecasting to ensure that our financial goals are being timely met and appropriate adjustments can be made; Fundraising and Advocacy to both meet the funding goals and full impact of a complete open digital library; and Open Science: Discoverability and Accessibility to reaffirm the mission of the campaign and ensures that the publications don’t sacrifice quality or quantity in order to produce independent, open access research.

Photo©wiki-cc Cristo Vlahos

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The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Discover our temperature controlled docking station: el-cell.com/products/docking-stations/pat-chamber

The Center for Research on Extreme Batteries by Eric Wachsman, Cynthia Lundgren, Esther Takeuchi, Kang Xu, Chunsheng Wang, Joseph Dura, David Jacobson, Kahlil Amine, and William Acker

ow much would you spend on a battery if your life depended on it? Rarely is that question asked as the vast majority of battery development is focused on bringing down battery cost for widespread consumer acceptance. However, for many industries, extremes in performance, environment, safety, and reliability are the primary criteria, and cost, while important, is not the deciding factor. Moreover, these extreme environmental and performance requirements are not met by conventional consumer batteries, or are even being considered as primary drivers for research and development by funding agencies like the Department of Energy (DOE) which is focused on transportation and stationary storage. Therefore, it was out of this vacuum that the Center for Research on Extreme Batteries (CREB) was formed to develop batteries to meet the extreme needs of the defense, aerospace, and biomedical industries.

Department of Defense Energy Storage Needs As C4ISR (Command, Control, Communications, Computers, Intelligence, Surveillance and Reconnaissance) reshapes the future battlefield, military infrastructure becomes more energy intensive. The Department of Defense (DoD) is seeking diversified solutions to the power needs of the battlefield, considering new approaches for power generation, energy storage, power distribution, alternative energy/ energy efficiency, and thermal management. Although technologies such as fuel cells, capacitors of both electrochemical and dielectric natures, photovoltaics, as well as alternate fuels are being actively developed, batteries will continue to play a central role. The categories of batteries used in DoD span multiple platforms, similar to commercial sector’s portable electronics, transportation and grid-storage, can be described as three main categories: (1) Soldier Power: These are either stand-alone battery packs or hybrid systems which can support electronic, sensing, and computing devices of dismounted soldiers for certain length of missions (Fig. 1); (2) Mobile Power: This is on-board power for combat and tactical vehicles as well as manned and unmanned autonomous vehicles (air,

ground underwater (UAV, UGV, UUV). Batteries for these platforms include two types: those serving as automotive power source as in unmanned vehicles, and those as part of Ancillary Power Units (APU), where they only support communication/surveillance functions of the platforms, especially when the main engine is switched off during the “silent watch”; (3) Local Grids: These are power distribution systems used for expeditionary camps and bases. Currently, larger energy storage battery packs are used here for UPS type capabilities/spot power and for integration with renewable (PV/wind). Beside those main categories, there are two unique battery types for military applications: reserve batteries, which serve to activate the munitions (munitions, missiles, smart-bombs, etc.) upon launching, and batteries for unattended ground sensors. Between the two key parameters, energy and power density, Soldier Power especially favors the former (>200 Wh/kg at cell level), because resupply and/or recharging (from mobile power or power grids) are usually inaccessible for the dismounted soldiers during extended duration missions; ideally soldiers would operate independently from energy resupply for up to 72 hours. For this same reason, and also due to limited charging infrastructures on battlefield, primary rather than rechargeable batteries have been traditionally preferred by the soldier, with mature Li/thionyl chloride and Li/ SO2 chemistries being the main batteries in use. However for future extended missions (72 hrs), rechargeable high energy batteries are preferred to reduce the weight carried by the soldier. On strategic level, employment of more rechargeable batteries is favored in order to reduce the logistic burden. As such, rechargeable batteries are gaining more and more penetration in the Soldier Power applications. Some Mobile and Grid Power applications emphasize power rather than energy densities (>10 kW/kg on cell level), because, like battery packs in hybrid electric vehicles, the energy output of the whole system is provided by the power conversions units, e.g., combustion engines, fuel cells, solar panels, etc. The exception is for the unmanned systems or fully electric platforms, where energy density determines the duration of that platform’s missions.

Fig. 1. Power-hungry gadgets on a dismounted soldier for a 72-hour mission (left). Soldier in the photo is U.S. Army Staff Sgt. Carlos Garcia, of Bravo Company, 2nd Battalion, 508th Parachute Infantry Regiment, taken in the Andar province of Afghanistan June 6, 2007 by U.S. Army Staff Sgt. Marcus J. Quarterman; Unmanned air (Stalker, upper right) and ground (Squad Mission Support System, lower right) vehicles (manufactured by Lockheed-Martin). 26

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Fig. 2. Temperature and radiation exposure for planetary space missions (from Ref. 2).

Besides energy and power, safety might be the single most important requirement for batteries that will be used in a battlefield environment. It is important that the battery pack carried by a soldier never experience thermal runaway; the batteries should also survive rough use such as crashing, impacting, and even ballistic penetration without generating fire or explosion. Battery packs in vehicles, APUs and local grids for camps or bases are better protected from such abuses than soldier-carried batteries; however, a unique exception is battery packs used in underwater vessels (submarines), where any thermal runaway process poses fatal danger to crew members because the oxygen in the confined space could be rapidly consumed. High tolerance against those military-specific abuses are usually achieved through robust packaging and engineering on the system or pack level, but solutions on a chemistry and materials level would be ideal considering both energy density and cost. Such a solution is best exemplified by the advanced aqueous electrolytes that are being jointly developed by the University of Maryland (UMD) and Army Research Lab (ARL), whose wide electrochemical stability window (>3.0 V) has enabled energy densities (>150 Wh/kg) competitive to that of commercial Li-ion batteries, with intrinsic safety on chemistry level ensured by their aqueous nature.1 This class of advanced aqueous battery chemistries could represent a main direction for future military battery development. Compared with their civilian counterparts, the batteries for military applications often have much more stringent requirements for temperature range (−40 °C to +75 °C). On a battery pack level, such extreme temperatures could be handled with thermal management such as air- or water-cooling systems or phase change materials as part of the packaging. However as space is usually at a premium in any military vehicle, the decrease in volumetric density for these solutions is a disadvantage. For Soldier Power, such systems add dead weight to the batteries and drive down the energy densities. Therefore the most ideal solution for both platforms would still be on a chemistry level, i.e., finding electrode and electrolyte materials that can operate within wide temperature ranges. Batteries for munitions and missiles have unique requirements. The most challenging is a 20 year shelf life, as these power sources are built into the platform and may be stored for up to 20 years before use. They usually have high power requirements so energy density is not as much a concern as the duration of use is limited.

The temperature requirements are even more extreme than for other batteries. Reliability is however the utmost requirement: munitions have to be activated upon launching. For unattended ground sensors, energy density is the prime consideration, as soldier lives and the mission are at put at risk replacing the batteries. But they need to be sufficiently power-intense for communications, which usually have a high power pulse at initiation. Unlike their civilian counterparts, especially those in the vehicle or grid-storage markets where large-scale application constantly induces cost and environmental concerns, batteries for military applications are less constrained by these standards, although they are still important.

Energy Storage for Future Space Missions For space exploration, high energy density is critical given extreme limitations on both mass and volume for rocket-launched payloads. But the battery requirements for NASA extend beyond extreme energy density to extremes in temperature and radiation exposure (Fig. 2). For example, the surface of Mars ranges from a high of 20 °C to a low of −125 °C, and for future missions to our other neighboring planet, Venus, the average temperature is 462 °C. As for deeper space such as the moons of Jupiter, radiation dose rates are several thousand times higher than on Earth; moreover, lifetime and reliability are mission critical as there is no one to change your batteries in space. To date, reliability concerns have dominated NASA’s battery selection so they have tended to stick with older lower energy density batteries that had a track record of high reliability in launched systems, slowly progressing from Ni-Cad, to Ni-H2, and only recently adopting Liion.2 However, future planetary missions cannot be achieved with those battery technologies, so a renewed focus on extreme batteries for space flight is critical to future mission success. One example of an extreme battery being developed for space applications is an all solid-state Li-S battery being developed at UMD under the NASA Game Changing, Advanced Energy Storage Program.3 Due to its Li metal anode, sulfur cathode, and novel ceramic electrolyte structure it has projected energy densities of ~540 Wh/ kg, more than double that of conventional batteries. Moreover, its

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

(continued on next page) 27

Wachsman et al.

Table I. Batteries uses for implantable medical devices.

(continued from previous page)

solid electrolyte has stable conductivity across the entire temperature range envisioned for NASA’s future planetary missions potentially allowing it to go where no battery has gone before.

Battery System Li/I2

Battery Power for Implantable Biomedical Devices Batteries utilized to power implantable biomedical devices have contributed to the widespread use of medical devices for the treatment of human disease.4,5 The devices monitor the condition of a patient and provide therapy on a predetermined schedule or as required. The implanted batteries are the sole source of energy and provide the power for monitoring, therapy as well as communication with the device. While the functional requirements for the batteries may vary with the type of device and therapy, some characteristics are demanded by all the medical applications. The batteries must provide many years of service, safety during installation and use, display predictable performance and be highly reliable. Additionally, high volumetric energy density is important to enable the design of small devices that minimize discomfort for the patient. Both primary and secondary batteries are used to power medical implants (Fig. 3). The power demands differ by orders of magnitude depending on the device. The varying demands are met by battery systems based on lithium metal anodes for primary batteries and by lithium ion systems for secondary batteries due to their high energy density and stability. Specifically, cardiac pacemakers typically require microampere levels of current and are most commonly powered by lithium/iodine type batteries which were the earliest lithium battery used for human implant.6 In contrast, implantable cardiac defibrillators (ICD) demand microampere level current for patient monitoring and ampere level pulses are needed to charge capacitors when needed to defibrillate the patient. ICDs are most often powered by lithium/silver vanadium oxide or lithium/ manganese oxide batteries. The internal electrodes are configured in multiplate or wound internal geometries to provide higher electrode surface area.7-9 Devices such as neurostimulators, and drug delivery systems are in the middle of the power requirement range needing milliampere level pulses. Some of these systems are powered by primary battery systems including lithium/manganese oxide,10,11 lithium/carbon monofluoride,12-15 or hybrid cathode systems based on silver vanadium oxide in conjunction with carbon monofluoride.16-20 Notably, some of the devices are designed with charging systems for the implementation of secondary batteries with lithium-ion being the battery system of choice.13,21,22 The voltage, capacity and energy density characteristics of medically relevant battery systems are summarized in Table I. While the functional performance of the batteries varies, high reliability, high volumetric energy density, long service life, state of discharge indication, and safety during implant and use are characteristics common to each successful medical battery.

Open Circuit Voltage 2.8*

Nominal Voltage

mAh/g Theoretical, Cathode Material

mAh/cm3 Theoretical, Cathode Material

mWh/g Energy Density of Battery

2.8†

211

1041

210-270*

Li/ MnO2

3.3†

3.0†

308

1540

270 (low rate)† 230 (high rate)†

Li/CFx

3.1

3.0

†

865

2335

440†

Li/SVO

3.24†

3.2†

315

1510

270†

C/LiCoO2

4.2

3.88

155

783

155‡

†

‡

*Ref. 23; †Ref. 24; ‡Ref. 25.

About CREB The goal of the Center for Research on Extreme Batteries (CREB) is to foster and accelerate collaborative research in advanced battery materials, technologies and characterization techniques with a focus on batteries for extreme performance, environments and applications, such as those needed for the defense, space, and biomedical industries. The concept grew out of a partnership between ARL and UMD, with the addition of National Institute of Standards and Technology (NIST) and NY BEST (Fig. 4). The CREB Steering Committee consists of the authors of this article. ARL and UMD have established a separate non-profit organization, the CREB Consortium,a administered by UMD, to participate in activities associated with CREB. Membership in the CREB Consortium is open to individuals, national and defense labs, universities, and industry through membership fees. Benefits of CREB Consortium membership include: • Access to unique research laboratories and prototyping/ manufacturing facilities applicable to battery research • Introduction to unique and state of the art characterization capabilities and guidance with their selection, application, and optimization for battery research • New ideas and collaborators with expertise in multiple disciplines • Ability to formulate joint proposals with partners to pursue external funding • Joint publications with nationally and internationally renowned experts in the field • Access to IP generated by CREB funding to members on a non-commercial basis • Unique technology transition pathways More information and how to join the CREB Consortium can be found at: http://creb.umd.edu/. © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F01163if.

Disclaimer: NIST is not a member of the CREB Consortium, and does not provide direction to, nor receive funding from the CREB Consortium. NIST involvement in CREB does not constitute an endorsement of the CREB Consortium or any companies mentioned herein nor does it imply that participation in the CREB Consortium is in any way a prerequisite for working with NIST on the important issues described here.

Fig 3. Implantable cardiac defibrillator battery schematic (R. DeMayo graphics).

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Fig 4. Diagram of the CREB structure.

References 1. L. Suo, O. Borodin, T. Gao, M. Olguin, J. Ho, X. Fan, C. Luo, C. Wang, and K. Xu, Science, 350, 938 (2015). 2. P. Beauchamp, R. Ewell, E. Brandon, and R. Surampudi, “Solar Power and Energy Storage for Planetary Missions”, Jet Propulsion Laboratory, California Institute of Technology (2015). 3. http://www.nasa.gov/press-release/nasa-selects-proposals-tobuild-better-batteries-for-space-exploration. 4. E. S. Takeuchi and R.A. Leising, MRS Bull., 27, 624 (2002). 5. D. C. Bock, A. C. Marschilok, K. J. Takeuchi, and E. S. Takeuchi, Electrochim. Acta, 84, 155 (2012). 6. R. J. Brodd, K. R. Bullock, R. A. Leising, R. L. Middaugh, J. R. Miller, and E. Takeuchi, J. Electrochem. Soc., 151, K1 (2004). 7. K. J. Takeuchi, A. C. Marschilok, S. M. Davis, R. A. Leising, and E. S. Takeuchi, Coord. Chem. Rev., 219-221, 283 (2001). 8. J. Drews, G. Fehrmann, R. Staub, and R. Wolf, J. Power Sources, 97-98, 747 (2001). 9. A. M. Crespi, S. K. Somdahl, C. L. Schmidt, and P. M. Skarstad, J. Power Sources, 96, 33 (2001). 10. D. R. Merritt and C.L. Schmidt, in Lithium Batteries, S.

Surampudi and V. Koch, Editors, PV 93-24, p. 138, The Electrochemical Society Proceedings Series, Pennington, NJ (1993). 11. D. R. Merritt and C.L. Schmidt, in Lithium Batteries V, N. Doddapaneni and A. R. Landgrebe, Editors, PV 94-4, p. 169, The Electrochemical Society Proceedings Series, Pennington, NJ (1994). 12. W. Greatbatch, C. F. Holmes, E. S. Takeuchi, and S. J. Ebel, Pacing Clin Electrophysiol., 19, 1836 (1996). 13. M. Nagata, A. Saraswat, H. Nakahara, H. Yumoto, D. M. Skinlo, K. Takeya, and H. Tsukamoto, J. Power Sources, 146, 762 (2005). 14. S. Davis, E. S. Takeuchi, W. Tiedemann, and J. Newman, J. Electrochem. Soc., 154, A477 (2007). 15. S. Davis, E. S. Takeuchi, W. Tiedemann, and J. Newman, J. Electrochem. Soc., 155, A24 (2008). 16. H. Gan, R. S. Rubino, and E. S. Takeuchi, J. Power Sources, 146, 101 (2005). 17. K. Chen, D. R. Merritt, W. G. Howard, C. L. Schmidt, and P. M. Skarstad, J. Power Sources, 162, 837 (2006). 18. P. M. Gomadam, J. Brown, E. Scott, and C. Schmidt, ECS Trans., 3(36), 45 (2007). 19. P. M. Gomadam, D. R. Merritt, E. R. Scott, and C. L. Schmidt, J. Electrochem. Soc., 154, A1058 (2007). 20. P. M. Gomadam, D. R. Merritt, E. R. Scott, C. L. Schmidt, and J. W. Weidner, ECS Trans., 11(30), 1 (2008). 21. J. Dodd, C. Kishiyama, M. Nagata, H. Nakahara, H. Yumoto, and H. Tsukamoto, in Lithium and Lithium-Ion Batteries, K. Striebel, K. Zaghib, and D. Guyomard, Editors, PV 9328, p. 360, The Electrochemical Society Proceedings Series, Pennington, NJ (2004). 22. R. S. Rubino, H. Gan, and E. S. Takeuchi, J. Electrochem. Soc., 148, A1029 (2001). 23. B. B. Owens, in Handbook of Batteries, D. Linden and T. B. Reddy, Editors, McGraw-Hill, New York, New York (2002). 24. D. Linden and T.B. Reddy, in Handbook of Batteries, D. Linden and T. B. Reddy, Editors, McGraw-Hill, New York (2002). 25. G. M. Ehrlich, in Handbook of Batteries, D. Linden and T. B. Reddy, Editors, McGraw-Hill, New York (2002).

ECS Electrochemistry

KNOWLEDGE BASE One site. Thousands of resources. 4 Over 1,000 electrochemical definitions 4 Dozens of articles by leading experts 4 Links to over 1,000 electrochemical websites 4 Over 3,000 books and proceedings volumes listed

http://knowledge.electrochem.org The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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ECS Future Meetings 2017

2017

231st ECS Meeting

SOFC-XV

232nd ECS Meeting

New Orleans, LA

Hollywood, FL

National Harbor, MD

May 28-June 2, 2017

July 23-28, 2017

(greater Washington, DC area)

Hilton New Orleans Riverside

Diplomat Hotel

October 1-6, 2017 Gaylord National Resort and Conference Center

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2018 233rd ECS Meeting

AiMES 2018

Seattle, WA

Cancun, Mexico

May 13-17, 2018

September 30-October 4, 2018

Seattle Sheraton and Washington State Convention Center

Moon Palace Resort

www.electrochem.org/meetings

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

PRiME 2016 October 2 – 7, 2016

Honolulu, Hawaii Photo © Hawaii Tourism Authority (HTA) / Joe Solem

elcome to Honolulu! We are excited to host PRiME 2016 once again in this captivating city. The Hilton Hawaiian Village and the Hawaii Convention Center have opened their doors to make this event a memorable one. PRiME 2016 will include 56 topical symposia and 4182 technical presentations.

This is the largest, most significant research conference in the world, and would not be possible without the joint effort of The Electrochemical Society, The Electrochemical Society of Japan, and our newest partner, The Korean Electrochemical Society. The following technical co-sponsors also helped make this meeting possible: Chinese Society of Electrochemistry, Electrochemistry Division of the Royal Australian Chemical Institute, Japan Society of Applied Physics, Korean Physical Society Semiconductor Division, and Semiconductor Physics Division of the Chinese Physics Society. PRiME has seen tremendous growth since the meeting was established in 1987. The first joint international meeting between ECS and ECSJ took place at this very same venue, providing a central location between the two societies in this mid-Pacific hub of communications. Here, ECS and ECSJ began to build what would become a major conference for the discussion of interdisciplinary research from around the world, ranging from topics in renewable energy and water sanitation to biomedical and communication technologies. This year marks PRiME’s seventh return to the beautiful island of Oahu. We’ve received a record number of abstracts and will be holding the 6th International Electrochemical Energy Summit focused on renewable energy, distribution, and storage. This year’s summit will include keynote presentations and remarks from the U.S. Department of Energy, New Energy and Industrial Technology Development Organization, Korea Institute of Energy Research, and the Hawaii State Energy Office.

Make sure to attend Monday evening’s Plenary Session, where participants from every symposium can come together to recognize some of the greatest minds in the field. The presidents of ECS, ECSJ, and KECS will welcome guests and introduce the highly anticipated lecturer, Michael Graetzel and his talk, “Photoelectrochemical Cells for the Generation of Electricity and Fuels from Sunlight.” Stop by the Exhibit Hall, located in Hall 2 of the Hawaii Convention Center, where you can network with your colleagues and learn about some of the top innovations in the industry. Make sure to stop by the Exhibit Hall often to catch the student and general poster sessions and visit our exciting lineup of international exhibitors. Use our meeting program and meeting scheduler on your mobile device to make the most of your time. If you have any additional questions, please do not hesitate to stop by the registration desk in the Hall 2 Foyer for further assistance. We thank you again for your continued support!

Krishnan Rajeshwar Hiroshi Nishihara ECS President

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ECSJ President

Yongkeun Son

KECS President

Special Meeting Section-PRiME 2016, Honolulu, HI-October 2-7, 2016

Welcome to PRiME 2016

PRiME 2016 October 2 – 7, 2016

Honolulu, Hawaii Photo © Hawaii Tourism Authority (HTA) / Chuck Painter

Special Meeting Section-PRiME 2016, Honolulu, HI-October 2-7, 2016

PRiME 2016 Leadership PRiME 2016 Organizing Committee ECS Co-Chair: Krishnan Rajeshwar ECSJ Co-Chair: Hiroyuki Uchida

ECSJ Leadership ECSJ Officers Hiroshi Nishihara, President Susumu Kuwabata, Vice President Atsushi Nishikata, Vice President

ECS: Christina Bock

Kenichi Udagawa, Vice President

ECS: D. Noel Buckley

Yoshinori Hirai, Vice President

ECS: Fernando Garzon

Akinori Konno, Executive Director

ECSJ: Yasushi Katayama

Mikako Saito, Executive Director

ECSJ: Wataru Sugimoto

Ayumi Koike, Treasurer Director

ECSJ: Shoso Shinguhara

Eiry Kobatake, Treasurer Director

KECS: Won-Sub Yoon

Atsuo Yamada, Editing Director

KECS : Jae-Joon Lee

Yasushi Katayama, Editing Director

ECS Leadership

Tadashi Takamizawa, Executive Director Shunya Ikezuki, Director of Branch & Committee Michiko Takeda, Director of Finance Minaki Sakamoto, Director of Publications

ECS Officers Krishnan Rajeshwar, President

KECS Leadership

Johna Leddy, Sr. Vice President Yue Kuo, 2nd Vice President Christina Bock, 3rd Vice President

KECS Officers

James Fenton, Secretary

Yongkeun Son, President

E. Jennings Taylor, Treasurer Roque Calvo, Executive Director & CEO

Myung Hwan Kim, Vice President

ECS Senior Management

Won Il Cho, Vice President

Heonsu Kim, Vice President

Roque Calvo, Executive Director/Chief Executive Officer

HyunSu Kim, Vice President

Tim Gamberzky, Chief Operating Officer

Woonsup Shin, Vice President

Mary Yess, Deputy Executive Director & Chief Content Officer

Won-Yong Lee, Vice President Nam-Gyu Park, Vice President Yung-Eun Sung, Vice President Yongsug Tak, Vice President Soo-Gil Park, Vice President

w w w .p r i m e- i n tl . or g

October 2 – 7, 2016

Honolulu, Hawaii

Photo © Hawaii Tourism Japan (HTJ)

PRiME 2016 Photo © Hawaii Tourism Authority (HTA) / Tor Johnson

Semiconductor Physics Division of Chinese Physics Society

Electrochemistry Division of the Royal Australian Chemical Institute

ShuShen Li, President

Anthony O’Mullane, Chair

DeZhen Shen, Vice President

Chuan Zhao, Secretary

ZuiMin Jiang, Vice President

Damien Arrigan, Treasurer

Yang Ji, Secretary General

Semiconductor Physics Division of the Korean Physical Society

The Chinese Society of Electrochemistry (CSE) Yan-Xia Jiang, Secretary General

Yong Min Kim, Secretary General

The Japan Society of Applied Physics (JSAP) Kazuo Hotate, President Shigeaki Zaima, Vice President Naoki Yokoyama, Vice President Seigo Kanemaru, Vice President

Photo © Hawaii Tourism Authority (HTA) / Chuck Painter

Photo © Hawaii Tourism Authority (HTA) / Tor Johnson

Photo © Dana Edmunds

Special Meeting Section-PRiME 2016, Honolulu, HI-October 2-7, 2016

Technical Co-Sponsors

Electrochemical Energy Summit 2016

Recent Progress in Renewable Energy Generation, Distribution, and Storage When:

October 2, 2016

Where:

Ballroom B and C | Hawaii Convention Center Followed by the Sunday Evening Get Together The International Electrochemical Energy Summit (E2S) brings together policy makers and researchers to educate attendees about the critical issues of energy needs and the pivotal research in electrochemical energy that can address societal needs. The 6th E2S Summit is designed to facilitate interactions and foster exchange between leading policy makers, researchers, and energy experts about society needs and technological energy solutions through a variety of formats: keynote presentations, poster sessions, networking opportunities, and associated receptions. With population growth and industrialization, global energy needs continue to grow as well. Economic, political, and environmental issues are largely dictated by energy needs. The sixth international ECS Electrochemical Energy Summit (E2S) will be focused around Recent Progress in Renewable Energy Generation, Distribution and Storage. The program on Sunday will include keynote presentations and remarks from DOE, NEDO, KIER, and the Hawaii State Energy Office followed by a poster session showcasing research, advancements or technologies within the clean energy and applicable works within Recent Progress in Renewable Energy Generation, Distribution and Storage.

CHAIR

Boryann Liaw, Hawaii Natural Energy Institute

ORGANIZERS

Adam Weber, Lawrence Berkeley National Laboratory Hiroyuki Uchida, University of Yamanashi Won-Sub Yoon, Sungkyungkwan University Mark Glick, Hawaii State Energy Administrator

KEY PARTICIPANTS Mark Glick Administrator, Hawaii State Energy Office Hawaii Department of Business, Economic Development & Tourism Electrochemical Energy Summit Moderator

Robert K. Dixon Director Office of Strategic Programs, U.S. Department of Energy Electrochemical Energy Summit Speaker

Eiji Ohira Director Fuel Cell and Hydrogen Technology Group, New Energy Technology Dept., New Energy and Industrial Technology Development Organization (NEDO) Electrochemical Energy Summit Speaker

Won-Yong Lee Principal Researcher, New and Renewable Energy Division, Korea Institute of Energy Research (KIER) Electrochemical Energy Summit Speaker

PROGRAM

1600h ...................................................................................................................................................Welcome and Opening Remarks 1620h ................................... DOE’s Efforts to Accelerate Federally-Funded Technology to the Marketplace by R. K. Dixon (U.S. Department of Energy) 1640h ........................................................................................................................Japan’s Policy and Activity on Hydrogen Energy by E. Ohira (New Energy & Industrial Tech Development Organization) 1700h ............................................Recent Trend in New and Renewable Energy Generation in Korea and KIER’s R&D Activities by W. Y. Lee (Korea Institute of Energy Research) 1720h ...............................................................................................................................................................................................Q&A 1730h .................................................................................................................................. Closing Remarks & Poster Session Begins

Sponsors

Symposia Sponsors

(continued)

Bronze Arbin Instruments A01 - Batteries and Energy Technology Joint General Session

Applied Microengineering Ltd. H02 - Semiconductor Wafer Bonding: Science, Technology and Applications 14

Bondtech Co., Ltd. H02 - Semiconductor Wafer Bonding: Science, Technology and Applications 14

Committee of Battery Technology, Japan A02 - Challenges in Advanced Analytical Tools and Techniques for Batteries: A Symposium in Honor of Prof. Zempachi Ogumi

FEI G05 - SiGe, Ge, and Related Materials: Materials, Processing, and Devices 7

Fuji Electric Co., Ltd. H02 - Semiconductor Wafer Bonding: Science, Technology and Applications 14

Gelest G03 - Atomic Layer Deposition Applications 12

Horiba, Ltd. C02 - Oxide Films: A Symposium in Honor of Masahiro Seo

Kanto Chemical Co., Inc. L02 - Molten Salts and Ionic Liquids 20

KOEI Chemical Company, Limited L02 - Molten Salts and Ionic Liquids 20

Musashino Engineering H02- Semiconductor Wafer Bonding: Science, Technology and Applications 14

Mitsubishi Heavy Industries Machinetool Co., Ltd. H02- Semiconductor Wafer Bonding: Science, Technology and Applications 14

Nichia Corporation H02 - Semiconductor Wafer Bonding: Science, Technology and Applications 14

Nippon Chemi-Con Corporation C02 - Oxide Films: A Symposium in Honor of Masahiro Seo

Park Systems Corp. G05 - SiGe, Ge, and Related Materials: Materials, Processing, and Devices 7

RASIRC G03 - Atomic Layer Deposition Applications 12

Sumitomo Metal Mining Co., Ltd. L02- Molten Salts and Ionic Liquids 20

Picosun G03- Atomic Layer Deposition Applications 12

X-FAB MEMS Foundry GmbH H02- Semiconductor Wafer Bonding: Science, Technology and Applications 14

The Electrochemical Society Interface â&#x20AC;˘ Fall 2016 â&#x20AC;˘ www.electrochem.org

Special Meeting Section-PRiME 2016, Honolulu, HI-October 2-7, 2016

Thank You to the 2016 PRiME Symposia Sponsors!

Symposium Topics and Organizers

Symposium Topics and Organizers Special Meeting Section-PRiME 2016, Honolulu, HI-October 2-7, 2016

A — Batteries and Energy Storage A01 — Batteries and Energy Technology Joint General Session M. Doeff, A. Manivannan, T. Jow, V. Kalra, Gao Liu, Z.-F. Ma Battery, Energy Technology, Chinese Society of Electrochemistry (CSE) A02 — Challenges in Advanced Analytical Tools and Techniques for Batteries: A Symposium in Honor of Prof. Zempachi Ogumi M. Inaba, R. Kostecki, V. Di Noto, Y. Uchimoto, H. Arai Battery, Energy Technology, ECSJ Battery A03 — Li-Ion Batteries C. Johnson, Y. Cui, Y. Zhang, G. Koenig, R. Kostecki, D. Guyomard, M. Winter, Y. Fukunaka Battery, The Electrochemical Society of Japan (ECSJ) A04 — Advances in Electrolytes for Lithium Batteries B. Lucht, T. Jow, S.-W. Song, Y. Meng, M. Ue, D.-W. Kim Battery, KECS Battery Division A05 — Beyond Li-ion Batteries J. Muldoon, V. Di Noto, S. Passerini, J. Lu, D. Im, M. Yakovleva, J.-W. Lee, K. Kang, J. Choi, B. Key, H. Kim, Y.-M. Kang, P. Shirvanian, J. Chen Battery, Physical and Analytical Electrochemistry, KECS Battery Division, Chinese Society of Electrochemistry (CSE) A06 — Failure Mode and Mechanism Analyses B. Y. Liaw, Y. Uchimoto, Y. Yang, W.-S. Yoon, J. Nanda, S. Pannala Battery, The Electrochemical Society of Japan (ECSJ), KECS Battery Division, Chinese Society of Electrochemistry (CSE) A07 — Electrochemical Capacitors and Related Devices: Fundamentals to Applications A. Balducci, T. Brousse, D. Bélanger, P. Simon, H. S. Park, P. Kumta, J. Long, M. Ishikawa, W. Sugimoto, K. Naoi, M. Morita, K.-B. Kim, Y.-Y. Xia Battery, Energy Technology, ECSJ Capacitor Technology, KECS Supercapacitor Division, Chinese Society of Electrochemistry (CSE) B — Carbon Nanostructures and Devices B01 — Carbon Nanostructures: From Fundamental Studies to Applications and Devices R. Bruce Weisman, S. V. Rotkin, H. Imahori, P. Atanassov Nanocarbons, Physical and Analytical Electrochemistry, The Electrochemical Society of Japan (ECSJ) C — Corrosion Science and Technology C01 — Corrosion General Poster Session R. Buchheit, S. Virtanen Corrosion C02 — Oxide Films: A Symposium in Honor of Masahiro Seo H. Habazaki, K. Azumi, A. W. Hassel, K. Hebert Corrosion, ECSJ Corrosion C03 — High Temperature Corrosion and Materials Chemistry 12 E. Opila, J. Fergus, P. Gannon, T. Markus, M. Nanko, D. Chidambaram High Temperature Materials, Corrosion, ECSJ Battery C04 — Pits & Pores 7: Nanomaterials – Fabrication Processes, Properties, and Applications P. Granitzer, R. Boukherroub, D. Lockwood, H. Masuda Corrosion, Luminescence and Display Materials, The Electrochemical Society of CD/USB Japan (ECSJ) C05 — Atmospheric -and- Marine Corrosion A. Nishikata, M. Sakairi, I. Cole, C. Leygraf, R. Srinivasan, E. Tada, H. Katayama, M. Itagaki Corrosion, ECSJ Corrosion C06 — Metallic, Organic and Composite Coatings for Corrosion Protection M. Rohwerder, G. Williams Corrosion

ECS Transactions available formats: –Electronic issue PDF CD/USB –Content on both a compact disc and USB 38

D — Dielectric

Science and Materials

D01 — Photovoltaics for the 21st Century 12 M. Tao, J. Fenton, J.-Y. Lee, P. Kulesza, M. J. Ko, J. J. Lee, V. Subramanian, N. Park, H. Jung, J. Noh, S. Hayase, T. Miyasaka, H. Segawa, H. Hamada Energy Technology, Dielectric Science and Technology, Electrodeposition, Electronics and Photonics, Industrial Electrochemistry and Electrochemical Engineering, Physical and Analytical Electrochemistry, ECSJ Photoelectrochemistry, Solar Cell Division of KECS D02 — Nonvolatile Memories 5 S. Shingubara, Z. Karim, B. Magyari-Kope, H. Kubota, J.-G. Park, K. Kobayashi, L. Goux, Y. Saito Dielectric Science and Technology, Electronics and Photonics, ECSJ Electronics D03 — Plasma Nano Science and Technology U. Cvelbar, S. Vaddiraju, P. Mascher, M. Sunkara Dielectric Science and Technology E — Electrochemical/Electroless Deposition E01 — Electroless Deposition:Principles and Applications 4: In Honor of Milan Paunovic and Mordechay Schlesinger S. Djokic, L. Magagnin, T. Homma, S. Yoshihara Electrodeposition, ECSJ Nano-Micro Fabrication E02 — Magnetic Materials Processes and Devices 14 C. Bonhôte, G. Zangari, Y. Kitamoto, T. Osaka, H. H. Gatzen Electrodeposition, ECSJ Nano-Micro Fabrication

CD/USB

E03 — Molecular Structure of the Solid-Liquid Interface and Its Relationship to Electrodeposition 8 G. Zangari, R. Alkire, T. Homma, L. Kibler Electrodeposition, Industrial Electrochemistry and Electrochemical Engineering, ECSJ Nano-Micro Fabrication E04 — Electrodeposition for Energy Applications S. Brankovic, M. Shao, P. Vereecken, R. Bhattacharya, S. H. Kang, Y. Fukunaka, J. Kim Electrodeposition, Energy Technology, ECSJ Nano-Micro Fabrication F — Electrochemical Engineering F01 — Industrial Electrochemistry and Electrochemical Engineering General Session J. Staser, V. Subramanian, D. Riemer, M. Morimitsu Industrial Electrochemistry and Electrochemical Engineering, ECSJ Industrial Electrolysis and Electrochemical Engineering F02 — Electrochemical Impedance Spectroscopy: In Honor of Bernard Tribollet M. Orazem, M. Itagaki, P. Vanýsek Industrial Electrochemistry and Electrochemical Engineering, Corrosion, Physical and Analytical Electrochemistry, The Electrochemical Society of Japan (ECSJ) F03 — Contemporary Issues and Case Studies in Electrochemical Innovation 2 E. J. Taylor, K. Ayers, K. Ohashi, J. Staser, G. Botte, M. Inman, M. Hashimoto, R. Alkire, M. Lowe Industrial Electrochemistry and Electrochemical Engineering, ECSJ Industrial Electrolysis and Electrochemical Engineering F04 — Membrane-based Electrochemical Separations 2 H. Xu, T. Gur Energy Technology, High Temperature Materials, Industrial Electrochemistry and CD/USB Electrochemical Engineering, Physical and Analytical Electrochemistry G — Electronic Materials and Processing G01 — High Purity and High Mobility Semiconductors 14 E. Simoen, R. Falster, O. Kononchuk, O. Nakatsuka, C. Claeys Electronics and Photonics, Dielectric Science and Technology, The Electrochemical CD/USB Society of Japan (ECSJ) G02 — Semiconductors, Dielectrics, and Metals for Nanoelectronics 14 S. Kar, K. Kita, D. Landheer, D. Misra Dielectric Science and Technology, Electronics and Photonics

CD/USB

G03 — Atomic Layer Deposition Applications 12 F. Roozeboom, S. De Gendt, J. Elam, O. van der Straten, C. Huffman, J. Dendooven, C. Liu Dielectric Science and Technology, Electronics and Photonics

CD/USB

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Symposium Topics and Organizers

G05 — SiGe, Ge, and Related Materials: Materials, Processing, and Devices 7 D. Harame, M. Caymax, G. Masini, S. Miyazaki, Q. Liu, R. Camillo-Castillo, A. Thean, A. Joseph, A. Mai, M. Ostling, A. Ogura, J.-M. Hartmann, A. Schulze, K. Saraswat Electronics and Photonics, Dielectric Science and Technology, The Electrochemical CD/USB Society of Japan (ECSJ) H — Electronic and Photonic Devices and Systems H01 — State-of-the-Art Program on Compound Semiconductors 59 (SOTAPOCS 59) M. E. Overberg, W. Johnson, T. Anderson, J. Hite Electronics and Photonics H02 — Semiconductor Wafer Bonding: Science, Technology and Applications 14 T. Suga, H. Baumgart, F. Fournel, M. Goorsky, K. Hobart, R. Knechtel, C. S. Tan Electronics and Photonics, Battery, The Electrochemical Society of Japan (ECSJ) CD/USB

H03 — Thin Film Transistors 13 (TFT 13) Y. Kuo Electronics and Photonics

CD/USB

K — Organic and Bioelectrochemistry K01 — Bioengineering Based on Electrochemistry K. Sode, S. Tsujimura, A. Simonian, R. Mukundan, S. C. Barton, S. Minteer, W. Tsugawa Organic and Biological Electrochemistry, Energy Technology, Sensor, ECSJ Bioengineering K02 — Recent Advances in the Application of Electrochemistry to Problems in Organic Chemistry and Biology J.-i. Yoshida, M. Atobe, K. Moeller, A. Fry Organic and Biological Electrochemistry, ECSJ Organic Electrochemistry L — Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry L01 — Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry General Session A. Suroviec, P. Kulesza, S. Minteer, P. Atanassov, B. Chin, W.-Y. Lee, D. Cliffel, T. Tatsuma, T. Torimoto, T. Ohno Physical and Analytical Electrochemistry, Sensor, ECSJ Photoelectrochemistry, KECS Physical Electrochemistry Division L02 — Molten Salts and Ionic Liquids 20 L. Haverhals, R. Mantz, P. Trulove, M. Ueda, M. Carter, E. Biddinger, A. Suroviec, S. Mukerjee, W. Reichert, F. Endres, A. Bund, A. Ispas, D. Fox Physical and Analytical Electrochemistry, Electrodeposition, Energy Technology, CD/USB Sensor, ECSJ Molten Salt

H04 — Low-Dimensional Nanoscale Electronic and Photonic Devices 9 C. O'Dwyer, Y.-L. Chueh, J.-H. He, M. Suzuki, S. Jin, S.-W. Kim, J. Ho, Z. Fan, Q. Li, G. Hunter, K. Takei CD/USB Electronics and Photonics

L03 — Electrode Processes 11 A. Hillier, S. Mukerjee, N. Hoshi, F. Matsumoto Physical and Analytical Electrochemistry, Energy Technology, ECSJ Interfacial Electrochemistry, ECSJ Molecular Functional Electrode

H05 — Gallium Nitride and Silicon Carbide Power Technologies 6 M. Dudley, K. Shenai, M. Bakowski, N. Ohtani, B. Raghothamachar Electronics and Photonics, Dielectric Science and Technology, The Electrochemical CD/USB Society of Japan (ECSJ)

L04 — Photocatalysts, Photoelectrochemical Cells, and Solar Fuels 7 N. (Nick) Wu, D. Chu, P. Kulesza, K. T. Nam, H. Park, V. Subramanian, H. Wang, J. J. Lee, M. Soriaga, N. Batina, T. Tatsuma, B. Ohtani, A. Kudo Energy Technology, Physical and Analytical Electrochemistry, Sensor, ECSJ Photoelectrochemistry, Solar Cell Division of KECS

H06 — Fundamentals and Applications of Microfluidic and Nanofluidic Devices 3 X. Xuan, S. Qian, S. Joo, J. Hsu, H. Baumgart, N. Hu Electronics and Photonics, Physical and Analytical Electrochemistry, Sensor H07 — Emerging Nanomaterials and Devices U. Schwalke, H. Baumgart, H. Hahn, F. Kreupl, M. Lemme, Q. Li, M. Orlowski, S. V. Rotkin Electronics and Photonics, Dielectric Science and Technology, Nanocarbons CD/USB I — Fuel Cells, Electrolyzers, and Energy Conversion I01 — Polymer Electrolyte Fuel Cells 16 (PEFC 16) D. Jones, A. Weber, V. Ramani, T. Fuller, R. Mantz, H. Uchida, F. Büchi, H. Xu, C. Coutanceau, J. Fenton, S. Mitsushima, T. Schmidt, K. Shinohara, K. SwiderLyons, H. Gasteiger, B. Pivovar, K. Ayers, K. Perry, S. Narayanan, P. Strasser, P. Shirvanian, Y.-t Kim, L. Zh Energy Technology, Battery, Industrial Electrochemistry and Electrochemical Engineering, Physical and Analytical Electrochemistry, ECSJ Fuel Cells, Chinese CD/USB Society of Electrochemistry (CSE) I02 — Solid State Ionic Devices 11 E. Wachsman, A. Manivannan, T. Ishihara, J.-H. Lee, P. Vanýsek, M. Carter High Temperature Materials, Energy Technology, Physical and Analytical Electrochemistry, Sensor, ECSJ Solid-State Chemistry, The Korean Electrochemical Society (KECS) I03 — Electrosynthesis of Fuels 4 X.-D. Zhou, H. Xu, T. Gur, G. Brisard, J. Staser, W. Mustain, J. Flake, M. Mogensen High Temperature Materials, Energy Technology, Industrial Electrochemistry and Electrochemical Engineering, Physical and Analytical Electrochemistry I04 — Energy/Water Nexus: Power from Saline Solutions J.-S. Park, C.-S. Kim, A. Herring Energy Technology J — Luminescence and Display Materials, Devices, and Processing J01 — Luminescence and Display Materials: Fundamentals and Applications A. Setlur, K. Mishra, J. Lin, T. Juestel, M. Brik Luminescence and Display Materials J02 — Materials for Solid State Lighting M. Raukas, K.-S. Sohn, R.-J. Xie, K. Toda Luminescence and Display Materials

M — Sensors M01— Chemical Sensors 12. Chemical and Biological Sensors and Analytical Systems M. Carter, Y. Shimizu, W.-Y. Lee, T. Yasukawa, R. Mukundan, A. Simonian, A. O'Riordan, L. Nagahara, O. Niwa, B. Chin, J. J. Lee CD/USB Sensor, ECSJ Chemical Sensor, KECS Sensor Division M02— Microfabricated and Nanofabricated Systems for MEMS/NEMS 12 P. Hesketh, J.-W. Choi, S. Minteer, A. Khosla, S. Mitra, O. Tabata, R.-I. Stefanvan Staden, P. Vanýsek, N. (Nick) Wu, S.-J. Young, H. Furukawa, T. Mineta, F. Hirose CD/USB Sensor, Physical and Analytical Electrochemistry, ECSJ Bioengineering M03— Electrochemical Analysis with Nanomaterials and Nanodevices Y. Piao, S. Hwang, I.-S. Shin, G. Diao, J. J. Lee, D. Cliffel Sensor, Physical and Analytical Electrochemistry, KECS Physical Electrochemistry Division Z — General Z01 — General Student Poster Session V. Subramanian, V. Chaitanya, K. Sundaram, P. Pharkya, W. Sugimoto, W.-S. Yoon All Divisions, The Electrochemical Society of Japan (ECSJ), The Korean Electrochemical Society (KECS) Z02 — Nanotechnology General Session O. Leonte, P. Atanassov, L. Chen, D.-W. Kim All Divisions, Interdisciplinary Science and Technology Subcommittee, The Electrochemical Society of Japan (ECSJ), The Korean Electrochemical Society (KEC) Z03 — Electrochemical Energy Summit (E2S) - Poster Session B. Y. Liaw, A. Weber, H. Uchida, W.-S. Yoon, M. Glick All Divisions, The Electrochemical Society of Japan (ECSJ), The Korean Electrochemical Society (KECS) Z04 — Electrochemical Energy Summit (E2S): Recent Progress in Renewable Energy Generation, Distribution, and Storage B. Y. Liaw, A. Weber, H. Uchida, W.-S. Yoon, M. Glick All Divisions, The Electrochemical Society of Japan (ECSJ), The Korean Electrochemical Society (KECS)

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Special Meeting Section-PRiME 2016, Honolulu, HI-October 2-7, 2016

G04 — Processing Materials of 3D Interconnects, Damascene and Electronics Packaging 8 K. Kondo, G. Mathad, W. -P. Dow, S. Armini, M. Hayase, M. Koyanagi, Y. Kaneko, F. Roozeboom, R. Akolkar Electronics and Photonics, Dielectric Science and Technology, Electrodeposition, CD/USB The Electrochemical Society of Japan (ECSJ)

Exhibitors

Technical Exhibit Special Meeting Section-PRiME 2016, Honolulu, HI-October 2-7, 2016

The exhibitors at PRiME will showcase some of the greatest innovations in the industry including cutting edge instruments, materials, systems, publications, and software, as well as other products and services.

Where:

The Exhibit Hall will be located in Hall 2 of the Hawaii Convention Center.

Exhibit Hours: Monday, October 3, 2016 1100-2200h................................................................................................................... Exhibitor Move-in Tuesday, October 4, 2016 1300-1600h....................................................................................................................Technical Exhibit 1800-2000h..........................................................Technical Exhibit, General & Student Poster Session Wednesday, October 5, 2016 0900-1400h....................................................................................................................Technical Exhibit 0930-1000h................................................................................................. Coffee Break in Exhibit Hall 1800-2000h........................................................................ Technical Exhibit & General Poster Session Thursday, October 6, 2016 0900-1200h....................................................................................................................Technical Exhibit 0930-1000h................................................................................................. Coffee Break in Exhibit Hall 1200-1600h................................................................................................ Technical Exhibit Tear Down

Exhibitors ALS Co.,Ltd Booth 306

Katsunobu Yamamoto Yamamoto@bas.co.jp 1-28-12, Mukojima Sumida-ku, Tokyo 131-0033 +81.3.3624.0331 Japan www.als-japan.com

ALS provides researchers with a wide range of products for electrochemistry and spectroelectrochemistry applications, including Bi-Potentiostat (Model 2325), Ring-Disk Electrode apparatus (RRDE3A), Spectrometer Systems (SEC2000) and Faraday cage (CS-3A). We also dealing with various kinds of Spectroelectrochemical cells (SEC-C/SEC-2F), Quartz Crystal Microbalances cell/Quartz crystal (QCM/EQCM) and Electrodes/Accessories for EC measurement same as their related items.

Bio-Logic USA Booths 214 & 216

David Carey david.carey@bio-logic.us 9050 Executive Park Drive, Suite 100C Knoxville, TN 37923 1.865.769.3800 USA www.bio-logic.net

Bio-Logic is the exclusive provider of EC-Lab electrochemical instruments. The EC-Lab family of products includes modular single-channel (SP-50/150/200/300) and multi-channel (VSP/ VMP3/VSP-300/VMP-300) potentiostats/galvanostats, High current potentiostats (HCP-803/1005) and easy to use software. Additionally, Bio-Logic offers a complete line of electrochemical accessories, including cells, electrodes, and ancillary instruments. Bio-Logic is also the provider of BT-Lab line of battery cyclers (MPG-2xx and BCS-8XX families), the SCAN-Lab line of localized electrochemical 40

scanning systems (M370 and M470 modular systems), and the MTLab materials analysis systems (MTZ-35 FRA and high temperature sample holder). Come to booths 312, 314, and 316 to see our exciting showcase of products.

Dioxide Materials Booth 105

Maria Gainer Maria.gainer@dioxidematerials.com 3998 FAU Blvd., Suite 300 Boca Raton, FL 33431 1.561.613.1991 USA www.dioxidematerials.com

Dioxide Materials™ is displaying Sustainion™ anion exchange membranes enabling alkaline water electrolyzers with up to 6 A/ cm² current at 2.05 V and 60 C, CO2 electrolyzers with up to 280 mA/ cm² at 3 V and room temperature. Preorders of membranes for researchers interested in beta-testing available before formal product announcement.

DropSens SL Booth 205 & 207

Paula Caldevilla Info@dropsens.com Parque Tecnológico de Asturias Edificio CEEI 33428 Llanera +34.985.277.685 Spain www.dropsens.com

DropSens designs instruments for Electrochemistry and Electroanalytical Research, with a clear point-of-care philosophy. They are focused on the manufacturing of screen-printed electrodes, providing researchers with a powerful platform for the development of electrochemical (bio)sensors: chemical, enzyme, immune and The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Exhibitors

FUJIFILM Dimatix, Inc. Literature Display

Eunice Wang ewang@dimatix.com 2250 Martin Avenue Santa Clara, California 95050 1.408.565.0670 USA www.dimatix.com

Inkjet printing allows creation of products like DNA arrays, electronics, displays and solar cells. The DMP-2831 is designed for micro-precision jetting a variety of functional fluids onto virtually any surface and minimizes waste of expensive fluid materials, thereby eliminating the cost and complexity associated with traditional product development and prototyping.and electrodes.

Gamry Instruments Booths 215 & 217

Cynthia Schroll cschroll@gamry.com 734 Louis Drive Warminster, PA 18974 1.215.682.9330 USA ww.gamry.com

Gamry Instruments designs and manufactures high-quality electrochemical instrumentation and accessories. Our full lineup includes single and multichannel potentiostats from 600 mA to 30 A (all capable of EIS), fully-integrated spectroelectrochemical setups for both UV/Vis and Raman, four-terminal battery holders and an EQCM that can handle any crystal from 1-10 MHz. Stop by to see our new potentiostats including one specially designed for testing batteries, fuel cells, and supercapacitors.

Gelest Literature Display

Gabrielle Lockwood glockwood@gelest.com 11 E. Steel Rd. Morrisville, PA 19067 1.215.547.1015 USA www.gelest.com

Gelest, Inc., headquartered in Morrisville, Pennsylvania, is recognized worldwide as an innovator, manufacturer and supplier of commercial and research quantities of organosilicon compounds, metal-organic compounds and silicones. Gelest serves advanced technology markets through a materials science-driven approach. The company provides focused technical development and application support for semiconductors, optical materials, pharmaceutical synthesis, diagnostics and separation science, and specialty polymeric materials: “Gelest – Enabling Your Technology.”

Heifei Ke Jing Materials Technology Co., LTD (KMT) Booth: 302

Tanglin An antanglin@kjmti.com 10 Ke Xue Yuan Street, Shushan District, Hefei, Anhui, 230031 +01186.400.060.9969 China www.kjmti.com/

KMT has been providing a total solution for materials research labs since 1995. KMT supplies ceramic, crystal, metallic substrates from A-Z and nano-powder. We also provides laboratory R&D equipment including mixing, cutting, polishing machines, high temperature muffle and tube furnaces, pressing machines, film coaters, glove boxes, high vacuum systems, high-pressure furnaces, RTP furnaces, CSS and PECVD furnace systems, high pressure and hydrogen furnaces, melting and casting systems, crystal growth systems as well as compact XRD/X-Ray orientation unit and equipment for battery and energy materials research.

Hohsen Corporation Booth 201

Daisuke Sakai sakai@hohsen.co.jp 8F Risona Senba Bldg. 4-21, 4-chome Minamisenba, Chuo-ku Osaka-shi Osaka 542-0081 +81.6.6253.2600 Japan www.hohsen.co.jp

Hohsen provides R&D / Pilot Line / Mass Production equipment, materials, parts, engineering and consulting services for Lithium-ion battery fabrication.

Hokuto Denko Corp. Booth 102

Takeshi Morita morita@hokuto-denko.co.jp 4-22-13, Himonya Meguro, Tokyo 152-0003 +81.3.3793.8787 Japan www.hokuto-denko.co.jp

HOKUTO DENKO has developed, manufactured and sold electrochemical measurement products since its foundation in 1958. The water quality measurement business was added in 1991. Hokuto Denko will continue selling an electrochemistry-based product and system to the world in future.

I²CNER Booth 203

Ruri Hirashima wpisyogai@jimu.kyushu-u.ac.jp 744 Motooka, Nishi-ku Fukuoka 819-0395 Japanwww.i2cner.kyushu-u.ac.jp/en/

+81.9.2802.6935

International Institute for Carbon-Neutral Energy Research (I2CNER) seeks to contribute to the advancement of low carbon emission and cost effective energy systems and improvement of energy efficiency. The array of technologies that I2CNER’s research aims to enable includes Solid Oxide Fuel Cells, Polymer Membrane based fuel cells, biomimetic and other novel catalyst concepts, and production, storage, and utilization of hydrogen as a fuel. (continued on next page)

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Special Meeting Section-PRiME 2016, Honolulu, HI-October 2-7, 2016

genosensors; also incorporating the advantages of Nanotechnology to Electrochemistry through our nanostructured sensors. In addition they have a wide variety of Bluetooth battery-powered Portable Potentiostats offering the main electrochemical techniques while retaining the accuracy of bigger instruments and with an easy-to-use computer interface. Their latest equipment releases in the field of Spectroelectrochemistry and Electrochemiluminescence have moved one step further the range of applications of their products.DropSens can also manufacture tailored instruments

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Exhibitors

Interactive

MFC Systems

Special Meeting Section-PRiME 2016, Honolulu, HI-October 2-7, 2016

Booth 114

Booth 213

Interactive provides Arc plasma deposition system(APD). APD is a unique technique to deposit ultra-thin films and nanoparticles by generating metal ions in a simple process. It can achieve an effect that cannot be obtained with other deposition methods such as particle deposition.The system can select nano-particle diameter within the range of approx. 1.5nm to 6nm.It is useful for the electrode of Fuel cell, LIB.

MFC Systems is an up-and-coming potentiostat design and manufacturing company based in the USA. Since 2014, we have offered the growing family of Squidstat™ potentiostats & galvanostats to researchers worldwide. Our modestly-priced, well-equipped products feature a wide selection of current ranges with easy-touse software and unique data backup systems. Pricing ranges from $2,400 to $9,600, with even lower-cost potentiostats in development. All software and technical support services are available for free. We are showcasing two new potentiostats at PRiME 2016. Both offer unprecedented value in terms of capabilities and pricing. Visit booth 213 to see them in action!

Yoshinori Shingaki shingaki@inter-active.co.jp TT-1 Building 11F, 14-8,1-chome, Nihombashi-Ningyocho, Chuo-ku, Tokyo +81.3.5695.1035 Japan www.inter-active.co.jp

Ivium Technologies Booths 111

Pete Peterson pete@ivium.us 961687 Gateway Blvd. Suite 201 D Fernandina Beach, FL 32034 1.800.303.3885 USA www.ivium.us

Ivium Technologies designs electrochemical instrumentation for the most demanding experiments. We are demonstrating the new CompactStat.h™ and IviumStat.h™ Potentiostats with 24-bit resolution. We’re also exhibiting the Vertex™ Potentiostat for labs on a budget, the nStat™ MultiChannel Potentiostat with up to 16 potentiostats, and the handheld pocketSTAT™ Potentiostat for portability

Maccor Booth 312

Mark Hulse m.hulse@maccor.com 2 S 49th W. Avenue Tulsa, OK 74107 1.918.446.1874 USA www.maccor.com

Maccor manufactures testing equipment for the battery and energy storage market (i.e. batteries, capacitors, fuel cells, etc.). Maccor Inc. was the pioneer, and is the world’s largest commercial manufacturer for this type of equipment. More companies rely on Maccor everyday for their battery and cell test equipment needs. Today Maccor has thousands of systems in operation in more than 50 countries.

McScience Inc. Booth 210

Matthew Son skson@mcscience.com B-1102, Digital Empire Bldg., 1156-16 Deogyeong Blvd., Youngtong Suwon, Kyeonggi-do 16690 +82.31.303.5789 Korea www.mcscience.com

McScience is a supplier of advanced technology products and solutions for Scientific Research, Photovoltaics, Industrial Manufacturing, Semiconductors and Microelectronics markets. Established in 2000, McScience has over 15 years of industry knowledge and field experience across a broad range of technologies to enhance the capabilities and productivity of its manufacturing, engineering and research applications.

Mark Sholin mark@mfcsystems.com 3116 S. Mill Avenue, Suite 238 Tempe, AZ 85282 1.480.703.1130 USA www.mfcsystems.com

Micrux Fluidic S.L. Booth 117

Ana Fernandez La Villa Anafv@micruxfluidic.com Edif. Severo Ochoa – l, 486, Auja. Julián Clavería, Oviedo, Asturias 33006 +34.984.151019 Spain www.micruxfluidic.com

Micrux Technologies (Asturias, SPAIN) is an innovative technology-based company founded in 2008. Micrux is focused on the design, development and manufacture of novel miniaturized analytical systems based on Lab-on-a-Chip (LOC) as well as thin film electrodes. These technologies can be used for research and educational activities in microfluidic and electrochemistry field in several research areas such as environment, agro-food and health. Micrux contributes to make the use of microfluidic and electrochemical devices more routinary in different research fields as well as in industry. Thus, Micrux works actively to transfer the basic research knowledge to the emerging Lab-on-a-Chip (LOC) & Pointof-Care (POC) industry. Micrux is proficient in microfluidics and electrochemical detection systems providing to their customers the latest innovations in microfluidic platforms, electrochemical sensors and analytical portable instrumentation for their research and educational activities.

Nissan ARC, Ltd. Booth 101

Hideto Imai imai@nissan-arc.co.jp 1 Natsushima-cho Yokosuka, Kanagawa 237-0061 +81.46.866.5814 Japan www.nissan-arc.co.jp

NISSAN ARC, LTD., an affiliate of Nissan Motor Co., Ltd., is a global analysis and consulting company that serves leading businesses, universities, and government research institutes. We offer world-class analysis services and consultancy to help customers’ innovations in R&D, engineering and product manufacturing, with our expertise and cutting-edge technologies.

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Exhibitors Novonix Battery Testing Services Inc. Booth 108

Novonix has taken its expertise in developing High Precision Charger (HPC) systems in Dr. Jeff Dahn’s lab to commercializing a turnkey HPC system. Novonix’s charger systems are designed for high precision measurements of the coulombic efficiency of Li-ion cells which has been shown to be useful in predicting cell lifetime/failure.

PAR/Solartron Booths 314 & 316

Ari Tampasis ari.tampasis@ametek.com 801 South Illinois Ave. Oak Ridge, TN 37830 1.865.483.2122 USA www.princetonappliedresearch.com

Princeton Applied Research is a leading manufacturer of laboratory instruments utilized for investigations in the field of electrochemistry, which includes batteries, fuel cells, corrosion, sensors and general physical chemistry. In business more than 50 years, we offer customers the benefit of knowledge, expertise, products, and solutions to support their particular research interest. Solartron Analytical is the global leader in Electrochemical Impedance Spectroscopy, providing more than 60 years of instrumentation development expertise for materials and electrochemical research. Solartron Analytical instruments and accessories are advancing the research into the physical and electrochemical properties of batteries, fuel cells, organic coatings, corrosion inhibitors, and sensors, as well as the characterization of materials for dielectrics, solar cells, display technologies, ferroelectrics, and composites.

Picosun Booth 115

Wilfredo Cabrera Wilfredo.cabrera@picosun.com 1651 N. Collins Blvd. Suite 224 Richardson, Texas 75080 1.214.790.0844 USA www.picosun.com

Picosun is the leading provider of high quality Atomic Layer Deposition thin film coating solutions for global industries and R&D. Picosun’s fully automated, SEMI compliant batch and cluster ALD systems enable cost-efficient, high volume industrial production whereas smaller scale lab tools allow cutting-edge research with unique upscalability to industrial environment.

Pine Research Instrumentation Booths 211 & 310

Diane White pinewire@pineinst.com 2741 Campus Walk Ave., Bldg. 100 Durham, NC 27705 1.919.782.8320 USA www.pineinst.com/echem

Product Systems Inc. (ProSys Inc.) Booth 204

Mark Beck sales@prosysmeg.com 1745 Dell Ave Campbell, CA 95008 1.408.871.2500 USA www.prosysmeg.com

ProSys Megasonic cleaning systems and transducers provide superior cleaning performance, substantially higher reliability, and a lower cost of ownership for manufacturers of submicron contamination-sensitive products. Megasonics is our core and only business. Our company focuses on delivering innovative technology with exceptional performance at a competitive cost.

Samsung SDI Co. Ltd. Booth 206

Byoung Hyu, Koh bhkoh@samsung.com 150-20, Gongse-Ro Giheung-Gu Technology Planning Group Yongin-Si, Gyeonggi-do 17084 Republic of Korea

+82.31.8006.3572 www.samsungsdi.co.kr

The world leader in the lithium-ion industry, Samsung SDI’s product portfolio includes rechargeable, advanced lithium-ion batteries for mobile devices, electrified vehicles and energy storage systems.

Scribner Associates, Inc. Booth 200

Jason Scribner jason@scribner.com 150 E Connecticut Ave. Southern Pines, NC 28387 1.910.695.8884 USA www.scribner.com

Scribner Associates specializes in advanced analytical hardware and software for electrochemical research and development. Our software packages such as ZPlot, ZView, MultiStat and CorrWare are recognized world-wide as the gold standard for instrument control and data analysis. On display will be the Model 850e Fuel Cell Test System, a turn-key instrument for PEM, DMFC and SOFC R&D. The 850e features multiple current ranges for high accuracy over a wide dynamic range, automated humidifier bypass valves for wet/dry cycling, automatic humidifier water fill, manual or automated inlet selector valves, integrated potentiostat functions, and accurate dew point control up to 5 SLM. The 850e is now CE certified. Scribner is pleased to introduce the Model 580 8-Channel Battery Cycler. The 580 is specifically designed for battery and capacitor discharge cycling and offers CC, CV, CP, and CR modes, 6 current ranges, cell resistance by HFR, 5-wire terminal measurement, and comes with user friendly software for instrument control and data analysis. All of our products are available for quick delivery and are backed by comprehensive technical support.

Pine Research Instrumentation designs, manufactures, and supports a full line of cost-effective, durable, and reliable electrochemical research instrumentation. Pine Research offers a variety of potentiostat/galvanostat systems including the WaveDriver and WaveNow, which are controlled using the powerful AfterMath software package. Specialty products include

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

(continued on next page)

Special Meeting Section-PRiME 2016, Honolulu, HI-October 2-7, 2016

David Stevens info@novonix.ca 1 Research Drive Dartmouth, NS B2Y-4M9 1.902.449.9121 Canada www.novonix.ca

unique quartz electrochemical cells for photoelectrochemistry and spectroelectrochemistry. Pine Research is still the world leader in rotating disk, ring-disk, and cylinder electrodes and related instrumentation. Quick and easy electrochemical measurements can be made with our carbon, platinum, or gold screen-printed electrodes.

Exhibitors (continued from previous page)

Toray Research Center, Inc.

Special Meeting Section-PRiME 2016, Honolulu, HI-October 2-7, 2016

Booth 304

Masayuki-Hatada Masayuki_hatada@trc.toray.co.jp Nihonbashi-honcho, Chuo-ku, Tokya 103-0023 +81.3.3245.5665 Japan www.toray-research.co.jp

Toray Research Center, Inc. (TRC) provides an extensive range of high quality material analysis services. We have 38 years of experience serving the world’s top R&D / manufacturing companies in a variety of industrial fields including LIB and FC. Learn how our benchmarking / degradation material analysis can work for you.

Toshima Manufacturing Co., Ltd. Booth 300

Kenji Sakai sakai@material-sys.com 1414 Shimonomoto Higashimatsuyama, Saitama 3550036 +81.493.24.6715 Japan www.material-sys.com

For worlds’ material researchers, we provide sputtering targets, powders, MOCVD precursors, MOD coating materials. They are applicable to Li-ion battery, superconductor, photocatalyst, and piezoelectric ferroelectric fields. Especially our LLZO for solid electrolyte in R&D as well as PZT for sensors in mass production are used all over the world.

Waterstar Booth 107

Bryan Boggs Bryan.boggs@tennantco.com 18650 Industrial Circle Parkman, Ohio 77080 1.440.996.0817 USA www.waterstarinc.com

Water Star Inc., A Wholly-Owned Subsidiary of Tennant Company, is a technology-driven company specializing in the innovation, development, and manufacture of precious metal coated titanium anodes (MMO – Mixed Metal Oxide or Dimensionally Stable Anodes), Cathodes, Cells, Assemblies, and Catalyzed Media.

Zahner-electrik GmbH Booth 116

Dr. Hans Schäfer hjs@zahner.de Thueringer Str. 12 D-96317 Kronach +49.9261.962119.0 Germany www.zahner.de

Zahner-elektrik is a manufacturer of high-end electrochemical and photo-electrochemical workstations with an experience of 35 years. IM6, Zennium and CIMPS systems are designed for outstanding accuracy and reliability and equipped with unique features to improve the quality of your experiments in solar cell, battery, fuel cell, and corrosion research and in many other fields of electrochemistry.

Don’t miss the opportunity to gain face-to-face time with these industry leading companies.

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Special Meeting Section-PRiME 2016, Honolulu, HI-October 2-7, 2016

PRiME 2020

October 4-9, 2020 Hawaii Convention Center & Hilton Hawaiian Village

2020

Honolulu H

SAVE THE DATE Photo by David Cornwell

Photo by Hawaii Tourism Authority (HTA) / Tor Johnson

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Volume 75– H o n o l u l u , H a w a i i

from the PRiME Honolulu meeting, October 2—October 7, 2016 The following issues of ECS Transactions are from symposia held during the Honolulu meeting. All issues are available in electronic (PDF) editions, which may be purchased, beginning on September 23, 2016, by visiting www.electrochem.org/ online-store. Some issues are also available in CD/USB editions. Please visit the ECS website for all issue pricing and ordering information. (All prices are in U.S. dollars; M = ECS member price; NM = nonmember price.)

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Ordering Information To order any of these recently-published titles, please visit the ECS Online Store, www.electrochem.org/online-store Email: customerservice@electrochem.org 6/24/16

Lithium Batteries as Electrochemical Sources of Energy by Tomáš Kazda and Petr Vanýsek

nergy can be stored in the form of chemical energy and this energy can be converted into electrical energy conveniently in an electrochemical cell and then again released when needed. Several electrochemical cells connected in series, done to increase the practical voltage, are called batteries. The name battery is now, incorrectly, but quite commonly, used even for a single cell and is used interchangeably for a single cell even in this article. There is a number of electrochemical systems that can store and then convert chemical energy to energy electrical, but those based on lithium, the lithium batteries, are the most prevalent and are used as a model system in this tutorial. There are two fundamental types of practical batteries, the primary (that can be used only once) and the secondary versions (that can be recharged after their use).

The Primary Battery The operating principle of a primary battery is shown in Fig. 1. The negative electrode is made from a foil of lithium metal which during operation uses up lithium to release electrons to the backing collector and the lithium ions, that are produced, dissolve in the nonaqueous solvent with an electrolyte and travel to the positive electrode. The positive electrode is made from a material that forms together with the lithium ions and the electrons supplied by the electrode a stable compound. Such material, used in about 80 % of the present day primary batteries, is manganese dioxide.1 The reaction on the negative electrode of the primary cell (the so called half-cell reaction) is oxidation of lithium Li → Li + + e − ,

(1)

the half-cell reaction on the positive electrode is MnO2 + Li + + e − → MnOOLi ,

(2)

which is simultaneous reduction of lithium ion and formation of a compound, and hence the overall cell reaction is MnO2 + Li → MnOOLi + energy . (3)

along with poorly defined activity of lithium in the electrolyte. More illustrative is to plot the energy density of an electrode vs. density of states for each particular electrode,3 as is shown in Fig. 2 for both the negative electrode LixC6 and the positive electrode LixCoO2. The energy for a single electron in LixC6 shown as 0.2 eV corresponds directly to potential 0.2 V and the energy for the Co4+/Co3+ redox couple LixCoO2 corresponds to 4.0 V. Thus, the nominal potential of this system is the difference between the two electrodes, 3.8 V. Once the reaction [3] on the two electrodes completes and all the available electrode material is used up, the battery has delivered all its stored electrical energy and is discharged. Because the reaction products are very stable, the battery cannot be recharged, which is the functional hallmark of a primary cell. Inability to be recharged is an obvious disadvantage; however, primary batteries have significant advantage in low self-discharge rate. A cell not connected to a circuit will lose only about 1 % of its energy per year. The primary lithium batteries can be fabricated in many shapes, forms and sizes ranging in the capacity from several milliampere hours (mAh) to tens of thousands of ampere hours (Ah). An ampere hour is a unit of capacity (charge) commonly used in electrochemical energy sources technology. It corresponds to a current of 1 A flowing for one hour, i.e., 3600 seconds, thus, it corresponds to the charge of 3600 C (coulombs). There are chemistry composition variations to the example given above. While the negative electrode is always metal lithium, the positive electrodes can be different, represented by three groups divided mostly by the amount of power the cell can deliver. The first group uses a solid positive electrode such as the already mentioned MnO2. These cells are intended for small power ranging in capacity from 10 mAh to 10 Ah. The second group utilizes a soluble (liquid) material with SOCl2 (thionyl chloride) and a SO2Cl2 (sulfuryl chloride) using graphite as the collection electrode and organic or inorganic electrolytes. These cells are mostly used for higher power in the range of capacities from 1 to 10000Ah. They work in broad temperature range from −50 °C up to above 100 °C. The last type is intended for very small power, manufactured in the capacity range of 1 to 100 mAh. The positive electrode is either iodine (I2) or lead iodide (PbI2). This type has the longest shelf life, in the range of 10 to 25 years. (continued on next page)

To use the volume of the battery efficiently, the positive and the negative electrodes are placed as close together as possible. To prevent their physical contact though, which would result in a short circuit, a porous separator from polypropylene or polyethylene foil is placed between them. The pores are impregnated with an electrolyte lithium perchlorate in a nonaqueous solvent propylene carbonate, which allows transport of the lithium ions between the two electrodes. The overall potential U of the cell can be given by the sum of the potentials of the two half-reactions, which is governed by the Nernst equation:2 U ( x) = E 0 −

+ RT a ( Li )( l ) ln a( Li + ) , + F a ( Li )( el )

(4)

where a(Li+)(l) is the activity of Li+ ions in the electrolyte (liquid) phase, a(Li+)(el) is the activity of Li+ ions in the electrode material, R is the universal gas constant, T is absolute temperature, F is the Faraday constant and E0 is the standard reduction potential of the Li/ Li+ couple. While the Nernst equation approach to the cell potential is pedagogically quite illustrative for cells with aqueous electrolytes and electrodes from pure metals, it is not useful in discussing cells with intercalated lithium, where the lithium ion activity is not known,

Fig. 1. Principle of the primary lithium battery.

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Kazda and Vanýsek

(continued from previous page)

(a)

(b)

Fig. 2. Schematic of electron energies E in eV vs. density of states NE in arbitrary units for: a) negative electrode LixC6; and b) positive electrode LixCoO2 (after Ref. 3).

The Secondary Battery (Accumulator, Storage Battery) In most applications the ability of recharging the electrochemical cell is preferred and thus secondary cells are constructed. Their fundamental design requires that the chemical reactions that lead to delivery of energy (and the cell discharge) can be reversed by applying electrical current flowing in the opposite direction. The most successful rechargeable lithium cells use as the negative electrode a graphite matrix that serves as storage for lithium atoms. Secondary cells do not use bare lithium metal for the negative electrode, because lithium alone tends to deposit during repeated charging (i.e., electrochemical reduction) in needle-like structures (whiskers) that can eventually grow towards the opposite electrode and short-circuit the cell. Typically, in the graphite structure six carbons are required to accommodate up to a single atom of lithium. The positive electrode is made from some material that can accommodate lithium metal atoms, which are formed from lithium ions receiving electrons from the positive electrode. An example of such matrix is LiCoO2. This ion/metal insertion is called intercalation. During discharge the lithium atoms lose electrons to the graphite and leave the graphite matrix (deintercalation) and as ions move to the positive electrode, from which the ions receive an electron and intercalate inside the positive electrode matrix. The diagram of the battery operation, both discharging and then charging, is shown in Fig. 3. The reaction on the negative electrode during discharge can be written as LixC6 → 6C + xLi + + xe −

(5)

and the discharge reaction the positive electrode is Li1− xCoO2 + xLi + + xe − → LiCoO2 and thus the full cell reaction is LiCoO2 + 6C O Li1− xCoO2 + LixC6 + energy

(6) (7)

Basically, the lithium metal (in a form of the positive ion) is shuttled through the electrolyte solution from the negative to the positive electrode, whereas the electrons removed from the lithium metal are shuttled from the negative to the positive electrode via an external electrical circuit, thus delivering electrical energy to the external load. Because of this fundamental function of the ion of lithium in the system, such cells are often called lithium-ion batteries. 48

When the cell is depleted, it can be recharged by applying external electrical potential—higher than the remaining potential of the cell— and the intercalated lithium atoms are moved back (in the form of lithium ions) to the opposite (original) side, to the left in the diagram in Fig. 3. Thus the discharging and charging process consists only of shuttling the lithium metal back and forth between the negative and the positive electrode. Because of this back and forth movement, this principle is sometimes described as the rocking-chair battery. The biggest advantage of this principle is a fact that an electrolyte serves just as an ionic conductor and is not involved in the reaction, so its quantity necessary for the correct function of the cell is very small, just a few microliters soaked into the separator, which increases the volumetric energy density of these batteries. The material which is used for the negative electrode is graphite and as materials for the positive electrodes are used compounds of lithium and various metal oxides (LiCoO2, LiFePO4, LiMn2O4, or LiNi0.33Mn0.33Co0.33O2). The electrolytes used in lithium batteries are the same as in the case of the primary lithium batteries; anhydrous and most frequently various mixtures of carbonates such as ethylene carbonate, dimethyl carbonate, or diethyl carbonate in which is dissolved a lithium salt (e.g., LiClO4, LiPF6). The obvious advantage of the secondary cell is its rechargeability. Unfortunately, the practical number of charging/discharging cycles is limited due to occurrence of side reactions that lead to change in chemical and mechanical constitution. The number of such cycles is in thousands. While primary lithium cells have exemplary shelf life longevity, the secondary lithium cells have still very serviceable parameters—typically loss of 5 % of capacity per year. The amount of chemical energy that a battery can store and then deliver as electrical energy is given by the algebraic product of the charge that can be stored in a given volume or mass of the intercalation material (expressed in ampere hours) and the potential associated with the charge transport. It is the high potential factor in the algebraic product that makes lithium so attractive for battery construction as it is the element with the most extreme negative potential (the standard potential is −3.04 V). Therefore, the typical amount of energy per volume or mass that such lithium cells can provide is 620 Wh/l or 250 Wh/kg. While energy (expressed in Wh) is the figure of merit of the total capacity of a given battery, another figure of merit is power, expressed in watts (W), which gives an idea of ability to deliver energy instantaneously. It is the amount of energy the cell can deliver per unit of time. For a given type of a cell it is usually proportional to the capacity of the cell, stated in ampere hours. There are some practical considerations involving lithium batteries that should be understood beyond the fundamental operating principles. Because of its extreme negative potential, lithium will react with water (it will reduce it to hydrogen, while forming lithium hydroxide). Therefore, the electrolytes used in all lithium systems are nonaqueous. Exposure of lithium to humidity, but also to air, will cause exothermic reaction, possibly rather catastrophic, if large amounts are involved. Accidental or deliberate opening of the battery to normal environment may be a problem. Likewise, the nonaqueous solvents are inherently flammable. While research is done in optimizing mixture that are minimally flammable, fire hazard is always consideration. This goes along with the fact that the modern batteries can often deliver high currents and if discharged too quickly (shorted) they can heat up quite dangerously. Therefore many commercial batteries contain electronic circuits preventing too fast discharge or charge. The possibility of whisker growing during repeated charging and discharging adds also to a possible danger. If the whisker grows throughout the cell and causes local short, not only the battery performance suffers; the short itself can cause local heating that could in extreme case lead so spontaneous, positive feedback discharge, known as the thermal runaway,4 which can lead to destruction of the battery and possible fire of the surrounding equipment.1,5 If the temperature of the cell reaches 90 °C, an exothermic decomposition of the solid electrolyte interface layer on the surface of the electrode begins, which will lead to the increase of the temperature inside the cell. Around 120 °C is the solid electrolyte interface completely decomposed and a direct reaction between the The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

About the Authors

(a)

Tomáš Kazda is an assistant lecturer in Brno University of Technology, Department of Electrical and Electronic Technology. He received his PhD from the Brno University of Technology, Czech Republic. His thesis deals with the cathode materials for Li-Ion batteries. He has several years of experience with work in the field of Li-Ion batteries mainly high-voltage cathode for Li-Ion batteries and in recent years with Li-S batteries. He also received a prize for a young scientist from the FEI Company in the 2013. He may be reached at kazda@feec.vutbr.cz.

(b)

Petr Vanýsek is an Emeritus Professor at Northern Illinois University and a Visiting Professor at the Central European Institute of Technology in Brno, Czech Republic. His research interests are in the field of physical and electroanalytical chemistry with recent focus on electrochemical energy storage. Vanýsek was the author of the very first installment of Chalkboard in Interface. He may be reached at pvanysek@ gmail.com. http://orcid.org/0000-0002-5458-393X

References 1. C. Julien, A. Mauger, A. K. Vijh, and K. Zaghib, Lithium Batteries: Science and Technology, Springer International Publishing, New York (2016). 2. W. Nernst, Z. Phys. Chem., 4, 129 (1889). 3. J. B. Goodenough and Y. Kim, Chem. Mater., 22, 587 (2010). 4. C. F. Lopez, J. A. Jeevarajan and P. P. Mukherjee, J. Electrochem. Soc., 162, A2163 (2015). 5. Handbook of Batteries, D. Linden and T. B. Reddy, Editors, McGraw-Hill, New York (2002).

Fig. 3. Principle of the secondary lithium-ion battery: a) the discharge process; and b) the charge process.

electrolyte and Li ions in the anode begins, which is accompanied by release of flammable hydrocarbon gases. At about 130 °C the polymer separator starts to melt, which allows massive short circuit between the electrodes. Additional temperature increase follows, which leads to decomposition of the metal oxide materials of the positive electrode which releases oxygen which then reacts with the electrolyte and the previously generated hydrocarbons. At this point the temperature reaches 250 °C and further temperature growth is unstoppable. © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F02163if.

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

ECS Classics Historical Origins of the Rotating Ring-Disk Electrode by Frank Dalton

ifty years ago, the Rotating Ring-Disk Electrode (RRDE), originally developed in Russia during the Cold War, became widely known as a powerful electroanalytical tool via the publication of a seminal series of theoretical papers1-7 by Albery, Bruckenstein, Johnson, and Napp. A history based on personal interviews8-15 and the scientific literature is told here, tracing the path of RRDE development from Moscow to Minneapolis to Oxford. Cold War Science Arriving by special invitation in Moscow on the evening of June 14, 1945, a group of fourteen American scientists were met at the airport by a delegation of their Russian counterparts.16-18 A series of eastbound flights over the previous four days had skirted war-torn Europe, carrying the scientists on a circuitous route across northern Africa, Iran, the Caucuses, and finally to Moscow. The occasion was the 220th Anniversary of the Academy of Sciences of the USSR (Fig. 1), and the fourteen visitors, representing a range of scientific disciplines, had been invited to dialogue and celebrate in grand style with their Russian colleagues over the next two weeks. Notably absent were the dozen American physicists who had also been invited. Two chemists, Irving Langmuir from the General Electric Company and Izaak Kolthoff from the University of Minnesota, were among the American visitors. As they were greeted on the tarmac, Langmuir and Kolthoff noticed the familiar face of

Alexander Frumkin in the Russian delegation. Frumkin was a leading electrochemist at Moscow State University, and he was also the Director of the Institute of Electrochemistry at the Academy of Sciences of the USSR. The scientific relationship between Frumkin and Kolthoff, linking Moscow to Minnesota (Fig. 2), traced back to a period in 1928 – 1929 when Frumkin presented lectures across the United States. The special anniversary celebration gave Frumkin a chance to show his American guests the research being performed in Moscow, and Langmuir recalls being duly impressed with the advances in electrochemistry and surface science made by the Russians during the war years.16 After the anniversary celebration ended, the American scientists completed their eastbound trip around the world, travelling across Siberia, through Alaska and back to the continental United States.17 As they travelled home, few if any were aware that the recently concluded celebrations were to mark a highpoint in scientific exchange between the East and West. Ten days after their plane

Fig. 1. A Soviet postage stamp commemorating the 220th Anniversary of the Academy of Sciences of the USSR in 1945.

Fig. 2. This 1962 photo illustrates a longstanding Moscow to Minnesota connection (left to right): Alexander Frumkin, Alexander Vinogradov, and Izaak Kolthoff discuss electroanalysis. By the time this photo was taken in 1962, Frumkin and Kolthoff had known each other for over thirty years. (Copyright © Vernadsky Institute of Geochemistry and Analytical Chemistry of the Russian Academy of Sciences. Used with permission.)

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

mass transport of species A to the disk surface (Fig. 4). Under these conditions, an expression for the limiting current (iLD), known as the Levich equation,23 can be written as follows: iLD = 0.62nD F (π r12 )CA* DA2/3v −1/ 6ω1/ 2

Fig. 3. Benjamin Levich (left) and Alexander Frumkin (right) at a conference in Prague (undated). (Copyright © J. Heyrovsky Institute of Physical Chemistry of the Czech Academy of Sciences. Used with permission.)

touched down in Minnesota, the United States successfully tested a nuclear weapon in the New Mexico desert. This deadly technical achievement by the physicists set into motion a series of events that chilled relations between the Russians and Americans. Authorities on both sides of the emerging East/West divide grew concerned about the transfer of technical knowledge to rival countries. Such concerns took a toll on free scientific exchange worldwide, but the burden was perhaps most acutely felt by scientists in the East. In June of 1947, Russian authorities enacted a new edict called the Responsibility for the Disclosure of State Secrets.18 This strict edict abolished several Russian scientific journals, severely curtailed the ability of Russian scientists to travel outside the Soviet bloc, introduced burdensome delays in the publication of new scientific findings, and restricted scientific publication in foreign languages. Operating under this edict for many years thereafter, Russian scientists who were the first to report a significant scientific breakthrough often found that their contributions went unnoticed by scientists in the West.

(2)

The terms appearing in Eq. 2 are the Faraday (F), the radius of the disk electrode (r1), the concentration of the electroactive species A in the bulk solution (CA*), the diffusion coefficient of the electroactive species (DA), the kinematic viscosity of the solution (ν), and the angular rotation rate of the disk electrode (ω). Electrochemists had long realized24 that both convection and diffusion contribute to the current observed at an electrode. Levich’s development of the rotating disk electrode (RDE) was significant because it provided an experimentally reproducible and mathematically well-defined way for an electrochemist to easily control the rate at which an electroactive species arrives at the electrode surface. Of course, in the early 1950s, commercial RDE equipment was unavailable, so Russian researchers constructed homemade electrode rotators using motors and pulley systems to control the rotation rate.8 Material resources were often scarce in Russian laboratories, so it was common to see fishing line used as the “belt” to connect the rotator pulleys. Also, in the absence of the advanced alumina and diamond slurries available to today’s electrochemists, the Russian scientists had to improvise other means for polishing electrode surfaces. They noticed that the marble floors of the famous Moscow subway system were always immaculately polished. The subway floor was cleaned and buffed using a red powder (likely containing iron oxide particles), and so they used this same powder to polish the world’s first rotating disk electrodes. Armed with the excellent mass transport control provided by the RDE, electrochemists in the East began exploiting the technique to make advanced electrochemical measurements. In 1957, Levich and Czech chemist Jaroslav Koutecký developed an expression for the RDE current which takes into account both the mass transport to the surface and the rate of the electrochemical half-reaction.25,26 The (continued on next page)

Rotating Disk Electrodes In the midst of this adverse political atmosphere, Frumkin and his colleagues were enjoying an era of rapidly increasing electrochemical knowledge. It was during this era, sometimes called the “Frumkin Epoch,”19 that hydrodynamic voltammetry using rotating electrodes was established. One of Frumkin’s outstanding younger colleagues at the Academy of Sciences in Moscow was Benjamin Levich (Fig. 3). At the age of twenty-five, Levich began exploring the role of solution convection on the rate of chemical reactions,20 and ten years later in 1952, he published a landmark volume on the subject titled Physicochemical Hydrodynamics.21,22 Levich’s book, initially published in Russian and known to only a few researchers in the West, contained an explanation of mass transport to the surface of a rotating disk. Mass transport at a rotating disk is said to be “uniformly accessible” because the flux of solution towards the disk surface does not vary with radial distance from the axis of rotation. This allowed Levich to use relatively simple one-dimensional mathematics to develop the mass transport theory for the rotating disk. His theory may be applied to the case of an electroactive species A being reduced at a rotating disk electrode (RDE) via a cathodic half-reaction (Eq. 1), A + nDe → B (1) where nD is the number of electrons involved in the half-reaction. If the potential of the RDE is held at (or swept to) a sufficiently negative potential, the cathodic current is limited only by the rate of

Fig. 4. Steady-state mass transport at the Rotating Disk Electrode (RDE) conveys material from the bulk solution towards the disk. The Levich equation predicts the limiting current (iLD) observed as species A is reduced to B.

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Koutecký-Levich equation (Eq. 3) expresses the overall disk current (iD) in terms of a kinetic contribution to the current (iK) and a mass transport limited portion of the current (the larger term in parenthesis in Eq. 3).  1 1  1 = +  iD iK  0.62nD Fπ r12CA* DA2/3v −1/ 6ω1/ 2 

(3)

If the disk current is measured over a range of rotation rates, the Koutecký-Levich equation may be used to extract the kinetic current by plotting the reciprocal of the disk current versus the reciprocal square root of the rotation rate. The y-intercept of such a plot corresponds to an “infinite” rotation rate where mass transport no longer influences the current (as ω → ∞, the larger term in parenthesis in Eq. 3 goes to zero.) This type of Koutecký-Levich analysis using an RDE provides a reliable way to measure heterogeneous rate constants for electrochemical half-reactions.

Rotating Ring-Disk Electrodes Frumkin realized that rotating electrodes had still more to offer, and he had long been interested in observing short-lived intermediate species generated during electrochemical reactions. In 1958, Frumkin proposed18 putting a separate concentric ring electrode around the rotating disk electrode to allow the (downstream) ring to collect any electrochemical intermediates generated by the (upstream) disk (Fig. 5). Frumkin told Levich about the idea, and they asked Lev

Nekrasov27 to build the first ever RRDE apparatus. Levich also added Yuriy Ivanov28 to the team to help develop the ring-disk mass transport theory. Perhaps as a portent of decades of RRDE research to come,29 the Russian team selected the aqueous oxygen reduction reaction (ORR) as the target system for their first RRDE investigations.30 The convection-diffusion mass transport at the RRDE only carries a fraction of the products generated at the disk electrode to the ring electrode. This fraction, known as the collection efficiency, is a key parameter in any RRDE experiment.2,23 For the case of a species A being reduced to B at the disk electrode via the half-reaction in Eq. 1, the limiting cathodic current at the disk is given by the Levich equation (Eq. 2). An anodic half-reaction may be used to detect B as it arrives at the ring electrode, as shown in Eq. 4: B → C + nR e (4) The ring half-reaction is often just the reverse of the disk half-reaction (involving the same number of electrons), but this is not always the case, so it is important here to explicitly differentiate between the number of electrons involved in the disk half-reaction (nD) and the number involved in the ring half reaction (nR). Mass transport at the RRDE carries some of the intermediate product B to the ring electrode while the majority is swept away into the bulk solution. The anodic limiting current at the ring electrode (iLR) can be written in terms of the cathodic limiting current at the disk electrode (iLD) as follows: iLR = −iLD (nR / nD ) N max (5) The maximum theoretical collection efficiency (Nmax) in Eq. 5 is a unitless value indicating the fraction of material from the disk that is theoretically expected to arrive at the ring. This fraction depends solely upon the dimensions of the disk and ring electrodes. Thus, the value of Nmax for a particular RRDE is a constant which can be computed from the machined radii of the disk and ring.2,28 The ring-disk geometry provided a unique way to probe the fate of unstable intermediates. Consider again the half-reactions described in Eq. 1 and Eq. 4, but in this case assume the intermediate product B is subject to decay to a non-electroactive product Z as follows (Eq. 6): k

B→Z

(6)

The existence of the competing decay pathway (governed by a homogeneous rate constant, k) means that less of the intermediate B arrives at the ring electrode than expected for the case where B is a stable product. This leads to a discrepancy between the observed limiting current at the ring and the maximum theoretical ring current predicted by Eq. 5. Carefully analyzing this discrepancy over a range of rotation rates yields kinetic information about the reaction in Eq. 6 and a way to measure the homogeneous rate constant.5-7 Frumkin and Levich realized that to obtain quantitative kinetic information for electrochemical intermediates, they would need a rigorous expression for the theoretical collection efficiency. Unfortunately, obtaining an exact equation for Nmax proved difficult. After applying some simplifying assumptions, Ivanov and Levich28 were able to derive an approximate expression for Nmax in terms of the disk radius (r1) and the inner (r2) and outer (r3) radii of the ring as follows (Eq. 7): r3 / r2

N max

1/ 3 ⌠  3  r 3   1 = 0.8 1 −      4  r2    ⌡1

φ2 dφ 3 (7) 1/ 3  3 3  r1   3 φ − 1 φ −       4  r2    

where

φ = r / r2 Fig. 5. Mass transport at the Rotating Ring-Disk Electrode (RRDE) first conveys species A from the bulk solution to the disk electrode where it is reduced to B. The species B is swept to the ring electrode and detected as an anodic current as it is oxidized to C. In some systems, as B transits from the disk to the ring, it may undergo a competing side reaction in solution, lowering the observed ring current. The RRDE may be used to probe the kinetics of such side reactions. 52

In addition to being an approximation, Eq. 7 also contains a troublesome integral that the Russian team was unable to analytically integrate. Numerical integration was required after substituting the empirically known disk and ring radii for a particular RRDE into Eq. 7.27 The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

While their initial reports confirmed that the RRDE geometry was a powerful tool for studying electrochemical intermediates, the Russian team also acknowledged27,28 that the error in their collection efficiency approximations was at least five percent. The error was later shown to be significantly larger.2 During the early 1960s, RRDE studies by Nekrasov30-33 continued to rely upon the approximate solution in Eq. 7. As long as an exact expression for the collection efficiency was unknown, many of the more interesting kinetic applications of the RRDE remained tantalizingly just out of reach.

Publication Problems The development of the RDE went largely unnoticed in the West during the 1950s because the initial research was reported only in Russian-language journals.34 So, when Frumkin’s team finished development of the RRDE, they sought a way to get the results published as widely as possible. Having worked over a decade under the strict constraints of the 1947 state secrets edict, Frumkin had devised a trick18 to get his work published in Western journals. First, he would break up a scientific report into its component parts and submit each part as a separate paper to one or more Russianlanguage journals. Acceptance of each component for publication by the Russian journals served as a vetting exercise, providing proof to the authorities that none of the components contained sensitive technical material. Then, Frumkin would quickly reassemble the vetted components into a unified report and submit it to a Western journal. There is evidence that Frumkin employed his trick with the initial RRDE publications during the year 1959. First, a short paper describing how an RRDE can detect peroxide formation during the reduction of oxygen was submitted by Frumkin and Nekrasov on March 3 to the Russian journal Doklady Akademii Nauk SSSR. This first paper27 contains only two references: one is to Levich’s earlier Physicochemical Hydrodynamics book,21 and the other is to a forthcoming RRDE paper. Next, the “forthcoming” paper28 was submitted separately (but to the very same journal) by Levich and Ivanov on April 11. This paper described the mathematical relationship between the ring current and the disk current. Finally, a combined paper30 (written in German and referencing both previous papers) was submitted by all four authors on June 15 to a newly established electrochemical journal in the West (the Journal of Electroanalytical Chemistry).

Western Pioneers

reacts with the target analyte in the diffusion layer adjacent to the disk surface. As the amount of titrant is gradually increased (by increasing the disk current), the endpoint is signaled by excess titrant reaching the ring electrode. Bruckenstein and Johnson were able to develop this novel technique in the absence of an exact expression for the RRDE collection efficiency because the endpoint could be discerned simply from the shape of the ring current vs. disk current curves. The Oxford and Minnesota groups became aware of each other by happenstance.9 Just as Albery was finishing his graduate work in 1964, a professor from the University of Minnesota, Maurice Kreevoy, paid a visit to Ronnie Bell at the PCL. Bell and Kreevoy shared an interest in fast proton exchange kinetics,38 and during his visit, Kreevoy was shown the pair of RDEs that Albery had used for his dissertation research. Kreevoy noticed the similarity between the Oxford equipment and the RRDE used by Bruckenstein for diffusion layer titrations. Albery, who had a natural affinity for the mathematics associated with mass transport at rotating electrodes, grew interested in Bruckenstein’s work at Minnesota.

Breaking the Ice When Kreevoy returned from his visit to Oxford, he let Bruckenstein know about Albery’s work with rotating electrodes. Bruckenstein was in the midst of making travel plans. A brief thaw in the Cold War had opened up an opportunity to revive the scientific link between Minnesota and Moscow previously established by Kolthoff and Frumkin. Bruckenstein (a former student of Kolthoff) was awarded the chance to work in Moscow as part of a scientific exchange program.18 He moved with his family in September of 1964 to work with Frumkin at both Moscow State University and the Institute for Electrochemistry at the Academy of Sciences of the USSR. Along the way to Moscow, Bruckenstein took a side trip to Oxford University to learn more about the rotating electrode equipment at the PCL. During the Oxford visit, Bruckenstein recalls8 being impressed with Albery’s mathematical skills (Fig. 6). Albery leveraged their common interest in rotating electrodes to arrange a post-doctoral position with Bruckenstein in Minnesota, but the arrangement would have to wait until the latter returned from Moscow. When Bruckenstein arrived in Moscow, he met many of the leading Russian electrochemists, including Frumkin, Levich, and Nekrasov. Bruckenstein had brought several books into Russia with his personal belongings, including a textbook containing a table of integrals. He had been warned ahead of time of the dangers of bringing Western literature into Russia (due to the risk it could impose on anyone receiving such literature), but he rightly supposed that a book on mathematics would be non-controversial. Any lingering concern was soon mitigated by a social visit to the home of Benjamin and Tanya Levich. Tanya had excellent command of English, and she had taught the language to Benjamin by reading

Adoption of rotating electrodes by Western scientists accelerated after 1962, when a new edition of Levich’s Physicochemical Hydrodynamics text was published in English.22 At the Physical Chemistry Lab (PCL) at Oxford University, Ronnie Bell and one of his graduate students, John Albery, began using pairs of rotating electrodes to measure fast proton exchange kinetics in the presence (continued on next page) of large background currents.35 One RDE was put into a strong acid solution and the other RDE was put into a weak acid solution. Albery balanced the signals from the two parallel RDE cells using a Wheatstone bridge circuit and was able to subtract out the large water dissociation background from the desired kinetic signal. Meanwhile, on the other side of the Atlantic, Stanley Bruckenstein at the University of Minnesota was studying acidbase equilibria and developing novel assays based on rotating electrodes.36 Together with his graduate student Dennis Johnson, Bruckenstein demonstrated how a “diffusion layer titration” could be performed using an Fig. 6. From left to right: Stanley Bruckenstein, Barry Miller, and John Albery in 1997. Albery RRDE.37 By controlling the current at the and Bruckenstein collaborated to put RRDE theory on solid ground in the summer of 1965. Miller disk electrode, a known amount of redox pioneered the rotating split ring-disk electrode and later collaborated with Bruckenstein to develop titrant can be generated at the disk electrode hydrodynamically modulated rotating disk voltammetry. (Copyright © Stanley Bruckenstein. Used with under steady-state conditions. This titrant permission.) The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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him Agatha Christie novels.39 Bruckenstein recalls that Levich subsequently needed a way to maintain and improve his ability to speak English. Levich took Bruckenstein over to a chest of drawers and showed him a top drawer full of material used to practice English. To Bruckenstein’s surprise, the entire drawer was full of Western detective story magazines. Soon after starting to work with his Russian colleagues, Bruckenstein learned of the troublesome integral appearing in the Russian equation for the RRDE collection efficiency. By consulting the table of integrals in his textbook and introducing a new variable into the earlier Russian derivation, Bruckenstein was able to solve the integral and provide the first closed form equation for the collection efficiency. N max =

 0.8  1  Y 3 + X 3   2X −Y   ln   + 3 tan −1  + 0.9069  (8)  3 3  2  (Y + X )    Y 3  

where X3 =

r33 3r13 3 1 Y 1 − and = − r23 4r23

While this closed form result was an improvement, it was still based upon the assumptions and approximations inherent to Ivanov and Levich’s original equation. Nevertheless, the troublesome integral had been eliminated, so Bruckenstein prepared a full report of his result in English. Then, working at a lab bench with Nekrasov over the course of two days, the pair of electrochemists carefully translated the report word-for-word into Russian. In early 1965, Bruckenstein submitted the paper40 to the Russian journal Elektrokhimiya (newly founded by Frumkin), and then he packed up his family and headed home to Minnesota.

The Summer of 1965 Meanwhile, Albery had been making his own plans to travel to Minnesota. Those who worked closely with Albery knew there was much more to him than initially met the eye. Albery came from a well-known British theatrical family, had once considered a career in theater, and for a time was even a scriptwriter for the satirical BBC television program That Was the Week That Was.41 Albery is remembered by his first graduate student, Michael Hitchman,9 as “energetic, urgent, distinctive, individualistic, and with a tremendous joie de vivre.” Rob Hillman11 recalls that Albery liked to be called a “professor of theatrical chemistry” and that “the theatrical input to John’s life meant that, whatever happened, things were not dull.” Perhaps most succinctly, Andy Mount12 remembers Albery as simply “a force of nature.”

When Bruckenstein returned home to Minnesota in 1965, he immediately put two of his graduate students, Dennis Johnson and Duane Napp (Fig. 7), to work on further developing the RRDE technique. Johnson15 recalls this as a time “when RRDEs had been thrust to the forefront of electroanalytical thought,” while Napp13 discerned the opportunity to get in on the ground floor of a powerful new electrochemical technique. As they awaited Albery’s arrival, the Bruckenstein group noticed that electrodes were not the only thing rotating in Minnesota that year. In May, a serious tornado struck a suburb of Minneapolis,42 damaging the apartment building in which Napp was living with his family. Johnson14 recalls an entire summer of heavy thunderstorms. Bruckenstein8 recalls driving out from under a tree just before it fell to the ground. Thus it was that Albery was not the only “force of nature” to strike Minnesota that summer, and upon his arrival, he proved to be fascinated with absolutely anything that rotated. Johnson reports15 that much to the consternation of his Midwestern hosts, during violent thunderstorms, Albery “would dangerously stand outside just to try to get a photo of a funnel on the ground!” Working in Bruckenstein’s lab, Napp and Johnson were both in awe of Albery, but they fondly recall a warm spirit of scientific comradery among all four members of the Minnesota RRDE team. Bruckenstein would propose an experiment, Napp and Johnson would work long nights polishing electrodes and acquiring the data, and Albery would develop the mathematical theory behind the results. The two graduate students rapidly generated results for review by Albery and Bruckenstein. Johnson14 recalls that Bruckenstein had learned to enjoy large cigars during his time in Russia, and when he would come into the lab to review fresh RRDE plots, “the cigar ashes would fall on the paper and Stanley would brush them off, thus smearing the ink.” Napp and Johnson soon got smart and began only showing Bruckenstein “yesterday’s results” where the ink on the plots had already dried. Interpretation of the RRDE results remained hampered by the approximations inherent in the RRDE collection efficiency equations developed in Russia. Hitchman reports9 that during this time, “Johnson and Napp were despondent that no matter how hard they tried, their experimentally measured collection efficiencies were always off by 15% or more from the predicted values.” Albery decided that an entirely new theory should be developed, and he tackled the problem starting from first principles using Laplace transformations and Airy functions.1 Albery’s new approach yielded an exact expression for the theoretical collection efficiency (Eq. 9) which was significantly more complex than the earlier Russian equation. α N max = 1 − G  β

 2/3 2/3 2 / 3  αγ   + β 1 − G (α )  − γ + γ G    β  

(9)

where 3

r  r  r  α =  2  − 1 and β =  3  −  2  and γ = 1 + α + β r  1  r1   r1  and the function G is defined as

(

)  +

 1/3 3  θ +1 G (θ ) = ln 4π  θ + 1 

Fig. 7. Dennis Johnson (left) and Duane Napp (right), shown here in 2016, performed all of the RRDE experiments in Bruckenstein’s lab during the summer of 1965. (Copyright © Darrel Untereker. Used with permission.) 54

 

 2θ 1/3 − 1  1 3 tan −1  + 2π 3  4 

This new equation fit the experimental data very well, and Albery and Bruckenstein published a report2 which carefully compared the new theory to the previous Russian reports. In addition to providing an exact equation for the collection efficiency, Albery’s mathematical approach (making use of Airy functions) provided a flexible foundation for extending the RRDE theory further. Suddenly, it was possible to predict the ring and disk currents for more complex cases (e.g., diffusion layer titration curves,4 kinetics of first5 and second6 order reactions involving intermediate species, and heterogeneous reaction kinetics7 at the ring electrode). The immense amount of experimental and theoretical work completed by the Minnesota team during the summer of 1965 culminated in seven RRDE papers1-7 published sequentially in the Transactions of the Faraday Society. The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

These seven papers, published 50 years ago, placed the RRDE geometry on a solid theoretical foundation and are the most commonly cited papers for the origin of the RRDE. These papers were later drawn together by Albery and Hitchman in a seminal volume titled Ring-Disc Electrodes.43 Given the importance of these RRDE theory papers, the casual observer might be forgiven for thinking that the RRDE had been developed at Oxford (or in Minnesota), not realizing how the Cold War obscured the true Russian origins of the technique. Indeed, even the Russian-language RRDE theory paper40 submitted by Bruckenstein to Elektrokhimiya before he left Moscow was not immune to the delays experienced by his Russian colleagues. By the time this paper appeared in the Russian journal, Bruckenstein had already published a correction to it in a Western journal,44 and in addition, Albery’s exact solution2 had already supplanted the Russian approach. Still later, Bruckenstein had the surreal experience of being contacted by Scripta Technica Ltd., a journal translation service, for assistance in translating the Elektrokhimiya article back into English.

The Bruckenstein School In 1968, Bruckenstein moved his research group to the University at Buffalo and continued working with rotating electrodes for many years.45-53 His contributions include additional RRDE theory,45 instrumentation improvements,46,52 and elucidating the mechanisms of electrochemical reactions,51 especially those involving metal deposition.47-50 Barry Miller (Fig. 6), who had independently pioneered the rotating split ring-disk electrode54 at Bell Laboratories, collaborated with Bruckenstein to develop the hydrodynamically modulated RDE technique,52,53 which uses a sinusoidal modulated rotation rate to increase signal sensitivity. Bruckenstein’s student, Dennis Johnson, went on to establish his own research group at Iowa State University and continued working with rotating electrodes for many years. One of the more interesting variants of the RRDE geometry developed by Johnson is the “rotating photoelectrode,” where the disk is a quartz window rather than an electrode.55,56 Light passing through the window can induce a photochemical reaction in the vicinity of the disk, and the resulting products are detected electrochemically as they are swept past the ring electrode.

Hillman and Richard Compton, Albery explored the application of alternating current to the disk electrode and developed theory to predict the ring current.67,68 And in some quite subtle experiments involving films deposited on the disk electrode, Mount and Albery were able to use the ring current to measure the flux of ions emitted by these films.71-73

The Ring of Fire In the 1970s, Allen Bard applied digital simulation techniques to the electrochemical response at an RRDE.75-80 After demonstrating the digital approach was in agreement with Albery’s earlier theoretical work,75,76 Bard developed simulations for additional electrochemical systems involving catalytic,77 dimerization,78 and isomerization79 reaction mechanisms. Bard also simulated and performed experiments involving electrogenerated chemiluminescence (ECL) using an RRDE.80 In these experiments, radical ion pairs generated at the two electrodes (e.g., radical cation R•+ at the disk and corresponding radical anion R•– at the ring) encounter and annihilate each other near the inner radius of the ring electrode, emitting a narrow ring of light affectionately called the “ring of fire.”

Commercialization The first few RRDE systems used in Bruckenstein’s lab were fabricated by the machine shop serving the dental school at the University of Minnesota (Fig. 8). Napp recalls13 that the dental school eventually decided that they could not keep up with the demand for RRDEs from the chemistry department. At this point, Napp contacted an old friend and Minnesota alum, Ted Hines, who owned a small machine shop in rural Pennsylvania called Pine Instrument Company. (continued on next page)

The Albery School Albery really enjoyed mathematics, and after he returned to England, the RRDE served as his mathematical playground for several decades. When simultaneously modelling the flow of solution at an RRDE, taking into account the effect of heterogeneous and homogeneous reaction rates (including the occasional photochemical reaction), and considering the concentration profiles of chemical species in solution, Albery could and would, within minutes, fill several pages of paper with complex differential equations. According to Phil Bartlett,10 graduate students who approached Albery with a question about their RRDE experiments would often emerge from his office clutching reams of handwritten notes and equations known fondly within the group as “Albery Screeds.” The wild complexity and multiple experimental parameters scribbled on these screeds could easily overwhelm a dazed graduate student staggering back into the laboratory. But no matter how complex the parameter space grew, Albery was always able to apply an approximation here or find a simple limiting case there which would bring the heady mathematics back down to earth and allow the student to perform a real-world experiment. While a modern electrochemist would likely model such complex systems using finite element analysis, Albery’s strong mathematical instincts allowed him to rapidly identify “short cuts” to simplify the math and keep moving. Albery and his students eventually extended the initial series of seven RRDE articles1-7 to a total of twenty-four papers,57-73 each paper bearing an enumerated title and covering additional theory or new variants of the ring-disk geometry. A rigorous theory for the ring current at the “rotating optical disc-ring electrode” (i.e., the “rotating photoelectrode” previously reported by Johnson) was developed and verified by Bartlett and other Albery students.74 Working with

Fig. 8. Bruckenstein’s lab used this RRDE apparatus at the University of Minnesota in 1968. The pulley diameters were optimized by Bruckenstein to provide rotation rates following a series of perfect squares (100, 200, 400, etc., RPM). The 2016 inset photo shows the very same rotator, now located at the University at Buffalo, highlighting the Soviet era coin that Bruckenstein affixed to the rotator to honor its Russian heritage.

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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Napp asked Hines if he would be interested in fabricating RRDE apparatus. Hines, a businessman concerned with return on investment, immediately asked how many RRDEs he might anticipate selling if he took the time to turn the RRDE into a commercial product. In what would later prove to be a gross underestimation of the size of the market, Napp told Hines that he might possibly sell about ten units. Perhaps taking some pity on the researchers at his alma mater, Hines agreed to make the first commercial RRDE units. In the fifty years since Napp’s underestimation, Pine has fabricated thousands of rotating electrodes. When Albery returned to Oxford in late 1965, his research group also needed RRDE instrumentation. The earliest Oxford rotators (Fig. 9) were often built using motors salvaged from surplus military aircraft.9 Rotation rate measurement was accomplished by exploiting the intensity fluctuations of the fluorescent lighting in the laboratory together with a stroboscopic disk attached to the top of the motor. In one amusing prank, Albery’s students devised the only known example of a bicycle-powered rotating electrode system (Fig. 10). The Oxford researchers were also fortunate to have the services of a fantastic machinist, Michael Heslop, who was able to machine rings and disks to very tight tolerances. With Albery’s encouragement, Heslop established an enterprise called Oxford Electrodes, the first commercial source for RRDEs based in the United Kingdom. A few years after Albery moved his group to Imperial College in London, another machinist, Michael Pritchard, joined Oxford Electrodes and continued the tradition of manufacturing precision hydrodynamic electrodes.11

first bipotentiostat circuit. The next day, they showed the astonished guest an RRDE voltammogram acquired with their new instrument and subsequently published a description of the circuit.46 Years later, Johnson worked with Hines to develop a commercial version of this bipotentiostat to be offered by Pine Instrument Company. Albery’s students also built homemade bipotentiostats, some of them quite beautifully designed (Fig. 9) and some built for more nefarious purposes. Like most graduate students, Albery’s students lived in mortal fear of their advisor actually coming into the lab and touching the experimental apparatus. As a defensive measure, his students built a device with several knobs on it which Albery could twist to his heart’s content, producing random data that Albery would then try to interpret back in his office. Bartlett recalls10 that when eminent electrochemists would visit the lab, Albery (always with an eye towards stagecraft) would have all of his students “stand by their benches” ready to produce an experimental result. Some students responded by designing special circuitry into their instrumentation that could always produce a satisfactory result on demand. In another Albery group tale, Danish graduate student Jens Ulstrup (now at the Technical University of Denmark) proudly completed construction of his potentiostat late one afternoon. He refused to turn on the power immediately, wanting instead to savor the moment. Overnight, his laboratory colleagues wired a radio inside the instrument and secured the case with additional screws. The next morning when Ulstrup powered on his potentiostat for the first time, he was greeted by the sound of a BBC morning program emerging from his instrument.

Full Circle

In 1972, Levich let it be known that he wished to emigrate to Israel with his family.81-83 His request was rejected on the grounds that he knew too many state secrets. During the resulting backlash from the authorities, Levich was stripped of his scientific appointments, Another problem facing RRDE researchers was the need for an prohibited from publishing, cut off from his colleagues, and subjected instrument that could simultaneously control two working electrodes to travel sanctions. Persecution of his family continued, and in May (ring and disk) in the same electrochemical cell. Bruckenstein’s of 1973, his son was involuntarily inducted into the army and sent to group initially wired several pieces of electronic equipment together Siberia. International pressure to release the Levich family started to to record data from their RRDE experiments. During a visit to build, and many of Levich’s international colleagues began working Minnesota by another well-known electrochemist (who shall remain to secure his freedom. nameless), Bruckenstein8 speculated aloud as to whether or not a Albery knew that his career had benefited greatly from the legacy single instrument could be constructed to provide simultaneous he had inherited from Levich’s original work with hydrodynamics, control of two electrodes. The visiting scientist bluntly stated that such and according to Hitchman,9 “John found the way Levich was being an instrument would be impossible to develop. Starting that evening treated as outrageous.” When Brian Spalding of Imperial College and working through the night, Bruckenstein, Johnson, and Napp London proposed that additional pressure be brought to bear on the wired several operational amplifiers together and produced their very authorities by holding a special conference84 to honor Levich, Albery joined in support. In July of 1977, scientists from all over the world, including Albery and his students, convened at Oxford for the “First International Conference on Physicochemical Hydrodynamics.” Seventy-three papers were presented, including seven papers pertaining to rotating disk and ring-disk geometries (presented by Albery, Hitchman, Miller, Bard, and others). Levich himself was invited to attend, but the authorities would not give him permission to travel. So, the scientists held a second conference the following year to continue their protest,85 and again Levich was denied the opportunity to attend. These efforts continued until Benjamin and Tanya Levich were eventually allowed to emigrate in 1978.86 They brought with them their collection of Agatha Christie novels that Tanya had used to teach English to Benjamin.87 In a later address to the “Fourth International Conference on Fig. 9. This photo shows a homemade bipotentiostat (left) and RRDE apparatus (right) in the Albery lab at Physicochemical Hydrodynamics,” Levich Oxford University. Michael Hitchman spent an entire year building this equipment in 1966 before he could recalled88 the first conference, stating that acquire his first voltammogram. (Copyright © Michael Hitchman. Used with permission.)

Bipotentiostats

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

References 1. W. J. Albery, “Ring-Disc Electrodes. Part 1.—A New Approach to the Theory,” Trans. Faraday Soc., 62, 1915 (1966). 2. W. J. Albery and S. Bruckenstein, “Ring-Disc Electrodes. Part 2.—Theoretical and Experimental Collection Efficiencies,” Trans. Faraday Soc., 62, 1920 (1966). 3. W. J. Albery, S. Bruckenstein, and D. T. Napp, “Ring-Disc Electrodes. Part 3.—Current-Voltage Curves at the Ring Electrode with Simultaneous Currents at the Disc electrode,” Trans. Faraday Soc., 62, 1932 (1966). 4. W. J. Albery, S. Bruckenstein, and D. C. Johnson, “Ring-Disc Electrodes. Part 4.—Diffusion Layer Titration Curves,” Trans. Faraday Soc., 62, 1938 (1966). 5. W. J. Albery and S. Bruckenstein, Fig. 10. Laboratory antics were quite common in the Albery group. This 1968 photo shows a bicycle“Ring-Disc Electrodes. Part 5.—Firstpowered rotating disk electrode apparatus. John Albery is brandishing a whip to motivate his students (upper-right corner), John Drury is providing the bicycle power, and Michael Hitchman (right) is Order Kinetic Collection Efficiencies pointing out the oversize RDE cell. (Copyright © Estate of John Albery. Used with permission.) at the Ring Electrode,” Trans. Faraday Soc., 62, 1946 (1966). it played “…an important role in my personal destiny, and I take 6. W. J. Albery and S. Bruckenstein, “Ring-Disc Electrodes. Part every opportunity to convey, again and again, my deepest thanks 6.—Second-Order Reactions,” Trans. Faraday Soc., 62, 2584 to the organizers of that conference.” In 1979, Levich accepted an (1966). invitation to become the Albert Einstein Professor of Science at City 7. W. J. Albery and S. Bruckenstein, “Ring-Disc Electrodes. Part College of New York (CUNY), where he served for just over six years 7.—Homogeneous and Heterogeneous Kinetics,” Trans. Farauntil his untimely death. His legacy lives on today at the Benjamin day Soc., 62, 2596 (1966). 8. S. Bruckenstein, University at Buffalo, Personal Interview, 14 Levich Institute for Physicochemical Hydrodynamics at CUNY. April 2016. 9. M. L. Hitchman, University of Strathclyde, Personal Interview, 29 April 2016. Acknowledgments 10. P. N. Bartlett, University of Southampton, Personal Interview, 28 Apr 2016. The author would like to thank Phil Bartlett, Stanley Bruckenstein, 11. A. R. Hillman, University of Leicester, Personal Interview, 4 Rob Hillman, Michael Hitchman, Dennis Johnson, Andy Mount, and May 2016. Duane Napp for agreeing to be interviewed for this article. Photos 12. A. R. Mount, University of Edinburgh, Personal Interview, 2 supplied by the Vernadsky Institute of Geochemistry and Analytical May 2016. Chemistry and by the J. Heyrovsky Institute of Physical Chemistry 13. D. T. Napp, Personal Interview, 27 May 2016. are appreciated. Special thanks are extended to Caroline Johnson and 14. D. C. Johnson, Iowa State University, Private Communication, 2 the Estate of John Albery for assistance with this project. Apr 2016. © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F03163if. 15. D. C. Johnson, “The Quiet Musings of a Mature (But Not Old!) Person,” SEAC Communications, 14(3), 10 (1998). About the Author 16. I. Langmuir, “Science and Incentives in Russia,” The Scientific Monthly, 63, 85 (1946). For the past ten years, Frank Dalton has been 17. A. L. Nadai, Diary of a Trip to Moscow and Leningrad to Atthe General Manager of Pine Research tend Celebrations of the 220th Anniversary of the Academy of Instrumentation (Durham, NC), a leading Sciences of the U.S.S.R. (July 1945). In Izaak Maurits Kolthoff manufacturer of rotating electrodes and other Papers, 1926-1994, University of Minnesota Archives. electrochemical research instrumentation. He 18. O. A. Petrii and S. Fletcher, The Frumkin Era in Electrochemearned a BS degree in chemistry from the istry. In Electrochemistry in a Divided World, F. Scholz, Ed., University of North Texas (1985) and a PhD Springer International Publishing, Switzerland (2015). degree in analytical chemistry from the University 19. A. J. Bard, G. Inzelt, and F. Scholz, Electrochemical Dictionary, of North Carolina (1990). Prior to working at Springer Science & Business Media, New York, (2012), p. 387. Pine, Dr. Dalton was a chemistry professor at 20. V. G. Levich, Acta Physicochim.U.R.S.S., 17, 257 (1942). Grove City College for many years. His areas of interest include 21. V. G. Levich, Physicochemical Hydrodynamics, Acad. Sci. software and electrical engineering pertaining to chemical Press, Moscow (1952). instrumentation, custom product manufacturing for scientific 22. V. G. Levich, Physicochemical Hydrodynamics, Prentice-Hall, research, and small business development. He can be reached at Englewood Cliffs, NJ (1962). efdalton@pineinst.com. 23. A. J. Bard and L. R. Faulkner, Electrochemical Methods: Fundamentals and Applications, 2nd Ed., John Wiley & Sons, New York, (2001), ch. 9. 24. C. W. Tobias, M. Eisenberg, and C. R. Wilke, “Diffusion and Convection in Electrolysis–A Theoretical Review,” J. Electrochem. Soc., 99, 359C (1952). The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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25. J. Koutecky and V. G. Levich, “An Application of a Rotating Disk Electrode to the Studies of Kinetic and Catalytic Processes in Electrochemistry,” Dokl. Akad. Nauk SSSR, 117, 441 (1957). 26. J. Koutecky and V. G. Levich, “The Use of the Rotating Disk Electrode in the Studies of Electrochemical Kinetics and Electrolytic Processes,” Zh. Fiz. Khim., 32, 1565 (1958). 27. A. N. Frumkin and L. N. Nekrasov, “Ring Disk Electrodes,” Dokl. Akad. Nauk SSSR, 126, 115 (1959). 28. Yu. B. Ivanov and V. G. Levich, “Investigation of Unstable Intermediate Products of Electrode Reactions by Means of a Rotating Disc Electrode,” Dokl. Akad. Nauk SSSR, 126, 1029 (1959). 29. U. A. Paulus, T. J. Schmidt, H. A. Gasteiger, and R. J. Behm, “Oxygen Reduction on a High-Surface Area Pt/Vulcan Carbon Catalyst: a Thin-Film Rotating Ring-Disk Electrode Study,” J. Electroanal. Chem., 495, 134 (2001). 30. A. N. Frumkin, L. N. Nekrasov, V. G. Levich, and Yu. B. Ivanov, “The Use of a Rotating Ring-Disk Electrode for Studying Intermediate Products of Electrochemical Reactions,” J. Electroanal. Chem., 1, 84 (1959). 31. L. N. Nekrasov and N. P. Berezina, “The Electrolytic Reduction of Copper on a Disc-Ring Electrode,” Dokl. Akad. Nauk SSSR, 142, 885 (1961). 32. L. N. Nekrasov and L. Müller, “Study of the Cathodic Reduction of Oxygen on Platinum in Alkaline Solutions Using a Rotating Disk and Ring Electrode,” Dokl. Akad. Nauk SSSR, 149, 1107 (1963). 33. L. Müller and L. N. Nekrasov, “Study of the Electroreduction of Oxygen on Smooth Platinum in Acid Solutions by the Method of a Revolving Disc Electrode with a Ring,” Dokl. Akad. Nauk SSSR, 154, 437 (1964). 34. Z. Galus, C. Olson, H. Y. Lee, and R. N. Adams, “Rotating Disk Electrodes,” Anal. Chem., 34, 164 (1962). 35. W. J. Albery and R. P. Bell. “Kinetics of Dissociation of Weak Acids Measured by a Rotating Platinum Disc Electrode,” Proc. Chem. Soc., (1963) 169. 36. S. Bruckenstein and T. Nagai, “The Rotated, Mercury-Coated Platinum Electrode,” Anal. Chem., 33, 1201 (1961). 37. S. Bruckenstein and D. C. Johnson, “Coulometric Diffusion Layer Titrations Using the Ring-Disk Electrode with Amperometric End Point Detection,” Anal. Chem., 36, 2186 (1964). 38. R. P. Bell, “Isotope Effects and the Nature of Proton-Transfer Transition States,” Discuss. Faraday Soc., 39, 16, (1965). 39. B. Hafling, “Ransomed Soviet Scientist Invited to University of Minnesota,” University of Minnesota Press Release, 19 February 1973. 40. S. Bruckenstein, “The Relations Between the Limiting Diffusion Currents at Rotating Disk, Ring, and Ring-Disk Electrodes,” Elektrokhimiya 2, 1085 (1966). 41. “Professor John Albery—Obituary,” The Telegraph, 13 December 2013. 42. C. Brown, “Minnesota Tornado Outbreak Still Vivid, 50 Years Later,” Minneapolis Star Tribune, 6 May 2015. 43. W. J. Albery and M. L. Hitchman, Ring-Disc Electrodes, Clarendon Press, Oxford (1971). 44. S. Bruckenstein and G. A. Feldman, “Radial Transport Times at Rotating Ring-Disk Electrodes. Limitations on the Detection of Electrode Intermediates Undergoing Homogeneous Chemical Reactions,” J. Electroanal. Chem., 9, 395 (1965). 45. S. Bruckenstein and G. Martinchek, “A Closed Form Expression for the Primary Resistance at a Ring Electrode,” J. Electrochem. Soc., 126, 1307 (1979). 46. D. T. Napp, D. C. Johnson, and S. Bruckenstein, “Simultaneous and Independent Potentiostatic Control of Two Indicator Electrodes. Application to the Copper(II)/Copper(I)/Copper System in 0.5M Potassium Chloride at the Rotating Ring-Disk Electrode,” Anal. Chem., 39, 481 (1967).

47. G. W. Tindall and S. Bruckenstein, “Voltammetric Rotating Ring-Disk Studies of Silver Deposition on Platinum at Underpotential,” Electrochim. Acta., 116, 245 (1971). 48. S. Bruckenstein and M. Z. Hassan, “Rotating Ring-Disk Study of the Reduction of Oxidized Platinum by Mercurous Mercury and Its Adsorption on Reduced Platinum,” Anal. Chem., 43, 928 (1971). 49. S. Bruckenstein and V. A. Vicente, “Rotating Gold-Ring Disk Study of Tin(II) in 4.0 Molar Hydrochloric Acid,” Anal. Chem., 44, 297 (1972). 50. M. Z. Hassan and S. Bruckenstein, “Voltammetry of Bismuth(III) at a Continuously Mercury-Coated Rotating Platinum Disk Electrode,” Anal. Chem., 46, 1827 (1974). 51. S. Bruckenstein and B. Miller, “Unraveling Reactions with Rotating Electrodes,” Acc. Chem. Res., 10, 54, (1977). 52. B. Miller, M. I. Bellavance, and S. Bruckenstein, “Feasibility and Applications of Programmed Speed Control at Rotating Ring-Disk Electrodes,” Anal. Chem., 44, 1983 (1972). 53. W. J. Albery, A. R. Hillman, and S. Bruckenstein, “Hydrodynamic Modulation at a Rotating Disk Electrode,” J. Electroanal. Chem., 100, 687 (1979). 54. B. Miller, “The Rotating Split Ring-Disk Electrode and Applications to Alloy Corrosion,” J. Electrochem. Soc., 116, 1117 (1969). 55. D. C. Johnson and E. W. Resnik, “Rotating Photoelectrode for Electrochemical Study of the Products of Photochemical Reactions,” Anal. Chem., 44, 637 (1972). 56. P. R. Gaines, V. E. Peacock, and D. C. Johnson, “Application of a Rotating Photoelectrode to a Photochemical Study of Fluorenol,” Anal. Chem., 47, 1373 (1975). 57. W. J. Albery, “Ring-Disc Electrodes. Part 8.—Transient Currents and First-Order Kinetics,” Trans. Faraday Soc., 63, 1771 (1967). 58. W. J. Albery, M. L. Hitchman, and Jens Ulstrup, “Ring-Disc Electrodes. Part 9.—Application to First-Order Kinetics,” Trans. Faraday Soc., 64, 2831 (1968). 59. W. J. Albery, M. L. Hitchman, and Jens Ulstrup, “Ring-Disc Electrodes. Part 10.—Application to Second-Order Kinetics,” Trans. Faraday Soc., 65, 1101 (1969). 60. W. J. Albery, “Ring-Disc Electrodes. Part 11.—General Theory of Transient Currents,” Trans. Faraday Soc., 67, 153 (1971). 61. W. J. Albery, J. S. Drury, and M. L. Hitchman, “Ring-Disc Electrodes. Part 12.— Application to Ring Current Transients,” Trans. Faraday Soc., 67, 161 (1971). 62. W. J. Albery, J. S. Drury, and M. L. Hitchman, “Ring-Disc Electrodes. Part 13.—The Laplace Transformation of Transients,” Trans. Faraday Soc., 67, 166 (1971). 63. W. J. Albery, J. S. Drury, and M. L. Hitchman, “Ring-Disc Electrodes. Part 14.—Kinetic and Transient Parameters,” Trans. Faraday Soc., 67, 2162 (1971). 64. W. J. Albery, J. S. Drury, and A. P. Hutchinson, “Ring-Disc Electrodes. Part 15.—Alternating Current Measurements,” Trans. Faraday Soc., 67, 2414 (1971). 65. W. J. Albery and J. S. Drury, “Ring-Disc Electrodes. Part 16.—A Comparison of Analytical and Numerical Solutions,” J. Chem. Soc., Faraday Trans. 1, 68, 456 (1972). 66. S. Bruckenstein, K. Tokuda, and W. J. Albery, “Ring-Disc Electrodes. Part 17.—Ring Response to Periodic Disc Electrode Forcing Functions,” J. Chem. Soc., Faraday Trans. 1, 73, 823 (1977). 67. W. J. Albery, R. G. Compton, and A. R. Hillman, “Ring-Disc Electrodes. Part 18.—Collection Efficiency for High Frequency A.C.,” J. Chem. Soc., Faraday Trans. 1, 74, 1007 (1978). 68. W. J. Albery and A. R. Hillman, “Ring-Disc Electrodes. Part 19.—Adsorption Studies at Low Frequency A.C.,” J. Chem. Soc., Faraday Trans. 1, 75, 1623 (1979). 69. W. J. Albery, M. G. Boutelle, P. J. Colby, and A. R. Hillman, “Ring-Disc Electrodes. Part 20.—A General Procedure for Deducing the Faradaic Component of a Disc-Current Transient from a Ring-Current Transient,” J. Chem. Soc., Faraday Trans. 1, 78, 2757 (1982). The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

70. W. J. Albery and E. J. Calvo, “Ring-Disc Electrodes. Part 21.— pH Measurement with the Ring,” J. Chem. Soc., Faraday Trans. 1, 79, 2583 (1983). 71. W. J. Albery and A. R. Mount, “Ring-Disc Electrodes. Part 22.—Theory of the Measurement of Proton Fluxes at the Disc,” J. Chem. Soc., Faraday Trans. 1, 85, 1181 (1989). 72. W. J. Albery and A. R. Mount, “Ring-Disc Electrodes. Part 23.—Studies of Proton Fluxes at a Thionine-Coated Electrode,” J. Chem. Soc., Faraday Trans. 1, 85, 1189 (1989). 73. W. J. Albery and A. R. Mount, “Ring-Disc Electrodes. Part 24.—Studies of Counterion Fluxes at a Thionine-Coated Electrode,” J. Chem. Soc., Faraday Trans. 1, 85, 3717 (1989). 74. W. J. Albery, P. N. Bartlett, A. M. Lithgow, J. Riefkohl, L. Romero, F. A. Souto, “The Rotating Optical Disc–Ring Electrode. Part 1.—Collection of a Stable Photoproduct,” J. Chem. Soc., Faraday Trans. 1, 81, 2647 (1985). 75. K. B. Prater and A. J. Bard, “Rotating Ring-Disk Electrodes I. Fundamentals of the Digital Simulation Approach. Disk and Ring Transients and Collection Efficiencies,” J. Electrochem. Soc., 117, 207 (1970). 76. K. B. Prater and A. J. Bard, “Rotating Ring-Disk Electrodes II. Digital Simulation of First and Second-Order Following Chemical Reactions,” J. Electrochem. Soc., 117, 335 (1970). 77. K. B. Prater and A. J. Bard, “Rotating Ring-Disk Electrodes III. Catalytic and ECE Reactions,” J. Electrochem. Soc., 117, 1517 (1970).

78. V. J. Puglisi and A. J. Bard, “Rotating Ring-Disk Electrodes IV. Dimerization and Second Order ECE Reactions,” J. Electrochem. Soc., 119, 833 (1972). 79. L. R. Yeh and A. J. Bard, “Rotating Ring-Disk Electrodes V. Isomerization and Reductive Coupling of Dialkyl Maleates,” J. Electrochem. Soc., 124, 189 (1977). 80. J. T. Maloy, K. B. Prater, and A. J. Bard, “Electrogenerated Chemiluminescence. V. Rotating-Ring-Disk Electrode. Digital Simulation and Experimental Evaluation,” J. Am. Chem. Soc., 93, 5959 (1971). 81. “Evgeny Levich—An Appeal,” Bulletin of Atomic Scientists, 29(10), 2 (1973). 82. R. J. Seltzer, “Dissident Soviet Scientists under Attack,” Chem. Eng. News, 54(13), 18 (1976). 83. “Soviets Turn Deaf Ear to Pleas for Levich,” Science, 197, 349 (1977). 84. D. B. Spalding, Physicochemical Hydrodynamics: V G Levich Festschrift, Vol. 1, Advance Publications Limited, London, (1977). 85. D. B. Spalding, “Protest by Conference,” New Scientist, 78, 288 (1978). 86. “Levich Waits 6½ Years to Leave the USSR,” New Scientist, 80, 747 (1978). 87. K. Klose, “After Years of Waiting, Soviet Scientist Emigrates,” Washington Post, 1 December 1978. 88. V. G. Levich, “Fourth International Conference of Physicochemical Hydrodynamics–Concluding Remarks,” Annals of the New York Academy of Sciences, 404, 527 (1983).

Announcing the Carl Hering Legacy Circle The Hering Legacy Circle recognizes individuals who have participated in any of ECS’s planned giving programs, including IRA charitable rollover gifts, bequests, life income arrangements, and other deferred gifts.

RL HERING A C

A C Y CIR C L

ECS thanks the following members of the Carl Hering Legacy Circle, whose generous gifts will benefit the Society in perpetuity: K. M. Abraham George R. Gillooly W. Jean Horkans Mary M. Loonam Carl Hering

Robert P. Frankenthal Stan Hancock Keith E. Johnson Edward G. Weston

Carl Hering was one of the founding members of ECS. President of the Society from 1906-1907, he served continuously on the Society’s Board of Directors until his death on May 10, 1926. Dr. Hering not only left a legacy of commitment to the Society, but, through a bequest to ECS, he also left a financial legacy. His planned gift continues to support the Society to this day, and for this reason we have created this planned giving circle in his honor.

To learn more about becoming a member of the Carl Hering Legacy Circle, please contact Karla Cosgriff, Development Director 609.737.1902 ext. 122 | karla.cosgriff@electrochem.org The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

socie PEOPLE t y ne ws

Paul Natishan Receives Navy Meritorious Civilian Service Award

Natishan, head of the Corrosion Science and Environment Effects Section at the U.S. Naval Research Laboratory (NRL), was bestowed on May 26, 2016 the Department of the Navy Meritorious Civilian Service Award for his outstanding performance and record of scientific achievements and contributions made to the Navy in the field of corrosion science and technology. The official press release notes that Natishan’s contribution to the field of corrosion science began by considering surface charge effects on passive film breakdown and the investigations of the role of chloride ions in these processes. The model of the pH of zero charge for pitting, proposed by Natishan and Edward McCafferty, explains the first step in the interaction of chloride ions with the oxide film of aluminum that lead to eventual breakdown of the oxide film and pitting corrosion. Later, he and William O’Grady pioneered the use of X-ray absorption spectroscopy (XAS) to observe the presence of chloride ions in the oxide film on aluminum and presented the first evidence that chlorides were present at the aluminum oxide/ aluminum interface. Paul Natishan is currently an associate editor in the field of corrosion science for the Journal of The Electrochemical Society. He was the ECS President in 2009-2010 and the ECS Secretary in 2000-2004. He received the Corrosion Division’s H. H. Uhlig Award in 2014. He is a fellow of both the ECS and NACE. He is currently an adjunct full professor at Duke University. aul

Paul Natishan (right), head of the Corrosion Science and Environment Effects Section at the U.S. Naval Research Laboratory (NRL), is presented the Department of the Navy Meritorious Civilian Service Award by NRL Commanding Officer, CAPT Mark Bruington (left), May 26, 2016. (Photo credit: U.S. Naval Research Laboratory/James Marshall.)

In Memoriam memoriam David Ramaker (b. 1943) member since 2000, Energy Technology Division, National Capital Section.

Together the Battery Division and the Physical and Analytical Electrochemistry Division sponsored a symposium at the 229th ECS Meeting, San Diego, May 2016, titled “Future and Present Advanced Lithium Batteries and Beyond—a Symposium in the Honor of Prof. Bruno Scrosati.” While Prof. Scrosati was originally expected to give his special invited talk, “The Lithium Battery Saga: From the Origin to the Future,” he was unable to go to San Diego. The organizers secured the certificate of recognition for Prof. Scrosati and delivered it to him to Italy. Pictured, while presenting the certificate, are from left Stefano Passerini, Bruno Scrosati and Vito Di Noto in front of the University of Rome La Sapienza, July 11, 2016. The certificate reads “... to Bruno Scrosati, an exceptional researcher and academic teacher, guide, and inspirer of many top-level scientists worldwide, in recognition of his pioneering discoveries of functional materials and mechanisms governing the operation of lithium-ion batteries. His studies and outstanding divulgation activity allowed breakthrough and fundamental advancements in the energy storage technology.”

Connect Share Discover ecsblog.org TheElectrochemicalSociety @ECSorg Find out what’s trending in the field and interact with a like-minded community through the ECS social media pages.

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Call for Nominations Technical Editor in Organic and Bioelectrochemistry for

Journal of The Electrochemical Society Deadline: September 19, 2016 ECS (The Electrochemical Society) is seeking to fill the position of Technical Editor of the Organic and Bioelectrochemistry Topical Interest Area for the Journal of The Electrochemical Society. The Organic and Bioelectrochemistry (OBE) Topical Interest Area (TIA) covers all aspects related to the electrochemical properties and behavior of organic and biological species. Specific areas include synthetic and mechanistic electrochemistry, including direct anodic and cathodic reactions as well as catalytic processes and paired electrosyntheses; electrochemistry in organic and biological media; organometallic electrochemistry and the role of metals in organic and biological electrode processes; modified electrodes; asymmetric organic electrosynthesis; new electrode materials for organic and biological electrosynthesis (such as biological nanowires and molecular wires); electronically-conducting polymers; fundamental aspects of biomolecular redox behavior of proteins and enzymes; enzymatic and microbial reactions; bioelectrocatalysis; electron transfer across bridges separating electrodes and soluble or anchored species; intramolecular dissociative and nondissociative electron transfer; and computational investigations of the mechanisms of organic and biological electron-transfer processes. The Journal of The Electrochemical Society (JES) has been in existence since 1902. Along with the ECS Journal of Solid State Science and Technology (JSS), JES and JSS provide unparalleled opportunities to disseminate basic research and technology results in electrochemical and solid state science and technology. JES and JSS each publish a minimum of 12 regular and focus issues each year. All ECS journals offer Author Choice Open Access (http://www.electrochem. org/oa/). ECS maintains 13 TIAs (see http://ecsdl.org/site/ecs/tia_ scopes.xhtml), and there is one Technical Editor for each TIA, supported by Associate Editors and an Editorial Advisory Board. Technical Editors for the ECS journals ensure the publication of original, significant, well-documented, peerreviewed articles that meet the objectives of the relevant journal, and are within the scope of the Society’s TIAs. The Society’s Technical Editors actively solicit manuscripts for their TIA through being involved in their technical community, engaging the ECS Divisions, and working with the staff to effectively communicate to their TIA’s stakeholders. Technical Editors ensure an efficient and fair peer review process and minimize lag time of manuscript submissions. They work to recruit and select editorial reviewers. Technical Editors are required to adhere to policies and procedures for: (a.) manuscript submission and authorship criteria; (b.) peer review, evaluation of decisions regarding publication, and methods for reconsideration of rejected manuscripts;

(c.) maintaining the scientific integrity and confidentiality of the peer review process; (d.) the identification and recommendation of theme/focus issues and supplements; (e.) handling conflict of interest and disclosure issues; and (f.) handling allegations and findings of scientific misbehavior and misconduct. Technical Editors must clearly communicate publication guidelines and policies and oversee compliance. Technical Editors also serve on the Governing Bodies of the Society’s Divisions, to ensure synergy between content in the ECS meetings and publications programs. Technical Editors serve as members of their respective Editorial Boards and attend the ECS biannual meetings. They work collaboratively with the Editors, the Publisher, and the Director of Publications to accomplish the objectives approved by the Publications Subcommittee and the Board of Directors. Nominees for the OBE Technical Editor must possess and maintain scientific knowledge of the scope of the OBE TIA (see http://ecsdl.org/site/ecs/tia_scopes.xhtml). Nominees must have qualities of leadership, integrity, technical breadth, creativity, motivation, and international reputation, and should be able to commit the necessary time to ensure efficient and effective performance of their duties. The Technical Editor oversees the review and disposition of manuscripts within his/her TIA, and works to develop content for the regular and special issues. A yearly honorarium is offered by the Society. Nominees must have published previously in a Society publication. They must be skilled in the arts of writing, editing, critical assessment, negotiation, and diplomacy. Technical Editors may not serve on the editorial boards of any non-ECS peer-reviewed technical journal. Technical Editors must adhere to the Society’s Code of Ethics policies. Preference will be given to candidates who are ECS members. A Technical Editor is appointed for a minimum of a two-year term, renewable for additional terms, up to a maximum of eight years. If selected as a finalist, candidates are expected to be available for webinar interviews with the Publications Subcommittee in November 2016. The Technical Affairs Committee will approve the appointment of the OBE Technical Editor in December 2016. Applications are due no later than September 19, 2016. Those interested should send the following: (1.) a letter indicating their qualifications for the position, stating why they are interested in the position, giving their previous experience with peer-reviewed journals, and noting the availability of their time to fulfill the duties of this position; and send (2.) a one-page résumé. Send all materials to ECS headquarters, to the attention of Mary Yess, ECS Deputy Executive Director & Publisher, mary.yess@electrochem.org. The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

t ech highligh t s Porous Magnesia Fibers as an Immobilizing Agent for Molten Salt in Thermal Batteries Key attributes of thermal batteries, such as their high energy density even after long term storage, have made them attractive for use in a variety of fields, from nuclear weapons to rocketry to fossil fuel production. To prevent leakage of the solid molten salt electrolytes employed in thermal batteries, immobilizing agents such as BN, Y2O3, MgO powders, etc., are typically added. Researchers at Southwest University of Science and Technology have proposed that the performance of thermal batteries could be improved by the use of MgO fibers as immobilizing agents. They hypothesized that MgO fibers, with a large number of small pores and increased contacting area, could enhance the immobilizing effect. Two preparation methods for synthesizing MgO fiber-based separators were examined, with the liquid nitrogen mixing technique producing material with a more homogenous pore structure. Electrochemical impedance spectroscopy, discharge, and electrolyte leakage experiments were performed to fully characterize the performance of both the MgO powder and the fiber-based separators synthesized. These experiments confirmed that the fiber-based separators exhibited higher ionic conductivity and discharge capacity and lower electrolyte leakage in comparison to the powder. In conclusion, the researchers have demonstrated a successful method for producing a MgO-fiber-based separator that could greatly enhance thermal battery performance. From: X. Liu, J. Liu, X. Liu, et al., J. Electrochem. Soc., 163, A617 (2016).

The Kinetics of Nucleation of Metastable Pits on Metal Surfaces: The Point Defect Model and its Optimization on Data Obtained on Various Metals Engineering advances that take advantage of the passivity of metals and alloys in corrosive environments have shaped modern civilization. Despite these advances and generations of studies on passivity, fundamental understanding of this phenomenon has proven to be unusually complex. Over the last several decades, researchers have developed the Point Defect Model (PDM), an analytic model of growth and breakdown of passive films, with the aim of holistically describing passivity. The premise of this model is that passive film growth and breakdown is governed by creation, annihilation and transport of point defects across the film. For the first time, researchers at the University of California, Berkeley evaluated the PDM against a diverse set of experimental data to gain insight on metastable pitting kinetics, an integral part of passivity breakdown leading to development of stable pitting. The authors report suitable agreement between model predictions and experimental data comprising nucleation rate of metastable pits and the total number of metastable pitting events. Fundamental metastable pitting parameters derived from

the model include number density of pitting sites and time to passive film dissolution over pitting sites. This work demonstrates the PDM as a means of theoretically understanding and studying metastable pitting on passive metal surfaces. From: P. Lu, G. R. Engelhardt, et al., J. Electrochem. Soc., 163, C156 (2016).

Advances in Scanning Electrochemical Microscopy Scanning electrochemical microscopy (SECM), a scanning probe technique developed in the 1980s in the Bard laboratories at the University of Texas, utilizes well established electrochemical techniques to quantify the chemistry of a substrate or solutions. The author builds upon previous reviews of the SECM technique by first addressing the basic principles behind each mode of operation, then exploring recent advances in the refinement of the method as well as in its application. Recently, there have been significant advances in tip design, specifically focused on the development of nanoelectrodes through which small scale structures, such as nanoparticles or even individual molecules, can be probed. While the advent of these new designs expanded the landscape over which this technique could be applied, the difficulty in fabricating and maintaining these electrodes has led to the development of a series of larger, more robust electrode types that preserve the resolution achieved by the more temperamental nanoelectrodes. In one such design, the geometry of the tip is exploited to improve resolution, while in another, individual metallic nanoparticles are adhered to a larger microelectrode tip, effectively reducing the size and increasing the resolution of the probe. Recently, SECM has been used to probe reactions taking place in biological systems – within bacterial biofilms and at and within bacterial cells. From: C. G. Zoski, J. Electrochem. Soc., 163, H3088 (2016).

Low Frequency Radio Wave Detection of Electrically Active Defects in Dielectrics Reliability challenges remain for three dimensional integrated circuits (3D-ICs). Detecting defects as they manifest themselves during stages of device fabrication will lower subsequent occurrences of early reliability failures. A multi-institutional team of researchers in the U.S. report using low frequency (<300 MHz) radio waves (RF) for detecting electrically active defects in 3D-ICs. Their paper, published in the JSS Focus Issue on Defect Characterization in Semiconductor Materials and Devices, describes their use of scattering information (focusing on the S21 insertion loss metric) from RF signals to characterize chemical changes in materials of construction. The researchers’ model device under test (DUT) consisted of copper-filled through-silicon vias (Cu-TSVs) having ozone-tetraethylorthosilicate (O3-TEOS) as the isolation liner dielectric. Five hundred temperature cycles were employed to drive

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material transformation byproducts to form at the interface, thereby creating differences in the S21 magnitude spectra compared to the stacked dies DUT in the as-received condition. Different types of defects were classified and their nature deduced from the spectral responses. The spatial distribution of these defect types also revealed inhomogeneity in the chemistry of the as-deposited O3TEOS films. The authors suggest that this nondestructive metrology technique could be optimized for use in characterization of massproduced Cu-TSVs. From: Y. S. Obeng, C. A. Okoro, P. K. Amoah, et al., ECS J. Solid State Sci. Technol., 5, P3025 (2016).

Non-Faradaic Current of DNA-Immobilized Microelectrodes for Biosensors Electrochemical biosensors typically operate under cyclic voltammetric or chronoamperometric conditions, which probe the binding affinity between receptors and ligands such as antibodies and antigens, as well as labeling moieties and redox mediators. Non-faradaic methods such as impedance spectroscopy do not always capture direct physical information about the species being probed. Researchers from National Tsing Hua University in Taiwan developed a method whereby non-faradaic current was measured for electrodes with immobilized DNA in a concentrated salt environment for biosensor applications. The characteristics of electric current for various surface modifications were successfully correlated to ion concentration, ion mobility, and the electric field in solution. Direct measurement of the transient current at a constant voltage was shown to avoid degradation of biomolecules often caused by oxidation/reduction reactions in the solution. Instead of an impedance measurement approach, their investigation directly explains the relationship between the electric current and the behavior of DNAcoated microelectrodes in solution. A highly sensitive biosensor was also demonstrated. Additionally, the team showed that three electrochemical indicators (the current level, the total charge, and the relaxation time) could be successfully used as detection signals for biosensors in concentrated salt solutions. From: C.-P. Hsu, Y.-F. Huang, and Y.-L. Wang, ECS J. Solid State Sci. Technol., 5, Q149 (2016)

Tech Highlights was prepared by David Enos, Eric Schindelholz, and Mara Schindelholz of Sandia National Laboratories, Colm O’Dwyer of University College Cork, Ireland, and Donald Pile of Nexeon Limited. Each article highlighted here is available free online. Go to the online version of Tech Highlights, in each issue of Interface, and click on the article summary to take you to the full-text version of the article.

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Atmospheric Corrosion

2nd Edition

Christofer Leygraf, Inger Odnevall Wallinder, Johan Tidblad, Thomas Graedel This book presents a comprehensive look at atmospheric corrosion, combining expertise in corrosion science and atmospheric chemistry the authors describe corrosion-induced devastating effects on structures and materials, examine the latest scientific tools available for preventing or minimizing corrosion damage, and emphasize new insights obtained through controlled experimental studies as well as computer modeling investigations. Complete with appendices discussing experimental techniques, computer models, and the degradation of specific metals, Atmospheric Corrosion, Second Edition builds on the topics covered in the first edition and has been expanded to include international exposure programs and the environmental effects of atmospheric corrosion.

ISBN: 978-1-118-76227-1 Cloth | August 2016 | 400pp ÂŁ83.50 | â&#x201A;Ź104.40 | $125.00

About the Authors Christofer Leygraf is Professor Emeritus at KTH Royal Institute of Technology, Division of Surface and Corrosion Science, Stockholm, Sweden. Inger Odnevall Wallinder is Professor at KTH Royal Institute of Technology, Division of Surface and Corrosion Science, Stockholm, Sweden. Johan Tidblad is Manager for the Section Corrosion Protection and Surface Technology at Swerea KIMAB, Stockholm, Sweden.

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249601

Tom Graedel is Professor Emeritus at Yale School of Forestry and Environmental Studies, New Haven, Connecticut, US.

Lithium-Ion Batteries— The 25th Anniversary of Commercialization by Zempachi Ogumi, Robert Kostecki, Dominique Guyomard, and Minoru Inaba

wenty five years have passed since lithium-ion batteries (LIBs) were commercialized in 1991 by Sony Corporation. With the rapid growth of portable electronic devices, such as camcorders, cellular telephone, smartphones, laptop computers, etc., LIBs have penetrated into our lives and are now an indispensable part of our comfortable living today. In addition, the urgent need for the reduction of CO2 emissions has stimulated the development of large-formatted LIBs for use in electric vehicles and for energy storage for the grid in conjunction with intermittent renewables. When LIBs came on the market in 1990s, battery researchers praised the success of the compact and light-weight LIBs based on the rocking-chair mechanism and thought that they were the ultimate in battery technology without any possible competitors even in the future. The energy density of commercially available LIBs has increased continuously and has doubled in the 18650 cells since the first-generation LIBs, without any change in the basic configuration. However, the increasing demands for high energy density from the market impose upon us to develop increasingly advanced types of LIBs and so-called “beyond lithium-ion batteries (beyond-LIBs)” that are not based on the Li-ion technology, for example, to realize electric vehicles with a driving range of over 500 km on a single charge. Now is an opportune time for us to go forward into the next 25 years of LIB technology. This issue of Interface features five articles on LIBs that look back over the history of LIBs and predict the future prospects for LIBs and beyond LIBs. These articles have been authored by researchers who rank amongst the most prominent researchers in the world, who have made great contributions to the commercialization and growth of LIBs. John B Goodenough introduces the principles, the components, and the energy storage mechanism of LIBs. He also discusses the problems of the battery materials in present commercially available batteries to foresee advanced batteries in a sustainable modern society. Yoshio Nishi looks back on the development of LIBs before and after their commercialization by Sony, especially focusing on carbon negative electrodes. From his experiences, he emphasizes several important factors in choosing active materials for positive and negative electrodes in batteries. J. R. Dahn, J. C. Burns, and D. A. Stevens introduce their technique for high precision coulometry, and emphasize the importance of the Coulombic efficiency to predict the life of LIBs. Jean-Marie Tarascon demonstrates many exciting and enriching issues in science and chemistry of LIBs from his diverse experiences as a battery researcher. He emphasizes that the balance between openmindedness and pragmatism in the battery community is important to further advance the limits of LIBs. Stefano Passerini and Bruno Scrosati outline the challenges and prospects for the development of advanced LIBs and beyond-LIB technologies. They conclude that the continuously increasing activity in the world-wide battery research will cause a positive change in the development of advanced LIBs and beyond-LIBs, though the road is still paved by a series of practical difficulties. The Battery Division is also planning social events to celebrate the 25th anniversary of the commercialization of LIBs at PRiME 2016. We hope to see you in Honolulu! © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F04163if.

About the Guest Editors Zempachi Ogumi is a Professor Emeritus of Kyoto University. He has been engaged in research on reactions of lithium ion batteries. After he retired, he had led the NEDO RISING battery project and is still working for the RISING II program. He has developed different kinds of in situ and operando observation technologies to elucidate the details of reactions of batteries, including Raman-, SPM-, synchrotron-X-ray-, and neutron-based methods. He was the President of the IBA, the Electrochemical Society of Japan, and the Japanese Solid State Ionics Society. He has published more than 250 scientific papers. He may be reached at ogumi@ scl.kyoto-u.ac.jp. Robert Kostecki is a Senior Scientist and Division Deputy Director in the Energy Storage and Distributed Resources Division at Lawrence Berkeley National Laboratory (LBNL). He is Chair of the Battery Division of The Electrochemical Society and Chair-Elect of the International Society of Electrochemistry. He is recognized for his groundbreaking work in the field of electrochemical energy storage and conversion systems, photocatalysis, and water treatment technologies. A pioneer in advanced characterization of electrochemical interfaces in Liion batteries, his research interests focus on fundamental interfacial phenomena that determine the function and performance of electrical energy storage systems, including degradation modes and failure mechanisms. He may be reached at r_kostecki@lbl.gov. Dominique Guyomard is the head of the “Electrochemical Energy Storage and Transformation Team” (EEST) at the Institut des Materiaux Jean Rouxel at Nantes, about 50 scientists including 20 staff researchers. This team gathers activities on batteries, on moderate and high temperature fuel cells and electrolysers, and on advanced spectroscopies and simulations. His expertise deals with basic and applied solid state electrochemistry and material and surface science, applied to the various fields of batteries. He is the current President of the IBA. He is a co-author of more than 220 journal papers and 30 patents. He may be reached at dominique.guyomard@cnrs-imn.fr. Minoru Inaba is a Professor of Department of Molecular Chemistry and Biochemistry, Doshisha University, Japan. He received his M. Sc. in 1986 and Dr. Eng. in 1995 from the Graduate School of Engineering, Kyoto University. He is now a Member-at-Large of the Battery Division, The Electrochemical Society, Inc. and the Chairperson of The Committee of Battery Technology, The Electrochemical Society of Japan. His research interests are fundamental aspects in lithium-ion batteries, polymer electrolyte fuel cells, and solid oxide fuel cells. He may be reached at minaba@mail.doshisha.ac.jp.

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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Batteries and a Sustainable Modern Society by John B. Goodenough

fter outlining the urgent need for realization of clean electrical energy generated by the sun for a sustainable modern society and the constraints of electrochemistry for this realization in a low-cost, safe rechargeable battery of long cycle life, recent advances in materials chemistry are outlined that provide an optimistic view that this realization may be possible in the relatively near future. All life on Earth is sustained by the conversion of solar energy into chemical energy by plants. The chemical energy stored in plants is delivered to mobile life by metabolic processes and to society by man as the heat of combustion with its attendant emission of polluting gases. Modern society has become dependent on the solar energy stored over millennia in fossil fuels; this energy store has allowed the exploitation of the resources of the planet Earth in a throwaway economy, which is not sustainable without recycling of these resources. The combustion of fossil fuels is not recyclable, and the attendant massive emission of gases contributes to global warming and can choke the inhabitants of large cities. Although the energy from fossil fuels can be supplemented by nuclear energy that delivers heat without the gases of combustion, nuclear energy is neither clean of pollutants nor as convenient as the energy stored in liquid or gaseous fuels. In summary, a modern society is not sustainable unless means other than plants are developed to harvest and store the sun’s energy and to deliver that energy as clean electric power without the pollutants from hydrocarbon combustion or the thermodynamic constraints on the efficiency of conversion of heat energy. Harvesting of the sun’s radiant energy by other means than by plants is possible with photovoltaic cells that convert it to electric power; nature converts it to hydropower and wind. The mechanical energy of hydropower can be stored in dams for conversion into electric power and windmills can convert wind energy into electric power. The heat delivered by nuclear fission is also transformed into electric power. The constant electric power delivered by nuclear energy needs to be stored for delivery to a variable demand or only used for the constant component of demand. On the other hand, radiant-solar and wind energies are diffuse and variable on diurnal and seasonal time scales. Although the electric power delivered by photovoltaic cells and windmills may be locally collected and transported over long distances, it needs to be stored for delivery as clean electric energy to a variable demand that may be either portable or stationary, distributed or centralized. A convenient long-term energy store of electrical energy as chemical energy that is delivered back as electrical energy is the rechargeable battery; the efficiency of the energy conversions in a battery is not constrained by thermodynamics other than by the heat loss associated with the internal battery resistance. Although the energy stored in the electrodes of a rechargeable battery is less dense and less versatile than the energy stored in a fossil fuel, its delivered energy is clean and can be portable. The challenge to the material chemist/engineer is to develop, with environmentally friendly materials, rechargeable batteries of high energy density that are safe and efficient with a long cycle and shelf life at a cost low enough to be commercially viable. There are three principal markets for a rechargeable battery: (1) powering portable hand-held devices, (2) powering electric road vehicles, and (3) stationary distributed or centralized electrical energy storage to supplement energy storage in the grid. Powering of handheld devices does not compete with fossil fuels, which is why today’s Li-ion batteries are ubiquitous. Powering electric vehicles for road transportation must compete with the internal combustion engine powered by a liquid fuel, normally a fossil fuel, of high energy density.

The hidden cost to the environment and to the economy for securing access to the fossil-fuel sources are not apparent to the individual customer at the gasoline pump. Increasing safely the volumetric energy density of a battery cell beyond that of a Li-ion battery at temperatures to −20°C is critical for batteries that power an electric vehicle. These batteries store and deliver dc electric power, so they are charged more efficiently by electric power from solar energy than from wind energy. The ac power from wind energy is more efficiently stored directly into the grid than in a rechargeable battery. For stationary electrical energy storage, the amount and cost, including shelf and cycle life, of energy stored in a single charge is more critical than the volumetric energy density and operation at low temperatures.

Battery Constraints Battery Stack

A battery may consist of an assembly of identical cells assembled in parallel to give a desired output current Ib and in series to give a desired voltage Vb to deliver a power Pb = IbVb over a time Δtb. The larger the amount of power that can be delivered by the individual cell, the fewer the number of cells that are needed in a battery for a given application and, therefore, the simpler the management of a stack of cells. The larger the area of the cell electrodes, the fewer the number of cells that need to be connected in parallel. Therefore, the material chemist/engineer concentrates initially on the performance per unit area of an individual cell, which normally begins with the design and testing of a cell the size of a large coin, i.e., a “coin cell”; but scaling to a large-area cell must be considered in the design of low-cost cell components.

Components of a Battery Cell

Figure 1 illustrates schematically a typical battery cell and the energies of the electronic states in the two electrodes and the electrolyte that separates them. A battery cell stores electrical energy as chemical energy in its two electrodes; the anode is the reductant and the cathode is the oxidant of the chemical reaction in a cell. The energy difference between the chemical potentials μA of the anode and the μC of the cathode is µ A − µC = eVOC (1) where Voc is the open-circuit voltage of the cell and e is the magnitude of the electron charge. The two electrodes are electronic conductors during charge and discharge so the μA and μC become the Fermi levels of the two electrodes. The two electrodes are separated by an electrolyte that conducts the ionic component of the chemical reaction between the electrodes but is an electronic insulator to force the electronic component into an external circuit that carries the current I. The mobile ion inside the cell is the working ion; it is normally a monovalent cation, but it may be an oxide ion or a multivalent cation. If the electrolyte is a liquid, the electrodes are kept apart by a porous separator that does not react with either electrode and is permeated by the liquid electrolyte. The energy window of the electrolyte is Eg = LUMO − HOMO

(2)

where the LUMO and HOMO are, respectively, the energies of the lowest-unoccupied and highest occupied molecular orbitals. An anode with a μA > LUMO reduces the electrolyte unless (or until) the reaction

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

(continued on next page) 67

Goodenough

(continued from previous page)

Efficiency of Electrical Energy Storage4In a rechargeable battery, the chemical reaction of each cell is reversible; chemical energy can be restored by reversing the discharge current Idis by applying a charging power Pch = IchVch. The efficiency of energy storage is 100 Pdis/Pch % with Vch = Voc + ηch and Vdis = Voc − η dis

Fig. 1. (a) Schematic of a battery cell. A = anode current collector, B = anode (reductant), C = electrolyte, D = cathode (oxidant), E = cathode current collector, F = separator. (b) Anode μA and cathode μC electrochemical energies relative to energy gap Eg of the electrolyte for a stable shelf life.

is pacified by the formation of a solid-electrolyte interphase (SEI) that is an electrolyte layer with a LUMO > μA. Similarly, a μC < HOMO oxidizes the electrolyte unless (or until) the cathode reaction is pacified by an SEI surface layer with a HOMO < μC. A solid electrolyte may act as a separator or as an interfacial layer in contact with an electrode on one side and a liquid electrolyte on the other side. In the latter case, the solid (crystalline, glass, amorphous mass, or polymer) may be referred to as the SEI across which the electrochemical potential of a solid electrode is lowered or raised to prevent a liquid electrolyte from being reduced by an anode with μA > LUMO or being oxidized by a cathode with μC < HOMO in Fig. 1b. Since the ionic conductivity inside the cell is much smaller than the electronic conductivity in the external circuit, a thin electrolyte is sandwiched between two large-area electrodes each contributing electronic conduction to a metallic current collector that delivers the electrons of the chemical reaction between the electrodes to the external circuit. The electrodes of a cell must make electronic contact with the current collector as well as ionic contact with the electrolyte, so small-particle reactants must be attached to or make contact with an electronically conducting porous matrix that contacts the current collector and is permeated by the electrolyte. This constraint limits the volumetric energy density of a small-particle electrode and, therefore, its application to a battery that powers a road vehicle. It should be noted that at open-circuit, only the electronic component of the chemical reaction between the electrodes is stopped; the ionic component inside the cell continues until the internal electric field between the electrodes make μA = μC. Whether the working ion is a cation or an anion, the cathode becomes positively charged and the anode negativity charged. That is why the cathode is the positive electrode of a battery at open circuit having a Voc of Eq. (1).

Electrical Energy Storage

Density of Stored Energy4The density of stored energy in a cell delivering electric power P = IV(q) at a constant current I = dq/dt is ∆t

Q(I )

∆E = ∫ IV (q )dt = ∫

V (q )dq = < V (q ) > ⋅ Q( I )

(3)

where q is the state of charge and Q(I) is the capacity, which is the amount of electronic charge per weight or volume that is delivered over the time Δt to complete the chemical reaction between the two electrodes: ∆t

Q(I )

Q( I ) = ∫ Idt = ∫

(4)

(5)

The ηch and ηdis are called the overvoltage (or the polarization) on charging and discharging, respectively, resulting from the internal battery resistance Rb = Rel + Rct, where Rel is the resistance to the transport of the working ion in the electrolyte and Rct is the sum of the resistance to ionic transport across electrode/ electrolyte interfaces and any solid/liquid interfaces within a complex electrolyte. The Coulombic efficiency in a rechargeable cell is the recovery of stored charge in a charge/discharge cycle (100 Qdis(I)n+1/Qch(I)n %). The capacity fade is a measure of the drop in cell capacity (100 Q(I)n+1/Q(I)n %) between charge/discharge cycle numbers (n+1) and n. Cycle life is the number of cycles before Q(I) drops to 80% of its starting value, which may be taken a few cycles after the initial charge where there is a large irreversible capacity loss in the first few cycles as a result of physical and/or chemical adjustments of the electrode. Capacity fading is the result of irreversible changes that occur in Q(I) as a result of the volume changes of the electrodes on cycling, but in the initial few charges of a cell assembled in a discharged state, capacity loss may also be the result of formation of an SEI at the anode in which the working ion is provided by the cathode. From Fig. 1b and Eq. (1), the Voc of a cell may be limited either by the inability to synthesize a cathode with μC more than 5 eV below the μA of metallic lithium, which normally makes Voc  5 V, or by the energy window of the electrolyte, Eq. (2). The SEI’s obtained with soluble additives in an organic-liquid electrolyte are amorphous electrolytes; these SEIs may continue to form during a charge if the volume changes in an active electrode particle increase the electrode/ electrolyte interface area by dendrite growth or by cracking the particle to create new surface area, thus contributing to capacity fade. If a solid (ceramic, glass, or polymer) electrolyte is stable on contact with an electrode surface, it can act as the SEI if the interface area is kept constant by a wetting of the electrolyte surface by the electrode.

Electrolyte Problem Aqueous Electrolytes

A conventional rechargeable cell uses an aqueous electrolyte, either alkaline or acidic, in which H+ is the working ion. With an alkaline electrolyte, the charged cathode is a layered NiOOH into which H+ is inserted reversibly on discharge to create Ni(OH)2. The Ni(III)/Ni(II) redox energy of this oxyhydroxide is well-matched to the HOMO of a liquid KOH electrolyte. The Fermi energy of Cd in a Ni-Cd cell is well-matched to the electrolyte LUMO in the reversible reaction. Cd + 2H 2O = Cd(OH) 2 + 2H + + 2e −

(6)

where the Cd(OH)2 mass remains near the anode surface. Alternatively, a metal-hydride MHx is an insertion host that releases H+ + eˉ on discharge and reforms on charge. A zinc/air battery uses gaseous oxygen as the cathode reactant, which requires development of inexpensive catalysts attached to a metallic substrate for the oxygenreduction reaction (ORR) O2 + 4eˉ + 4H+ = 2H2O on discharge and, on charge, for the reverse oxygen evolution reaction (OER) of O from 2H2O. However, the 1.23 eV energy window of an aqueous electrolyte limits a long shelf life to a Voc ≲ 1.5 V. For example, the 2-V leadacid battery does not have a long shelf life in partially discharged states owing to the agglomeration and crystallization of the insulating product PbSO4, which is called sulfation.

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Organic-Liquid Electrolyte

An organic-liquid electrolyte has a window Eg ≈ 3.0 eV, but the H+ ion is not mobile in these electrolytes. However, the Li+, Na+, and K+ ions can be released from soluble-salts to give a working-ion conductivity σi = 10ˉ2 to 10ˉ1 S cmˉ1 at 25°C. Since an alkali metal is immiscible with an organic-liquid electrolyte, dendrites commonly form and grow during plating across an alkali-metal/organic-liquid interface; the dendrites can grow across a thin electrolyte to the cathode to give an internal short-circuit with incendiary consequences if the electrolyte is flammable. As a result, batteries containing an organicliquid electrolyte do not use a solid alkali-metal anode. The first Li-ion battery used layered graphite into which Li is intercalated reversibly to LiC6 with a loss of only about 0.2 V in Voc; but on a fast charge, Vch becomes large enough to plate lithium on the carbon anode. Therefore, the rate of recharge of the Li-ion battery with a carbon anode has been slow. Another difficulty with the carbon anode is a μA > LUMO of the organic-liquid electrolyte, which has required introduction of an additive into the electrolyte to form an SEI during charge, and the Li+ of the SEI is robbed from the cathode on the first charge since the battery is assembled in a discharged state to keep the anode free of metallic lithium. It is the volumetric capacity of the cathode that limits the volumetric energy density <V(q)>·Q(I) of a cell. Nevertheless, the layered Li1-xCo1-xNixO2 cathode gives a voltage Voc ≈ 4.0 V versus Li+/ Li0 for 0 ≤ y ≤ 0.5, which is well-matched to the HOMO of an organiccarbonate liquid electrolyte and it is metallic, which allows the use of large particles needed for a large volumetric energy density. Two approaches have been used to increase the rate of charge of a Li-ion battery: the use of (1) an insertion-compound anode having a Voc more than 1.2 V lower than with a metallic-lithium anode, e.g., the spinel Li[Li1/3Ti5/3]O4 and layered LixTiNb2O7; (2) a Si, Sn, or Sb anode forming an alloy of large capacity with Li at a Voc over 0.4 V below that with a metallic-lithium anode. A large volume expansion on alloying, over 300% in the case of Si, has been thought to make it necessary to fabricate the anode as an assembly of small particles embedded or encapsulated in carbon or a polymer, which lowers the volumetric capacity and leaves a large anode surface area for SEI formation. Nevertheless, the Enevate Co. has developed a novel geometry for a Si anode that gives a large capacity and cycle life with a fast charge. Conversion reactions in which Li insertion displaces a cation have also been investigated, but these also involve a volume change. The realization of a safe alkali-metal anode promises to provide the needed energy density and cycle life.

Polymer-gel/Oxide Composites

A polymer gel is a porous polymer membrane permeated by a liquid electrolyte. The polymer and oxide of the separator needs to be chemically stable on contact with both the anode and the cathode. Low-cost polymer gels have been fabricated as cross-linked membranes with thiolene chemistry. The addition of inexpensive oxide particles, e.g., Al2O3, SiO2, or Sb2O3, can be used to block anode dendrites from crossing over to the cathode; the oxides strengthen, but reduce the flexibility, of the polymer membrane. Alternatively, a glass-fiber membrane has been used as the oxide component with a polymer coat leaving the glass-fiber membrane sufficiently porous for permeation by a liquid electrolyte. These membranes are better Li+ or Na+ conductors if the mobile ions are exposed only to Fˉ or C=O terminal species on the polymer; the terminal C−Oˉ of polyethylene oxide attracts Li+ too strongly for fast Li+ transport. Metal-organic framework (MOF) compounds can also be fabricated as membranes that can absorb a liquid electrolyte. These several different membrane separators may be used as separators in flow-through batteries having organic-liquid electrodes containing a soluble redox molecule; an organic liquid electrolyte allows choosing redox molecules that give a higher voltage and a more stable separator than the Nafion membrane used in today’s aqueous-electrolyte flow-through battery. Although these polymer-gel/oxide composite separators can block dendrites from an alkali-metal anode, they do not solve the anode problem; dendrite formation and growth continues to create new anode surface area on charge and, therefore, more SEI area to generate an irreversible loss of Li+ from the cathode to give a continuing capacity fade.

Solid Electrolytes

The safety hazard with a flammable organic-liquid electrolyte has stimulated work on solid electrolytes for an all-solid-state battery. A solid electrolyte may be a ceramic, a glass, or a polymer. A dry polymer electrolyte is preferred since crystalline electrodes change volume on charge/discharge cycling and maintenance of a stable ionic contact across an interface between a crystalline electrode and a ceramic or glass electrolyte in a rechargeable battery is a challenge, particularly for the cathode. However, on the anode side, plating/ stripping of a metallic anode can restrain the anode volume change to be perpendicular to the interface if the anode wets the surface of both the electrolyte and the current collector. A challenge is to develop a Li+ or Na+ dry-polymer electrolyte with an ionic conductivity σI > 10ˉ3 S cmˉ1 at room temperature and a LUMO above the Fermi energy of the alkali-metal anode. A promising strategy for meeting this challenge is to develop a cross-linked polymer membrane containing pendant molecules extending into the interstitial space that neither attract the mobile alkali ion strongly nor impede its motion. However, if the mobile ion is introduced with a salt, the movement of the salt anion away from the anode surface may create a local electric-doublelayer capacitance that lowers the voltage for the onset of an anodepolymer chemical reaction. This problem can be addressed. Meanwhile, a glass-solid electrolyte having a σI > 10ˉ2 S cmˉ1 and an activation energy for ionic motion that is < 0.1 eV has been developed and shown to be wet by an alkali-metal anode. The longterm stability of the solid/solid interface is under testing. These developments promise to provide a step improvement in the energy density, rate of charge, and cycle life of a rechargeable alkali-metal battery cell. The cathode of an all-solid-state battery cell commonly consists of particles bonded to an electronically conducting fiber or porous mass that allows particle access on discharge to both the electrolyte working ions and electrons from the cathode current collector. If the chemically active cathode particles are electronic insulators, they need to be small particles, which makes difficult realization of a large volumetric capacity. To date, all-solid-state batteries with a ceramic solid electrolyte have had a small capacity. However, a small amount of liquid or polymer electrolyte contacting the cathode would not pose a safety problem and would allow use of conventional strategies for a high-capacity cathode. Electric power can also be stored in an electric-double-layer capacitance at an electrode/electrolyte interface. This strategy is used in an electrochemical capacitor, commonly called a supercapacitor. A Li+ or Na+ glass electrolyte having a huge dielectric constant because of the presence of electric dipoles has recently been reported. With this electrolyte and high-surface-area metallic electrodes, supercapacitors with an electric-power-storage capacity approaching (overlapping) that of present-day rechargeable batteries, but with a much more rapid charge/discharge and longer cycle life, may be achieved. The exploration of cycling cells with current collectors of widely different Fermi levels is in its infancy, and the electrochemical performance of cells that combine a chemical as well as a capacitive storage of electric power remains relatively unexplored.

The Cathode Problem Insertion Compound Hosts

The capacity of the cathode limits the capacity of a cell and, therefore, the volumetric energy density of a rechargeable battery cell, Eq. (3). Today’s Li-ion batteries commonly use layered Li1-xCo1-yNiyO2 particles embedded in carbon permeated by an organic-liquid electrolyte. The capacity of the cathode is limited by the solid-solution range of Li in the layers between the close-packed Co1-yNiyO2 layers; oxygen is evolved for x > xc = 0.55 with y = 0, but the oxygen evolution may be delayed to a larger xc for y ≤ 0.8. However, a y = 1 doesn’t result in good ordering of the Li into alternate layers of the structure. The loss of oxygen from the cathode on a deep charge requires monitoring the cell charge as well as the rate

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Goodenough

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of charge to restrict the Li extraction to x < xc. On the other hand, a Li1-x[Ni1-2yMnyCoy]O2 layered oxide permits extraction to xc = 1 provided y < 1/3 is small enough to keep the voltage to V < 4.75 V. The development of a metallic insertion compound for a sodium-ion rechargeable battery has proven more difficult. The cyanoperovskite structure of Prussian blue, e.g., Na2MnFe(CN)6, offers an insertionhost cathode particle with an acceptable specific capacity on a fast (5C) charge/discharge cycle down to temperatures T < −20°C; but the poor electronic conductivity requires attachment of relatively small cathode particles onto electronically conducting fibers that contact the cathode current collector and also allow absorption of an organic-liquid electrolyte to provide the active particles access to the working ions of the electrolyte. The small size of the active particles has prevented realization of the needed volumetric energy density for a battery powering an electric road vehicle. Whether the recent discovery of growth of Prussian-blue particles at defects in carbon nanotube fibers can provide the needed volumetric energy density is yet to be determined.

Alternative Cathodes

The highest specific-energy cathodes would use an element capable of reacting with two alkali-metal cations per cathode atom as is illustrated by the reactions 16Li + S8 = 8Li2S and 4Li + O2 = 2Li2O. These reactions have prompted a strong effort to develop an S8 and an air (O2) cathode with a metallic-lithium anode. The use of a gaseous air cathode has, to date, been restricted to cells with an aqueous electrolyte. Higher voltages could be obtained with a solid electrolyte stable in water, but those stable in water have not been stable on contact with an alkali-metal anode. Use of a Li+ or Na+ polymer electrolyte on the anode side of a solid electrolyte stable in water may allow realization of a Li-air or Na-air rechargeable battery; low-cost transition-metal oxide catalysts for a Li-air battery are known. Much work has been devoted to the development of a viable sulfur cathode in an organic-liquid electrolyte. The intermediate species Li2Sx with 2 ≤ x ≤ 8 are soluble in the organic-liquid electrolyte, and the soluble molecules may move to the anode or to an insulator separator surface where they are not oxidized back to a solid molecule on charge, thereby producing a rapid capacity fade. The development of a cathode architecture that confines the charged S8 particles in mesoporous conductive fibers and/or captures soluble species on conductive surfaces making contact with the cathode current collector

has prohibited realization of a sulfur cathode with sufficient volumetric capacity for an electric vehicle. An all-solid-state cell with the glass electrolyte, a metallic-lithium anode, and a sulfur relay embedded in a carbon/glass mix on a copper current collector plates reversibly the anode lithium on the cathode during discharge which introduces a new battery-cell concept of exceptional performance. The discovery of a glass electrolyte having a huge dielectric constant and a stability to 10 V versus Li+/Li0 may offer electric doublelayer capacitors of larger capacity for storage of electrical energy. These capacitors provide an extremely fast discharge and exhibit no capacity fade on cycling. All that is required, in addition to the glass electrolyte, is a metallic cathode having a large surface area contacting the electrolyte. In summary, the advent of fast alkali-ion polymer and glass electrolytes that permit reversible plating/stripping of metalliclithium or metallic-sodium anodes appears to permit realization in the near future of safe, rechargeable lithium and sodium batteries with sufficiently low cost and cycle life for commercially viable, clean electrical energy storage that can be competitive with the energy stored in a fossil fuel. © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F05163if.

About the Author John B. Goodenough is a Professor of Materials Engineering at The University of Texas at Austin. After returning from World War II, he received a PhD in Physics from the University of Chicago in 1952, was a Group Leader of The MIT Lincoln Laboratory from 1952-1976 where he helped to develop the magnetic memory element of the first RAM of the digital computer and engaged in fundamental studies of transition-metal oxides. From 1976-1986, he was Professor and Head of the Inorganic Chemistry Laboratory of the University of Oxford, England, where he developed the cathodes that have enabled the Li-ion battery, and since 1986 he has held the Virginia H. Cockrell Centennial Chair of Engineering at The University of Texas at Austin where he has continued the development of the rechargeable battery, catalytic electrodes for the solid oxide fuel cell, and the use of high pressure to study the transition from localized to itinerant d electrons in transitionmetal oxides. He may be reached at jgoodenough@mail.utexas.edu.

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

The Dawn of Lithium-Ion Batteries by Yoshio Nishi

n the 1980s many kinds of mobile gadgets such as cassette players and 8 mm video cameras began to emerge extensively into the market for outdoor use. In addition, so-called IT equipment, including cellular phones and notebook computers, had been winning popularity. Although primary batteries were dominant until the 1970s, secondary batteries such as nickel-cadmium (Ni-Cd) batteries eventually took their place for mobile gear in the 1980s. However, Ni-Cd, a typical small-sized secondary battery, had several drawbacks as a power source for portable devices, e.g., low energy density and environmental issues. And furthermore, the energy density of Ni-Cd batteries had reached the technological limit by the middle of the 1980s. Sony Corporation started its battery business in the mid-1970s. Its main battery products in those days were primary batteries, e.g., alkaline manganese and silver oxide cells. To adapt Sony’s battery business to the above mentioned trends, the development of novel rechargeable cells was a pressing necessity. Sony began the development of secondary batteries in 1985, and started to investigate the possibility of cells with lithium-based negative electrodes, and, first in the world, succeeded in the development of the secondary lithium-ion secondary battery (LIB) in 1990.

How the LIB Was Born Theoretically, Li metal is very promising as an active material for the negative electrode. To realize the Li negative electrode, several drawbacks had to be overcome. One was dendrite formation, which resulted in a poor cycle performance, and the other was the safety problem. How were these drawbacks overcome? When a metallic Li negative electrode is charged, twig- or needle-shaped deposits called “dendrite” are formed. These deposits are apt to go through separators and to cause internal short circuits, resulting in a fire. In addition, dendritic lithium deposits easily drop off from the substrate, resulting in poor cycle characteristics. To resolve this issue, we investigated Li alloys in place of metallic Li. For example, Li alloys with aluminum, Wood’s alloy, and carbonaceous materials were tested. Wood’s alloy absorbed Li and formed Li containing alloys, but it included cadmium, which is environmentally hazardous. Moreover, its melting point is about 70°C, too low for a negative electrode. A Li-aluminum alloy showed very poor cycle performances in our trial products. Thus, the Licarbon alloy was tested ultimately. The industrial mass production of Li-carbon alloys was very difficult. Consequently, Li+ ion dissolved in the electrolyte was one candidate for a Li source, and a Li+ containing positive electrode was another candidate. When Li+ ion-dissolved electrolytes were used, a large amount of electrolyte was required to raise the discharge capacity. This was not acceptable. The final candidate for the Li source was the positive electrode. In this case it was necessary that Li+ could be electrochemically inserted in and extracted from the positive electrode. Thus, we decided to investigate Li+ containing positive electrode materials, and finally LiCoO21 was adopted. When the LiCoO2-graphite cell is assembled, the charge/discharge reactions are as follows: Li+ ions are retained between CoO2 layers in the positive electrode. When the cell is charged, Li+ ions leave the positive electrode and travel through the electrolyte to the negative electrode and are doped between the layers of graphite forming a Li-C alloy. This alloy is called a Li-graphite intercalation compound. When the cell is discharged, Li+ ions in graphite leave the negative electrode, travel through the electrolyte and go back to the CoO2 layers. Therefore, only the transport of Li+ ions through the electrolyte between the positive and negative electrodes was observed during

the charge and discharge reactions, and hence we gave the name of “lithium ion secondary battery” to this electrochemical system. There are three types of carbonaceous materials that could be applied to the negative electrode of LIBs. These were graphite, graphitizable carbon, and non-graphitizable carbon. Graphite had a strictly layered structure and Li+ ions could be doped in every interlayer. Graphitizable carbon is also called “soft carbon” and also has the layered structure, but was slightly disordered. When soft carbon is heat-treated at a temperature of around 3000°C, it transforms into graphite and this is the reason why it is named graphitizable carbon. Li+ ions could be doped in most of the interlayers. Non-graphitizable carbon is also called “hard carbon” because it is very hard to be broken. It consists of randomly oriented crystallites, and never transforms into graphite even when heat-treated at a temperature of 3000°C. Li+ ions could be doped between the crystallites and the micro-pores surrounded by these crystallites. After five years of effort to investigate the novel electrochemical cell, Sony announced in 1990 that we had succeeded in the development of the LIB. In LIBs of the first generation (φ20 × 50 mm), which were introduced into the market in 1991, soft carbon was adopted as an active material for the negative electrode. The discharge capacity of the soft carbon, which was heat-treated in the temperature range of 1200–1400°C, was about 220 mAh•g⁻1. The charging voltage of the cell was 4.1 V and it had an energy density of 80 Wh•kg⁻1, considerably higher than the nickel-metal hydride or Ni-Cd cells at that time. However, we were not completely satisfied. Much effort was required to improve the factors contributing to the performance of the LIB including energy density, drain capability, cyclic performance, and discharge ability at low temperatures.

Hard Carbon It is well known that the interlayer spacing (d002) of graphite is 0.335 nm. When lithium ions are intercalated into the layers of graphite, the d002 spacing expands up to 0.372 nm. Although the d002 spacing of soft carbon is slightly broader than that of graphite, it is still considerably narrower than 0.372 nm, which means that d002 expansion of coke due to the intercalation of lithium ions is inevitable. In the case of soft carbon, when the heat-treatment temperature (HTT) was raised, the d002 spacing shrank and the discharge capacity decreased. Furthermore cycle performance deteriorated. In consideration of this behavior of coke, we assumed that carbonaceous materials with the d002 spacing broader than 0.372 nm might be smoothly doped with lithium ions without the d002 expansion and that they might be doped with much more lithium ions than soft carbon and graphite. Because suitable precursors for hard carbon could hardly be expected to be available commercially in those days, we started our trail of hard carbon by synthesizing poly(furfuryl alcohol) (PFA) resin, which is a well-known precursor of hard carbon. PFA resin was prepared by the polymerization of a furfuryl alcohol monomer using phosphoric acid as a catalyst, and hard carbon was obtained by carbonization of the PFA resin followed by heat-treatment at 800–1500°C. The resulting carbonaceous material had a d002 spacing broader than 0.372 nm, which meant that this hard carbon could be smoothly doped with lithium ions without expansion of the d002 spacing and that it might be doped with much more lithium ions than soft carbon.2 The d002 spacing of PFA carbon is compared with that of soft carbon as a function of heat-treatment temperature (HTT) in Fig. 1. It is clearly seen that the d002 spacing of the hard carbon is considerably

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Table I. The characteristics of hard carbon (PFA carbon) heat treated at various temperatures. HTT

Discharge Capacity

d002

(°C)

(mAh•gˉ 1)

(nm)

800

Fig. 1. The effect of HTT on d002 of hard carbon (PFA-C) and soft carbon (COKES).

wider than those of the soft carbon and graphite, being wider than 0.372 nm when heat treated at temperatures below 1500°C. Table I shows the discharge capacity of PFA carbon. The discharge capacity of PFA carbon reached almost 320 mAh•g⁻1 when heat treated at 1100°C. The cycle performances were by far better when sintered at 1100–1200°C than those of soft carbon. The ionic state of lithium species doped between graphite layers and hard carbon layers was investigated by applying the 7Li-NMR technique. Figure 2 shows the results for graphite doped with various amounts of lithium. The Knight shift of LiCl was taken as 0 ppm. In graphite doped with lithium equivalent to less than 372 mAh•g⁻1, a Knight shift peak corresponding to metallic lithium did not appear. A tiny peak of lithium metal was observed when Li doping reached 372 mAh•g⁻1, which is equivalent to the theoretical lithium content in LiC6. The height of this peak rose as the amount of doped lithium increased beyond the value of 372 mAh•g⁻1, which meant that all the excess lithium deposited on the surface of graphite was metallic lithium.

265

0.380

Cycle 10

1,000

310

0.380

1,110

318

0.380

>1,000

1,200

312

0.380

>1,000

1,300

310

0.376

650

1,400

298

0.371

On the other hand, in the case of the hard carbon (Fig. 3), no peak of metallic lithium could be observed even when it was charged to 450 mAh•g⁻1. A small peak of metallic lithium appeared for the first time at 500 mAh•g⁻1 on charging. Although no deformation of the electrodes could be observed in the initial cycles, it is clear that significant deformation was brought about by the expansion of the graphite d002 spacing after 100 cycles as shown in Fig. 4. This figure is a cross-sectional view of a cell taken by a CT scanner, a nondestructive inspection method. This deformation invites the capacity fade of the cell. Hard carbon was very stable during charge/discharge cycles. This stability was due to the broader spacing between the layers. As mentioned above, no expansion of the d002 spacing due to Li insertion could be observed. This outstanding property prevented deformation of the negative electrode even after 200 cycles as shown in Fig. 5. In 1992, the hard carbon was applied as the negative electrode active material of Sony’s second-generation LIBs (φ18 × 65 mm, socalled 18650 cell), and the adoption of the hard carbon enabled LIBs to be charged at 4.2 V without rapid capacity fade during cycling.3 The practical energy density was 120 Wh•kg⁻1, about 50% higher than that of the soft carbon cells.

Performance That Users Expect for LIBs

On the basis of the results with the hard carbon negative electrode, we pursued the improvement of its performance, and finally achieved a practical discharge capacity of 550 mAh•g⁻1. For graphite, the theoretical discharge capacity is 372 mAh•g⁻1 and the practically attainable capacity is ca. 350 mAh•g⁻1. Therefore, we believed hard

Fig. 2..7Li spectra of graphite doped with various amounts of lithium. Knight shift of LiCl is taken as 0 ppm. 72

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Fig. 3..7Li spectra of hard carbon doped with various amounts of lithium. Knight shift of LiCl is taken as 0 ppm.

carbon to be a very attractive anode active material. However, it was not long before we noticed that the gravimetric energy density was not an ace in the hole. Our clients taught us that the volumetric energy density was much more important because the size of a cell is predetermined for ordinary applications. The density of graphite is ca. 2.15–2.25 g•cm⁻3 and that of hard carbon ca. 1.45–1.55 g•cm⁻3. Thus, the volumetric discharge capacities of graphite and hard carbon were estimated at ca. 750–790 and ca. 800–850 mAh•cm⁻3, respectively, and the difference between them was very small in terms of the volumetric energy density. When LiCoO2 is used as the active material for the positive electrode, the average voltage of a graphite cell is 3.7 V and that of a hard carbon cell 3.6 V, which means that the energy density of the former is 2.8–2.9 Wh•cm⁻3 and that of the latter 2.9–3.1 Wh•cm⁻3. Furthermore, the initial charge and discharge efficiency of graphite is ca. 95% and that of hard carbon ca. 85%. Thus hard carbon’s advantages were greatly reduced by its poorer properties in the density, average voltage and initial efficiency. Moreover, the discharge curve profile of the graphite cell was almost flat and that of the hard carbon cell was rather sloping. When the cutoff voltage was set at 3 V, as is the case of conventional applications such as personal computers and cellular phones, the discharge capacity of the hard carbon cell was reduced. Recently, however, the hard carbon anode has been revised upward. As mentioned above, the hard carbon Li-ion cell is somewhat behind graphite cells in the discharge capacity. However, they surpass the latter in the following aspects: cycle life; drain capability; and acceptability to quick charge These are essential for hybrid electric vehicles (HEVs), for example, and many automobile manufacturers are trying to apply the hard carbon LIBs to their HEVs. Sony’s hard carbon Li-ion cells were adopted as the power source of the European Rosetta spacecraft and lander that made history on the 12th of Nov. 2014 by landing on a comet 3 billion miles from the Earth. The Rosetta spacecraft left the Earth in March 2004, and the batteries had been operating for more than 10 years. This splendid achievement shows that hard carbon cells have excellent cycle life and durability. (continued on next page)

Fig. 4..Computerized tomograms of LIB with graphite negative electrodes.

Fig. 5..Computerized tomograms of LIB with hard carbon negative electrodes.

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Nishi

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THE ELECTROCHEMICAL SOCIETY

Monograph Series

The following volumes are sponsored by ECS, and published by John Wiley & Sons, Inc. Order your copy from the ECS Online Store today! Atmospheric Corrosion (2nd Edition) By C. Leygraf, I. Odnevall Wallinder, J. Tidblad, and T. Graedel (2016) 400 pages, ISBN 978-1-118-76227-1 Molecular Modeling of Corrosion Processes: Scientific Development and Engineering Applications Edited by C. D. Taylor and P. Marcus (2015) 272 pages, ISBN 978-1-118-26615-1 Electrochemical Power Sources: Batteries, Fuel Cells, and Supercapacitors By V. S. Bagotsky, A. M. Skundin, and Y. M. Volfkovich (2015) 400 pages, ISBN 978-1-118-46023-8 Modern Electroplating (5th Edition) Edited by M. Schlesinger and M. Paunovic (2014) 736 pages, ISBN 978-0-470-16778-6 Lithium Batteries: Advanced Technologies and Applications Edited by B. Scrosati, K. M. Abraham, W. A. van Schalkwijk, and J. Hassoun (2013) 392 pages, ISBN 978-1-118-18365-6 Fuel Cells: Problems and Solutions (2nd Edition) By V. S. Bagotsky (2012) 406 pages, ISBN 978-1-118-08756-5 Uhlig’s Corrosion Handbook (3rd Edition) Edited by R. Winston Revie (2011) 1,296 pages, ISBN 978-0-470-08032-0 Electrochemical Impedance Spectroscopy By M. E. Orazem, and B. Tribollet (2008) 560 pages, ISBN 978-0-470-04140-6 Fundamentals of Electrochemical Deposition (2nd Edition) By M. Paunovic and M. Schlesinger (2006) 373 pages, ISBN 978-0-471-71221-3

Conclusions It can be emphasized from our experience mentioned above that the following factors are essential for the selection of battery materials, especially active materials for the positive and negative electrodes: a) The volumetric energy density is as important as the gravimetric energy density because, in general, the cell size is predetermined. Materials with a lower specific density are not preferable from this point of view. b) The cutoff voltage influences the discharge capacity. A cell with a sloping discharge profile is disadvantageous. c) The initial charge and discharge efficiency should be as high as possible. © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F06163if.

About the Author Yoshio Nishi is a retired senior vice president and chief technology officer of the Sony Corporation. He graduated in 1966 from the Faculty of Applied Chemistry of the Department of Technology at Keio University in Tokyo and immediately joined Sony, where he rose through the ranks to become corporate research fellow, vice president, and president of the company’s materials laboratories. He engaged in research and development on fuel cells, materials for electroacoustic transducers, and electrochemical cells with nonaqueous electrolytes. In 1991 his team succeeded in the commercialization of the first lithium-ion secondary batteries (LIB). In 1994 he received technical awards from both the Electrochemical Society of Japan (ECSJ) and The Electrochemical Society (ECS) in recognition of his contributions to LIB technology. He also received the Kato Memorial Award from the Kato Foundation for Promotion of Science (Japan) (1998), the Ichimura Award from the New Technology Development Foundation (Japan) (2000), and the Charles Stark Draper Prize from the National Academy of Engineering (USA) (2014) in recognition of his contributions to LIB technology, and the Technical Award from the Japan Society for Biotechnology and Agrochemistry (1998) for his study on bacterial cellulose. He may be reached at yoshio.nishi@jp. sony.com.

References 1. J. B. Goodenough, Japanese Pat. S63-59507 (1980). 2. Y. Nishi, in Lithium Ion Batteries, M. Wakihara and O. Yamamoto, Editors, Ch.8, Wiley, New York (1998). 3. Y. Nishi, J. Power Sources, 100, 101 (2001).

Fundamentals of Electrochemistry (2nd Edition) Edited by V. S. Bagotsky (2005) 752 pages, ISBN 978-0-471-70058-6 Electrochemical Systems (3rd Edition) By J. Newman and K. E. Thomas-Alyea (2004) 672 pages, ISBN 978-0-471-47756-3

ECS Members will receive a discount. See the ECS website for prices.

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Importance of Coulombic Efficiency Measurements in R&D Efforts to Obtain Long-Lived Li-Ion Batteries by J. R. Dahn, J. C. Burns, and D. A. Stevens

ithium-ion batteries are now being used in applications where long lifetime is required, such as implantable biomedical devices, electric vehicles, and grid energy storage systems. In biomedical applications it would be ideal if the battery lasted as long as the patient, in vehicles the battery should last as least as long as the vehicle, and in grid storage, ideally the battery should last many decades, perhaps ultimately 50 years or more. “It is hard to make a Li-ion battery last a long time, but even harder to prove that it will.” The quotation above comes from Craig Schmidt of Medtronic Corp., a manufacturer of implantable biomedical devices. How can one be sure a Li-ion battery will last for decades without actually testing it under real application conditions for decades? That is the problem. Many researchers and users of Li-ion cells try to demonstrate lifetime by doing rapid charge-discharge cycles around C-rate or even faster, where every full cycle can take 2 h or less. One thousand cycles, enough to drive a battery electric vehicle like a Tesla Model S

Fig. 1. Percentage of initial capacity versus cycle number (top panel) and versus time for LiFePO4/graphite 26650 size Li-ion cells. The cell tested at high rate (1.5 C charge and 2.5 C discharge) was tested at 60°C. The cell tested at low rate (C/56 charge and discharge) was tested a 55°C.

about 400,000 km can be collected in under three months. However, it would typically take longer than a decade for an electric vehicle to be driven that distance. The issue with making conclusions about lifetime based on high-rate cycling experiments is that unwanted parasitic reactions1,2 between the charged electrode materials and the electrolyte in a Li-ion cell are occurring all the time, whether the cell is being cycled or not. These unwanted reactions occur at a low rate, but accelerate with both increasing temperature and increasing cell voltage. As Phillippe Biensan of SAFT eloquently stated: “High rate cycling ‘beats the clock’ on parasitic reactions.” The top panel in Fig. 1 shows capacity versus cycle number for LiFePO4/graphite 26650-size cells tested at elevated temperature. The cells lose very little capacity over 500 cycles when charged and discharged at high rate where the entire experiment takes about 500 h. However, when the cells are charged and discharged about once every 100 h, the cells lose 50% capacity in only 50 cycles. The lower panel in Fig. 1 shows that the cells lose about the same capacity in the same testing time. Figure 1 illustrates extremely well how high-rate cycling can be used to “beat the clock” on parasitic reactions. In 2010, Smith et al.3 proposed that high accuracy measurements of the coulombic efficiency of Li-ion cells could be used to help determine their lifetime. Smith et al. defined the coulombic efficiency (CE) of a Li-ion cell as CE = [Charge delivered during discharge]/[charge stored during previous recharge] Basically, if there are no unwanted parasitic reactions occurring in a Li-ion cell and if the electrodes show no mechanical degradation, then the coulombic efficiency of that cell will be exactly unity, i.e., 1.00000…. The greater the departure of the CE from unity, under fixed testing conditions, the shorter the lifetime of the Li-ion cell. In 2010, most measurements of coulombic efficiency in the literature were made with traditional battery testing equipment. It is not the purpose of the authors of this article to disparage particular research papers, so Fig. 2 shows mock data typical of that found in early literature papers. Figure 2a shows the way coulombic efficiency is reported in over 90% of literature papers that report it. The vertical scale is normally selected so as to emphasize that the coulombic efficiency is near 1.0. Figure 2b shows the same mock data as in Fig. 2a plotted on an expanded scale which shows the typical noise levels found in traditional measurements of coulombic efficiency. Smith et al.3 carefully considered the sources of this noise and showed how it could be reduced. A “back of the envelope” calculation can be used to estimate the coulombic efficiency required for a 10-year lifetime based on a daily charge and discharge where only electrolyte oxidation by a one-electron reaction, which ultimately consumes the electrolyte and causes cell failure, occurs during each cycle. An 18650-size Li-ion cell with a capacity of 3.0 Ah and 5 g of electrolyte having a solvent with an average molar weight of 100 g/mole would require about 1.3 Ah of charge to totally oxidize the electrolyte. Over the 3600 cycles of this cell over 10 years, an average inefficiency of 1.3 Ah/ [3.0 Ah × 3600] = 0.00003 would occur during each cycle, meaning that the cell would require a coulombic efficiency of about 0.99997. Based on Fig. 2b, it is clear that traditional data simply has too much noise to be able to determine coulombic efficiency to such accuracy.

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Smith et al.3 and later Bond et al.4 built high-precision chargers expressly purposed for measuring CE with high accuracy and precision. Based on the considerations in Bond et al.,4 a 100 channel ultra high precision charger (UHPC), shown in Fig. 3, was assembled at Dalhousie University. This instrument can measure CE to an accuracy of ±0.00003 and a precision of ±0.00001, when cells are housed in temperature controlled environments stable to ±0.1°C during operation. The instrument is built from high-accuracy Keithley 2602B current supplies, Keithley 2002 multimeters and precision resistors (0.2 ppm/°C) from Texas Components. The UHPC cost about $1 M USD to build in 2012-2013 or about $10,000 USD per testing channel. Figure 4 shows results collected using the high-precision charger (HPC)3 by Burns et al.5 on LiCoO2/graphite prismatic cells with different electrolyte additives. Figures 4a, b, and c show the coulombic efficiency, charge endpoint capacity and discharge capacity versus cycle number, respectively, of cells with different electrolyte additives as indicated during short term testing at C/20 between 2.8 and 4.075 V at 40°C. Note the fidelity of the data in Fig. 4a and excellent reproducibility of pair cells compared to Fig. 2b. Figure 4a shows that cells with 2% VC have the highest coulombic efficiency and Fig. 4b shows the same cells have the smallest charge endpoint capacity motion, indicating the least amount of electrolyte oxidation. Based on Fig. 4a and b, cells with 2% VC are expected to have the longest lifetime. Figure 4c shows that it is very difficult to distinguish between the four types of cells based on their short term discharge capacity versus cycle number curves.

Fig. 2. “Mock data” representative of typical literature results for coulombic efficiency versus cycle number. Panel b) shows the same data as panel a) but on an expanded scale. 76

Fig. 3. Photograph of the 100-channel ultra-high-precision charger at Dalhousie University.

Figure 4d shows ongoing long term charge-discharge cycle testing results for the same cells collected at 55°C on a traditional charger. The cells have been tested between 2.8 and 4.075 V at C/10 for over 4 years so far. The cell with 2% VC will clearly have the longest lifetime as predicted by the short term measurements. After three years of testing (around 1300 cycles) the cells were stopped and their coulombic efficiencies were measured again using the high precision charger at C/20 and at 40°C. Table I shows that the CE of the cell with 2% VC had reached 0.99992 ± 0.00003 and was still the largest of all the cells. The CE increases, compared to that measured in Fig. 4a, with cell age because of the thickening of passivating layers on both the positive and negative electrodes which slow the unwanted parasitic reactions. Based on the results in Fig. 4 and Table I, our research group has pushed the use of high-precision coulometry forward as a method for screening the effectiveness of advanced electrolytes and electrode material coatings for high voltage Li-ion cells. As an example, increased energy density of Li[Ni0.6Mn0.2Co0.2]O2/graphite (NMC622/ gr) cells can be obtained by increasing the upper charging potential from a typical value of 4.2 V to 4.4 or 4.5 V. In order to use high-precision coulometry effectively, it is essential that high-quality, highly reproducible Li-ion cells be used for such studies. In our laboratory, small machine-made 402035 size (40 × 20 × 3.5 mm thick) pouch type Li-ion cells are obtained from a reputable manufacturer without electrolyte. Electrolyte is added in our laboratory before the cells are vacuum sealed. The effect of coatings on the NMC622 particles on coulombic efficiency and cell lifetime6,7 can be explored by preparing batches of pouch cells with coated NMC622 particles and with uncoated NMC622 particles. Figure 5 shows the results of UHPC measurements and subsequent long term testing experiments on the same sets of cells. Results for two cell types (coated and uncoated NMC622) and five different electrolytes (Control = 1 M LiPF6 in EC:EMC, 2% VC in control and proprietary electrolytes A, B are C) are shown. Duplicate cells were tested in all cases and error bars represent the spread from the average result. Figure 5a shows the CE measured during the 16th cycle at 40°C between 2.8 and 4.4 V at 40°C. Figure 5a shows that cells with electrolyte B with either coated or uncoated NMC622 have the best CE. Figure 5b shows the result of aggressive long term charge-store-discharge testing on the same cells. The testing was conducted at 40°C using a C/5 charge to 4.4 V followed by a 24-h open circuit period at top of charge, followed by a C/5 discharge to 2.8 V for a total time of 34 hours per cycle. Figure 5b shows the time (in months) for the cells to reach 90% of their initial capacity. Figure 5b shows a very good correlation with Fig. 5a and also shows that both uncoated and coated NMC622 cells with electrolyte B are better than all other cells. Figure 5 shows the importance of both coatings and designed electrolytes for high energy density Li-ion cells. The use of ultra-high-precision coulometry can dramatically shorten the time required in the search for cells with longer life time. The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Fig. 4. (a-c) High-precision coulometry data collected on LiCoO2/graphite Li-ion cells at 40°C from Ref. 5. (a) Coulombic efficiency, (b) charge endpoint capacity, and (c) discharge capacity all versus cycle number. The cells were charged and discharged between 2.8 and 4.075 V at C/20. The electrolytes used in the cells are indicated in the legend. Two cells of each type were tested. (d) Long term (>4 years) charge-discharge cycle testing of the cells described in panels a-c. The long term testing was done at 55°C between 2.8 and 4.075 V at C/10. Table I. Coulombic efficiencies of the cells in Fig. 4d after 3 years of testing at 55°C. The CE measurements were made under the same conditions as those made in Fig. 4a. Electrolyte

CE after 3 years of testing at 55°C

Control – 1M LiPF6 in EC:EMC 3:7

0.99980 ± 0.00003

Control + 0.3 TMOBX

0.99983 ± 0.00003

Control + 0.3% TMOBX + 2% VC

0.99989 ± 0.00003

Control + 2% VC

0.99992 ± 0.00003

EC = ethylene carbonate; EMC = ethylmethyl carbonate; TMOBX = trimethoxy boroxine; VC = vinylene carbonate

Researchers and companies around the world are now recognizing the importance of high-precision coulometry. For example, Yoshio Ukyo at Kyoto University has recently completed construction of an ultra high precision charger that should have better specifications than the Dalhousie unit. However, this was achieved at even greater cost. Two industrial firms, Novonix (www.novonix.ca – Canada) and Bio-logic (www.biologic.info – France) have now begun offering instruments suitable for ultra-high-precision coulometry with specifications very similar to the Dalhousie unit. These instruments are much more affordable than the Dalhousie system. Figure 6 shows a photo of a 96 channel Novonix system installed at a major Li-ion battery company. The Novonix system is also supplied with the highly stable temperature boxes, in which to place the cells under test, required for UHPC measurements. In addition, Arbin Instruments (http://www.arbin.com/index.php/products/highprecision-test-station – USA) is now producing a high-current charger which has good specifications for high-precision coulometry. Just as a potentiostat is an essential tool for all electrochemists, ultrahigh-precision chargers are an essential tool for those looking to develop and verify Li-ion cells with long lifetime. It is also worth noting that “beyond” lithium ion technologies such as non-aqueous Na-ion and Mg-ion will also need to attain extremely high coulombic efficiencies to attain decades-long lifetimes. High-precision coulometry will be essential in the development of those technologies as well.

Fig. 5. (a) Coulombic efficiency versus cycle number, measured at cycle 16, for NMC622/graphite cells tested at 40°C between 2.8 and 4.4 V at C/20. The cells had different electrolytes as indicated in the legend and had either NMC622 with a surface coating (“coated”) or uncoated NMC622. (b) Number of months of testing until cells attained 90% of their initial capacity during long-term charge-store discharge cycle testing conducted after the testing panel (a) was completed. The long-term tests were made using a charge current of C/5 to 4.4 V, a storage period of 24 h at top of charge and a discharge at C/5 to 2.8 V. The tests were made at 40°C. Notice the strong correlation between panels (a) and (b).

Fig. 6. Photograph of a 96 channel Novonix ultra high precision charger, including temperature controlled environments (for example, two of them are numbered 3 and 4) installed at a major Li-ion cell company.

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Acknowledgments The authors would like to acknowledge NSERC and 3M Canada for funding of the work. The authors acknowledge the Canada Foundation for Innovation and the Nova Scotia Research and Innovation Trust for the funds required to build the ultra high precision charger at Dalhousie University. Contributions in data collection by Rajalakshmi Senthil Arumugam and Aaron Smith are gratefully acknowledged.

About the Authors Jeff Dahn has been working on rechargeable Li batteries since 1978 and on Li-ion batteries since 1987. He is currently the NSERC/Tesla Canada Industrial Research Chair and a Canada Research Chair at Dalhousie University in Halifax, Canada. He works in the Dept. of Physics and Atmospheric Science at Dalhousie University. Dahn has received numerous awards including the ECS Battery Division Research Award (1996) and the ECS Battery Division Technology Award (2011). He may be reached at jeff.dahn@dal.ca. Chris Burns has a BSc from St. Francis Xavier University and MSc and PhD (2015) degrees from Dalhousie University. Chris Burns’ PhD work focused on developing and applying high precision coulometry methods. Burns is now the CEO of Novonix Battery Testing Services Inc. which is located in Dartmouth, Nova Scotia, Canada. He may be reached at chris.burns@novonix.ca.

David Stevens has BSc in Applied Chemistry from RMIT. He worked at Comalco Research Centre in Australia before completing a PhD at Dalhousie University in 2000. David Stevens discovered Na insertion in hard carbon, now a leading candidate for the negative electrode in Naion cells. Stevens has worked extensively on developing hardware and software for high precision coulometry. He is now the CTO of Novonix Battery Testing Services Inc. which is located in Dartmouth, Nova Scotia, Canada. He may be reached at david.stevens@novonix.ca.

References 1. A. J. Smith, H. M. Dahn, J. C. Burns, and J. R. Dahn, J. Electrochem. Soc., 159, A705 (2012). 2. D. A. Stevens, R. Y. Ying, Reza Fathi, J. N. Reimers, J. E. Harlow, and J. R. Dahn, J. Electrochem. Soc., 161, A1364 (2014). 3. A. J. Smith, J. C. Burns, S. Trussler and J. R. Dahn, J. Electrochem. Soc., 157, A196 (2010) 4. T. M. Bond, J. C. Burns, D. A. Stevens, H. M. Dahn, and J. R. Dahn, J. Electrochem. Soc., 160, A521 (2013). 5. J. C. Burns, N. N. Sinha, Gaurav Jain, Collette M. VanElzen, W. M. Lamanna, A. Xiao, Erik Scott, J. Choi, and J. R. Dahn, J. Electrochem. Soc., 159, A1105 (2012). 6. Y.-K. Sun, M.-J. Lee, C. S. Yoon, J. Hassoun, K. Amine, and B. Scrosati, Adv. Mater., 24, 1192 (2012). 7. Y. Kim, H. S. Kim, and S. W. Martin, Electrochim. Acta, 52, 1316 (2006).

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The Li-Ion Battery: 25 Years of Exciting and Enriching Experiences by J. M. Tarascon

he Li-ion battery (LIB) was first commercialized by SONY in 1991.1 In the twenty five years that have passed, LIB technology has changed the world by enabling numerous technological advances in portability and mobility, and is intimately tied into future energy management strategies for protecting our planet. How did this happen? Having been part of this adventure since the early stages, I will here recall through a few examples how this technology came to light, how collegial competition advanced the field to its current state, and how exciting and thoughtful this adventure has been. The LIB revolution sprouted its roots in the 1970s with the realization that inorganic layered chalcogenides could reversibly intercalate alkali guest atoms with preservation of the framework structure—that is, through topotactic redox reactions.2 This observation spurred the idea of making rechargeable Li batteries, which were first commercialized in the late 1980s by Moli Energy. The excitement was short-lived and the Li/MoS2 cells were rapidly recalled from the market due to serious safety setbacks leading to battery explosion, caused by uncontrolled Li dendrite growth upon cycling. Luckily, scientists immediately (1980s) bounced back from this hitch and proposed to mitigate dendritic Ligrowth by the use of either a polymeric membrane acting as a physical barrier or by replacement of the Li-metal electrode with an insertion carbon electrode, hence leading to the birth of the Li-metal polymer3 and Li-ion batteries,4 respectively. Li-ion battery technology has matured consistently during the last quarter century,5 with nearly a doubling of energy density (110 Wh/ kg → 200 Wh/kg); such growth is unique in the general battery history. Progress has been incremental, involving different periods of scientific and technological advances, mainly driven by societal demands (e.g., user’s performing exigencies) and evolving societal trends (e.g., sustainability). These periods and their corresponding sources of collaborative or competitive research are next placed in their context and described as personally experienced.

The Maturation Stage: 1980 – 2000 Initially, efforts were primarily directed at optimization and understanding of the core Li-ion technology components, namely electrodes, electrolytes, and interfaces. Well-defined rules were established, generally favoring incremental improvements over challenges to the paradigm; the screening for new insertion compounds was very selective. An ideal electrode should possess an open-framework structure, have high electronic conductivity and fast Li+ diffusion, be easily made from cheap chemical elements in large particles for minimizing parasitic reactions on the surface, and also be thermally and chemically stable (Fig. 1). The list of criteria was further lengthened when designing electrodes for Li-ion batteries as the positive electrode must be the source of Li+ and be of high voltage to ensure a high energy density cell. Owing to these last two rules, the search was narrowed to oxides, which have higher redox voltages than their chalcogenide counterparts (O being more electronegative than S). Overall, only three compounds met these specifications during the first fifteen years: the layered compounds LiCoO26 and LiNiO2,7 and the “3-dimensional” LiMn2O48 spinel phase. In contrast to LiNiO2, which was abandoned at an advanced development stage due to intractable safety issues associated with the poor thermal stability of the charged Li1-xNiO2 phase, LiCoO2 was rapidly implemented in commercial Li-ion cells. LiCoO2/C Li-ion cells dominated the market until the arrival of the chemically substituted layered oxides

LiNixCoyAlzO2 and LiNixCoyMnzO2, referred to as the NCA9 and NMC10 phases, respectively, which have become the most common cathode material in today’s batteries for powering portable electronics and electric vehicles (EVs). Implementation of the LiMn2O4 phase, on the other hand, was more problematic due to its tendencies towards Mn dissolution11 during cycling and catalytic promotion of electrolyte decomposition. Nearly 15 years of tedious research were necessary to commercialize LiMn2O4/C Li-ion cells, which are presently used in EVs. Its market penetration is therefore limited because the energy density and reliability of LiMn2O4-based cells fall short of other technologies such as Li-NMC/C. Thus we may wonder if such a research effort was worthwhile: yes, it was. Mastering the complex and uncooperative LiMn2O4/C system has been a rich learning playground. It led to major advances in Li-ion cell components, in particular electrolyte formulation. It also facilitated a better understanding of interfacial issues via the development of new approaches (surface treatments, electrolyte additives, …) that are routinely used nowadays in optimizing electrode materials. Let us recall that it is through the LiMn2O4/C journey that dimethyl carbonate (DMC) was identified12 as the prime additive to ethylene carbonate (EC) for obtaining electrolyte compositions exceedingly stable upon oxidation up to near 5 V at 55 °C (Fig. 2). The DMC-based electrolyte formulation (1 M LiPF6 in EC-DMC (50/50 by weight %)) developed for optimizing LiMn2O4/C is now commercialized under the brand name LP30 and is used worldwide in many laboratories for materials screening. To minimize Mn dissolution, surface coating/encapsulation techniques enlisting the use of chelating agents (acetylacetone) or protecting inorganic layers (borates), as well as fluorine surface treatments and electrolyte additives, were also initiated during that period.11 Similar surface science approaches are now routinely used to enhance the lifetime of today’s electrodes and Li-ion systems. Worth also recalling is the use of extra Li in Li1+xMn2O4 as a Li reservoir to make up for the irreversible capacity of the carbon electrode during the first charge of the battery, and also protecting it from the risks of an over discharge down to 0 V.

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Fig. 1. Established criteria for the search of “ideal” electrode materials back to the 1980s.

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Fig. 2. Voltammograms at 55 °C of a LiMn2O4/Li cell using EC+DEE (1:1) + IM LiClO4 electrolyte (curve a) and the new electrolyte composition: DMC+EC(1:2) + 1M LiPF6 (curve b). The scan rate was 10 mV/h.

During the same period, we witnessed the progressive change from carbon cokes to graphitized carbons at the negative electrode.13 Massive efforts were devoted to mastering the solid electrolyte interface (SEI)14 formed at the negative electrode, which governs the cell performance, safety, and cell lifetime. The SEI can be viewed as a gift from nature without which the Li-ion technology would not operate properly; it can also be regarded as the Holy Grail for researchers owing to its complexity. In spite of the arsenal of available characterization techniques that have been employed through these studies we are still far from a full understanding of the SEI. The quest to achieve complete command over the SEI provides persistent challenges as its morphology/composition/density/thickness is chemistry dependent and also influenced by operating conditions. Mastering its formation thus requires a field-trial approach, which is scientifically frustrating, but also where battery manufacturers have been able to develop competitive advantages. Regarding cell configurations, the same era witnessed the emergence of the first practical plastic Li-ion battery (Fig. 3), based on a polymeric system15 that is both thermo-fusible, mechanically robust, and compatible with the panel of current Li-ion batteries. Development of the polymer matrix—a copolymer of vinylidene fluoride with hexafluoropropylene (PVDF-HFP) loaded with

Fig. 3. Schematic of a plastic Li-ion battery with on top a view showing the inside of the cell with the 3 plastic laminates sandwiched between the copper and aluminum grids and at the bottom a view of the sealed cell. 80

inorganic fillers (SiO2)—was inspired from common practices in plastic processing technology. It entails the use of a dibutyl phthalate (DBP) plasticizer that is substituted by the liquid electrolyte at the last stage of cell processing through an extraction/activation step, thus enabling most of its assembly in an ambient environment. Teamwork and cross-disciplinary efforts were central to the success of the plastic battery endeavor; without Bellcore’s in-house expertise in plastics, the technological hurdles encountered in the development of flat configuration batteries would have not been solved at that time. In parallel, significant advances were made with the engineering of the separator membrane used in non-aqueous Li-ion cells; namely, the shift from single to multiple (PP-PE-PP) layering to tune the separator shut-down temperature. Moreover, inspired by the work on plastic Li-ion, ceramic-coated separators were developed31 and are now broadly used in various Li-ion batteries to enhance their safety while preserving performances. Throughout this period, the Li-ion technology underwent tremendous maturation, unifying an extensive body of research to ensure reliable, long lasting and safe consumer products. Simultaneously, awareness became heightened that the energy density of LIBs, dictated by the available oxide cathode materials, was nearly reaching its limit, thereby summoning further material innovations and a new era of battery research.

The Blooming Age: 2000 – 2010 The foreseen limitations in pursuing classical materials strategies spurred scientists to think outside of the box and pursue new bullish approaches. Amusingly, most of the efforts were essentially challenges to the preconceived ideas on which the LIB industry was founded. The ambiance was as if scientists were recovering their freedom; new ideas were eagerly discussed at meetings and blossoming, some of which had great practical impacts. In the 2000s, scientists decided, in light of the benefits brought by nanomaterials in microelectronics and elsewhere, to study the effect of adding size as an extra dimensional parameter to composition, temperature, and pressure on electrode materials performances. This was a distinct rejection of old taboos against the practical use of nanomaterials—enhancers of parasitic reactions. Owing to early success, this avenue of research has turned into a massive exploration of the nanomaterial approach, giving birth to the Li-ion battery “nanomania” era which has benefited the Li-ion battery technology in many ways as briefly illustrated next. It is by combining the dual nanosizing—carbon-nano-painting16 technique that the insulating compound LiFePO4,17 disregarded until 1997, was turned into today’s most praised electrode material for powering EVs. Size reduction decreases the ion travelling time from the core to the surface of the particle while enrobing the particles with a conducting layer enhances the electronic percolation, both leading to electrodes with enhanced kinetics. Using such nano-composites we could obtain the material’s theoretical capacity (170 mAh/g), and more ironically, LiFePO4/C Li-ion cells made from such electrodes are better that any competing Li-ion technologies in terms of rate performances. This approach was then heavily implemented in the screening of new polyanionic compounds with the discovery of attractive Fe-based borates, silicates and fluorosulphates. Nano-sizing has also enabled the resolution of a twenty-yearold problem pertaining to the use of silicon- or tin-based negative electrodes. Li-based silicon-alloys were known, since the 1970s,18 to have high capacities (3579 mAh/g for Li15Si4). But because of significant volume changes leading to particle fracturing and loss of electronic contacts upon cycling, the capacity retention was very poor. This challenge was solved by moving to nano Si particles, which demonstrate the unique ability to release stress without fracturing. The development of nanostructured Sn-based electrodes led to the NEXELION technology, marketed in 2005 and then abandoned because of short lifetime. Similarly, Li-ion cells based on nanostructured Si anodes were marketed, but rapidly withdrawn because of deceiving performances at elevated temperatures due to parasitic reactions associated with the high surface area of Si nanoparticles. This indicates that the integration of nano-Si electrodes into practical cells is not fully The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Overall, nanomaterials have been beneficial to the battery community, but wisdom has to prevail as “nano” does not always rhyme with better in terms of electrode performance. Other key parameters, such as a material’s redox potentials, must be considered prior to nanosizing. Lastly, making nano-materials or nano-structures for their own sake is not a compelling strategy.

The Sustainability Thrust: 2008 – …

Fig. 4. Voltage composition curve for a CoO/Li cell using 1 M LiPF6 in EC:DMC electrolyte with at the bottom a TEM image showing the formation of the nanocomposite Co/Li2O.

solved. To overcome this issue, the new 18650 models were made of less enriched C/Si electrodes (Si ~ 5%). Meanwhile, novel electrode architectures such as yolk-shell Si structures19 and pomegranate-like Si composites continue to be actively explored at the laboratory scale to enhance capacity retention. This is conceptually elegant but poorly practical. Lastly, binary oxides20 having neither an open structure nor chemical elements able to alloy with Li+, previously rejected on the basis of the initial rules, were shown to reversibly uptake and remove Li via a novel reaction mechanism termed “conversion”. Through this process (Fig. 4), the oxide is electrochemically reduced, according to the following reaction MxOy + 2y e⁻ + 2y Li+  x M0 + y Li2O, with the final product being a homogeneous nanocomposite made of metal nanoparticles in a Li2O matrix. These reactions, as opposed to classical insertion reactions that are mostly limited to 1e⁻ per 3d metal atom, can enlist 2 or even more electrons per 3d metal atoms, hence enabling electrodes with staggering capacities. Moreover, such conversion reactions can be extended to intermetallic hydrides, nitrides, sulfides and fluorides and their potential tuned from ~0.2 V (hydrides) to ~3 V (fluorides), hence enabling the design of either positive or negative electrodes. The benefits, however, are negated by inherent drawbacks of such conversion reactions, including a large initial irreversibility and poor energy efficiency due to a high polarization between charge and discharge. Such drawbacks, which are intrinsic to the system, have not been overcome despite the humongous amount of prior and ongoing studies focused on the structuring of these electrodes. Conversion reactions were considered a breakthrough, and the initial report has been cited more than 4000 times, but no practical implementation has so far been realized. Looking back at this period provides mixed feelings and even some guilt as we have drawn the community into an impasse. Although early warnings were put forward to highlight the complexity of such reactions, the risks did not adequately resonate. Why? Most likely because these conversion reactions were the perfect playground for innovative nanoarchitectured materials leading to beautiful TEM images that seem to open the gate to “high-impact” scientific journals, irrespective of their usefulness.

Evidence for the key role that Li-ion battery technology will have in large-scale applications (EVs) came to the forefront in 2008, stemming from controversial debates about lithium resources and materials abundances.21 Nearly at the same time, early integrated life cycle assessment estimations on battery systems identified the process of making electrode materials as the main contributor to CO2 emissions and energy costs during battery assembly. Thus began a surge in research efforts to design electrode materials with minimal environmental footprints, facilitated by eco-efficient synthetic routes. The arrival of electrode materials based on minerals such as LiFePO4 was a significant push towards satisfying the long-term demand for materials sustainability, but further efforts were needed. To bypass the energy-hungry ceramic processes, as indicated in Fig. 5, chemists turned back to “soft chemistry” approaches and demonstrated the synthesis of LiFePO4 by a variety of hydrothermal/ solvothermal routes at temperatures lower than ~150 °C. Additionally, the utility of ionic liquids serving as both reacting media and structural directing agent to prepare LiMPO4 (M = Fe and Mn) phases with tailormade morphologies was demonstrated at temperatures near ~200 °C. The richness of the ionic liquid chemistry was further exploited to synthesize at 250 °C a novel family of 3d-metal based fluorosulphates out of which LiFeSO4F, made from abundant and low-cost chemical elements, turns out to show the highest Fe3+/Fe2+ redox potential (3.95 V) ever reported for an inorganic compound.22 This drive towards sustainability led also to the development of bio-inspired processes enlisting either viruses or bacteria as both nucleating and templating agents to enable the preparation of Co3O4, Si, and Fe2O3 electrodes. While elegant, the scale-up of such processes remain to be seen. In the quest for zero CO2 footprint electrodes, organic molecules were reconsidered, but with a different twist than in the 1980s. Emphasis was placed on organic molecules that could be synthesized via “green chemistry” from natural organic sources, molecules that are biodegradable and are not resource limited.23 Within this context, the feasibility of making renewable organic Li-ion batteries using conjugated dicarboxylates (Li2C8H4O4) as negative electrodes and oxocarbons (Li4C6O6) as positive electrodes was successfully (continued on next page)

Fig. 5. Three-fold pyramid schematic stressing the benefits of lowering the synthesis temperature of electrode materials which are energy saving and better control of size, shape, and texture.

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demonstrated. Although quite attractive sustainability-wise, such batteries will never outperform present Li-ion technology with respect to performance due to the low gravimetric density of the organic molecules together with the need to add copious amounts of carbons within the electrodes to achieve decent kinetics, both of which penalize the overall cell gravimetric energy density. For such reasons, organic renewable batteries will target large volume applications where cost is more important than energy density and for which weak volume energy is not a penalty. Both of the above examples are important advances in the development of sustainable and greener Li-ion batteries. Nevertheless, life cycle analyses remain to be done to truly confirm the eco-efficient viability of these approaches.

Rebirth: 2012 – Present Since its inception, the Li-ion technology has relied on cationic redox reactions, with LiCoO2 being the most widely used positive electrode. The feasibility of electrochemically stabilizing the CoO2 end-member24 of the LixCoO2 system—as demonstrated in the late 1990s—raised an intriguing question: was Co3+ oxidized into Co4+, which is a less common oxidation state, or was the anionic network being oxidized, which is distinctly unusual in inorganic chemistry. Based on magnetic measurements indicating that Co3+ was not fully oxidized, oxidation of the anionic network was put forward and explained by a migration of the d-band into the p-band. This leads to an extreme situation in which the cation becomes more electronegative than the anion so that electrons are poured into the d-band leaving behind sp holes, which indicates the formation of (O2)n- dimers.25 Surprisingly, such an explanation raises many controversies although this type of hole chemistry had brilliantly been developed by J. Rouxel 10 years earlier within the sulfides26 and also heavily discussed with regard to the high Tc cuprates superconductors. A lack of experimental evidence at that time was at the origin of such reticence. It took nearly 15 years, until the discovery27,28 of the high capacity (>280 mAh/g) Lirich NMC electrodes (which are still the subject of endless debates as to whether they are nanoscale intergrowths or single phases of a solid solution) for the ligand-hole/anionic redox activity proposition to find its full importance. The presence of anionic redox species was indeed unambiguously demonstrated (Fig. 6) within the Li-rich NMC layered

Fig. 6. The voltage composition curve for a Li2IrO3/Li cell cell cycled at C/10 (e.g., 1 Li in ten hours). The HRTEM image collected along the [010] axis when the cell was fully charged is shown in a) together with in b) the [001] HAADFSTEM and ABF-STEM images of the same sample which is enlarged in c) to highlight the short projected distances which are marked with dumbbells. 82

oxides via combined XPS and EPR measurements29 with (OO)-like dimer species being directly visualized by ADF-STEM in the high capacity layered Li-rich oxide Li2IrO3.30 This marked the end of the 25-year-old belief that the capacity of insertion compounds was solely linked to their cationic redox activity, and the beginning of a new era in the quest for high capacity electrode materials by taking advantage of cumulative cationic and anionic redox processes. Research along this direction has already been fruitful as witnessed by the recent reports of two new Li1.3Mn0.4Nb0.3O2 and Li4Mn2O5 phases having capacities exceeding 300 mAh/g and showing oxygen redox activity. Many others are in the pipeline. Whether such attractive Li-rich materials will ever be commercialized remains an open question, as their voltage fade upon cycling, their transport properties and surface stability are not yet fully understood. For sure, had it not taken 15 years for the idea of anionic redox activity to be compellingly demonstrated and accepted by the community, we might already have the answer. Within this era of intense research and competition and pushed by societal demands for improved energy storage technologies, we should not forget what is the essence of this field. New ideas should always be promoted and supported as a chance for transformational leaps within the research community or for society, but we should also be questioning the real impact of a new discovery in terms of application. Finding balance between open-mindedness and pragmatism regarding the limits of these discoveries will bring our community back on track to push the limits of the Li-ion technology further.

What Have We Learned and Where Do We Go Now? Despite the initial commercial failures associated with Li-metal anodes, Mother Nature has been kind to us with the Li-ion technology; while its chemistry is undoubtedly complex, it is also the simplest of other known battery technologies, in particular relative to Pbacid batteries. This could explain to some degree why it took two centuries to realize a 5-fold increase in the energy density of all battery technologies combined, and only 25 years to double that of the Li-ion technology. This rapid development has taught us about the importance of inter-disciplinary and synergetic approaches through which questions aimed at a precise technical problem have led to profound scientific knowledge and vice versa. A union between scientific and technological knowledge is therefore essential, provided we do not fall into the counterproductive paranoia of confidentiality. Technical diversity has been a crucial attribute to the battery community, constantly fueling the field with new ideas and new concepts. With such richness, however, we are often faced with the dilemma of distinguishing between hype and reality. Separating the wheat from the chaff is time consuming and could be minimized by scientists more openly stating the challenges and limitations associated with their new advances rather than remaining protective; one area in particular that would be well served by increased transparency and non-idealized reporting is Li-air research. Through the journey in search of new electrode materials we also learned that the discovery of new phases does not necessarily lead to outstanding energy density improvements. Hundreds of new compounds were synthesized and the cruelty is that after 25 years we are still using layered oxides and carbonaceous materials at the positive and negative electrode, respectively. Let us hope that computational approaches like the materials genome initiative (MGI) or electrolyte genome project (CITE) will yield practical benefits to the Li-ion technology and enable a progression beyond iterative empirical development efforts. Nevertheless, scientists and engineers should be proud of what they have achieved over the last 25 years. Many of these advancements might never have materialized without the outstanding developments realized in parallel within the field of in situ analytical techniques, which have been essential to identify local structural changes, interface evolutions, and parasitic reactions during cycling. Computational theory has been inspiring and a source of lively discussions throughout this journey, although significant improvements in predictive capability are still needed. Regardless, the Li-ion supremacy will prevail for The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

many years, with hopefully many as-yet unforeseen improvements. I am sure, to quote J. B. Goodenough, that “If you live long enough, pleasant surprises come your way.” © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F08163if.

Acknowledgments The author is indebted to A. Grimaud and J. Kurzman for their critical reading of the manuscript and the battery community for giving me the honor to be part of it .

About the Author Jean-Marie Tarascon is Professor at the College de France holding the chair “Chemistry of Solids – Energy” and director of the French network on electrochemical energy storage (RS2E). His present research is mainly devoted to the synthesis, characterization, and determination of structure/property relationships of battery materials with emphasis in identifying new Li reactivity mechanisms and developing new ecoefficient synthesis processes for enhanced sustainability. He is the author of more than 600 scientific papers, and holds about 85 patents. He may be reached at jean-marie.tarascon@ college-de-france.fr.

References 1. T. Nagaura and K. Tozawa, Prog. Batt. Solar Cells, 9, 209 (1990) 2. J. Rouxel, M. Danot, and M. Bichon, Bull. Soc. Chim., 11, 3930 (1971). 3. M. Armand, J.-N. Chabagno, and M. J. Duclot, in Fast Ion Transport in Solids Electrodes and Electrolytes, P. Vashishta, J.-N. Mundy, and G. K. Shenoy Editors, p. 131, North-Holland, Amsterdam (1979). 4. D. W. Murphy, F. J. DiSalvo, J. N. Carides, and J. V. Waszczak, Mater. Res. Bull., 13, 1395 (1978). 5. J.-M. Tarascon and M. Armand, Nature, 414, 359 (2001). 6. K. Mizushima, P. C. Jones, P. J. Wiseman and J. B. Goodenough, Mater. Res. Bull., 15, 783 (1980). 7. M. Thackeray, W. I. F. David, P. Bruce, and J. B. Goodenough, Mater. Res. Bull., 18, 461 (1983). 8. J. R. Dahn, U. von Sacken, M. W Juzkow and H. Al-Janaby, J.

Electrochem. Soc., 138, 2207 (1991). 9. T. Ohzuku, A. Ueda and M. Kouguchi, J. Electrochem. Soc., 142, 4033 (1995). 10. N. Yabuuchi and T. Ohzuku, J. Power Sources, 119, 171 (2003). 11. G. Amatucci and J.-M. Tarascon, J. Electrochem. Soc., 149, K31 (2002). 12. J.-M. Tarascon and D. Guyomard, Solid State Ionics, 69, 293 (1994). 13. R. Fong, U. von Sacken, and J. R. Dahn, J. Electrochem. Soc., 137, 2009 (1990). 14. E. Peled, J. Electrochem. Soc. 126, 2047 (1979). 15. J.-M. Tarascon, A. Gozdz, C. Schmutz, F. Shokoohi, and P. Warren, Solid State Ionics, 86, 49 (1996). 16. A. K. Padhi, K. S. Nanjundaswamy, C. Masquelier, S. Okada, and J. B. Goodenough, J. Electrochem. Soc. 144, 1609 (1997). 17. N. Ravet, J. B. Goodenough, S. Besner, M. Simoneau, P. Hovington, and M. Armand, Abstract #127, 196th ECS Meeting, Honolulu, HI, Oct. 17-22 (1999) 18. A. N. Dey, J. Electrochem. Soc., 118, 1547 (1971). 19. H. Wu and Y. Cui, Nano Today, 7, 414 (2012). 20. P. Poizot, S. Laruelle, S. Grugeon, L. Dupont, and J.-M. Tarascon, Nature, 407, 496 (2000). 21. D. Larcher and J.-M. Tarascon, Nat. Chem., 7, 19 (2014). 22. J.-M.Tarascon, N. Recham, M. Armand, J-N. Chotard, P. Barpanda, W. Walker, and L. Dupont, Chem. Mater., 22, 724 (2010). 23. P. Poizot and F. Dolhem, Energ. Environ. Sci., 4, 2003 (2011). 24. G. G. Amatucci, J.-M. Tarascon, and L. C. Klein, J. Electrochem. Soc., 143, 1114 (1996). 25. J.-M. Tarascon, G. Vaughan, Y. Chabre, L. Seguin, M. Anne, P. Strobel, and G. Amatucci, J. Solid State Chem., 147, 410 (1999). 26. J. Rouxel, Chem.-Eur. J., 2, 1053 (1996). 27. Z. Lu, L. Y. Beaulieu, R. A. Donaberger, C. L. Thomas, and J. R. Dahn, J. Electrochem. Soc., 149, A778 (2002). 28. M. M. Thackeray, C. S. Johnson, J. T. Vaughey, N. Li, and S. A. Hackney, J. Mater. Chem., 15, 2257 (2005). 29. M. Sathiya, G. Rousse, K. Ramesha, C. P. Laisa, H. Vezin, M. T. Sougrati, M.-L. Doublet, D. Foix, D. Gonbeau, W. Walker, A. S. Prakash, M. Ben Hassine, L. Dupont, and J.-M. Tarascon, Nat. Mater., 12, 827 (2013). 30. E. McCalla, A. M. Abakumov, M. Saubanère, D. Foix, E. J. Berg, G. Rousse, M.-L. Doublet, D. Gonbeau, P. Novák, G. Van Tendeloo, R. Dominko, and J.-M. Tarascon, Science, 350, 1516 (2015). 31. Z. Zhang, US Patent N° 6432586.

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Lithium and Lithium-Ion Batteries: Challenges and Prospects by Stefano Passerini and Bruno Scrosati

espite the many recurrent international meetings to set worldwide agreements for CO2 emission reduction targets, global temperature is constantly increasing, this in turn is originating a serious concern on the fate of our planet. Obviously, a larger utilization of renewable energy source plants (REPs) and a wider road distribution of noemission, full electric vehicles (EVs) are goals to be urgently met. However, due to their sporadic nature, solar and wind sources require a suitable system to storage and return energy on demand, and the EVs require an efficient source to power the electric engine. In virtue of their high-energy characteristics, lithium-ion batteries (LIBs) appear as ideal candidates for fulfilling both requests. However, the present LIB technology, based on the graphite-lithium cobalt oxide intercalation chemistry,1 is not yet adequate since it is still lacking in terms of energy density and, especially, cost.2 Therefore, new, advanced LIB systems are needed and this explains the intensive R&D programs in progress in various academic and industrial laboratories worldwide.3 Indeed, the number of papers published in the field of LIBs have been increasing tremendously in recent years, with contributions mainly from Asia, but also from Europe and the U.S., see Fig. 1.

LIB Electrodes: Anodes The most common anode for LIBs is graphite (Fig. 2). Although still largely used for batteries addressed to the electronic market, and in some cases also for the EV one, the low specific capacity (∼370 mAhg-1) reduces its chances to be selected as the anode of choice for the development of advanced LIBs. A popular material proposed as anode in replacement of graphite is lithium titanium oxide, Li4Ti5O12 (LTO). Although benefitting by a very high structural stability upon operation (resulting in almost zero volume change), this material has found few practical applications due to the limited specific capacity (∼175 mAhg-1) and high voltage (∼1.5 V vs Li), both affecting the battery overall energy density.1,2 Certainly, the most appealing materials as LIB advanced anodes are lithium-metal, Li-M (M = Sn, Si, …) alloys which assure a specific capacity much higher than that of graphite both on gravimetric and volumetric bases (see Fig. 3), as well as a relatively low de-lithiation voltage (∼0.4 V vs Li). However, the lithium alloying process is accompanied by an unacceptable volume expansion (exceeding 250 % in the case of Si) which induces severe strains, leading to fracture and pulverization of the electrode and hence, to a rapid end of its cycling life (see Fig. 4). Another class of promising anodes are the socalled “conversion electrodes,” formed by nanosized metal oxides, MO (M = Co, Fe, Cu, Mn, Ni, …). Figure 5 shows the electrochemical process of, for example, cobalt oxide (CoO). The interest in these conversion materials relies on their specific capacity value which in theory is much higher than that offered by the insertion counterparts. However, a series of issues, including limited cycling stability and poor charge-discharge energy efficiency, have so far limited the practical exploitation of these anodes.

LIB Electrodes: Cathodes Research on LIB cathodes has been very active with the development of various materials to be proposed as an alternative to the common, high cost and slightly toxic lithium cobalt oxide, LiCoO2 (LCO), including lithium iron phosphate (LFP), lithium nickel manganese cobalt oxide, LiNi0.32Mn0.33Co0.33O2 (NMC), lithium manganese oxide, LiMn2O4 (LMO) and lithium nickel cobalt aluminium oxide, LiNi0.8Co0.15Al0.05O2 (NCA). Among them, a very popular material is LFP, due to its structural stability which is much higher than that of LCO, thereby preventing oxygen release upon overcharge and hence, assuring safer LIB operation. However, LFP cycles at 3.5 V vs Li and this considerably reduces its practical value. More promising in this respect is lithium nickel manganese oxide LiNi0.5Mn1.5O4 (LNMO) which operates at much higher voltages to the point that its combination with a graphite anode may in principle give a LIB of about 4.5 V with a specific capacity of the order of 140 mAh g-1, leading to a very high theoretical energy density of 630 Wh kg-1. The charge process of this material, however, requires electrolytes withstanding 5 V vs Li that are not yet available, at least at the low cost required for commercial cells.

LIB Electrolytes: Liquids and Solids Presently, solutions of a lithium salt (mostly LiPF6) in organic carbonate mixed solvents (e.g., ethylene carbonate-dimethyl carbonate EC:DMC) are the most commonly used LIB electrolytes. However, serious safety concerns associated with their flammability exist. Indeed, several accidents have occurred with LIBs, which have caught fire either in storage or during operation. The pressing need to address this issue has promoted intensive worldwide research of alternative, more stable materials. The most promising are ionic liquids, i.e., room temperature molten salts. Due to their high thermal stability and low volatility (thus low flammability), combined with a good ionic conductivity, they are presently viewed as the electrolyte (continued on next page)

Fig. 1. Time-evolution of publications on lithium-ion batteries and breakdown by involved countries (source: Scopus). The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Passerini and Scrosati

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media that can consistently enhance battery safety.5,6 Other choices are polymer, e.g., mixture of a lithium salt and poly(ethylene oxide) PEO or crystalline (still under development) solid membranes. Many excellent reviews reporting the proprieties of these advanced electrolytes are available in the literature,5-8 hence they will not further discussed here.

LIB: Full Battery Development Rather scarcer is the literature demonstrating that the new anode, cathode and electrolyte materials discussed in the previous sessions can be successfully combined to obtain a practically valid full battery. The reasons for this are various. A major reason is the difficulty of balancing electrodes having non-matching specific capacity values. For instance, great attention is presently devoted to silicon as anode alternative to graphite.9 However, proper Si electrodes may operate with a capacity about one order of magnitude higher than that of conventional LIB cathodes. In addition, the anode-to-cathode cell balance is seriously compromised by the high irreversible capacity experienced by the silicon anode in its initial cycling response, as well as by the already mentioned large volume variations occurring during the electrochemical charge-discharge process (see Fig. 4). Both these aspects greatly influence the overall cell performance. The initial irreversible capacity issue may be partially addressed by a pre-lithiation

Fig. 2. Scheme of graphite structure. The electrochemical process involves the intercalation-de-intercalation of Li+ ions in and out the graphene layers with a 2D mechanism.

procedure, which however is difficult in practical applications. The volume variation with the associated irreversible strain in the electrode bulk requires one to move to special electrode morphologies, such as composites formed by the dispersion of nano-sized silicon particles in a carbon matrix.10 Unfortunately, these nanocomposites are affected by a low tap density and a large surface area, the former depressing the volumetric specific density (Wh l-1) of the battery and the latter increasing the degree of electrolyte decomposition. Consistent attention is presently devoted to the so-called “beyond lithium-ion batteries,” including lithium-air, lithium-sulfur, sodiumion and magnesium.11 However, due to the many remaining issues, the development of effective full cells is in these cases even more complicated than in that of conventional LIBs. For instance, the limiting factors in lithium-air batteries that still hinder their practical development, are the low kinetics and the limited stability of the carbon-oxygen electrode, as well as of the reactivity of the lithium metal anode.12,13 A similar issue, with the addition of the so-called “shuttle effect,” i.e., the dissolution of the polysulphides from the cathode and their migration to the anode with resulting cell failure, is seriously compromising the future of the lithium-sulphur battery.14 The fear of a rapid depletion of the world reserves of lithium, although not yet being a sure fact, has motivated an increasing interest in sodium-ion batteries, NIBs.14 In this case the development of full cells is prevented by the lack of suitable electrode materials. For instance, graphite, namely the common LIB anode, cannot be used for NIBs since the large-size Na+ ions cannot be inserted in between the graphite layers without inducing irreversible exfoliation.15 Although a few promising cathode materials have been reported, the practical development of NIBs remains a goal to be met. Finally, the main problem with magnesium batteries is in the unsatisfactory performance of related electrolyte and cathode materials.16 Triggered by the latest investments in Europe and Asia, large research efforts are presently devoted to graphene, namely a carbon monolayer packed into a two-dimensional (2D) honeycomb lattice.17 Indeed, this intriguing material is of consistent basic interest for LIBs, since it is in principle capable of operating both as anode and cathode.18 On the other hand the practical use of graphene as a LIB electrode is hindered by many issues that render its immediate use for the development of a full cell system quite improbable, which the exception of few recently reported promising cases.19,20 Recently, considerable attention has been raised by the report of a rechargeable aluminum-ion battery, AIB.21 Although claimed to be of practical importance in terms of rate capability and cycle life, it is unlikely, due to its low energy density, that this battery can be of relevance for REPs and EVs. The latest trend in the field is the revitalization of metallic lithium as an advanced anode material for the development of lithium batteries (LBs), a target only possible by the use of an electrolyte medium capable of preventing dendrite growth with the associated serious safety hazard, the most appropriate being a solid electrolyte. Unfortunately, the majority of the electrolytes of this type suffer due to very poor ionic conductivity at room temperature;22 hence, the solid-state LBs are poor performers at RT as they are affected by a high ohmic polarization. In conclusion, the road for the development of efficient LIBs and LBs appears to be still paved by a series of practical difficulties. However, in view of the continuously increasing worldwide activity in the field, we may reasonably foresee a positive change of course in the near future. © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F09163if.

Fig. 3. Gravimetric and volumetric specific capacity of Li-M (M = Sn and Si) alloys in comparison with those of graphite (C). 86

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About the Authors Stefano Passerini is Professor at the Karlsruhe Institute of Technology, Helmholtz Institute Ulm (Ulm, Germany) since January 1, 2014. Formerly Professor at the University of Muenster (Germany), he co-founded the MEET battery research centre at the University of Muenster (Germany). His research activities are focused on electrochemical energy storage in batteries and supercapacitors. Co-author of more than 400 scientific papers (H-Index of 56), a few book chapters and several international patents, he has been awarded in 2012 the Research Award of The Electrochemical Society Battery Division. Since 2015 he is serving as Editor-in-Chief of the Journal of Power Sources. He may be reached at stefano.passerini@kit.edu. http://orcid.org/0000-0002-6606-5304 Bruno Scrosati, formerly Full Professor at the University of Rome La Sapienza, is presently affiliated with Helmholtz Institute Ulm, Germany, and the Italian Institute of Technology in Genova, Italy. He has been Visiting Professor at the University of Minnesota and at University of Pennsylvania, in the U.S., and Hanyang University, Seoul, Korea. He received the title of Doctor in Science “honoris causa,” from the University of St. Andrews in Scotland, from the Chalmers University in Sweden, and from the University of Ulm in Germany. He was awarded the Research Award from the Battery Division of The Electrochemical Society, the XVI Edition of the Italgas Prize, and the Vittorio de Nora award of The Electrochemical Society. He has been President of the Italian Chemical Society and of The Electrochemical Society. He was European Editor of the Journal of Power Sources and is presently member of the editorial boards of various international journals. Professor Scrosati is author of more than 600 scientific publications; various books and chapters in books and 18 patents. His H-factor is 76. He may be reached at bruno.scrosati@ gmail.com. http://orcid.org/0000-0001-7382-1465

References 1. B. Scrosati and J. Garche, J. Power Sources, 195, 2419 (2010). 2. B. Scrosati, J. Hassoun, and Y.-K. Sun, Energ. Environ. Sci., 4, 3287 (2011).  3. M. Armand and J. M. Tarascon, Nature, 451, 652 (2008). 4. H. D. Yoo, E. Marchevich, G. Salitra, D. Sharon, and D. Aurbach, Mater. Today, 17, 110 (2014). 5. I. Osada, H. de Vries, B. Scrosati, and S. Passerini, Angew. Chem. Int. Ed., 55, 500 (2016). 6. G. E. Gebrekidan, M. Armand, B. Scrosati, and S. Passerini, Angew. Chem. Int. Ed., 53, 13342 (2014). 7. J. Hassoun and B. Scrosati, J. Electrochem. Soc., 162, A2582 (2015). 8. M. Armand, F. Endres, D. R. Macfarlane, H. Ohno, and B. Scrosati, Nat. Mater., 8, 621 (2009).

9. J. Szczech, and S. Jin, Energ. Environ. Sci., 4, 56 (2011). 10. A. S. Arico, P. Bruce, B. Scrosati, J-M. Tarascon, and W. Van Schalkwijk, Nat. Mater., 4, 366 (2005). 11. J.-W. Choi and D. Aurbach, Nat. Rev. Mater., DOI 10.1038/ natrevmats.2016.13. 12. J. Hassoun, F. Croce, M. Armand, and B. Scrosati, Angew. Chem. Int. Ed., 50, 2999 (2011). 13. H.-G. Jung, J. Hassoun, J.-B. Park, Y.-K. Sun, and B. Scrosati, Nat. Chem., 4, 579 (2012). 14. N. Yabuuchi, K. Kubota, M. Dahbi, and S. Komaba, Chem. Rev., 114, 11636 (2014). 15. S. Y. Hong, Y. Kim, Y. Park, A. Choi, N.-S. Choi, and K. T. Lee, Energ. Environ. Sci., 6, 2067 (2013). 16. H. D. Yoo, I. Shterenberg, Y. Gofer, G. Gershinky, N. Pour, and D. Aurbach, Energ. Environ. Sci., 6, 2265 (2013). 17. K. S. N. Geim, Nat. Mater., 6, 183 (2007). 18. R. Raccichini, A. Varzi, S. Passerini, and B. Scrosati, Nat. Mater., 14, 271 (2015). 19. O. Vargas, A. Caballero, J. Morales, G. A. Elia, B. Scrosati, and J. Hassoun, Phys. Chem. Chem. Phys., 15, 20444 (2013). 20. J. Hassoun, F. Bonaccorso, M. Agostini, M. Angelucci, M. G. Betti, R. Cingolani, M. Gemmi, C. Mariani, S. Panero, V. Pellegrini, and B. Scrosati, Nano Lett., 14, 4901 (2014). 21. M.-C. Lin, M. Gong, B. Lu, Y. Wu, D-Y. Wang, M. Guan, M. Angell, C. Chen, J. Yang, B-J. Hwang, and H. Dai, Nature, DOI:10.1038/nature 14340. 22. P. Knauth, Solid State Ionics, 180, 911 (2013).

Fig. 4. The lithium alloying in metals such as Sn and, particularly, Si results in a very large volume expansion which rapidly leads to morphological disruptions and hence, to the end of the electrode’s life.

Fig. 5. Scheme of the electrochemical process of a typical example of conversion electrodes, i.e., cobalt oxide, CoO.

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ECS Division Awards The Corrosion Division Herbert H. Uhlig Award was established in 1972 to recognize excellence in corrosion research and outstanding technical contributions to the field of corrosion science and technology. The Award will consist of $1,500 and an appropriately worded scroll and the recipient may receive (if required) financial assistance from the Corrosion Division toward travel expenses to the Society meeting at which the award is presented. Materials are due by December 15, 2016. The High Temperature Materials Division J. Bruce Wagner, Jr. Award was established in 1998 to recognize a young Society member who has demonstrated exceptional promise for a successful career in science and/or technology in the field of high temperature materials. The award consists of an appropriately worded scroll and the sum of $1,000. The recipient may receive (if required) complimentary registration and up to $1,000 in financial assistance toward travel expenses to the Society meeting at which the award is made. Materials are due by January 1, 2017.

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AWARDS NE W AWA MEMBERS PROGRAM RDS The Battery Division Research Award was established in 1958 to recognize excellence in battery and fuel cell research, and encourage publication in ECS outlets. The award recognizes outstanding contributions to the science of primary and secondary cells, batteries and fuel cells. The award consists of a certificate and the sum of $2,000. Materials are due by March 15, 2017. The Battery Division Technology Award was established in 1993 to encourage the development of battery and fuel cell technology, and to recognize significant achievements in this area. The award is given to those individuals who have made outstanding contributions to the technology of primary and secondary cells, batteries, and/or fuel cells. The award consists of a certificate and the sum of $2,000. Materials are due by March 15, 2017. The Battery Division Postdoctoral Associate Research Award Sponsored by MTI Corporation and the Jiang Family Foundation was established in 2016 to encourage excellence among postdoctoral researchers in battery and fuel cell research. Candidates should show exceptional promise that includes leadership, advocacy, outreach or teaching, in addition to excellence in scientific research during their postdoctoral assignment. Two awards are presented annually consisting of a certificate, the sum of $2,000, and complimentary meeting registration for each winner. Materials are due by March 15, 2017. The Electrodeposition Division Research Award recognizes outstanding research contributions to the field of electrodeposition and encourages the publication of high quality papers in this field in the Journal of The Electrochemical Society. The award shall be based on recent outstanding achievement in, or contribution to, the field of electrodeposition and will be given to an author or co-author of a paper that must have appeared in the Journal or another ECS publication. The award consists of a certificate and the sum of $2,000. Materials are due by April 1, 2017. The Electrodeposition Division Early Career Investigator Award was established in 2015 to recognize an outstanding early career researcher in the field of electrochemical deposition science and technology. Early recognition of highly qualified scientists is intended to enhance his/her stature and encourage especially promising researchers to remain active in the field. The award consists of a scroll, a $1,500 prize and complimentary meeting registration. Materials are due by April 1, 2017.

Section Awards The Canada Section W. Lash Miller Award was established in 1967 to recognize publications and/or excellence in the field of electrochemical science and technology and/or solid state science and technology. The recipient will be a Canada resident who has obtained his/her last advanced education degree no more than 15 years before the year of the award. The award consists of a $1,500 CAD prize. Materials are due by December 31, 2016.

Student Awards The Corrosion Division Morris Cohen Graduate Student Award was established in 1991 to recognize and reward outstanding graduate research in the field of corrosion science and/or engineering. The award, for outstanding Masters or PhD work, is open to graduate students who have successfully completed all the requirements for their degrees as testified to by the student’s advisor, within a period of two years prior to the nomination submission deadline. The award consists of a certificate and the sum of $1,000. Materials are due by December 15, 2016. The Battery Division Student Research Award recognizes promising young engineers and scientists in the field of electrochemical power sources. The award is intended to encourage the recipients to initiate or continue careers in the field. Eligible candidates must be enrolled in a college or university at the time of the nomination deadline. The award consists of a certificate and the sum of $1,000. Materials are due by March 15, 2017.

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The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

NE W MEMBERS ECS is proud to announce the following new members for April, May, and June 2016.

Members

Azrilawani Ahmad, Kuala, Terengganu Malaysia Jong Hyun Ahn, Seoul, South Korea Masanori Asano, Nishinomiya, Hyogo, Japan Rohini Bala Chandran, Berkeley, CA, USA Mickael Boinet, Northborough, MA, USA Doron Burshtain, Herzliya Center, Israel Moon Jong Choi, Daegu, South Korea Mei-Yin Chou, Taipei, Taiwan ChihWei Chu, Taipei, Taiwan Francesco Ciucci, Kowloon, Hong Kong Timothy Cook, Buffalo, NY, USA Kris Dahl, Pittsburgh, PA, USA Daniel Dobkin, Sunnyvale, CA, USA John Druce, Fukuoka, Japan Kailin Du, San Jose, CA, USA Allan East, Regina, SK, Canada Elizabeth Endler, Houston, TX, USA Kieran Fahy, London, UK Firooz Faili, Los Gatos, CA, USA Begona Ferrari Fernandez, Madrid, Spain Alexander Freigang, San Diego, CA, USA Marina Freitag, St.-Sulpice, VD, Switzerland Tsuyohiko Fujigaya, Fukuoka, Japan Randal Goffe, Everett, WA, USA Maxim Gongalsky, Moscow, Russia Alon Gorodetsky, Irvine, CA, USA Alexis Grimaud, Paris, France Axel Guyon, Palo Alto, CA, USA Masato Hamano, Gardena, CA, USA Meenakshi Hardi, Glendale, WI, USA Shinichi Hashimoto, Sendai, Miyagi, Japan Steve He, Palo Alto, CA, USA Amanda Hefer, Roodepoort, South Africa Ming-Che Ho, Zhongli Taoyuan, Taiwan Chien-Yu Huang, Taipei, Taiwan Yu Huang, Los Angeles, CA, USA Irina Ionica, Grenoble, Isere, France Irene Irene, Bristol, UK Hannah Israel, Palo Alto, CA, USA Debdeep Jena, Ithaca, NY, USA Xinfang Jin, Columbia, SC, USA R. G. Waruna Jinadasa, Oxford, OH, USA A. T. Charlie Johnson, Philadelphia, PA, USA Ishak Karakaya, Ankara, Turkey Hideaki Kasai, Akashi, Hyogo, Japan Hong Jin Kim, Malta, NY, USA Young-Bae Kim, Gwangju, South Korea Brian Koch, Berkley, MI, USA Elizabeth Kocs, Oak Park, IL, USA Frank Kramer, New Haven, CT, USA Bijandra Kumar, Louisville, KY, USA Donghwa Lee, Gwangju, South Korea Jennifer Lee, Cambridge, UK Woon Young Lee, Incheon, South Korea Yong Min Lee, Daejeon, South Korea Yujin Lee, Incheon, South Korea Kexun Li, Tianjin, China Yan Li, Beijing, China Zhilin Li, Beijing, China

Yi-Rung Lin, Pasadena, CA, USA Matthew Lindell, Woodbury, MN, USA Christopher Macey, Columbia, MD, USA Mohammad Ali Mahmoudzadeh, Vancouver, BC, Canada Marina Mariano, New Haven, CT, USA Andrej Matsnev, North Augusta, SC, USA James McClennan, Bedworth, Warwickshire, UK Ulises Medina, National City, CA, USA Matthew Millard, Cambridge, MA, USA Na Ni, London, UK Greg Nigon, Portland, OR, USA Ricardo Nogueira, Abu Dhabi, U.A.E. Vladimir Oleshko, Gaithersburg, MD, USA Ozlem Ozcan, Berlin, Germany Jeung Hun Park, Yorktown Heights, NY, USA Erika Parra, Malden, MA, USA Raghuveer Patlolla, Guilderland, NY, USA Oliver Pecher, Cambridge, Cambridgeshire, UK Zhenmeng Peng, Akron, OH, USA Nestor Perea Lopez, University Park, PA, USA Sung Gyu Pyo, Heukseok-dong Dongjakgu, South Korea Cedric Reboul-Salze, Boucherville, QC, Canada Gerhard Rizzo, Buchs, SG, Switzerland Richard Robinson, Ithaca, NY, USA Jose Rojo, Madrid, Spain Maryam Salari, Malden, MA, USA Antonio Sanchez-Herencia, Madrid, MAD, Spain Eaden Saw, Sunnyvale, CA, USA Manning Schmidt, Portland, OR, USA Baskar Selvaraj, New Taipei City Zhonghe District, Taiwan Fatih Sen, Lisle, IL, USA Dong-Hwa Seo, Seoul, South Korea Minglian Shi, Irvine, CA, USA Masahiro Shimizu, Nagano, Japan Heungjoo Shin, Ulsan, South Korea Hyeon Jin Shin, Gyunggi-do, South Korea Clinton Smith, Palo Alto, CA, USA Pradeep Sow, Vancouver, BC, Canada Anna Stefanopoulou, Ann Arbor, MI, USA Peter Stein, Darmstadt, HE, Germany Richard Stocker, Hinckley, Leicestershire, UK Joseph Sullivan, Enfield, NH, USA Liumin Suo, Cambridge, MA, USA Arek Suszko, San Diego, CA, USA Lobat Tayebi, Milwaukee, WI, USA Helena Tellez, Fukuoka, Fukuoka, Japan Kevin Tenny, Leawood, KS, USA Takashi Teranishi, Okayama, Okayama, Japan Dave Thomas, Newport, UK Vladimir Tripkovic, København, Denmark Kohsuke Tsuchiya, Kakamigahara, Gifu, Japan Hiroshi Uchida, Tokyo Kanto, Japan

Bryan Unruh, Fort Worth, TX, USA Peter Ventzek, Austin, TX, USA Chao Wang, Baltimore, MD, USA Chiu-Yen Wang, Taipei, Taiwan Han Wang, Los Angeles, CA, USA Shaopeng Wang, Tempe, AZ, USA Gang Wu, Buffalo, NY, USA Huili Grace Xing, Ithaca, NY, USA Heng Yang, Pasadena, CA, USA Rusen Yang, Plymouth, MN, USA Yongan Yang, Lakewood, CO, USA Chih Han Yen, Taichung, Taiwan Tanghong Yi, San Diego, CA, USA Hyun Deog Yoo, Chicago, IL, USA Akira Yoshino, Clifton Park, NY, USA Jianqing Zhao, Suzhou, Jiangsu, China Hongli Zhu, Boston, MA, USA

Student Members

Prashant Acharya, Fayetteville, AR, USA Sarah Aderyani, Houston, TX, USA Siti Norbaya Ahmad Nor, Cambridge, UK Kamyar Ahmadi, Houston, TX, USA Bengisu Akpinar, Ankara Cankaya, Turkey Kamrul Alam, Houston, TX, USA Sarmad Alhasan, Orlando, FL, USA Mohammad Al-Mamun, Blacksburg, VA, USA Fuma Ando, Yokohama, Kanagawa, Japan Takahito Aoyama, Aoba-ku Sendai, Miyagi, Japan Wentika Asih, Yokohama, Kanagawa, Japan Dowon Bae, Kgs. Lyngby, Denmark Seon Yeong Bae, Gyeongsangnam-do, South Korea Jinseok Baek, Kyoto, Kyoto, Japan Hanan Baker, New York, NY, USA Stefanie Baker, Pittsburgh, PA, USA Manmadharao Banki, Houston, TX, USA Mara Beltran Gastelum, Tijuana, Baja California, Mexico Angelica Benavidez, Albuquerque, NM, USA Ellen Benn, Baltimore, MD, USA Merit Bodner, Graz, ST, Austria Steven Brown, Cambridge, MA, USA Michael Brunell, Kenilworth, Warwickshire, UK Mark Buckwell, London, London, UK Adam Burak, Midvale, UT, USA Wai Leong Mickey Chan, Hong Kong, Hong Kong Qiaowan Chang, Hong Kong, Hong Kong Nikhil Chaudhari, Houston, TX, USA Neil Chavan, Fairborn, OH, USA Jun-Yao Chen, Taoyuan, Taiwan Zairan Cheng, Osaka, Japan Seshuteja Chepyala, Tallahassee, FL, USA Laxmi Kishore Sagar Chiluka, Ghent, Belgium Isabel Chino, Indio, CA, USA Samuel Chiovoloni, New Britain, CT, USA Yevedzo Chipangura, Duluth, MN, USA Ming-Hui Chiu, Thuwal, Saudi Arabia

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

NE W MEMBERS Yong-Wook Choi, Bochum, NW, Germany Habin Chung, Pohang GyeongBuk, South Korea Brittanie Clendenin, Antelope, CA, USA Kevin Cole, Toronto, ON, Canada Nathanial Cooper, Davis, CA, USA Erin Creel, Albany, CA, USA Rodrigo Da Silva, Ribeirao Preto, Sao Paulo, Brazil Pallavi Daggumati, Emeryville, CA, USA Sanjana Das, Las Vegas, NV, USA Pedro Dick, Porto Alegre, Rio Grande do Sul, Brazil Ashutosh Divekar, Golden, CO, USA Emily Do, Santa Ana, CA, USA Thalía Domínguez Bucio, Southampton, Hampshire, UK Bowen Dong, Cleveland, OH, USA Hui Dong, Houston, TX, USA Mahrokh Dorri, Quebec, QC, Canada Letian Dou, El Cerrito, CA, USA Nan-Qi Duan, Wuhan, Hubei, China Shanmugha Sundaram Duraisamy, Belfast Jordanstown, UK Ghada Dushaq, Masdar City Abu Dhabi, U.A.E. Mohammed Effat, Sai Kung Hong Kong, Hong Kong Erica Eggleton, Bozeman, MT, USA Saina Emrani, Orange, CA, USA Yuyi Feng, Konstanz, BW, Germany Shelby Foster, Fayetteville, AR, USA Mallory Fuhst, Ann Arbor, MI, USA Jacinthe Gamon, Paris Il le de France, France Shuang Gao, Lexington, KY, USA Karelid Garcia Tapia, Delegacion Cuauhtemoc, Distrito Federal, Mexico Grace Gaskin, Cleveland Heights, OH, USA William Gent, Redwood City, CA, USA Michael George, Toronto, ON, Canada Michael Gervasoni, Los Angeles, CA, USA Brian Gerwe, Seattle, WA, USA Habte Ghebremichael, Steelton, PA, USA Saman Gheytani, Houston, TX, USA Greg Ghosn, Upland, CA, USA Manuel Gliech, Berlin, Germany Heiko Gräbe, Renningen, BW, Germany Adora Graham, Layton, UT, USA Jungmin Ha, La Jolla, CA, USA Shima Haghighat, Los Angeles, CA, USA Yasmine Hajar, Ottawa, ON, Canada Qi Han, Cleveland, OH, USA Andre Hansford, Auburn, AL, USA Fang Hao, Houston, TX, USA Qian He, San Diego, CA, USA Suhith Hemanth, Kgs Lyngby, Denmark Alexandra Henriques, Miami, FL, USA Mariana Hildebrand, London, UK David Horvath, Salt Lake City, UT, USA Jiazhi Hu, Lexington, KY, USA Dion Hubble, Seattle, WA, USA Jingshu Hui, Urbana, IL, USA Evan Jahrman, Federal Way, WA, USA Ahmed Jalal, Miami, FL, USA Darshika Jauhari, Cleveland Heights, OH, USA

Lisa Je, Brooklyn, NY, USA Erin Jenrette, Virginia Beach, VA, USA Kim Jensen, Kgs. Lyngby, Denmark Qing Ji, Houston, TX, USA Yan Jing, Houston, TX, USA Malin Johansson, Uppsala, Sweden Scott Johnson, Ann Arbor, MI, USA SungHoon Jung, Seongnam-si Gyeonggido, South Korea Yara Kadria-Vili, Houston, TX, USA Haitham Kalil, Cleveland, OH, USA Wei-Chih Kao, Taipei City, Taiwan Alireza Karimaghaloo, Merced, CA, USA Pawanjit Kaur, Houston, TX, USA Xinyou Ke, Shaker Heights, OH, USA Khawlah Kharashi, Ruston, LA, USA Chang Sub Kim, Cambridge, MA, USA Jeonghan Kim, Pohang GyeongBuk, South Korea Kihwan Kim, Cleveland, OH, USA Charlotte Kirk, Stanford, CA, USA Vaclav Knap, Aalborg North Jutland, Denmark Daichi Koretomo, KOCHI, Japan Simon Korte, Steinfurt, NW, Germany Jeffrey Kowalski, Cambridge, MA, USA Pushpendra Kumar, Thuwal Mekka, Saudi Arabia Siddhartha Kumar, Oxford, OH, USA Arwa Kutbee, Jeddah, Saudi Arabia Jesse Kysar, Battle Ground, WA, USA Nouha Labyedh, Heverlee Flemish Brabant, Belgium Matthew Lacroix, Fort Collins, CO, USA Vikram Lakhanpal, Olathe, KS, USA Chiu Lam, Goleta, CA, USA Long Le, Golden, CO, USA Maxime Leclerc, Notre-Dame-de-Ham, QC, Canada Kuan-yi Lee, TX, USA Libin Lei, Columbia, SC, USA Chao Li, Los Angeles, CA, USA Li Li, Cleveland, OH, USA Ling Li, Chicago, IL, USA Wanlu Li, New York, NY, USA Yifei Li, Ames, IA, USA Chiying Liang, Storrs, CT, USA Ching-Wei Lin, Houston, TX, USA Chun-Cheng Lin, Changhua, Taiwan, Taiwan Ye Lin, Columbia, SC, USA Simon Lindberg, Goteborg, Sweden Ilya Lisenker, Boulder, CO, USA Giuliana Litrico, Sherbrooke, QC, Canada Chenjuan Liu, Uppsala Uppland, Sweden Jin Liu, Worcester, MA, USA Selina(Peng) Liu, Montreal, QC, Canada Ya-han Liu, Tainan, Taiwan, Taiwan Yang Liu, Chicago, IL, USA Ryan Longchamps, Huntsville, AL, USA Ciana Lopez, Albuquerque, NM, USA Monica Lopez de Victoria, San Juan, PR, USA Ernesto Lopez Lopez, Toluca, Estado de México, Mexico Edward Loya, Lexington, KY, USA Ziheng Lu, Kowloon Hong Kong, Hong Kong

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Jing Luo, Taipei, Taiwan Abniel Machin, San Lorenzo, PR, USA Yusaku Magari, Kami Kochi, Japan Tarso Martins, Porto Alegre, Rio Grande do Sul, Brazil Victoria Mattick, Irmo, SC, USA Frank McGrogan, Cambridge, MA, USA Kim McKelvey, Salt Lake City, UT, USA Kevin McKenzie, Washington, DC, USA Ryan McNeilly, Westlake, OH, USA Connor Medlang, Export, PA, USA Laura Merrill, South Bend, IN, USA Jeremy Miller, Dundas, ON, Canada Kelly Miller, Erie, PA, USA Liu Min, BeiJing, PR, China Gioele Mirabelli, Cork, Ireland Ishwar Mishra, Houston, TX, USA Adrian Mora, Vancouver, BC, Canada Samantha Morelly, Philadelphia, PA, USA Albert Mufundirwa, Kyushu, Fukuoka, Japan Daniel Muirhead, Toronto, ON, Canada Shrijit Mukherjee, Gainesville, FL, USA Masoumeh Naghizadeh, London, ON, Canada Kyle Nagy, Ann Arbor, MI, USA Tejas Naik, Mumbai, MH, INDIA Mohammadreza Nazemi, Atlanta, GA, USA Farhang Nesvaderani, North Vancouver, Canada Ram Neupane, Houston, TX, USA Vinh Nguyen, Golden, CO, USA Jinesh Niroula, Stillwater, OK, USA Masashi Nishimoto, Sendai, Miyagi, Japan Geng Niu, Highland Park, IL, USA Shohei Ogawa, Pittsburgh, PA, USA Mehmet Ozdemir, Storrs, CT, USA Gioele Pagot, Padova, ITALY Varada Menon Palakkal, Baton Rouge, LA, USA Georgios Papacharalampos, Tempe, AZ, USA Pritesh Parikh, La Jolla, CA, USA Alagar Raj Paulraj, Stockholm, Sweden Lele Peng, Austin, TX, USA Alexandra Perebikovsky, Irvine, CA, USA Jhon Petafiel Castro, Porto Alegre RS, Brazil Elizabeth Peterson, Lincoln, NE, USA William Phillips, Carson City, NV, USA Jason Pickering, Grafton, OH, USA Julia Ponce, Guildford, Surrey, UK Fan Qin, Houston, TX, USA Jiaxu Qin, Seattle, WA, USA Shiyi Qin, Cleveland Heights, OH, USA Xueping Qin, Hong Kong, Hong Kong Yazmin Rivera Lugo, Ciudad de México, Distrito Federal, Mexico Lucas Robinson, West Lafayette, IN, USA Sandra Rodriguez Beltran, Garden Grove, CA, USA Yue Rong, Gainesville, FL, USA Mattia Saccoccio, Hong Kong, Hong Kong Ryota Saito, Ueda, Nagano, Japan Jennifer Satterwhite, Coventry, CT, USA Alexander Schenk, Graz, ST, Austria Martin Schneider, Leichhardt, New South Wales, Australia 91

NE W MEMBERS Madeline Sciullo, Gainesville, FL, USA Mahnazossadat Seyednourani, Lowell, MA, USA David Shahin, Springfield, VA, USA Jaewook Shin, San Diego, CA, USA Carolina Silva Carrillo, Ciudad de Mexico, Distrito Federal, Mexico Andrew Simonson, Salt Lake City, UT, USA Shivkant Singh, Houston, TX, USA Dhaivat Solanki, Houston, TX, USA Shaowei Song, Houston, TX, USA Dongmyung Suh, Athens, OH, USA Aiyue Tang, Beijing, China Jian-Fu Tang, Tainan City, Taiwan, Taiwan Daniel Taylor, Silver Spring, MD, USA Cole Tenold, Perry, IA, USA Alvaro Tesio, Ciudad Autonoma de Buenos Aires, Argentina Gerald Timuda, Yokohama, Kanagawa, Japan Bernhard Tjaden, London, London, UK Cuong Tran, Nomi, Ishikawa, Japan

Nam Tran, Minneapolis, MN, USA Zachary Traverso, Townsend, MA, USA Diana Trejo Martínez, San Joaquín, Qro, Mexico Daniel Trimarco, Kgs. Lyngby Copenhagen, Denmark Chi-Ting Tsai, Tainan City, Taiwan, Taiwan Pei-Ying Tsai, Taipei, Taiwan, Taiwan Shandirai Tunhuma, Pretoria Gauteng, South Africa Refik Uguz, Ankara, Turkey Renato Valente, Porto Alegre, Rio Grande do Sul, Brazil Hongqian Wang, Evanston, IL, USA Luyuan Paul Wang, Singapore, Singapore Tao Wang, Salt Lake City, UT, USA Robin White, Vancouver, BC, Canada Grant Williamson, Seattle, WA, USA Jazlynn Wisener, Fayetteville, AR, USA Mark Wolf, Chicago, IL, USA Erik Wu, La Jolla, CA, USA Yuyin Xi, Seattle, WA, USA Xing Xing, San Diego, CA, USA

Zelong Xing, Hong Kong, Hong Kong Xin Yang, Columbia, SC, USA Yuebin Yang, Kowloon, Hong Kong Yuze Yao, Hong Kong, Hong Kong Parisa Yasini, Philadelphia, PA, USA Elahe Yousefi, Tehran, IRAN Hung-Yi Yu, Taichung, Taiwan, Taiwan Mengying Yuan, Houston, TX, USA Nicole Yuede, Saint Charles, MO, USA Carolin Zachaeus, Berlin, Germany Jesus Zapata, Ciudad de México, Distrito Federal, Mexico Long Zhang, Lexington, KY, USA Lulu Zhang, Hong Kong, Hong Kong Tong Zhang, Muenster, NW, Germany Yige Zhao, Beijing, China Shanshan Zhou, Lexington, KY, USA Shangqian Zhu, Hong Kong, Hong Kong Xinhua Zhu, Brussels, Belgium Zhuan Zhu, Houston, TX, USA Shiqiang Zhuang, Harrison, NJ, USA Ying Zou, Juelich, NW, Germany

Benefits of ECS Student Membership Annual Student Membership Dues Are Only $30

w Open Access Article Credit Publish a paper in an ECS journal as open access and avoid the article processing charge w Student Grants and Awards Student awards and support for travel available from ECS Divisions w Student Poster Sessions Present papers and participate in student poster sessions at ECS meetings w ECS Member Article Pack 100 full-text downloads from the Journal of The Electrochemical Society (JES), ECS Electrochemistry Letters (EEL), ECS Journal of Solid State Science and Technology (JSS), ECS Solid State Letters (SSL), Electrochemical and Solid-State Letters (ESL), and ECS Transactions (ECST) w Interface Receive the quarterly members' magazine with topical issues, news, and events w Discounts on ECS Meetings Valuable discounts to attend ECS spring and fall meetings w Discounts on ECS Transactions, Monographs, and Proceedings Volumes ECS publications are a valuable resource for students

www.electrochem.org/student-center The Electrochemical Society 92

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t ST ech UDENT highligh NE WS ts

ECS 2016 Summer Fellowship Winners Each year ECS awards summer fellowships to assist students in continuing their graduate and postdoctoral work during the summer months in a field of interest to the Society. Congratulations to the following five summer fellowship recipients in 2016. The reports of the 2016 fellowship recipients will appear in the winter issue of Interface. Soo Kim is the recipient of the 2016 ECS Edward G. Weston Summer Fellowship. He is a PhD candidate of Materials Science Department at Northwestern University (advisor: Chris Wolverton), specializing in research and development of advanced battery cathode materials. He received his BSE in Chemical Engineering at the University of Michigan in Ann Arbor in 2008 (advisor: Philip Savage) and MS in Chemical Engineering at Carnegie Mellon University in 2009 (advisors: Lorenz Biegler and Myung S. Jhon). Before pursuing a doctorate degree in computational materials research, he worked in Samsung to develop lithium-ion battery cathode materials (Li4Ti5O12, LiFePO4, and LiNixCoyMnzO2) in industrial-scale (2010-2011); and as a staff scientist at Korea Institute of Science and Technology (KIST) with Byung-Won Cho and Kyung Yoon Chung (2011-2013) to focus on the complex structural ambiguities in Li2MnO3-based cathode materials. Soo published 15 papers and 8 patents on the work related to the rechargeable battery materials development in last 4 years. His present research interests include the design of new materials for batteries, fuel cells, thermoelectrics, and other alternative energy storage systems by combining both computation and experiments. Yelena Gorlin is the recipient of the 2016 ECS Colin Garfield Fink Postdoctoral Summer Fellowship. She is currently a postdoctoral scholar in Hubert Gasteiger’s laboratory at the Technical University of Munich, where she leads the synchrotron characterization sub-group of the laboratory. Yelena began her academic career at Massachusetts Institute of Technology (MIT), double majoring in Chemical Engineering and Biology and graduating with a Bachelor of Science in 2006. Subsequently, she received a PhD in Chemical Engineering from Stanford University in 2012. Her PhD thesis was conducted under the supervision of Thomas Jaramillo and focused on the development of manganese oxide based catalysts for oxygen electrocatalysis. After finishing her PhD, Yelena has completed several postdoctoral projects in the area of in situ/operando characterization of electrochemical processes using the synchrotron based X-ray absorption spectroscopy technique. Yelena has co-authored 18 peer-reviewed publications and has been a recipient of multiple awards including Outstanding Poster at Stanford Synchrotron Radiation Laboratory User Meeting (October 2012), Alexander von Humboldt Foundation Postdoctoral Fellowship (January 2014-April 2016), and ECS travel grants from Energy Technology (2010, 2015) as well as Battery (2016) Divisions and from Polymer Electrolyte Fuel Cell (PEFC) symposium organizers (2013). For her summer fellowship, she has proposed to advance the progress in the development of lithium-sulfur battery through cyclic voltammetry and rotating disc electrode studies of the battery’s discharge reactions.

Charuksha Walgama is the recipient of the 2016 ECS Joseph W. Richards Summer Fellowship. Charuksha obtained a BS in Chemistry from the University of Kelaniya, Sri Lanka. Immediately after graduation, he worked there as a Temporary Assistant Lecturer for one year. In fall 2012, he joined Oklahoma State University (OSU), where he began his doctoral research work in the field of Biological Electroanalytical Chemistry under the supervision of Sadagopan Krishnan. His thesis research focuses on studying catalytic properties of metalloproteins bound to various nanostructures modified electrode surfaces and developing a liver enzyme based cost-effective electrochemical technology for in vitro metabolic profiling and drug metabolism/inhibition assays. Findings from his research have been published in peer-reviewed journals and presented at numerous regional and national meetings. He received several other awards and fellowships including an ECS PAED travel award (2015), a Distinguished Graduate Fellowship Award (2015-2017 from OSU Graduate College), the Creativity Innovation and Entrepreneurship Scholar Award (2015 from OSU Spears School of Business), and the Dermer Scholarship award given for Outstanding Graduate Students (2016 from OSU Chemistry Department). In the future, Charuksha envisions himself to be an entrepreneurial researcher. Muhammad Boota is the recipient of the 2016 ECS F. M. Becket Summer Fellowship. He received his BS in Industrial Chemistry (2009) from GC University (Pakistan), and a MS in Chemistry (2011) from Uppsala University (Sweden) and University College London (United Kingdom). He joined a joint Erasmus Mundus MS program (2011–2013) in “Materials for Energy Storage and Conversion (MESC),” which he completed at Paul Sabatier University (France), Warsaw University of Technology (Poland), University of Picardie Jules Verne (France), and Drexel University (USA). He has been offered several prestigious fellowships including the Erasmus Mundus fellowship, the Marie Curie Fellowship, Graduate Research Fellowship, ECS Summer Fellowship and several other prestigious awards. Boota is currently a PhD candidate in Materials Science and Engineering at Drexel University working on redox-active composites or energy storage systems under the supervision of Yury Gogotsi. In addition to one patent, he has co-authored more than 13 publications in the reputed journals. Boota is the president of the Philadelphia ECS Student Chapter and is involved in various outreach activities at Drexel. In April 2016, he led the effort to organize “1st Philadelphia Electrochemical Society Symposium,” which attracted leading electrochemists and helped to initiate several new collaborations.

2016 Summer Fellowship Committee Vimal Chaitanya, Chair New Mexico State University Bryan Chin Auburn University

Peter Mascher McMaster University Bryan McCloskey Lawrence Berkeley National Laboratory

Kalpathy B. Sundaram University of Central Florida

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

t ST ech UDENT highligh NE WS ts Michael Metzger is the recipient of the 2016 ECS Herbert H. Uhlig Summer Fellowship. Michael received his diploma in Physics from the Technical University of Munich in 2012. During his studies he developed a strong passion for research in the field of energy conversion and storage. Currently, Michael is a PhD candidate in the group of Hubert Gasteiger at the Technical University of Munich where he is evaluating materials degradation mechanisms in lithium-ion batteries using On-line Electrochemical Mass Spectrometry (OEMS) and other electrochemical and spectroscopic techniques. In particular, Michael’s research focuses on understanding and mitigating the

anodic instability of electrolytes, additives and electrode components, e.g., conductive carbon black, in high-voltage lithium-ion cells. Within the framework of BASF’s Scientific Network on Electrochemistry and Batteries, he effectively collaborated with other research groups, e.g., Brett Lucht’s group at the University of Rhode Island, and worked as a visiting PhD student in Doron Aurbach’s group at the Bar-Ilan University in Israel. Michael has co-authored 9 peer-reviewed journal articles and presented his research at numerous international conferences including invited talks at the 56th Japanese Battery Symposium in Nagoya and the EMN Meeting on Batteries in Orlando. Recently, he was awarded the 2016 Evonik Research Prize. Michael is a founding member of the ECS Student Chapter Munich in which he co-organizes workshops and enjoys discussing science with his fellow colleagues.

Student Chapter News British Columbia Student Chapter Young Electrochemists Symposium (YES) 2016 The ECS British Columbia Student Chapter held its 5th annual BC Young Electrochemists Symposium on July 29, 2016 in the Chemical and Biological Engineering Department building at the University of British Columbia (UBC) in Vancouver. The day-long symposium featured five presentations by well-known scientists from both academia and industry—namely, Dr. Kjeang and Dr. Leach from SFU, and Dr. Stolar, Dr. Campbell, and Dr. Bruce from Ballard Power, NanoOne, and ZincNyx respectively. The event also included a presentation by Dr. Zhao from Mitacs Canada, which provided students the opportunity to ask questions about the postdoctoral and research fellowship offered by Mitacs Canada for various disciplines. Additionally, the symposium incorporated a 3-minute thesis and poster competition for students. Many proud partners funded the event, including the Department of Chemistry at Simon Fraser University, the Department of Chemical and Biological Engineering at University of British Columbia, Ballard Power, NanoOne, ECS Canada Section,

and ECS. The poster competition prizes were sponsored by Ballard Power (1st prize), ECS Canada Section (2nd prize) and NanoOne (3rd prize). The event attracted more than 64 attendees from different departments at the University of British Columbia and Simon Fraser University, as well as visiting scholars from Japan. Registration for the event was free and included breakfast, lunch and coffee. This year, the chapter hosted the symposium’s reception during the poster competition. Free drinks and appetizers were provided. Winners of the 3MT/poster competition were Audrey Taylor (Simon Fraser University) (1st prize), Elizabeth Fisher (University of British Columbia) (2nd prize), and Mahdieh Atighilorestani (University of Victoria) (3rd prize). The 3MT/poster competition featured 17 contestants. Each participating student gave an overview of their research during a judged 3MT, and then delivered a more detailed presentation during the poster competition at the reception. All of the speakers were given appreciation gifts.

Gary Leach during his speech on plasmonics and electrochemistry.

Audrey Taylor (left) received 1st prize (Ballard Power award) from Gary Leach (right).

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

t ST ech UDENT highligh NE WS ts University of Iowa Student Chapter In March 2016, the University of Iowa Student Chapter had the pleasure of hosting ECS President Krishnan Rajeshwar from the University of Texas at Arlington. During his visit, Prof. Rajeshwar met with the student chapter to discuss careers in electrochemistry, research endeavors with UI faculty, and gave a wonderful lecture on solid state materials electrochemistry. In April 2016, the University of Iowa ECS student chapter was granted the opportunity to tour some of the laboratories and facilities at Argonne National Laboratory. This was the student chapter’s first field trip and provided a view of electrochemical science at the forefront of electrochemistry in numerous areas. Overall, it was a very fruitful visit for the student chapter and provided a look at cutting edge electrochemical research.

Outside the Advanced Photon Source at Argonne National Laboratory, from left to right are Anthony Lucio, Junnan Wang, Kaylee Lovander, Matthew Lovander, Jacob Lyon, and Nadeesha Rathuwadu.

Attendees gather for a photo during the multi-departmental colloquium lecture at the University of Iowa. From left to right are Nadeesha Rathuwadu, Jeffrey Landgren, Jonathan Koonce, Junnan Wang, Krishnan Rajeshwar (invited speaker), Jacob Lyon, Matthew Lovander, Anthony Lucio, and Johna Leddy (faculty advisor).

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

t ST ech UDENT highligh NE WS ts Montreal Student Chapter The 6th Annual ECS Montreal Student Symposium took place on June 10, 2016 at McGill University in Montreal, Canada. The event was graciously sponsored by Metrohm Canada, Pine Research Instrumentation, ECS Canada Section, Snowhouse, Gamble Technologies, Centre Québécois sur les matériaux fonctionnels (CQMF), McGill Chemistry, Association Étudiante du Secteur des sciences de l’Université du Québec à Montréal, and the PostGraduate Students’ Society of McGill University. Over 100 attendees took part in the symposium, hailing from 11 universities and research centers in Quebec, Ontario, New York, and California. The attendees enjoyed 14 talks and 17 posters, including the two invited presentations of Richard Crooks (University of Texas at Austin) and Mickael Dollé (Université de Montréal). Prof. Crooks’ talk, “Quantitative Electrochemical Detection of Biological Analytes at Sub-Picomolar Levels using a Simple Paper Sensor,” discussed a novel paper analytical device for the sensitive detection of biological substrates. On a completely different note, Prof. Dollé discussed the development of new materials and manufacturing processes for battery materials in his presentation entitled “Materials and Processing Challenges for the NextGeneration.” Student prizes were presented for the top two oral and poster presentations. Nicholas Payne (McGill University) was awarded best oral presentation for his talk “Probing Passivating Porous Films by Scanning

Electrochemical Microscopy,” while Darpandeep Aulakh (Clarkson University) received second prize for her talk entitled “Advanced Porous Materials as Versatile Storage and Separation Platforms.” On the poster side, Laure Kayser (McGill University) received first prize for her poster on “Palladium-Catalyzed and Metal-Free Multicomponent Approaches to Conjugated Polymers,” while Majid Rasool received second prize for his poster on “The Effect of Ball Milling on Crystallinity and Electrochemical Behavior of Low Temperature Li2FeSiO4 Orthorhombic Phase.” The ECS Montreal Student Chapter would like to thank all of its sponsors and attendees for a great event! Further information about the ECS Montreal Student Chapter can be found at http://ecsmontreal.blogspot.com or on the ECS Montreal Student Chapter Facebook page.

The 6th ECS Montreal Student Symposium attracted more than 95 attendees from universities and research centers in Quebec, Ontario, New York, and California.

Students in discussions during the poster session.

The ECS Montreal Student Chapter Committee for 2016. From left to right: Samantha Gateman (Vice-President), Laurence Savignac (Secretary), David Polcari (President), and Danny Chhin (Treasurer).

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

t ST ech UDENT highligh NE WS ts

ECS STUDENT PROGRAMS

Awarded Student Membership Summer Fellowships

ECS Divisions offer Awarded Student Memberships to qualified full-time students. To be eligible, students must be in their final two years of an undergraduate program or enrolled in a graduate program in science, engineering, or education (with a science or engineering degree). Postdoc students are not eligible. Memberships include generous meeting discounts, an article pack with access to the ECS Digital Library, a subscription to Interface, and much more. uApply www.electrochem.org/student-center uQuestions customerservice@electrochem.org uDeadline Renewable yearly

The ECS Summer Fellowships were established in 1928 to assist students during the summer months.

Travel Grants Several of the Society’s divisions and sections offer Travel Grants to students, postdoctoral researchers, and young professionals presenting papers at ECS meetings. Please be sure to review travel grant requirements for each division and sections. In order to apply for a travel grant, formal abstract submission is required for the respective meeting you wish to attend. uApply www.electrochem.org/travel-grants

The next round of fellowships will be presented in 2017. Please visit the ECS website for complete rules and nomination requirements.

uApply www.electrochem.org/fellowships uQuestions awards@electrochem.org uDeadline January 15, 2017

uQuestions travelgrant@electrochem.org

uNote Applicants must reapply each year

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

t ST ech UDENT highligh NE WS ts University of Texas at Austin Student Chapter The University of Texas at Austin Student Chapter had three significant events in spring 2016. They included two outreach events and one seminar. Explore UT is an open house that the University of Texas at Austin which is held annually to showcase for the neighboring community the importance of academic interests in higher education. This outreach event was held this year on March 5, 2016. The ECS Student chapter had four tables thanks to the Cockrell School of Engineering at UT Austin and was able to showcase four demonstrations. The demos included: (1) Model fuel cell car; (2) gummy bear crystal structures; (3) crystal geodes that can be grown at home; and (4) invisible ink to demonstrate redox reactions.

The second outreach event was the Meridian School science day held on April 9, 2016. Meridian is a K-12 public, tuition-free charter school and their science fair is held each year for students and families to encourage family learning outside of the classroom. The instruction included: (1) a model fuel-cell car; (2) marshmallow crystal structures; and (3) an invisible ink redox reaction demonstration using household products of vitamin C tablets and iodine. ECS hosted a student seminar with three students – Shao-fei Wang (Postdoc), Sheng-Heng Chung (Postdoc) and Wangda Li (PhD candidate) to discuss the state of lithium battery developments today with a focus on lithium-sulfur batteries and nickel-rich lithium ion cathode materials.

Jeff Dahn during his presentation, “It is hard to make a Li-ion battery last a long time, but even harder to prove that it will,” at the 1st ECS Student Chapter Munich Symposium.

Thomas Schmidt during his presentation, “Oxygen Evolution on Non-Noble Metal Catalysts,” at the 1st ECS Student Chapter Munich Symposium.

Seminar on the current state of lithium batteries hosted by the ECS Student Chapter at UT Austin.

University of Utah Student Chapter One of the more memorable activities the University of Utah Student Chapter was involved in recently was a fifth grade field trip. Fifth graders from a local elementary school visited the campus and the chapter organized four interactive tables to demonstrate electricity, magnetism, light/spectroscopy, and acid/base chemistry. The chapter

used potato and lemon circuits to light up LEDs at the electricity table, played with ferrofluids at the magnetism table, used different lenses at the light/spectroscopy table, and changed the pH of tap water by blowing into it with a straw at the acid/base table. Both the fifth grade students and the students from the local chapter enjoyed this event.

Using lemons to light up LEDs.

Testing pH of household items.

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

2015 Y e a r in RE vie w

Discover Your Community

Your ECS membership defines you as a leader in your field – as someone who believes in: • Disseminating scientific research in the most accessible ways • Advancing the science by bridging the gaps between academia, industry, and government

• Mentoring young people through networking and by providing quality training and education • Honoring our heroes of the past, recognizing colleagues changing our lives now, and seeking those who are designing the future of our field

“I just like to disseminate my results. To share what I’ve done with others and help grow the field. That’s why I’m a member.” – Researcher and 12-year ECS member

MEMBERSHIP BENEFITS l

The ECS Member Article Pack—$3,300 VALUE—100 free downloads from all ECS journals giving you access to full-text articles in the ECS Digital Library, including the top publications in solid state and electrochemical science and technology: w Journal of The Electrochemical Society w ECS Journal of Solid State Science and Technology w ECS Electrochemistry Letters w ECS Solid State Letters w ECS Transactions w Electrochemical and Solid-State Letters

Open Access Article Credit—$800 VALUE—receive a complimentary article processing waiver to publish a paper in an ECS journal as Open Access.

Discounts each time you attend an ECS biannual meeting, meet colleagues and mentors face-to-face and participate in top-level symposia and networking get-togethers.

Free one-year subscription to Interface, the quarterly magazine of record for the Society, delivered to your door, filled with the latest developments in the field and news and information for and about ECS members.

Exclusive access to the ECS Member Directory providing contact information for colleagues around the world.

Discounts on ECS products and services, including the ECS Monograph Series published by John Wiley & Sons.

Recognition for your achievements through ECS’s robust honors and awards program.

Plus, you will be notified immediately as new member benefits, discounts, and opportunities are added!

Admission to ongoing educational programs— allowing you to attend comprehensive one-day courses at exceptional member savings.

Jo T in el O ec D E CS tro A ch em Y .o !

Questions about membership? Contact customerservice@electrochem.org l 609.737.1902, ext. 100

100

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

231st ECS MEETING May 28-June 2, 2017 Hilton New Orleans Riverside

Photo by New Orleans Convention & Vistors Bureau

NEW ORLEANS L

CALL FOR PAPERS Photo by Richard Nowitz

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Photo by New Orleans Convention & Vistors Bureau

Abstract Submission: www.electrochem.org/231cfp

Photo by Richard Nowitz

231st ECS MEETING May 28-June 2, 2017

NEW ORLEANS L

General Information

The 231st ECS Meeting will be held in New Orleans, Louisiana, USA from May 28 – June 2, 2017 at the Hilton New Orleans Riverside. This international conference will bring together scientists, engineers, and researchers from academia, industry, and government laboratories to share results and discuss issues on related topics through a variety of formats, such as oral presentations, poster sessions, panel discussions, tutorial sessions, short courses, and exhibits. The unique blend of electrochemical and solid state science and technology at an ECS Meeting provides an opportunity and forum to learn and exchange information on the latest scientific and technical developments in a variety of interdisciplinary areas.

Deadlines

For all deadlines, please refer to the next page.

Abstract Submission

To give an oral or poster presentation at the 231st ECS Meeting, you must submit an original meeting abstract for consideration via the ECS website, no later than December 16, 2016. Faxed, e-mailed, and/or late abstracts will not be accepted. Meeting abstracts should explicitly state objectives, new results, and conclusions or significance of the work. Once the submission deadline has passed, the symposium organizers will evaluate all abstracts for content and relevance to the symposium topic, and will schedule all acceptable submissions as either oral or poster presentations. In February 2017, Letters of Acceptance will be sent via email to the corresponding author of all accepted abstracts, notifying them of the date, time, and location of their presentation. Regardless of whether you requested a poster or an oral presentation, it is the symposium organizers’ discretion to decide how and when it is scheduled.

Paper Presentation

Oral presentations must be in English; LCD projectors and laptops will be provided for all oral presentations. Presenting authors MUST bring their presentation on a USB flash drive to be used with the dedicated laptop that will be in each technical session room. Speakers requiring additional equipment must make written request to meetings@electrochem.org at least one month prior to the meeting so that appropriate arrangements may be worked out, subject to availability, and at the expense of the author. Poster presentations must be displayed in English, on a board approximately 3 feet 10 inches high by 3 feet 10 inches wide (1.17 meters high by 1.17 meters wide), corresponding to their abstract number and day of presentation in the final program.

Meeting Publications

ECS Meeting Abstracts—All meeting abstracts will be published in the ECS Digital Library (www.ecsdl.org), copyrighted by ECS, and all abstracts become the property of ECS upon presentation. ECS Transactions—All full papers and posters presented at ECS meetings are eligible for submission to the online proceedings publication, ECS Transactions (ECST). The degree of review to be given each paper is at the discretion of the symposium organizers. Some symposia will publish an “enhanced” issue of ECST, which will be available for sale at the meeting and through the ECS Digital Library. Please see each individual symposium listing in this Call for Papers to determine if there will be an “enhanced” ECST issue. In the case of symposia publishing “enhanced” issues, submission of a full-text manuscript to ECST is mandatory and required in advance of the meeting. Some symposia will publish a “standard” issue of ECST, for which all authors are encouraged to submit their full-text papers. Please see each individual symposium listing in this Call for Papers to determine if there will be a “standard” ECST issue. Upon completion of the review process, papers from the “standard” issues will be published shortly after their acceptance. Once published, papers will be available for sale through the ECS Digital Library. Please visit the ECST website (www.ecsdl.org/ECST) for additional information, including overall guidelines, deadlines for submissions and reviews, author and editor instructions, a manuscript template, and more. ECS Journals–Authors presenting papers at ECS meetings, and submitting to ECST, are also encouraged to submit to the Society’s technical journals: the Journal of The Electrochemical Society, and ECS Journal of Solid State Science and Technology. Although there is no hard deadline for the submission of these papers, it is considered that six months from the date of the symposium is sufficient time to revise a paper to meet the stricter criteria of the journals. “Instructions to Authors” are available from the ECS website. If publication is desired elsewhere after presentation, written permission from ECS is required. 102

Hilton New Orleans Riverside

Short Courses

Three short courses will be offered on Sunday, May 28, 2017 from 900-1630h. Short courses require advance registration and may be cancelled if enrollment is under 10 registrants in the respective course. The following short courses are scheduled: 1) Fundamental of Electrochemistry: Basic Theory and Thermodynamic Methods, 2) Technical Leadership & Decision Making, and 3) Imaging, Modeling, and Simulation of Li-Ion Battery Microstructures in 2D, 3D, and 4D. Registration opens February 2017.

Technical Exhibit

The 231st ECS Meeting will include a Technical Exhibit, featuring presentations and displays by over 40 manufacturers of instruments, materials, systems, publications, and software of interest to meeting attendees. Coffee breaks are scheduled in the exhibit hall along with evening poster sessions. Interested in exhibiting at the meeting with your company? Exhibitor opportunities include unparalleled benefits and provide an extraordinary chance to present your scientific products and services to key constituents from around the world. Exhibit opportunities can be combined with sponsorship items and are customized to suit your needs. Please contact Casey Emilius at 1.609.737.1902, ext. 126 for further details.

Meeting Registration

All participants—including authors and invited speakers—are required to pay the appropriate registration fees. Hotel and meeting registration information will be posted on the ECS website as it becomes available. The deadline for discounted early-bird registration is May 1, 2017.

Hotel Reservations

The 231st ECS Meeting will be held at the Hilton New Orleans Riverside. Please refer to the meeting website for the most up-to date information on hotel availability and information about the blocks of rooms where special rates have been reserved for participants attending the meeting. The deadline for hotel reservations is May 1, 2017.

Letter of Invitation

Individuals requiring an official letter of invitation should email abstracts@electrochem. org ; such letters will not imply any financial responsibility of ECS.

Financial Assistance

ECS divisions and sections offer travel grants to students, postdoctoral researchers, and young professionals to attend ECS biannual meetings. Applications are available online at www.electrochem.org/travel-grants and must be received no later than the submission deadline of Friday, February 17, 2017. Additional financial assistance is very limited and generally governed by symposium organizers. Individuals may inquire directly to organizers of the symposium in which they are presenting to see if funding is available. For general travel grant questions, please contact travelgrant@electrochem.org.

Sponsorship Opportunities

ECS biannual meetings offer a wonderful opportunity to market your organization through sponsorship. Sponsorship allows exposure to key industry decision makers, the development of collaborative partnerships, and potential business leads. ECS welcomes support in the form of general sponsorship at various levels. Sponsors will be recognized by level in Interface, the Meeting Program, meeting signage, and on the ECS website. In addition, sponsorships are available for the plenary and keynote talks and other special events. These opportunities include additional recognition, and may be customized to create personalized packages. Advertising opportunities for the Meeting Program as well as in Interface magazine are also available. Please contact Casey Emilius at 1.609.737.1902, ext. 126 for further details. For Symposium Sponsorship opportunities, contact John Lewis at 1.609.737.1902, ext. 120.

Contact Information

If you have any questions or require additional information, contact ECS. The Electrochemical Society 65 South Main Street, Pennington, NJ, 08534-2839, USA tel: 1.609.737.1902, fax: 1.609.737.2743 meetings@electrochem.org

www.electrochem.org The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Photo by Richard Nowitz

231st ECS MEETING

NEW ORLEANS L

May 28-June 2, 2017

Hilton New Orleans Riverside

Symposium Topics A— Batteries and Energy Storage

I03 — Renewable Fuels via Artificial Photosynthesis 2

A01 — Joint General Session: Energy Storage and Energy Conversion

I04 — Solid-Gas Electrochemical Interfaces 2 – SGEI 2

A02 — Large-Scale Energy Storage 8

I05 — From Electrode to Systems: Invited Perspectives and Tutorials on Fuel Cell Technology in Memory of Dr. H. Russell Kunz

A03 — Battery Electrolytes A04 — Battery Safety A05 — Lithium-Ion Batteries and Beyond A06 — Battery Student Slam 1 B— Carbon Nanostructures and Devices

B01 — Carbon Nanostructures for Energy Conversion B02 — Carbon Nanostructures in Medicine and Biology B03 — Carbon Nanotubes - From Fundamentals to Devices B04 — Endofullerenes and Carbon Nanocapsules B05 — Fullerenes - Chemical Functionalization, Electron Transfer, and Theory: In Memory of Professor Robert Haddon B06 — Graphene and Beyond: 2D Materials B07 — Inorganic/Organic Nanohybrids for Energy Conversion B08 — Porphyrins, Phthalocyanines and Supramolecular Assemblies C— Corrosion Science and Technology

C01 — Corrosion General Session D— Dielectric Science and Materials D01 — Emerging Materials for Post CMOS Devices/Sensing and Applications 8 D02 — Plasma Nano Science and Technology D03 — Dielectrics for Interconnect, Interposers, and Packaging E— Electrochemical/Electroless Deposition E01 — Green Electrodeposition 4 E02 — Metallization of Flexible Electronics F— Electrochemical Engineering F01 — Electrochemical Engineering General Session and NET Award Symposium F02 — Characterization of Porous Materials 7 F03 — Multiscale Modeling, Simulation, and Design F04 — Applications of Electrochemistry to Additive Manufacturing F05 — Pulse and Pulse Reverse Electrolytic Processes G— Electronic Materials and Processing G01 — Processes at the Semiconductor Solution Interface 7 G02 — Silicon Compatible Materials, Processes, and Technologies for Advanced Integrated Circuits and Emerging Applications 7 G03 — Organic Semiconductor Materials, Devices, and Processing 6 H— Electronic and Photonic Devices and Systems H01 — Wide Bandgap Semiconductor Materials and Devices 18 H02 — Solid-State Electronics and Photonics in Biology and Medicine 4 H03 — Properties and Applications of 2-Dimensional Layered Materials 2 I— Fuel Cells, Electrolyzers, and Energy Conversion I01 — Oxygen or Hydrogen Evolution Catalysts for Water Electrolysis 3 I02 — Materials for Low Temperature Electrochemical Systems 3

I06 — Crosscutting Metrics and Benchmarking of Transformational LowCarbon Energy-Conversion Technologies K— Organic and Bioelectrochemistry K01 — The 80th Birthday Trifecta in Organic Electrochemistry in Honor of Jean Lessard, Albert Fry, and Dennis Peters K02 — Electron Transfer in Biological Systems L— Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry L01 — Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry General Session and Grahame Award Symposium L02 — Ion-Conducting Polymeric (or, Polymer-based) Materials L03 — Electrochromic and Chromogenic Materials L04 — Electroanalytical Aspects of Environmental and Groundwater Problems M— Sensors M01 — Sensors, Actuators and Microsystems General Session M02 — Nano/Bio Sensors Z— General Z01 — General Society Student Poster Session Z02 — Nanotechnology General Session Z03 — Solid State Topics General Session Z04 — Sustainable Materials and Manufacturing 2 Z05 — Nature-Inspired Electrochemical Systems 2

Important Dates and Deadlines* Meeting abstract submission opens..........................................................August, 2016 Meeting abstract submission deadline...............................December 16, 2016 Notification to Corresponding Authors of abstract acceptance or rejection.................................................February 6, 2017 Technical Program published online......................................................February, 2017 Meeting registration opens...........................................................................February, 2017 Travel Grant application deadline.............................................. February 17, 2017 ECS Transactions submission site opens for “enhanced” issues................................................................February 10, 2017 ECS Transactions submission site opens for “standard” issues..................................................................February 17, 2017 Meeting Sponsor and Exhibitor deadline (for inclusion in printed materials)...........................................February 24, 2017 ECS Transactions submission deadline for “enhanced” issues.................................................................................March 10, 2017 Travel Grant approval notification................................................................April 7, 2017 Hotel and Early-Bird meeting registration deadlines.................. May 1, 2017 231st ECS Meeting – New Orleans, LA.............................. May 28 – June 2, 2017 ECS Transactions submission deadline for “standard” issues........................................................................................June 11, 2017 *a full schedule of dates and deadlines may be found at http://www.electrochem.org/ symposium-organizer-info#231

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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Your article. Online. FAST! More than 125,000 articles in all areas of electrochemistry and solid state science and technology from the only nonprofit publisher in its field.

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VOL. 23, NO. 2 Summer 2014

IN THIS ISSUE 3 From the Editor:

Working With Stuff

9 From the President:

The Grandest Challenge of Them All

11 Orlando, Florida

ECS Meeting Highlights

36 ECS Classics–

Hall and Héroult and the Discovery of Aluminum Electrolysis

39 Tech Highlights 41 Twenty-Five Years of

Scanning Electrochemical Microscopy

43 Studying Electrocatalytic

Activity Using Scanning Electrochemical Microscopy

47 Measuring Ions with

Scanning Ion Conductance Microscopy

www.electrochem.org

VOL. 23, NO. 2

www.ecsdl.org

If you haven’t visited the ECS Digital Library recently, please do so today!

25 Years of Scanning Electrochemical Microscopy

53 Electrochemistry at the Nanoscale: The Force Dimension

61 Functional Electron

Microscopy for Electrochemistry Research: From the Atomic to the Micro Scale

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The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

Leading the world in electrochemistry and solid state science and technology for more than 110 years

Call for Papers Fifteenth International Symposium on Solid Oxide Fuel Cells

SOFC-XV

Sponsored by the High Temperature Materials Division of The Electrochemical Society and The SOFC Society of Japan

www.electrochem.org/sofc-xv

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

105

SOFC-XV

Fifteenth International Symposium on Solid Oxide Fuel Cells Hollywood, Florida, USA July 23-28, 2017

Information

The Fifteenth International Symposium on Solid Oxide Fuel Cells (SOFCXV) will be held in Hollywood, Florida, USA from July 23 – 28, 2017 at the Diplomat Resort and Spa. This international symposium will bring together scientists, engineers, and researchers from academia, industry, and government laboratories to share results and discuss issues related to Solid Oxide Fuel Cells and Electrolyzers. This meeting provides an opportunity and forum to learn and exchange information on the latest scientific and technical developments relating to SOFCs and SOECs.

Important Dates and Deadlines

For important deadlines, please refer to the next page.

Abstract Submission

To give an oral or poster presentation at SOFC-XV, you must submit an original meeting abstract for consideration via the SOFC website, no later than February 3, 2017. Faxed, e-mailed, and/or late abstracts will not be accepted. Meeting abstracts should explicitly state objectives, new results, and conclusions or significance of the work. Because the number of time slots for oral presentations is limited, it is likely that not all requests for oral presentations can be accepted, which means that oral contributions might be moved into a poster session. Therefore, research groups that submit more than one abstract should seek a reasonable balance between oral and poster presentations. Please note: No abstracts will be scheduled for presentation without the submission of a corresponding manuscript to ECS Transactions (see page 3). Once the submission deadline for manuscripts has passed, the symposium organizers will schedule all acceptable submissions as either oral or poster presentations. In late April 2017, Letters of Acceptance will be sent via email to the corresponding authors of all accepted submissions, notifying them of the date, time, and location of their presentation.

Paper Presentation

Technical Exhibit

The SOFC-XV Meeting will include a Technical Exhibit, featuring presentations and displays by manufacturers of instruments, materials, systems, publications, and software of interest to meeting attendees. Coffee breaks are scheduled in the exhibit hall along with evening poster sessions. Interested in exhibiting at the meeting with your company? Exhibitor opportunities include unparalleled benefits and provide an extraordinary chance to present your scientific products and services to key constituents from around the world. Exhibit opportunities can be combined with sponsorship items and are customized to suit your needs. Please contact Casey Emilius at 1.609.737.1902 ext. 126 or casey. emilius@electrochem.org, for further details.

Meeting Registration

All participants—including authors and invited speakers—are required to pay the appropriate registration fees. Hotel and meeting registration information will be posted on the SOFC website as it becomes available. The deadline for discounted early-bird registration is June 16, 2017.

Hotel Reservations

The SOFC-XV Meeting will be held at the Diplomat Hotel in Hollywood, Florida, USA. Please refer to the meeting website for the most up-to date information on hotel availability and information about the blocks of rooms where special rates have been reserved for participants attending the meeting. The deadline for hotel reservations is June 16, 2017.

Letter of Invitation

Individuals requiring an official letter of invitation should email abstracts@ electrochem.org ; such letters will not imply any financial responsibility of ECS.

Sponsorship Opportunities

The SOFC meeting offers a wonderful opportunity to market your organization through sponsorship. Sponsorship allows exposure to key industry decision makers, the development of collaborative partnerships, and potential business leads. ECS welcomes support in the form of general sponsorship at various levels. Sponsors will be recognized by level in Interface, the Meeting Program, meeting signage, and on the ECS website. In addition, sponsorships are available for events such as the coffee breaks and the SOFC banquet. These opportunities include additional recognition, and may be customized to create personalized packages. Advertising opportunities for the Meeting Program as well as in Interface magazine are also available. Please contact Casey Emilius at 1.609.737.1902 ext. 126 or casey. emilius@electrochem.org, for further details.

Contact Information

If you have any questions or require additional information, contact ECS.

Meeting Publications

ECS Meeting Abstracts—All meeting abstracts will be published in the ECS Digital Library (www.ecsdl.org), copyrighted by ECS, and all abstracts become the property of ECS upon presentation. ECS Transactions—The authors of all oral and poster presentations scheduled for SOFC-XV are obligated to submit a full text paper to the online proceedings publication, ECS Transactions (ECST) (see page 3). Abstracts will not be scheduled for presentation without a corresponding full-text ECST paper. Upon completion of the review process, papers from this issue will be published nine days prior to the start of the meeting. Once published, papers will be available for sale through the ECS Digital Library. Please visit the ECST website (www.ecsdl.org/ECST) for additional information, including overall guidelines, deadlines for submissions and reviews, author and editor instructions, a manuscript template, and more. ECS Journals–Authors presenting papers at ECS meetings, and submitting to ECST, are also encouraged to submit to the Society’s technical journals: the Journal of The Electrochemical Society, and ECS Journal of Solid State Science and Technology. Although there is no hard deadline for the submission of these papers, it is considered that six months from the date of the symposium is sufficient time to revise a paper to meet the stricter criteria of the journals. “Instructions to Authors” are available from the ECS website. If publication is desired elsewhere after presentation, written permission from ECS is required. 106

The Electrochemical Society 65 South Main Street, Pennington, NJ, 08534-2839, USA tel: 1.609.737.1902, fax: 1.609.737.2743 meetings@electrochem.org

www.electrochem.org

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

SOFC-XV

Fifteenth International Symposium on Solid Oxide Fuel Cells Hollywood, Florida, USA July 23-28, 2017

The Fifteenth International Symposium on Solid Oxide Fuel Cells (SOFC-XV) will provide an international forum for the presentation and discussion of the latest research and developments on solid oxide fuel cells (SOFCs), solid oxide electrolysis cells (SOECs), and related topics. Papers are solicited on all aspects of solid oxide fuel cells and electrolyzers. Following is a partial list of topics to be addressed: (1) materials for cell components (e.g. electrolyte, electrodes, interconnection, and seals); (2) fabrication methods for cell components, complete cells, and stacks; (3) cell designs, electrochemical performance, and modeling; (4) stack designs and their performance; (5) utilization of different fuels with or without reformation; (6) stationary power generation, transportation, and military applications; and (7) prototype SOFC and SOEC systems, field test experience, cost, and commercialization plans.

Abstracts should be submitted electronically by February 3, 2017 to the ECS at www.electrochem.org/sofc2017cfp. Any questions and inquiries should be sent to the symposium organizers: Dr. S. C. Singhal, Pacific Northwest National Laboratory, e-mail: singhal@pnnl.gov; or Professor T. Kawada, Tohoku University, e-mail: kawada@ee.mech. tohoku.ac.jp. All papers presented will be included in an electronic issue (on USB drive as well as on a CD-ROM) of ECS Transactions which will be available at the meeting. All authors are obligated to submit their full text manuscript no later than April 7, 2017. All manuscripts should be submitted online, and must include an MS Word version to allow editors to make minor formatting/editorial changes. Abstract Submission: www.electrochem.org/sofc2017cfp

Important Deadlines Abstract submission opens................................ August, 2016 Manuscript submission site opens..................... August, 2016 Abstract submission deadline.....................February 3, 2017 Meeting registration opens..................................March, 2017 Manuscript submission deadline....................... April 7, 2017 Technical Program published online.....................April, 2017

Meeting Sponsor and Exhibitor deadline (for inclusion in printed materials).................. April 21, 2017 Notification to Corresponding Authors of submission acceptance or rejection..............April 24, 2017 Hotel and Early-Bird meeting registration deadlines..........................June 16, 2017 15th International Symposium on Solid Oxide Fuels – Hollywood, FL........ July 23-28, 2017

www.electrochem.org/sofc-xv

The Electrochemical Society Interface • Fall 2016 • www.electrochem.org

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Altmetrics in the ECS Digital Library What Are Altmetrics? Altmetrics are a better way for authors to track the discussion surrounding their work. Where the Journal Impact Factor reports aggregate data for a journal, altmetrics report data for individual articles. By providing article level metrics, altmetrics allow authors to see not only how much attention their work is receiving, but where the attention is coming from, and at an earlier stage than traditional metrics.

How to Boost Your Altmetric Rankings • Publish open access so that more readers can view your research. • Like, tweet, and share. • Start a conversation and actively promote your work.

How Are Altmetric Scores Generated? Data comes from: • Online reference managers (Mendeley, CiteULike) • Mainstream media (newspapers and magazines) • Social media (Twitter, Facebook, blogs, etc.) Data is weighted based on: • Volume: How much attention is an article getting? • Sources: Which sources are mentioning the article? • Authors: Who is talking about the article?

Open Access and Altmetrics Are Complementary Open access and altmetrics work cooperatively to help articles reach their full impact. Altmetrics further ECS’s pledge to Free the Science by providing both transparent publication as well as transparent assessment of research.

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