Interface Vol. 26, No. 1, Spring 2017 by The Electrochemical Society

Research

for

Interdisciplinary

VOL. 26, NO. 1 Spring 2017

IN THIS ISSUE 3 From the Editor:

Perspectives on the Future of Interface

7 Pennington Corner:

The ECS 115th Anniversary, Once Again â&#x20AC;&#x153;We Stand Out to Seaâ&#x20AC;?

28 Special Section:

231st ECS Meeting New Orleans, Louisiana

36 ECS Classics:

Acheson, Silicon Carbide, and the Electric Arc

41 Looking at Patent Law 45 Tech Highlights 47 Interdisciplinary Research for Next Generation Electrolytes Used in Electrochemical Systems

49 Increasing Fuel Cell

Efficiency by Using Ultra-Low Equivalent Weight Ionomers

55 Breaking the Scales:

Electrolyte Modeling in Metal-Ion Batteries

61 Ion Conduction in

Next Generation

Electrolytes

Microphase-Separated Block Copolymer Electrolytes

69 Strategies for Developing

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FROM THE EDITOR

Perspectives on the Future of Interface

s we look back with satisfaction on the first 25 years of Interface, the question that arises almost immediately is what the future has in store for this publication. The field of publishing is changing rapidly and it is essential that Interface, along with other ECS publications, is at the forefront in terms of driving change while concurrently catering to the best interests of our membership and the broader community. The issue of indexing/archiving and peer review of technical feature articles has been a recurrent theme in most discussions on the future of Interface. We have now committed to indexing all articles moving forward and are engaged in an effort to index prior articles. However, the feature articles in Interface are still not peer-reviewed in the strictest sense. Each article does go through two levels of review, first by the guest editor and then by the Interface editors. However, the changes recommended are largely editorial in nature. Much thought has gone into how one could provide authors with an opportunity to contribute to Interface, while simultaneously being able to point towards a peer-reviewed contribution. From another viewpoint, these deliberations have also looked into the issue of how best to capture some of the excellent content being published in Interface in other archival Society publications. We now have a mechanism in place that addresses these issues that we will pilot in the coming year. Recently, the Journal of The Electrochemical Society (JES) and the ECS Journal of Solid State Science and Technology (JSS) announced a new category of contributions, namely “Perspective” articles: brief articles that offer insights into emerging or established fields of potential interest to readers of ECS journals. These articles are not intended to announce new results but rather present an assimilation of advances, potential trends, and/or innovative applications. These Perspective articles will be both peer- and editor-reviewed (by the appropriate technical editor), with the innovation being that the peer review process will take into account that the Perspective article content can be rather subjective. At first glance, there is quite a bit of similarity between a typical Interface feature article and the proposed Perspectives. The Perspective article will outline, at a broader level, where research is going in the area described in the Interface article, and describe competing thoughts and gaps in the knowledge. It will have some paragraphs dealing with speculation, and will have deeper analysis, discussion, and quantitative insight. At Interface, we intend to offer each contributing author (or set of authors) an opportunity to contribute an amended version of their article as a Perspective article on the same topic to JES/JSS for publication subject to passing the peer-review process. We will also extend an opportunity to past authors to contribute invited Perspectives based on their submissions. We hope this initiative will bring closer coordination between Interface and JES/JSS. Given the increasing number of specialized focus issues being published by JES/JSS, it should be possible in future to coordinate Interface special issues with selected focus issues. Of course, this is just one initiative that has advanced to the implementation stage. We recognize that there are a lot of amendments that can be incorporated that will ensure that Interface continues to serve the best interests of our community. Rather than a top-down approach wherein these changes are conceived and driven by the Society or the Interface Advisory Board, we would like to solicit inputs from the membership (and the community at large). I invite you to write to us with your thoughts on how best Interface can continue serving the Society in the future. To paraphrase Yogi Berra, it is tough to make predictions, especially about the future. However, we can and should speculate. In this spirit, we look forward to your “Perspective” on the future of Interface!

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: Vijay Ramani, ramani@wustl.edu; Petr Vanýsek, pvanysek@gmail.com Guest Editor: Christopher G. Arges, carges@lsu.edu Contributing Editors: Donald Pile, donald.pile@gmail.com; Alice Suroviec, asuroviec@berry.edu 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 2017 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 8,500 scientists and engineers in over 75 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. All recycled paper. Printed in USA.

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47 49 55 61 69

Interdisciplinary Research for Next Generation Electrolytes Used in Electrochemical Systems by Christopher G. Arges Increasing Fuel Cell Efficiency by Using Ultra-Low Equivalent Weight Ionomers by Michael Yandrasits, Matthew Lindell, Mark Schaberg, and Mike Kurkowski Breaking the Scales: Electrolyte Modeling in Metal-Ion Batteries by Ryan Jorn and Revati Kumar Ion Conduction in Microphase-Separated Block Copolymer Electrolytes by Yu Kambe, Christopher G. Arges, Shrayesh N. Patel, Mark P. Stoykovich, and Paul F. Nealey Strategies for Developing New Anion Exchange Membranes and Electrode Ionomers by Michael A. Hickner

Vol. 26, No. 1 Spring 2017

the Editor: 3 From Perspectives on the Future of Interface

Corner: 7 Pennington The ECS 115th Anniversary, Once Again “We Stand Out to Seaˮ

9 Society News Section: 28 Special 231st ECS Meeting

New Orleans, Louisiana

33 People News Classics: 36 ECS Acheson, Silicon Carbide, and the Electric Arc

41 Looking at Patent Law 45 Tech Highlights 74 Section News 76 Awards Program 80 New Members 82 Student News

On the cover . . .

The three platforms represent aligned (top), partially aligned (middle), and anti-aligned (bottom) ion conducting microdomains in block copolymer electrolyte films integrated into an electrochemical cell. The aligned domain yields the least resistance leading to the brighter lightbulb. Cover image by Peter Allen, Institute for Molecular Engineering. The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

Pennington Corner

The ECS 115th Anniversary, Once Again “We Stand Out to Seaˮ

In April 1902, upon the conclusion of the Society’s first meeting in Philadelphia, the Society’s first president wrote the column below, which was printed in the Society’s first publication, explaining the rationale to form The American Electrochemical Society. Evidence accumulates on every hand that the analogue of the specialist in science is the society which specializes. Whether for good or ill, whether some of its influences are narrowing in some directions or not, the society which specializes is the necessary corollary of the scientific specialist; the latter came perforce into existence, has made the whole world his debtor, and is recognized as the present factor for progress; the former is coming perforce into existence, will soon make the world its immeasurable debtor, and will be a wonderfully potent factor in future scientific progress. Such is the force, the necessary condition, which has brought into existence The American Electrochemical Society. … Its functions should be those of bringing electrochemists into personal contact with each other; of disseminating among them all the information known to, and which can be spared by, their coworkers; to stimulate original thought in these lines by mutual interchange of experience, and by papers and discussions; to stimulate electrochemical work all over the world. … Such a society … being, therefore, a necessity, a pressing need, its formation was inevitable. It came. … The results have justified the insight of the projectors of the society, the first meeting has been an enthusiastic success, the organization now exists, its future is one of assured usefulness. With confidence we stand out to sea. —Joseph W. Richards Transactions of The American Electrochemical Society Vol. 1, No. 1 (1902)

As a staff member of ECS for 36 years, I am a student of our history, and so, have great admiration for Joseph Richards and the other scientists and engineers from that era who had the vision and courage to break away from the American Chemical Society. They founded the Society because forces at that time created the “necessary conditions” to bring into

existence a new organization dedicated to the advancement of electrochemistry. One hundred and fifteen years later this same dedication to electrochemistry prevails and the science has advanced to become the key to progress in communications, transportation, and medical technologies, and offers solutions for clean water, renewable energy, and the general sustainability of our planet. The growing importance of electrochemistry has stimulated a robust publications program at ECS; and we are experiencing revolutionary changes that have created both challenges to our future and opportunities to advance our science at a pace never before experienced. In response to the dramatic changes in research publishing, ECS has launched the Free the Science initiative with the goal to take down the paywalls and create unobstructed access to the ECS Digital Library for researchers, and really anyone, from anywhere in the world. Similar to the Society’s original formation in 1902, this initiative was started because there were forces that created the necessary conditions for ECS to advance content dissemination toward open science—the open exchange of information. Free the Science is an initiative that supports the creation of a completely new model for publishing that will drive the broadest access of the important research in our library. ECS is embracing this opportunity to advance our science and address the associated challenges created by the broken scholarly publications system. The ultimate goal is to stay true to our foundersʼ ideals and secure the Society’s future as a steward and leader of dissemination in electrochemical and solid state science and technology. ECS is leading an inevitable change that will revolutionize scholarly communications, and building a model to disseminate science to fully accomplish our mission. The Society’s current leadership has demonstrated the same vision and courage as the founding fathers but we face many challenges and the future of ECS is only assured with the support of our community. As we pass another milestone in time, we look to the future and say once again, “With confidence we stand out to sea.”

Roque J. Calvo ECS Executive Director http://orcid.org/0000-0002-1746-8668

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

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A Good Principle Is Applicable to Everything An Interview with Isamu Akasaki

n June 8, 2016, Yue Kuo, an ECS fellow and vice president of The Electrochemical Society, traveled to the Akasaki Institute at Nagoya University in Japan to talk with Isamu Akasaki, a Nobel Prize winner and ECS life member. Professor Akasaki is a materials scientist specializing in semiconductor science and technology. He is a pioneer of efficient blue light-emitting diodes which have enabled bright and energy-saving white light sources. He shares the 2014 Nobel Prize in Physics with Hiroshi Amano and Shuji Nakamura for this work. Prior to their groundbreaking work, scientists had produced LEDs that emitted red or yellow-green light, but not blue. Blue had been thought impossible or impractical to make. Blue LEDs became commercially available in 1994. The new combination of blue, green, and red LEDs produces white light, and blue LEDs coated with YAG:Ce yellow phosphor appear white to the eye and can be developed for much less energy than that from incandescent and fluorescent lamps, which contain toxic mercury. Prof. Akasaki’s work helped lead to the development of blue semiconductor lasers, which proved useful for high-capacity optical-media devices such as Blu-ray disc players. What follows is an edited transcript of the conversation between Yue Kuo and Isamu Akasaki, which they had in English. Yue Kuo: Professor Akasaki, thank you for spending the time to talk with me. I represent ECS in congratulating you for your outstanding achievements in science. Hopefully, you can share your experiences with our scientific community all over the world, and give special advice to our members and also to young researchers.

Yue Kuo (left) and Isamu Akasaki (right).

late Konosuke Matsushita, the founder of Matsushita Electric, now Panasonic Company. YK: So he had a vision?

IA: Right. And the purpose of this new institute was for researchers, and new, quite new, materials and new devices for future electronics. Isamu Akasaki: Thank you. Yes. This is where I started to do the research exploring electronic materials and devices. YK: Maybe you can start by talking about your background and In 1968, I developed high quality gallium arsenide with the growing up. world’s highest electron mobility by vapor phase epitaxy. And in IA: I was born in Chiran in Kagoshima Prefecture. It’s the southern 1970, my group developed the part of Kyushu Island. It’s a small brightest gallium phosphide red town on the peninsula, but I grew up LED known at the time. In 1967, in the city of Kagoshima. I graduated This made me wonder if it would be I began vapor phase epitaxial from Kyoto University in 1952 and growth of aluminum nitride—not possible to make a brighter image by joined the Kobe Kogyo Corporation, the gallium nitride, but aluminum now Fujitsu Limited, where I applying transparent single crystals, nitride—and determined the angular worked on fluorescent materials, frequencies of the longitudinal and rather than powders. screens, and vacuum tubes for TV. the transverse optical-phonons by YK: CRTs? fitting the calculated reflectivity to the Reststrahlen band, which we found in the grown AlN crystal. IA: Yes, CRTs. A powder was applied to the inner surface of the It’s a material which I later used as a buffer material when we grew tubes, and the fluorescent screen emitted a high light when they were GaN on sapphire substrate in 1985. In the 1980s, I considered AlN, excited by the electron beam radiations. I have been working on GaN, SiC, and ZnO as a buffer material to buffer strain between GaN luminescence (light emission without heat generation) ever since this and sapphire, and we chose AlN at the beginning because I had been first experience. familiar with AlN since 1967. I noticed a considerable amount of light was absorbed by the I had an insight during the early stage of gallium nitride based powder. This made me wonder if it would be possible to make semiconductor research, into the great potential of the blue light a brighter image by applying transparent single crystals rather emitters, and to pioneer a new field founded on the unique properties than powders. We now call this epitaxial growth of light-emitting of nitride semiconductors, namely the toughness, the wider direct crystalline film, but it was nothing but a pipe-dream at that time. energy gaps, the higher thermal conductivity, and also nontoxicity. It was then that the transistor first appeared, and they were mainly That is a short history of my work before I grew gallium nitride on a single crystal. And transistors were being investigated at the Kobe single-crystal. headquarters of the company. Being a semiconductor, germanium

“

does not emit light. Still, single crystal rather than powders appealed to me. In 1959, I moved to the newly created Department of Electronics at Nagoya University here, where I held the position of research associate, assistant professor, and then associate professor. Then, in 1964, I was invited to the newly established Matsushita Research Institute Tokyo, which was a new laboratory established by the

(Ed. Note: In 1999, Dr. Akasaki was awarded the ECS Solid State Science and Technology Award, now called the Gordon E. Moore Medal for Outstanding Achievement in Solid State Science and Technology. He had with him during this interview the original notes he used to make his acceptance speech. Below is an excerpt from what he read to Dr. Kuo.)

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

(continued on next page) 9

socie t y ne ws (continued from previous page)

IA: It is a great honor and a real pleasure for me to be awarded the ECS Solid State Science and Technology Award. … I started research work on semiconductor in 1959. That was a time when I worked on epitaxial vapor growth of germanium. … I am deeply moved that the research on wide-band gallium nitride and the related materials are currently one of the most “hot” research areas. It took just a quarter century, Isamu Akasaki since 1974, when I first grew the gallium nitride single crystal film by molecular beam epitaxy. … Because of the help of many coresearchers and students, I am indebted to say that without their support, it would not have been possible. I really owe my accomplishment to my collaborators at Matsushita Research Institute Tokyo, Y. Koide and H. Amano, and the many coresearchers at Nagoya University. I’m very thankful to my seniors, colleagues, and family members who have enlightened and supported me.… Finally, but not least, I’d like to wish The Electrochemical Society continued prosperity for many years to come. Thank you very much!

the purpose of this new institute “isAnd for researchers, and new, quite new, materials and new devices for future electronics. Where I started to do the research now, explore electronic materials and devices.

YK: That’s great. If I can have this copy, I’ll send it to ECS for their records. Thank you. Would you say the first blue LED was presented at an ECS meeting? IA: Yes. That was an oral presentation, and a very short abstract YK: That’s very important. I don’t know if you’re aware, for example in semiconductor, another very important paper we talk about is Gordon Moore’s, and Moore’s law. Similar to your occasion, Moore’s law was first articulated at an ECS section meeting. IA: Really? YK: Yes. ECS is very glad to have the most important papers published in ECS journals. This is very important historical information. Would you talk about your philosophy? You have done research for so many years, you must have developed your own personal view. IA: Philosophy? YK: Yes. IA: No pain, no gain. And as Thomas Edison said, “Genius is one percent inspiration and 99 perspiration.” (Ed. Note: Thomas Edison was an ECS member for 28 years, having joined the Society in 1903.) I say this to younger people, experience is the best teacher. That is, sometimes there is no royal road to learning.

YK: That’s very useful advice. I’m sure when you started working with gallium nitride, probably a lot of people resisted it by saying, “Why do you do this?” Was it very tough to persuade people?

I say this to younger people— “experience is the best teacher. That is, sometimes there is no royal road to learning.

IA: That (gallium nitride) is a tough material, so that is very important, most important. And most people had given up on gallium nitride research, or shifted to zinc selenide. But I worried about the instability of zinc selenide. On the other hand, the gallium nitride is very tough, has a wider energy gap which means that it can be used with UV emitters, and a very high electron saturation mobility. This means that it is very promising for high-speed/high-powered devices. So I didn’t think to do research on zinc selenides. YK: Never? IA: Never. YK: But when you started, even aluminum nitride, at that time must have been a novel idea. IA: Yes. I grew aluminum nitride crystals in 1967, and I first studied its optical properties and then made blue phosphor. But I wasn’t satisfied with the photoluminescence or cathodoluminescence. I wanted to make electroluminescence, so I thought to make aluminum gallium nitride mixed crystals, but at that time it was too difficult. Of course, I made aluminum gallium nitride, but actually the data showed a mixture of AlN and GaN, not an AlGaN alloy. Not so the other times that I didn’t use MOVPE (metalorganic vapour phase epitaxy). YK: There was no MOCVD (metalorganic chemical vapour deposition)? IA: Yes. And MOVPE was proposed by H. M. Manasevit, et al., and this had succeeded in many variety of compounds, except gallium nitride. Manasevit’s group published only one paper on the growth of nitrides by this method in 1971, but never employed the method for the growth of nitride semiconductors thereafter. (Ed. Note: The paper mentioned here was published by ECS. See H. M. Manasevit, F. M. Erdmann, and W. I. Simpson, “The Use of Metalorganics in the Preparation of Semiconductor Materials: IV. The Nitrides of Aluminum and Gallium,” J. Electrochem. Soc., 118, 1864 (1971).)

is penetrated “byMya way single thread. ˮ Crystal quality is greatly affected by the growth method and condition. GaN can be grown by HVPE (hydride vapor phase epitaxy) proposed by P. Maruska, et.al., by MBE, or by MOVPE (also called OMVPE or MOCVD). I compared these methods. The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

socie t y ne ws In the case of HVPE, crystal quality was degraded by appreciable reverse reactions, and the growth rate was too fast to fabricate device structure with thin layers of nanometers. MBE was prone to nitrogen deficiency and the growth rate was so slow at that time. On the other hand, MOVPE seemed to be the method that was more suitable for the growth of GaN, because this method has advantages as follows: 1. This method simply has no reverse reactions. 2. All the source materials are gases, so that all the important parameters, such as growth rate, AlGaN, GaInN alloy compositions, and also impurity doping could be readily controlled by the flow rate of the source gases. Note that the growth rate, alloy composition control, and impurity doping are very important to produce high-performance LEDs and laser diodes. Thus, I decided to adopt MOVPE as the optimal growth method for GaN and its alloys in 1979 at Matsushita Research Institute Tokyo. The second decision was a substrate. I chose sapphire as the substrate as before, because it was chemically stable even under harsh MOVPE growth condition (1000 °C in NH3 atmosphere and is relatively similar to GaN in terms of crystal symmetry). Actually the fact that today’s GaN crystals and LEDs are mostly grown on sapphire by MOVPE proves that these decisions were not wrong. MOVPE has more fractions in the other ways. The same thing with gallium aluminum nitride.

ECS Publications Authored by Isamu Akasaki (Partial List) •

I. Akasaki and H. Kobayasi, “Etching Characteristics and Light Figures of the {111} Surfaces of GaAs,” J. Electrochem. Soc., 112, 757 (1966).

•

I. Akasaki and T. Hara, “Mechanism of Vapor Growth and Properties of GaAs1-xPx,” Abstract 4, p. 8, The Electrochemical Society Extended Abstracts, Vol. I-1, Dallas, Texas, May 7-12, 1967.

•

I. Akasaki, M. Hashimoto, and T. Hara, “Epitaxial Growth of Sulfur Doped GaAs1-xPx Alloys and Their Physical Properties,”Abstract 100, p. 72, The Electrochemical Society Extended Abstracts, Vol. I-3, Dallas, Texas, May 7-12, 1967.

•

I. Asao and I. Akasaki, “Structural and Electrical Properties of Vapor-Grown GaP,” Abstract 231, p. 575, The Electrochemical Society Extended Abstracts, Vol. 72-2, Miami Beach, Florida, October 8-13, 1972.

•

Y. Shimura, N. Mazda, Y. Ohki, I. Asao, and I. Akasaki, “GaP LED Fabricated by Vapor Phase Epitaxial Growth and Zn-Diffusion,” Abstract 157, p. 374, The Electrochemical Society Extended Abstracts, Vol. 75-1, Toronto, Canada, May 11-16, 1975.

•

Y. Koide, H. Itoh, N. Sawaki, and I. Akasaki, “Epitaxial Growth and Properties of AlxGa1-XN by MOVPE,” J. Electrochem. Soc., 133, 1956 (1986).

•

I. Akasaki, H.Amano, M. Kito, K. Hiramatsu, and K. Sawaki, “Pure-Blue Electroluminescence from MG-Doped GaN Grown by MOVPE,” Abstract 673, State-of-the-Art Program on Compound Semiconductors (SOTAPOCS X), Los Angeles, California, May 7-12, 1989, J. Electrochem. Soc., 136, 229C (1989).

•

H. Amano, M. Kitoh, K. Hiramatsu, and I. Akasaki, “Growth and Luminescence Properties of MgDoped GaN Prepared by MOVPE,” J. Electrochem. Soc., 137, 1639 (1990).

•

I. Akasaki and H. Amano, “Widegap Nitride Semiconductors for UV-Blue Light Emitting Devices,” Abstract 673, p. 959, The Electrochemical Society Extended Abstracts, Vol. 93-1, Honolulu, Hawaii, May 16-21, 1993.

•

I. Akasaki and H. Amano, “Widegap Column-III Nitride Semiconductors for UV/Blue Light Emitting Devices,” J. Electrochem. Soc., 141, 2266 (1994).

YK: I see. So this is one of the most important methods? IA: Yes I think so. In 1979, I decided to adopt MOVPE. YK: Yes, that’s very important. IA: The first time we reported growth of gallium nitride by MOVPE was in 1984. YK: From your experience, do you remember if there was a moment when you felt, “Wow, this must be it?” Sometimes we get good work, research, and people may not feel it’s important but we say, “I know this is important.” Eventually someday, people recognize it. IA: It’s, yes. This is my personal, I’m not sure if this English is correct or not. (Ed. Note: Dr. Akasaki showed Dr. Kuo a sentence of Kanji , which is a Japanese version of Chinese characters on an old philosophy that means “My way is penetrated by a single thread.”) YK: Yes, I understand. That’s important. I think this was probably talked about first by Confucius. That’s basic physics. Let us summarize our conversation. What would be a very good summarization of your research or your advice? And do you think this sentence (Yue Kuo points to the philosophic sentence Prof. Akasaki showed before) would be good for the young people to stick to? No pain, no gain, I think everyone can understand it. It is very important. I really appreciate you spending the time to talk with me and the members of ECS. IA: Please give them my best regards.

Read and download at no cost, Isamu Akasaki's research published by ECS.

www.electrochem.org/akasakiresearch

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

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ECS Recognizes CIDETEQ as It Celebrates a Milestone “ECS—The Electrochemical Society extends warm congratulations and good wishes to Centro de Investigación y Desarrollo Tecnológico en Electroquímica on the milestone occasion of its 25th anniversary, commends CIDETEQ for its history of outstanding contributions, and offers best wishes for many more years of success and achievement.” So reads the scroll presented to CIDETEQ by ECS Past President Daniel Scherson at the organization’s celebratory event and symposium held in Santiago de Querétaro, Querétaro, Mexico, October 20-21, 2016.

From left to right are Julia Tagueña, deputy director of science development of the National Council of Science and Technology, Gabriel Siade, general director of CIDETEQ, Rebeca del Rocio Peniche, vice president of the Autonomous University of Querétaro, and Yunny Meas, emeritus researcher and former general director of CIDETEQ.

Dan Scherson (left), ECS past president, with Yunny Meas (right), co-chair of the CIDETEQ symposium.

In the

issue of

ECS Thanks 2016 Reviewers

The Electrochemical Society relies upon the technical expertise and judgement of the many individuals who, as reviewers, help to maintain the high standards characteristic of the Society’s peer-reviewed journals (Journal of The Electrochemical Society and ECS Journal of Solid State Science and Technology). We greatly appreciate the time and effort put forth by these individuals, and express our sincere thanks for their hard work and support.

• The summer 2017 issue of Interface will feature the ECS Industrial Electrochemistry and Electrochemical Engineering Division. The issue will be guest edited by John Staser (Ohio University). It will include articles the following technical articles (titles are tentative) that highlight activities of interest to the division: “Chlor-alkali Production, Safety, and Industrial Leadership,” by Ben Zingman; “Ammonia Electrolysis and Water Sustainability,” by Gerri Botte; “Electrochemical Extraction of Metal Commodities: A Sustainable Future?” by Antoine Allanore; “Gas Diffusion Electrodes for Energy Efficient Manufacturing of Chlorine and Other Chemicals,” by Ernesto Silva Mojica.

For a complete list of the 2016 reviewers, please go to:

• Highlights from the ECS Meeting in New Orleans. Don’t miss all the photos and news from the ECS spring 2017 meeting in New Orleans.

www.electrochem.org/reviewers_2016

• 2016 Annual Report and Year in Review will provide a look back at the Society’s highlights and achievements of 2016.

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

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Five Questions for Technical Editor Venkat Subramanian Venkat Subramanian is the Washington Research Foundation Innovation Professor of Chemical Engineering and Clean Energy at the University of Washington. His research efforts focus on computational models to bridge nextgeneration energy materials to battery management systems. Subramanian has recently been named a new technical editor of the Journal of The Electrochemical Society, concentrating in the electrochemical engineering topical interest area. What do you hope to accomplish in your role as technical editor? I am humbled and honored to be a Journal of The Electrochemical Society technical editor and I hope to help improve the impact factor and reach of our journal without losing the rigor we are known for. In particular, the electrochemical engineering topical interest area serves a critical role in taking fundamental electrochemistry to industrial applications. My current aim is to promote both traditional and new industrial applications of electrochemistry across different scales. What are some of the biggest barriers for authors and for readers in the current publishing model? Once I had a proposal rejected in my early academic career wherein the reviewer criticized me for not being aware of a recent article. I called the program officer to convey my unfortunate situation of not having access to the specified journal at my institution. While there are interlibrary loans or other such mechanism, they are not optimal for making progress in research. Research requires instantaneous and immediate access. If you don’t have it, you lose out to your competitors who have such access. Note that every proposal is (and should be) reviewed on its merit and not resources available at a particular institution. Open access is critical for researchers and scientists. What is the role of the journal impact factor in scientific publishing? Whether we like it or not, perception matters. Many academic departments have become highly interdisciplinary. Impact factor plays a big role in tenure and promotion decisions and there may be only one faculty member working in the field of electrochemistry. While I personally don’t read or benefit much from journals with high a impact factor,* I

will strive hard to promote and improve the impact factor of the Journal of The Electrochemical Society and the perception about ECS journals in the scientific community. What sets the Journal of The Electrochemical Society apart from others like it in the field? ECS and the Journal of The Electrochemical Society are inclusive and open to accepting folks and researchers from various fields. ECS is friendly towards students and I very much appreciate the fact that ECS has not increased student membership fees and student registration fees drastically. To give an example, a classic paper on battery modeling as applied for lithium-ion batteries was published in the Journal of The Electrochemical Society in 1993 by John Newman’s group. While there are hundreds of follow-on papers (many published in very high impact factor journals), even as of today, this is the standard model and improvements to these models have been minimal in my humble opinion. What role do you think electrochemistry has in solving some of society’s most pressing issues? This is an opportune time to consolidate and enhance the status and role of electrochemistry and electrochemical engineering in chemical and other engineering, chemistry, and material science curricula and departments across the country. In recent years, energy research has had a resurgence of interest due to concerns about humanity’s environmental footprint, due to issues such as the large-scale production of carbon dioxide and concerns about security and rapid global development. Technological innovations will be essential in addressing this global challenge. For fossil fuel systems, the emphasis has been on carbon dioxide mitigation and control of fine particle and other pollutant emissions. The development of next-generation biofuels from plant-based sources will require a systems approach to account for all of the associated environmental, human, and economic costs. Advances in materials to accelerate the development and implementation of cost effective solar-based technologies and energy-storage technologies will be essential. The training of a future workforce of broadly educated engineers and scientists, with strong technical skills will be essential. In this important area of research, electrochemists and electrochemical engineers are needed to play an active role in addressing these challenges. *Subramanian’s current research involves mathematical formulation, simulation, and optimization. Most math oriented publications are typically not published in high impact journals.

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

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Five Questions for Technical Editor Janine Mauzeroll Janine Mauzeroll is an associate professor at McGill University in Québec, where she leads a research group focused on topics ranging from electrochemistry in organic and biological media to electronicallyconducting polymers. Her work combines experimental and theoretical electrochemical methods and applies them to biomedical and industrial problems such as multidrug resistance in human cancer cells, neurotransmitter release, biosensor design, and high-speed scanning electrochemical microscopy. Mauzeroll has recently been named a new technical editor of the Journal of the Electrochemical Society, concentrating in the organic and bioelectrochemistry topical interest area. What do you hope to accomplish in your role as technical editor? I see no greater need than the one related to the promotion of fundamental research as a necessary partner to applied and industry-driven science. As technical editor, I will put emphasis on complete experimental and full disclosures to generate “go to” manuscripts. Moving forward, I hope to convince established researchers to continue sending in manuscripts by offering them visibility, such as special issues in or keynote addresses at symposia. We need to seek out new researchers and deliver on our promise to provide a respectful and efficient review. How has the rise of open access changed the current scholarly publishing model? The rise of open access is a game changer and step forward for science. Strongly influenced by funding agencies, who have financed the publishing costs related to figures, covers and, general publishing costs, it is now a requirement in several countries that all publicly funded research be open access. In removing this budgetary constraints, we promote a publishing model focused on a desired target audience and impact. Additionally, ECS’s Free the Science initiative will lead to a more general access to reliable and good scientific information, which is a basic requirement for further innovation and discoveries. In removing these constraints, more resources are being diverted to supporting the pillars of our research:

students and fellows. Knowledge sharing basically forces us to move away from our protectionism inclinations and focus on our next great idea. Why is access to scholarly research so important? My graduate advisor, Allen J. Bard, would often say: “We don’t want to reinvent the wheel.” If you don’t know that the wheel exists, significant loss of time and resources are unavoidable. Access to scholarly research in my mind is on equal footing to access to information and freedom of speech. As individuals, researchers, universities, and societies, it’s a basic right. What makes the peer review process such a central part of ECS’s publication process? Peer review is based on the idea that if your work is scientifically sound and has merit, unbiased colleagues will recognize this. It’s the final step in a long process of validation that started when you decided to check with your lab-mate if your calculations were correct, when your colleagues proofread your draft, when the editor perused your paper and decided to send it out for review, and when the referees delved into the work to provide you with comments to put forth the best possible paper. Peer review in ECS journals provides quality control ensuring that if you invest the time and resources to further your research with an ECS paper, you won’t be wasting eight months of your student’s time. What role does electrochemistry have in solving some of society’s most pressing issues? Electrochemistry offers some unique solutions to society’s most important problems. For example, the major problem now in application of renewable energy, is arguably not cost of production, but how to store energy produced from intermittent sources. Batteries and fuel cell electrolysis combinations are very attractive technologies to this end. In terms of providing health care to a rapidly growing and aging world population, electrochemistry has a major role to play in the development of point-of-care diagnostic tools and implantable monitoring sensors. Finally, from an environmental perspective electrochemical based sensors are well suited for remote inflow or online monitoring of water. They are low cost, easily combined with spectroscopic methods, and able to inform on quality of both natural waters and effluents from municipalities or industries.

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 14

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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 Classics–Historical Origins of the Rotating Ring-Disk Electrode

63 Tech Highlights 65 Lithium-Ion Batteries— The 25th Anniversary of Commercialization

67 Batteries and a Sustainable

liThium-ion BATTeries The 25Th AnniversAry The 25Th AnniversAry of of CommerCiAlizATion CommerCiAlizATion VOL. 25, NO. 3

www.ecsdl.org

www.electrochem.org

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

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

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Focus on Focus Issues ECS publishes focus issues of the Journal of The Electrochemical Society (JES) and the ECS Journal of Solid State Science and Technology (JSS) that highlight scientific and technological areas of current interest and future promise. These issues are handled by a prestigious group of ECS technical editors and guest editors, and all submissions undergo the same rigorous peer review as papers in the regular issues. Beginning in 2017, all focus issue papers are open access at no cost to the authors. ECS is waiving the article processing charge (APC) for all authors of focus issue papers as part of the Society’s ongoing Free the Science initiative. (See page 27 in this issue for more information about this important initiative.)

Recent JES Focus Issues • Selected Papers from IMLB 2016 with Invited Papers Celebrating 25 Years of Lithium Ion Batteries. [JES 164(1) 2017] Doron Aurbach, JES technical editor/guest editor. This focus issue is devoted to papers from the 18th International Meeting on Lithium Batteries, the most important international conference in the Li battery community. The issue includes a special section of invited papers by selected scientists and engineers considered as leaders and pioneers of the field. The papers in this issue cover a wide range of topics: new anodes, cathodes, various types of electrolyte solutions, additives, novel seperators relation to Li-ion batteries, solid state batteries, lithium-sulfur batteries, Na-ion batteries, and the development of new analytical tools in batteries research. • Biological Fuel Cells. [JES 164(3) 2017] David Cliffel, JES technical editor; Shelley D. Minteer, Scott Calabrese Barton, and Plamen Atanassov, guest editors. Among the topics covered in this focus issue are fundamental and applied developments in microbial fuel cells; the development of sensors for studying the biofilms; use of alternative members for separating anodes and cathodes, electrode materials development; and the study of the use of microbial fuel cells with the glycerol waste byproduct of biodiesel production and prototype development. • Biosensors and Micro-Nano Fabricated Electromechanical Systems. [JES 164(5) 2017] Rangachary Mukundan, JES technical editor; Peter Hesketh, William Heineman, Ajit Khosla, and Osamu Niwa, guest editors. This issue focuses on new developments in biosensing and micro-nanofabrication methods for chemical sensors, as well as biosensing systems and microA glassy carbon electrode set for spinal cord stimulation, nanodevices. Among the many illustrative of the JES Focus high-quality papers in this issue Issue on Biosensors and is an excellent review on recent Mirco-Nano Fabricated advances in Al-, Ga-, and In-doped Electromechanical Systems. ZnO nanostructures. Also included (Photo courtesy of Sam is a review of the current directions Kassegne, NSF – The Center in the field of dielectrophoresis by a for Sensorimotor Neural leading authority in this discipline. Engineering.)

Recent JSS Focus Issues • Properties, Devices, and Applications Based on 2D Layered Materials. [JSS 5(11) 2016] Fan Ren and Stefan De Gendt, 2 0technical 16 JSS editors; Lain-Jong Li and Daniel S. P. Lau, guest editors. This focus issue provides a forum for the latest research on material properties, device physics, fabrications and applications of 2D based materials including boron nitrides, black phosphorous, and transition metal dichalcogenides/ oxides beyond graphene. It features a balance between original theoretical and experimental research in basic physics, device physics, novel materials, and device structures, processes, and systems. • Ultrawide Bandgap Materials and Devices. [JSS 6(2) 2017] Fan Ren, JSS technical editor; Travis Anderson and Jennifer Hite, guest editors. This timely focus issue arose from the understanding that wide bandgap device technology has matured and become limited by fundamental material properties. A new class of ultrawide bandgap materials are emerging (AlGaN, AlN, diamond, Ga2O3, BN) that offer potentially improvided figure of merit over GaN and SiC for power devices. • Thermoelectric Materials & Devices: Phonon Engineering, Advanced Materials, and Thermal Transport. [JSS 6(3) 2017] Stefan De Gendt, JSS technical editor; Colm O’Dwyer, Renkun Chen, Jr-Hau He, Jaeho Lee, and Kafil M. Razeeb, guest editors. This issue along with the ECS symposium series “Thermoelectric and Thermal Interface Materials” provide a forum for high quality and cutting edge dissemination of research papers, review articles, and communications spanning the fundamental science of heat conduction, advances in thermoelectric and thermal interface materials, and their application to the development of heating, cooling, energy harvesting, and technology development for electronic, photonic, and related devices.

A comparison of conventional, wide bandgap, and ultrawide bandgap materials, illustrative of the JSS Focus Issue on Ultrawide Bandgap Materials and Devices.

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

societ y ne ws • Nanocarbons – In Memory of Sir Harry Kroto. [JSS 6(6) 2017] Francis D’Souza, JSS technical editor; Shunichi Fukuzumi and R. Bruce Weisman, guest editors. Prof. Kroto was best known for his pioneering role in discovering that pure carbon can exist in the form of a hollow soccer ballshaped molecule, name “buckminsterfullerene.” This breakthrough won Kroto and his colleagues Sir Harry Kroto (Photo credit: The Richard Smalley and King’s School, Canterbury). Robert Curl the 1996 Nobel Prize in Chemistry, and is generally viewed as launching the field of nanotechnology. This focus issue covers different aspects of nanocarbons basic and applied research.

Upcoming Focus Issues • JES Focus Issue on the Progress in Molten Salts and Ionic Liquids • JES Focus Issue on Oxygen Reduction and Evolution Reactions for High Temperature Energy Conversion and Storage • JES Focus Issue on Mathematical Modeling of Electrochemical Systems at Multiple Scales in Honor of John Newman To see the calls for papers for upcoming focus issues and for links to the published JES and JSS focus issues, visit

www.electrochem.org/focusissues

The new PAT-Tester First fully integrated tester for the PAT series • 16 independent channels • Compatible with all PAT series test cells • Each channel with potentiostat / galvanostat / EIS • Integrated Peltier temperature control (+5°C to +80°C) • Intuitive software with most advanced graphing capabilities

Please visit our website for more information: el-cell.com/products/tester/pat-tester-i-16

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Staff News Shannon Reed joined the ECS staff as the director of membership services in September 2016, and is responsible for managing and developing membership, member education, and award programs administered through the membership services department. Shannon earned his BA in psychology and MBA from Wesley College. He worked both a full- and part-time job in customer service throughout his college career while also completing a graduate assistantship. It was through his assistantship that he found a passion for member involvement and engagement. His role as a graduate assistant in student life encompassed managing student programs, a freshmen residence hall and reconciling student organization budgets. Upon finishing his graduate degree, Shannon accepted a position at Sam Houston State University followed by a position at the University of Houston to manage their on campus housing complexes, create new and innovative programs to engage their communities and enhance the students’ experience of oncampus living. Shannon brings a unique set of experiences to the ECS membership department. He is excited and committed to engage the member base, to encourage student chapter development and section cultivation, and to enhance the value of an ECS membership through professional development and other forms of programming. ECS Executive Director Roque Calvo shared that “we are thrilled to have Shannon on the staff. He has great enthusiasm for the value of membership in communities like ECS and his experience will be helpful in creating connections with our student constituents.”

Conference on Lithium Sulfur Batteries ECS is sponsoring the Lithium Sulfur Batteries: Mechanisms, Modelling and Materials (LiSM3) 2017 Conference, taking place April 26-27 in London. This year marks the second Li-SM3 conference, which will bring together top academics, scientists, and engineers from around the world to discuss lithium sulfur rechargeable battery chemistry research. The four main topics that will be discussed at the conference are: • Mechanisms: how and why Li-S operates in the way it does and how this presents fundamental issues that need to be resolved. • Modelling: how the Li-S chemistry can be modelled and what insights this gives us into how the cell works, in turn helping direct research. • Materials: what new materials can be used to solve the issues seen in Li-S chemistry, turning it into a viable product for the market. • Applications: system designers and users give their thoughts on what performance they need to make their products work, to help set research goals for the community. The conference will include four keynote speakers, including ECS member Ratnakumar Bugga, who will deliver a talk entitled “High Energy Density Lithium-Sulfur Batteries for NASA and DoD Applications.” For more information visit

www.lism3.org

Upcoming ECS Sponsored Meetings In addition to the ECS biannual meetings and ECS satellite conferences, ECS, its divisions, and sections, sponsor meetings and symposia of interest to the technical audience ECS serves. The following is a partial list of upcoming sponsored meetings. Please visit the ECS website (www.electrochem.org/upcoming-meetings) for a list of all sponsored meetings. • Lithium Sulfur Batteries: Mechanisms, Modelling and Materials (Li-SM3); London, UK; April 26-27, 2017, www.lism3.org • 100 Years of Canadian Electrochemistry Conference, Canadian Society for Chemistry (CSC), Toronto, ON, Canada, May 28-June 1, 2017, www.csc2017.ca • SSI-21, 21st International Conference on Solid State Ionics; Padova, Italy; June 18-23, 2017, www.chimica.unipd.it/ssi21 • Next Generation Electrochemistry (NGenE); Chicago, IL, USA; June 26-30, 2017, www.energyinitiative.uic.edu/energy/ngene • Energy, Water, and Environmental Sciences Symposium of the 46th World Chemistry Congress, São Paulo, Brazil, July 9-14, 2017, www.iupac2017.org/symposia.php#ee • The First International Semiconductor Conference for Global Challenges (ISCGC 2017); Nanjing, China; July 16-19, 2017 • 68th Annual Meeting of the International Society of Electrochemistry; Providence, RI; August 27-September 1, 2017, www.annual68.ise-online.org • 18th International Conference on Advanced Batteries, Accumulators and Fuel Cells (ABAF 18), Brno, Czech Republic, September 10-13, 2017, www.aba-brno.cz • 6th International Conference on Electrophoretic Deposition: Fundamentals and Applications (EPD-2017); Gyeongju, South Korea; October 1-6, 2017, www.engconf.org/conferences/materials-science-including-nanotechnology/electrophoreticdeposition-vi-fundamentals-and-applications 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 • Spring 2017 • www.electrochem.org

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New Division Officer Slates New officers for the spring 2017–spring 2019 term have been nominated for the following divisions. All election results will be reported in the summer 2017 issue of Interface.

Electronics and Photonics Division Chair Colm O’Dwyer, University College Cork Vice Chair Junichi Murota, Tohoku University 2nd Vice Chair Robert Lynch, University of Limerick Secretary Soohwan Jang, Dankook University Treasurer Yu-Lin Wang, National Tsing Hua University Members-at-Large Travis Anderson, Naval Research Laboratory Albert Baca, Sandia National Labs Helmut Baumgart, Old Dominion University D. Noel Buckley, University of Limerick George Celler, Rutgers University Yu-Lun Chueh, National Tsing Hua University Cor Claeys, IMEC M. Jamal Deen, McMaster University Erica Douglas, Sandia National Laboratories Manfred Engelhardt, Infineon Technologies AG Takeshi Hattori, Hattori Consulting International Jennifer Hite, Naval Research Laboratory Andrew Hoff, University of South Florida Hiroshi Iwai, Tokyo Institute of Technology Qiliang Li, George Mason University Mingha Pan, Huazhong University of Science and Technology Fred Roozeboom, Eindhoven University of Technology Jerzy Ruzyllo, Pennsylvania State University Tadatomo Suga, University of Tokyo Motofumi Suzuki, Kyoto University

Energy Technology Division Chair Andy Herring, Colorado School of Mines Vice Chair Vaidyanathan Subramanian, University of Nevada Reno Secretary William Mustain, University of Connecticut Treasurer Katherine Ayers, Proton Energy Systems, Inc. Minhua Shao, Hong Kong University of Science and Technology Iryna Zenyuk, Tufts University Members-at-Large Christina Bock, National Research Council of Canada Huyen Dinh, National Renewable Energy Laboratory James Fenton, University of Central Florida Thomas Fuller, Georgia Institute of Technology Lauren Greenlee, University of Arkansas Jean St-Pierre, University of Hawaii Kunal Karan, University of Calgary Ahmet Kusoglu, Lawrence Berkeley National Laboratory Mani Manivannan, Global Pragmatic Materials Sanjeev Mukerjee, Northeastern University Sri Narayan, University of Southern California Vito Di Noto, Universita degli Studi di Padova Peter Pintauro, Vanderbilt University Bryan Pivovar, National Renewable Energy Laboratory Krishnan Rajeshwar, University of Texas at Arlington Adam Weber, Lawrence Berkeley National Laboratory Gang Wu, University at Buffalo-SUNY Hui Xu, Giner Inc.

Get involved in your Society! ECS Annual Business Meeting and Luncheon 231st ECS Meeting in New Orleans Tuesday, May 30 All members should attend! Purchase tickets when you register Early bird: $55 Regular: $65 On-site: $75

www.electrochem.org/231

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

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ECS Division Contacts High Temperature Materials

Battery

Christopher Johnson, Chair Argonne National Laboratory johnsoncs@cmt.anl.gov • 630.252.4787 (U.S.) Marca Doeff, Vice Chair Shirley Meng, Secretary Brett Lucht, Treasurer Doron Aurbach, Journals Editorial Board Representative Corrosion

Sannakaisa Virtanen, Chair Friedrich-Alexander-Universität Erlangen-Nürnberg virtanen@ww.uni-erlangen.de • +49 09131/85-27577 (DE) Masayuki Itagaki, Vice Chair James Nöel, Secretary/Treasurer Gerald Frankel, Journals Editorial Board Representative Dielectric Science and Technology

Yaw Obeng, Chair National Institute of Standards and Technology yaw.obeng@nist.gov Vimal Chaitanya, Vice Chair Gangadhara Mathad, Secretary Puroshothaman Srinivasan, Treasurer Stefan De Gendt, Journals Editorial Board Representative

Turgut Gür, Chair Stanford University turgut@stanford.edu • 650.815.8553 (U.S.) Gregory Jackson, Sr. Vice Chair Paul Gannon, Jr. Vice Chair Sean Bishop, Secretary/Treasurer Raymond Gorte, Journals Editorial Board Representative

Industrial Electrochemistry and Electrochemical Engineering

Douglas Riemer, Chair Hutchinson Technology Inc. riemerdp@hotmail.com • 952.442.9781 (U.S.) John Staser, Vice Chair Shrisudersan (Sudha) Jayaraman, Secretary/Treasurer Venkat Subramanian, Journals Editorial Board Representative Luminescence and Display Materials

Madis Raukas, Chair Osram Sylvania madis.raukas@sylvania.com • 978.750.1506 (U.S.) Mikhail Brik, Vice Chair/Secretary/Treasurer Kailash Mishra, Journals Editorial Board Representative Nanocarbons

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

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

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 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

Mekki Bayachou, Chair Cleveland State University m.bayachou@csuohio.edu • 216.875.9716 (U.S.) Graham Cheek, Vice Chair Diane Smith, Secretary/Treasurer Janine Mauzeroll, Journals Editorial Board Representative Physical and Analytical Electrochemistry

Pawel Kulesza, Chair University of Warsaw pkulesza@chem.uw.edu.pl • +482.255.26344 (PL)) Alice Suroviec, Vice Chair Petr Vanýsek, Secretary Robert Calhoun, Treasurer David Cliffel, Journals Editorial Board Representative Sensor

Nianqiang (Nick) Wu, Chair West Virginia University nick.wu@mail.wvu.edu • 304.293.3111 (U.S.) Ajit Khosla, Vice Chair Jessica Koehne, Secretary Larry Nagahara, Treasurer Rangachary Mukundan, Journals Editorial Board Representative The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

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Division News The Battery Division The 25th anniversary of the commercialization of the lithium-ion battery (LIB) was celebrated at the PRiME 2016 meeting in Honolulu, HI. Special events included a plenary session with contributions from a number of notables who played key roles in LIB research and development, and a reception was held on Sunday night of the meeting. Roque Calvo, ECS executive director, interviewed John Goodenough, Zempachi Ogumi, Martin Winter, Mike Thackeray, and Stan Whittingham on their perspectives of this noteworthy milestone for a podcast, available now on the ECS website (http://www.ecs.podbean.com/). The Battery Division business luncheon was held on Tuesday, October 4, 2016 at the PRiME meeting. Several winners of Battery Division awards were announced at the luncheon, including recipients of the inaugural MTI/Jiang Family Foundation postdoctoral awards (Yelena Gorlin of the Technische Universität München and Liumin Suo of the Massachusetts Institute of Technology) and the new K. M. Abraham student travel awards (Jingshu Hui of the University of Illinois at Urbana-Champaign and Jarrod Milshtein of the Massachusetts Institute of Technology). Many thanks to MTI, the Jiang Family Foundation, and K. M. Abraham! At the PRiME meeting, the Battery Division Technology Award was given to Dominique Guyomard and the Battery Division Research Award shared by Yang Shao-Horn and N. Imanishi. The Battery Division Student Research Award went to B. D. Polat Karahan. Shirley Meng, currently the treasurer of the Battery Division, also received the ECS Charles W. Tobias Young Investigator Award. A reception was held in honor of all the award winners on Wednesday evening at the meeting. Jingshu Hui (left), one of two recipients of a student travel grant funded by a donation from K. M. Abraham, pictured on the right.

Yoshio Nishi, retired executive from Sony Corporation, presented the industry perspective during the PRiME meeting Sunday night reception for the 25th anniversary of LIB market launch.

Robert Kostecki (left), Battery Division chair, with Dominique Guyomard (right), 2016 recipient of the Battery Division Technology Award.

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

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From left to right are John Goodenough, Stan Whittingham, Mike Thackeray, Zempachi Ogumi, and Martin Winter. All were interviewed for an ECS podcast.

Silver/Silver Chloride Reference Electrode Stable Reference 0.047 Volts vs. SCE Widely used Non-toxic Custom glass available Always in stock. Made in USA. Robert Kostecki (left), Battery Division chair, with Liumin Suo (middle) and Xiaoping Jiang (right) of MTI. Liumin Suo was one of two recipients of the MTI/Jiang Family Foundation postdoctoral awards, initiated in 2016.

www.koslow.com “Fine electrochemical probes since 1966”

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

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websites of note by Alice H. Suroviec

Wolfram|Alpha

• Wolfram|Alpha is a computational search engine that uses an extensive collection of built-in data and algorithms to answer computation questions using a web-browser interface. It is a free website designed by the programmers behind the Mathematica software package. www.wolframalpha.com

NRELMatDB

• NRELMatDB is a computational materials database that primarily contains information on materials for renewable energy applications such as photovoltaic materials, and materials for photo-electrochemical water splitting. This website is a growing collection of computed properties of stoichiometric and fully ordered materials. It is a very useful database for those needing comparative data. NREL (National Renewable Energy Laboratory) www.materials.nrel.gov

NSF Science360 News

• This is a website hosted by the National Science Foundation (NSF) to gather breaking STEM news from a variety of sources including: directly from scientists, colleges and universities, dozens of science and engineering centers, and from peer-reviewed journals. It is a collection of video overviews, interviews, and articles. It is a great way to keep up with current topics in all areas of science. National Science Foundation www.news.science360.gov/files

About the Author Alice Suroviec is an associate professor of bioanalytical chemistry and chair of the department of chemistry and biochemistry at Berry College. She earned a BS in chemistry from Allegheny College in 2000. She received her PhD from Virginia Tech in 2005 under the direction of Mark R. Anderson. Her research focuses on enzymatically modified electrodes for use as biosensors. She is currently the vice chair of the ECS Physical and Analytical Electrochemistry Division and an associate editor for the Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry topical interest area in the Journal of the Electrochemical Society. She can be reached at: asuroviec@berry.edu.

Erratum Recently, an astute reader of Interface sent us the following message in which he identified a calculation error in the fall 2016 issue. Dear Editors, I want first to express my gratitude about this great magazine. My request concerns the article written by J. R. Dahn, J. C. Burns, and D. A. Stevens, p. 75. There is a calculation shown on p. 75 and the result helps in understanding what should be the accuracy of battery cyclers. This calculation is quite trivial but the printed result is wrong. We can read at the bottom of the second column, “1.3 Ah/[3.0 Ah × 3600] = 0.00003.” This is wrong because 1.3/(3 × 36000) = 0.0012037, which is 4 times more than the printed result. This could be considered as an innocent typo and maybe it is, but the problem is that this wrongly calculated number is then used afterwards as a specification for the main technological breakthrough of the article. Effectively on page 76, the first paragraph says, “This instrument can measure CE to an accuracy of ±0.0003 and a precision of ±0.00001.” I estimate something should be corrected. Nicolas Murer Application Engineer BioLogic SAS

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

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Development News Six Ways to Give to ECS

Editors Give Back Our editorial team has long helped ECS maintain a standard of excellence in publishing by giving of their time and expertise. Several of them have also chosen to give ECS their financial support for Free the Science by donating a portion or all of their editor stipends. This act of generosity illustrates one of the many ways that members of the ECS community can unconventionally give back to the Society. Whether it’s foregoing stipends or award prizes, waiving speaker fees or donating royalties, ECS members and leadership continue to find ways to further contribute to the Society to ensure its future. We thank the following members of our editorial team for their meaningful contributions to and leadership in the Society: Rangachary Mukundan, David Cliffel, Thomas Schmidt, Nae-Lih Wu, Dennis Peters, Jeffrey Fergus, and Charles Hussey.

Giving Societies Unveiled In celebration of our 115th anniversary, ECS has recently launched a donor recognition program to acknowledge all of the individuals and organizations supporting ECS beyond membership dues and meeting sponsorship. These gifts strengthen the Society’s future and its role as a leading independent, nonprofit scientific organization. In addition to the Carl Hering Legacy Circle, which acknowledges people who have made a planned gift or documented their future intentions to include ECS in legacy plans, ECS has created four new societies to recognize the generosity of individuals and organizations. Demonstrating deep commitment to ECS are members of the 1902 Society, which recognizes lifetime giving $20,000 or more. The following individuals and organizations will be inducted this spring: Applied Nanoflourescence; K. M. Abraham; James Acheson; Ralph Brodd; Larry Faulkner; Foundazione Oronzio de Nora Casella; Bob Gower; Intel Corporation; Katalin Voros; Bill and Melinda Gates Foundation; Jerry Woodall; and Toyota Research Institute of North America, a division of Toyota Motor Engineering & Manufacturing North America, Inc. (TEMA). We are excited and proud to be recognizing our donors for their generosity and involvement with the Society! All donors will be acknowledged in the ECS Annual Report. To learn more about how you can participate, please email development@electrochem.org or visit our “support” pages under the About ECS section of www.electrochem.org.

• • • • • •

Donate $115 in honor of our 115th anniversary Make a gift of stock Give a gift at checkout time when you’re registering for an ECS meeting, joining ECS, or renewing your membership Donate your stipend, royalties, or speaker fees Make a small recurring gift each month Make a planned gift and join the Carl Hering Legacy Circle

Visit

www.electrochem.org

and click the red DONATE button. Contact development@electrochem.org

ECS Giving Societies The 1902 Society—A Lifetime Designation Recognizing lifetime giving totaling $20,000 or more ECS Circuits Society—Recognizing Yearly Giving Levels Supercapacitors—annual giving $10,000+ Catalysts—annual giving $5,000+ Partners—annual giving exceeds $2,500+ Sustainers—annual giving exceeds $1,000+ Elements—annual giving exceeds $500+ Atoms—annual giving exceeds $100+ Renewables—annual giving exceeds $25+ The Founders Society— Honorary and Emeritus Member Recognition For honorary, emeritus, and lifetime members who have donated $150 annually The Edison Society—Fellow Recognition For ECS fellows who have donated $250 or more annually Carl Hering Legacy Circle Recognizing members who make gifts, or share their intentions to do so, through their estates, IRA charitable rollovers, or other legacy gift planning tools.

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

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Development News Hilton Worldwide Supports ECS Scientists Worldwide ECS is pleased to announce that the Hilton brand of hotels has extended its involvement with ECS by becoming a sponsor of ECS’s travel grant program for biannual meetings. ECS has long benefited from a relationship with Hilton, as they provide exceptional spaces and service during our meetings, especially as meeting attendance has grown over the years. This new collaboration, that helps the next generation of scientific leaders attend our meetings, is another example of how companies can support the Free the Science campaign. “Free the Science is not just about publishing,” says Karla Cosgriff, ECS director of development. “It’s about creating and sharing content

and ECS meetings provide an excellent venue to do just that. We are grateful and proud to partner with Hilton as their focus and values on sustainability directly align with the impact that our sciences make in the world.” “On behalf of Hilton, I am delighted to be part of the ECS’s Free the Science campaign,” said Matt Stumpf, assistant managing director of sales of Hilton Worldwide and ECS’s primary corporate contact. “I speak for everyone at Hilton when I say that we appreciate your business, embrace your mission, and look forward to collaborating on more meaningful programs just like this one.” Stay tuned to the next issue of Interface to see who received Hilton’s support.

Corrosion Division Donations In December 2016, the corrosion community lost a great mind and visionary. Hugh Isaacs made significant contributions to the field of electrochemistry, namely in the pitting corrosion area, during his career. (See the In Memoriam notice about Dr. Isaacs on page 33 of this issue.) To honor his work and influence on corrosion science, ECS, with the support of Hugh’s family, is creating a special collection of Dr. Isaacs’ work in the ECS Digital Library that will be free and open to everyone. The collection supports

ECS’s larger Free the Science initiative that will revolutionize the way our community shares research, supporting the advancement of our sciences and ensuring that ECS continues to thrive as an independent, nonprofit scientific society. If you would like to make a contribution to support the Hugh Isaacs Collection in the ECS Digital Library, please email development@electrochem.org or donate online at www.electrochem.org and indicate “Isaacs Collection” in the recognition section of the donation form.

Board Giving—A Vote of Thanks! In 2016 our board members gave so much more than their time, commitment, and leadership. ECS is proud to announce that board giving has reached an all-time high at 77% participation, with 100% participation from the executive committee. Their leadership in the organization is unprecedented and we appreciate their willingness to give back to ECS in numerous ways!

For more resources on giving visit:

www.electrochem.org/give

Members of the board and donors with donor event featured speaker, John B. Goodenough (seated), at PRiME. 26

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

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Development News Free the Science Week in April This year ECS is celebrating its 115th anniversary and we will be marking this milestone all year long in each of our program areas. In 1902, ECS (known then April 3-9, 2017 as The American Electrochemical Society) formed as a venue to discuss, publish, and disseminate important developments in the growing field of electrochemistry. Today it is more important than ever that we continue to advance and spread the good work of our community. To meet these needs and fulfill our mission, we have launched the Free the Science campaign that aims to provide open access to the entire ECS Digital Library, for authors and readers. This year, in honor of our anniversary, we will take down all paywalls in our Digital Library twice. Once in April for Free the Science Week, marking the first meeting of ECS, and once in October for International Open Access Week. Stay tuned for more information and please share this exciting news with your colleagues!

Free the Science News Do you want to hear more about open access? Our Free the Science monthly news blast will keep you updated with timely issues in open access, highlighting important international trends and reminding you about special events.

Visit

www.freethescience.org and click the Subscribe button.

Expanded Free the Science Advisory Board ECS has expanded the Free the Science Advisory Board to include important voices in scholarly communications as well as members of the board of directors. The advisory board, which is broken into three subcommittees for fundraising, finances, and open access, now includes: Co-Chairs E. J. Taylor (Faraday Technologies) Tetsuya Osaka (Waseda University) Members Craig Arnold (Princeton U.) Cor Claeys (imec) Lili Deligianni (IBM) Gerald Frankel (Ohio State U.) Fernando Garzon (U. of New Mexico) Robert Kostecki (Lawrence Berkeley National Lab) Louise Page (PLOS) Matt Spitzer (COS) Brian Stoner (RTI International) Stuart Swirson (ASME) Esther Takeuchi (Stony Brook U.) Greg Tannenbaum (SPARC) Martin Winter (Münster U.)

Ex-Officio Members Christina Bock (National Research Council of Canada) Dennis Hess (Georgia Institute of Technology) James Fenton (U. of Central Florida) Jeffrey Fergus (Auburn U.) Yue Kuo (Texas A&M U.) Johna Leddy (U. of Iowa) Krishnan Rajeshwar (U. of Texas at Arlington) Robert Savinell (Case Western Reserve U.) Dan Scherson (Case Western Reserve U.) Staff Liaisons Roque Calvo, ECS Executive Director and CEO Karla Cosgriff, ECS Director of Development Tim Gamberzky, ECS COO Mary Yess, ECS Deputy Executive Director, CCO, and Publisher

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

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“E

Special Meeting Section l NEW ORLEANS, LA

• Five days of technical programming across 46 symposia • Over 2,000 abstracts • More than 1,700 oral presentations, with 400+ invited speakers • 375 posters during two evenings of poster sessions • 16 hours of exhibit hall time over three days

e ECS a th

l S e a rc

oin us at this international conference as scientists, engineers, and researchers from academia, industry, and government laboratories come together to share results and discuss issues on related topics, through oral presentations, poster sessions, panel discussions, tutorial sessions, short courses, exhibits, and more. The unique blend of electrochemical and solid state science and technology at an ECS meeting provides you with an opportunity to learn and exchange information on the latest scientific developments across a variety of interdisciplinary areas in a peer-to-peer forum. If that isn’t enough, you will be able to spend your downtime in the center of one of the most enjoyable cities in the U.S. Not just the home of jazz music, New Orleans is also famous for its rich history, colorful neighborhoods, world class cuisine, and never ending good times!

ps to re l

Hilton New Orleans Riverside

NEW ORLEANS

May 28-June 1, 2017

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Photo by Richard Nowitz

231st ECS MEETING

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• Daily morning coffee breaks • Complimentary WiFi in meeting rooms • Special program for nontechnical registrants

The ECS Lecture Monday, May 29

“A Risk Look at Energy Development” Way Kuo, City University of Hong Kong

Way Kuo is president at City University of Hong Kong. He is a member of the U.S. National Academy of Engineering, and a foreign member of the Chinese Academy of Engineering and Russian Academy of Engineering. Professor Kuo specializes in design for the reliability of electronics systems and also nuclear energy, and is the author of Critical Reflections on Nuclear and Renewable Energy (2014).

Award Winning Speakers (Check the meeting app for times.) Society Award Winning Speakers Doron Aurbach, Bar Ilan University ECS Allen J. Bard Award in Electrochemical Science

Paul Kohl, Georgia Institute of Technology ECS Gordon E. Moore Medal for Outstanding Achievement in Solid State Science and Technology

Division Award Winning Speakers Hiroshi Iwai, Tokyo Institute of Technology Dielectric Science and Technology Division Thomas D. Callinan Award

Muhammad Boota, Drexel University Industrial Electrochemistry and Electrochemical Engineering Division H. H. Dow Memorial Student Achievement Award

D. Noel Buckley, University of Limerick Electronics and Photonics Division Award

Bahareh Alsadat Tavakoli Mehrabadi, University of South Carolina Industrial Electrochemistry and Electrochemical Engineering Division Student Achievement Award

Hubert Gasteiger, Technische Universität München Energy Technology Division Research Award Ahmet Kusoglu, Lawrence Berkeley National Laboratory Energy Technology Division Supramaniam Srinivasan Young Investigator Award Antoni Forner-Cuenca, Paul Scherrer Institut (PSI) / ETH Zürich Energy Technology Division Graduate Student Award 28

Shunichi Fukuzumi, Osaka University Nanocarbons Division Richard E. Smalley Research Award Viola Birss, University of Calgary Physical and Analytical Electorchemistry Division David S. Grahame Award The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

Short Courses Sunday, May 28

ECS short courses are all-day classes designed to provide students and professionals with an in-depth education on a wide range of topics. Taught by academic and industry experts, the small class size makes for an excellent opportunity for personalized instruction helping both novices and experts advance their technical expertise and knowledge.

Short Course 1 Technical Leadership and Decision Making Dennis Hess, Instructor

Short Course 2 Fundamentals of Electrochemistry: Basic Theory and Thermodynamic Methods Jamie Noël, Instructor

Short Course 3 Imaging, Modeling, and Simulation of Li-Ion Battery Microstructures in 2D, 3D, and 4D Jeff Gelb and Steve Harris, Instructors

Professional Development Workshops (Check the meeting app for times) These are offered as a two-part series to provide attendees with an opportunity to enhance their networking and career search skills.

Special Events (Check the meeting app for times) Sunday Evening Get Together

General Student Poster Session

All attendees are welcome to this event that kick starts the week with tasty desserts, libations, and ample time to mingle.

A long standing ECS tradition, with cash prizes awarded for the top presentations by eligible students.

Receptions in Honor of H. Russell Kunz, and Jean Lessard, Albert Fry, and Dennis Peters

Student Mixer This is a key networking opportunity, a must for all student attendees!

Come raise a salute in honor of these outstanding scientists, teachers, and friends.

Annual Society Business Meeting and Luncheon Join us as we celebrate the many successes of 2016 and look forward to an even brighter future! Since 1902, ECS has facilitated advancements in electrochemistry and solid state science and technology. Learn more about our programs and history at the ECS booth in the exhibit hall and consider making a $115 gift to commemorate our anniversary. Visit www.electrochem.org and click Donate.

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

Special Meeting Section l NEW ORLEANS, LA

Essential Elements for Employment Success Résumé Review Panel of Professionals

Symposium Topics, Organizers, and Sponsoring Divisions A — Batteries and Energy Storage

D — Dielectric Science and Materials

A01 — Battery and Energy Technology Joint General Session

A. Manivannan, S. R. Narayan, Robert Kostecki, Christopher Johnson, Plamen Atanassov Energy Technology, Battery

A02 — Large-Scale Energy Storage 8

Trung Nguyen, Adam Weber Energy Technology, Battery, Industrial Electrochemistry and Electrochemical Engineering

Applications 8 Durga Misra, Peter Hesketh, Zia Karim, Stefan De Gendt, Yaw Obeng, P. Srinivasan, Slava V. Rotkin CD/USB Dielectric Science and Technology, Sensor, Nanocarbons

D02 — Plasma Nano Science and Technology

Uros Cvelbar, Mahendra Sunkara, Peter Mascher Dielectric Science and Technology

A03 — Battery Electrolytes

Wladyslaw Wieczorek, Patrik Johansson, Marek Marcinek, Brett Lucht, Vito Di Noto Battery, Physical and Analytical Electrochemistry

D01 — Emerging Materials for Post CMOS Devices/Sensing and

CD/USB

E — Electrochemical/Electroless Deposition E01 — Green Electrodeposition 4 CD/USB

A04 — Battery Safety

Christopher Orendorff, Bor Yann Liaw, D. H. Doughty, Thomas Barrera, Guangsheng Zhang, Gerardine Botte Battery, Industrial Electrochemistry and Electrochemical Engineering

Sudipta Roy, Giovanni Zangari, Sachio Yoshihara Electrodeposition

E02 — Metallization of Flexible Electronics

Luca Magagnin, Yosi Shacham-Diamand, Takayuki Homma Electrodeposition

F — Electrochemical Engineering

Special Meeting Section l NEW ORLEANS, LA

A05 — Lithium-Ion Batteries and Beyond

Gary Koenig, Christopher Johnson, Yangchuan Xing, James Wu Battery

A06 — Battery Student Slam 1

Brett Lucht, Ying Meng, John Muldoon, Robert Kostecki, Marca Doeff, Gary Koenig Battery

B — Carbon Nanostructures and Devices B01 — Carbon Nanostructures for Energy Conversion

Jeffrey Blackburn, Vito Di Noto, Plamen Atanassov, Michael Arnold, Stephen Doorn, David Cliffel, Christina Bock Nanocarbons, Energy Technology, Physical and Analytical Electrochemistry

B02 — Carbon Nanostructures in Medicine and Biology

Tatiana DaRos, Daniel Heller, Fotios Papadimitrakopoulos, Ardemis Boghossian, Mekki Bayachou, James Burgess Nanocarbons, Organic and Biological Electrochemistry

B03 — Carbon Nanotubes - From Fundamentals to Devices:

In Memory of Mildred Dresselhaus Stephen Doorn, Yury Gogotsi, Pawel Kulesza, Ming Zheng, Slava V. Rotkin, R. Bruce Weisman Nanocarbons, Physical and Analytical Electrochemistry

B04 — Endofullerenes and Carbon Nanocapsules

Shangfeng Yang, Alan Balch, Luis Echegoyen, Steven Stevenson Nanocarbons

B05 — Fullerenes - Chemical Functionalization, Electron Transfer, and

Theory: In Memory of Robert Haddon Dirk Guldi, Nazario Martín, Francis D’Souza Nanocarbons

B06 — Graphene and Beyond: 2D Materials

Michael Arnold, Yaw Obeng, Haim Grebel, Richard Martel, Andreas Hirsch, Slava V. Rotkin Nanocarbons, Dielectric Science and Technology, Physical and Analytical Electrochemistry

B07 — Inorganic/Organic Nanohybrids for Energy Conversion

Hiroshi Imahori, Vaidyanathan Subramanian, Prashant Kamat Nanocarbons, Energy Technology

B08 — Porphyrins, Phthalocyanines and Supramolecular Assemblies

Karl Kadish, Roberto Paolesse, Tomas Torres, Nathalie Solladie, Norbert Jux Nanocarbons, Organic and Biological Electrochemistry, Physical and Analytical Electrochemistry

C — Corrosion Science and Technology C01 — Corrosion General Session

Sannakaisa Virtanen, Masayuki Itagaki Corrosion

F01 — Electrochemical Engineering General Session

Douglas Riemer, Luis Diaz, John Staser Industrial Electrochemistry and Electrochemical Engineering

F02 — Characterization of Porous Materials 7

John Staser, Christina Bock Industrial Electrochemistry and Electrochemical Engineering, Battery, Energy Technology

F03 — Multiscale Modeling, Simulation, and Design

Venkat Subramanian, Scott Calabrese Barton, John Harb, Luis Diaz, Gerardine Botte Industrial Electrochemistry and Electrochemical Engineering, Energy Technology

F04 — Applications of Electrochemistry to Additive Manufacturing

Maria Inman, E. Taylor, Richard Alkire, Douglas Riemer Industrial Electrochemistry and Electrochemical Engineering, Electrodeposition

F05 — Pulse and Pulse Reverse Electrolytic Processes

E. Taylor, Elizabeth Podlaha, Maria Inman Industrial Electrochemistry and Electrochemical Engineering, Electrodeposition

G — Electronic Materials and Processing G01 — Processes at the Semiconductor Solution Interface 7

Colm O’Dwyer, Arnaud Etcheberry, Andrew Hillier, Robert Lynch, Philippe Vereecken, Heli Wang, Mahendra Sunkara, D. Noel Buckley Electronics and Photonics, Dielectric Science and Technology, Electrodeposition, Energy Technology, Physical and Analytical CD/USB Electrochemistry

G02 — Silicon Compatible Materials, Processes, and Technologies for

Advanced Integrated Circuits and Emerging Applications 7 Fred Roozeboom, Kuniyuki Kakushima, P. J. Timans, E. P. Gusev, Zia Karim, Stefan De Gendt, Hemanth Jagannathan Electronics and Photonics, Dielectric Science and Technology CD/USB

H — Electronic and Photonic Devices and Systems H01 — Wide Bandgap Semiconductor Materials and Devices 18

Vidhya Chakrapani, Scott Calabrese Barton, John Zavada, Soohwan Jang, Travis Anderson, Jennifer Hite CD/USB Electronics and Photonics, Energy Technology

H02 — Solid-State Electronics and Photonics in Biology and Medicine 4

Yu-Lin Wang, Wenzhuo Wu, Andrew Hoff, M. Deen, Chih-Ting Lin, Zoraida Aguilar, Lluis Marsal, Zong-Hong Lin CD/USB Electronics and Photonics, Sensor

H03 — Properties and Applications of 2-Dimensional Layered Materials 2

Lain-Jong Li, Jr-Hau He, Shu Ping Lau, Joshua Robinson, D. Landheer, Richard Martel, Colm O’Dwyer Electronics and Photonics, Dielectric Science and Technology, Nanocarbons

CD/USB

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

I — Fuel Cells, Electrolyzers, and Energy Conversion

M — Sensors

I01 — Oxygen or Hydrogen Evolution Catalysts for Water Electrolysis 3 Hui Xu, Vijay Ramani, Pawel Kulesza Energy Technology, Industrial Electrochemistry and Electrochemical CD/USB Engineering, Physical and Analytical Electrochemistry

M01— Sensors, Actuators and Microsystems General Session

I02 — Materials for Low Temperature Electrochemical Systems 3

M02— Nano/Bio Sensors

Minhua Shao, Peter Pintauro, Elizabeth Biddinger, Svitlana Pylypenko Energy Technology, Industrial Electrochemistry and Electrochemical Engineering, Physical and Analytical Electrochemistry

I03 — Renewable Fuels via Artificial Photosynthesis 2

Nianqiang (Nick) Wu, Deryn Chu, Huyen Dinh, Nicolas Gaillard, Pawel Kulesza, Ayyakkannu Manivannan, Eric Miller, Vaidyanathan Subramanian, Heli Wang Energy Technology, Organic and Biological Electrochemistry, Physical and Analytical Electrochemistry, Sensor

Alex Simonian, Jessica Koehne, Raluca-Ioana Stefan-van Staden, Leyla Soleymani, Larry Nagahara, M. Sailor, Sushanta Mitra, Daniel Heller, Ajit Khosla, Ramaraja Ramasamy Sensor, Nanocarbons, Organic and Biological Electrochemistry

Z — General Topics Z01 — General Student Poster Session

Venkat Subramanian, V. Chaitanya, Kalpathy Sundaram, P. Pharkya, Alice Suroviec All Divisions

Z02 — Nanotechnology General Session

I04 — Solid-Gas Electrochemical Interfaces 2 - SGEI 2

Bilge Yildiz, Stuart Adler, Ellen Ivers-Tiffée, Tatsuya Kawada High Temperature Materials

Jin-Woo Choi, Peter Hesketh, Dong-Joo Kim, Ajit Khosla, Nianqiang (Nick) Wu, Rangachary Mukundan, M. Sailor, Praveen Sekhar Sensor

CD/USB

I05 — From Electrode to Systems: Invited Perspectives and Tutorials on

I06 — Crosscutting Metrics and Benchmarking of Transformational Low-

Carbon Energy-Conversion Technologies Huyen Dinh, Eric Miller Energy Technology

K — Organic and Bioelectrochemistry K01 — The 80th Birthday Trifecta in Organic Electrochemistry in Honor of

Z03 — Solid State Topics General Session

Kalpathy Sundaram, O. Leonte, Gary Hunter, Kiyoshi Shimamura, Hiroshi Iwai, Meng Tao Dielectric Science and Technology, Electronics and Photonics, Energy Technology, Luminescence and Display Materials, Organic and Biological Electrochemistry, Sensor

Z04 — Sustainable Materials and Manufacturing 2

Gerardine Botte, John Harb, Nianqiang (Nick) Wu, S. R. Narayan, E. Taylor, Arumugam Manthiram, John Stickney, Katherine Ayers, Gautam Banerjee, Gregory Jackson All Divisions, Interdisciplinary Science and Technology Subcommittee

Jean Lessard, Albert Fry, and Dennis Peters Mekki Bayachou, Flavio Maran Organic and Biological Electrochemistry

K02 — Electron Transfer in Biological Systems

James Burgess, David Cliffel, Shelley Minteer, Daniel Heller, Alice Suroviec, William Mustain Organic and Biological Electrochemistry, Nanocarbons, Physical and Analytical Electrochemistry

L — Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry

Each symposium will publish an issue of ECS Transactions. Issues are available in CD/USB CD/USB format or as Electronic (PDF) editions. Preordered CD/USB editions can be picked up at the meeting.

L01 — Physical and Analytical Electrochemistry, Electrocatalysis,

and Photoelectrochemistry General Session and Grahame Award Symposium Alice Suroviec, Andrew Hillier Physical and Analytical Electrochemistry

L02 — Ion-Conducting Polymeric (or Polymer-based) Materials

Vito Di Noto, Ahmet Kusoglu, Stephen Paddison Physical and Analytical Electrochemistry, Battery, Energy Technology

L03 — Electrochromic and Chromogenic Materials

Pawel Kulesza, Aline Rougier, Xungang Diao, Delia Milliron Physical and Analytical Electrochemistry

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

Special Meeting Section l NEW ORLEANS, LA

Fuel Cell Technology in Memory of H. Russell Kunz Hui Xu, James Fenton, Vijay Ramani, Shimshon Gottesfeld, Hubert Gasteiger, Adam Weber, Thomas Zawodzinski, Thomas Schmidt Energy Technology, Industrial Electrochemistry and Electrochemical Engineering, Physical and Analytical Electrochemistry

O. Leonte, Z. Chen, Leyla Soleymani All Divisions, Interdisciplinary Science and Technology Subcommittee

Volume 77– N e w O r l e a n s , L o u i s i a n a

from the New Orleans, LA meeting, May 28—June 1, 2017

The following issues of ECS Transactions are from symposia held during the New Orleans meeting. All issues are available in electronic (PDF) editions, which may be purchased, beginning on May 19, 2017, by visiting www.electrochem.org/pubsstore. 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.)

Available Issues Vol. 77 Battery Electrolytes No. 1 CD/USB................... M $130.00, NM $163.00 PDF ......................... M $118.49, NM $148.11

Vol. 77 Wide Bandgap Semiconductor Materials and Devices 18 No. 6 CD/USB................... M $96.00, NM $119.00 PDF ......................... M $80.86, NM $101.08

Vol. 77 Emerging Materials for Post CMOS Devices/ No. 2 Sensing and Applications 8 CD/USB................... M $96.00, NM $119.00 PDF ......................... M $58.09, NM $73.85

Vol. 77 Solid-State Electronics and Photonics in Biology and Medicine 4 No. 7 CD/USB................... M $105.00, NM $131.00 PDF ......................... M $95.53, NM $119.41

Vol. 77 Plasma Nano Science and Technology No. 3 CD/USB................... M $96.00, NM $119.00 PDF ......................... M $73.83, NM $91.04

Vol. 77 Properties and Applications of 2-Dimensional No. 8 Layered Materials 2 CD/USB................... M $96.00, NM $119.00 PDF ......................... M $59.08, NM $73.85

Vol. 77 Processes at the Semiconductor Solution Interface 7 No. 4 CD/USB................... M $118.00, NM $147.00 PDF ......................... M $107.03, NM $133.79

Vol. 77 Oxygen or Hydrogen Evolution Catalysts for Water Electrolysis 3 No. 9 CD/USB................... M $118.00, NM $147.00 PDF ......................... M $93.80, NM $133.79

Vol. 77 Silicon Compatible Materials, Processes, and No. 5 Technologies for Advanced Integrated Circuits and Emerging Applications 7 CD/USB................... M $96.00, NM $119.00 PDF ......................... M $74.84, NM $95.33

Vol. 77 Solid-Gas Electrochemical Interfaces 2 – SGEI 2 No. 10 CD/USB................... M $103.00, NM $129.00 PDF ......................... M $93.80, NM $117.25

Forthcoming Issues Following the conclusion of the New Orleans meeting, each of the below symposium will publish an issue of ECS Transactions. These issues, once available, can be purchased as electronic (PDF) editions, by visiting www.electrochem.org/pubsstore. Please visit the ECS website for all issue pricing and ordering information. A01: Battery and Energy Technology Joint General Session

G03: Organic Semiconductor Materials, Devices, and Processing 6

A02: Large-Scale Energy Storage 8

I02: Materials for Low Temperature Electrochemical Systems 3

A04: Battery Safety

I03: Renewable Fuels via Artificial Photosynthesis 2

A05: Lithium-Ion Batteries and Beyond

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

A06: Battery Student Slam 1 B01: Carbon Nanostructures for Energy Conversion B02: Carbon Nanostructures in Medicine and Biology

I06: Crosscutting Metrics and Benchmarking of Transformational Low-Carbon Energy-Conversion Technologies

B03: Carbon Nanotubes - From Fundamentals to Devices

K01: The 80th Birthday Trifecta in Organic Electrochemistry in Honor of Jean Lessard, Albert Fry, and Dennis Peters

B04: Endofullerenes and Carbon Nanocapsules

K02: Electron Transfer in Biological Systems

B05: Fullerenes - Chemical Functionalization, Electron Transfer, and Theory: In Memory of Professor Robert Haddon

L01: Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry General Session and Grahame Award Symposium

B06: Graphene and Beyond: 2D Materials B07: Inorganic/Organic Nanohybrids for Energy Conversion B08: Porphyrins, Phthalocyanines and Supramolecular Assemblies C01: Corrosion General Session E01: Green Electrodeposition 4 E02: Metallization of Flexible Electronics F01: Electrochemical Engineering General Session 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

L02: Ion-Conducting Polymeric (or Polymer-based) Materials L03: Electrochromic and Chromogenic Materials L04: Electroanalytical Aspects of Environmental and Groundwater Problems M01: Sensors, Actuators and Microsystems General Session M02: Nano/Bio Sensors Z01: General Student Poster Session Z02: Nanotechnology General Session Z03: Solid State Topics General Session Z04: Sustainable Materials and Manufacturing 2

Ordering Information To order any of these recently-published titles, please visit the ECS Online Store, www.electrochem.org/pubsstore Email: customerservice@electrochem.org 2/24/17

socie PEOPLE t y ne ws

In Memoriam memoriam Hugh S. Isaacs

Henry F. Ivey, Jr.

(1936–2016)

(1921–2016)

Isaacs, an ECS member since 1967, was a passionate ambassador for electrochemical science and engineering and was a leading figure in the corrosion community for over four decades. He passed away on Long Island on December 5, 2016. His work has influenced a generation of electrochemists across the world. Dr. Isaacs obtained his bachelor’s degree in metallurgy from The University of Witwatersrand in his native South Africa, and then moved to Imperial College London, where he obtained a diploma in nuclear engineering, and a PhD in metallurgy in 1963. His doctoral work was his first foray into electrochemistry, working with molten salt-metal systems. Following the completion of his studies, Dr. Isaacs worked at the Atomic Energy Research Establishment at Harwell and then for the South African Atomic Energy Board in Pretoria, continuing his work in high temperature electrochemistry. In 1967, he moved to the Department of Applied Science at Brookhaven National Laboratory where, with a brief period at Oak Ridge National Laboratory (19721974), he was to spend the rest of his professional life. Dr. Isaacs made seminal contributions to the field of localized corrosion, and was a key innovator in the application of new techniques, notably in the use of synchrotron radiation to study localized dissolution processes and in scanning electrochemical systems to map surface reactivity. Dr. Isaacs published over 130 papers and was the recipient of numerous prestigious awards including an Outstanding Achievement Award, U.S. Department of Energy (1983); the Sam Tour Award, Corrosion Section, ASTM (1983); H. H. Uhlig Award of The Electrochemical Society (1993); and the W. R. Whitney Award from NACE International (2000). Before he passed, Dr. Isaacs was confirmed as the latest awardee of the UK Institute of Corrosion U. R. Evans Award, which will be awarded posthumously in 2017. Dr. Issacs will be remembered by all who knew him as a quiet and modest, but inspirational colleague, generous with both his time and ideas. He was a kind and supportive mentor to younger scientists, and a man who never lost his scientific curiosity and excitement for new ideas. The electrochemical community has lost a brilliant scientist, an esteemed colleague, and above all a dear friend. He will be greatly missed. He was an ECS fellow and emeritus member. ugh

Information for this notice was contributed, in part, by Mary Ryan. To honor his work and influence on corrosion science, The Electrochemical Society, with the support of Hugh’s family and friends, is creating a special collection of Hugh’s work in the ECS Digital Library that would be free and open to everyone: The Hugh Isaacs Collection in the ECS Digital Library. If you would like to contribute, contact development@electrochem.org, or see the donation instructions on page 26 of this issue.

enry Ivey

joined ECS in 1955 and became an honorary member in 1980, and served, for several years, as an editor of the Journal of The Electrochemical Society. Dr. Ivey was born in Augusta, Georgia, June 16, 1921. He graduated from the Academy of Richmond County in Augusta. In 1940 he received an AB degree summa cum laude, with a major in physics and a minor in mathematics; in 1940 he was awarded a master’s degree in science. He spent WWII at MIT as a civilian scientist working for the United States Office of Scientific Research and Development. In 1944, he was awarded a PhD in physics from MIT with a thesis entitled, “Devoted to Special War Research.” The thesis work was on display devices for the microwave radar systems. In 1946, he joined the Research Department of Westinghouse Corporation in Bloomfield, New Jersey. He was then the manager of the Phosphor Division, which was devoted to luminescence in general and the recently discovered phenomenon of electroluminescence. In August 1957, he popularized this phenomenon in Scientific American. He published Electroluminescence and Related Effects (Academic Press, New York 1963). Around that time he was appointed manager of the Optical Physics Department of Westinghouse Research and Development Center in Pittsburgh, which lasted twelve years. His last Westinghouse appointment was as an advisory scientist for technology assessment. He retired from Westinghouse in 1986, having worked for the same company for almost 40 years. He was author or coauthor of 52 published papers and 3 patents. His hobby was jazz and he donated his immense collection of recordings to Florida Atlantic University, where it occupies two rooms with floor-to-ceiling bookshelves. He was a member of the Dielectric Science and Technology Division. Henry Ivey passed away September 28, 2016.

Florian B. Mansfeld (1938–2016)

Mansfeld, born on March 6, 1938, was an ECS member since 1969. He passed away on October 12, 2016 in Thousand Oaks, California. Over the years, Dr. Mansfeld played a very important role in The Electrochemical Society. He was a recipient of the ECS H. H. Uhlig Award (2002) and the Vittorio de Nora Award (2006). For his extensive research into corrosion science and engineering, he received the Alexander von Humboldt Research Award [Germany] in 1979 and 1983, Sam Tour Award of ASTM in 1984, the Wesley W. Horner Award of ASCE in 1993, and the prestigious Willis Rodney Whitney Award of NACE in 1988, among others. Florian was a fellow of both NACE and ECS. He maintained a very high professional profile and active involvement at meetings of The Electrochemical Society, NACE, Gordon Research Conferences, and the recurring Fischer Symposium in Germany (with his life-long friend Wolfgang Lorenz, who founded the Symposium in the 1970s). He was a highly-cited author of articles related to corrosion, its measurement, control, understanding, and mitigation. He was particularly well known lorian

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In Memoriam memoriam (continued from previous page)

for his application of electrochemical methods such as impedance spectroscopy to the measurement of corrosion rates under complicated conditions, and was a leader and champion in that research area. His research on practical corrosion systems and problems, and his passion for scientific objectivity, openness, and accuracy, were his trademarks throughout his entire career. Florian was a commanding figure at scientific meetings, in much the same way as his mentor and long-time friend, Herb H. Uhlig. Both have left their mark on the scientific/corrosion communities. Dr. Mansfeld received his BS in physics in 1960, his MS in physical chemistry in 1964 and his PhD in physical chemistry from the University of Munich, Germany. After a post-doc at MIT in the laboratory of H. H. Uhlig, he joined Rockwell International Science Center in Thousand Oaks where he was manager of the Interfacial Phenomena Department. During this period, he received the prestigious Alexander von Humboldt Award. From 1985 to 2013, he was Professor of Materials Science and Engineering at the University of Southern California, where he served as chair of the department for nine years. He was appointed Professor Emeritus in August 2013. As is the case with many truly talented people, one only begins to truly appreciate their insight and contributions in hind-sight, often when they are no longer with us and making those contributions. Dr. Mansfeld’s positive influence will be missed by the corrosion science and engineering community. He was an ECS emeritus member and a past chair of the Corrosion Division. Information for this notice was contributed, in part, by Martin Kendig and Barry MacDougall.

Roger Washburne Staehle (1934–2017)

oger W. Staehle, became an ECS member in 1965 and made enormous scientific and engineering contributions to these fields, but was best known for his friendship, generosity, and drive to support and recognize the work of others. Dr. Staehle was born on February 4, 1934 and went on to study metallurgical engineering at The Ohio State University, graduating in 1957. Following this extensive education in nuclear technology, he returned to get his PhD at OSU and graduated in 1965. After, he immediately joined the metallurgical engineering faculty and then founded the Fontana Corrosion Center (FCC), building it into one of the largest and most influential academic corrosion laboratories in the world. By the end of the 1970s, Dr. Staehle had a group of over 40 people in the FCC, with a major focus on materials degradation in commercial nuclear power. He educated many dozens of graduate students and hosted visiting scientists from around the world, many of whom assumed very responsible positions and effected important technical advances. He left OSU in 1979 to become dean of the Institute of Technology at the University of Minnesota (College of Science and Engineering), a position he held until 1983. Dr. Staehle received many awards and was a fellow of NACE International and The Electrochemical Society. He received the W. R. Whitney Award from NACE. He was elected to the U.S. National Academy of Engineering in 1978, when he was 44 years

old, becoming one of the youngest to be elected to NAE. In the last 20 years, Dr. Staehle focused considerable efforts to build collaborative interactions in China, aimed primarily, but not exclusively, on issues related to materials degradation in commercial nuclear power reactors. He initiated and organized four major symposia in China, the first of which was “Materials Problems in Light Water Nuclear Power Plants: Status, Mitigation, Future Problems,” in 2005. Subsequent symposia were related to water chemistry, welding issues, and failure and mitigation. Roger was single-handedly responsible for attracting the best of the world’s experts in each aspect of each symposium, and each symposium attracted about 200 engineers and scientists from throughout China. In 2008, Dr. Staehle conceived and organized a week-long conference on stress corrosion crack (SCC) initiation in Beaune, France involving 130 scientists who met to exchange ideas, define critical experiments, and discuss experimental techniques. Many similar efforts were instigated by Roger in areas such as lead and sulfur effects in steam generators, alloys with improved SCC resistance, etc. In 2010, Roger undertook a massive effort to bring together world experts in diverse fields who could speak to the issues of fundamental understanding and modeling of SCC. The series of four annual meetings brought together about 40 international experts for a week-long workshop, “Quantitative Micro-Nano (QMN) Approach to Predicting SCC of Fe-Cr-Ni Alloys.” Roger realized the importance of such a meeting, defined the content, identified and invited the experts, and solicited support from about a dozen agencies and companies. Unfortunately, Dr. Staehle became ill after a fall during his morning walk. He died several weeks later on January 16, 2017, with members of his family at his bedside. He is survived by his brother, George, and his children, Elizabeth, Eric, Sara, Erin and William. He was a member of the Corrosion Division. Information for this notice was contributed, in part, by Mary Ilg and Peter Andresen.

Samares Kar (1942–2017)

Kar became an ECS member in 1998 and was a founding co-organizer of the Symposium on Physics and Technology of High-k Gate Dielectrics. In this capacity, he maintained rigorous standards and made the symposium one of the most successful in ECS history, attracting wide participation by lead researchers in the field. Dr. Kar was born in Kolkata, India on January 4, 1942 and he received his BTech degree in 1962 from the Indian Institute of Technology, Kharagpur, and his MS and PhD degrees from Lehigh University in 1968 and 1970 respectively, all in electrical engineering. Prior to his graduate studies, he worked as a design engineer and a project engineer at companies in Hamburg, Germany. Post graduate studies, Dr. Kar joined the Fraunhofer Institute for Applied Solid State Physics, Freiburg, Germany, as a member of its scientific staff, and remained there till 1974. He then returned to India to become a member of faculty at the Indian Institute of Technology, Kanpur, where he worked for over three decades. At IITK he developed several demanding courses in solid state electronics and contributed to the entry of many bright young students into the field and their eventual emergence as amares

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In Memoriam memoriam stalwarts. He single-handedly built up a first class MOS fabrication and characterization facility to enable his research and maintained it with exacting care. It was truly a formidable achievement in an era and environment with little support or understanding of semiconductors. His research interests have included MOS tunnel devices, Schottky barriers, MOS admittance spectroscopy, ion-beaminduced damage at the Si–SiO2 interface, transparent conductors, and solar cells. His seminal work on ultrathin (2–4 nm) SiO2 gate dielectrics, carried out four decades ago, still provides an important foundation for the current and future generation CMOS chips. He extended it later to high-k gate dielectrics. He traveled extensively attending conferences and giving seminars around the world, and had held visiting professorships at the Pennsylvania State University in 1979 and Lehigh University in 1981. He continued his research for several years past his retirement in 2004. Recently he edited a volume on High Permittivity Gate Dielectric Materials (Springer 2013) and authored the two lead review chapters. Suman Datta, Chang Family Professor of Engineering Innovation at Notre Dame University, says, “I am so sorry to hear the news. Prof. Kar taught me solid state materials when I was an undergraduate. I vividly recall his passionate lectures on space groups and crystal families. He introduced me to solid state. The past and current students of IIT Kanpur will miss him dearly.” S. Ashok, professor of engineering science at the Pennsylvania State University has known Samares for nearly 40 years and has spent countless hours with him at IITK, Penn State, and conference venues around the world. He has been privy to Dr. Kar’s wideranging scientific interests, formidable intellect, and deep concern for society at large—aspects of his usually not in view under the somewhat melancholic exterior and occasionally irascible personality. Samares Kar was nothing if not intense in his devotion to work, with meticulous attention to every little experimental detail and exacting standards for himself and others. He truly lived the life of a karma yogi, never expecting any returns. He was a member of the Dielectric Science and Technology Division Dr. Kar passed away on January 13, 2017 at his home in Kolkata, India and is survived by his wife of 45 years, Dr. Rita Kar. Information for this notice was contributed by Durga Misra.

Graham Wood (1934–2016)

raham Wood, DSc, FREng, FRS, joined ECS in 1983, and became a towering figure in the somewhat arcane subject that we know of as corrosion science. He was born on February 6, 1934 in Farnborough, Kent, England. Clearly, 1934 was an auspicious time for corrosion science as Bob Rapp and Roger Staehle were all also born within a few weeks of each other. Dr. Wood’s parents had met at Down House, the former home of Charles Darwin, while it was being run as a school; later, Dr. Wood’s described an interest in science due to childhood visits to Down House, after it had become the Darwin museum. Dr. Wood attended Christ’s College, Cambridge University, where he graduated in natural sciences. Subsequently, he undertook a PhD with T. P. (Sam) Hoar, collaborated with Ulick Evans, and continued as a postdoctoral researcher with Alan Cottrell. He moved to the then University of

Manchester Institute of Science and Technology (UMIST) in 1961 as lecturer in corrosion science in the Department of Chemical Engineering. The UMIST Chemical Engineering Department was run in those days by T. K. (Ken) Ross, who recognized early in his career that corrosion and materials degradation of chemical plant was a major threat to operations and so built up a strong research group in corrosion science and strongly supported Graham’s appointment in 1972 as Britain’s first Professor of Corrosion Science. From 1972 to 1982 Graham built this up to a steady state of around ten academic (faculty) staff with associated support staff, with the MSc programme in Corrosion Science and Engineering (established earlier in 1961) feeding into PhD research. He also set up CAPCIS (now part of Intertek), under the direction of David Gearey, when it became apparent that the demand from industry for consultancy services far exceeded the capacity of academic staff to deliver. As head of the Corrosion and Protection Centre, Dr. Wood was a demanding taskmaster on colleagues, but even more so on himself. Famously in January one year, he circulated a set of typewritten memos (no emails in those days) where he insisted that his secretary dated them 25th December “because that’s when I wrote them.” However, away from the direct focus of work he always had time on a personal basis for even the most junior of technical staff, ensuring that he was on first-name terms with everyone who contributed to his work. From Manchester, Dr. Wood kick-started, mentored, and supported the careers of innumerable people and was in touch with a world-wide network of corrosionists. After 1982, he increasingly took a back seat in the day-to-day operations of the Corrosion and Protection Centre and focused more on academic administration while ensuring that he kept his hand in guiding and mentoring research students and directing novel research. Over the years leading to his retirement in 1999, Dr. Wood served in various roles up to Dean of Faculty and finally Deputy Principal. Dr. Wood was a principal consultant to the Electric Power Research Institute (EPRI) in collaboration with John Stringer for many years and was the first chair from outside North America of the Gordon Research Conference on Corrosion. He spent two periods as president of the predecessor bodies to the UK Institute of Corrosion and was chair of the International Corrosion Council for many years. His most notable work at Manchester was carried out in collaboration with Howard Stott (in oxidation and hot corrosion) and George Thompson (in passivity and the properties of anodic films). Amongst other prizes and awards, he received the Beilby Medal and Prize from the Society of Chemical Industry in 1972 and in 1983 was presented with the U. R. Evans Award of the Institute of Corrosion. In the same year, he was awarded the Carl Wagner Memorial Award of The Electrochemical Society and was appointed an ECS life member. In 1987, the European Federation of Corrosion presented Graham with its premier prize, the Cavallaro Medal and, in 1990, he was elected to the Fellowship of Engineering (now the Royal Academy of Engineering) as FREng. Finally, and following on from Davy, Faraday, Bengough, and Evans, in 1997 Dr. Wood was elected to Fellowship of the Royal Society (FRS), the highest UK scientific honor. Rather unassuming, intensely private, but unfeasibly talented, Dr. Wood was a true “gentlemen scientist.” His passing deserves reflection on a life well lived. He was a member of the Corrosion Division. He passed away November 4, 2016. Excerpted from obituary written by Stuart Lyon, Corrosion and Protection Centre, School of Materials, The University of Manchester, UK Licensed under CC BY-NC

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ECS Classics Acheson, Silicon Carbide, and the Electric Arc by Petr Vanýsek

he discovery of an electric arc can be tied to the use of an electrochemical energy source. Sir Humphry Davy described in 1800 an electric discharge using electrochemical cells1 that produced what we would call a spark, rather than an arc. However, in 1808, using an electrochemical battery containing 2000 plates of copper and zinc, he demonstrated an electric arc 8 cm long. Davy is also credited with naming the phenomenon an arc (Fig. 1). An electric arc was also discovered independently in 1802 by Russian physicist Vasily Petrov, who also proposed various possible applications including arc welding. There was a long gap between the discovery of the electric arc and putting it to use. Electrochemical cells were not a practical source to supply a sustained high current for an electric arc. A useful application of this low voltage and high current arc discharge became possible only once mechanical generators were constructed. Charles Francis Brush developed a dynamo, an electric generator, in 1878, that was able to supply electricity for his design of arc lights. Those were deployed first in Philadelphia and by 1881 a number of cities had electric arc public lights. Once that happened, the application and new discoveries for the use of the electric arc followed. Electric arc for illumination was certainly in the forefront. First, electric light extended greatly the human activities into the night and second, public street electric lights, attracting masses of spectators, were the source of admiration, inspiration, and no doubt, more invention. The electric arc became an essential tool leading to a number of discoveries in science and technology and to a number of technological processes. In the anglophone and certainly in the American awareness of the invention of artificial light, it is Edison and the light bulb that come to mind; without doubt the light bulb evokes the notion of the glass envelope of Edison’s construction. But the invention of useful artificial electric light precedes Edison’s patent of a carbon filament of 1879 by a few years. Before the light bulb, electric arc lighting became quickly popular, but it had many disadvantages. Among these, the most significant was that the graphite rods, as they burned off, became shorter, the distance between them longer, and the arc

Fig. 1. Classical diagram of a DC electric arc. During the operation the positive electrode was used up much faster, thus forming a crater on its tip. 36

eventually flamed out. Pavel Yablochkov came up with a design for how to move the rods closer, in an automated fashion, to maintain a constant arc. He received in 1876 a French patent for this selfregulated electric arc lighting design. The high temperature in the arc made it useful for lighting, but made it equally useful for many technical operations as well. Electric arc welding became practical and was demonstrated at the International Exposition of Electricity in Paris in 1881. Heating and melting with an arc was practiced around that time as well. The heat, melting, and simultaneous electrochemistry in the melt led to aluminum preparation by Hall and Heroult, in 1886 and 1888, respectively.2 Various experiments with electric arc followed, one of which led to the great discovery of Edward Goodrich Acheson, who invented manufacturing of carborundum and patented the process in 1893. Acheson (Fig. 2) was born March 9, 1856 in Washington, Pennsylvania and was raised in Pennsylvania coal country. He quit school at the age of 16 in order to work and support his family when his father became seriously ill and subsequently died in 1873. Acheson labored on the railroad, but spent his after-work hours studying science and electricity, and conducting his own homemade experiments. One story tells about his practical and profitable electrochemical experiments at this time. He purchased inexpensive yellow-metal pocket watches, used the family silverware forks (made actually from silver at the time) as anodes, and silver-plated the watch cases, which he then sold for a profit. He designed a dynamo and was interested to find employment with some manufacturer of electrical equipment. He approached Edward Weston (of Weston Standard Cell fame) who was manufacturing electroplating dynamos in a shop in Newark, New Jersey, but was turned down for employment. In 1880 Acheson was hired by Thomas Edison as a draftsman and technician at Edison’s Menlo Park New Jersey laboratories. Acheson must have been impressed by the new technology electricity was providing. His involvement with electric arc lighting was first-hand. He learned all the details of electric arc lighting in the preparation for the International Exposition of Electricity in Paris in 1881, the same event where the Yablochkov invention was going to be displayed. After the exposition, Acheson worked for Edison subsidiaries in Europe, where he oversaw the first installations of electric lighting in Belgium, Holland, and Italy. He returned to New York in 1884 and for a year worked as a General Electric electrician for Edison Electric Light Company (1884-85). In 1885 he left Edison and was successful in inventing an anti-induction telephone wire, which he patented and then sold to George Westinghouse for some handsome cash and stock in the Standard Underground Cable Company. Because Westinghouse was Edison’s arch-rival, Acheson’s relationship with Edison soured. In 1885-86, Acheson worked as a superintendent of the Consolidated Lamp Company of Brooklyn and also worked on his own, with the support of a few financial backers, to design a new style of a dynamo. This effort, however, ended in failure. Acheson was hired to work for the Standard Underground Cable Company for three years (1886-89) where he worked as an The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

Fig. 2. Edward Goodrich Acheson.

electrician, until he decided to establish himself on his own. In partnership he operated a small lighting plant in Monongahela City, Pennsylvania. Its electricity was used for lighting only at night. During the day he was using the dynamo for his experiments. Acheson made his most famous discovery and invention, silicon carbide (trade name Carborundum), in 1891 using the Monongahela City dynamo. Acheson was by his own words3 always interested in a method through which carbon could be crystallized (into a diamond modification) to produce abrasive materials. His experimental plan in Monongahela was to cause carbon to be dissolved in melted silicate of alumina, and by cooling the melt to exert high pressure on carbon and cause it to crystallize. The very first experimental design was a furnace made from an iron bowl lined with carbon serving as one electrode. In the central cavity was placed a mixture of carbon and clay (a silicate), and a rod of carbon was placed in the middle of the mixture as a second electrode. Current was passed through the system and after a period of time the cooled mass was broken apart and examined. A few bright blue crystals, very hard, were found close to the carbon electrodes. A new furnace design involved a refractory brick cavity, 10 × 4 × 4 inches in size, allowing experimentation with electrode placement. The electrical supply apparatus could supply regulated current from 100 to 200 A and potential from 1 to 50 V. This was alternating current, so the effects of the current were not electrochemical but solely temperature-based. Again, upon varying conditions, it was possible to produce larger quantities of the hard material. While it was hard, it was also brittle, thus use of the powder as an abrasive became the prime consideration. At that time Acheson felt there was a need to name the material. As the material was displaying various colors, sapphire blue to ruby red, it was reminiscent of another mineral, corundum, which can display similar colors. Acheson coined the name carborundum from carbon, the principal component of the mix, and the name of the mineral corundum, knowing that the clay in the mix contained alumina, a structural component of corundum. Soon thereafter he realized that the chemical composition was different. There was little aluminum in the material and shortly the compound was determined to be silicon carbide. Acheson wrote, “The fitness of the name, in the eyes of the chemist, is, in view of the now known composition of the substance, doubtful, while in commerce, although phonetic and of pleasing effect in print, it is, perhaps, a trifle lengthy.”3 Still, the name stuck and is in use to this day.

Acheson founded The Carborundum Company in 1891 to market the material for use in dental products, gem polishing, grinding wheels, knife sharpeners, and whetting stones. In 1897 he patented an improved electrical furnace for firing silicon carbide, leading to the construction of the world’s largest industrial furnace at his factory. His discovery of silicon carbide has been called one of the most important discoveries in modern industry, but Acheson was a better chemist and inventor than businessman, and he was fired from the presidency of his Carborundum Company in 1901. The firm has been sold several times since then, and is now part of the SaintGobain/Norton Industrial conglomerate. The world exhibitions or expositions organized in various cities were the premier events to introduce both culture and new technologies to the world. The synthetic silicon carbide, carborundum, was introduced to the world at the Chicago World’s Columbian Exposition. The event lasted from May 1 to October 30, 1893. It was notable for quite a few events. Electric lighting generated using the alternating current promoted by Nikola Tesla over Thomas Edison’s direct current was used to light the fairground. The first Ferris wheel was installed there in June. The Austrian-Bohemian pencil maker Koh-i-noor brought yellow lacquered pencils to the fair and these were hugely popular, remaining a staple to this day. And the Carborundum Co. displayed its industrial production of cutting wheels, catching the eyes of investors from Austria. Arnold Weissenberger, an investor from the Austrian investment bank Länderbank, traveleled to Chicago to the exhibit accompanied by a professor from Prague University, Friedrich Steiner. They acquired the carborundum patent rights for Austria-Hungary and for Russia. The International Carborundum Works were established with Wilhelm Kaufmann as a director. Their quick acquisition at the Columbian exhibit allowed the immediate establishment of a plant in Europe—the Austrian Carborundum Company at Benateck, Bohemia, now in the Czech Republic, in a town known now by its Czech name Benátky nad Jizerou (Fig. 3 and 4). Carborundum production there started in 1893 and the availability of grinding stones (continued on next page)

Fig. 3. The first and oldest carborundum furnace in Benátky nad Jizerou (courtesy Carborundum Electrite a. s., Benátky nad Jizerou).

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of various shapes and purposes made the use of bladed tools, that became easily dulled, more efficient. An oblong scythe stone, with its sheet metal sheath filled with water to keep it lubricated became the visual attribute of a farmer for most of the twentieth century. The stones are still in production and the Czech Carborundum Electrite (now Swarovski Holding) is still producing abrasives (Fig. 5). The Czech connection has not been exclusively on the manufacturing side. The crystallographic structure of carborundum produced by the Czech factory in Benatky was established by a Prague professor, F. Becke.4 To use the electric arc furnace, ready access to electricity was needed. The very first company to receive power from the Niagara Falls Power Company, when it opened in 1895, was the Pittsburgh Reduction Company founded by Charles M. Hall, renamed in 1907 as the Aluminum Company of America and better known as ALCOA. The second one was the Carborundum Company, founded by Edward Goodrich Acheson. His original small plant in Monongahela City used 135 horsepower of electricity and was able to produce 45 tons per year of the abrasive powder. It was then being sold at $440 a pound, less than half the price of diamond dust. Still, he was losing money until the move to Niagara, where the ability to produce the material at quantity lowered the costs and opened new markets. In 1907 the production of carborundum in the USA was reported to be 7,532,670 lb, valued at $451,960, and the only producer was the Carborundum Company at Niagara Falls. Their furnace was 30 ft in length and 12 ft wide, with power consumption of 1600 kW and current about 20,000 A. The Columbian Expedition in Chicago created even more overseas interest. In 1894 the Austrian Carborundum Company began operating a plant at La Bâthie, Savoy, France. And in 1895 construction of a hydroelectric power station at La Bâthie was begun, with one intended purpose being the use of the electricity to manufacture more carborundum. Since then, the manufacturing of carborundum has become more international, with The Canadian Carborundum Co. established in Niagara Falls, The Carborundum Co. in Manchester, England and Deutsche Carborundum Werke

Fig. 5. Scythe carborundum whetstone and quiver, early 21st century (photo author).

in Reisholz by Düsseldorf, Germany, for manufacture of grinding wheels and sharpening stones. A German company manufacturing carborundum at Badisch-Pheinfelden has constructed a facility of 3000 hp capacity. And there was also constructed plant Gotthardwerke in Bodio, Switzerland, once the water from the Ticino River was harnessed. Small amounts of naturally occurring silicon carbide were found in 1893 by French chemist Henri Moissan while he was examining rock samples from Diablo Canyon in Arizona. At first, he believed they were diamond crystals, but he identified them as silicon carbide in 1904. Later in his life the mineral was named moissanite in his honor. Moissan won the 1906 Nobel Prize in chemistry for his work in isolating fluorine from its compounds. In our story he has yet another notoriety. Just like Acheson, he also attempted to prepare synthetic diamonds through exposure of carbon to high temperature. And just like Acheson, he used an electric arc furnace of his own design (Fig. 6). He popularized the use of the electric arc in industry and in the laboratory by publishing his book The Electric Furnace.5 Acheson was responsible for numerous other chemical discoveries, including Aquadag, a graphite-based coating used in cathode ray tubes, Oildag, a lubricant additive based on colloidal graphite in oil, and an improved method for making graphite. The dag in the trade names stood for Deflocculated Acheson Graphite. Synthetic graphite had commercial value and thus the Acheson Graphite Co. was formed in 1899. The means for making silicon carbide is still referred to as the Acheson process. Acheson is the namesake of The Electrochemical Society’s Edward G. Acheson Medal, which he established through a charitable gift to the Society on September 27th, 1928.6 He was a charter member of ECS and the ECS president in 1908-1909. Acheson died July 6, 1931 in New York.

Fig. 6. Diagram of the electric arc furnace as described by Moissan (from Ref. 5). Fig. 4. Historical picture of a trade show display of carborundum products in Vienna (courtesy Carborundum Electrite a. s., Benátky nad Jizerou). 38

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Acheson observed, about his silicon carbide discovery, “You have heard that ‘fools rush in where angels fear to tread,’ and had I been a chemist, it is probable that such an experiment would not have been worthy of consideration, and certainly would not have been attempted. Be this as it may, the experiments were made with results more or less satisfactory.”3 © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F01171if.

Acknowledgment This research was carried out under the project CEITEC 2020 (LQ1601) with financial support from the Ministry of Education, Youth and Sports of the Czech Republic under the National Sustainability Programme II.

References 1. H. Davy, Journal of Natural Philosophy, Chemistry, and the Arts (Nicholson’s Journal), Vol. IV, 326 (1800). 2. T. R. Beck, “ECS Classics: Hall and Héroult and the Discovery of Aluminum Electrolysis,” Electrochem. Soc. Interface, 23(2), 36 (2014). 3. E. G. Acheson, “Carborundum: Its History, Manufacture, and Uses,” J. Franklin Inst., 136, 194 (1893). 4. F. Becke, Z. Kristallogr. Cryst. Mater., 24, 1 (1895). 5. H. Moissan, The Electric Furnace, Edward Arnold, London (1904). 6. R. J. Calvo, “Pennington Corner: Gift Horse,” Electrochem. Soc. Interface, 20(3), 7 (2011).

About the Author Petr Vanýsek grew up in Czechoslovakia, in the part of the country now known as the Czech Republic, where he received a doctorate in physical electrochemistry. His scientific career developed in the USA, where he went through the ranks of tenure track and tenured faculty at the Department of Chemistry and Biochemistry at Northern Illinois University. Now an Emeritus at NIU, he is currently working at the Central European Institute of Technology in Brno, Czech Republic. The Czech connection enabled him to discover the ties of early Carborundum production in Bohemia. Vanýsek has long involvement with ECS on a number of committees including four years as the society secretary. Presently, he is a co-editor of Interface, chair of the Europe Section, and secretary of Physical and Analytical Electrochemistry Division. He can be reached at pvanysek@gmail.com. http://orcid.org/0000-0002-5458-393X

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The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

Looking at Patent Law: Why Are Patents Often Referred to as Intellectual Property? by E. Jennings Taylor and Maria Inman

he subject of this column is patents, inventions, and inventors. According to U.S. law,1 patented inventions may be afforded the right to exclude others from

“[M]aking, using, offering for sell or selling the invention throughout the United States or importing the invention into the United States. …”

Note that a patent does not give one the right to use or practice the patented invention; rather the patent provides a right to exclude others from using or practicing the subject invention. Additionally, this right is for a period of 20 years from filing for utility patents. And finally, the rights associated with U.S. patents are limited to the U.S. Patents are often referred to as a type of “intellectual property,” the others being copyrights, trade secrets, and trademarks. Interestingly, U.S. law stipulates2 that patents “[S]hall have the attributes of personal property. …” A helpful analogy is to compare a personal residence or real property to patents (Fig. 1). Similar to real property, a patent is a “social artifact” in it is also “created” from the public domain.3 Specifically, real property has an owner or owners and may be sold and/or purchased subject to the terms of a contract. Similarly, patents have an inventor or co-inventors. If the inventors are employed by Real Property Δ Owner

Intellectual Property ↔

Δ Sell/Purchase ↔ Δ Charge Rent ↔ Δ Pay Taxes ↔ Δ Repossessed ↔ Δ Trespass ↔

Δ Inventor/Assignee Δ Sell/Acquire Δ Charge License Fee Δ Pay Maintenance Fees Δ Abandoned Δ Infringe

Δ Mortgage

↔

Δ Loan/Financing

Δ Deed

↔

Δ Claims “metes and bounds”

Δ Survey/Title Search

↔

Δ Examination/Prior Art Search

a company, university, or the federal government, they generally assign their rights in the subject invention to their employer via an employee “intellectual property rights” agreement. If the inventor or co-inventors are independent or not subject to an intellectual property rights agreement, then they are the assignees of the patent. Patents may similarly be sold and acquired by their assignees. In addition, the owner of real property may rent the property subject to the terms of a rental or lease agreement. These terms generally include the length of the lease, the frequency of payments, and who is responsible for the utilities and upkeep of the real property. The assignee of a patent may similarly license the patent subject to the terms of a license agreement. These terms generally include length of the license, the frequency of the payments, and the basis of the payments may include a percent of product sales or of manufacturing savings. In order to maintain ownership, taxes must be paid to the municipality where the real property resides. Similarly, for a patent to remain in force the assignee must pay maintenance fees to the U.S. Patent & Trademark Office. If these taxes/maintenance fees are not paid, the real property or patent are repossessed or abandoned, respectively. As part of the right to “exclude others” noted above, the owner of real property may collect damages for trespassing in a court of law and the assignee of a patent may collect damages for infringing the patent in a court of law. And, the owner/assignee may use the real property/ patent as collateral for a mortgage or to secure a loan or financing, respectively. Patent law requires that a patent contain a specification or written description of the invention and4 “[C]onclude with one or more claims particularly pointing out and distinctly claiming the subject matter … as the invention …”

Fig. 1. Analogous terms in real property and patents.

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

(continued on next page)

Taylor and Inman

(continued from previous page)

As noted by former Judge Giles S. Rich of the Court of Appeals for the Federal Circuit (i.e., the patent court)5 “The name of the game is the claim.” Whereas the deed defines the boundaries of ownership of real property, the claims of a patent define the boundaries of the patent. In the case of real property, modern surveying methods lead to precise determination of the boundaries of the real property. In the case of a patent, the boundaries are often referred to as the “metes and bounds” of the patent. The “metes and bounds” description is derived from an early system of defining the boundaries of real property, where the boundaries are described by the local geography of the parcel of land. For example, begin at the oak tree at the fork of the creek and proceed towards the large granite rock; after twenty paces turn due east and proceed towards another oak tree; after fifty paces … and so on until the boundaries of the property have been “defined.” By definition, the “metes and bounds” is a less precise way of describing the boundaries and is appropriate for describing the boundaries of a patent in intellectual property space. The final informal analogy between real property and a patent is related to ensuring that there are no legal encumbrances in order to present a clear title to the real property or to the issued patent. Specifically, when a prospective owner initiates the purchase of a parcel of land, a survey/title search is conducted for real property to ensure there are no previous owners or legal encumbrances on the real property. When an inventor/assignee files a patent application, an examination/prior art search is performed to ensure there are no previous owners of all or part of the claimed invention. In both cases there are associated fees in the form of “closing costs” and “filing and issue fees” for real property and patents, respectively. Figure 2 depicts the examination (i.e., prosecution) of a patent application using the real property analogy. In Fig. 2a, the claims representing the “metes and bounds” of the patent application are defined in the public domain. In Fig. 2b, neighboring prior art references or disclosures are identified by the examiner during the prior art search. These prior art references generally include patents, published patent applications, and other publications. In Fig. 2c, because there is no overlap in the boundaries of the neighboring prior art and the patent application, the patent issues as claimed. As noted above, the purpose of examination of the patent application by the U.S. Patent & Trademark Office is to ensure that there are no legal encumbrances or previous owners of any or all of the invention claimed in the patent application. There are two concepts that determine whether or not an invention is patentable. First, the invention must be novel and not anticipated by the prior art.6 A patent application rejection due to lack of novelty is generally based on a single prior art reference with the same or “equivalent” claims of the

(a)

patent application. Second, the invention must be non-obvious to one of “ordinary skill in the art.”7 A patent application rejection due to obviousness is generally based on a combination of two or more prior art references. (As a cautionary note, technical obviousness and legal obviousness are very different and will be the subject of a subsequent Interface column.) A rejection by the U.S. Patent & Trademark Office based on lack of novelty and/or obviousness is generally stating that if the patent application were to be issued as claimed, the resulting patent would “trespass” on one or more prior art references. In this case, either the scope of the claims of the patent application is limited by amending the claims to overcome the prior art reference or references or the patent application is abandoned. Figure 3 depicts the real property analogy of the examination (i.e., prosecution) of a patent application which is modified to overcome the prior art rejection. In Fig. 3a, the claims representing the “metes and boundsˮ of the patent application are defined in the public domain. In Fig. 3b, a prior art reference overlapping part of the claims of the patent application is identified by the examiner during the prior art search. In this case, the scope of the claims of the patent application are limited by amendment to overcome the prior art reference and the patent issues with the claims of reduced scope as depicted in Fig. 3c. A conceptual example of the situation described in Fig. 3 could be as follows. Assume a first inventor invents a television (TV) using black and white display technology. The inventor contacts a professional, who could be either a patent attorney (who is admitted to the patent bar and holds a law degree) or a patent agent (who is admitted to the patent bar, but does not have a law degree) to discuss the potential patentability of the invention. The patent attorney determines that the invention meets the basic criteria of usefulness required by the patent statute8 “[U]seful process, machine, manufacture, or composition of matter … may obtain a patent …” The patent attorney conducts a prior art search and reviews the prior art with the inventor. Based on this review, they believe the invention is both novel6 and non-obvious.7 The patent attorney prepares a patent application describing the TV with a black and white display. Since they did not identify any related prior art, the patent broadly claims a TV, without limiting the TV to a black and white display. The patent application is submitted to the U.S. Patent & Trademark Office, the examiner conducts a prior art search, and “allows” the TV patent to issue as filed. Subsequent to the first TV invention, assume a second inventor invents a color TV. The second inventor contacts a different patent attorney who determines that the invention meets the basic criteria of usefulness.8 They conduct a prior art search and believe the invention is both novel6 and non-obvious.7 The patent attorney prepares a patent application describing the TV with a color display. Since the patent attorney and inventor did not identify any related prior art, the patent broadly claims a TV, without limiting the TV to a color display.

(b)

(c)

Fig. 2. Real property analogy of the examination of a patent application with neighboring art.

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

During a prior art search by the U.S. Patent & Trademark Office, the examiner discovers the prior art patent of the first inventor claiming a TV and rejects the patent application of the second inventor based on a lack of novelty6. The patent attorney reviews the office action with the second inventor and agrees with the basis of the examiner’s prior art rejection. Recall that although the first inventor of the prior art TV patent was only making TVs with black and white picture tubes, the first inventor had broadly claimed a TV, and did not limit the claims to a TV with a black and white picture tube. Therefore, the “metes and boundsˮ of the color TV patent application of the second inventor overlapped the metes and bounds of the prior art TV patent of the first inventor. Based on the advice of the patent attorney, the second inventor agrees to amend and limit the claim to a TV with a color picture tube. By doing so, the amended patent application limited to a TV with a color picture tube no longer overlaps the claims of the prior art TV patent and issues as a U.S. patent. Recall from above that a patent gives one the right to exclude others from practicing the invention but not the right to practice the invention. In this case, the first inventor of the prior art TV patent can continue making TVs and selling them in the market place as long as they do not use the color picture tube covered in the color TV patent. Specifically, the first inventor can only make TVs with a black and white picture tube. In contrast, the second inventor of the patent claiming a TV with a color picture tube could not practice his/her patent because that would infringe on the prior art TV patent, which broadly claimed a TV. In legal terms, the inventor of the color TV patent does not have the “freedom to operate” regarding the patented color TV invention. A likely outcome of this situation is a cross license by the holders of the two patents in order to fully exploit the much bigger color TV market. In fact, this is precisely the purpose of the U.S. patent system9 “[T]o promote the progress of science and the useful arts …” In summary, patents have a number of attributes analogous to real property. This analogy provides a basis for understanding the patent application and examination process. In our next Interface column, we will briefly discuss the constitutional basis of the U.S. patent system and the distinction between the inventor/co-inventor of a patent and the author/co-author of a journal publication. In a subsequent column, we will discuss the obviousness rejection and some strategies to overcome such rejection. © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F02171if.

Listen to the ECS Podcast with E. J. Taylor on small business, patents, and science at

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(a)

About the Authors E. Jennings Taylor is the Founder of Faraday Technology, Inc., a small business focused on developing innovative electrochemical processes and technologies based on pulse and pulse reverse electrolytic principles. Taylor leads Faraday’s patent and commercialization strategy and has negotiated numerous field of use licenses, as well as patent sales. In addition to technical publications and presentations, Taylor is an inventor on forty patents. Taylor is admitted to practice before the United States Patent & Trademark Office (USPTO) in patent cases as a patent agent (Registration No. 53,676) and is a member of the American Intellectual Property Law Association (AIPLA). Taylor has been a member of The Electrochemical Society for thirty-eight years and is a Fellow of ECS and currently serves as treasurer. http://orcid.org/0000-0002-3410-0267

Maria Inman is the Research Director of Faraday Technology, Inc. where she serves as Principal Investigator on numerous project development activities and manages the companies pulse and pulse reverse research research portfolio. In addition to technical publications and presentations, Inman is competent in patent drafting and patent drawing preparation and is an inventor on seven patents. Inman is a member of ASTM and has been a member of The Electrochemical Society for twenty-one years. Inman serves as a member of numerous committees for ECS.

References 1. 35 U.S.C. §154(a)(2) Contents and term of patent; provisional rights. 2. 35 U.S.C. §261 Ownership; assignment. 3. P. L. Speser, The Art and Science of Technology Transfer, p. 22, John Wiley & Sons, New York (2006). 4. 35 U.S.C. §112(b) Specification; Conclusion. 5. G. S. Rich, “The Extent of the Protection and Interpretation of Claims-American Perspectives” International Review of Industrial Property and Copyright Law 21, 497, 499, 501 (1990). 6. 35 U.S.C. §102 Conditions for patentability; novelty. 7. 35 U.S.C. §103 Conditions for patentability; non-obvious subject matter. 8. 35 U.S.C. § 101 Inventions patentable. 9. United States Constitution, Article I, Section 8, Clause 8.

(b)

(c)

Fig. 3. Real property analogy of the examination of a patent application with prior art rejections.

The Electrochemical Society Interface • Spring 2017 • 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 PRiME issues are now published and are all available in electronic (PDF) editions, which may be purchased by visiting www.electrochem.org. Some issues are also available in CD/USB editions. Please visit the ECS website for all issue pricing and ordering information.

Available Issues HON A01 Batteries and Energy Technology Joint General Session HON A02 Challenges in Advanced Analytical Tools and Techniques for Batteries: A Symposium in Honor of Prof. Zempachi

HON H01 State-of-the-Art Program on Compound Semiconductors 59 (SOTAPOCS 59)

HON A03 Li-Ion Batteries

HON H02 Semiconductor Wafer Bonding: Science, Technology and Applications 14

HON A04 Advances in Electrolytes for Lithium Batteries HON A05 Beyond Li-Ion Batteries HON A06 Failure Mode and Mechanism Analyses HON A07 Electrochemical Capacitors and Related Devices: Fundamentals to Applications HON B01 Carbon Nanostructures: From Fundamental Studies to Applications and Devices HON C01 Corrosion General Poster Session HON C02 Oxide Films: A Symposium in Honor of Masahiro Seo HON C03 High Temperature Corrosion and Materials Chemistry 12 HON C04 Pits & Pores 7: Nanomaterials – Fabrication Processes, Properties, and Applications HON C05 Atmospheric –and– Marine Corrosion HON C06 Metallic, Organic and Composite Coatings for Corrosion Protection HON D01 Photovoltaics for the 21st Century 12 HON D02 Nonvolatile Memories 5 HON D03 Plasma Nano Science and Technology HON E01 Electroless Deposition: Principles and Applications 4: In Honor of Milan Paunovic and Mordechay Schlesinger HON E02 Magnetic Materials Processes and Devices 14 HON E03 Molecular Structure of the Solid-Liquid Interface and Its Relationship to Electrodeposition 8 HON E04 Electrodeposition for Energy Applications HON F01 Industrial Electrochemistry and Electrochemical Engineering General Session HON F02 Electrochemical Impedance Spectroscopy: In Honor of Bernard Tribollet HON F03 Contemporary Issues and Case Studies in Electrochemical Innovation 2 HON F04 Membrane-based Electrochemical Separations 2

HON H03 Thin Film Transistors 13 (TFT 13) HON H04 Low-Dimensional Nanoscale Electronic and Photonic Devices 9 HON H05 Gallium Nitride and Silicon Carbide Power Technologies 6 HON H06 Fundamentals and Applications of Microfluidic and Nanofluidic Devices 3 HON H07 Emerging Nanomaterials and Devices HON I01

Polymer Electrolyte Fuel Cells 16 (PEFC 16)

HON I02

Solid State Ionic Devices 11

HON I03

Electrosynthesis of Fuels 4

HON I04

Energy/Water Nexus: Power from Saline Solutions

HON J01 Luminescence and Display Materials: Fundamentals and Applications HON K01 Bioengineering Based on Electrochemistry HON K02 Recent Advances in the Application of Electrochemistry to Problems in Organic Chemistry and Biology HON L01 Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry General Session HON L02 Molten Salts and Ionic Liquids 20 HON L03 Electrode Processes 11 HON L04 Photocatalysts, Photoelectrochemical Cells, and Solar Fuels 7 HON M01 Chemical Sensors 12: Chemical and Biological Sensors and Analytical Systems HON M02 Microfabricated and Nanofabricated Systems for MEMS/NEMS 12 HON M03 Electrochemical Analysis with Nanomaterials and Nanodevices HON Z01 General Student Poster Session HON Z02 Nanotechnology General Session HON Z03 Electrochemical Energy Summit (E2S) - Poster Session

HON G01 High Purity and High Mobility Semiconductors 14 HON G02 Semiconductors, Dielectrics, and Metals for Nanoelectronics 14 HON G03 Atomic Layer Deposition Applications 12 HON G04 Processing Materials of 3D Interconnects, Damascene and Electronics Packaging 8 HON G05 SiGe, Ge, and Related Materials: Materials, Processing, and Devices 7

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

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

02/06/17

t ech highligh t s Performance of Three-Dimensional LiMn2O4 /Carbon Composite Cathodes Prepared Via Sol-Gel Impregnation

With the ever advancing improvements in electronics and display technologies, it is crucial that Li-ion batteries are able to rise to the challenge of powering next generation consumer electronics. Consequently, the development of electrode materials for Liion batteries that are capable of delivering high capacities with stable capacity retention is of the utmost importance. Researchers from the University of Bremen have investigated the fabrication of 3D composite cathodes consisting of LiMn2O4 particles deposited directly onto an electrically conductive matrix of carbon fibres via solgel impregnation. The electrochemical performance of the composite cathodes was evaluated as a function of the number of sol impregnation steps. Through systematic galvanostatic cycling, the researchers determined that high capacity cathodes could be obtained from increased filling of the carbon matrix with the LMO sol. A cathode sample after four filling cycles demonstrated a discharge capacity of 132 mAh g-1 after 50 cycles, corresponding to ~ 89% of the theoretical capacity of LiMn2O4. Additionally, as a proof-ofconcept, LMO cathodes were cycled against Lithium Titanate (LTO) anodes in a solid state battery (SSB) setup. The evaluation of these cells offers valuable insight for future SSB applications. From: I. Bardenhagen, J. Glenneberg, F. Langer, et al., J. Electrochem. Soc., 163, A2539 (2016).

Structure and Corrosion Performance of a Non-Chromium Process (NCP) Zr/Zn Pretreatment Conversion Coating on Aluminum Alloys Chromate conversion coatings have long been the standard for the protection of aluminum alloys in marine applications. Due to the toxicity of chromate, industry is being pushed away from these chemistries to chromate-free replacements, such as non-chromated process (NCP) and trivalent chromium process (TCP) chemistries, developed by the Naval Air Systems Command (NAVAIR). In this work, a laboratory-produced NCP coating was benchmarked against a commercially available TCP coating. Under immersion conditions, NCP was found to ennoble the open circuit and pitting potentials, increase the polarization resistance by an order of magnitude, and suppress the anodic activity of an AA2024 substrate, indicating that it functioned primarily as an anodic inhibitor. However, for neutral salt fog exposure and aggressive beach exposure, the NCP was found to be less effective, exhibiting a higher dissolution rate than that achieved with a TCP coating, and an inability to prevent galvanic attack when coupled to a stainless steel fastener. The ineffectiveness in inhibiting corrosion under such aggressive conditions was attributed to the composition of the NCP film, which is a combination of Zr(OH)2 and Zn(OH)2, both of which are

more soluble, and the NCP film’s lower adhesion strength than that of Cr(OH)3 that makes up the TCP coating. From: L. Li, B. W. Whitman, C. A. Munson, et al., J. Electrochem. Soc., 163, C718 (2016).

Triple-Switchable Biosensors and an AND Logic Gate Based on Binary Assembly of Weak Polyelectrolyte Multilayers and Hydrogel Films Switchable electrode interfaces responsive to physical, chemical, or biological signals have attracted immense research interest during the last decade because of their potential applications in biosensors and bioelectronics. An example of such interfaces was recently reported by a group of researchers from several universities and institutes in China. On the surface of pyrolytic graphite electrodes, the authors first assembled a polyelectrolyte film via layer-by-layer coating with poly(allylamine hydrochloride) and poly(acrylic acid). A second hydrogel film was then formed on top of the polyelectrolyte layer by radical polymerization of N,N-diethylacrylamide in the presence of horseradish peroxidase. The resulting binary films exhibited clear and reversible on-off behavior towards pH, temperature, and sulfate concentration changes, as demonstrated by the electrode responses to K3Fe(CN)6. Similar behavior was observed when the electrodes were used to electrocatalytically reduce H2O2 with K3Fe(CN)6 as the mediator. The authors demonstrated that the pH-sensitivity of the system originated from the inner polyelectrolyte layer due to the presence of free amino and carboxyl groups, while the thermo- and salt-sensitivities were attributed to the structure change of the outer poly(N,N-diethylacrylamide) layer. Finally, an AND logic gate was constructed with the three stimuli factors as the input and the electrode current as the output. From: H. Yao, X. Luo, T. Yang, et al., J. Electrochem. Soc., 163, H1104 (2016).

Synthesis and Electrochromic Characterization of Graphene/V2O5/MoO3 Nanocomposite Films Vanadium pentoxide, V2O5, is an electrochromic material that, while possessing attractive properties, has some disadvantages that prevent it from being commercialized. Among these drawbacks are cycle reversibility and stability, and slow response rate. To address these drawbacks, researchers from China and Russia collaborated on a project developing a graphene/V2O5/MoO3 (GVM) nanocomposite xerogel film. They fabricated films via successive dip-coating in a sol comprised of one or more of these materials. Characterizing these different films enabled them to discriminate between the impacts of the graphene and MoO3 additions. The MoO3 addition lowered the potential difference between the anodic and cathodic peaks. Graphene was incorporated to improve the electrical conductivity, and thus increase the reversibility and the response rates. At the

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

50th cycle, decrease in charge density with cycling for the GVM film was approximately half that of the V film. Both the coloration and bleaching times decreased below 1.5 s, from 1.6 s and 2 s, respectively, for the GVM film. Corresponding improvement in the measured optical modulation, the range in percent transmittance, was found for the GVM film (25%) compared to the V, VM, and GV films. These significant performance improvements for the GVM film are encouraging with respect to it becoming a fast-switching electrochromic material. From: X. Ma, S. Lu, F. Wan, et al., ECS J. Solid State Sci. Technol., 5, P572 (2016).

Demonstration of Direction Dependent Conduction through MoS2 Films Prepared by Tunable Mass Transport Fabrication The range of applications for two dimensional (2D) materials are increasing due in part to the unique characteristics they exhibit compared to their bulk counterparts. The physical and optical properties of 2D transition metal dichalcogenides (TMDs) make them ideal for use as semiconductor layers in modern transistor technologies. Molybdenum disulfide (MoS2) is a notable TMD material due in part to its direct band gap when formed in a 2D structure. The deposition of defect-free long range 2D surfaces continues to be a challenge for transistor development and integration into existing processing methods. Belgian-based researchers have developed a facile method for the cost-effective deposition of large area MoS2 films through the sulfurization in H2S of thermally evaporated Mo layers. Their paper, published in the JSS Focus Issue on Properties, Devices and Applications Based on 2D Layered Materials, demonstrates the important role played by interface roughness to the underlying substrate and mechanical stress during H2S treatments at varied pressures in determining the nature of the resulting film. The processes were optimized through mass transport smoothing to form MoS2 films that conformally coat the substrate. The techniques developed in this paper will be important for the low cost deposition of multifunctional MoS2 films for future device applications. From: D. Chiappe, M. Mongillo, I. Asselberghs, et al., ECS J. Solid State Sci. Technol., 5, Q3046 (2016).

Tech Highlights was prepared by Colm Glynn and David McNulty of University College Cork, Ireland, David Enos of Sandia National Laboratories, Zenghe Liu of Verily Life Science, and Donald Pile of Rolled-Ribbon Battery Company. 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 fulltext version of the article.

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Interdisciplinary Research for Next Generation Electrolytes Used in Electrochemical Systems by Christopher G. Arges

t is an exciting time to be involved in electrochemical research, a field that is at the forefront in addressing the global challenges of our time—avoiding climate disruption and enabling proliferation of clean energy technologies. Electrochemical research plays a vital role in advancing numerous cutting-edge technologies, while broadly impacting the global economy and our standard of living. It is mind-boggling to contemplate the number of people across the globe that own at least one battery—an electrochemical device—and how prevalent it is among technologies encountered in our everyday life. Additionally, the field of electrochemical science and engineering has made its presence strongly felt across a variety of industries spanning commodity and specialty chemicals, healthcare, data information and processing, materials, and consumer products. While the vitality and relevance of electrochemical science and engineering to society is indisputable, it is remarkable to observe its migration to the interface of other scientific disciplines. To illustrate this broader point, this special issue of Interface is dedicated to “Next Generation Electrolytes for Electrochemical Devices” with the ultimate intent being to show how other scientific disciplines are contributing to the development of new electrolyte materials used in electrochemical devices. Prior to discussing the individual contributions in this issue, I would be remiss if I failed to talk about the importance of electrolytes for electrochemical systems. Electrodes and electrolytes comprise the heart of all electrochemical devices. Transcending the current state-of-the-art in electrochemical devices necessitates continued materials research in both these disparate domains. The term disparate is selected because the properties, function, and composition of electrode and electrolyte materials are quite different and often require different skill sets. As is well known, electrolytes are required to be ion conducting while electron insulating while often serving as a mechanically resilient separator between two electrodes. Electrodes, on the other hand, demand electron conduction and are often meso/micro-porous to enable multicomponent species transport. Contemplating these radical differences leads me to reminisce of the song “Love and Marriage,” sung famously by Frank Sinatra, and the lyrical line, “You can’t have one without the other.” And so, the future of electrochemical devices hinges on the concurrent advancement of both electrodes and electrolytes. Of these two different components, electrolytes are near and dear to my heart as working on polymer electrolytes was how I got my start in the electrochemical business. As a newly-minted father in the past year and half, a favorite book of mine to read to my daughter is You Are Stardust by Elin Kelsey because of its two subtle references to electrochemical science—in particular electrolytes. The book states on one page, “Salt still flows through your veins, your sweat, and your tears. The sea within you is as salty as the ocean.” On another page the book states, “Inside your brain, electricity stronger than lightning, powers your every thought.” These two pages demonstrate the critical role electrolytes play in our bodies serving as primary function for our cerebral activity and show the profound impact that they have on us as bioelectrochemical machines. This issue of Interface touches upon a few materials research directions to enhance electrolyte materials for electrochemical devices. Although this issue is not intended to be a comprehensive survey of electrolyte development activities and is not technology specific, it aims to convey the pathway to development of next generation electrolytes

by drawing upon other scientific disciplines. Some of the peripheral scientific disciplines are relatively mature, such as synthetic organic/ polymer chemistry, while others, such as directing the self-assembly of block copolymers and multi-scale ab-initio simulations coupled with atomistic simulations, are comparatively new. The first contribution in this issue hails from industry and is from 3M Corporation, which is engaged in the development of new perfluorosulfonic acid (PFSA) ionomers capable of high proton conductivity under dry conditions. The new PFSAs offer the enticing prospect of simplifying the balance of plant of low temperature fuel cell power plants thereby lowering their costs. The second contribution highlights emerging computational methodologies for the design of new electrolyte materials for lithiumion and sodium-ion batteries. In this contribution, Jorn and Kumar discuss the combination of different molecular modeling techniques (e.g., ab initio and molecular dynamics) that capture bulk electrolyte and electrode-electrolyte interface behavior at spatial and temporal scales that cover several orders of magnitude. The third contribution by Kambe, et al., reports on efforts to perfectly align the ionic domains in polymer electrolyte materials from one electrode to another in electrochemical cells with the overall goal to improve the ionic conductivity of these materials. Achieving such an ambitious goal draws upon knowledge from the polymer physics community. Finally, Mike Hickner at Penn State reviews the tremendous strides made in the chemical design of anion exchange membranes (AEMs) for alkaline electrochemical applications. In his contribution, he focuses on alkaline stability and the need for AEMs for high current density operation in electrochemical cells. In particular, the poor alkaline stability of AEMs has plagued electrochemical researchers for nearly half a century. However, rigorous efforts by numerous researchers within the past five years are finally putting this problem to rest. Overall, I hope you enjoy these contributions for the development of next generation electrolytes for electrochemical systems. As stated earlier, it is exciting to see the blending of electrochemical science with other scientific disciplines. © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F04171if.

About the Guest Editor Christopher G. Arges is the Gordon A. and Mary Cain Assistant Professor in the Cain Department of Chemical Engineering at Louisiana State University. His research interests center on polymer science and advanced lithography for electrochemical materials that address 21st century challenges in water and energy. Dr. Arges earned his BS, MS, and PhD in chemical engineering from University of Illinois at UrbanaChampaign (2005), North Carolina State University (2008), and Illinois Institute of Technology (2013). After obtaining his PhD, he pursued a postdoctoral fellowship at the Institute for Molecular Engineering at the University of Chicago and Argonne National Laboratory. He can be reached at carges@lsu.edu. http://orcid.org/0000-0003-1703-8323

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Increasing Fuel Cell Efficiency by Using Ultra-Low Equivalent Weight Ionomers by Michael Yandrasits, Matthew Lindell, Mark Schaberg, and Mike Kurkowski

nyone who has ever worked in a research lab developing technology for an electrochemical cell can tell you the efficiency is never high enough for a given market. This is especially true for proton exchange fuel cells (PEMFC) that run on hydrogen and oxygen from the air. This technology has great promise for use in transportation applications, enabling fully electric powered vehicles that can be rapidly refilled.1 For these applications, the limits of efficiency are continually pushed in an effort to minimize the size and weight of the battery of cells (i.e., fuel cell stack), increase the power output by running at higher current densities, or simply to increase the fuel economy and range of a hydrogen powered vehicle. One of the primary sources of efficiency loss is the ionic resistance of the proton exchange membrane (PEM). These membranes serve as the electrolyte in the cell and are made from ion conducting polymers, or ionomers. Unlike most electrolytes, the resistance of a PEM varies during operation depending on the water content within the membrane. External humidification of the hydrogen and oxygen (from air) are often needed to assure the membrane resistance is not so high as to compromise the system efficiency. New membrane technology is needed to create high performance PEMs that can operate under the most challenging conditions, where the water content of the membrane is low and resistance to proton transport is typically high.

Today’s Ionomer Technology Perfluorosulfonic acid (PFSA) type ionomers, such as DuPont’s Nafion and, more recently, 3M’s and Solvay’s ionomers, have long been the preferred materials for proton exchange fuel cell membranes.2,3 These membranes serve as the polymer electrolyte in electrochemical cells that run on hydrogen and oxygen. When used in combination with mechanical reinforcements4,5 and peroxide/free radical scavenging additives,6,7 this class of ionomers has demonstrated excellent durability and performance in both accelerated laboratory testing8 and end-use applications.9 The structures of the three main PFSA ionomers used today are shown in Fig. 1, where it is evident that, while the length and type of side chain varies, the essential nature of the polymer is nearly the same. Another similarity is that the polymer backbone largely consists of tetrafluoroethylene (TFE) units. The number of TFE units (n) varies with equivalent weight, where average n-values between 4 and 7 are typical. One advantage of using TFE in the backbone is that a relatively small number of CF2 units are necessary for the polymer to crystallize. Membranes made from these ionomers serve as the electrolyte in hydrogen fuel cells and facilitate the conduction of protons from the anode to the cathode. This conductivity, however, is highly dependent on the water content, or hydration, of the membrane. A common way to describe the degree of hydration is the number of water molecules (nH2O) per sulfonic acid group, or lambda (λ = nH2O/nSO3H). In the fully hydrated state, λ can be as high as 22 and proton conductivities over 200 mS/cm are commonly achieved by these membranes. Not surprisingly, lambda decreases with a reduction in humidity and, as a consequence, the proton conductivity decreases. It is for this reason that, despite the fact that water is a reaction product of the fuel cell, the incoming hydrogen and air streams are humidified in an effort to

maximize the membrane conductivity. The ionomer conductivity plays a crucial role in the ultimate goal of reducing the overall resistance of the membrane. The need to humidify the incoming gases adds cost, complexity, and weight to a fuel cell system and is undesirable for systems used in transportation applications where the sensitivity to these factors is especially acute. Therefore, any improvements in membrane resistance under drier conditions aide in simplifying humidification systems or result in the need for fewer cells to achieve the same performance.

New Ionomers One way to increase the proton conductivity of an ionomer is to increase the number of acid groups per unit volume, in other words, decrease the equivalent molecular weight of polymer per acid group. The most obvious way to do this is to decrease the amount of TFE co-monomer in the polymerization. This approach, however, has inherent limitations for PFSA systems, in that the molecular weight of the acid functional monomer is usually fixed based on the production methods available for each supplier. From a practical point of view, equivalent weights of about 700 g/mol are generally considered the lower limit for traditional PFSA systems. In addition, decreasing the TFE content will result in a decrease in backbone crystallinity.10 The retention of crystallinity is important because the small domains of crystalline regions serve to tie the polymer chains together in a type of physical crosslink. The presence of these crosslinks is necessary for fabrication of durable membranes that resist excessive swelling or solubility in water. One way to retain the backbone crystallinity, while decreasing the equivalent weight, is to add multiple acid groups onto a side chain. In this case, the polymer backbone can be retained while simultaneously increasing the acid content and, therefore, conductivity. Perfluoro bis(sulfonyl)imides have been suggested for use as polymer electrolytes and offer the potential to be used as both an additional acid functionality and a side chain extender.11,12 This (continued on next page)

Fig. 1. Polymer structure for the three most common PFSA ionomers used in commercial proton exchange membrane fuel cells.

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

Yandrasits, et al.

(continued from previous page)

functionality is especially attractive since the proton in the Rf-SO2N(H)-SO2-Rf structure is extremely acidic due to the strong electron withdrawing of the fluorocarbon and SO2 segments. In fact, the acid strength is very similar to that of the traditional perfluoro sulfonic acid group.13 For purposes of ionic conductivity, the bis(sulfonyl)imide and sulfonic acid functionality are considered protogenic groups since the proton is easily dissociated in both cases. Recently, 3M has synthesized ionomers with multiple bis(sulfonyl) imide groups per side chain by a sequential reaction process. The synthetic scheme is based on functionalizing the PFSA sulfonyl fluoride precursor polymer and is outlined in Fig. 2. Rather than following the traditional hydrolysis and acidification process used to make the acid form of the PFSA ionomers, as shown in Fig. 1, the polymer was reacted with anhydrous ammonia to make the sulfonamide functionality (step 1). This sulfonamide was then further reacted with 1,3 perfluoropropane disufonyl fluoride (step 2) to make a polymer with side chains containing a bis(sulfonyl)imide group and a terminal sulfonyl fluoride. The reaction can be terminated at this step and the polymer converted into the acid form using traditional methods (step 3) or the cycle can be repeated up to three times by adding ammonia followed by more 1,3 perfluoropropane disufonyl fluoride (repeating steps 1 and 2) to make a polymer with multiple imide groups per side chain. The case where the ionomer contains one bis(sulfonyl) imide per side chain, with terminal sulfonic acid, has been designated perfluoro imide acid (PFIA) and when there are multiple bis(sulfonyl) imide groups per side chain it has been designated perfluoro ionene chain extended (PFICE). The equivalent weights of a series of PFICE ionomers, synthesized from the sulfonyl fluoride precursor polymer with an equivalent weight of 700 g/mol, are shown in Table I. The numeric extension denotes the total number of protogenic (imide and acid) groups. For example, PFICE-3 contains two bis(sulfonyl)imide groups and one terminal sulfonic acid group. The PFIA ionomer is a special case of PFICE ionomer, with one bis(sulfonyl)imide and one sulfonic acid group. The theoretical values represent the case where the reaction efficiency is 100% for all attachment steps. In reality, this efficiency was not achieved and the measured EW was somewhat higher. As expected, the deviation between the theoretical and measured EW increased with the number of sequential additions. The in-plane proton conductivities of the various ionomers at 80 °C as a function of relative humidity are shown in Fig. 3. Three different equivalent weight PFSA ionomers are shown with dotted lines (1100 EW Nafion, 825 EW and 725 EW 3M ionomers), a 620 EW PFIA ionomer synthesized from an 800 EW precursor polymer, and the 438 EW PFICE-4 ionomer from Table I. Clearly, the ionic conductivity values increased with greater acid content for the ionomers, while ionic conductivity of all ionomers decreased with lower relative

Table I. Theorectical and measured equivalent weights for PFICE samples. Ionomer

Number of imide groups

Theoretical EW (g/mol)

Titrated EW (g/mol)

PFICE-2

501

534 ± 7

PFICE-3

431

475 ± 5

PFICE-4

397

438 ± 3

humidity. Interestingly, the slope of the PFIA and PFICE-4 lines (on a log scale) were approximately parallel to each other and to the PFSA controls.

Why All the Trouble to Develop New Ionomers?

The objective of this work was to increase the proton conductivity of the ionomer while maintaining a water-insoluble membrane with good physical integrity. By starting with a perfluoro sulfonyl fluoride polymer backbone of 700 or 800 g/mol, it was our expectation that the backbone crystallinity would remain, and, therefore, the water insolubility, while the ion exchange capacity would increase. In other words, each additional bis(sulfonyl)imide functionality increased the overall acid content but left the backbone unchanged. It is clear from Fig. 3 that the ionic conductivity increased with these new ionomers over all humidity ranges, but it is worth considering the implications of these improvements in actual fuel cell operating conditions. Starting with the higher humidity conditions at 90% RH, the conductivity of the PFIA ionomer was over two times higher than Nafion (335 vs. 147 mS/cm) and nearly four times higher for the PFICE-4 ionomer (567 vs. 147 mS/cm). Making a few simple assumptions, such as a 20 μm thick membrane and operating at 1.5 A/ cm2, voltage loss due only to membrane resistance at these conditions can be calculated using Ohm’s law (V=I*R). For the Nafion membrane the voltage loss was calculated to be 20 mV, the PFIA about 9 mV and the PFICE-4 about 5 mV. While these differences can be significant at times, they represent only a modest improvement at best and would not likely justify the additional effort and cost associated with these new, ultra-low equivalent weight ionomers. However, looking at the other end of the humidity range, where the conditions are significantly drier, the same comparisons were made with dramatically different conclusions. At 30% RH the ionic conductivities of Nafion, PFIA and PFICE-4 membranes were 11, 44, and 70 mS/cm, respectively. Using these values in the same analysis as above, the voltage loss due to membrane resistance at a current density of 1.5 A/cm2 was calculated to be 275, 68, and 43 mV respectively. This several hundred millivolt reduction in voltage loss due to lower membrane resistance can be put into context by converting these values into loss of efficiency. For instance, one simple measure is the ratio of the calculated voltage loss to the equilibrium potential of the hydrogen-oxygen reaction (1.23 V). Under fully hydrated conditions, the efficiency loss due to membrane resistance only was 1.7, 0.7 and 0.4% for Nafion, PFIA, and PFICE-4 respectively. Again, these differences may be significant in some situations but are generally very small values. The more interesting case, however, is where the membrane humidification is low. For the Nafion membrane a 22% efficiency loss was calculated. This value is unacceptable and would generally prevent a system design that would be expected to operate at these dry conditions. PFIA membrane provides a much larger contrast with voltage losses under the same conditions, approximately 5% loss and the PFICE-4 an even further improvement of only about 3.5% loss in efficiency. It is important to note that this analysis was based solely on the losses that were attributed to the membrane resistance and does not take into Fig. 2. Reaction scheme for pefluoro ionene chain extended (PFICE) ionomers. The number of imide account other losses in the cell such as the

attachments is represented by m and the total number of protogenic groups is m+1. 50

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

Fig. 3. Conductivity versus humidity at 80 °C for selected PFSA, PFIA, and PFICE-4 based ionomers.

cathode overpotential and resistances due to other cell components such as electrodes, interfaces, or bipolar plates. Figure 4 shows the calculated efficiency loss for a 20 μm membrane operating at 1.5 A/ cm2 over the entire humidity range based on the conductivities for all the membranes shown in Fig. 3. Figure 4 highlights the value of highly conductive membranes under low humidity conditions and, at the same time, shows that large increases in ionic conductivity under saturated conditions may have very little impact on the overall system efficiency. The benefit of extending the operating range to these low RH conditions can be realized in the form of simplified balance of plant (i.e., smaller humidifiers) or in the reduction of the number of cells needed in a stack to reach a target voltage under dry conditions.

What Are the Limits?

a diminishing return effect where each additional bis(sulfonyl)imide linkages provides a lesser impact on reducing the equivalent weight. Total water uptake is another area of concern as the number of acid groups per volume is increased. In the case where there is no TFE polymer backbone, an ionene polymer based on the 1,3 perfluoropropane disufonyl fluoride and ammonia step polymer is expected to be fully water soluble and, therefore, not a useful membrane material. This expectation is supported by a similar ionene reported by DuPont, based on the 1,4 perfluorobutane disulfonyl fluoride precursor.14 This ionene polymer was reported to have an average molecular weight of 9,430 g/mol, and was highly watersoluble. One advantage of pursuing the PFICE route is that the TFE containing backbone has long enough sequences of CF2 units to provide crystalline domains and serve as physical crosslinks that allow the ionomer to swell but not dissolve. A water solubility test, where a quantity of membrane is placed in a Soxhlet extractor with refluxing water for four hours, provides a good estimate of the watersoluble fraction of a given ionomer. In the traditional PFSA case, all equivalent weights between 700 and 1100 g/mol exhibit a small degree of solubility (<10 wt%) but are generally regarded as insoluble. The soluble fraction, however, increased slowly with greater acid content (approaching 700 g/mol) and became fully soluble once the equivalent weight dropped below about 600-700 g/mol. This was generally associated with the combined effects of the increased hydrophilic acid groups and the loss of backbone crystallinity. PFIA ionomers with an equivalent weight of about 620 g/mol, synthesized from a PFSA precursor polymer of 800 EW (n~4.5), had similar solubility as the 825 EW PFSA (~8 wt%). The PFICE series with EWs as low as 440 g/ mol that were synthesized from a 700 EW (n~3.5) PFSA precursor backbone also retained approximately the same solubility as that of the 700 EW PFSA (~10 wt%) The water uptake and swelling extent in hot water, on the other hand, continued to increase as the equivalent weight was decreased. This observed relationship was not surprising because lambda (the number of water molecules per acid group) was expected to be the same for each acid group regardless of its location on the polymer side chain. The practical result is that a greater number of acid groups per unit mass will absorb a greater number of water molecules (i.e., swell). Swelling mitigation is important for extended durability under operating conditions where the cell experiences very wet and dry conditions, such as an automotive drive cycle. The continual expansion and contraction cycles are thought to ultimately result in membrane fatigue failure and premature end of life due to gas crossover.15 This issue is especially challenging for the PFICE approach. Even with exceptional conductivity and low water solubility, there is

Clearly, the increase in conductivity at low relative humidly has the potential to simplify and improve fuel cell systems, but what are the limits to this approach? What are the consequences of adding even more acid groups to the ionomer side chain? In order to answer this question, the conductivity at one reference point (80 °C and 50% RH) versus equivalent weight is plotted (continued on next page) and shown in Fig. 5. The trend of higher ionic conductivity values with decreasing equivalent weight is expected and has been previously reported for PFSAs.5 Interestingly, both the PFIA and PFICE samples were in good agreement with the PFSA trend. Based on this comparison, it appears that the conductivity is simply a function of equivalent weight as there is no observed deviation, either positive or negative, due to the incorporation of bis(sulfonyl)imide-based protogenic groups. This is undoubtedly an oversimplification but provides a first approximation for estimating the lower limits of this approach. In addition to the measured data, the “ionene” limit is indicated in Fig. 5 with a red dashed line at 293 g/mol. This represents the case where there is no longer a perfluorinated backbone containing tetrafluoroethylene segments, but is simply the polymeric version of the ionene side chain, such as that made from a step wise polymerization of 1,3 perfluoropropane disufonyl fluoride and ammonia. Extrapolating the data to this limit indicates that the conductivity would increase by an additional 50% for this polymer compared to the PFICE-4 sample. Certainly any improvement is desirable but the benefit of this additional increase in conductivity is expected to be very modest. Practical issues also arise with such a material. For example, the number of bis(sulfonyl)imide groups needed to reduce the equivalent weight by a given amount increases Fig. 4. Efficiency loss due to membrane resistance calculated from conductivities as the equivalent weight is reduced. In other words, there is shown in Fig. 3. The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

Yandrasits, et al.

(continued from previous page)

no guarantee that the PFICE durability will be competitive with its higher equivalent weight PFSA or PFIA cousins. These ionomers will most likely need to rely on similar peroxide savaging additives and mechanical supports in order to make membranes with the requisite durability comparable to today’s commercial PFSA membranes.

The Future with New Ionomers

The need to keep perfluoro-sulfonic acid type membranes fully humidified to maintain high proton conductivity values presents a limit in designing the most efficient fuel cell systems. This has prompted the search for new ionomers that can operate under drier conditions. Simply increasing the content of acid functional monomers used in traditional PFSA membranes is not practical due to the fact that these polymers start to become water soluble at equivalent weights below about 600-700 g/mol. Adding more than one protogenic groups per side chain offers a possibility to increase the acid content (reduce the equivalent weight) and, simultaneously, maintain enough tetrafluoroethylene units in the backbone to form physical crosslinks and remain insoluble in water. The bis(sulfonyl)imide group is ideally suited for use as both an additional protogenic group and a side chain extender to a terminal sulfonic acid group. Polymers made with this approach exhibited exceptional ionic conductivities at all relative humidity conditions, though meaningful increases in cell efficiency at high current densities were only realized under the driest conditions. Membranes made with these ionomers have the potential to simplify fuel cell systems by reducing the need for external humidifiers or reducing the overall stack size. © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F05171if.

Acknowledgments This research was supported in part by the U.S. Department of Energy, Cooperative Agreement No. DE - EE0006362. DOE support does not constitute an endorsement by DOE of the views expressed in this presentation.

About the Authors Michael Yandrasits is currently the fuel cell membrane research group leader at 3M’s Corporate Materials Research Lab. He earned his bachelor’s degree in chemistry from Illinois State University and PhD in polymer science from the University of Akron. Dr. Yandrasits has worked in 3M’s research labs over twenty-four years, in the last 16 years in fuel cell membrane development. He has over 30 issued U.S. patents, primarily in the area of fuel cell technology. He has been the principle investigator for two Department of Energy funded contracts in the proton exchange membrane field and most recently an Advanced Research Projects Agency- Energy (ARPA-E) grant to develop commercially viable anion exchange membranes. He may be reached at mayandrasits@mmm.com. http://orcid.org/0000-0002-9493-0588

Matthew Lindell is currently the lead synthetic chemist in 3M’s Electrochemical Components Lab. He has a BS in chemistry and a BS in cell and molecular biology from Winona State University, Winona, MN. He has worked in 3M’s research labs for three years primarily in the field of synthesis and characterization of perfluorinated ionomers. He is currently contributing to two Department of Energy (DOE) funded projects aimed at developing new ionomers for improved membranes and electrode layers for fuel cell applications. He may be reached at mlindell@mmm.com. http://orcid.org/0000-0002-0725-8122

Mark Schaberg is a recently retired product development scientist in 3M’s Energy Components Program. Exploring and combining the fields of fluorine, organic, and polymer chemistry has evolved into exploring fishing spots on Minnesota’s 10,000 lakes, hikes on the Colorado plateau, as well as, volunteering for the American Red Cross, Meals on Wheels and Let’s Go Fishing Organizations. He may be reached at mschaberg7@gmail.com.

Fig. 5. Conductivity versus equivalent weight for three sets of ionomers. PFSA type ( ), PFIA ( ) and PFICE ( ).

Michael Kurkowski is currently a research scientist in 3M’s Electrochemical Components Lab. He has a BS in biology from St. John’s University, Collegeville, MN. He has worked in 3M’s Fuel Cell Lab for fifteen years running test stations and more recently performing physical characterizations of ionomers created for fuel cell and flow battery applications. He is currently contributing to two Department of Energy funded projects aimed at developing new ionomers for improved membranes for fuel cell applications. He may be reached at mjkurkowski1@mmm.com.

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

References 1. F. Wagner, B. Lakshmanan, and M. Mathias, J. Phys. Chem. Lett., 1, 2204 (2010). 2. S. J. Hamrock and M. A. Yandrasits, J. Macromol. Sci. Polymer Rev., 46, 219 (2006). 3. K. A. Mauritz and R. B. Moore, Chem. Rev., 104, 4535 (2004) 4. Y. Tang, A. Kusoglu, A. Karlsson, M. Santare, S. Cleghorn, and W. Johnson, J. Power Sources, 175, 817 (2008) 5. M. Yandrasits, J. H. Lee, Y. Yi, D. Pierpont, S. Hamrock, and M. Schonewill, US patent application US 20130101918. 6. Frank D. Coms, Han Liu, and Jeanette E. Owejan, ECS Trans., 16(2), 1735 (2008). 7. M. Frey, S. Hamrock, G. Haugen, and P. Pham, US patent 8,092,954. 8. M. Hicks, D Pierpont, P Turner, and T Watschke, ECS Trans, 1(8), 229 (2006).

9. K. Wipke, S. Sprik, J. Kurtz, T. Ramsden, C. Ainscough, and G. Saur, “National Fuel Cell Electric Vehicle Learning Demonstration Final Report” Technical Report NREL/TP-560054860, July 2012. 10. T. Gierke, G. Munn, and F. J.Wilson, Polym. Sci. Polym. Phys. Edn, 19, 1687 (1981). 11. J. S.Wainright, R. F., Savinell, D. D. DesMarteau, J-J. Ma, K. Sung, and L. Zhang, Proceedings of the Symposium on Electrode Materials and Processes for Energy Conversion and Storage, ECS, (1994). 12. M. S. Schaberg, J. E. Abulu, G. M. Haugen, M. A. Emery, S. J. O’Conner, P.N. Xiong, and S. J. Hamrock, ECS Trans., 33(1), 627 (2010). 13. A. Koppel, et al., J. Am. Chem. Soc., 1166, 3047 (1994). 14. C. H. Hsu, C. Junk, F. Uckert, M. Teasley, A. Feiring, C. DuBois, Z. Y. Yang, V. Petrov, and N. Daoud, US Patent 8568616 B2. 15. Y. H. Lai, C. K. Mittelsteadt, C. S. Gittleman, and D. A. Dillard, J. Fuel Cell Sci. Technol., 6(2), Feb 20, 2009.

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 ca

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 Masayuki Dokiya Robert P. Frankenthal George R. Gillooly Stan Hancock

Carl Hering W. Jean Horkans Keith E. Johnson Mary M. Loonam 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

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Breaking the Scales: Electrolyte Modeling in Metal-Ion Batteries by Ryan Jorn and Revati Kumar

he choice of electrolyte is literally at the center of lithium wide range of length scales.8 The challenge for modeling electrolytes and sodium energy storage devices as it provides the lies in the disparity between methods used at different length-scales: pathway for metal ion transport between the electrodes the basic physics included, level of parameterization, and the types during charge-discharge cycling. However, zoom in on of questions each method is capable of addressing pertaining to the the electrode interface during battery operation and it electrochemistry of solvents and salts. Hence the same methods used becomes clear that the electrolyte’s role is not always to serve as a to model chemical reactions at the electrode surface (based in quantum passive resistor. The organic solvent molecules used to dissolve metal mechanics) cannot be readily applied to describe the evolution of salts in commercial batteries, namely cyclic and linear carbonates, the interface on the order of nanoseconds. Likewise, the appropriate frequently react with the electrified interfaces to form surface films simulations for describing longer time- and length-scales (classical that in turn effect device performance.1 These films trap metal ions, molecular dynamics) do not readily incorporate reactive events and preventing them from participating in the charge transfer reactions normally cannot be used to predict chemical dynamics. From the necessary to power an external circuit, and can grow to tens of perspective of the state-of-the-art in computational modeling, lithium nanometers in thickness while accumulating over the lifetime of the and sodium ion electrolytes provide an exciting new frontier for battery.2 The quest to design a “better” electrolyte is thus complicated developing novel approaches that connect the quantum and classical by potential degradation at the electrode surface weighed against worlds while offering significant motivation to meet global challenges transport properties tens of nanometers from the interface.3 In both in energy storage and sustainability. In what follows, the current cases, the manner in which metal ions are coordinated by solvent, impact of modeling on electrolyte research is briefly assessed with co-solvent, additives, and counter-anions at the atomic level has been particular emphasis placed on efforts to bridge orders of magnitude linked to the chemistry of the breakdown products as well as to trends in length- and timescales. Two case studies will be discussed to demonstrate the utility of force-matching as a specific means of in ionic conductivity in the bulk phase.4,5 Connecting the molecular structure of the electrolyte with connecting quantum and classical approaches to model electrolytes macroscopic charge cycling performance requires computational for energy storage. (continued on next page) strategies that can span several orders of magnitude in spatial and temporal scales (see Fig. 1), from the solvation shell and diffusion of lithium (nanometers and nanoseconds) to the development of surface films (tens of nanometers and microseconds) and the effect of both on the lifetime and performance of the battery on the devicescale. Word-limit constraints on this article do not permit even a cursory examination of the wealth of experimental techniques that have been used to study electrolytes across these disparate spatial and time regimes in both half and full cell configurations (for excellent reviews, see Ref. 6 and 7). Even so, a simplified summary of these efforts points to common challenges in performing such experiments with sufficient spatial and temporal resolution in operando. As a result, many questions remain unanswered concerning the surface chemistry of electrolytes, the process of film formation, and the mechanism for ion transfer from the electrolyte to the electrode. Given the slow progress of various spectroscopic, microscopic, and surface imaging methods across decades of research, a natural question that arises is whether there is another approach that could lend complementary insights to the behavior of electrolytes in electrochemical energy storage devices and provide guidelines for their continued development. In contrast to the early years of lithium-ion Fig. 1. An illustration of the multiscale nature of electrochemical systems—the properties at the battery research, computational modeling is microscale (indicated by the top leftmost panel) are effected by the formation of surface films and now contributing an important role in studying electrolyte structuring at the interface (indicated by the top right panel for an electrolyte comprised of electrolyte properties and processes across a ethylene carbonate and LiPF6) and ultimately is reflective of the metal ion solvation shell (shown in the bottom panel for a single lithium ion).

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Jorn and Kumar

transfer processes,22 and to better understand the solvation of metal ions at normal operating temperatures.23,24 Recent reports have proven the effectiveness of the AIMD approach (at the DFT level and combined with efficient periodic boundary conditions software) to investigate the stability of the electrolyte breakdown products at the electrode surface after the initial reaction.25 Results from these AIMD studies and from time-independent quantum calculations have provided greater insights into the role of one- and two-electron reductions as well as a rationale for lithium fluoride production due to electrolyte decomposition. The advantage of AIMD simulations is built on its independence of parameterization and hence significant predictive power for exploring chemistries that are difficult to probe experimentally. At the same time, a major drawback of these simulations is their computational expense, which restricts the length and time scales studied to the order of a nanometer and tens of picoseconds, respectively. On a more technical level, the results are also often DFT functional dependent (i.e., the map that provides the energy for a given electron density) and a judicious choice of functional is required that Fig. 2. (Left) Sketch of a snapshot from an AIMD simulation of LiPF6 in ethylene is often validated against experimental observables. carbonate. The colored spheres represent the nuclei and the bubble the electron cloud. When attention is shifted from the reactivity at the (Right) A sketch of the same snapshot in a simulation using an empirical model. The atoms are represented by spheres and the bonds by cylinders. electrodes to the bulk conductivity of the electrolyte, classical molecular dynamics becomes the method of choice since it can access sufficiently long timescales to follow diffusive motion. In contrast to AIMD, classical simulations rely on atomistic empirical to provide the forces on the nuclei of the electrolyte in a Introduction to Computational Modeling models given configuration rather than upon the solution of the Schrödinger equation. Empirical force models are developed based on intuition for Because the term “computational modeling” has different the energetics of chemical bonds, data from quantum calculations, and meanings to different researchers, it is pertinent to clarify the different fitting parameters based on experimental observables such as density regimes of simulation used to study electrochemistry in metal-ion and heat of vaporization. In a sense, these models coarse-grain the batteries (see Fig. 2). Starting at the smallest length scale, the timeelectronic aspect of the system to represent the electrolyte by atomic independent Schrödinger equation provides a complete quantum particles that interact with each other as a function of geometric mechanical description of the solvent molecules and ions in the coordinates: Distances, angles, dihedral angles, etc. These models are electrolyte, albeit with frozen nuclei (the limit of 0 Kelvin). To solve typically non-reactive in that they do not allow for changes in bond the Schrödinger equation for systems of practical interest, Density topology and hence cannot be used to model chemical reactions. Functional Theory (DFT) has become the standard for predicting Classical force models, often referred to as force-fields, consist of an the equilibrium solvation structures of small clusters of molecules intramolecular component that includes energy terms for bonds, angles 9,10 11 embedded in an implicit solvent, the solvation energies of salts, and dihedrals, and an intermolecular, or more properly a non-bonded, the positions of the HOMO and LUMO of electrolyte species,12 and component. Most non-reactive empirical models, or force-fields, are the reaction pathways for reduction and oxidation of carbonates with broadly divided into two categories based on the types of non-bonded 13-17 commonly used salts such as lithium hexafluorphosphate (LiPF6). interactions: effective pair potentials and many-body models. The By developing reliable protocols for calculating reduction potentials effective pair potentials are the most common and typically include for solvent and salt combinations, DFT methods have been connected Coulomb interactions between atomic sites that bear partial charges as with high-performance computing resources to perform guided well as Lennard-Jones type van der Waals interactions between atomic 12,18 searches for new candidate electrolyte materials. While several sites.26 However, the real “quantum mechanical” potential energy “high-throughput” endeavors are currently being pursued to discover consists of not only interactions between every pair of particles, but new electrolytes, it is important to note that they often neglect the also higher order terms representing the response of the electrons on role of the electrode surface to keep the calculations manageable. It an atom to the electric field of its neighbors. Even though the twois known that interactions between the electrolyte species and the body term is dominant, often up to 80% of the total energy, these electrode often produce multiple new reaction pathways and shift the many-body effects become especially important at interfaces. The energetic positions of molecular orbitals from their bulk electrolyte many-body interactions can be included partially by using effective 19,20 values. Protocols are advancing for lithium-ion batteries in which two-body models that are parameterized to experiment, accounting for an initial screening in the absence of the electrode is supplemented some of the polarization effects in an implicit mean-field manner.27 with more detailed calculations to avoid such restrictions. Clearly, While a number of general force fields, such as OPLS-AA,28 efforts that account for the effects of the surface without significantly AMBER,29 and COMPASS,30 have been developed for organic compromising high throughput is an important priority for realizing compounds, transferability of these models to new types of molecules new electrolyte materials. remains a concern. Often empirical models are developed specifically By allowing the nuclei to move in response to electronic forces in for the systems under study, or at least modified for the specific a quantum simulation, greater sampling of reaction coordinates and ions under consideration. On the other hand, models that include molecular geometries is enabled in real time. Rather than propagate the many-body effects, such as polarizable models, are inherently more full time-dependent Schrödinger equation, two assumptions are made: transferable but come with additional computational cost. There has 1) the nuclei remain classical objects; and 2) the motion of the nuclei is been significant effort made, specifically by Borodin and Smith, to much slower than that of the electrons such that they can be essentially develop highly accurate many-body polarizable force-fields for de-coupled as represented by the Born-Oppenheimer approximation. several organic electrolytes including carbonates, polymers, and ionic Solving the electronic Schrödinger equation and propagating the nuclei liquids that demonstrate greatly improved transport characteristics as classical objects—also known as ab initio molecular dynamics and solvation structures when compared with standard pair interaction (AIMD)—has been used extensively to model electrolyte reactions models.31,32 Interestingly, a recent series of quantum calculations 21 at the carbon anode and metal oxide cathode, the related electron using a wavefunction embedding technique have hinted at the need to (continued from previous page)

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

consider not just dipoles for atomic sites, but also quadrupoles in the molecular response to accurately describe common solvent molecules such as dimethyl carbonate (DMC).33

Building Bridges between Length and Time Scales: Multi-Scale Modeling

in the context of other classical force fields, parameterization does create uncertainty about the transferability of the optimized model to other species. Technically, one is also restricted to using the model to simulate the system under the same conditions as the reference trajectory (temperature, concentration, etc.); however the results can be surprisingly robust as discussed below.

Force-Matching Lithium Surprisingly, given the individual successes of static quantum calculations, AIMD, and classical molecular dynamics, relatively little and Sodium Ion Electrolyte Systems work has been pursued to connect these methodologies in a consistent manner. With regard to simulations of ion transport, progress has been We have previously used the force-matching algorithm to develop made on integrating simulation cells containing multiple phases (i.e., atomistic empirical models from DFT-based AIMD simulations for electrode, surface film, and electrolyte) to calculate energy barriers to two very different electrolytes: A carbonate-based electrolyte with Li+ ion transfer and on bridging information from quantum simulations as the charge transport species and an ether-based electrolyte with a to describe mesoscale transport in surface films.34 For an explicit sodium salt.39,40 In both cases, improvements in the representation of connection of energetics from quantum and classical simulations, the the solvation shell around the metal ion were noted and contrasted work of Borodin and Smith stands apart as a tour de force of model with previous work using generic force-field models as well as AIMD. development from extensive single point energy calculations using Classical simulations for the system consisting of 1.5 M LiPF6 in quantum calculations.31,32 Apart from these contributions, reports of ethylene carbonate (EC) revealed that on average, the coordination extensive force field development for battery electrolytes have been around the Li+ ion was a little less than five with around 0.5 anion sparse. As an alternative, others have also made use of the passage of equivalents (PF6-) in the first solvation shell and showed improved information from classical models to quantum calculations by using agreement with the AIMD results. The solvation shell structure agreed empirical models to generate likely solvation structures that are used well with previous many-body potential simulations, having the in static DFT calculations in order to enhance sampling.35 oxygen of the carbonyl group in the EC tightly coordinated to the cation An area that has received increasing attention has been the and a diffusion coefficient in agreement with previous calculations. development of reactive classical molecular dynamics models However, it was noted that an over coordination of the ion persists and to connect information on chemical reactions with surface film likely requires fitting three-body interaction terms to capture more of development on the nanometer length scale. Degradation of carbonates the many-body polarizability. In contrast to the simulation of lithium on lithium metal electrodes has been studied using the ReaxFF ions in solution, our work with sodium triflate dissolved in diglyme approach in which the bond order of atoms is used to update the force showed that at the same concentration, the triflate is more strongly model “on-the-fly” and allow for chemical reactions to take place.36,37 bound to the sodium ion with a large fraction existing in contact Kinetic Monte Carlo has also been adapted to monitor film growth by ion pairs with an average coordination of one triflate equivalent per using a classical molecular dynamics approach that randomly allows sodium ion at a concentration of 1.5 M salt solution. Even at very for bond breaking/formation events in a manner consistent with low concentrations (0.5 M) contact ion pairs are formed, unlike in the underlying reaction rates.38 Validation of these approaches with the case of lithium ions in EC. In Fig. 3, sample solvation structures continued experiments remains critical to assessing their utility, but (continued on next page) they provide first glimpses into the reactive nature of the electrodeelectrolyte interface. In general, the pursuit of reactive force-fields remains a grand challenge (a) (b) in the field of simulations of soft matter systems and the studies mentioned here represent a growing aspect of electrolyte modeling – in particular at the electrode-electrolyte interface. Variational force-matching provides an algorithm that has been successful in constructing empirical “pair potentials” for a number of soft condensed matter systems, including organic electrolytes for batteries.39,40 The principle behind this method is to parameterize a classical model to reproduce the forces on select sites from a higher-resolution approach, hence the term force-matching. For example, one can carry out a DFT-based ab initio molecular dynamics simulation of the system of interest, in principle containing all of the information on the forces and responses, and then develop a simpler atomistic model by modifying parameters in the expressions for the atomic forces to reproduce the AIMD results. The fitting process can be iterated using dynamically uncorrelated snapshots taken from the DFT simulation to minimize the differences between the model forces and the actual forces present in the quantum simulation for a variety of configurations. In this manner certain degrees of freedom (electronic degrees in the above example) are coarse-grained out to develop a cheaper representation of the Fig. 3. Sample solvation structures are shown for the a) lithium ion in 1.5 M LiPF6 in ethylene system that nonetheless retains key information carbonate and b)sodium ion in 1.5 M sodium triflate in diglyme (sodium/lithium atoms represented encoded in the forces. As previously mentioned as magenta spheres, oxygen as red spheres, sulfur as yellow, fluorine as cyan spheres, carbon as grey spheres and hydrogen as white spheres).

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Jorn and Kumar

(continued from previous page)

are shown for both the lithium ion (1.5 M LiPF6 in EC) as well as the sodium ion (1.5 M sodium triflate in diglyme) that illustrates the above discussion. By using the force-matching procedure, we were able to construct simple pairwise models capable of accurately describing the coordination of metal ions in diverse electrolytes at a scale readily extended to the highly heterogenous electrode interface. While unraveling the nature of the molecular structure and charge transport in bulk electrolytes is important, the true power of molecular simulations lies in its ability to provide insight at the electrode-electrolyte interface. With a simple model in hand that can be readily connected to generic force-fields, simulations can now be built to describe the complex interface formed during electrolyte degradation. In the case of lithium-ion cell technologies, several components are known to build up at the electrode surface including lithium fluoride, lithium carbonate, and oligomers of carbonate subunits such as dilithium ethylenedicarbonate (Li2EDC). Using our force-matched models, we have simulated the lithium ion electrolyte held between two graphitic electrodes with a voltage applied between the two electrode surfaces. Since these models are non-reactive, the set up more accurately describes a supercapacitor than a functioning battery. However, this approach does enable us to study the structure and dynamics of the interface in relation to the bulk, which may have implications for the solvation structures used in future reactive methods. In the simulations of LiPF6 in EC, we observed that the Li+ ion is not present in the first layer next to the negative electrode except at very high applied voltages, unlike the case of the counterion (PF6-) that is present in the double layer at the positive electrode. Hence, it is the organic solvent that solvates both positive and negative electrodes rather than the salt ions. In addition to the pure electrodeelectrolyte interface, the electrode-SEI-electrolyte interface was also considered. Interestingly, phase separation of the inorganic layer near the electrode surface and the organic layer closer to the electrolyte was observed in agreement with experiments pertaining to surface film composition. These studies are ongoing and have implications in the study of battery aging wherein layered SEI interfaces impact battery performance.

Outlook for Electrolyte Modeling Computational modeling of electrolytes is currently developing along two complementary tracks: 1) searching for new combinations of solvents and salts enabled by 2) developing greater understanding of the basic electrochemistry of these species at the electrode interface. Continued progress in simulating the bulk properties of electrolytes as well as the electrode-electrolyte interface will advance both of these objectives, however this effort will require the development of new computational strategies to connect the microscopic structure to predictions of macroscopic performance. A few reports have been published recently towards this end, however there is still significant need to advance multi-scale methods capable of accurately capturing charge transport and chemical events in the context of the mesoscale morphology at the electrode surface. A substantial aspect of this challenge is the development of novel chemically reactive algorithms to model sufficient length- and timescales to consider film formation and its impact on ion transport. Modeling efforts along these lines that institute a synergistic approach with experiments will result in a far deeper understanding of processes in electrolytes as well as at electrolyte interfaces. These types of investigations should result in the end-goal of developing predictive models that will accelerate the development of “designer” electrolytes with tailored properties. © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F06171if.

About the Authors Ryan Jorn is an assistant professor of physical chemistry at Villanova University. He performed his doctoral work at Northwestern University which focused on modeling energy and charge transport in molecular junctions. After receiving his PhD, he moved to the University of Chicago and Argonne National Lab where he developed multiscale simulations of both aqueous and non aqueous electrolytes as a postdoctoral researcher. He joined the faculty of Villanova University in 2013 where his research interests remain focused on modeling materials for energy storage and studying charge transport at complex interfaces. He may be reached at ryan.jorn@villanova.edu. http://orcid.org/0000-0002-0192-9298

Revati Kumar is an assistant professor of computational chemistry at Louisiana State University. She received her doctoral degree from the University of Wisconsin-Madison. Her interest in electrolytes for battery technologies started during her postdoctoral days at the University of Chicago and Argonne National Laboratory. Her current research interests include the development of empirical models to study complex chemical systems such as electrolytes for next generation batteries, novel materials such as metal organic frameworks, macromolecules etc. She may be reached at revatik@lsu.edu. http://orcid.org/0000-0002-3272-8720

References 1. M. Gauthier, T. J. Carney, A. Grimaud, L. Giordano, N. Pour, C. Hao-Hsun, D. P. Fenning, S. F. Lux, O. Paschos, C. Bauer, F. Maglia, S. Lupart, P. Lamp, and Y. Shao-Horn, J. Phys. Chem. Lett., 6, 4653 (2015). 2. F. A. Soto, Y. Ma, J. M. Martinez de la Hoz, J. M. Seminario, and P. B. Balbuena, Chem. Mater., 27, 7990 (2015). 3. E. M. Erickson, E. Markevich, G. Salitra, D. Sharon, D. Hirshberg, E. de la Llave, I. Shterenberg, A. Rozenman, A. Frimer, and D. Aurbach, J. Electrochem. Soc., 162, A2424 (2015). 4. D. M. Seo, O. Borodin, D. Balogh, M. O’Connell, Q. Ly, S.-D. Han, S. Passerini, and W. A. Henderson, J. Electrochem. Soc., 160, A1061 (2013). 5. A. von Wald Cresce, O. Borodin, and K. Xu, J. Phys. Chem. C, 116, 26111 (2012). 6. K. Xu, Chem. Rev., 104, 4303 (2004). 7. K. Xu, Chem. Rev., 114, 11503 (2014). 8. A. Abraham, L. M. Housel, C. Lininger, D. C. Bock, J. Jou, F. Wang, A. C. West, A. C. Marschilok, K. J. Takeuchi, and E. S. Takeuchi, ACS Cent. Sci., 2, 380 (2016). 9. O. Borodin, and G. D. Smith, J. Phys. Chem. B, 113, 1763 (2009). 10. O. Borodin, M. Olguin, P. Ganesh, P. R. C. Kent, J. L. Allen, and W. A. Henderson, Phys. Chem. Chem. Phys., 18, 164 (2016). 11. E. Jónsson, and P. Johansson, Phys. Chem. Chem. Phys., 14, 10774 (2012). 12. L. Cheng, R. S. Assary, X. Qu, A. Jain, S. P. Ong, N. N. Rajput, K. Persson, and L. A. Curtiss, J. Phys. Chem. Lett., 6, 283 (2015). 13. H. Tavassol, J. W. Buthker, G. A. Ferguson, L. A. Curtiss, and A. A. Gewirth, J. Electrochem. Soc., 159, A730 (2012). 14. T. Li, L. Xing, W. Li, Y. Wang, M. Xu, F. Gu, and S. Hu, J. Power Sources, 244, 668 (2013). 15. Y. Okamoto, J. Electrochem. Soc., 160, A404 (2013). 16. L. Xing and O. Borodin, Phys. Chem. Chem. Phys., 14, 12838 (2012).

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17. Y. Wang, S. Nakamura, M. Ue, and P. B. Balbuena, J. Am. Chem. Soc., 123, 11708 (2001). 18. M. Korth, Phys. Chem. Chem. Phys., 16, 7919 (2014). 19. O. Borodin, M. Olguin, C. E. Spear, K. W. Leiter, and J. Knap, Nanotechnology, 26, 354003 (2015). 20. N. Kumar and D. J. Siegel, J. Phys. Chem. Lett., 7, 874 (2016). 21. K. Leung, J. Phys. Chem. C, 117, 1539 (2013). 22. K. Leung and J. L. Budzien, Phys. Chem. Chem. Phys., 12, 6583 (2010). 23. M. T. Ong, O. Verners, E. W. Draeger, A. C. T. van Duin, V. Lordi, and J. E. Pask, J. Phys. Chem. B, 119, 1535 (2015). 24. P. Ganesh, D.-e. Jiang, and P. R. C. Kent, J. Phys. Chem. B, 115, 3085 (2011). 25. K. Leung, F. Soto, K. Hankins, P. B. Balbuena, and K. L. Harrison, J. Phys. Chem. C, 120, 6302 (2016). 26. C. J. Cramer, Essentials of Computational Chemistry, 2nd ed., John Wiley & Sons Ltd., West Sussex (2004). 27. O. Borodin, G. D. Smith, and R. Douglas, J. Phys. Chem. B, 107, 6824 (2003). 28. W. L. Jorgensen, D. S. Maxwell, and J. Tirado-Rives, J. Am. Chem. Soc., 118, 11225 (1996). 29. J. Wang, R. M. Wolf, J. W. Caldwell, P. A. Kollman, and D. A. Case, J. Comp. Chem., 25, 1157 (2004). 30. H. Sun, J. Phys. Chem. B, 102, 7338 (1998). 31. O. Borodin and G. D. Smith, J. Phys. Chem. B, 110, 6279 (2006). 32. O. Borodin and G. D. Smith, J. Phys. Chem. B, 110, 6293 (2006). 33. T. A. Barnes, J. W. Kaminski, O. Borodin, and T. F. Miller, J. Phys. Chem. C, 119, 2863 (2015). 34. Y. Li, K. Leung, and Y. Qi, Acc. Chem. Res., 49, 2363 (2016). 35. M. Shakourian-Fard, G. Kamath, K. Smith, H. Xong, and S. K. R. S. Sankaranarayanan, J. Phys. Chem. C, 119, 22747 (2015). 36. D. Bedrov, G. D. Smith, and A. C. T. van Duin, J. Phys. Chem. A, 116, 2978 (2012). 37. S.-P. Kim, A. C. T. van Duin, and V. B. Shenoy, J. Power Sources, 196, 8590 (2011). 38. N. Takenaka, Y. Suzuki, H. Sakai, and M. Nagaoka, J. Phys. Chem. C, 118, 10874 (2014). 39. R. Jorn, R. Kumar, D. P. Abraham, and G. A. Voth, J. Phys. Chem. C, 117, 3747 (2013). 40. J. Wahlers, K. D. Fulfer, D. P. Harding, D. G. Kuroda, R. Kumar, and R. Jorn, J. Phys. Chem. C, 120, 17949 (2016).

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Ion Conduction in Microphase-Separated Block Copolymer Electrolytes by Yu Kambe, Christopher G. Arges, Shrayesh N. Patel, Mark P. Stoykovich, and Paul F. Nealey

on-conducting polymers are attractive electrolytes for molecular architecture consist of two chemically distinct polymer electrochemical devices because of their superior safety in chains that microphase separate into periodic morphologies with sizes comparison to liquid electrolytes (e.g., lower flammability, ranging from 3 to 100 nm (see Fig. 1a).5,6 The chemically distinct prevention of dendrite shorting, and reduction of the crossover nanoscale domains facilitate the expression of the properties of the of unwanted species), compact cell design (e.g., 10 μm thick individual constituents, such that two or more disadvantageously membrane separators), and the ease of their integration in solid state (continued on next page) cells. For device integration, the ionconducting polymer must also exhibit high conductivity and robust mechanical (b) (a) properties over a wide range of thermal, electrochemical, and chemical conditions, while satisfying cost and scalability requirements. At the molecular level, there are two classes of ionconducting polymers: neutral polymers with dissolved salts enabling both cation and anion conduction (e.g., polyethylene oxide with dissolved LiTFSI for lithiumion batteries), or polymers that contain ionic moieties tethered to the polymer (c) backbone with oppositely charged mobile counter-ions (e.g., sulfonated polystyrene for electrodialysis). One key material challenge for ionconducting polymers is the inverse correlation between ionic conductivity and mechanical properties. For example, Fenton, et al.,1 demonstrated in 1973 the ability of poly(ethylene oxide) (PEO) to dissolve salts into its amorphous matrix and conduct ions. The conductivity of the salt was found to improve with increasing segmental mobility of the PEO chains (often achieved by heating PEO above its glass transition temperature Tg) and (d) the elimination of crystallinity. However, these changes at the molecular level diminished the mechanical properties of the material (e.g., often reported in terms of elastic modulus2,3) leading to a soft film. Similarly, ion-conducting polymers with tethered ionic groups experience higher ionic conductivity with increased ionic loadings, but excessive swelling due to large water uptake at high loadings compromises mechanical properties of the membrane.4 In recent years, block copolymer electrolytes (BCE), a sub-class of ion- Fig. 1. Schematic showcasing the morphologies formed via block copolymer self-assembly and alignment. (a) conducting polymers, have generated The molecular structure of block copolymers where the red domain is a neutral block while the blue domain considerable attention from the is an ion conducting block. (b) (top) Through-plane alignment that provides mechanical structure allows electrochemical community as a means transport of the ions throughout the membrane, while the in-plane alignment (bottom) restricts transport to bypass this tradeoff in conductivity through the thickness direction of the film. (c) Scanning electron micrographs at different extents of BCP versus mechanical properties. Block alignment showing thin-film defects and (d) a simplified schematic of aligned BCEs showing how an ion may copolymers (BCPs) with the simplest travel from the top to bottom in each system. White circles highlight a few positions in the film where ions are unable to traverse the film.

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Kambe, et al.

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correlated properties may be independently expressed in a single material. Therefore, BCEs may be designed from the molecular level to have one domain that is an ion conductor while the other domain maintains the mechanical structure of the overall material. Functionalization of the ion-conducting domain can be accomplished either before or after the BCP is self-assembled into its nanoscale architecture. Functionalization before microphase separation enables a wider variety of chemistries to be used, but introduction of the ionic components post-self-assembly may simplify the thermodynamic driving forces for microphase separation and enable standardized processing.7-11 To date, diverse BCEs have been synthesized with an ion-conducting block (e.g., a Li salt dissolved in poly(ethylene oxide), sulfonated poly(styrene), or poly(n-methyl pyridinium iodide)) and a neutral polymer block (e.g., poly(styrene), poly(methyl butylene), or poly(ethylene)) selected to optimize the ion conductivity and mechanical response of the material, respectively.11-13

Although BCEs offer the prospect for high ionic conductivity with the desired mechanical properties, achieving conductivities comparable to their homopolymer counterparts or commercially available random copolymers (e.g., Nafion®) has remained elusive. An ideal BCE would exhibit ion-conducting and mechanical domains that span the entire thickness of the membrane providing continuous and percolating pathways for ion conduction. However, this idealized structure does not commonly occur in real BCP systems. As illustrated in Fig. 1b-d, the mechanically stiff domains free of ionic moieties form nanoscale barriers that impede ion transport. When these barriers are not controlled, they can block the ideal pathways for ion conduction and increase the length and tortuosity of the available transport pathways, thereby reducing the ion conductivity of the bulk film. Elabd and Hickner14 suggested in a notable review that future research priorities for BCEs should aim at understanding how nuanced attributes of the self-assembled morphology (e.g., grain boundaries and local defects in the microstructure that arise during self-assembly) influence the ion transport behavior.

(a)

(b)

(c)

Fig. 2. Characterization of alignment of block copolymer domains using complementary real-spacing imaging and scattering methods. Birefringence, SAXS, and cross-section TEM (from left to right) of poly(styrenesulfonate-block-methylbutylene) aligned through-plane using (a) mechanical shear and (b) electric fields. [Adapted with permission from Ref. 12. Copyright 2010 American Chemical Society.] (c) Birefringence, cross sectional AFM, and SAXS (from left to right) of a through-plane magnetic field aligned poly(ethylene oxide-block-6-(4’-cyanobiphenyl-4-yloxy)-hexyl methacrylate) with LiClO4 dissolved in the poly(ethylene oxide) layer. [Adapted with permission from Ref. 17. Copyright 2010 American Chemical Society.] 62

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One approach to achieving continuous domains throughout BCEs is to introduce external fields to align the self-assembled nanoarchitecture. Using external field alignment techniques, microphase separated domains of the BCE can be aligned parallel to the desired transport direction (e.g., with through-plane alignment in membranes) and can be connected from one side of the BCE to the other by eliminating all of the barriers in the percolating pathways in the ion-conducting domain. Figure 1b demonstrates how through-plane alignment is preferred to the alignment orthogonal to the thickness direction (i.e., in-plane alignment) because most electrochemical devices are sandwich-type cells. Sandwich cells, found in fuel cells and flow batteries, require through-plane aligned membranes because the membrane separator in the sandwich design provides separation of fluid reactants. Significant research has been focused on aligning the ionic domains of microphase separated BCEs to improve material function and to characterize transport behavior.12,15-18 In this contribution, we highlight recent advances in aligning BCEs and emphasize the role of the microphase separated structure and domain alignment on the ion-conducting pathways. Although the constituent ion-conducting polymer and the selection of ion-conducting materials are critical for such applications, such considerations are only briefly discussed here and the reader is instead directed to other reviews on BCEs and ionconducting polymers.14,19,20

Methods of Alignment and Characterization Mechanical Alignments

Mechanical alignment is considered one of the most versatile thick-film alignment techniques due to its applicability to a diverse set of BCPs. To date, BCP films have been aligned through methods such as mechanical shear,21,22 compression,12 extrusion,23,24 and roll casting.25 The degree of alignment can be controlled by manipulating variables such as the molecular weight, volume ratio of polymer segments, viscoelastic properties of each polymer component, shear rate (or shear frequency for dynamic shearing), force amplitude, and force direction.21,22,26-29 In one example, Albalak, et al.,25 reported a roll-casting technique to align poly(styrene-block-butadiene-blockstyrene) in the through-plane direction using constant shear. Shear and compression alignment techniques were also successfully applied to the BCE poly(styrenesulfonate-block-methylbutelyne) by Park, et al.12 Although the origin of assembly in mechanical alignment is ascribed to the differences in mechanical properties of each domain, the explicit theory behind the mechanism is still debated.

Electric Field Alignment

Electric field alignment is attractive because of its strong effect on noncharge carrying materials and the inverse relationship of field strength to electrode separation distance. This uniquely enables electric fields to align a wide range of materials through-plane more effectively than other methods, making it attractive for many membrane applications. The extent of alignment of a lamellar-forming BCP is proportional to the local energy (Δg) of the interface of the BCP in relation to the electric field: 2

∆ε 2 2 (1) ∆g ∼ E (qEfield i q AB ) <ε > where Δε is the difference in the dielectric constant of the two polymer domains, < ε > is the space averaged dielectric constant, E is the strength of the electric field, and (qEfield i q AB ) is the dot product of the vectors between the applied electric field and the normal to the polymer domain interface, respectively.30-33 As the system approaches full alignment, the driving force behind alignment decreases substantially, thus requiring a BCP with a large dielectric difference or the application of a large electric field. Both direct and alternating electric fields have successfully oriented the different blocks in BCPs.34 Alternating field alignment is particularly useful for domains with mobile ions that may accumulate and otherwise form a counter field in a direct field setup. Amundson, et al.,32 was the first to align poly(styrene-block-methylmethacrylate) BCPs under an electric

field. More recently, Park, et al.,12 achieved alignment of the protonconducting BCE poly(styrenesulfonate-block-methylbutylene) using an electric field.12 In an attempt to scale up the process, electric field alignment systems were integrated into roll-to-roll manufacturing.35 However, the need to kinetically trap the aligned structure prior to removing the electric field and the dielectric breakdown limits of polymeric materials are impediments to large-scale implementation of such processing methods.

Magnetic Field Alignment

Exposure to magnetic fields is another promising technique for the alignment of BCPs, in part because it eliminates the need for direct material contact and therefore is more amenable to roll-toroll and other scalable manufacturing processes in comparison to other alignment methods. Additionally, due to the lack of a dielectric breakdown, a large magnetic field can be applied to align the system. The alignment occurs when |Δfm| V >> kT where V is the volume of a BCP domain and

∆ψ =

(2)

(ψ A −ψ B ) (ψ A / φ A ) + (ψ B / φB )

(3)

where B is the magnitude of the magnetic field, μ0 is the permittivity constant, ψA and ψB are the magnetic susceptibilities of the two polymer domains, and θ is the angle between the magnetic field and the normal to the domain interfaces in the BCP.36 Similar to the electric field alignment method, magnetic field strength and the BCP permittivity differences can be increased to counter balance the reduction in energetic driving force for alignment as the alignment is achieved. Osuji, et al.,17,18,36-40 successfully employed large magnetic fields (>3 T) to align BCEs with the aid of liquid crystal (LC) or crystalline moieties with large Δψ.A recent report has also shown high extents of alignment using LC-free BCPs such as poly(styrene-block4-vinylpyridine) with a strong magnetic field (6 T).37

Characterization of Structure

The morphology of aligned BCPs has been characterized by complementary methods that provide information on the average structure, such as small angle x-ray scattering (SAXS) and birefringence, in combination with higher resolution and real-space approaches such as electron microscopy (transmission electron microscopy—TEM) to access local structural information. Figures 2a and b highlight the aforementioned structural characterization of aligned BCE films. In-situ birefringence and two-dimensional (2D) SAXS data were collected for the aligned samples to show the degree of increase in alignment in the through-plane direction. Bulk scattering techniques, such as SAXS, are attractive due to the large cross-sectional areas (i.e., mm scale) that can be characterized, allowing acquisition of statistical structural information including the degree of alignment. Cross-sectional AFM may also be used to visualize the BCP structure, as shown in Fig. 2c, enabling the direct characterization of the nanoscale structure in addition to verifying alignment and identifying defects. Using the evidence in Fig. 2a and b, Park, et al.,12 demonstrated alignment of poly(styrenesulfonate-block-methylbutylene) (PSSblock-PMB) using mechanical shear (Fig. 2a) and electric field (Fig. 2b). Comparing the birefringence data, the mechanical shear alignment yielded a degree of alignment four times better than the electric field. The surface TEM probing the structure orthogonal to the throughplane direction showed perpendicular orientation of the domains in both mechanical and electric field alignment samples, suggesting alignment through the film. In Fig. 2c, Osuji, et al.,38 demonstrated alignment of poly(ethylene oxide-block-6-(4’-cyanobiphenyl-4yloxy)-hexyl methacrylate) (PEO-block-PLA/CB) with dissolved LiClO4 using a large magnetic field. Here, the birefringence has a higher signal contrast and the 2-dimensional SAXS shows a narrow set of points on the horizontal axes indicating a high degree of alignment in comparison to the electric field and shear alignment.

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Morphological Contributions to Conductivity The conductivities of the BCEs characterized in the prior section are compiled in Table I, including for the cases when the BCEs were aligned between the electrodes, aligned parallel to the electrodes, and randomly assembled. Here we discuss the reported conductivities in terms of their absolute magnitudes, as well as the relative enhancement in effective conductivity upon well-controlled alignment. First, the absolute conductivity of the PEO-block-PLA/CB with dissolved LiClO4 aligned by magnetic field, which showed the highest degree of alignment from the structure characterization, is discussed in relation to its maximum theoretical conductivity.17 The theoretical conductivity of a LiClO4/PEO based BCE with ideal alignment may be predicted using a geometric model that simply determines the ionic conductivity based on the volume fraction of the conducting phase (ϕc ), the morphological contribution of the microphase separated BCE (fst), and the known ionic conductivity of the corresponding homopolymer (σhomopolymer): (4)

A secondary metric for BCEs is the relative enhancement in ion conductivity upon alignment processing (A = σaligned/σrandom), which enables a comparison of the impact of alignment across different materials and processes. The relative change in conductivity between aligned and randomly isotropic transport pathways vary widely in the literature, ranging from A = 10 to 0.8. It is interesting to note that PSS-block-PMB showed a decrease in conductivity when aligned by shear and electric fields suggesting a nontrivial relationship between conductivity and alignment. In contrast, films aligned by magnetic fields were reported to achieve an enhancement in ion conductivity of A =10,17 which exceeds predictions based on effective medium theory (EMT) that suggest a maximum of A = 2 for polymer blends with heterogeneous structure.43 The theoretical maximum of A = 2 is achieved from reductions in tortuosity and path length for an already percolated network. We postulate that the enhancement in conductivity larger than A = 2, which was for a magnetically aligned system, was due to the addition of new percolating pathways that participate in ion conduction which was not considered in the theoretical predictions. Such observations add to the growing evidence suggesting that local defects and boundaries between well-aligned regions, which are challenging to characterize in thick films with near perfect alignment, prevent the percolation of many ion-conducting pathways.

Probing the Local Structure

Recently we reported a method that combines precise control Using conservative values for LiClO4 dissolved in PEO (64:1 molar ratio EO:Li+ at 50 °C)41 and ϕc = 0.23,, the estimated maximum σBCE over the nanoscale structure of a BCE and a device design capable for a perfectly aligned system (fst = 1) is 0.028 mS/cm. Despite the of electrochemical measurements with a high signal-to-noise ratio observed increases in conductivity with alignment, even one as large to elucidate how the morphology impacts ion transport in BCEs.11 as that achieved by the magnetic alignment methods of Majewski, Thin film self-assembly techniques were utilized because they form et al.,17 the peak performance of a film of this BCE material has charge transport pathways with specific alignments and geometries. been experimentally measured to be 3 × 10-3 mS/cm at 50 °C which An interdigitated electrode (IDE) design enabled ionic conductivity remains an order of magnitude smaller than the maximum theoretical measurements with large signal-to-noise ratios for the self-assembled conductivity. It also falls two orders of magnitude below the desired thin-film BCEs. Furthermore, the thin-film self-assembled BCEs were ion conductivity for Li ion battery applications (0.1 mS/cm near structurally characterized on the IDE (see Fig. 3). This system allowed 25 °C).42 We caution that such analyses require ionic conductivity the exact structure of the ion-conducting pathways to be imaged, while data of the homopolymer that is acquired using methods consistent also quantifying structural attributes of the material, using simple topwith measuring the BCE variant. Hence, it is recommended that best down metrology tools such as scanning electron microscopy (SEM). practices simultaneously report the ion conductivity of both the BCE Similar methods have been applied, for example, using lamellar BCP in and homopolymer (provided the homopolymer electrolyte conductivity thin films to template the fabrication of highly tortuous gold nanowire can be measured). It is important to point out that unlike homopolymer pathways.44 From electrical measurements on these structures it was electrolytes, the ion-conducting block in the BCE can tolerate high discovered that, in a randomly isotropic system even when thoroughly ionic loadings because the adjacent non-ionic block provides interconnected, only a small number of paths actively participate in mechanical integrity. A homopolymer identical in composition to the electrical conduction. Using such approaches, Arges, et al.,45 showed ion-conducting BCE may suffer from poor mechanical properties and that ion conductivity in self-assembled, thin films of poly(styrenedissolve or excessively swell in water/solvent if the ionic loadings are block-2vinylpyridine/n-methyl pyridinium iodide) (PS-block-P2VP/ high. Nevertheless, it is clear that BCEs are not achieving a majority NMP+ I-) significantly increased with a decreasing density of defects of their theoretical conductivity even with highly aligned structures that terminate conduction pathways, as may arise with varying as confirmed through SAXS and cross-sectional AFM/TEM. Such interconnectivity of the ion-conducting domain (see Fig. 3b and c). observations may be attributed, in part, to defects, grain boundaries, and Table I. Ion conductivities reported in the literature as a function of alignment method for BCEs. The BCEs have terminal pathways that are present at been examined when aligned in the channel direction, without alignment, and in an anti-aligned direction as concentrations below the detection illustrated. Single ion conductors (SI) and neutral polymers with dissolved salts (DS) are represented. Method of Mechanical Conductive BCE Conductivity capabilities of available metrology Alignment T (°C) RH (%) Ref ϕc Alignment Segment Segment Type (mS/cm) techniques. It is critical to note that, 31 as alignment approaches near perfect levels, it becomes progressively more PSS Park, et al. 25 98 35 PMB (20 mol % SI 0.465 difficult to quantify defect densities and Mechanical [12] sulfonated) the distribution of defect types due to the 45 inability of real-space characterization methods to probe sufficient surface 28 areas/volumes. Quantifying individual PSS defects in percolating pathways and Park, et al. 25 98 35 Electric PMB (20 mol % SI 0.465 [12] determining the extent of alignment sulfonated) thus requires advanced metrology that 35 can resolve features <50 nm in samples with thicknesses >1 µm over surface 3E-4 areas of several cm2, which is not a Majewski, PEO/LiClO4 25 — et al. 3E-5 Magnetic PLA/CB DS 0.23 trivial task. (1:120) [17]

4E-7

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In addition, Chintapalli, et al.,46 introduced a method of relating the local morphology acquired from TEM micrographs of a poly(styreneblock-ethylene oxide: LiTFSI) BCE to conductivity by simulating a 2D electric potential. Based on the success of these initial studies of thin film systems in capturing the local structure and conductivity, it may be concluded that BCE alignment will require significantly higher degrees of control to take advantage of the dual property nature of the material. Beyond alignment of the BCE domains, a topological parameter of morphology that is critical for ion transport is the fraction of the possible pathways that actively participate in ion conduction. Although alignment of the domains enables a higher percentage of the domains to form conduction pathways, the domains must be exceptionally well aligned (i.e., >>99% aligned) to eliminate sufficient defects as to allow the majority of the ion-conducting pathways to become accessible.

Future Directions

alternative conducting polymers must be considered without regard for their mechanical properties, as the neutral domain of the BCE can independently dictate the overall mechanical behavior. One possible candidate exhibiting these properties is poly(propylene carbonate) (PPC).54 PPC has a wide electrochemical window (4.6 V vs Li+/Li) and high room-temperature conductivity (0.3 mS/cm). As an ionconducting homopolymer, however, the Li salt concentration in PPC could not be increased further without resulting in poor mechanical properties.55 By incorporating PPC in a BCE, a significantly higher ionic loading may be realized, thereby simultaneously enhancing the conductivity and meeting the desired mechanical attributes of the material.

Closing Thoughts In this review, we have surveyed methods for controlling and characterizing the alignment of ion-conducting nanostructures in BCEs. Although high degrees of alignment in BCE domains have been reported, there remains significant room for improvement. Even exceptionally well-aligned BCEs exhibit conductivities that are a fraction of the theoretical maximum, and we postulate that the lower than anticipated conductivities are a by-product of the high

Interpreting recent insights on the role of the global and local structure on ion conductivity in aligned BCEs provides an optimistic outlook and a clear path for future research. To ensure that BCEs become competitive candidates for electrochemical device integration, it will be important to: i.) achieve precise structural control of thick films, ii.) further (b) develop tools for characterizing (a) 2D and three-dimensional (3D) structures at the nanoscale, and iii.) engineer materials with higher ion conductivities to raise the maximum theoretical conductivity of perfectly aligned BCE. Characterization tools that provide the automated and highthroughput acquisition of images with nanoscale resolution such as critical dimension SEM (CD-SEM)47,48 may find value here by determining alignment and defect densities over (c) much larger areas, as might electron tomography methods49 that allow for real-space visualization in 3D. Molecularlevel modeling to understand defect annihilation mechanisms in BCP materials may also provide insight into how to achieve perfect alignment,50-53 and may be extended to consider the energy landscapes for defect populations in the presence of shear, electric, or magnetic fields or under directed self-assembly. In addition, achieving BCE materials with the conductivity necessary for device integration will also require improving the maximum theoretical conductivity of the ion-conducting domain. As previously calculated, BCEs with LiClO4 dissolved in PEO reached a maximum theoretical conductivity of 0.0276 mS/ cm at 50 °C, which is still a Fig. 3. Thin film BCP self-assembly as a platform for definitively elucidating local ion transport behaviors. (a) factor of 3.6 below the targeted Interdigitated electrode design used to characterize both the structure and conductivity of BCEs. Electrochemical data for poly(styrene-block-2vinylpyridine/n-methyl pyrdinium iodide) showing (b) the dependencies of ionic conductivity on room temperature performance the defect density in the unaligned system. The dotted line is provided as a guide for the eye and the different markers of 0.1 mS/cm. Therefore, to represent data gathered from different volume fraction films of PS-block-P2VP as shown in (c) where the increasing raise the maximum theoretical volume fraction of the interconnected P2VP domain (shaded red) increases the total connectivity of the conducting conductivity of a BCE, domain. The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

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fraction of nonpercolated conduction paths that arise from the small population of local defects that remain in the self-assembled structure. Quantification of the defect density and types of defects is a significant challenge for existing methods because of the large areas that must be probed at high resolution. To understand how a low density of defects can affect conductivity, self-assembly techniques and thin film characterization methods have been employed and preliminary studies have elucidated the importance of specific defect populations on the termination and percolation of pathways for ion conduction. It is therefore proposed that increasing the number of percolated domains in an aligned system, in addition to developing better 2D/3D metrology techniques and raising the maximum theoretical conductivity through materials design, would lead to BCE systems with better performance characteristics. Building upon the recent structural insights and the demonstration of alternative alignment approaches for BCEs, we anticipate that the field will make immense progress and exhibit significant growth in the coming years. © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F07171if.

Acknowledgments This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. Y. Kambe was supported by the National Science Foundation Graduate Research Fellowship under Grant no. DGE-1144082.

About the Authors Yu Kambe is one of the inaugural PhD candidates at the Institute for Molecular Engineering at the University of Chicago and is a recipient of the National Science Foundation Graduate Research Fellowship (2016). He is also a guest graduate scholar at Argonne National Laboratory Materials Science Division. His research interests focus on molecular and morphological structure-function relationships for electrochemical applications. Yu earned his BS in materials science and engineering from Cornell University (2013). He came to the PhD program bringing with him a cumulative seven years of industry experience working in fields such as: nanomaterials, Li-ion batteries, and transparent conductive films for device integration. He can be reached at ykambe@ uchicago.edu. http://orcid.org/0000-0002-1422-350X

Christopher G. Arges is the Gordon A. and Mary Cain Assistant Professor in the Cain Department of Chemical Engineering at Louisiana State University. His research interests center on polymer science and advanced lithography for electrochemical materials that address challenges in water and energy. Dr. Arges earned his BS, MS, and PhD in chemical engineering from University of Illinois at Urbana-Champaign (2005), North Carolina State University (2008), and Illinois Institute of Technology (2013), respectively. After getting his PhD, he did a postdoctoral fellowship at the Institute for Molecular Engineering at the University of Chicago and Argonne National Laboratory. He can be reached at carges@lsu.edu.

Shrayesh N. Patel is currently an assistant professor in the Institute for Molecular Engineering at the University of Chicago. Previously, he was a postdoctoral research scientist at the University of California, Santa Barbara in the Materials Research Laboratory and received his PhD in chemical engineering at the University of California, Berkeley. Prof. Patel’s research expertise resides at the intersections of polymer science, organic electronic materials, and electrochemistry. His research has focused on revealing the limits of electrical performance of semiconducting polymers for transistors and thermoelectrics. In addition, his work has focused on the application of simultaneous electronic and ionic conducting block copolymers for lithium battery electrodes. He can be reached at shrayesh@uchicago.edu. http://orcid.org/0000-0003-3657-827X

Mark Stoykovich is a senior lecturer in the Institute of Molecular Engineering at the University of Chicago. His research is motivated by important engineering challenges in the fields of advanced lithography, flexible electronics, biosensing, and polymer flocculation, and has focused on materials design and characterization through the control of molecular-level interactions, surfaces, interfaces, and nanoscale structures. He was previously a faculty member at the University of Colorado Boulder, and received BS degrees in chemical engineering and chemistry from MIT (2000) and a PhD in chemical engineering from the University of Wisconsin–Madison (2007). He can be reached at stoykovich@uchicago.edu. http://orcid.org/0000-0001-9040-5658

Paul F. Nealey is currently the Brady W. Dougan Family Professor at the Institute for Molecular Engineering of the University of Chicago, and a senior scientist at Argonne National laboratory. His research interests include nanofabrication techniques based on advanced lithography and directed self-assembly, dimension dependent material properties of nanoscopic macromolecular systems, and quantitative 3D characterization of the structure of soft materials. He is a fellow of the American Physical Society, NSF Career Award recipient, the Camille Dreyfus Teacher-Scholar Award, the Nanoscale Science and Engineering Forum Award from the American Institute of Chemical Engineers, the Arthur K. Doolittle Award from the American Chemical Society, the 2015 Intel Outstanding Researcher Award in Patterning, and the 2016 Semiconductor Industry Association—Semiconductor Research Corporation University Researcher Award. Professor Nealey earned a BS from Rice University and PhD from MIT—both in chemical engineering. He can be reached at nealey@uchicago.edu. http://orcid.org/0000-0003-3889-142X

http://orcid.org/0000-0003-1703-8323

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30. K. Amundson, E. Helfand, X. Quan, S. D. Hudson, and S. D. Smith, Macromolecules, 27, 6559 (1994). 31. K. Amundson, E. Helfand, X. Quan, and S. D. Smith, Macromolecules, 26, 2698 (1993). 32. K. Amundson, Macromolecules, 24, 6546 (1991). 33. Y. Tsori, Rev. Mod. Phys., 81, 1471 (2009). 34. S. A. Mullin, G. M. Stone, A. A. Teran, D. T. Hallinan, A. Hexemer, and N. P. Balsara, Nano Lett., 12, 464 (2012). 35. J. Y. Lee, J. H. Lee, S. Ryu, S. H. Yun, and S. H. Moon, J. Memb. Sci., 478, 19 (2015). 36. P. W. Majewski, M. Gopinadhan, and C. O. Osuji, J. Polym. Sci. Part B Polym. Phys., 50, 2 (2012). 37. Y. Rokhlenko, M. Gopinadhan, C. O. Osuji, K. Zhang, C. S. O’Hern, S. R. Larson, P. Gopalan, P. W. Majewski, and K. G. Yager, Phys. Rev. Lett., 115, 2 (2015). 38. X. Feng, M. E. Tousley, M. G. Cowan, B. R. Wiesenauer, S. Nejati, Y. Choo, R. D. Noble, M. Elimelech, D. Gin, and C. O. Osuji, ACS Nano, 8, 11977 (2014). 39. M. Gopinadhan, P. W. Majewski, and C. O. Osuji, Macromolecules, 43, 3286 (2010). 40. P. Deshmukh, M. Gopinadhan, Y. Choo, S-k. Ahn, P. W. Majewski, S. Y. Yoon, O. Bakajini, M. Elimelech, C. O. Osuji, and R. M. Kasi, ACS Macro Lett., 3, 462 (2014). 41. A. Vallée, S. Besner, and J. Prud’Homme, Electrochim. Acta, 37, 1579 (1992). 42. J. B. Goodenough and Y. Kim, Challenges for Rechargeable Li Batteries, 587 (2010). doi:10.1021/cm901452z 43. J. Sax and J. M. Ottino, Polym. Eng. Sci., 23, 165 (1983). 44. K. M. Diederichsen, R. R. Brow, and M. P. Stoykovich, ACS Nano, 9, 2465 (2015). 45. 45. C. G. Arges, Y. Kambe, M. Dolejsi, G.-P. Wu, T. Segal-Peretz, J. Ren, C. Cao, G. S. W. Craig, and P. F. Nealey, Interconnected Ionic Domains Enhance Conductivity in Microphase Separated Block Copolymer Electrolytes, Journal of Materials Chemistry A, (accepted in press), (2017). 46. M. Chintapalli, K. Higa, X. C. Chen, V. Srinivasan, and N. P. Balsara, Polym. Phys., 55, 266 (2017). 47. B. Bunday, Gaps analysis for CD metrology beyond the 22nm node. in SPIE 8681, Metrology, Inspection, and Process Control for Microlithography XXVII, 86813B (2013). 48. J. R. Michael, C. Y. Nakakura, T. Garbowski, A. L. Eberle, T. Kemen, and D. Zeidler, Microsc. Microanal., 21, 697 (2015). 49. T. Segal-Peretz, J. Winterstein, M. Doxastakis, A. RamierzHernandez, M. Biswas, J. Ren, H. S. Suh, S. B. Darling, J. A. Liddle, J. W. Elam, J. J. de Pablo, N. J. Zaluzec, and P. F. Nealey, ACS Nano., 9, 5333 (2015). 50. F. A. Detcheverry,D. Q. Pike, U. Nagpal, P. F. Nealey, and J. J. de Pablo, Soft Matter, 5, 4858 (2009). 51. C. Liu, A. Ramirez-Hernandez, W. Han, G. S. W. Craig, Y. Tadai, H. Yoshidai, H. Kang, S. Ji, P. Gopalan, J. J. de Pablo, and P. F. Nealey, Macromolecules, 46, 1415 (2013). 52. R. Ruiz, H. Kang, F. A. Detcheverry, E. Dobisz, D. S. Kercher, T. R. Albrecht, J. J. de Pablo, and P. F. Nealey, Science, 321, 936 (2008). 53. W. Li, P. F. Nealey, J. J. de Pablo, and M. Müller, Phys. Rev. Lett., 113, 1 (2014). 54. J. G. Thevenin and R. H. Muller, J. Electrochem. Soc., 273–280 (1987). 55. J. Zhang, J. Zhao, L. Yue, Q. Wang, J. Chai, Z. Liu, X. Zhou, H. Li, Y. Guo, G. Cui, and L. Chen, Adv. Energy Mater., 5, 1 (2015).

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Strategies for Developing New Anion Exchange Membranes and Electrode Ionomers by Michael A. Hickner

nion exchange membranes are one of the most visible areas for new materials development in membranebased electrochemical systems. Because anion exchange membranes in many instances facilitate high internal device pH, it is possible to employ new catalysts that are corrosion resistant in base in addition to gaining access to reaction pathways that are not accessible in acidic environments with known catalysts. Significant progress has been realized in anion exchange membrane fuel cells, water electrolyzers, flow batteries, and electrochemical cells enabled by new membrane chemistries (see Fig. 1). Despite the red-hot pursuit of new materials in this area, no commercially-available anion exchange membrane exists that is a.) optimized for high current density cell operation and b.) resilient in alkaline media for prolonged periods of time at elevated temperatures (80 °C or above). Materials from Tokuyama, Fumatech, Fujifilm, and others have begun to make inroads in this area, but a “Nafionequivalent” does not exist for electrochemical cells that operate under basic conditions. Thus, groups studying high pH electrochemical devices have had to rely on custom synthesis of anion exchange membranes to make headway in this field. As a result, a wealth of new anion exchange membrane structures has been reported and a number of outstanding results have been widely recognized. This article discusses some of the most promising routes to new anion conductive materials for membranes, porous electrodes, and other uses such as surface modifiers. Pitfalls for scaling up the reported chemistry are discussed as are potential pathways forward. The intent of this article is not to provide comprehensive information on everything that has been done in this field. For an overarching list of activities in anion exchange membranes, the reader is referred to these excellent reviews.1-4 Rather, this article serves as a primer to how the electrochemical community might access and promote new material developments in this field.

current generation of materials. Bauer, et al., explored the effect of different cations on the stability of poly(styrene) and poly(sulfone) based anion exchange membranes.15 This early report foresaw the lack of a stable AEM for electrochemical applications and proposed DABCO-crosslinked materials as a possible solution. Tomoi, et al., have perhaps had the largest impact on the current state of anion exchange membranes.16 In this seminal paper, alkyl spacers were placed between the aromatic rings and quaternary ammonium cations in poly(styrene)-based resins. The spacers between the aromatic ring and the cationic group dramatically increased the alkaline stability of the materials compared to benzyl-tethered cations to styrene. While Tomoi’s early work on spacers was geared towards stable cationic polymers for phosphonium phase transfer catalysts,17 these insights on the effects of spacer chains have been verified in the current literature in a number of reports. Overall, it is clear that side chains should be pursued with all haste. However, it remains difficult to scale-up this type of chemistry despite recent promising progress.18-20 Research by Xu,21 Hibbs,22 Holdcroft,23 Jannasch,24 Bae,25 Li,26 and others have pushed a plethora of new anion exchange membranes into the community (see Fig. 2). Newly reported chemical structures for membranes and ionomers currently outweigh promising device results. However, exploration of many possibilities for new anion exchange membranes has resulted in some interesting and new emerging trends, outlined below, for the rationale design of high-performance, longlifetime materials. While attachment of robust cations lends the function of ionic conductivity to the membrane, the polymer backbone is a critical component to ensure chemical and mechanical stability (continued on next page)

Modern History of AEMs for Electrochemical Devices Radiation grafted membranes pioneered by Varcoe and Slade were one of the first embodiments of anion exchange membranes specifically geared towards high-performance electrochemical devices.5-7 Varcoe and Slade made rapid progress between 2002 and 2008 in applying their unique radiation grafted membranes to fuel cells and also making breakthroughs in the soluble anion exchange ionomer needed for high current density electrodes.8 The work of Varcoe and Slade on new materials, along with reports of noble metal-free fuel cells and new membranes by Zhuang, et al.,9 generated tremendous interest across the globe and teams of electrochemical researchers and polymer chemists quickly formed. Today, radiation grafted membranes from Varcoe,10 and Zhuang’s membranes11 and catalysts,12 lead the field because of the breakthroughs and device insights made possible by the advent of these new materials. Before the acceleration of the recent work in anion exchange membrane for alkaline electrochemical devices and redox flow batteries, there had been much previous work on anion exchange membranes for water treatment applications (e.g., electrodialysis). Key reviews of the older literature in this field can be found in References 13-14. A couple of important papers have provided direction for the

Fig. 1. Anion exchange membrane devices and materials opportunities.

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of the material.27,28 The community is beginning to recognize that polymers with electron withdrawing groups in the backbone, such as poly(sulfone)s, do not hold up well under high pH conditions. Electron withdrawing groups in the backbone of aromatic polymers cause sites for nucleophilic attack by hydroxide with subsequent decreases in molecular weight and ultimately membrane mechanical failure. Measurements of chemical degradation and molecular weight decreases through chain scission have demonstrated the drawback of poly(sulfone)-based AEMs. To combat backbone stability issues, poly(styrene), poly(phenylene), poly(fluorene), and other unique aromatic polymers free of electron withdrawing groups in the backbone have been reported with promising results. Poly(styrene) is an interesting choice due to its low cost, existing infrastructure in anion exchange membranes for water treatment, and synthetic diversity. However, poly(styrene)-based membranes have poor mechanical properties and require novel block copolymer strategies or mechanical supports for robust membrane performance and they can degrade quickly under strong oxidizing environments. In this regard, Varcoe and Gubler’s29 fabrication of radiation grafted membranes, both for AEMs and PEMs, based on styrenic monomers makes a lot of sense. The scale-up potential of poly(fluorene), poly(phenylene), ROMP-based backbones, and biphenyl alkylene polymers30 are still to be demonstrated. Poly(phenyelene oxide) is an electron-rich aromatic backbone with moderate stability in base. This polymer has been an excellent platform for AEM development due to its ease of chemical modification and large-scale synthesis. However, poly(phenylene oxide) is susceptible to degradation under the most stringent conditions of high temperature (above 80 °C) and high pH (1-4 M NaOH)31 and under oxidative conditions.32 Under milder conditions at 60 °C, many materials have demonstrated high

(a)

pH stability, so it is difficult to find the most promising materials using low-temperature degradation measurements. Nevertheless, PPO continues to be an accessible material platform for many groups, but carbon-carbon bonded backbones free of ether linkages will likely be one of the ultimate solutions to high stability AEMs under basic conditions. In addition to exploring the possibilities for robust polymer backbone architectures, extensive work on surveying appropriate cations has been performed. Many initial reports on anion exchange membranes employed the benzyltrimethyl ammonium cation. This type of cation has proven to yield high conductivity membranes with reasonable stability and is very easy and inexpensive to synthesize with aromatic polymer backbones. New cation structures by Yan, et al., and others have energized the field in the search for novel cations and greatly expanded the pallet of possibilities.33-40 However, many new types of cations have not been validated across a number of independent groups in materials or devices. Additionally, many novel cations can be expensive. Kreuer, et al., has recently published an extensive study of model compound cation stability and these observations are currently being followed up in polycationic materials.41 Other work has shown that ammonium-based cations appear to yield the most promising device performance, but there are some indications that the cations may need to be further optimized for use as an ionomer in the catalytic electrode layers.42 It should be mentioned that there is a perfluorinated AEM analogous to sulfonated PFSAs.43 TOSFLEX with a perfluorinated backbone and a cationic side chain has been reported some time ago. However, these materials are very difficult to access by non-specialists in perfluorinated polymer chemistry and the fate of continued TOSFLEX research is unclear. Another path to attain perfluorinated AEMs entails starting from commercially available perfluorinated sulfonyl fluoride precursor materials. Several research groups have shown recent promising results in preparing AEMs from the sulfonyl fluoride form

(b)

Fig. 2. Some common a) backbones and b) cations for anion exchange membranes. 70

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perfluorinated polymers and the carboxylate form of Nafion.44-46 These membranes derived from commercially available precursors, still require further optimization for robust alkaline stability at elevated temperatures and for use in electrochemical devices with high current density operation. Overall, there is a large pallet of possible AEMs with different polymer backbones, cation linkers, and cationic headgroups. There are also some recent concepts in composite membranes.47 Despite the high visibility activity in research on anion exchange membranes, scale-up and the open availability of square meters of membranes and liter quantities of ionomer solutions are still barriers to widespread development and detailed study of the performance of membranebased electrochemical devices based on AEMs. The following section provides some guidance to think about scale-up possibilities of these materials.

Scale-Up Strategies To provide AEMs in large-enough scale for continued progress in devices, simple, inexpensive, and industrially-relevant synthesis routes are required. To this end, brominated PPO has served as a key material to produce AEMs at the square meter scale. The presence of benzylic methyl groups on poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) provides a facile pathway to mild and inexpensive bromination of the benzylic methyl groups for subsequent functionalization by tertiary amines or phosphines. This route has been demonstrated widely since high molecular weight PPO is available on the commercial scale and the bromination and amination reagents are readily accessible and easy to handle. This benzylic bromination/amination route is also relevant to other polymers that contain benzylic methyl groups. The key to the success of this route is that it is based on a commercial polymer platform and the polymer synthesis does not have to proceed from scratch. Bringing a new polymer backbone to market is exceedingly difficult, so judicious choices are needed when considering platform

materials for AEMs. This realization about the true barriers to polymer scale-up may prompt more exploration and optimization of styrenic, ether-based, and polyolefin polymer backbones for use in anion exchange membranes since these types of polymers are all widely available in the commercial sphere. However, to date, there has not been enough in-device testing and analysis of degradation mechanisms to predict which backbones show the most promising attributes under device operation and oxidative conditions. Chloromethylation in its various forms (including the Wright method of in-situ chloromethyl methyl ether generation48 and paraformaldehyde route49) will be difficult to push forward to industrial-scale synthesis. The use of chloromethyl methyl ether is a non-starter in many facilities. Additionally, any small amounts of reagent left in the reaction mixture will be prohibitively expensive to dispose of in an environmentally-benign way. The community has gotten a lot of mileage out of chloromethylation and its variants to kick-start the field, but for AEMs that have a chance of making a large-scale impact in the field, chloromethylation is not the preferred strategy even though it is a route to modify many aromatic polymers. In many cases, well-designed syntheses will bypass chloromethylation while still resulting in the target AEM. Figure 3 compares free-radical bromination and chloromethylation routes for similar poly(sulfone)type AEMs.50-52 The extra step required in the bromination route to synthesize benzylmethyl-containing polymers can impose a large barrier to scale-up since introducing a new polymer to the market is difficult. Therefore, leveraging commercial polymer backbones and appropriate modification chemistries that can be practiced at scale is important going forward. While the processes described above are easy to accomplish on the laboratory scale, more industrially-relevant syntheses are likely needed. Therefore, the participation of companies and custom synthesis houses that have the capability for multi-kg scale polymer synthesis and large-scale membrane casting are needed in the community. (continued on next page)

Fig. 3. Comparison of (left) bromination and (right) chloromethylation routes to poly(sulfone)-based AEMs. The Electrochemical Society Interface â&#x20AC;˘ Spring 2017 â&#x20AC;˘ www.electrochem.org

Hickner

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Perspective and Conclusions As the work toward new materials discovery for anion-conductive polymers has progressed over the last decade, the community has settled on a few key lessons to move the field forward: • Benzyltrimethyl ammonium-based polymers are stable enough for beginning membrane studies, but for 1000s hours of lifetime, advanced AEMs with new backbones and new cations are likely needed and a concerted push towards new stability motifs is recommended. • Mechanical reinforcement of new anion-conductive membranes is required for robust MEA integration and cyclic performance. In some cases, robust mechanical reinforcement will extend the lifetime of tested devices somewhat until a more intrinsically stable polymer comes to the fore. • Cell performance optimization studies on control materials are badly needed. • In-device degradation pathways are completely unknown. • Standardized testing methodologies are required for key material properties including chemical stability, conductivity, mechanical properties, and device performance and degradation. • New devices and application targets will continue to move the field forward with partnerships between polymer chemists, catalyst and materials developers, electrochemical engineers, and industry. Over a number of studies, aromatic polymers with benzyltrimethyl ammonium cationic groups have shown reasonable performance. In specialized examples, the lifetime of these types of membranes have been extended to over 1000 hours, but the cell conditions must be carefully optimized and controlled.53 This lack of data on how to preserve membrane health by designing stable MEAs and operating cells for maximum lifetime is a direct result of limited availability of materials for cell fabrication and testing. Open availability of thin membranes and high conductivity ionomer solutions will help to clarify the issues surrounding device lifetime and show the community new pathways for device optimization. All membranes that have met DOE performance requirements for polymer electrolyte membrane fuel cells (PEMFCs) outlined in the Fuel Cell Technologies Office Multi-Year Research, Development, and Demonstration plan have used mechanical supports—such as those in GORE-SELECT membranes. The need for supported membranes is driven by extremely thin membranes (10-25 μm) to yield low cell resistance and to ease water management issues in the cell. The mechanical supports enable wet-dry cycling requirements to be met in operating cells. Thus, it is reasonable to extrapolate that the best AEMs will have to incorporate mechanical supports. Pintauro, et al., has demonstrated electrospun AEMs with superior mechanical properties.54 Additionally, composite and supported membranes have been reported, including the intrinsically supported samples of Varcoe. In order for device testing to proceed, support strategies and thin membranes on the order of 25 μm or less will be needed. There has been much recent progress in the pursuit of high power density alkaline fuel cells, even though lifetime reports have been more rare. The gains from 100 mW/cm2 to 300 mW/cm2 to 1.5 W/cm2 in a few short years have been tremendous. Additionally, alkaline electrolyzers have demonstrated some significant gains in performance with limited use of precious metals.55,56 Access to materials from Varcoe, Yan, Hickner, Zhuang, Ramani, and others have made these cell studies possible. However, work on extending the lifetime of anion exchange membrane electrochemical cells and the fundamentals of stability and degradation are still in their infancy. So far, the field has approached

AEM stability by examining the nucleophilic or hydroxide resistance of the materials. Degradation studies employing modeling,57 small molecules,36,41,58 and polymers31,35 have all contributed to a growing body of work outlining the most hydroxide resistant building blocks for these materials. However, the mechanisms operating in high reactivity hydroxide environments may not be representative of what is occurring in an electrochemical device—especially in regard to oxidative stress and not fully hydrated conditions (e.g., low humidity). We know from PEMs that aromatic and aliphatic polymers are particularly susceptible to radicals and oxidation—as evidenced by their poor Fenton stability. The lack of stability in aromatic and aliphatic PEMs in the presence of reactive oxygen species (ROS) is one main reason that perfluorinated backbones have been pushed forward. It remains to be determined if device operation at high pH imposes similar constraints. In conclusion, anion exchange membranes and our understanding of these materials have come a long way in the last decade. We now have cells that show power densities of over 1 W/cm2, where not too long ago 100 mW/cm2 was a struggle. However, there is still much work to do. The field needs widely available materials for cell performance, optimization, and device degradation studies. Additionally, materials need to be mechanically and chemically robust. Finally, the promise of many anion exchange membrane devices relies on the use on nonprecious metals for catalysis in high pH environments. Much more work is needed on catalysts for this environment and the associated challenges of membrane electrode assembly fabrication and device testing with non-precious metal electrodes need to be pursued. © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F08171if.

Acknowledgements M.A.H. acknowledges the Corning Foundation for the Corning Faculty Fellowship. The Materials Research Institute and the Institutes for Energy and the Environment are acknowledged for infrastructure support at The Pennsylvania State University. The National Science Foundation (DMREF grant CHE-1534326), and the U.S. Department of Energy (EERE grant DE-EE0006958, ARPA-E grant DEAR0000776) are acknowledged for current research support. Mike Hickner thanks Christopher G. Arges for editorial support.

About the Author Mike Hickner is an associate professor and the Corning Faculty Fellow in the Department of Materials Science and Engineering, with appointments in the Department of Chemical Engineering and the Department of Chemistry at The Pennsylvania State University. Additionally, he is the associate director of the Materials Research Institute, an organization composed of 200 faculty members to promote materials research on campus through central facilities, large centers, and innovative interdisciplinary research. His research group at Penn State is focused on the synthesis and properties of ioncontaining polymers, measurement of water-polymer interactions using spectroscopic techniques, and the application of polymeric materials in energy and water treatment technologies. Hickner’s work has been recognized by Young Investigator Awards from ONR and ARO, a 3M Nontenured Faculty Grant, the Rustum and Della Roy Innovation in Materials Research Award, and a Presidential Early Career Award for Scientists and Engineers from President Obama. He is on the Editorial Advisory Board of Macromolecules and ACS Macro Letters and is a member of The Electrochemical Society Editorial Advisory Committee. He has co-authored 8 patents and over 150 publications that have been cited more than 12,000 times. He can be reached at hickner@matse.psu.edu.

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The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

t ech SEC TION highligh NE WS ts Europe Section The ECS Europe Section held its election in the late 2016. The members of the new executive committee, for January 1, 2017 through December 31, 2018 are: Chair Petr Vanýsek, Northern Illinois University, USA, and Central European Institute of Technology, Brno, Czech Republic Vice Chair Renata Solarska, University of Warsaw, Poland Secretary Davide Bonifazi, Cardiff University, UK Treasurer Roberto Paolesse, University of Rome Tor Vergata, Italy Past Chair Enrico Traversa

Members-at-Large Ainara Aguadero, Imperial College, London Nicolas Alonso-Vante, Universite de Poitiers Krzysztof Bieńkowski, University of Warsaw Noel Buckley, University of Limerick Andreas Bund, TU Ilmenau Stefan De Gendt, IMEC Geir Haarberg, Norwegian University of Science and Technology Adriana Ispas, TU Ilmenau Deborah Jones, University of Montpellier Pawel Kulesza, University of Warsaw Robert Lynch, University of Limerick Philippe Marcus, CNRS-ENSCP (UMR 7045) Krysztof Miecznikowski, University of Warsaw Iwona Rutkowska, University of Warsaw Patrick Schmuki, University of Erlangen Zbigniew Stojek, University of Warsaw Benjamin Wilson, Aalto University TKK

India Section Now in its fifth year, the ECS India Section annual school has come to be recognized as India’s most prestigious and most sought after electrochemistry teaching program for researchers. This year’s school was conducted by S. R. Narayan of the Loker Hydrocarbon Research Institute, University of Southern California. The four-day school was held in Tamil Nadu, India, August 20-24, 2016. The theme of the school was “Electrochemical Energy Storage and Conversion: Materials, Processes and Applications.” The school was attended by 87 participants drawn from the industry and academia across the country. The riveting discourses over 14 lectures covered an entire gamut of fundamental and applied topics.

S. R. Narayan (left) was welcomed by the ECS India Section Chair Vijayamohanan K. Pillai (right).

The fifth edition of the school also marked the end of five years of yeoman service rendered by T. Prem Kumar. He was at different periods the secretary, counsellor, and co-chair of the ECS India Section. Generous sponsorship came from Applied Materials, Adilab Technologies, BioLogic Science Instruments, and Inkarp Instruments. The last three sponsors mentioned displayed battery testing equipment at an exhibition that was arranged during the school.

Present at the valediction of the 2016 ECS India Section school were (left to right): D. Jeyakumar, secretary; S. R. Narayan; T. Prem Kumar, vice chair; N. Vaidehi; and M. Sathish, treasurer.

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

t ech SEC TION highligh NE WS ts Canada Section The ECS Canada Section held its fall symposium at the University of Ontario Institute of Technology on November 12, 2016. The meeting was organized by Brad Easton and Mohammadreza Ghavidel. The symposium theme was “Interdisciplinary Electrochemistry” and attracted more than 75 attendees. It was comprised of morning and afternoon sessions, a poster session with best poster awards, followed by a wine and cheese reception. Janine Mauzeroll of McGill University delivered the keynote presentation, titled “Redox Triggered Vesicles: A Promising Approach for Drug Delivery.”

Janine Mauzeroll delivered the keynote presentation at the ECS Canada Section’s fall symposium.

The three student poster awards were presented to: Nakkiran Arulmozhi (First Place, Queens University), Matthew Genovese (Second Place, University of Toronto), Jeffrey Henderson (Third Place, Western University). Further details about this meeting and other ECS Canada Section activities can be found online at www.electrochem.ca.

First place student poster award winner Nakkiran Arulmozhi (center) with conference organizers Mohammadreza Ghavidel (left) and Brad Easton (right).

San Francisco Section The ECS San Francisco Section held its annual meeting in May 2016 at Stanford University. The event was organized to recognize the winner of the 2016 ECS San Francisco Section Daniel Cubicciotti Student Award, which went to Yiyang Li from Stanford University. Honorable mentions were Katherine Harry (UC Berkeley), William Nguyen (Stanford), and Andrew Scheuermann (Stanford). Both the winner and the three honorable mention recipients gave a presentation on their research and extracurricular activities at the section’s annual meeting. In addition, the section also organized a joint event with the California Section of the American Chemical Society in October 2016. The event was initiated with a group lunch for audience from both, industry and academia, was used to network, and was followed by a seminar entitled “New Soft-Matter Nanomaterials at the Interface of Polymer Science and Structural Biology” given by Ronald Zuckermann, senior scientist at Lawrence Berkeley National Laboratory. Finally, the audience enjoyed a tour at Molecular Foundry, Lawrence Berkeley National Laboratory, a Department of Energyfunded nanoscience research facility, which provides users from around the world with access to cutting-edge expertise and instrumentation in a collaborative, multidisciplinary environment.

Attendees gathered at Molecular Foundry, Lawrence Berkeley National Laboratory during the 2016 ACS-ECS joint meeting.

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AWARDS NE W MEMBERS Program

Awards, Fellowships, Grants ECS distinguishes outstanding technical achievements in electrochemistry, solid-state science and technology, and recognizes exceptional service to the Society through the Honors & Awards Program. Recognition opportunities exist in the following categories: Society Awards, Division Awards, Student Awards, and Section Awards. ECS recognizes that today’s emerging scientists are the next generation of leaders in our field and offer competitive Fellowships and Grants to allow students and young professionals to make discoveries and shape our science long into the future.

See highlights below and visit www.electrochem.org for further information.

ECS Society Awards The Edward Goodrich Acheson Award was established in 1928 for distinguished contributions to the advancement of any of the objects, purposes, or activities of The Electrochemical Society. The award consists of a gold medal, a wall plaque, a $10,000 prize, life membership, and complimentary meeting registration. Materials are due by October 1, 2017. The Charles W. Tobias Young Investigator Award was established in 2003 to recognize outstanding scientific and/or engineering work in fundamental or applied electrochemistry or solid state science and technology by a young scientist or engineer. The award consists of a scroll, a $5,000 prize, life membership, complimentary meeting registration, and travel assistance to the designated meeting. Materials are due by October 1, 2017.

ECS Division Awards 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 (JES). 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 coauthor of a paper that appeared in JES or another ECS publication. The award consists of a scroll and a $2,000 prize. Materials are due by April 1, 2017.

The Electrodeposition Division Early Career Investigator Award recognizes an outstanding young researcher in the field of electrochemical deposition science and technology. Early recognition of highly qualified scientists is intended to enhance the scientist’s stature and encourage especially promising researchers to remain active in the field. The award consists of a scroll and a $1,000 prize. Materials are due by April 1, 2017. The Electronics and Photonics Division Award was established in 1968 to encourage excellence in electronics research and outstanding technical contribution to the field of electronics science. The award consists of a scroll, a $1,500 prize, and the choice between travel assistance of up to $1,000 or life membership. Materials are due by August 1, 2017. The Energy Technology Division Research Award was established in 1992 to encourage excellence in energy related research. The award consists of scroll, a $2,000 prize and membership in the energy technology division for as long as the recipient is an ECS member. Materials are due by September 1, 2017. The Energy Technology Division Supramaniam Srinivasan Young Investigator Award was established in 2011 to recognize and reward an outstanding young researcher in the field of energy technology. The award consists of a scroll, a $1,000 prize, and complimentary meeting registration. Materials are due by September 1, 2017. The SES Research Young Investigator Award of the Nanocarbons Division was established in 2007 to recognize and reward one outstanding young researcher each year in the field of fullerenes, carbon nanotubes, and carbon nanostructures. The award consists of a scroll, a $500 prize, and complimentary meeting registration. Materials are due by September 1, 2017.

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AWARDS NE W AWA MEMBERS PROGRAM RDS

Student Awards

Section Awards

The Georgia Section Outstanding Student Achievement Award was established in 2011 to recognize academic accomplishments in any area of science or engineering in which electrochemical and/or solid state science and technology is the central consideration. The award consists of a $500 prize. Materials are due by August 15, 2017.

The Europe Section Alessandro Volta Medal was established in 1998 to recognize excellence in electrochemistry and solid state science and technology research. The award consists of a silver medal and a $2,000 prize. Materials are due by September 1, 2017 (deadline extended).

The Energy Technology Division Graduate Student Award was established in 2012 to recognize promising young engineers and scientists in fields pertaining to this division. The award consists of a scroll, a $1,000 prize, complimentary student meeting registration, and complimentary admission to the ETD business meeting. Materials are due by September 1, 2017.

The Korea Student Award was established in 2005 to recognize academic accomplishments in any area of science or engineering in which electrochemical and/or solid state science and technology is the central consideration. The award consists of a $500 prize. Materials are due by September 30, 2017.

The Industrial Electrochemistry and Electrochemical Engineering Division H. H. Dow Memorial Student Achievement Award was established in 1990 to recognize promising young engineers and scientists in the field of electrochemical engineering and applied electrochemistry. The award consists of a scroll and a $1,000 prize to be used for expenses associated with the recipient’s education or research project. Materials are due by September 15, 2017.

Awards Winners Join us in celebrating your peers as we extend congratulations to all! The following awards are part of the ECS Honors and Awards Program, one that has recognized professional and volunteer achievement within our multidisciplinary sciences for decades.

Society Awards Winners Allen J. Bard Award in Electrochemical Science

Gordon E. Moore Medal for Outstanding Achievement in SSS&T

Doron Aurbach is a professor in the Department of Chemistry at Bar-Ilan Univerity in Israel, where he founded and currently leads the Electrochemistry Group. Under his supervision, 50 PhD and 70 MSc students received their degrees. Aurbach’s team researches the electrochemistry of active metals, nonaqueous electrochemical systems, electrochemical intercalation processes, electrochemical water desalination, and electronically conducting polymers. Additionally, they develop rechargeable high energy density batteries and supercapacitors, as well as novel electroanalytical and spectro-electrochemical methods for sensitive electrochemical systems. Aurbach has published more than 540 peer-reviewed papers, which have received more than 37,000 citations. He serves as a technical editor for the Journal of The Electrochemical Society and has been named fellow by ECS (2008), ISE (2010), and MRS (2012). He is the head of the Israel National Research Center for Electrochemical Propulsion.

Paul Kohl received his PhD in chemistry from the University of Texas in 1978. After graduation, Kohl was employed at AT&T Bell Laboratories from 1978-1989. In 1989, he joined the faculty of the Georgia Institute of Technology in the School of Chemical and Biomolecular Engineering, where he is currently a regents’ professor and holder of the Hercules Inc. Thomas L. Gossage Chair. Kohl is a past editor of the Journal of The Electrochemical Society, Electrochemical and Solid-State Letters, and Interface. He is a past president of ECS and past director of the Semiconductor Research Corporation Interconnect Focus Center.

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AWARDS NE W MEMBERS Program Division Awards Dialectic Science & Technology Division Thomas D. Callinan Award Hiroshi Iwai has worked in the semiconductor industry for 26 years. After receiving BE and PhD degrees from the University of Tokyo, he worked at both Toshiba Corporation and Tokyo Institute of Technology. Currently, he is a professor emeritus at the Tokyo Institute of Technology, and a vice dean and distinguished chair professor of National Chiao Tung University in Taiwan. Iwai is highly recognized for his significant contributions for the development of dielectric films. Those contributions include introduction of BPSG film reflow to integrated circuits; finding plasma induced damage on gate insulator; prevention of boron penetration of gate oxide by RTN gate SiO2; and the introduction of 1.5 nm tunneling gate oxide to CMOS. Additionally, Iwai is the chair of the ECS Japan Section. He has served as an organizer of many ECS symposia and has been a member of various Society committees. Iwai coauthored over 1,000 international and 500 domestic papers in journals and conferences proceedings.

Electronics and Photonics Division Award D. Noel Buckley is a professor emeritus of physics at the University of Limerick in Ireland and an adjunct professor of chemical engineering at Case Western Reserve University. He was ECS president from 2008 to 2009 and previously served as an associate editor for both the Journal of The Electrochemical Society and Electrochemical and Solid-State Letters. Buckley’s ECS publications experience expanded into his role on the editorial advisory board of ECS Transactions. Additionally, he served as chair of the ECS Europe Section, as well as chair, secretary, and treasurer of the ECS Electronics and Photonics Division. From 1979 to 1996, Buckley was a member of the technical staff at Bell Laboratories, where he played a key role in the epitaxial crystal growth and characterization of compound semiconductors for high performance optoelectronics. Prior to Bell Labs, Buckley did his postdoctoral research under Wayne Worrell at the University of Pennsylvania. Currently, his research activities include vanadium flow batteries, nanopore structures in compound semiconductors, and stress in electrodeposited metal nanofilms for microelectronics applications.

Energy Technology Division Research Award Hubert Gasteiger began his career in electrochemistry in 1993 when he received his PhD in chemical engineering from UC Berkeley, followed by postdoctoral fellowships at the Lawrence Berkeley Laboratory and Ulm University. He moved on to join the Fuel Cell Activities program of GM/Opel (Honeoye Falls, NY, USA), leading catalyst and membrane electrode assembly (MEA) research. He was promoted to GM technical fellow in 2004. 78

In 2007, he joined Acta S.p.A. (Italy), working on alkaline membrane-based technologies. After a one-year visiting professorship at MIT (2009) with Yang Shao-Horn, working on lithium-air batteries, he was appointed chair of technical electrochemistry at the Technical University of Munich, where he is now focusing on materials, electrode, and diagnostics development for fuel cells, electrolyzers, and lithium-ion batteries. Gastegier is an ECS fellow, received the 2012 Grove Medal for fuel cell research, the 2015 David C. Grahame Award of the ECS Physical and Analytical Electrochemistry Division, and the George C.A. Schuit Lectureship at the University of Delaware in 2015.

Energy Technology Division Supramaniam Srinivasan Young Investigator Award Ahmet Kusoglu is a research scientist in the energy technology area at Lawrence Berkeley National Laboratory (LBNL), where he works on polymer materials for electrochemical devices and related electrochemical-mechanical phenomena for energy applications. Kusoglu joined LBNL in 2010 as a postdoctoral fellow to study membrane transport and degradation in fuel cells. His research at Berkeley has focused on modeling and diagnostics of ionomers and their interfaces in an effort to understand and improve their functionalities in electrochemical energy devices. Prior to joining the lab, he received his PhD in mechanical engineering from the University of Delaware. Kusoglu has published over 35 papers in peer-reviewed journals and a book chapter on fuel cell membranes. His current research interests involve the characterization and modeling of degradation, transport, and structure/function relationships in ionomers and thin films.

Energy Technology Division Graduate Student Award

Antoni Forner-Cuenca studied chemical engineering at the University of Alicante, where he graduated with honors. He completed his PhD at the Swiss Federal Institute of Technology in Zürich (ETHZ) in 2016 and performed his doctoral research in the Paul Scherrer Institute’s Electrochemistry Laboratory under the supervision of Pierre Boillat and Thomas. J. Schmidt. Forner-Cuenca’s work focuses on the development of novel porous materials for advanced water management in polymer electrolyte fuel cells (PEFCs). In the frame of his PhD thesis, a method based on electron radiation grafting has been applied to porous substrates to modify the hydrophobicity of the inner surfaces, leading to materials with patterned wettability. The use of these modified materials in PEFCs lead to significant performance improvements. In March 2017, Antoni will join the laboratory of Prof. Brushett at the chemical engineering department of the Massachusetts Institute of Technology as a postdoctoral fellow to work on advanced electrodes for non-aqueous redox flow batteries.

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

AWARDS NE W AWA MEMBERS PROGRAM RDS Industrial Electrochemistry and Electrochemical Engineering Division H. H. Dow Memorial Student Achievement Award Muhammad Boota is currently a PhD candidate in material science and engineering at Drexel University, where he’s working on redox-active hybrid materials for electrochemical energy storage systems under the supervision of Yury Gogotsi. Boota received his BS from Government College University in Pakistan and MS from Uppsala University in Sweden and University College London. He went on to join a joint Erasmus Mundus MS program in Materials for Energy Storage and Conversion which he completed at Paul Sabatier University (France), Warsaw University of Technology (Poland), University of Picardie Jules Verne (France), and Drexel University (U.S.). Boota has been offered prestigious fellowships and awards, including the Erasmus Mundus Fellowship, the Marie Curie Fellowship, Graduate Research Fellowship, and ECS Summer Fellowship. 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 the 1st Philadelphia Electrochemical Society Symposium at Drexel University.

Industrial Electrochemistry and Electrochemical Engineering Division Student Achievement Award Bahareh Alsadat Tavakoli is a postdoctoral fellow at the Center of Catalysis for Renewable Fuels at the University of South Carolina (USC). She received her PhD in chemical engineering in 2006 from USC, where she performed research in electrocatalysis, fuel cells, and corrosion under the supervision of John W. Weidner. Tavakoli’s research efforts include both computational and experimental design for high temperature corrosion and PEM fuel cell analysis. The outcome of this work has been used in Savannah River National Laboratory and the National Renewable Energy Laboratory. Prior to obtaining her PhD, Tavakoli received both her BS and MS degrees from Sharif University of Technology in Tehran, Iran. During this time, her research focused on the analysis of polymer electrolyte membrane fuel cells (PEMFC), where she and her team developed a computational fluid dynamic model for the PEMFC performance.

Nanocarbons Division Richard E. Smalley Research Award Shunichi Fukuzumi earned BS and PhD degrees in chemical engineering at Tokyo Institute of Technology in 1973 and 1978, respectively. After working as a postdoctoral fellow (1978-1981) at Indiana University, he joined the Department of Applied Chemistry at Osaka University as an assistant professor in 1981 and was promoted to a full professor in 1994. His research interests are artificial photosynthesis and electron transfer chemistry. He is now a distinguished professor of Ewha Womans University, designated professor of Meijo University, and professor emeritus of Osaka University. He has published more than 1,083 scientific publications and 36,700 citations with h-index 93.

Physical and Analytical Electrochemistry Division David S. Grahame Award Viola Birss is a world leader in the area of electrochemistry at surfaces and interfaces and in nanomaterials development for a wide range of clean energy applications. She is recognized for making seminal contributions to the understanding of hydrous oxide surface films, and more recently her team has been developing electrocatalysts and support materials for high-temperature and lowtemperature fuel cells, electrolysis cells, and supercapacitors. Birss is currently a professor of chemistry and has been a Tier I Canada Research Chair in Fuel Cells and Related Energy Systems at the University of Calgary since 2004. Throughout her career, Birss has been the recipient of numerous prestigious scientific awards and honors and is a fellow of the Royal Society of Canada, ECS, and the Canadian Society for Chemistry. Additionally, Birss was a co-founder and leader of both the Western Canada Fuel Cell Initiative and the Solid Oxide Fuel Cells Canada Network and is currently the scientific director of the Calgary Advanced Energy Storage and Conversion Research Technology group.

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

NE W MEMBERS ECS is proud to announce the following new members for October, November, and December 2016.

Members

Srikanth Allu, Oak Ridge, TN, USA Melvin Arias, Santo Domingo, Dominican Republic Roy Baguley, Cochrane, AB, Canada David Chang, San Jose, CA, USA Peter Chang, Cupertino, CA, USA Qing Chen, Haidian Qu, Beijing Shi, China Zhengjian Chen, Guiyang, Guizhou, China Byung Doo Chin, Yongin, South Korea Peter Chu, Jhongh City, Taiwan, Taiwan Martin Desilets, Sherbrooke, QC, Canada Thomas Donnelly, Coventry, West Midlands, UK Donald Dornbusch, Columbia, MO, USA Eric Dow, Barrington, RI, USA Ronggui Du, Xiamen, China Santiago Fajardo, Madrid, Spain Michael Falcinelli, Boxford, MA, USA Halbert Fischel, Las Vegas, NV, USA Cynthia Ginestra, Houston, TX, USA Xiao Gong, Singapore, Singapore Xin Guo, Wuhan, China Patrick Herring, Redwood City, CA, USA Robin Jacobs-Gedrim, Albuquerque, NM, USA Olga Kasian, Dusseldorf, NW, Germany Hyeong Kim, Gwangju, South Korea Abhishek Kumar, Oak Ridge, TN, USA Tatiana Lastovina, Rostov-on-Don Rostov Area, Russia Juan Li, Nantou County, Taiwan Christopher Mallinson, Basingstoke, Hampshire, UK Arjan Mol, Delft, Zuid-Holland, Netherlands Taiki Morishige, Suita, Osaka, Japan Mototaka Ochi, Kobe, Hyogo, Japan Tae-Sik Oh, Auburn, AL, USA Marjorie (Marie-Georges) Olivier, Mons, Hainaut, Belgium Jan Oredsson, Oslo, Norway Siva Palani, Newnan, GA, USA Robert Pattillo, Morris, AL, USA Francisco Perez, Trujillo Madrid, Spain Mireille Poelman, Mons Hainaut, Belgium Godwin Severa, Honolulu, HI, USA Manish Sharma, Bayport, NY, USA Roger Sonnemans, Meijel, Netherlands Daniel-Ioan Stroe, Aalborg East, Denmark Gottfried Suppan, Urcuqui, Imbabura, Ecuador Reyhan Taspinar, Arlington, MA, USA Markus Valtiner, Dusseldonf, Germany Hidetoshi Wada, Settsu, Osaka, Japan Anthony Wilby, Newport, UK Yu Yan, Beijing, China Omar Yepez, The Woodlands, TX, USA Masahiro Yoshino, Koshigaya, Saitama, Japan Beniamin Zahiri, Vancouver, BC, Canada John Zhang, Altamont, NY, USA Xiuling Zhu, Dalian Liaoning, China

Student Members

Bilen Akuzum, Philadelphia, PA, USA Shahid Ali, Aalborg, North Jutland, Denmark Nikolaos Antonatos, Liverpool, Merseyside, UK Karina Asheim, Trondheim, Sor-Trondelag, Norway Marco Balabajew, Oxford, Oxfordshire, UK Ryan Baldwin, Reno, NV, USA Michael Barta, Seattle, WA, USA Logan Beers, Reno, NV, USA Michael Bending, Reno, NV, USA Ella Bentin, Oxford, Oxfordshire, UK Ryan Bernadett, Nevada City, CA, USA Omonayo Bolufawi, Tallahassee, FL, USA Victoria Bridewell, South Bend, IN, USA Joel Nino, Bugayong Lincoln, NE, USA Saheed Bukola, Clemson, SC, USA Chris Burns, Charlottesville, VA, USA Danielle Butts, Los Angeles, CA, USA Margaret Calhoun, Nashville, TN, USA Xi Cao, Rolla, MO, USA Wasu Chaitree, Tallahassee, FL, USA Ren-Jie Chang, Oxford, Oxfordshire, UK Sean Chapman, Spring Hill, FL, USA Kudakwashe Chayambuka, GENK, Limburg, Belgium Ting Chen, Oxford, Oxfordshire, UK Chia-Ju Chou, Taipei City, Taiwan, Taiwan Ting-Mao Chou, Taipei, Taiwan, Taiwan Tin-Mao Chou, Hsinchu, Taiwan, Taiwan Mallory Clites, Philadelphia, PA, USA Samuel Coles, Oxford, Oxfordshire, UK Michael Curtice, Jamestown, OH, USA Andrew Dawson, Los Angeles, CA, USA Astrid De Clercq, Muenchen, BY, Germany Stewart Dickson, St Andrews, UK Maricor Divinagracia, Quezon City, Metro Man, Philippines Debasmita Dwibedi, Bangelore, India Lars Erik Andreas Ehnbom, College Station, TX, USA Ayman El-Zoka, Toronto, ON, Canada Mohamed Fadl, Oxford, Oxfordshire, UK Cody Falconer, Reno, NV, USA Frank Fan, Cambridge, MA, USA Farinaz Firouzan, Arlington, TX, USA Amirhossein Foroozan, Ebrahimy Toronto, ON, Canada Dominic Forstermann, Oxford, Oxfordshire, UK Steffen Frensch, Aalborg, Nordjylland, Denmark Ming Gao, Gainesville, FL, USA Yilun Gong, Oxford, Oxfordshire, UK Jack Gritton, College Park, MD, USA Abhay Gupta, Austin, TX, USA Jan Habedank, Garching bei Muenchen, BY, Germany Fatima Hamade, Auburn, AL, USA Cayla Harvey, Sparks, NV, USA Spencer Hawkins, College Station, PA, USA

Brian Heligman, Austin, TX, USA Jeffrey Henderson, Oshawa, ON, Canada Emily Hitz College, Park, MD, USA Tuan Hoang, Waterloo, ON, Canada Kyle Hofstetter, Calgary, AB, Canada Mohammad Kabir, Hossain Arlington, TX, USA Md Mosaddek Hossen, Albuquerque, NM, USA Wei-Tzu Hou, Taoyuan City, Taoyuan Dist, Taiwan Jing Huang, Hong Kong, Hong Kong, China Gabrielle Hunt, Boston, MA, USA Zadariana Jamil, White City, London, UK Yun-Ting Jao, Hsinchu, Taiwan, Taiwan Christian Jeppesen, Aalborg, Nordjylland, Denmark Ivana Jevremovic, Trondheim, SorTrondelag, Norway Sitong Jia, Hong Kong, Hong Kong, China Abhay Jith, Erakulam, KL, India Thomas Jones, Chester, Cheshire, UK Anitha Jose, Cochin, KL, India Jose Juarez-Rolon, Portola, CA, USA Huang Jun, Beijing, China Hidetaka Kariya, Sendi, Miyagi, Japan Jitti Kasemchainan, Oxford, Oxfordshire, UK Saeed Kazemiabnavi, Ann Arbor, MI, USA Jobeda Jamal Khanam, Tallahassee, FL, USA Francis Kinyanjui, Oxford, Oxfordshire, UK Jiri Kulhavy, Oxford, Oxfordshire, UK Saeed Lafmejani, Aalborg, Denmark Jessica LaLonde, Cleveland, OH, USA Joseph Lambert, Plainfield, IL, USA Byeongyong Lee, Atlanta, GA, USA Yi Teng Lee, Reno, NV, USA Erik Lindberg, Cleveland, OH, USA Fabian Linsenmann, Muenchen, BY, Germany Cong Liu, Sendai, Miyagi, Japan Nicholas Loeve, Bondi, New South Wales, Australia Adeline Loh, Penryn Cornwall, UK Thomas Lonsdale, Oxford, Oxfordshire, UK Santamon Luanwuthi, Oxford, Oxfordshire, UK Salvatore Luiso, Raleigh, NC, USA Liuba Lukina, Heverlee, Flemish Brabant, Belgium Tyler Lyons, Columbus, OH, USA Wenjie Ma, Hong Kong, Hong Kong Seyed Saeed Madani, Aalborg, Nordjylland, Denmark Jenna Malley Boston, MA, USA Jasna Mannayil Cochin, KL, India Katie McCay, Trondheim, Sor-Trondelag, Norway (continued on next page)

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

NE W MEMBERS (continued from previous page)

Todd Miller, Medford, MA, USA Gholamreza Mirshekari, Cookeville, TN, USA Mojtaba Momeni, London, ON, Canada Joy Marie Mora, Quezon City, Metro Man, Philippines Krishnan Murugappan, Oxford, Oxfordshire, UK Venkat Nemani, Urbana, IL, USA Michelle Nguyen, Reno, NV, USA Aondoakaa Nomor, Newcastle-upon-Tyne, Cumbria, UK Raisa Oliveira, Lisboa, Portugal Joseph Ortenero, Tuscaloosa, AL, USA Menghsuan Pan, Cambridge, MA, USA Demetra Pantelis, Gainesville, FL, USA Alexander Pateman, Oxford, Oxfordshire, UK Yi Peng, Santa Cruz, CA, USA Jesse Phillips, Broken Arrow, OK, USA Trishna Raj, Oxford, Oxfordshire, UK Keaton Ramsey, Cullman, AL, USA Savitha Rangasamy, Erode, TN, India M. Azam Rasool, Leuven, Belgium Ying Ren, Xi’an, China Reyixiati Repukaiti, Corvallis, OR, USA Subhasis Roy, Athens, OH, USA

Rico Rupp, Louvain-la-Neuve, Brabant Wallon, Belgium Anju S, Kochi, KL, India Dinesh Sabarirajan, Medford, MA, USA Farshid Salimijazi, Cookeville, TN, USA Manu Shaji, Cochin, KL, India Sneha Shanbhag, Pittsburgh, PA, USA Manav Sharma, Medford, MA, USA Trishank Sharma, Vancouver, BC, Canada Kumar Siddharth, Sai Kung, Hong Kong, Hong Kong Gurvinder Singh, Trondheim SorTrondelag, Norway Shikhar Singh, College Station, TX, USA Amir Peyman Soleymani, Cookeville, TN, USA Rodica - Elisabeta Stroe, Aalborg, Denmark Desiree Mae Sua-an, Quezon City, Metro Man, Philippines Shichen Sun, Miami, FL, USA Behrouz Takabi, College Station, TX, USA Harsh Tamakuwala, College Station, TX, USA Trae Taylor, Reno, NV, USA Kendall Teichert, Ann Arbor, MI, USA Naresh Kumar Thangavel, Detroit, MI, USA Kristian Thorbjornsen, Trondheim, SorTrondelag, Norway

Kuan Tian, Wuhan, Hubei, China Drew Tomchyshyn, Toronto, ON, Canada Yu-Hsiang Tsao, Hsinchu, Taiwan Siddesh Umapathi, Rolla, MO, USA Abbas Vali, Arlington, TX, USA Ankit Verma, College Station, TX, USA Dunyang Wang, Berkeley, CA, USA Naixiang Wang, Hung Hom, KLN, Hong Kong Muan Wei, Toronto, ON, Canada Andreas Werbrouck, Harelbeke, WestVlaanderen, Belgium Samuel Wheeler, Lymington, Hampshire, UK Stephen Wilke, Evanston, IL, USA Denise Wirth, Tulsa, OK, USA Yingwei Wu, Oxford, Oxfordshire, UK Fei Xiao, Hong Kong, Hong Kong, China Daniel Yanchus, Toronto, ON, Canada Ming-Han Yang, Taoyuan City, Taiwan, Taiwan Yao Yao, Hong Kong, Hong Kong Joseph IV Yap, Quezon City, Metro Man, Philippines Ronald Zeszut, Cleveland, OH, USA Yilu Zhang, Hong Kong, Hong Kong, China Yiqing Zhang, Chicago, IL, USA Rong Zhao, Auburn, AL, USA Tianze Zhu, Oxford, Oxfordshire, UK

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 The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

t ST ech UDENT highligh NE WS ts Belgium Student Chapter The ECS Belgium Student Chapter organized three major activities in 2016. In the beginning of the year, the chapter traveled to the research center of Toyota Motor Europe, where Bill Halliden, senior manager of Toyota R&D, discussed the importance of global research and the history of Toyota in the European market. The chapter also toured the research and engineering facilities, took part in Q&A sessions, and got a personal look of Toyota’s battery lab. In March 2016, the chapter paid a visit to Gent University’s solid state physics research department, where experts discussed the latest developments in the field. During this trip, the chapter visited

Flanders Materials Centre (FLAMAC), where students got a firsthand view of high-throughput experiments being conducted with small-scale samples. In December 2016, the chapter explored the latest commercial and academic developments in solar cell technologies. The trip included visits to Soltech, a manufacturer of customized photovoltaic models, and IMEC, where the group learned about the history of photovoltaic development and the current issues and challenges related to the technology.

Members of the ECS Belgium Student Chapter are shown in front of Soltech, Tienen.

Case Western Reserve University Student Chapter The ECS Case Western Reserve University Student Chapter was established in April 2016. Members of the newly founded chapter participated as teaching assistants in the Workshop on Electrochemical Measurements, an event hosted yearly by the Ernest B. Yeager Center for Electrochemical Sciences. This workshop was attended by nearly 50 academic and industry professionals with an interest in gaining a foothold in electrochemical theory and measurements. Working alongside electrochemical instrument company representatives from Pine, Metrohm, Gamry, and Ametek, student chapter members instructed a variety of workshops, as well as contributed to lectures. The chapter also established a seminar series, where faculty and professionals working in the field are invited to speak about their work. The first two seminars focused on the biomedical field, with talks by Thomas Mortimer, Professor Emeritus of Biomedical Engineering, and Chung-Chiun Liu, Wallace R. Person Professor of Sensor Technology and Control. The chapter plans to continue the seminar series, reaching out to electrochemists from across the globe. There are additional plans to expand the chapter’s activities to include professional development and volunteer outreach.

Uziel Landau, professor at Case Western Reserve University, engaged in a discussion of neural electrodes.

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

t ST ech UDENT highligh NE WS ts Hong Kong University of Science and Technology Student Chapter In June 2016, the ECS Hong Kong University of Science and Technology (HKUST) Student Chapter had the pleasure of hosting ECS Past President Daniel A. Scherson from Case Western Reserve University. During his visit, Prof. Scherson gave a seminar about the oxidation dynamics of well-defined CO on Pt that attracted more than 50 attendees from different departments of the university. After the seminar, Prof. Scherson met with the chapter students and gave them advice on both research and career development. In July and November 2016, the chapter participated in three workshops on fuel cell electric vehicles, led by Prof. Minhua Shao, the faculty advisor of the chapter. About 100 secondary school

students from Hong Kong took part in these workshops. They assembled model fuel cell electric vehicles and used used solar cells to generate oxygen and hydrogen as fuels for the vehicles and tested the output power of the vehicles by a multimeter. These interactive and hands-on activities helped spark their enthusiasm in engineering. Later in 2016, the chapter invited Prof. Guohua Chen, Department Head of the Chemical and Biomolecular Engineering of HKUST to give a lecture on communication skills, on November 21, 2016. In his two-hour lecture, Prof. Chen gave students advices on how to make an effective presentation by sharing many of his personal experiences.

Members of the Hong Kong University of Science and Technology Student Chapter are seen here at the June 2016 seminar. From left to right: Xuewu Ou, Prof. Minhua Shao, Lulu Zhang, Minghao Zhuang, Qiaowan Chang, Shangqian Zhu, Fang Fu, Prof. Daniel A. Scherson, Xueping Qin, Yuze Yao, Mickey Chan, Oluwaseun John Dada, and Prof. Haiyan Wang.

Look Out !

We want to hear from you! Students are an important part of the ECS family and the future of the electrochemistry and solid state science community . . .

• What’s going on in your student chapter? • What’s the chatter among your colleagues?

• What’s the word on research projects and papers? • Who’s due congratulations for winning an award?

Send your news and a few good pictures to interface@electrochem.org. We’ll spread the word around the Society. Plus, your student chapter may also be featured in an upcoming issue of Interface!

www.electrochem.org/student-center The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

tech ST UDENT highlights NE WS Norwegian University of Science and Technology Student Chapter The ECS Norwegian University of Science and Technology Student Chapter arranged two events in November 2016, one recruitment event and one social dinner to welcome all new formal and informal chapter members. The first event, aimed to catch the interest of future MSc students prior to their choosing a thesis topic, started with a talk from Prof. Frode Seland about research possibilities within electrochemistry. Prof. Seland also elaborated on future job opportunities for people with a background in electrochemistry, with an example from industry further described by Torjus Åkre, a previous graduate student at the department and current Glencore Nikkelverk AS employee. Additionally, three PhD candidates talked about their research: Heidi Thuv (lithium-air batteries), Babak Khalaghi (electrolysis),

and Kristian F. K. Thorbjørnsen (PEM water electrolysis). Further conversations between chapter members, university students, and professors continued after the main talks in smaller groups during lunch. The recruitment of MSc students from the corresponding event resulted in 14 students now working actively with projects concerning electrochemistry who will finish their MSc theses in June 2017. These students were welcomed at a dinner and mixer, which also functioned as a welcome for all new PhD candidates and postdocs. The event included a presentation by Prof. Geir Martin Haarberg that focused on the history of the electrochemistry research field from the establishment of the university in 1910 until the present day.

Participants at the annual electrochemistry seminar for the ECS Norwegian University of Science and Technology Student Chapter.

University of Kentucky Student Chapter The ECS University of Kentucky Student Chapter and the university’s Department of Chemical and Materials Engineering hosted Dr. Steve Martin from Iowa State University on October 19, 2016. Dr. Martin’s seminar, titled “New Solid State Na+ Ion Conducting Glassy Solid Electrolytes and Their Use in All Solid State Lithium Ion Batteries,” gave insights into glassy solid electrolytes, with a particular emphasis on highly conducting sulfide-based chemistries. The graduate students met with Dr. Martin and discussed their current research on energy-related materials and solid state ionics. Members of the Kentucky Student Chapter with their guest speaker (left to right): Shuang Gao, Xiaowen Zhan, chapter chair, Dr. Mona Shirpour, chapter faculty advisor, Dr. Steve Martin, guest speaker, and Long Zhang. 84

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

tech ST UDENT highlights NE WS University of Maryland Student Chapter The ECS University of Maryland Student Chapter held a yearend mixer in Hyattsville, MD on December 8, 2016. Dinner was provided by the chapter, allowing the members to mingle and discuss the previous year’s accomplishments while planning future chapter endeavors. Topics included Congressional Visit Day, Adventure in Science at the National Institute of Standards and Technology, upcoming meetings, and potential guest speakers. It was also an opportunity to celebrate the graduations of two prominent members in the past semester and bid farewell to them.

Advertisers Index Ametek........................................................................... 1 Bio-Logic....................................................... back cover El-Cell.......................................................................... 17 Gamry............................................................................ 2 Koslow.......................................................................... 23 Pine......................................................inside front cover Scribner.......................................................................... 6 Stanford Research Systems.......................................... 4 Zahner-elektrik GmbH & Co KG................................ 8

University of Maryland Student Chapter members discussed their accomplishments and future plans over dinner at their year-end mixer. From left to right are Tanner Hamann, Griffin Godbey, Evans Gritton, Steve Lacey and Albert Painter.

University of Pittsburgh Student Chapter The ECS University of Pittsburgh Student Chapter recently helped organize the 2nd Annual Electrochemical Energy Symposium at Carnegie Mellon University, along with the Scott Innovation Institute and Pittsburgh Plate & Glass Industries. The two-day event

consisted of a seminar series and a poster session with various reputed electrochemists at Carnegie Mellon University and the University of Pittsburgh, discussing a variety of topics including lithiumsulfur batteries, dendritic structures in lithium metal anodes, battery management, lithium-ion batteries, fuel cells, and electrocatalysis.

Participants at the 2nd Annual Electrochemical Energy Symposium that was co-organized by the ECS University of Pittsburgh Student Chapter. The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

tech ST UDENT highlights NE WS University of Virginia Student Chapter In November 2016, the ECS University of Virginia Student Chapter hosted Dr. Gary Koenig, Jr. from the university’s Chemical Engineering Department. His talk, titled “Lithium-Ion Battery Particle Dispersions as Flow Redox Couples for Energy Storage Applications,” gave an insight into the recent progress made in research on flow batteries that have the electrochemical energy stored in solid particles, as opposed to dissolved transition metals. The talk concluded with a brief overview of his research group’s focus: synthesis and characterization of lithium-ion battery electrode active materials and the impacts of particle organization on electrode properties. The student chapter concluded the year with guest speaker Dr. Eric Schindelholz (ECS Morris Cohen Award Recipient 2015) from Sandia National Laboratories. Dr. Schindelholz was invited to present a seminar highlighting his work on atmospheric corrosion, linking thermodynamic and kinetic considerations of the surface environment (e.g., electrolyte) to corrosion behavior, followed by a discussion on career paths for recent graduates. Both seminars were well received and brought together students and faculty from various departments. There was also an opportunity to meet both speakers prior to and after their respective seminars, which initiated possible collaborations.

Gary Koenig gave a talk to the University of Virginia Student chapter on the topic of lithium-ion batteries.

Altmetrics in the ECS Digital Library What Are Altmetrics? Altmetrics report data for individual articles. By providing article level metrics, authors 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 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?

(10) Google+ (12) news outlets (17) Facebook

137

(3) blogs (23) Twitter

How to Increase Your Altmetric Ranking

• Publish open access to increase access to your research. • Like, tweet, and share research. • Start a conversation and promote your work.

www.electrochem.org · www.ecsdl.org The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

tech ST UDENT highlights NE WS

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.

Please visit the ECS website for complete rules and nomination requirements.

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

uApply www.electrochem.org/travel-grants uQuestions travelgrant@electrochem.org

uNote Applicants must reapply each year

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

easy steps.

Here!

Renew in

SHIp ER

M E M C I b T A

Ren

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AWARDS NE W MEMBERS Program

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1 2

In your active membership, click Enroll Now and follow steps for setup.

Select My Memberships from the My Account Links menu.

QUESTIONS: Contact customerservice@electrochem.org. 88

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

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. (Number in parentheses indicates years of membership)

Benefits of Membership Discounts on: • • • •

Advertising in print and online Meeting registrations Exhibits and sponsorships Access to ECS Digital Library

Benefactor Hydro-Québec (10) Industrie De Nora S.p.A. (34) Pine Research Instrumentation (11) Saft Batteries, Specialty Batteries Group (35) Scribner Associates, Inc. (21) Zahner-elektrik GmbH & Co KG (1)

AMETEK-Scientific Instruments (36) BASi (2) Bio-Logic USA/Bio-Logic SAS (9) Duracell (60) Gamry Instruments (10) Gelest, Inc. (8)

Patron EL-Cell GmbH (3) Energizer (72) Faraday Technology, Inc. (11) IBM Corporation (60)

Lawrence Berkeley National Laboratory (13) Panasonic Corporation, AIS Company (23) Toyota Research Institute of North America (9)

Sponsoring Axiall Corporation (22) Central Electrochemical Research Institute (24) Ford Motor Company (3) GS-Yuasa International Ltd. (37) Honda R&D Co., Ltd. (10) IMERYS Graphite & Carbon (30) Medtronic Inc. (37) Molecular Rebar Design (1) NEXT ENERGY - EWE-Forschungszentrum für Energietechnologie e.V. (9)

Nissan Motor Co., Ltd. (10) Permascand AB (14) TDK Corporation, Device Development Center (24) Technic Inc. (21) Teledyne Energy Systems, Inc. (18) The Electrosynthesis Company, Inc. (21) Tianjin Lishen Battery Joint-Stock Co., Ltd. (3) Toyota Central R&D Labs., Inc. (37) Yeager Center for Electrochemical Sciences (19) ZSW (13)

Sustaining 3M Company (28) General Motors Corporation (65) Giner, Inc./GES (31) International Lead Association (38) Kanto Chemical Co., Inc. (5) Karlsruhe Institute of Technology (1) Leclanche SA (32)

Los Alamos National Laboratory (9) Occidental Chemical Corp. (75) Quallion, LLC (17) Sandia National Laboratories (41) SanDisk (3) Targray (1)

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 Shannon Reed, director of membership services at 609.737.1902 ext. 107 or shannon.reed@electrochem.org.

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