Interface Vol. 22, No. 4, Winter 2013 by The Electrochemical Society

VOL. 22, NO. 4 Winter 2013

IN THIS ISSUE 3 From the Editor: A Phase Transition

7 From the President: Science and Technology on a Global Scale and the Societyâ&#x20AC;&#x2122;s Role

San Francisco, California: Meeting Highlights

18 Candidates for Society Office

42 The Chalkboard: The Potentiostat and the Voltage Clamp

45 Tech Highlights 47 High Temperature Materials for Energy Conversion

49 Highlights from the 2013 National Science Foundation SOFC-PPP Workshop

High Temperature Materials for Energy Conversion 55 Reversible Solid Oxide Fuel Cell Technology for Green Fuel and Power Production

63 Design of Materials

for Solar-Driven Fuel Production by Metal-Oxide Thermochemical Cycles

69 High Temperature Materials Corrosion Challenges for Energy Conversion Technologies

103 Cancun, Mexico Call for Papers

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The Electrochemical Society Interface â&#x20AC;˘ Winter 2013

The Electrochemical Society Interface â&#x20AC;˘ Winter 2010

FROM T HE EDITOR

A Phase Transition he title of my editorial column read “Transitions and Interfaces” when I assumed editorship duties of this magazine back in summer of 1999. After approximately 15 years, I am returning to this theme to close the circle. As of the end of this year, I will be relinquishing the editorship to assume duties as the Third Vice-President of the Society. This will represent a “phase transition” for me, and hopefully, the growth of a new phase with all the exciting possibilities that come with it. It has been an incredibly fun ride, and as with any long journey, there were invariably a few bumps along the road that had to be deftly navigated. These included disasters (natural and man-made) both within and outside of the Society, and some (like Hurricane Sandy) had a direct and tangible effect on the production of this magazine. However, the important thing is that, thanks to the diligent efforts of several individuals, including the dedicated staff in Pennington, NJ, we were able to deliver, what I would hope, was a quality product that faithfully represents this Society. Before signing off for the last time as the Editor, I have many people to thank. First and foremost is my “partner-in-crime,” Mary Yess, the Managing Editor of Interface, who has been an absolute rock through all these years. Through her previous involvement with this magazine before my term as the Editor began, she could provide valuable counsel and continuity at the outset. I could immediately sense the passion she brought to producing these magazine pages, and am so happy that we hit it off right from the beginning. This was a partnership in the true sense of the word and I would like to think that our skills meshed beautifully as in any successful team. Dennis Hess: you, Mary, and the other members of the ECS Interface Editor search committee (bravely?) entrusted the magazine in my hands back in 1999; I hope I have not disappointed you all! Many thanks also go to Subhash Singhal and the other members of the Publications Subcommittee for their support through the years. Being able to work with talented production managers such as Ellen Popkin and Dinia Agrawala was also a boon. Their considerable talents lie behind what you see in terms of the stunning cover illustrations to the quality layout in the feature article pages, the advertisements, and culminating in the back cover of this magazine. I thank all the people who provided feedback to me, both via numerous e-mail messages, phone calls, and hallway conversations that proved to be invaluable in gauging how we were doing as a members’ magazine. In this regard, how can I not forget to mention all the guest editors and feature article authors who contributed mightily to this magazine over the years? The contributing editors regularly and diligently furnished columns for us and they include, among others, Mike Kelly, Donald Pile, and Zoltan Nagy. As I begin to learn all of the intricate aspects of my new “job” as an ECS Vice-President, the collegiality of the senior members of the Society leadership team—Tetsuya Osaka, Paul Kohl, Dan Scherson, Christina Bock, and Lili Deligianni—has been both heart-warming and striking. This collegiality has always been a hallmark of our Society and there is no better example of that, at least in my mind, than Roque Calvo, the current Executive Director of ECS. Roque, I hope you will not mind my sharing hilarious stories of your very first trip to my native country, India, including the challenges of eating very hot Indian curry, and chance encounters with prancing peacocks right on the lawn in front of our guesthouse in CECRI, Karaikudi! Friendships like these I have made over the years (and will continue to make in the future) with the Society staff and membership are much cherished. This journey and the many phase transitions began for me back in 1978 with the Boston ECS meeting. Finally, a simple thanks to my family: my wonderful wife, angel, and soul mate, Rohini (Ro) for her steadfast support for more than 36 years; and our beautiful daughters, Reena and Rebecca, for keeping everything in perspective. Ro was a sounding board for many of the ideas and thoughts expressed in my editorial columns, and my initial drafts undoubtedly benefitted from her liberal use of red ink edits and queries. Vijay Ramani and Petr Vanýsek: We all wish you both the very best as you take over the co-editorship reins; I hope you will have as fun and invigorating a ride as I had for 15 years with this magazine. And as always, stay tuned!

Krishnan Rajeshwar Editor The Electrochemical Society Interface • Winter 2013

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 Editor: Krishnan Rajeshwar, rajeshwar@uta.edu Guest Editor: Jeffrey Fergus, ferguje@auburn.edu Contributing Editors: Donald Pile, donald.pile@gmail. com; Zoltan Nagy, nagyz@email.unc.edu Managing Editor: Mary E. Yess, mary.yess@electrochem.org Production & Advertising Manager: Dinia Agrawala, interface@electrochem.org Advisory Board: Bor Yann Liaw (Battery), Sanna Virtanen (Corrosion), Durga Misra (Dielectric Science and Technology), Giovanni Zangari (Electrodeposition), Jerzy Ruzyllo (Electronics and Photonics), A. Manivannan (Energy Technology), Xiao-Dong Zhou (High Temperature Materials), John Staser (Industrial Electrochemistry and Electrochemical Engineering), Uwe Happek (Luminescence and Display Materials), Luis Echegoyen (Nanocarbons), Jim Burgess (Organic and Biological Electrochemistry), Andrew C. Hillier (Physical and Analytical Electrochemistry), Nick Wu (Sensor) Publications Subcommittee Chair: Dan Scherson Society Officers: Tetsuya Osaka, President; Paul Kohl, Senior Vice-President; Dan Scherson, 2nd Vice-President; Krishnan Rajeshwar, 3rd Vice-President; Lili Deligianni, Secretary; Christina Bock, 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 2013 by The Electrochemical Society. Periodicals postage paid at Pennington, New Jersey, and at additional mailing offices. POSTMASTER: Send address changes to The Electrochemical Society, 65 South Main Street, Pennington, NJ 08534-2839. The Electrochemical Society is an educational, nonprofit 501(c)(3) organization with more than 8000 scientists and engineers in over 70 countries worldwide who hold individual membership. Founded in 1902, the Society has a long tradition in advancing the theory and practice of electrochemical and solid-state science by dissemination of information through its publications and international meetings.

All recycled paper. Printed in USA.

The Electrochemical Society Interface â&#x20AC;˘ Winter 2013

Vol. 22, No. 4 Winter 2013

High Temperature Materials for Energy Conversion by Jeffrey W. Fergus

Highlights from the 2013 National Science Foundation Solid Oxide Fuel Cell Promise, Progress, and Priorities (SOFC-PPP) Workshop by Jason D. Nicholas

Reversible Solid Oxide Fuel Cell Technology for Green Fuel and Power Production by Nguyen Q. Minh and Mogens B. Mogensen

the President: 7 From Science and Technology on a Global Scale and the SocietyĘźs Role

Francisco, CA 8 San Meeting Highlights for 18 Candidates Society Office

24 Society News 36 People News Chalkboard: 42 The The Potentiostat and the Voltage Clamp

Design of Materials for SolarDriven Fuel Production by MetalOxide Thermochemical Cycles by Mark D. Allendorf, James E. Miller, and Anthony H. McDaniel

the Editor: 3 From A Phase Transition

High Temperature Materials Corrosion Challenges for Energy Conversion Technologies by Elizabeth Opila

The Electrochemical Society Interface â&#x20AC;˘ Winter 2013

45 Tech Highlights 74 Section News 76 Awards 79 New Members 83 ECS Fellowship Reports 93 Student News Mexico 103 Cancun, Call for Papers On the cover . . .

Scanning electron micrograph of diffusion couple between manganese oxide and chromium oxide. (Photo taken by Kangli Wang, Auburn University, 2009.) Cover design by Dinia Agrawala

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The Electrochemical Society Interface • Winter 2013

From the President

Science and Technology on a Global Scale and Society's Role he 20th century was a time of advancement led by many discoveries and inventions that had their origin in the United States. At the beginning of the 21st century, the U.S. still led the world in science and technology growth. The advancement of the iPhone led by Steve Jobs involves a model for future innovations, and much can be learned from the achievements made in the United States. However, lately we have seen leadership emerging from many Asian countries in the technological sector. Significant developments in engineering and technology in Japan in the ‘80s (and even in the ‘90s), have been steadily supplanted by corresponding activity in newly-developing Asian countries such as Korea over the past ten years. Trends, drawn over a 15-year window, are illustrated in the accompanying graphic for six selected consumer products made in Japan for the world global market. Nobel Prizes in the sciences—a good metric for knowledge development that has had impact—had been primarily awarded to Europeans and North Americans in the past; however the number of Nobel laureates from Japan has been increasing, amounting to a total of 19 winners as of 2013. According to a recent interview with David Pendlebury, a U.S. Thomson Reuters analyst, the number of original Japanese research papers reached its peak of 9.4% in 2002, and then 5.8% in 2012. Recently, the number of original research papers published by China has become large. It is especially significant that the list of the top ten researchers cited in 2012 included three Chinese scientists. This suggests that the contribution of China is not only voluminous but high in quality. Envisioning a candidate from China for the Nobel Prize in chemistry or physics is no longer a stretch. Thus, the leadership in the areas of science and technology in the 21st century may be geographically divided into three regions: Asia, Europe, and the United States. Given this backdrop, and the fact that ECS has been an international organization from its earliest days, it is reasonable to expect that the Society will play an even greater role as a forum for facilitating dialogue/ collaboration in electrochemical and solid-state sciences and

engineering. For example, energy- and environment-oriented projects especially have become two of the most important issues for our planet, and the increasing interest in these two areas will have a synergistic effect on the development and growth of our Society. ECS recognizes the importance of energy in the sustainability of our planet, and recognizes the role that electrochemistry can play. The successful Electrochemical Energy Summit series continued at the 224th fall meeting of the Society this October. This recent meeting, held in San Francisco, was a great success with more than 3,000 attendees, and included many important energy-related symposia. Looking ahead, in March 2014, ECS and the Chinese Society of Electrochemistry will hold the Electrochemical Conference on Energy and the Environment (ECEE) in Shanghai. As an organization that brings together scientists and engineers from Asia, Europe, and the U.S., and many other countries from around the globe, ECS will undoubtedly contribute to the health of our planet, now and in the future.

Tetsuya Osaka ECS President

The Electrochemical Society Interface • Winter 2013

224 th

ECS MEETING San Francisco, CA

October 27—November 1, 2013 San Francisco Travel Association photo by P. Fuszard.

San Francisco Travel Association photo.

Highlights from the Meeting in San Francisco

lobal energy needs continue to grow with economic, political, and environmental issues largely dictated by energy challenges. The third international ECS Electrochemical Energy Summit (E2S) kicked off the 224th ECS meeting in San Francisco, and set the tone for a week of presentations, posters, and

panel discussions from and among leading policy makers and energy experts about societal needs and technological energy solutions. Over 3100 attendees took in not only energy-related presentations, but other topics in electrochemistry and solid state science and technology, from a selection of over 2800 papers in 50 symposia and 40 exhibits.

The Electrochemical Energy Summit (E2S) panelists gathered before their talks. From left to right are: Heather Cooley, Co-Director of the Pacific Institute’s Water Program; Congressman Jerry McNerney, 9th District of California; Meredith Younghein, a Policy and Programs Analyst with the State Water Resources Control Board and on the Energy Division of the California Public Utilities Commission; and E2S organizer Robert Glass, Senior Scientist in the Physical and Life Sciences Directorate at Lawrence Livermore National Laboratory.

Among the highlights of the Energy Summit was the Energy Research Group Showcase. Shown here is Drexel University presenting its work. Other participants included Duke University, FMC Lithium, Lawrence Berkeley National Laboratory, Sandia National Laboratories, Stanford Woods Institute for the Environment, University of British Columbia, University of Kansas, University of Maryland, University of Toronto, and the University of the West of England.

Another feature of E2S was an energy-themed poster session. Posters were selected from all poster submissions that were relevant to the Summit’s energy theme. Shown here (right photo) is a participant from the Georgia Institute of Technology. 8

The Electrochemical Society Interface • Winter 2013

Sunday kicked off the meeting with a full day of E2S events and activities. Robert Glass, Senior Scientist in the Physical and Life Sciences Directorate at Lawrence Livermore National Laboratory (LLNL), introduced the Sunday invited speakers and the Q&A sessions. The opening day’s program included a series of speakers; an Energy Research Group Showcase; an energy research poster session; and an Educational Outreach Program/Fuel Cell Car Competition organized by the IE&EE Division of ECS. Congressman Jerry McNerney, 9th District of California, was Sunday’s keynote speaker. He is the only renewable energy expert in Congress and sits on the U.S. House Committee on Energy & Commerce, the oldest standing legislative committee in the U.S. House of Representatives. The Congressman, who holds a PhD in mathematics, served several years as an engineering contractor to Sandia National Laboratories in New Mexico. In 1990 Congressman McNerney moved to California, accepting a senior engineering position with U.S. Windpower, Kenetech. Dr. McNerney later began working as an energy consultant for PG&E, FloWind, the Electric Power Research Institute, and other utility companies.

The Congressman was followed by a presentation on “Energy– Water Nexus: Opportunities and Challenges,” given by Heather Cooley. Ms. Cooley is Co-Director of the Pacific Institute’s Water Program. She conducts and oversees research on an array of water issues, including the connections between water and energy, sustainable water use and management, and the impact of climate change on water resources. Next up was Meredith Younghein, who focused her presentation on the topic of “Program and Policy Innovations at the Water-Energy Nexus.” Ms. Younghein is on a dual assignment as a Policy and Programs Analyst with the State Water Resources Control Board and the Energy Division of the California Public Utilities Commission. Throughout Sunday and through midday Monday, attendees had an up-close look at a Honda FCX Clarity car and the Mercedes Benz B Class FCell car on display, courtesy of the California Fuel Cell Partnership. The California Fuel Cell Partnership is a collaboration of organizations, including auto manufacturers, energy providers, government agencies, and fuel cell technology companies, that work together to promote the commercialization of hydrogen fuel cell vehicles.

The ECS Meeting in San Francisco was fortunate to have the participation of Congressman Jerry McNerney, 9th District of California (center), who joined ECS President Tetsuya Osaka (left) and ECS Executive Director Roque Calvo (right) for a conversation following McNerney’s talk.

Attendees had a great opportunity on Sunday and Monday to see two different hybrid cars provided by the California Fuel Cell Partnership (CaFCP). Juan Contreras, of the CaFCP, gave meeting attendees a tour of one of the hybrid vehicles on display.

The Sunday program concluded with a reception and the twelfth IE&EE Division’s Educational Outreach Program. This was the first time that the IE&EE Division brought the program to an ECS meeting, and it was great to see all those future scientists and engineers working away on their mini fuel cars, getting ready for the race. Over 90 students from Galileo Academy of Science and Technology and Lowell High School worked under the guidance of Gerri Botte, her students from the Ohio University Student Chapter of ECS, and members of the IE&EE Division. The program aims to foster the younger generation’s interest in the fields of electrochemistry and electrochemical engineering and is designed to create awareness of electrochemical energy conversion devices.

(continued on page 13)

Students from Galileo Academy of Science and Technology and Lowell High School worked under the guidance of Gerri Botte (bottom left photo), her students from the Ohio University Student Chapter of ECS, and members of the IE&EE Division.

The Society’s Carl Wagner Memorial Award was established in 1980 to recognize a mid-career achievement and excellence in research areas of interest of the Society, and significant contributions in the teaching or guidance of students or colleagues in education, industry, or government. Marc T. M. Koper (right) was presented with the 2013 award by ECS President Tetsuya Osaka (left).

ECS President Tetsuya Osaka (right) thanked Fernando Garzon (left) for his outstanding contributions as ECS President during Dr. Garzon’s 20122013 term.

ECS President Tetsuya Osaka welcomed the 2013 Class of ECS Fellows. In the front row (left to right) are: Shelley Minteer, Johna Leddy, (President Osaka), Elizabeth Opila, Héctor Abruña, and Jan Robert Selman. In the back row (from left to right) are: Nancy Dudney, Gary Hunter, Martin Winter, Enrico Traversa, Jiri Janata, Sanjeev Mukerjee, and Kalpathy Sundaram. 10

The Electrochemical Society Interface • Winter 2013

Petr Vanýsek (left) was thanked by ECS President Tetsuya Osaka (right) for his service as the Interim Editor of the Society’s electrochemistry journals.

Every year the Society selects two of the best papers published in the Journal of The Electrochemical Society (JES) for the Norman Hackerman Young Author Awards. Receiving his award for the best paper in solid state science and technology is Balavinayagam Ramalingam (left). He received his award from ECS President Tetsuya Osaka (right). The winning paper was entitled, “Multi-Layer Pt Nanoparticle Embedded High Density Non-Volatile Memory Devices” [JES, 159, 4, H393 (2012)]. Unable to attend the ceremony were Kelley “Sykes” Mason and Kiersten Horning, who received the award for the best paper in electrochemical science and technology. The winning paper was entitled, “Investigation of a Silicotungstic Acid Functionalized Carbon on Pt Activity and Durability for the Oxygen Reduction Reaction” (JES, 159, 12, F871).

The Electrochemical Society Interface • Winter 2013

ECS President Tetsuya Osaka (right) thanked Andrew Gewirth (left) for his service as an Associate Editor and Technical Editor for the ECS electrochemistry journals.

ECS presented the first Outstanding Student Chapter Award to the University of Maryland Student Chapter. ECS President Tetsuya Osaka (center) presented the award to Chapter President Colin Gore (left). Looking on is the Chapter’s faculty adviser Eric Wachsman (right).

Tuesday evening in the Exhibit Hall was filled with activity: attendees visiting the many exhibitors; the organizers and judges listening to presentations from participants in the General Student Poster Session; attendees excited to hear the winners of the Lithium Batteries monograph giveaway, sponsored by John Wiley & Sons; and people perusing the Society’s journals at the ECS Exhibit booth.

Bruno Scrosati (left photo, at left), KM Abraham (left photo, at right), and Walter van Schalkwijk (above photo) were ready to sign copies before the special book signing of the newly-published Lithium Batteries monograph. Unable to attend the meeting with the fourth editor, Jusef Hassoun. The monograph is the latest in the series sponsored by ECS and published with John A. Wiley & Sons. 12

The Electrochemical Society Interface • Winter 2013

(continued from page 9)

On Monday, the E2 Summit continued with a special symposium on the Energy–Water Nexus, which featured invited speakers who examined the role of electrochemistry in addressing the intersection of these two critical resource issues, from policy considerations to scientific breakthroughs. The symposium was organized by Eric D. Wachsman, Director of the University of Maryland Energy Research Center, and the William L. Crentz Centennial Chair in Energy Research with appointments in both the Department of Materials Science and Engineering, and the Department of Chemical Engineering at the University of Maryland. In addition to organizing the symposium, Dr. Wachsman also served as a moderator for the lively panel discussion that followed the presentations. Serving as the other moderator was Carl Hensman of the Water, Sanitation, and Hygiene team within the Global Development Program of the Bill & Melinda Gates Foundation. Prior to joining the foundation, Dr. Hensman was an Energy Program Manager for King County, Washington (Seattle) focusing on resource recovery in the Wastewater Treatment Division.

Eric Wachsman, Director of the University of Maryland Energy Research Center, organized the Energy–Water Nexus Symposium, which featured invited speakers who examined the role of electrochemistry in addressing the intersection of these two critical resource issues.

The speakers on the Energy–Water Nexus panel included Mike Hightower, a Distinguished Member of the technical staff in the Energy Surety Engineering and Analysis Department at Sandia National Laboratories; Antonio Busaliacchi, Chair, National Academy of Sciences/National Research Council (NAS/NRC) Board on Atmospheric Sciences and Climate; Amul Tevar, ARPA-E Fellow who is working in energy–water, energy storage control systems (AMPED); Michael Hoffman, a member of the Engineering & Applied Science faculty at Caltech; and Bruce Hamilton, a program director at the National Science Foundation where he is a member of the cross-NSF Implementation Group for the Science, Engineering, and Education for Sustainability (SEES) investment area.

America’s Energy Future: Science, Engineering, and Policy Challenges All of the E2S activity was capped by The ECS Lecture given on Monday by Mark Wrighton of the Washington University (St. Louis, MO) to a packed audience. Mark Wrighton is the 14th Chancellor of that university and joined that institution in 1995 after two decades of path-breaking research in photoelectrochemistry, chemically-modified electrodes, and mechanistic inorganic photochemistry at the Massachusetts Institute of Technology (MIT). Wrighton also served on the administration at MIT in varying roles as a department chair, dean, and provost. After completing his undergraduate education from Florida State University, he earned a PhD in chemistry from the California Institute of Technology under the joint tutelage of George Hammond and Harry Gray. Wrighton is one of the youngest professors tenured at MIT and he has been active in public and professional affairs throughout his career. The plenary talk’s theme grew out of Wrighton’s involvement as the Vice-Chair of National Research Council (NRC)’s Committee on America’s Energy Future (AEF). NRC convened this committee and charged it to study this country’s future energy options; the report from the committee became public in the spring of 2009. (Ed. Note: A Summary Edition is available on the Web from the National Academies Press.) (continued on next page)

The Energy–Water Nexus Symposium hosted a panel discussion. From left to right are: Bruce Hamilton, a program director at the National Science Foundation; Clement Cid, California Institute of Technology; Antonio J. Busaliacchi, Chair, National Academy of Sciences/National Research Council (NAS/NRC) Board on Atmospheric Sciences and Climate; Amul Tevar, ARPA-E Fellow working in energy–water, energy storage control systems (AMPED); Mike Hightower, a Distinguished Member of the technical staff in the Energy Surety Engineering and Analysis Department at Sandia National Laboratories; organizer and panel moderator Eric Wachsman, Director of the University of Maryland Energy Research Center; and Carl Hensman, Water, Sanitation, and Hygiene team within the Global Development Program of the Bill & Melinda Gates Foundation. The Electrochemical Society Interface • Winter 2013

(continued from previous page)

election cycles, and the need for incentives and taxes to curtail carbon emissions and to promote cleaner options. He wryly noted that the 50 states in the U.S. had virtually 50 energy policies. Most daunting, infusion of considerable capital and funding will be needed to secure efficiency gains and enable expensive options like nuclear. All in all, this talk nicely dovetailed with the ongoing discussions on energy and the environment at the meeting.

The ECS Olin Palladium Award Lecture

Mark Wrighton (center) delivered The ECS Lecture at the San Francisco meeting. ECS President Tetsuya Osaka (right) thanked Dr. Wrighton for his talk. ECS Senior Vice-President Paul Kohl (left) introduced Dr. Wrighton whose lecture was on the topic of “America’s Energy Future.”

The speaker was introduced to the audience by the ECS Senior Vice-President, Paul Kohl. Wrighton began his lecture by noting the leadership role that the Society has played in discussing the important topic of energy. As examples, he noted the energy summit that was held concurrent with the meeting in San Francisco, and the demonstration of hybrid vehicle technology and battery technologies. He then showed names of the 25 members of the NEC Committee and noted that 80% of them were National Academy members. Dr. Wrighton began his interesting lecture by first noting the motivating factors underlying the NRC AEF Committee’s charter. These could be grouped under concerns with the environment, national security, and economic competitiveness. A major conclusion emerging from the AEF report was that we must transform the manner in which energy is generated and used. While technology options were considered by the Committee, options not covered by the study scope included conservation, exploration and extraction, and the global situation. The speaker then turned to a summary of the eight major findings from this study. A critical issue was also identified as carbon emissions from the continued and increasing use of fossil fuels. It was noted that China was the major CO2 emitter among the non-OECD nations. The Mauna Loa observatory in Hawaii, which has monitored CO2 emissions, now reports a level of ~400 ppm (v/v) for this greenhouse gas. Turning to the concluding portion of this fast-moving talk, Wrighton suggested that nuclear and renewable energy options could be expanded from present levels. He underlined the criticality of searching for energy sources with minimal CO2 emissions from their use. On a cautionary note, Japan was identified as a country with ~30 % of its electricity generated from nuclear sources. However, plans for the construction of 14 new plants were abandoned in the light of the Fukushima disaster. The uncertainty associated with uranium supply also constitutes another drawback with this energy option. On the other hand, to what extent is the abundance and low cost of natural gas going to delay expanding the role of renewables in the future energy mix? Photovoltaics R&D has been intense in this country and elsewhere but concerns with economics/grid parity and the concomitant pressure on land use for farming continue to challenge an increasing role for this clean energy option. Plugging of renewable energy sources into the electric grid also will require a viable storage strategy to combat their intermittency. Wrighton wrapped up his talk by identifying some policy challenges including the unfortunate dependency of energy R&D emphasis on

The Olin Palladium Award lecture entitled, “Mathematical Modeling of Lithium Ion Cells and Batteries,” was given by Ralph White on Monday afternoon. Dr. White is a Professor of Chemical Engineering and a Distinguished Scientist at the University of South Carolina. He received his PhD from the University of California at Berkeley in 1977 under the direction of John Newman. After a distinguished career at Texas A&M University spanning 16 years, he moved to the University of South Carolina where he served both as chair of the Department of Chemical Engineering and as dean of the college. Professor White’s career accomplishments have garnered numerous awards and recognitions including elections as a Fellow of ECS, American Institute of Chemical Engineers, and American

Ralph White (right) was the recipient of the 2013 Olin Palladium Award, and received his Medal from ECS President Tetsuya Osaka (center). John Newman (left) introduced Dr. White earlier on Monday, when Prof. White gave his award talk. The Society’s Palladium Award was established in 1950 for distinguished contributions to the field of electrochemical or corrosion science. It is one of the Society’s most prestigious awards.

Association for the Advancement of Science. He has also served as a Treasurer of the Society. After being introduced to the audience by John Newman, Dr. White began his award lecture by acknowledging the contributions of his 50 PhD and 39 Master’s students, and thanking family members, many of whom were present at the talk. Professor White’s award lecture provided a summary of the capabilities of mathematical modeling of both single Li ion cells and battery packs constituting these individual cells. He noted, as a practical example of the application of Li battery technology, that the Chevrolet Volt vehicle had 288 such cells assembled into a 16.5 kWh battery pack module. Mathematical models are useful as a design enabler in that they guide cell design by predicting the effect of changing parameters on cell performance. Physics-based models, such as the ones Prof. White described in his talk, generate predictive profiles of voltage-time charge/discharge profiles as a function of operating condition. The speaker discussed the underpinning features of models (P2D and P3D) (continued on page 16)

The Electrochemical Society Interface • Winter 2013

Symposium in Honor of Adam Heller Celebrating his 80th Birthday

Adam Heller spoke at a symposium in his honor at the ECS fall 2013 meeting.

Adam and Ilana Heller at a dinner following the symposium in Prof. Heller’s honor.

A symposium held in San Francisco honored Adam Heller on the occasion of his 80th birthday. Twentynine invited lectures spanned topics pioneered by Dr. Heller, including photovoltaics, novel batteries, and electrochemical solutions to biomedical challenges. Dr. Heller opened the symposium with a perspective of his career thus far, titled “At 80: The Joy of Uncovering Truths and Building People-Serving Products.” Other highlights included the 2013 ECS Gerischer award winner, Arthur Nozik (NREL), who described his contributions to photoelectrochemical and quantum dot-based solar energy conversion; and Kazuhito Hashimoto, who discussed bioelectrochemical control of the circadian clock. In closing the session, Heller observed: “It’s unbelievably important—and that’s perhaps the most important thing—that we, in this room, are speaking twelve different mother tongues… Suddenly it comes to your mind that science has not only created a community of the people that are leading the world, the cutting edge of what makes people move forward. But not in the sense of the technology only, but that we are the exemplary group of people able to work with each other, love each other, and be very good friends with each other. So, I cannot thank you more, and more deeply, for your friendship.” A dinner event was also held on Monday night in a restaurant in the city and was attended by Prof. Heller’s family, students and postdoctoral fellows both past and present, and a multitude of friends both from inside and outside of the Society. These two events held in concurrence with the ECS fall meeting exemplified the affection and admiration with which Prof. Heller is held by the scientific community.

Adam Heller (4th from left) gathered with his colleagues at the symposium held in his honor at the ECS meeting in San Francisco. In the front row on the far right is Interface Editor Krishnan Rajeshwar.

The Electrochemical Society Interface • Winter 2013

(continued from page 14)

at the single-particle level including the Butler-Volmer formalism. How these models could extend to situations inside an actual module (Quallium 72 Ah) was outlined. Thus the physics-based model can be extended to multiple dimensions to predict the temperature distribution in a Li ion cell for a given set of operating conditions. Application of these models to design a thermal management system was discussed to ensure that the heat generated in the cell is rapidly removed before causing overheating and thermal runaway of the cell. Such a discussion is particularly poignant in the face of recent problems with fires caused by overheating in Li ion cells in airplanes and automobiles.

Thermal management systems are also enabled by models on battery packs as discussed in the next part of the award lecture. How circuits could be balanced to extend battery life of the packs and how control algorithms could be developed to ensure successful operation of the battery over the life of the pack formed the topic for the next phase of the award lecture. Overall, Dr. White’s talk provided a clear demonstration of the power of predictive mathematical models for Li ion cells and battery packs. Meeting Highlights were prepared by Krishnan Rajeshwar and Mary Yess, Interface’s Editor and Managing Editor respectively. All photos are by Dave Bush Fine Photography, San Francisco, CA.

PEFC 13 Award Winners During the PEFC 13 Symposium in San Francisco, the symposium conducted a competition for the best student posters. Out of 30 competitors presenting generally high quality work, the judges chose four posters as winners. Two poster presenters tied for the first place award of $1,000 (each). They were Yuichi Seno from Yamanashi University (Kofu, Japan), with a poster entitled, “Electrochemical Properties of Pt Catalysts Supported on Nb-Doped SnO2 with Network Structure;” and Iryna V. Zenyuk from Carnegie Mellon University for her poster

entitled, “Coupling of Deterministic Contact Mechanics Model and Two-Phase Model to Study the Effect of Catalyst Layer|Microporous Layer Interface on Polymer Electrolyte Fuel Cell Performance.” Yuta Ikehata from Doshisha University (Kyoto, Japan). with his poster entitled, :Scale-Up Synthesis of Au Core/Pt Shell Structured Catalysts and Their Electrochemical Properties,” shared the second prize of $500 each together with Takuya Tsukatsune from Kyushu University, Japan for his poster entitled, “Electrochemical Properties and Durability of Electrocatalysts Supported on SnO2.”

Winners of the PEFC 13 Symposium’s student poster session competition posed with three of the organizers. Pictured from left to right are: Yuichi Senoo (Yamanashi University), James Fenton (organizer), Yuta Ikehata (Doshisha University), Hubert A. Gasteiger (organizer), Takuya Tsukatsune (Kyushu University), Thomas J. Schmidt (organizer), and Iryna V. Zenyuk (Carnegie Mellon University).

The Electrochemical Society Interface • Winter 2013

TheElectrochemical ElectrochemicalSociety SocietySeries Interface • Winter 2013 e

candidates for societ y office The following are biographical sketches and candidacy statements of the nominated candidates for the annual election of officers for ECS. Ballots (and instructions for voting either online or by mail) will be sent in January 2014 to all Voting Members of the Society. The office not affected by this election is that of the Secretary.

Candidate for President

Candidates for Vice-President

Paul A. Kohl is a Regents’ Professor and Hercules Inc./ Thomas L. Gossage Chair in Chemical and Biomolecular Engineering at the Georgia Institute of Technology. He received a PhD in Chemistry from The University of Texas at Austin under Allen J. Bard. He was employed by AT&T Bell Laboratories from 1978 to 1989, where he was involved in creating new chemical processes for electronic components, including photoelectrochemical processing of semiconductors, highspeed electrodeposition, analysis of next generation semiconductor materials components, including electron and surface microscopy, and new materials and structures for advanced packaging of integrated circuits. In 1989, he joined the faculty of Georgia Tech, where he is currently Director of the Interconnect Focus Center, one of six Semiconductor Research Corporation/ DARPA MARCO Focus Centers. His research interests include electrochemical devices for energy conversion and storage, such as fuel cells and batteries, electrochemical deposition of metals for electronic packaging, new low dielectric constant materials for electronic devices and packages, and novel materials for electronic interconnect. Paul Kohl has 250 journal publications, 57 U.S. patents, and 400 conference presentations. Paul Kohl has been a member of ECS since 1976. He is an ECS Fellow and has received the Carl Wagner and Thomas D. Callinan Awards. He has held a number of editorial positions including Founding Editor of Interface (1992-1995), Editor of the Journal of The Electrochemical Society (1995-2007), Founding Editor of Electrochemical and Solid-State Letters (1998-2003), and a Journal Divisional Editor (1985-1990). He was the first Chair (1995-1996) and cofounder of the Georgia Section. He has held a number of ECS volunteer positions including member of the Publication Committee (1987-2008), Technical Affairs Committee (1991-1994), Electronics Division advisor (1991-1994),

Johna Leddy joined The Electrochemical Society while a graduate student at the University of Texas. She earned her BA at Rice University. After a postdoctoral appointment in the fuel cell program at Los Alamos National Labs and tenure at the City University of New York, Queens College, Leddy joined the chemistry faculty at the University of Iowa, where she is affiliated with the Environmental Science and the Applied Math and Computer Science Programs. Dr. Leddy and her group work in varied domains of electrochemical research: fundamentals of kinetics and transport, physical manipulation of electrocatalysis, electrochemical generation and storage, sensors, modified electrodes, electroanalysis, and modeling. A first physical manipulation of catalysis is achieved on introduction of micromagnets to electrodes, where dramatically-increased currents scale with magnetic moment and magnetic fields. This platform technology is demonstrated to increase efficiencies in batteries, fuel cells, Grätzel cells, and photoelectrocatalytic cells for H2 evolution (HER). Micromagnets of sufficient field allow near diffusion limited electrolysis of CO at platinum. A second physical manipulation of catalysis is the ultrasonic irradiation of electrodes in a thin solvent layer. Kinetics for O2 reduction (ORR) and methanol electrolysis are substantially improved. In the thin layer, frank cavitation is not observed and only electrode processes are impacted. Other projects include modification of electrodes with films of nonuniform density to control transport; breath sensors for ethanol, smoking by-products, and acetone; electroanalytical methods for characterizing films; and ammonia generation at algae modified electrodes. The efforts have generated papers in the Journal of The Electrochemical Society, Electrochemical and Solid-State Letters, and ECS Transactions, 200 presentations, and 25 U.S. Patents with 25 published, pending applications. Leddy co-authored the solution manual for Electrochemical Methods, and she is a Fellow of ECS.

P eter S. Fedkiw, Alumni Association Graduate Professor and Head of the Department of Chemical and Biomolecular Engineering at North Carolina State University, received his BChE degree in 1974 from the University of Delaware and his PhD in chemical engineering in 1979 at the University of California, Berkeley. Professor Fedkiw joined the NCSU faculty in 1979 and was promoted to Associate and Full Professor in 1983 and 1989, respectively. From 1995 to 2008 Fedkiw was a part-time, Intergovernmental Personnel Act employee of the Chemical Sciences Division, U.S. Army Research Office (ARO) in Research Triangle Park, NC. He supported ARO’s Advanced Energy Conversion Program by advocating, formulating, and managing basic research activities underpinning portable power systems for the dismounted warrior. Professor Fedkiw was named Guest Professor in the College of Materials Science and Chemical Engineering, Zhejiang University in 2007. He has advised 17 postdoctoral research associates and directed 43 graduate students, the majority of whom were PhD candidates. Professor Fedkiw’s research expertise is electrochemical engineering, and in his 34-year career at NCSU he has published in a variety of areas including: theoretical studies of current-distribution problems; electrochemical-based masstransfer separation processes; optimal control of electrochemical reactors; polymer electrolyte membrane reactors for electrosyntheses and fuel cells; electrodeposition of nanocrystalline metals and nanocrystalline composites; composite electrolytes and nanofiber anodes for rechargeable lithium (ion) batteries; and oxygen reduction electrocatalysts, among others. Fedkiw has published over 110 peerreviewed papers and has received seven patents issued or pending. His students and he have presented over 130 papers, posters, and talks, the majority of which have been at ECS meetings.

(continued on page 20

The Electrochemical Society Interface • Winter 2013

Candidates for Treasurer E. Jennings (EJ) Taylor is Chief Technical Officer and Intellectual Property Director at Faraday Technology Inc., an electrochemical engineering company that he founded in 1991. His vision for Faraday was to explore the possibilities of pulse and pulse reverse electrolysis and shift the focus of electrochemical process technologies from chemical additions and often hazardous electrolytes to “electric field” control with simple, environmentally benign electrolytes. With contributions from a very talented Faraday staff, Dr. Taylor has collaborated on (1) electrodeposition processes for copper for electronic applications, chrome coatings, alloys for SOFC interconnects, lead-free tin solders and fuel cell catalysts; (2) electrochemical surface finishing for automotive gears, stainless steel valves and niobium superconducting radio frequency cavities, titanium and nickel aerospace engine components, and fuel cell and flow battery bipolar plates; (3) electrochemical water treatment technologies; (4) novel electrochemical cells for printed circuit boards; and (5) corrosion sensing technologies. These activities have led to approximately 120 technical papers and approximately 33 patents with numerous conference presentations and patents pending. Dr. Taylor and his colleagues at Faraday were recognized by the National Association of Surface Finishers for contributions to the field of pulse/pulse reverse surface finishing with the 2008 Blum Scientific Achievement award. He has recently guided Faraday through a strategic acquisition and continues to serve as Chief Technical Officer at Faraday and Intellectual Property Director for the parent corporation, Physical Sciences Inc. Dr. Taylor is passionate about innovation and Faraday’s technologies are commercialized through the process of “open innovation” whereby Faraday works closely with corporate clients to demonstrate engineering readiness and manufacturability at the bench- and pilot-scale, then transitions the manufacturing process to the client’s facility. The competitive advantage associated with the technology is typically transferred to the client via patent licensing, although Faraday has also sold eight patents. Taylor has a BA in chemistry (1976) from Wittenberg University, and MS and PhD degrees in materials science (1981) from the University of Virginia where he studied The Electrochemical Society Interface • Winter 2013

under Glenn Stoner. His dissertation research was directed toward oxygen reduction kinetics related to fuel cells and conducted at Brookhaven National Laboratory under the direction of S. Srinivasan, W. O’Grady, J. McBreen, and G. Stoner. Subsequently, he obtained an MS in Technology Strategy and Policy (1991) from Boston University and is admitted to the U.S. Patent & Trademark Office bar (Reg. No. 53,676). Dr. Taylor joined ECS in 1979 while a non-resident graduate student at Brookhaven National Laboratory. After receiving his PhD in 1991 from the University of Virginia, Dr. Taylor conducted battery research at the corporate R&D center for International Nickel Corp., served as Manager of Fuel Cell Research at Giner Inc., and served as Manager of Electrochemical Technologies at Physical Sciences Inc. Dr. Taylor has served on various National Science Foundation Advisory Committees including as past Chair and current member of the Small Business Innovation Research program AdComm, member of the Engineering Directorate AdComm, and member of the Business and Operations AdComm. He also serves on several nonprofit boards including the Wright Brothers Institute, a “collaboratory” whose mission is to promote innovative solutions and commercialization related to U.S. Air Force technologies. Dr. Taylor is also committed to student education and Faraday has provided intern opportunities for undergraduate and graduate students, patent law students, and high school science and math teachers. During his 30+ years as a member of the ECS, Dr. Taylor has served as Secretary, Treasurer, Vice-Chair, and Chair of the Boston Section of the Society. He currently chairs the Sponsorship Committee, serves on the Development Committee and is a member of the Executive Committee of the Industrial Electrolytic and Electrochemical Engineering Division. He has presented an ECS Tutorial titled “Intellectual Property for Electrochemical Scientists, Engineers, and Technologists,” and recently presented an ECS “Hot Topic” breakfast briefing entitled, “The Role of Small Businesses in the Innovation Ecosystem.”

I am deeply honored to be nominated for the position of Treasurer of ECS. I understand both the stewardship and fiduciary responsibilities associated with being a member of the Society’s Executive Board and the Office of Treasurer. I accept these responsibilities without reservation.

Enrico Traversa in 1986 received his “Laurea” (Italian Doctoral Degree), summa cum laude, in chemical engineering from the University of Rome La Sapienza. In March 2013 he joined the King Abdullah University of Science and Technology (KAUST) as Professor of Materials Science and Engineering, after being, from April 2012, the Director of the Department of Fuel Cell Research at the International Center for Renewable Energy, Xi’an Jiaotong University, China. He joined the University of Rome Tor Vergata in 1988, where since 2000, he has been a Professor of Materials Science and Technology, now on leave of absence. At the same university, from 2001 to 2008 he was the Director of the PhD Course of Materials for Health, Environment, and Energy. From January 2009 to March 2012, he was a Principal Investigator at the International Research Center for Materials Nanoarchitectonics (MANA) at the National Institute for Materials Science (NIMS), Tsukuba, Japan, leading a unit on Sustainability Materials. Professor Traversa is an author of more than 500 scientific papers (more than 310 of them published in refereed international journals) and 16 patents, and edited 28 books and special issues on journals. He is listed in the Essential Science Indicators/Web of Science as a highly cited researcher, both in the Materials Science and Engineering categories, and his h-index is 44. Elected in 2007 in the World Academy of Ceramics, he was also elected to its Advisory Board (2010-2014). In 2011 he was a recipient of the Ross Coffin Purdy Award of the American Ceramic Society for the best paper on ceramics published in 2010. He was recipient in 2011 of a “1000 Talent” Scholarship from the Government of China. He served The Electrochemical Society on several committees, and he was Chair of the High Temperature Materials Division (2009-2011). He was elected a Fellow of the Electrochemical Society in 2013. From 2003 to 2009, he was member of the International Relations Committee of the Materials Research Society (MRS). He is currently Editor-in-Chief of Materials for Renewable and Sustainable Energy and an Associate Editor for the Journal of Nanoparticle Research. He is one of the Volume Organizers of the MRS Bulletin for 2014.

(continued on page 21)

Statement of Candidacy

candidates for societ y office

Paul A. Kohl (continued from page 18)

Energy Division advisor (1991-1994), Editor selection committee (1990 and 2003), and Long Range Planning Committee (19911995). He is currently the Chair of the Technical Affairs Committee. Johna Leddy (continued from page 18)

Professor Leddy, who chaired the Physical and Analytical Electrochemistry Division, served as Secretary of the Society from 2008-2012. She has served on the standing committees of Finance, Individual Membership, and Nominating, and has chaired Education, Society Meeting, and the Ways and Means committees. Leddy served on the New Technologies Subcommittee and the Publication Committee, and is now a member of Publications Subcommittee. Leddy co-organized six student poster sessions and 21 symposia for ECS, including the first Electrochemical Energy Summit. She has edited numerous ECS volumes, chaired the Summer Graduate Fellowships Committee, and helped establish a new ECS Society award. Leddy is well-versed in the activities, achievements, and uncertainties of the Society. Statement of Candidacy All professional societies face challenges of membership, meetings, mission, and relevance. ECS has weathered much of the storm well. The Society’s research domain remains highly-relevant. Meetings are thriving, where record breaking attendance is common, as attendees regularly number more than a third of the Society’s 8,000 members. ECS is actively committed to its mission— to promote and disseminate research in electrochemical and solid state science and technology. To remain viable and relevant, it is critical that ECS continue to acknowledge and to engage its challenges and opportunities. The first challenge is to ensure the viability of ECS publications. ECS is the last not-forprofit publisher in electrochemistry. What unique attributes as a societal publisher allow ECS to disseminate research and to preserve the integrity of the science? ECS provides rigorous review and attends to the scientific acumen of its members. As a Society, ECS is uniquely positioned to ensure high quality scientific content and to exploit the interplay between ECS meetings and publications. As a not-for-profit publisher, ECS can explore new publication media and employ tools, such as Open Access, that are less attractive to commercial publishers. To promote its mission, ECS must be able to effect change rapidly and remain true to its tradition of scientific excellence. 20

A first opportunity evolves from recognition that ECS is increasingly international, with more than half our members from outside of North America. How can ECS promote worldwide participation in its activities? ECS can engage with other scientific organizations. ECS meetings and publications are forums for exchange of ideas. Publications use electronic media. Exploiting electronic tools at meetings and workshops, ECS can further promote scientific excellence and worldwide participation. For both publications and meetings, timely planning and execution of ideas is critical. A second opportunity lies in promoting researchers early in their careers. Invitations to young researchers to become authors and speakers recognizes new ideas in electrochemistry. Support for meeting attendance promotes membership and broadens the technical program. A third opportunity to promote electrochemistry and solid state science and technology is in expanding extra-societal education. ECS is a dynamic environment for the interplay among researchers in industry, academia, and the national labs of many countries. It has been a privilege to work with ECS members committed to the common goals of electrochemical and solid state research. It would be an honor to use my experience at ECS to promote ECS members in their mission to preserve the integrity of the science and to disseminate electrochemical and solid state research. Peter S. Fedkiw (continued from page 18)

Professor Fedkiw has been a member of The Electrochemical Society since joining in 1975 as a graduate student. He is also a member of the American Chemical Society, American Institute of Chemical Engineers (AIChE), American Association for the Advancement of Science, and Sigma Xi. He was chair for the AIChE Annual Meetings programming area in Electrochemical Fundamentals. He has been an active participant in ECS meetings and governance. He helped organize in its formative years the highly successful General Student Poster Session. He has been a member and/or chair of the following Society Committees: Ad Hoc Gift Committee, Audit, Contributing Membership, Development, Education, Finance, Financial Policy, New Technology Subcommittee, Society Meeting, and Ways and Means. Within the ECS IE&EE Division, he has been a member of the New Electrochemical Technology Award Committee and the Student Awards Committee. Dr. Fedkiw was Society Treasurer and member of the Executive Committee from 2002 to 2006, and he was elected ECS Fellow in 2003.

Statement of Candidacy The Electrochemical Society at 111 years old is the premier member-driven organization for the collection and dissemination of knowledge in solid-state and electrochemical science and technology. Because of exemplary leadership of past ECS officers, generous volunteer efforts from members, and professional and dedicated headquarters staff, the Society has grown into the world-class organization that it is today. The 8,000 ECS members encompass approximately 70 countries, and it is our members who are the Society’s most valuable resource. It is imperative that Society leadership continues to conduct ECS business with a mindset that serves our members’ interests and professional needs while focusing on the mission of ECS to advance the theory and practice of electrochemical and solid-state science and technology. If elected, I will strive to assure the Society is a fluid organization, poised to respond to opportunities that benefit our members and align with the Society’s mission. Because of our worldwide membership, Society leadership must support initiatives that sustain and expand our international presence. The Society has made great strides in this regard and efforts must persist to serve constituents by continuing to sponsor jointly conferences with international organizations and groups of similar mission and to hold ECS annual meetings outside of the continental United States. The grandchallenge type problems are best addressed through interdisciplinary approaches and international collaborations, and ECS offers venues to exchange the latest scientific and technical developments while fostering interactions among the world’s leading scientists and engineers. The life blood of future Society membership is students. An investment in this human resource will ensure a healthy and vitalized ECS, and growth in student membership and student chapters will be a focus of my efforts as a member of the Executive Committee. I will work to increase the number of student chapters worldwide and seek means to enable increased number of students to present their work at Society meetings. Challenges continue to confront the Society’s publications from competition with commercial publishers. Society leadership must assure the viability and growth of our publications in this competitive environment while maintaining core values. The Society’s decision to publish four journals to better reach and serve target audiences was the right move and care must now be taken to provide avenues for the cross-fertilization of ideas and approaches across the “wet” and “dry” sides of the Society. I will work with publication editors and staff to define and implement creative approaches to continue ECS publications as the pre-eminent source The Electrochemical Society Interface • Winter 2013

of scientific and engineering knowledge in electrochemical and solid-state science and technology without compromise in quality and scholarly content. Clearly, new Society programs or activities come at a financial cost and risk; we must not be timid in new undertakings but we must be fiscally prudent. As a past ECS Treasurer, I am attuned to these issues, and I will work with headquarters staff, Society officers, and the Board of Directors to assure our Society remains fiscally sound and resources are marshaled wisely for the benefit of members. I am honored and humbled to stand as a candidate for Vice President. The Societyâ&#x20AC;&#x2122;s history has demonstrated that the combination of the right executive leadership along with informed member input has enabled ECS to adapt well to evolving circumstances and challenges. With your support and vote, I intend to enhance the value the Society provides members and lead our venerable organization in its second century of service to the electrochemical and solid-state science and engineering community. E. Jennings (EJ) Taylor (continued from page 19)

As a member of ECS for over 30 years, I fully appreciate the strong impact ECS has had on my professional development and career. I will work diligently to ensure that ECS remains on solid financial footing and continues to be a leader in the area of electrochemical science and engineering. I appreciate the technical breadth and diversity of ECS and I will work with all levels of governance of ECS to ensure continued success. I also understand the importance of the three-legged stool of ECS: academia, national laboratories, and industry, and will work with all to enhance the collaborative opportunities available within the framework of ECS. Finally, I believe that my experience on various ECS committees and nonprofit boards, as well as my entrepreneurial experience will provide a useful perspective regarding ECS governance issues, especially those related to fiduciary duties. In summary, I am passionate about innovation, the advancement of electrochemical science and technology, and student education, and will continue to look for ways for ECS to promote these issues into the future. If elected I will diligently perform my fiduciary duties and tirelessly support the strategic direction of ECS.

The Electrochemical Society Interface â&#x20AC;˘ Winter 2013

Enrico Traversa (continued from page 19)

Statement of Candidacy I am honored and delighted to be nominated as a candidate for the ECS Treasurer position. I have been an active member of ECS for over 15 years and I have served the Society on several committees, and in the HTM Division, of which I am now the Past Chair. I have organized symposia at meetings, together with editorial activity as an editor of proceedings volumes and ECS Transactions volumes. It will be a privilege to continue to serve ECS in one of its prominent leadership roles such as the Treasurer. ECS has taken a very important role in my professional career and I will feel compelled by the duty to preserve the financial health of ECS and to foster and expand for the future a financially sound Society. The main activities for revenue for ECS are publications and meetings. In these fields, new habits in the research communities are creating fierce competition, which is mostly detrimental for nonprofit peer societies. ECS is aware of these problems and actions have been taken in the recent past, the most important of which is the creation of four new journals. In the position of Treasurer, if elected, I will try to contribute to confirming the role of ECS as leader in the publication of electrochemical science and technology research, and in organizing increasingly successful meetings. Another important feature of ECS that has always attracted me is its truly international nature. As evident from my past accomplishments, breaking borders to foster international collaboration has been one of my main ideals and goals. I am sure that the targets of innovation may be reached at a faster speed through international collaboration, for the common benefit. I will contribute to maintain and expand international nature of ECS, trying to involve the Society in new countries emerging in electrochemical research, not yet represented significantly in the Society.

ECS Appreciates the support of the

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socie t y ne ws

New Editors for Interface ECS is pleased to announce the appointment of Vijay Ramani and Petr Vanýsek as Co-Editors of Interface. Because Interface is at the next turning point in its growth, the ECS Publications Subcommittee selected two editors: one focused on the outreach, education, and news areas, and one focused on the technical articles. Co-Editor Petr Vanýsek will cover primarily current content and the future development of departments such as Society, Student, and Section News. Professor Vanýsek will also work with guest contributor Zoltan Nagy on the ECS Classics series. Co-Editor Vijay Ramani will be responsible primarily for the featured technical articles in the magazine, Tech Highlights, and The Chalkboard series. While these areas are the primary responsibilities for Ramani and Vanýsek, there will be a great deal of overlap as they perform their editorial roles and bring new ideas to the magazine. We welcome Drs. Ramani and Vanýsek and will be eager to see where they will take us on the pages of Interface. Vijay Ramani is the Hyosung S. R. Cho Endowed Chair Professor of Chemical Engineering at Illinois Institute of Technology, Chicago. His research interests lie at the confluence of electrochemical engineering, materials science, and renewable energy technologies. Current research directions in his group include multi-functional electrolyte and electrocatalyst materials for electrochemical systems, analyzing the source and distribution of overpotential (losses) in electrochemical systems, mitigating component degradation in electrochemical devices, and in situ diagnostics to probe electrochemical systems. NSF, ONR, and DOE currently fund his research, with mechanisms including an NSF CAREER award in 2009 and an ONR Young Investigator Award (ONR-YIP) in 2010. He also received the 3M Non-tenured Faculty Award in 2010 and the Supramaniam Srinivasan Young Investigator Award from the ECS Energy Technology Division in 2012. He is the immediate past Chair of the ECS Industrial Electrochemistry and Electrochemical Engineering Division, and Vice President of Area 1E of AIChE. He holds an Extraordinary Professorship in Chemical Resource Beneficiation at North West University, South Africa, and an Adjunct Professorship in Chemical Engineering at IIT-Madras. Dr. Ramani has a PhD in from the University of Connecticut, Storrs, and a BE from Annamalai University, India, both in chemical engineering.

Petr Vanýsek received his PhD in physical electrochemistry from the Czechoslovak Academy of Sciences and began his academic career in the U.S. first as a postdoctoral associate at the University of North Carolina. After a short stint as a faculty in residence at the University of New Hampshire, he moved as an analytical chemist to his present academic department at Northern Illinois University, where he is now a full professor in the Department of Chemistry and Biochemistry. Here Vanýsek also served a three-year administrative appointment as the Director of Graduate Studies. He teaches courses in general chemistry, electrochemistry and analytical chemistry, as well as giving special outreach lectures on alternate sources of energy, nanotechnology, and applications of impedance spectroscopy. Dr. Vanýsek’s research interests are in analytical instrumentation, sensors, impedance spectroscopy, and electroanalytical methodology, as well as in the physical electrochemistry of interfaces between immiscible fluids, particularly focused on X-ray reflectivity visualization of the molecular structure of such interfaces. His interests, which straddle both material sciences and electroanalytical chemistry, led to his involvement in two ECS Divisions, Sensor and Physical and Analytical Elecrochemistry; at different times he served on the executive committees of both. Professor Vanýsek, who became an ECS member in 1986, was involved in numerous elected and appointed positions, where he offered his services to the Society. He was the Society Secretary from 2004 to 2008 and he served as the Interim Editor of the Journal of The Electrochemical Society from 2012 to 2013. He also represents ECS to the Federation of Materials Societies.

ECS celebrates the many successful achievements of members of the electrochemical and solid-state science community. We thank you for your dedication to scientific research and discovery, for the innovations you continually develop that are fueling an energy revolution, and, above all, for your commitment to helping to make the world a better place for generations to come. While nonprofit is our tax status, we need funds to continue our programs and services. Through generous supporters like you, we will be able to reach our goals and broaden dissemination of our scientific content.

We hope we can count on your support with a gift to The Electrochemical Society To make a tax-deductible donation, please visit

www.electrochem.org/donate

The Electrochemical Society Interface • Winter 2013

socie t y ne ws

Volume 58– S a n F r a n c i s c o , C a l i f o r n i a from the San Francisco meeting, October 27—November 1, 2013 The following issues of ECS Transactions are from symposia held during the San Francisco meeting. All issues are available in electronic (PDF) editions, which may be purchased by visiting http://ecsdl.org/ECST/. Some issues are also available in soft or hard cover 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. 58

No. 1

Polymer Electrolyte Fuel Cells 13 (PEFC 13) CD/USB........................ M $212.00, NM $265.00

Vol. 58 No. 2

Electrochemical Synthesis of Fuels 2 HC ................................M $141.00, NM $177.00

Vol. 58 No. 3

High Temperature Experimental Techniques and Measurements HC ..............................M $92.00, NM $115.00

Vol. 58 No. 4

Gallium Nitride and Silicon Carbide Power Technologies 3 HC..............................M $127.00, NM $159.00

Vol. 58 No. 5

Nonvolatile Memories 2 HC.............................M $94.00, NM $117.00

Vol. 58 No. 6

Semiconductor Cleaning Science and Technology (SCST) 13) HC.............................M $102.00, NM $127.00

Vol. 58 No. 7

Semiconductors, Dielectrics, and Metals for Nanoelectronics 11 HC ...........................M $117.00, NM $147.00

Vol. 58 No. 8

State-of-the-Art Program on Compound Semiconductors (SOTAPOCS) 55 -and- LowDimensional Nanoscale Electronic and Photonic Devices 6 HC.............................M $114.00, NM $143.00

Vol. 58 No. 9

ULSI Process Integration 8 HC.............................M $92.00, NM $115.00

Vol. 58 No. 10

Atomic Layer Deposition Applications 9 HC.............................M $92.00, NM $115.00

Vol. 58 No. 11

Photovoltaics for the 21st Century 9 SC.............................TBD

Forthcoming Issues SAN A0

Special Lectures - 224th ECS Meeting

SAN A1

Student Posters (General) - 224th ECS Meeting

SAN A2

SAN D1

Corrosion Posters (General) - 224th ECS Meeting

SAN G1

Alkaline Electrolyzers

SAN G2

Synthesis and Electrochemical Engineering General) - 224th ECS Meeting

SAN D2

Atmospheric Corrosion

Nanotechnology (General) - 224rd ECS Meeting

SAN D3

Degradation of Carbon Structural Materials

SAN H1

SAN A3

The Energy Water Nexus

SAN D4

Carbon Nanostructures 4 - Fullerenes to Graphene

SAN B1

Energy Technology/Battery--Joint Session (General) - 224th ECS Meeting

Mass Transport Phenomena in Localized Corrosion

SAN I1

SAN D5

Physical and Analytical Electrochemistry (General) - 224th ECS Meeting

SAN B2

Battery Chemistries Beyond Lithium Ion

Oxide Films: A Symposium in Honor of Clive Clayton on his 65th Birthday

SAN I2

SAN B3

Battery Safety

SAN D6

SAN I3

SAN B4

Computational Science of Battery Materials

Biodegradable and Bioabsortable Metals and Materials

Invitational Symposium in Honor of Adam Heller on his 80th Birthday

SAN E1

Photoelectrochemistry and Photoassisted Electrocatalysis

SAN I4

SAN B5

Electrochemical Capacitors: Fundamentals to Applications

Solid State Topics (General) - 224th ECS Meeting

SAN E7

Physical and Electrochemistry in Ionic Liquids 3

SAN I5

Electrode Processes 8

SAN B8

Intercalation Compounds for Rechargable Batteries

Processing, Materials, and Integration of Damascene and 3D Interconnects 5

SAN F1

SAN J1

Sensors, Actuators, and Microsystems (General) - 224th ECS Meeting

SAN B9

Interfacial Phenomena in Battery Systems

Current Trends in Electrodeposition An Invited Symposium

SAN F2

SAN J2

Impedance Techniques, Diagnostics, and Sensing Applications

SAN B10

Lithium-Ion Batteries

Emerging Materials and Processes for Energy Conversion and Storage

Stationary and Large-scale Electrical Energy Storage Systems 3

SAN F3

Fundamentals and Applications of Electrophoretic Deposition

SAN J3

SAN B12

Luminescence and Display Materials Fundamentals and Applications

SAN F4

Fundamentals of Electrochemical Growth - From UPD to Microstructures 3

SAN J4

Microfluidic MEMS/NEMS, Sensors and Devices

SAN F5

Emerging Opportunities in Electrochemical Deposition for Nanofabrication

SAN J6

Sensors for Agriculture

Ordering Information To order any of these recently-published titles, please visit the ECS Digital Library, http://ecsdl.org/ECST/ Email: customerservice@electrochem.org The Electrochemical Society Interface • Winter 2013

25 09/09/13

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ECS Welcomes New Staff Member Dan Fatton has joined ECS as Director of Development. He has considerable experience in fundraising, previously serving for five years as Outreach & Development Director for New Jersey Future, a public policy nonprofit dedicated to smart growth. Dan managed individual and corporate giving, breaking revenue records and also spearheading transportation policy initiatives. Prior to his tenure with New Jersey Future, Dan managed the New Jersey State Employees Charitable Campaign and founded a major giving program for EarthRights International, a nonprofit focused on human rights and the environment. Dan received a master’s degree in City and Regional Planning from the Bloustein School of Planning and Public Policy at Rutgers University and his bachelor’s degree from James Madison University. Dan founded Ideal Image Consulting in 2010, building upon

his ten-year career in nonprofit development and communications. His consulting clients have included the New Jersey Bicycle & Pedestrian Coalition, Conserve Wildlife Foundation of New Jersey, and the National Wildlife Habitat Council. Dan has provided technical assistance to the community pilot program for the Shaping NJ antiobesity initiative, and served on the steering committee for the Partnership for Healthy Kids-Trenton. He is a member of the Trenton Green Team, serves as board president for the I Am Trenton Community Foundation, and chairs Trenton Cycling Revolution, a bicycle and pedestrian advocacy organization. Dan is a fellow of the 2012 class of Leadership New Jersey. ECS Executive Director Roque Calvo announced Dan’s appointment by saying, “With his background and experience, Dan is a valuable addition to the staff at a very important time for ECS. The opportunities created with renewable energy sources have made electrochemical science and technology an increasingly important discipline, and Dan will have an important role in communicating our message and generating vital funds to support programs in this area.”

NON-TENURE TRACK FACULTY POSITIONS Dwight Look College of Engineering TEXAS A&M UNIVERSITY

The Dwight Look College of Engineering at Texas A&M University invites applications for non-tenure track faculty positions. Specifically targeted are candidates with experience and interests in materials corrosion in extreme service conditions. Applicants for the non-tenure track titles of associate professor or professor of engineering practice must have a Ph.D., Master or Bachelor level degree in materials science and engineering, physics, chemistry or in a related field, and significant industry and/or government lab experience. Candidates for associate professor or professor of engineering practice may be considered for multi-year appointments. The successful applicants will be expected to teach at the undergraduate and graduate level, develop curriculum and implement new teaching methods related to distance education and outreach programs, participate in the department's mission, and serve the profession. It is also expected that the candidate will supervise undergraduate / graduate research and collaborate with other faculty on externally funded research projects in the field. Strong written and verbal communication skills are required. Applicants will be evaluated based on current credentials and potential for impact in delivering real-world scenarios related to engineering education. The Texas A&M Engineering Experiment Station (TEES), a state agency of Texas, also seeks research faculty in the non-tenure track titles of associate research professor or research professor with research experience and interests in materials corrosion in extreme service conditions. Candidates for these titles must have a Ph.D. in materials science and engineering, physics, chemistry or in a related field, and research experience and accomplishments relative to the rank being sought. Successful candidates will be expected to develop and maintain a funded quality research program in materials corrosion, and contribute to improving the economic development and quality of life in Texas and the nation. Applicants must apply and include a cover letter clearly stating the position being sought, curriculum vitae, teaching statement, and a list of four references (including their postal addresses, telephone numbers and e-mail addresses) to the web site: www.tamuengineeringjobs.com/applicants/Central?quickFind=54963 The full position ad can be found at msen.tamu.edu. Full consideration will be given to applications received by February 15, 2014. Applications received after that date may be considered until positions are filled. It is anticipated that the appointment will begin in fall 2014.

The Electrochemical Society Interface • Winter 2013

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The Electrochemical Society Interface • Winter 2013

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ECS Division Contacts

Battery

Industrial Electrochemistry and Electrochemical Engineering

Bor Yann Liaw, Chair University of Hawaii at Manoa bliaw@hawaii.edu • 808.956.2339 (U.S.)

Gerardine Botte, Chair Ohio University botte@ohio.edu • 740.593.9670 (U.S.)

Robert Kostecki, Vice-Chair Christopher Johnson, Secretary

Venkat Subramanian, Vice-Chair

Marca Doeff, Treasurer

E. Jennings Taylor, Secretary/Treasurer

Luminescence and Display Materials Corrosion Shinji Fujimoto, Chair Osaka University fujimoto@mat.eng.osaka-u.ac.jp • 81.6.6879.7469 (Japan) Rudolph Buchheit, Vice-Chair

Anant A. Setlur, Chair GE Global Research Center setlur@ge.com • 1.518.387.6305 (U.S.) Madis Raukas, Vice-Chair

Mikhail Brik, Secretary/Treasurer

Barbara A. Shaw, Secretary/Treasurer

Dielectric Science and Technology Oana Leonte, Chair Berkeley Polymer Technology odleonte@comcast.net • 510.537.9413 (U.S.) Dolf Landheer, Vice-Chair Yaw Obeng, Treasurer Peter Mascher, Secretary

Nanocarbons Bruce Weisman, Chair Rice University weisman@rice.edu • 713.348.3709 (U.S.) Luis Echegoyen, Vice-Chair Dirk Guldi, Treasurer Slava V. Rotkin, Secretary

Organic and Biological Electrochemistry

Electrodeposition Giovanni Zangari, Chair University of Virginia gz3e@virginia.edu • 434.243.5474 (U.S.) Elizabeth Podlaha-Murphy, Vice-Chair Philippe Vereecken, Treasurer Stanko Brankovic, Secretary

James Burgess, Chair Case Western Reserve University jdb22@po.cwru.edu • 216.368.4490 (U.S.) Mekki Bayachou, Vice-Chair

Graham Cheek, Secretary/Treasurer

Physical and Analytical Electrochemistry Electronics and Photonics Andrew Hoff, Chair University of South Florida hoff@usf.edu • 813.974.4958 (U.S.) Mark Overberg, Vice-Chair Edward Stokes, 2nd Vice-Chair

Junichi Murota, Secretary Fan Ren, Treasurer

Robert Mantz, Chair Army Research Office robert.a.mantz@us.army.mil • 919.549.4309 (U.S.) Pawel Kulesza, Vice-Chair Andrew Hillier, Secretary

Alanah Fitch, Treasurer

Sensor Energy Technology Adam Weber, Chair Lawrence Berkeley National Laboratory azweber@lbl.gov • 1.510.486.6308 (U.S.) Scott Calabrese Barton, Vice-Chair Andrew Herring, Secretary

Vaidyanathan (Ravi) Subramanian, Treasurer

Michael Carter KWJ Engineering mcarter58@earthlink.net • 510.405.5911 (U.S.) Bryan Chin, Vice-Chair Nianqiang (Nick) Wu, Secretary

Ajit Khosla, Treasurer

High Temperature Materials Xiao-Dong Zhou, Chair University of South Carolina zhox@cec.sc.edu • 1.803.777.7540 (U.S.) Turgut Gur, Sr. Vice-Chair Paul Gannon, Secretary/Treasurer

Gregory Jackson, Jr. Vice-Chair

The Electrochemical Society Interface • Winter 2013

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DSC: The New Paradigm for Coin Cell Battery Testing

NEW Heat Signature is A Key Component for Battery Development and Testing The High Temperature Coin Cell Module is a new calorimeter module specially dedicated to coin cell battery studies. Coupled with a battery analyzer, one can perform discharge tests to evaluate battery condition, cycle batteries to improve performance and gain insight into overall battery condition in an isothermal or temperature scanning mode.

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The Electrochemical Society Interface • Winter 2013

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New Division Officers New officers for the 2013-2015 term have been elected for the following Divisions.

Electrodeposition Division (The Division voted to affirm the current Executive Committee remain in office for the 2013-2015 term.) Chair Giovanni Zangari, University of Virginia Vice-Chair Elizabeth Podlaha-Murphy, Northeastern University Secretary Stanko Brankovic, University of Houston Treasurer Philippe Vereecken, IMEC Members-at-Large Ingrid Shao, IBM Corporation Natasa Vasiljevic, University of Bristol

High Temperature Materials Division Chair Xiao-Dong Zhou, University of South Carolina Senior Vice-Chair Turgut Gur, Stanford University Junior Vice-Chair Greg Jackson, Colorado School of Mines Secretary/Treasurer Paul Gannon, Montana State University Members-at-Large Stuart Adler, University of Washington Mark Allendorf, Sandia National Laboratories Roberta Amendola, Montana State University Timothy Armstrong, Carpenter Technology, Corporate Research & Development Sean Bishop, Kyushu University Fanglin (Frank) Chen, University of South Carolina Zhe (Joseph) Cheng, Florida International University Wilson Chiu, University of Connecticut Koichi Eguchi, Kyoto University Emiliana Fabbri, Nanomaterials for Fuel Cells Group Fernando Garzon, Los Alamos National Laboratory Robert Glass, Lawrence Livermore National Laboratory Srikanth Gopalan, Boston University

The Electrochemical Society Interface â&#x20AC;˘ Winter 2013

Ellen Ivers-Tiffee, University of Karlsruhe Cortney Kreller, Los Alamos National Laboratory Xingbo Liu, West Virginia University Torsten Markus, Forschungszentrum Juelich Toshio Maruyama, Tokyo Inst of Technology Patrick Masset, Fraunhofer UMSICHT-ATZ Nguyen Quang Minh Mogens Mogensen, DTU Energy Conversion Jason Nicholas, Michigan State University Juan Nino, University of Florida Elizabeth Opila, University of Virginia Emily Ryan, Boston University Subhash Singhal, Pacific Northwest Labs Enrico Traversa, University of Rome Anil Virkar, University of Utah Eric Wachsman, University of Maryland Werner Weppner, Christian-Albrechts University Kielc Mark Williams, URS Corporation Leta Woo, Lawrence Livermore National Laboratory Eric Wuchina, Naval Surface Warfare Center Carderock Division Shu Yamaguchi, The University of Tokyo Harumi Yokokawa, National Institute of Advanced Industrial Science & Technology

Luminescence and Display Materials Division Chair Anant Setlur, GE Global Research Center Vice-Chair Madis Raukas, Osram Sylvania Secretary/Treasurer Mikhail Brik, University of Tartu Members-at-Large Holly Comanzo, GE Global Research Center Uwe Happek, University of Georgia Charles Hunt, University of California, Davos Marco Kirm, University of Tartu David Lockwood, National Research Council â&#x20AC;&#x201C; Canada Alok Srivastava, GE Global Research Center

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www.ecee2014.com

ECEE 2014

is the first Electrochemical Conference on Energy & the Environment, a major international conference that covers a unique blend of topics pertaining to energy and the environment. A joint meeting of The Electrochemical Society (ECS) and the Chinese Society of Electrochemistry (CSE), ECEE 2014 is a unique forum for the discussion of interdisciplinary research from around the world through a variety of formats, such as invited and keynote oral presentations, poster sessions, and exhibits.

Symposium topics include: • Electrochemical Energy Storage (E1)

• Electrochemical Fundamentals (E3)

• Electrochemical Energy Conversion (E2)

• Environmental Electrochemistry (E4)

Learn about the Keynote Speakers: Please visit www.ecee2014.com

IMPORTANT DEADLINES & INFORMATION: u Early Bird Registration Deadline: February 14, 2014 u Sponsorship & Exhibit Opportunities available: Please inquire at sponsorship@electrochem.org u Hotel Accommodations: Now accepting reservations

For more information about the first-ever

Electrochemical Conference on Energy & the Environment,

a joint meeting of ECS and CSE, please continue to visit the ECEE 2014 website. 32

www.ecee2014.com

The Electrochemical Society Interface • Winter 2013

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websites of note by Zoltan Nagy

The Aluminum Smelting Process: How the Hall-Heroult Process Works A detailed description of the high-temperature molten-salt electrolysis process. Aluminum properties. Discovery and extraction a brief history. Process basics. Detailed description of a cell and its basic functioning. How an aluminum smelter is made, Process thermodynamics - enthalpy, free energy, cell voltage. The voltage drop in the electrolyte. Some important figures. Bath chemistry. Electrolyte properties. Current efficiency. Cell thermal balance. Anode effect. Influence of magnetic fields. • http://www.aluminum-production.com/

Electrochemical Reactions - Electrolytic Cells Fairly detailed discussion of general electrochemistry, minus kinetics. Voltaic cells. Predicting spontaneous redox reactions from the sign of Eo. Standard-state reduction half-cell potentials. The Nernst equation. Faraday’s law. The electrolysis of aqueous and high-temperature molten NaCl. Electrolysis of water. • Department of Chemistry, Purdue University • http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch20/electro.php • http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch20/faraday.php

Electrochemical Processing of Refractory Metals in High-Temperature Molten-Salts The refractory metals comprise the elements Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W. They are also known as the transition elements and are found in the periodic table in Groups 4, 5, and 6. Electrochemical processing is used extensively in the primary extraction of these metals (electrowinning), the purification and recycling (electrorefining), and the formation of coatings (electroplating). Electrolysis in fused salts as well as other nonaqueous media has enormous potential for materials processing. First, because of the special attributes of nonaqueous electrolytes, electrochemical processing in these media has an important role to play in the generation of advanced materials with specialized chemistries or tailored microstructures (electrosynthesis). Second, as environmental quality standards rise beyond the capabilities of classical metals extraction technologies to comply, electrochemical processing may prove to be the only acceptable route from ore-to-metal. • D. R. Sadoway, (MIT) • http://web.mit.edu/dsadoway/Desktop/dsadoway/www/58.pdf

About the Author Zoltan Nagy is a semi-retired electrochemist. After 15 years in a variety of electrochemical industrial research, he spent 30 years at Argonne National Laboratory carrying out research on electrode kinetics and surface electrochemistry. Presently he is at the Chemistry Department of the University of North Carolina at Chapel Hill. He welcomes suggestions for entries; send them to nagyz@email.unc.edu.

The Electrochemical Society Interface • Winter 2013

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ECS Co-sponsored Conferences for 2014 In addition to the regular ECS biannual meetings, ECS, its Divisions, and Sections co-sponsor meetings and symposia of interest to the technical audience ECS serves. The following is a list of the co-sponsored meetings for 2014. Please visit the ECS website for a list of all cosponsored meetings. • China Semiconductor Technology International Conference 2014 (CSTIC 2014), March 16-17, 2014 – Shanghai, China • 14th Topical Meeting of the International Society of Electrochemistry, March 29-April 1, 2014 — Nanjing, China • 15th Topical Meeting of the International Society of Electrochemistry, April 27-30, 2014 — Niagara Falls, Canada • Shechtman International Symposium on Sustainable Mining, Minerals, Metal and Materials Processing, June 28-July 4, 2014 —

Cancun, Mexico

• 65th Annual Meeting of the International Society of Electrochemistry, August 31-September 5, 2014 — Lausanne, Switzerland • Fifth International Conference on Electrophoretic Deposition: Fundamentals and Applications (EPD-2014), October 5-10, 2014 —

Hernstein, Austria

To learn more about what an ECS co-sponsorship could do for your conference, including information on publishing proceeding volumes for co-sponsored meetings, or to request an ECS co-sponsorship of your technical event, please contact ecs@electrochem.org.

In the

issue of

• The spring 2014 issue will focus on the topic of ionic liquids. Guest edited by Frank Endres and Andreas Bund, the featured articles include: “Simulation of the Interface Electrode/Ionic Liquid,” by Maxim Fedorov; “Electrochemical Interfaces with Ionic Liquids,” by Natalia Borissenko, Rob Atkin, and Bernd Roling; “Electrodeposition in Ionic Liquids,” by Adriana Ispas; and “Vacuum Electrochemistry in Ionic Liquids,” by Stefan Krischok and Oliver Hoefft. • See a preview of the 225th ECS meeting in Orlando, Florida, May 11-16, 2014. Learn more about the exciting symposia planned for the meeting, including sessions on energy-related materials and devices; ubiquitous sensing,

energy harvesting, and the “Internet of Things;” solar fuels and photocatalysts; carbon nanostructures; and many more. You also get an advance look at the Short Courses being offered at the meeting, along with other special activities and events. Want an even earlier look? Visit http://www.electrochem.org/meetings/biannual/225/ now. • Confused about Open Access? Want to know the Society’s plans for meeting the mandates of the U.S. and UK? Need to understand Creative Commons licenses? You’ll find answers in a comprehensive article on the subject in the spring issue. • Tech Highlights continues to provide readers with free access to some of the most interesting papers published in the ECS journals, including articles from the Society’s newest journals: ECS Journal of Solid State Science and Technology, ECS Electrochemistry Letters, and ECS Solid State Letters. • Don’t miss the next edition of Websites of Note, Interfaceʼs regular look at interesting websites.

The Electrochemical Society Interface • Winter 2013

225th ECS Meeting

ORLANDO, FL Hilton Orlando Bonnet Creek

General Topics • • • • • • • •

Batteries, Fuel Cells, and Energy Conservation Chemical and Biological Sensors Corrosion Science and Technology Electrochemical/Electroless Deposition Electrochemical Engineering Fuel Cells, Electrolyzers, and Energy Conversion Organic and Bioelectrochemistry Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry

• • • • • •

Carbon Nanostructures and Devices Dielectric Science and Materials Electronic Materials Processing Electronic and Phototonic Devices and Systems Luminescence and Display Materials, Devices, and Processing Physical Sensors

*Please carefully check the symposium listings; some abstracts may have alternate submission deadlines.

Now Available! Discounted hotel rates start at $205 and are now available at the meeting headquarters hotel, the Hilton Orlando Bonnet Creek Hotel. The early-bird reservation deadline is April 11, 2014, or as soon as the block sells out!

Important Deadlines . . . • Early-bird registration opens in January 2014 – Deadline is April 11, 2014. • Travel grants are available for student attendees, and for young faculty and early career attendees. Applications are due January 1, 2014.

• Early-bird registration and hotel discounts are available until April 11, or until the block sells out! Reserve early!

More . . . • Short Courses are tentatively planned for the meeting: Basic Impedance Spectroscopy, •

Fundamentals of Electrochemistry, Grid Scale Energy Storage, Solar Energy Conversion, Battery Safety, Chemical/Biological Sensors, and Survey of Materials Characterization Techniques. Please check the ECS website for the final list of offerings. Full papers presented at ECS meetings will be published in ECS Transactions. Visit the ECS website for more details.

Please visit the Orlando Meeting page for more information: The Electrochemical Society Interface • Fall 2013

www.electrochem.org/orlando

San Francisco, CA • Special Meeting Section

May 11-16, 2014

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Robert Savinell Named Distinguished University Professor

obert F. Savinell, the George S. Dively Professor of Engineering in the Department of Chemical Engineering at Case Western Reserve University (CWRU), has been named a Distinguished University Professor. This pemanent, honorific title Robert F. Savinell recognizes the outstanding contributions of full-time, tenured CWRU professors with exceptional academic records of research, scholarship, teaching, and service. Professor Savinell is Editor of the ECS Electrochemical Science and Technology (EST) journals. As Editor, Professor Savinell leads a prestigious team of Technical Editors and Associate Editors for the ECS flagship, Journal of The Electrochemical Society (JES), as well as for one of the Society’s latest peer-reviewed offerings, ECS Electrochemistry Letters (EEL).

Savinell is a past Chair of the ECS IE&EE Division and is a Fellow of ECS. He is also a Fellow of the American Institute of Chemical Engineers and the International Society of Electrochemistry. Dr. Savinell holds a BS in Chemical Engineering, Cleveland State University, and an MS and PhD in Chemical Engineering, both from the University of Pittsburgh. He was Dean of the Case School of Engineering at CWRU from 2000 to 2007, is the former Director of the Ernest B. Yeager Center for Electrochemical Sciences at CWRU, and currently serves on the Advisory Board of the CWRU Great Lakes Energy Institute. Professor Savinell’s research program addresses electrochemical solutions to energy conversion and energy storage challenges, with recent emphasis on high temperature PEM fuel cells, flow batteries for large scale energy storage, and understanding materials and durability issues of electrochemical capacitors. His research focuses on understanding the thermodynamic, kinetic, and transport processes at electrochemical interfaces and within electrochemical systems through experimental and simulation approaches, and the wider scope spans fundamental investigations through translational research toward commercial application.

Henry Tuller Elected Vice-President of ISSI

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arry L. Tuller, of the Department of Materials Science and Engineering at MIT, was elected Vice-President/President-Elect of the International Society of Solid State Ionics (ISSI). Elections were held for new officers at the 19th meeting of the International Meeting on Solid State Ionics (SSI-19), held in Kyoto during the week of June 2nd and attended by nearly 900 participants. The stated goals of ISSI are “to promote science and technology related to ionic transport in solids” Harry L. Tuller and to “provide an international and interdisciplinary forum for scientists in this field.” Solid State Ionics forms the underpinnings of many key clean energy technologies including high energy density batteries, fuel and electrolysis cells, dye sensitized solar and photo-electrolysis cells, emission catalysts, and sensors. Professor Tuller successfully ran on a platform emphasizing the need for educating the public, government agencies, industry, and universities on the critical need for clean energy and the strategic contributions that the field of solid state ionics can and the needs to insure progress along these lines.

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The Electrochemical Society Interface • Winter 2013

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Jamal Deen Receives Major Honors he week of May 6, 2013 has been an amazing one in the professional life of Indo-Guyanese engineering scientist scholar, Jamal Deen. He is the Senior Canada Research Chair in Information Technology, Professor of Electrical and Computer Engineering, and Professor of Biomedical Engineering and Director, Micro- and NanoSystems Laboratory, McMaster University, Hamilton. On Monday in Regina, Dr. Deen was presented with the McNaughton Gold Medal, the highest award for engineers in Canada from IEEE, the largest professional society in the world. The short citation was “For pioneering contributions to modeling of semiconductor devices.” An important goal of the IEEE Canada awards are to recognize the distinguished and outstanding contributions and achievements of engineers, and to promote excellence and positive role models in society.

On Friday May 10, Dr. Deen was honored as the 2013 Winegard Lecturer at the University of Guelph. His Winegard lecture, to more than a hundred attendees, was entitled “Biosensors—Playing at the Crossroads of Engineering and the Sciences” where he emphasized the fun he has had doing research over the past three decades. The Winegard Lecture, made possible and named in honor of Guelph’s former president William Winegard, who was also a federal Minister of State (Science and Technology) as well as Minister for Science, “is an annual event that brings a world-renowned academic or industry professional” to broad audience that includes university faculty, staff, and students as well as the general public. The lecture is also to “encourage interaction and foster professional relationships between students (undergraduate and graduate), professors, researchers, alumni, and industry associates,” with a recognized leader in their field. Professor Deen’s lecture was extremely well-received with the lecture lasting just under hour and the questions and answers period an additional hour. Feedback from the attendees were uniformly very positive with several comments speaking to the accessible and enthusiastic manner in which the lecture was presented. The lecture was divided into three parts. The first part was on a most precious environmental commodity, water—its properties, importance to our good health, distribution and problems. The second part was on microbiological contaminants in water and how these bacterial contaminants can be recognized by parts of their DNA structure. The final part used ideas in the first two parts toward the development of low-cost, high sensitivity, and easy-to-use biosensors and sensing systems by Prof. Deen with his collaborators and team of researchers. On May 11, the University of the West Indies presented him with a Vice Chancellor’s Award in recognition of his “exceptional scholarly work in engineering and science, exemplary professionalism, and dedicated volunteerism.” His speech contained several of the sentiments expressed earlier in the week as the McNaughton Gold Medal winner. In addition, he stated, “As an academic from the Caribbean region, I have been fortunate to win many awards. However, this recognition here tonight means a lot to me and my family, and it will be very dearly treasured throughout our lives.” This article was written by Adit Kumar.

Jamal Deen with the McNaughton Gold Medal Award plaque.

In his speech to the awards ceremony attendees, Prof. Deen emphasized that “while this award is being presented to me, it is really recognition of the exceptional and sustained efforts of my family and teams of talented students, gifted researchers, and remarkable collaborators. Throughout my career, I have been fortunate to work with exceptional researchers. They have taken our ideas and proposals to new heights, and are largely responsible for the high academic reputation and respect earned from my peers.” His speech included the statement that “it is critical that we never lose faith in ourselves and our abilities. We should all have dreams, and we should pursue them with passion. Over my career I have been a constant dreamer. Do not lose faith if the outcome is less than stellar. It is quite possible that such outcomes may provide lasting learning experiences upon which even greater successes are achieved.” On May 8, Prof. Deen was presented with the McMaster Engineering Research Award at the Faculty of Engineering’s Annual “Applause and Accolades” Gala. This award recognizes his “world-class status and peer-recognitions as a researcher, as well as his sustained research efforts and leadership in the faculty of engineering.” The Electrochemical Society Interface • Winter 2013

Jamal Deen (center), his youngest son Tariq Deen (left), and Dr. Deen’s wife Meena Deen (right), at McMaster Engineering Research Award event. 37

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In Memoriam memoriam Joseph Grover Gordon II (1945-2013)

esearch chemist and research manager Joseph Grover Gordon II was born on December 25, 1945 in Nashville, Tennessee. He was one of four children. After briefly attending Atkins High School in North Carolina, Dr. Gordon went on to graduate from the prestigious Phillips Exeter Academy in 1963. Dr. Gordon earned his AB degree in chemistry and physics from Harvard College in 1966. He received his PhD in inorganic chemistry from Richard Holm at MIT in 1970. Professor Gordon was an Joseph Grover Gordon II assistant professor in chemistry at the California Institute of Technology from 1970-1974. During this period he discovered a new class of 1-D organometallic conductors based on metal isocyanides. In January 1975, he joined the research staff at the IBM San Jose Research Center (later the Almaden Research Center). During a fruitful IBM Research Division career spanning 33 years, he held increasingly more responsible technical and advisory management positions including assignments on local and divisional Research Director technical staffs. In research Dr. Gordon pioneered in important areas of interfacial electrochemistry (1975-1994). With Jerry Swalen, Dr. Gordon made the first use of surface plasmons as probes of Langmuir films on metal surfaces, and went on to develop this method to study charged metal electrode-aqueous electrolyte interfaces. Other key projects included the application of quartz microbalance technology to electrochemistry with Kay Kanazawa, in situ surface EXAFS and in situ interfacial X-ray diffraction measurements with Owen Melroy and Michael Toney. During this period Dr. Gordon and the interfacial electrochemistry group enjoyed significant interactions with

university groups (Puerto Rico, Cornell, Purdue) and young visiting researchers from Berlin, Mainz, Zurich, Padua, Bologna, Bordeaux, and Sapporo. Additionally Dr. Gordon lead efforts that contributed greatly to understanding the mechanism of electroless copper plating (printed wire boards) and the corrosion of magnetic alloys ( recording heads) in major IBM technologies. Joseph Gordon was a successful technology manager. In areas of support and technology he headed IBM departments for Materials Science and Analysis, Batteries and Displays, New Directions in Science and Technology, and was the Research Relationship Manager for Health Care. Prior to retirement (2009) Dr. Gordon was the Senior Manager of Materials for Advanced Technology with the responsibility of developing an exploratory battery materials research program and evaluating new battery technology for ThinkPad strategic planning (Raleigh, NC) and development in Japan. After retirement Dr. Gordon joined Applied Materials Inc., as Senior Director for the Advanced Technologies Group and in 2013 he was appointed CTO of Energy Storage Solutions. Throughout his career Dr. Gordon combined strong commitments to scientific research and technology. Dr. Gordon published numerous research papers in journals of the American Chemical Society, The Electrochemical Society, and the American Physical Society; and he was credited with twelve United States Patents including several for novel electrophoretic displays (with Mark Hart and Sally Swanson). Within IBM, Dr. Gordon was recognized many times for scientific and technical achievements. He was a member of professional organizations that included: the American Chemical Society, American Physical Society (Fellow 2000), AAAS, Society for Analytical Chemistry, The Electrochemical Society, and the National Research Council. In 1990, he was awarded the Black Engineer for Outstanding Technical Achievement and in 1993 the National Organization of Black Chemists and Chemical Engineers awarded Dr. Gordon the Percy L. Julian Award. Joseph Grover Gordon II passed away on September 13, 2013. He is survived by his wife Ruth M., son Perry (wife Alyshia), grandson Graystone, two brothers, and a sister. This notice was submitted by Daniel Buttry and Michael R. Philpott.

The Electrochemical Society Interface â&#x20AC;˘ Winter 2013

socie PEOPLE t y ne ws

In Memoriam memoriam Eric M. Pell (1923-2013) M. Pell, former President of The Electrochemical Society, passed away on Wednesday, August 14, in his home in Webster, New York. Dr. Pell was born September 22, 1923 in Rättvik Sweden. In 1931, after his mother passed away, he moved with his father to Milwaukee, Wisconsin. There he completed his early education, and later attended Deep Springs Junior College in California. In 1944, Dr. Pell went to Marquette University where he earned a degree in electrical engineering. He was Eric M. Pell accepted into the Navy’s radar program and was in the U.S. Naval Reserve from 1943-1946. After his service, Dr. Pell received his doctorate in physics from Cornell University. Dr. Pell worked for ten years as a research physicist for the General Electric Research Laboratory where he researched phenomena related to semiconductors, and electrical characteristics of n-p junctions and ionic interactions in solids. This research led to the invention of the lithium-drift nuclear particle detector, 29 publications, and eight patents. In 1961, Dr. Pell began working for Xerox Corporation at the Joseph C. Wilson Technology Center. He was charged with building a research group for solid state physics, and assumed various research and development management capacities. Dr. Pell became the manager of Xerox’s Fundamental Research Laboratory in 1965, where he was able to work with physicist Chester Carlson, the inventor of xerography. Dr. Pell served as the Organizing Chair and Co-Editor for the 1968 International Conference on Electrophotography, and in 1969 he became the Chair of the Ad Hoc Committee on Electrography for the Institute of Electrical and Electronics Engineers. The same year, Dr. Pell was the Editor of the proceedings of the 1969 Third International

rik

The Electrochemical Society Interface • Winter 2013

Conference on Photoconductivity. This was also the year that Dr. Pell first became a member of The Electrochemical Society. After joining ECS, Dr. Pell immediately became involved in the Electronics Division, serving as Vice-Chair for General Electronics in 1969-1970, and as Chair in 1971-1972. He later served on the Technical Affairs Committee, becoming Chair in 1978-1979, and was also the Chair of the Honors and Awards Committee from 1974-1977. Dr. Pell was elected Vice-President of ECS in 1977. He became the President of The Electrochemical Society in 1980-1981, and was awarded an Honorary Membership in 1983. Dr. Pell’s career at Xerox led him to become the manager of their Webster Physics Research Laboratory in 1985. There he was able to recruit, train, and manage the company’s team researching amorphous photoconductors. In 1986, Dr. Pell was presented with the Edward Goodrich Acheson Award for distinguished contributions to the advancement of the objects, purposes, and activities of ECS. Thirteen years later, in 1989, Dr. Pell retired from his job at Xerox and began working on his book, From Dreams to Riches, a history of xerography, which was later published in 1998. Dr. Pell was a recipient of the Marquette University Distinguished Alumnus of the Year Award in 2012. In his interview for the award write up he is quoted as saying, “I define success as achievement of one’s personal ambitions and enjoying the satisfaction one experiences as a result.” Erik M. Pell was active in many organizations throughout his lifetime. He was a Fellow of the American Physical Society, served on the Cornell Council, and was a Senior Member of the Institute of Electrical and Electronics Engineers. He served as Chair of the Cornell Graduate School Fund, Trustee of Deep Springs, Trustee of The Harley School of Rochester, and President of the Alumni of Deep Springs and Telluride Association. Dr. Pell was a member of the Society of Professionals, Scientists, and Engineers, the American Association for the Advancement of Science, and the New York Academy of Sciences. He was also involved in the scientific research society Sigma Xi, as well as the honors societies Phi Kappa Phi, Tau Beta Pi, Eta Kappa Nu, and Sigma Pi Sigma. Dr. Pell was extremely accomplished, and led a fulfilling and challenging life. He will be remembered by all for his innumerable contributions to The Electrochemical Society, as well as many others.

2 014

17th International Meeting on Lithium Batteries Como, Italy w June 10-14, 2014 IMLB 2014 (www.imlb.org) is the premier international conference on the state of lithium battery science and technology, as well as current and future applications in transportation, commercial, aerospace, biomedical, and other promising sectors. Convening in the heart of downtown Como/Cernobbio at Villa Erba, the conference is expected to draw 1,200 experts, researchers, and company representatives involved in the lithium battery field. This international meeting will provide an exciting forum to discuss recent progress in advanced lithium batteries for energy storage and conversion. The meeting will focus on both basic and applied research findings that have led to improved Li battery materials, and to the understanding of the fundamental processes that determine and control electrochemical performance. A major (but not exclusive) theme of the meeting will address recent advances beyond lithium-ion batteries. All areas of lithium battery related science and technology will be covered, such as, but not limited to: • general and national projects • anodes and cathodes • nanostructured materials for lithium batteries • liquid electrolytes and ionic liquids • polymer, gel, and solid electrolytes • issues related to sources and availability of materials for Li batteries

• Li battery recycling • electrode/electrolyte interface phenomena • safety, reliability, cell design and engineering • primary and rechargeable Li cells • industrial production and development for HEVs, PHEVs, and EVs • latest developments in Li battery technology

International Organizing Committee Chairs (in alphabetical order) • Doron Aurbach, Bar Ilan University, Tel Aviv, Israel • Peter Bruce, University of St.Andrews, Scotland • Rosa Palacin, ICMAB-CSIC Campus, Bellaterra, Spain • Bruno Scrosati, Helmholtz Institute Ulm, Germany

• Jean-Marie Tarascon, Université de Picardie Jules Verne, France • Josh Thomas, Uppsala University, Sweden • Margret Wohlfahrt-Mehrens, Center for Solar Energy and Hydrogen Research Baden-Württemberg, ZSW, Ulm, Germany

International Scientific Committee (in alphabetical order) • KM Abraham, E-KEM Science, USA • Khalil Amine, Argonne National Lab, USA • Yi Cui, Stanford University, USA • Juergen Garche, FCBAT, Ulm, Germany • Li Hong, China • Youn-Jun Kim, Korea Electronics Technology Institute (KETI), Korea • Marina Mastragostino, University of Bologna, Italy • Aleksandar Matic, Chalmers University of Technology, Sweden

• Linda Nazar, Waterloo University, Canada • Zempachi Ogumi, University of Kyoto, Japan • Tetsuya Osaka, Waseda University, Tokyo Japan • Stefano Passerini, Muenster University, Germany • Yang Shao-Horn, MIT, USA • Yang-Kook Sun, Hanyang University, Seoul, Korea • Osamu Yamamoto, Mie University, Japan • Yang Yong, Xiamen University, China

The Meeting Venue IMLB 2014 will be held in Como, Italy, in the same location where two successful previous meetings convened. The site of the meeting is the Villa Erba (www.villaerba.it) convention center, which is set magnificently on the lake shore on the edge of the 15th century villa. IMLB 2014 is being managed by ECS with logistical support provided by Centro Volta (www.centrovolta.it). General sessions, breaks and lunches, and the technical exhibit will be held at the spacious Padiglione Centrale at Villa Erba, and posters will be on display for the entire five days of the event. The Villa Erba is centrally located at the heart of one of Europe’s premier destinations, and offers six centuries of charm, atmosphere, and beauty. An astounding park, with vast lawns, magnificent trees, and an historical garden surrounds the exhibition centre and the Villa—a green heaven where one can relax in between sessions and meeting.

Visit www.imlb.org for deadlines, submission information, and more. 40

The Electrochemical Society Interface • Winter 2013 IMLB 2014 is sponsored and managed by ECS (www.electrochem.org).

2 014 w IMLB Call for Papers w

Abstracts due January 10, 2014 To ensure that the highest levels of scientific discovery are presented at IMLB 2014, the meeting will be limited to 1,200 delegates. Presentations will be carefully reviewed and selected by a special scientific committee. Oral presentations will be selected by the scientific committee of IMLB 2014. The number of posters will be limited to between 400 and 500. All posters will be on view and available for discussion during the entire five-days of the meeting. IMLB 2014 will include presentations related to: • Li battery anodes • Li battery cathodes • Li battery electrolyte systems (solutions, polymeric, solid-state)

• Li-sulphur systems • Li-oxygen systems • magnesium batteries • sodium batteries

• interfaces • diagnostic challenges • safety matters • redox and flow nonaqueous battery systems

Publication Opportunities All authors who are invited to submit an abstract to IMLB also will have the opportunity to submit a full paper to ECS Transactions (ECST). We are also pleased to announce that selected presentations will be invited for publication in a Focus Issue of the Journal of The Electrochemical Society (JES). Unlike ECST, JES follows a rapid, continuous publication model with individual articles published online every day having full final citation details. All papers will undergo the journal’s high standards of quality peer review.

Symposium Topics Topic 5: Li-Oxygen Systems

Topic 1: Electrode Materials Presentations that reflect: 1. cycle life, 2. cycling efficiency approaching 100%, 3. impressive rate capability, and, 4. proven excellent wide temperature performance of these electrodes. Presentations that will not be accepted: Many hundreds of thousands of papers have already been published on topics such as graphite; soft/hard carbons; LixTiOy and conversion reactions as negative electrodes; LiFePO4, LiMO2,(M = transition metal); and Lix[MnNiCo]Oy , LixVOy, Li[MnNi]2O4 spinel cathodes for Li ion batteries. These presentations will not be considered.

Topic 2: Electrolytes Presentations that reflect the development of new electrolyte solutions possessing very wide electrochemical windows (with an emphasis on high anodic stability, > 5 V vs. Li) and good performance in a wide temperature range. These may include reports on new solvents, salts, and additives. It is recommended that such studies include a good understanding of the limiting (surface) reactions of the new electrolyte systems.

Topic 3: New Electrodes

Presentations that discuss the true stability of oxygen cathodes and possibly relevant electrolyte solutions. Work on electrocatalysis for these systems is also interesting, provided that the effect of the catalysts presented on possible side reactions is discussed as well.

Topic 6: Li-Sulphur Systems Presentations must reflect prolonged cycle life and practically high loading of sulfur (per cm2). Systems that are too exotic and that may reflect good performance by very low specific content of sulfur may not be considered for presentation. Special attention should be given to the practical reversibility of negative electrodes for these systems.

Topic 7: Application of New and Novel Analytical Tools Reports on the application of new and novel analytical tools in the above fields are encouraged.

Topic 8: Computational Work Related to Experimental Reality

Presentations on new electrodes (both positive and negative) for rechargeable magnesium and sodium batteries, provided that they include appropriate, concluding structural studies.

Reports on proven computational work connected to experimental reality are encouraged.

Topic 4: Novel Magnesium Electrolyte Solutions

Although there is a clear interest in these types of battery systems (including flow/redox systems), only those that have a wide enough common denominator to the above systems (e.g., nonaqueous electrolyte solutions, metal ion insertion electrodes) will be positively considered. While the main criteria are purely novelty and high level of science, some preference will be given to young presenters (students, post-doctoral fellows).

Presentations on novel electrolyte solutions for rechargeable Mg batteries, provided that they reflect new concepts and are suitable for both reversible Mg anodes an Mg insertion cathodes. Presentations on new Mg insertion electrodes (with proven reversibility approaching 100%) will be positively considered as well.

Topic 9: Systems for Load-Leveling Applications

Important Deadlines • January 10, 2014 – Abstracts due • February 1, 2014 – Sponsorship deadline

The Electrochemical Society Interface • Winter 2013 www.imlb.org Visit

• June 23, 2014 – ECS Transactions website opens • September 30, 2014 – Journal of The Electrochemical Society manuscript submissions deadline

for complete details.

41 2 014

The Potentiostat and the Voltage Clamp by Jackson E. Harrar

n the history of science and technology, there have been many instances when two or more persons have independently created an invention or concept at almost the same time, but for various reasons, one inventor takes precedence or credit. Examples are the telephone, the integrated circuit, calculus in mathematics, and the theory of evolution. Once the invention or concept is introduced, further development soon proceeds along a single path. A rare instance is an innovation that was developed by two different scientists in two different fields at almost the same time, and then widely used for many years in these two fields without the investigators being aware of the other application. This happened in the case of the potentiostat and the voltage clamp, which are basically similar instruments, but whose actual applications are quite dissimilar. Both the potentiostat and the voltage clamp operate on the principle of negative feedback control. Both instruments employ an amplifier in a feedback arrangement to control the voltage (or electrode potential) in, respectively, an electrolytic cell or a biological specimen. In their simplest forms, they are essentially the same circuit. In the early 1940s, Archie Hickling at the University of Leicester, England, who was working in the field of electrochemistry, invented the potentiostat and coined the apt name for the device.1 He used the potentiostat to control the voltage (i.e., the potential) of an electrode to perform electrolysis in an electrolytic cell. In the late 1940s, at the University of Chicago, Kenneth Cole, with the help of George Marmont, invented an electronic circuit called a voltage clamp,2 which was used to investigate ionic conduction in nerves. Concurrently, these voltage clamp techniques were adopted by Alan Hodgkin, Andrew Huxley, and Bernard Katz at Cambridge University in England for their research in this field. In 1963, Hodgkin and Huxley were awarded the Nobel Prize in Physiology or Medicine for this work. Further development and elaboration of these circuits has been carried on for many years, including the marketing of many commercial instrumentsâ&#x20AC;&#x201D;some for electrochemistry and some for biochemistry 42

and biophysics. In electrochemistry, potentiostats are used for fundamental studies of electrode processes, analytical chemistry, battery research, the synthesis of chemicals, and corrosion research. Variations of the voltage clamp are employed in research on the properties of living biological cells. Adaptations of these instruments have also been made to control the electric current rather than voltage. During most of this time, however, research in these disparate fields of electrochemistry and electrophysiology, and their investigators, has remained virtually independent.

The Potentiostat Figure 1 shows a simplified version of a potentiostat connected to a three-electrode electrolytic cell. The electrolysis current in the electrolytic cell is provided by the output of the amplifier (Amp) to the cell via the counter electrode (CE). The desired or studied reaction takes place at the working electrode (WE). The reference electrode (RE) senses the potential at the working electrode

Amp +

and this signal is transmitted to the negative input of the differential amplifier, where it is compared to the desired control voltage (E) at the positive input. The amplifier is a DCcoupled, differential input amplifier. It has a high open-loop gain (>105), fast response, and its inputs have high input impedances so very little current (nanoamperes) flows in this part of the circuit. The amplifier, by the action of negative feedback, continuously adjusts its output voltage and current to keep the potential measured by the reference electrode equal to the control voltage. The electrolysis current flowing between electrodes CE and WE is measured by additional instrumentation (M) in either the counter electrode part (as shown) or the working electrode part of the circuit. In electrochemistry, potentiostats are used with working electrodes of inert elements (e.g., platinum, gold, mercury, and carbon), semiconductors, and for corrosion studies, the metal of interest. Sizes range in area from >100 cm2 for controlled-potential coulometry and electrosynthesis, to very small (radius <103 cm) microelectrodes for

Cell

Fig. 1. Simplified potentiostat and three-electrode electrolytic cell. The Electrochemical Society Interface â&#x20AC;˘ Winter 2013

chemical analysis and fundamental studies.3 Counter electrodes are usually made of platinum, while reference electrodes are most often made of silver, coated with silver chloride, or mercury-mercurous chloride (saturated calomel).

The Voltage Clamp Figure 2 shows a simplified version of a “two-electrode” voltage clamp connected to an apparatus in which the properties of the membrane of a biological specimen are examined. The specimen in this arrangement is contained in a bathing medium such as saline solution. The electrodes (CE and RE) penetrate the membrane of the specimen. Electrode CE is the current-carrying electrode within the specimen, while the second electrode (RE) senses the potential (with reference to ground) across the membrane. The current flows from electrode CE through the membrane of the specimen to ground. Measurements of the current, in either the amplifier output circuit (M) or the ground circuit, yields information on the properties of the membrane. The electrodes typically are constructed of fine-tipped glass pipets containing a chlorided silver wire or platinum, and the experiments are often performed on a microscope stage. The similarity of the voltage-clamp configuration to that of the potentiostat is readily apparent. The amplifier/feedback voltage clamp circuit functions the same way it does as a potentiostat to impose a potential equal to the command voltage at the membrane. As in potentiostatic circuits, the current passing through the membrane in measured with auxiliary circuitry not shown in the figure. In the study of nerve cells, early work in voltage clamping revealed information on how sodium and potassium

Amp + E

ions are transported through ion channels in the membrane.2,4 Later studies have dealt with calcium and chloride ion flow. Advances in technique and instrumentation in the field of electrophysiology have led to an apparatus for clamping with a single intracellular electrode, and patch clamping, which enables measuring the properties of single ion channels in a membrane.5,6 For the invention of the patch clamp technique, Bert Sakmann and Erwin Neher received the 1991 Nobel Prize in Physiology or Medicine.

Common Problems in the Experiments Although the electronic circuits of potentiostatic and voltage clamps are similar, the laboratory apparatus and experiments using them are quite different. Nevertheless, some problems that complicate the experiments are present in both fields. Electrophysiologists are always dealing with extremely small microelectrodes which have high resistances that may introduce errors in potential control.6 Certain investigations using potentiostats also employ very small working electrodes, and when more exact potential control is required, solution resistances exist that may have to be compensated, particularly at the working electrode.7 There are also many electrical capacitance effects that complicate the measurements. First of all, a cell membrane itself constitutes an electrical capacitance that must be charged before the desired potential is established. This is analogous to potentiostatic work in which the working electrode/solution double-layer capacitance must first be charged. There are also “stray” capacitances in both electrolytic and voltage

Biological Specimen in Bathing Solution

Fig. 2. Simplified two-electrode voltage clamp and biological specimen. The Electrochemical Society Interface • Winter 2013

clamp arrangements that can influence the measurements of high-speed signals.6 The stability of the cell/feedback loop in controlling the potential may also be an issue. In the case of potentiostatic measurements, this was examined in terms of classical control-system theory in the 1960s and 1970s,7 and has also been addressed for voltage clamp systems.6,8 Data interpretation in electrophysiology may also be complicated because the microelectrode contacts a point while the cell is obviously three dimensional. The patch clamp technique is advantageous in this respect because the microelectrode in this configuration is attached directly to an ion channel or small group of ion channels. In both electrochemistry and electrophysiology, quite sophisticated instrumentation has been designed and techniques of data interpretation have been developed to deal with all of these problems.5-9

History Further development of potentiostatic and voltage clamp instrumentation from the simple circuits described here has proceeded in parallel. The first circuits used amplifiers that were assembled from the individual electronic components (resisters, capacitors, and vacuum tubes). Some early potentiostats also used mechanical servomechanisms. The advent during the 1950s of commercially available, plug-in, modular amplifiers, called operational amplifiers,10 or “op amps,” made possible many extensions of the basic potentiostat and voltage clamp and more elaborate circuits.6,9 At first, using these modular op amps, experimenters who were not trained engineers, but who were versed in electronics, could assemble their own functioning instruments. Quite advanced instruments incorporating integrated-circuit operational amplifiers are now commercially available for many specialized applications in electrochemistry, analytical chemistry, and studies in electrophysiology. These instruments embody features that enable measurement of the electric current during voltage control, or control of the current instead of voltage, operation with very small or very large electrodes, and operation under computer control. Op amps are typically incorporated in the instruments for impedance buffering, current measurement, and resistance compensation. Returning to a theme of this article, for many years, research in the fields of electrochemistry and electrophysiology has still remained largely independent. Companies marketing instruments and apparatus target one field or the other, but usually not both because the marketing differences are significant. Only a few scientists and engineers in each discipline have been aware of work in the other field. Advances in each field might have occurred somewhat faster if there had been more interaction. 43

Harrar

4. E. R. Kandel, J. H. Schwartz, and T. M. Jessell, Essentials of Neural Science and Behavior, Chapter 10, Appleton & Lange, Norwalk, CT, (1995). 5. T. G. Smith, Jr., H. Lecar, S. J. Redman, and P. W. Gage, Eds., Voltage and Patch Clamping with Microelectrodes, American Physiological Society, Bethesda, MD, (1985). 6. The Axon CNS Guide to Electrophysiology & Biophysics Laboratory Techniques, Molecular Devices Corporation, Sunnyvale, CA, (2006). 7. D. K. Roe, in Laboratory Techniques in Electroanalytical Chemistry, 2nd ed., P. T. Kissinger and W. R. Heineman, Eds., Chapter 7, Marcel Dekker, New York, (1996). 8. A. S. Finkel and P. W. Gage, in Reference 5, Chapter 4. 9. P. T. Kissinger, in Reference 7, Chapter 6. 10. The George A. Philbrick Archives, (2013), http://www.philbrickarchive.org.

About the Author

(continued from previous page)

However, it now appears that some common ground is being cultivated. There is at least one company that the author is aware of that sells both potentiostats and electrophysiology equipment. In analytical electrochemistry, the invention of ionselective electrodes stimulated research on the properties of laboratory-synthesized membranes. A home glucose monitor is based on electrochemical measurement, and chemical compounds in the brain have been measured using electroanalytical techniques. The technique of cyclic voltammetry has become popular for examining the properties of biological molecules. And at conferences of The Electrochemical Society and the American Chemical Society, there are now many symposia on biomedical research.

Jackson E. Harrar obtained his PhD in chemistry from the University of Washington in 1958. He retired from a 42-year career at the Lawrence Livermore National Laboratory in 2000. His research was in electroanalytical chemistry and instrumentation, electrosynthesis, and geothermal chemistry. He may be reached at jharrar@mindspring.com.

References 1. A. Hickling, Trans. Faraday Soc., 38, 27 (1942). 2. A. Huxley, “Kenneth S. Cole,” Biographical Memoirs, National Academy of Science, Washington, DC, (1996). 3. A. J. Bard and L. R. Faulkner, Electrochemical Methods, 2nd ed., J. Wiley, New York, (2000).

ORLANDO, FL May 11-16, 2014

225th ECS Meeting

Hilton Bonnet Creek

ECS Future Meetings 2014 225th Spring Meeting Orlando, FL

May 11-16, 2014 Hilton Bonnet Creek

226th Fall Meeting

Cancun, Mexico October 5-10, 2014 Moon Palace Resort

2015 227th Spring Meeting Chicago, IL

May 24-28, 2015 Hilton Chicago

228th Fall Meeting Phoenix, AZ

October 11-16, 2015 Hyatt Regency Phoenix & Phoenix Convention Center

2016 229th Spring Meeting San Diego, CA

May 29-June 3, 2016 Hilton San Diego Bayfront & San Diego Convention Center

PRiME 2016

Honolulu, HI

October 9-14, 2016 Hawaii Convention Center & Hilton Hawaiian Village

The Electrochemical Society Interface • Winter 2013

t ech highligh t s Hydrogen Absorption into Titanium under Cathodic Polarization: An In Situ Neutron Reflectometry and EIS Study Significant hydrogen (H) absorption into titanium can result in a substantial reduction in mechanical properties. The H of concern is electrochemically generated at the metal surface through corrosion processes or cathodic protection. In order for hydrogen to penetrate the oxide on the titanium surface (which is otherwise a barrier to hydrogen ingress), the oxide must be reduced to a degree (TiIV → TiIII). This increases the conductivity of the film and facilitates electron transport across the oxide/solution interface, permitting the reduction of protons and subsequent uptake of H. In this work, the authors used neutron reflectometry to probe hydrogen uptake into the metal, combined with electrochemical impedance spectroscopy to probe the nature of the metal oxide. Two threshold potentials were identified at which significant changes took place—the first at approximately -0.37 VSCE, and then the second at -0.6 VSCE. The first threshold was found to be related to the onset of local oxide conductivity and the underpotential deposition of Dads on the metal surface and its subsequent absorption into the metal. At the second threshold, the oxide is reduced (i.e., TiO2 → TiOOH) and rendered ineffective as a hydrogen permeation barrier, allowing significant hydrogen uptake to take place. This work represents the first instance where the -0.37 VSCE potential regime has been identified as a threshold related to hydrogen uptake. From: J. Electrochem. Soc., 160, C414 (2013). Electrochemical Detection of Amyloid-Beta Aggregation in the Presence of Resveratrol Amyloid-β is a generic term describing abnormally fibrillated proteins possessing a β-pleated sheet conformation. The formation and deposition of amyloid fibril plaques are known to be associated with Alzheimer’s disease. A better understanding of the pathway to the fibrillization is highly desired and important for finding effective treatments for the disease, but efficient methods to monitor the process are still lacking. In the recent J. Electrochem. Soc. focus issue on organic and biological electrochemistry, researchers from the University of Toronto Scarborough reported an electrochemical method to detect amyloid-β aggregation using electrochemical impedance spectroscopy (EIS). In this method, a gold electrode surface was first modified with N-hydroxysuccinimide-activated lipoic ester that could subsequently bind amyloid monomers covalently. The electrode was then incubated in solutions containing free amyloid monomers under different conditions while the charge transfer resistance of the electrode was monitored with [Fe(CN)6]3−/4− as the redox probe. The EIS result indicated the inhibition effect of resveratrol, a polyphenolic bioflavonoid compound, on amyloid aggregation. This effect was also confirmed with Thioflavin T fluorescence assay and

The Electrochemical Society Interface • Winter 2013

transmission electron microscopy. Compared with the established fluorescence method, the EIS technique is label-free and easy to prepare. Its potential application lies in the area of fast screening drug candidates for Alzheimer’s disease. From: J. Electrochem. Soc., 160, G3097 (2013). Silicon CMOS Ohmic Contact Technology for Contacting III-V Compound Materials A crucial technological development for full integration of both silicon-complementary metal-oxide semiconductor (CMOS) and templated III-V optoelectronic technology involves ohmic contacts that need to be mutually compatible. A suitably complementary and functional ohmic contacting metallurgy could potentially enable seamless planar monolithic integration of these disparate technologies. Researchers at Massachusetts Institute of Technology have developed routes towards CMOS-compatible ohmic contacting technologies to buried III-V films using silicide metallurgies. Specifically, they report on the use of NiSi/Si/III-V dual heterojunction contact structures. A benefit of this approach is the ability to control contact resistivities by the Si/III-V interface, and also prevent unwanted interactions between the deposited metal and the buried III-V layers. The group demonstrated the approach with Si-encapsulated III-V device layers based on Si/InxGa1-xAs and report low contact resistivities in these test structures. Additionally, they demonstrate the feasibility of CMOS compatibility of III-V layers using NiSi/Si/III-V interfaces, by fabricating a GaAs/AlxGa1-xAs laser with NiSi top contacts that performed equally well compared to those fabricated with a traditional III-V metallization strategy. The researchers posit that similar methods could be extended to phosphide- or nitride-based films to widen the range and improve flexibility of Si/III-V interfaces and ohmic contact metallurgy for full monolithic integration. From: ECS J. Solid State Sci. Technol., 2, P324 (2013). Electrochemical Properties of Li3Fe0.2Mn0.8CO3PO4 as a Li-Ion Battery Cathode High-throughput ab initio computation has identified carbonophosphates as candidate materials for intercalation cathodes in higher energy density lithium ion batteries. Interest has centered on Li3MnCO3PO4, which has a high theoretical specific capacity of 231 mAh/g and average voltage of 3.7 VLi /Li, but has exhibited capacity degradation in practice; and Li3FeCO3PO4,which has high cyclability, but a lower theoretical capacity. The authors, from Massachusetts Institute of Technology, suspected the poor cyclability of Li3MnCO3PO4 may arise from residual sodium ion (~17%) after the Li-Na ion-exchange method is applied to the sodium-containing precursor made in the lab. Since the lab-made Li3FeCO3PO4 product contains no residual sodium, the authors set out to substitute iron for some manganese +

in the Li3MnCO3PO4 material in an attempt to improve both capacity and cyclability performance. A Li3Fe0.2Mn0.8CO3PO4 product was made and tested, delivering slightly better capacity than Li3FeCO3PO4. Because of its higher discharge voltage, the new material also has a greater practical energy density. The researchers were able to demonstrate stable capacity retention for cycles 4 through 25. The reason why the Fe-doped Mn form of the carbonophosphate performs better remains unknown. Nonetheless, the authors suggest that these results show promise for employing doping and structural tuning strategies in carbonophosphates for performance improvements. From: ECS Electrochem. Lett., 2, A81 (2013). Passivation Properties of a UV-Curable Polymer for Organic Light Emitting Diodes Organic light-emitting diodes (OLEDs) are used in a variety of commercial applications, particularly in displays for mobile phones and smart phones. One of the key technological challenges for OLED displays is that device performance degrades in the presence of water and oxygen. Glass encapsulation of the devices provides excellent long-term protection against the harmful effects of moisture and air ingress. Recently, researchers from Jilin University in China described the elegant use of a commercially available UV-curable polymer (NOA63 from Norland Products) to provide barrier protection of OLED devices during pre-commercial stages, including research, development, fabrication, and testing. The authors report that a simple spin-coating process, followed by a 50 mW/cm2 UV cure, produced a barrier coating that did not diminish luminance-voltage and current-voltage characteristics. Further, the barrier coating was shown to have a water vapor transmission rate of only 0.031 g/m2/day, among the best reported for a single polymer barrier coating. Finally, the long-term luminance of the OLEDs, while only 60% that of OLEDs protected by a glass encapsulant, was approximately 7-fold better than unencapsulated devices. The authors conclude that this approach would be powerful for protecting OLEDs during short-term studies in the laboratory, or as an elementary moisture barrier prior to implementing more sophisticated, long-term encapsulation strategies. From: ECS Solid State Lett., 2, R31 (2013).

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High Temperature Materials for Energy Conversion by Jeffrey W. Fergus he High Temperature Materials Division (HTM) of The Electrochemical Society was initially established in 1922 as the Electrothermics Division, and in 1982 took its current name to better reflect the research interests of its members. These research interests include the properties, processing, and application of materials at high temperatures and encompass a broad range of materials types and applications. High temperatures are often needed in processing materials through sintering, casting, and other heat treatments and are encountered in applications such high-speed aircraft and energy-conversion technologies. The HTM Division sponsors several recurring symposia including Solid Oxide Fuel Cells, Solid Ionic Devices, Ionic and Mixed Conducting Ceramics, and High Temperature Corrosion and Materials Chemistry, each of which has been offered at least eight times. In addition, new symposia are developed to address emerging technology areas, such as Electrochemical Synthesis of Fuels and Electrochemical Utilization of Solid Fuel, which will be offered for the second time at the San Francisco and Orlando meetings, respectively. Other new symposia to be offered in the upcoming year include High Temperature Experimental Techniques and Measurements and Mechanical-Electrochemical Coupling in Energy Related Materials and Devices. The trend in topic areas has led to discussions about another change in the name of the Division to reflect two common aspects of papers in HTM symposia: device/process design and energy applications. Some papers in HTM symposia focus on materials properties, but others focus on design of the process or device, and the name High Temperature Materials may imply a materials focus. The other is that many papers focus on energy applications. Both of these aspects, especially the latter, are reflected in the focus of this issue. The articles in this issue highlight the importance of high temperature materials in energy conversion technologies. One of the advantages of high temperatures is that reaction kinetics increase with increasing temperature. This advantage is evident in solid oxide fuel cells, which do not require costly platinum catalysts and can be used with a wider variety of fuels as compared to low temperature fuel cells. The high temperature provides an added advantage of increased efficiency. These advantages and other aspects of solid oxide fuel cells are discussed in the first article of this issue, which summarizes

The Electrochemical Society Interface â&#x20AC;˘ Winter 2013

a recent NSF-sponsored workshop entitled Solid Oxide Fuel Cells: Promise, Progress and Priorities. The second article is related and discusses reversible solid oxide fuels cells, which can be used for both power generation and for fuel production. The third article is also related to fuel production, but on a topic not typically associated with high temperature materialsâ&#x20AC;&#x201D; solar energy conversion. In particular, the article discusses the use of metal-oxide reduction-oxidation for the production of carbon monoxide and hydrogen fuels using solar energy by solar thermochemical fuel production (STFP). Such carbonneutral fuel production is critical to meet the growing demands for fuels in transportation and other sectors. The fourth article is on a topic that is applicable to most, if not all, high temperature applicationsâ&#x20AC;&#x201D;corrosion. As noted above, one of the advantages of high temperature operation is the accelerated chemical reaction rates. This is an advantage for desired reactions, but a disadvantage for undesired reactions. The importance of corrosion in a variety of energy conversion technologies, including Rankine and Brayton cycles, nuclear power, solid oxide fuel cells, thermoelectric energy conversion, and concentrated solar power, is discussed. The articles in this issue provide a few examples of the application of high temperature materials in energy conversion technologies. It is worth noting that this is not the only area where high temperature materials are used, but the topic of energy conversion has assumed increasing importance due to growth in worldwide energy demands and the threat of climate change resulting from the accumulation of greenhouse gases.

About the Author Jeffrey W. Fergus is Editor of ECS Transactions and Past Chair of the High Temperature Materials Division. After receiving his PhD from the University of Pennsylvania and a postdoctoral appointment at the University of Notre Dame, he joined the materials engineering faculty at Auburn University, where he is currently a professor. His research interests are in the high temperature and solid state chemistry of materials, including the chemical degradation of materials and materials for electrochemical devices, such as chemical sensors, batteries, and fuel cells. He may be reached at jwfergus@eng.auburn.edu.

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Highlights from the 2013 National Science Foundation Solid Oxide Fuel Cell Promise, Progress, and Priorities (SOFC-PPP) Workshop by Jason D. Nicholas olid Oxide Fuel Cells (SOFCs) and Solid Oxide Electrolysis Cells (SOECs) (i.e., SOFCs operated in reverse) are solid-state devices that can be used to (a) convert between chemical and electrical energy and/or (b) drive chemical reactions. These capabilities make them attractive for energy conversion, energy storage, chemical sensing, chemical separation, and chemical synthesis applications. To articulate the unique benefits of these promising technologies and spur consensus on a successful SOFC/SOEC development path, leaders from academia, industry, the U.S. government, and the public policy community (identified in Table I) came together on July 11-12, 2013 for a National Science Foundation (NSF) sponsored Solid Oxide Fuel Cell Promise, Progress, and Priorities (SOFC-PPP) workshop. Highlights from the workshop are summarized here. Readers are referred to www.sofcwg.org for the full workshop report and whitepapers highlighting the unique benefits of these technologies for various constituencies.

Promise Although SOFC/SOEC technology can be used for a variety of applications such as gas sensing, gas purification, etc., the workshop participants agreed that the greatest promise for these devices lay in (1) using SOFCs for environmentally-friendly electricity generation, and (2) using SOECs for energy storage, carbon capture, and chemical synthesis. SOFCs as a Clean and Efficient Path to a CO2-Neutral Economy Powered by H2 , Biofuel, or Solar-fuels—SOFCs have many characteristics which make them attractive for producing electricity from fuels or energy-carriers (i.e., chemicals that are used for “temporary” energy storage and are not viewed as energy sources in and of themselves). First, SOFCs have the highest theoretical and demonstrated efficiencies of any chemical to energy conversion technology: 50-60%1-6 when electricity alone is valued, and 70-90%4-6 when both electricity and high quality waste heat are valued. As shown in Fig 1., SOFCs also have some of the highest gravimetric and volumetric power densities of any electricity generation technology.7 Unlike competing energy conversion technologies (continued on next page) The Electrochemical Society Interface • Winter 2013

Table I. 2013 SOFC-PPP Workshop Participants. Individual Institution Stuart Adler University of Washington Michele Anderson Office of Naval Research George Antos National Science Foundation Scott Barnett Northwestern University Noriko Behling Freelance Author Viola Birss University of Calgary, Canada Sean Bishop Kyushu University, Japan Zhe Cheng Florida International University William Chueh Stanford University Whitney Colella Strategic Analysis, Inc. Singaravelu Elangovan Ceramatec, Inc. Jeffrey Fergus Auburn University Gary Fischman National Science Foundation Hossein Ghezel-Ayagh Fuel Cell Energy, Inc. Raymond Gorte University of Pennsylvania Sossina Haile Caltech Michael Hill Trans-Tech Inc. Kevin Huang University of South Carolina Masaki Kawai NGK Insulators Cortney Kreller Los Alamos National Laboratory Burtrand Lee Petroleum Research Fund John Lemmon Advanced Research Projects Agency-Energy Daniel Lewis Rensselaer Polytechnic Institute Meilin Liu Georgia Institute of Technology Lynnette Madsen National Science Foundation Rodger McKain LG Fuel Cell Systems U.S., Inc. Nguyen Minh The University of California at San Diego Mohan Misra ITN Energy Systems, Inc. Mogens Mogensen Technical University of Denmark, Riso Daniel Mumm University of California, Irvine Yeshwanth Narendar Saint-Gobain Ceramics and Plastics, Inc. Jason Nicholas Michigan State University Eranda Nikolla Wayne State University Elizabeth Opila University of Virginia Nina Orlovskaya University of Central Florida Joshua Persky Protonex Technology Corporation Randy Petri Versa Power, Inc. Shriram Ramanathan Harvard University Jon Rice Ultra Electronics AMI, Inc. Kazunari Sasaki Kyushu University, Japan Justin Scott The Minerals, Metals and Materials Society Prabhakar Singh University of Connecticut Subhash Singhal Pacific Northwest National Laboratory Jacob Spendelow Department of Energy Efficiency and Renewable Energy Program S.K. Sundaram Alfred University Erik Svedberg The National Academy of Sciences Scott Swartz NexTech Materials Masaru Tsuchiya Si Energy Systems, LLC Anil Virkar University of Utah Eric Wachsman University of Maryland Mark Williams URS Corp. Bilge Yildiz Massachusetts Institute of Technology 49

Nicholas

(continued from previous page)

such as gas turbines, SOFC efficiencies are size independent; making them effective for applications ranging from 1 Watt to multiMegawatts. Examples of these applications include: • 1 – 100W personal device power packs; • 100W – 10kW uninterruptible power supplies; • 2 – 5kW tractor trailer hotel load and/ or refrigerated trailer auxiliary power units; • 1 – 10kW unmanned aerial, ground, and underwater vehicles; • 1 – 15kW natural gas pipeline metering stations, radar stations, cell-phone tower power units, and infrastructure support applications; • 100W – 100kW distributed solar energy and smart grid energy storage applications; • 20 – 40kW automotive hybrid units; • 60 – 90kW automotive power plants; • 1kW – 10MW residential, commercial, and industrial applications; and • 100 – 500MW central power stations. SOFCs also have the ability to utilize a variety of fuels and energy-carriers (hydrogen, ethanol, biofuel, gasoline, natural gas, syngas, landfill gas, jet-fuel, etc).7,8 Debate currently exists on whether CO2-free energy-carriers (such as hydrogen), or CO2neutral energy-carriers that uptake/release CO2 when they are produced/consumed (such as bio- or solar-derived hydrocarbons) are best for use with renewable electricity generation. However, ~80% of annual world energy demand is projected to be met with hydrocarbon fuels for at least the next 30 years,9 suggesting that R&D into the clean use of hydrocarbons should remain a worldwide priority. This is especially true for the United States, where new hydrocarbon recovery technologies (such as hydraulic fracturing) have lowered natural gas costs10 and are projected to:

SOFCs are beneficial in the near term because hydrocarbon-fueled SOFCs produce ~50% less CO2, ~90% less NOx, ~90% less SOx, and virtually no particulates or volatile organic compounds, on a per Watt basis, compared to conventional hydrocarbon-fueled power plants.12 In addition, SOFC anode exhaust streams can provide concentrated CO2 for enhanced oil recovery or carbon sequestration. SOFCs are beneficial in the long term because the percent of renewably generated, CO2-neutral H2, biofuels, and/or solar-fuels used in centralized or distributed SOFC electricity generation facilities could be increased without the need for additional infrastructure. SOFCs can be used in large-scale (i.e., multi-megawatt) centralized power plants (where they benefit from $/kW cost reductions),13,14 or in distributed (i.e., pointof-use) power generation units (where they are less vulnerable to attack and weatherrelated power-outages caused by damage to the above-ground electricity distribution network). In fact, the benefits of distributed SOFCs has already led companies such as Verizon Communications to install cell-phone tower SOFC units.15 If SOFCs for distributed combined heat and power applications can be made economical, a huge market awaits in the 55% of the homes and businesses already connected to the U.S. natural gas distribution grid.16

SOECs for Energy Storage, Carbon Capture, and Chemical Synthesis.— SOECs have many characteristics which make them attractive for renewable (solar, wind, tidal, etc.) energy storage. First, SOECs have the highest fuel production to consumed electricity ratios of any electrical to chemical energy conversion technology, thanks to their reversible catalysts and their high operating temperatures.17,18 Unlike batteries, SOEC electrodes remain inert during the energy storage process, allowing them to store as much energy as desired. Further, SOECs can store this energy in liquid hydrocarbons that have 2-5 times the gravimetric and volumetric energy densities of Li-ion batteries.7,19 Alternatively, SOECs can store electrical energy by converting H2O and/or CO2 into H2 and/or syngas (CO + H2), and SOFC/SOEC combinations used for energy storage and conversion have modeled efficiencies of 60% (which is more than double those encountered today).20 SOECs can also be used to upgrade biomass energy sources, produce high energy density liquid transportation fuels (such as gasoline) for subsequent use in SOFCs, capture carbon in condensed phases, and produce designer chemicals. For instance, SOEC-produced syngas can be used in conventional processes to produce fuels, lubricants, fertilizers, plastics, adhesives, pharmaceuticals, synthetic

• make the U.S. the world’s largest oil producer by 2017,11 • make the U.S. the world’s largest natural gas exporter by 2020,9 and • make natural gas the domestic fuel by 2030.11

most-used

This new era of cheap, domesticallyproduced natural gas is an opportunity to develop and deploy SOFCs and SOECs that can reduce the environmental impact of today’s hydrocarbon based economy while simultaneously providing the infrastructure for a CO2-neutral economy utilizing biofuels, solar fuels, or hydrogen. 50

Fig. 1. Gravimetric and volumetric power densities for various electricity generation technologies. Note that gas turbine efficiency scales with system size, and only large (~1 MW and greater) gas turbines exhibit specific powers greater than SOFCs. Also note that batteries have been excluded from this plot because they are an energy storage, not an electricity generation, technology. This figure was modified from Ref 7 with gas turbine data from Ref. 56 and 57. Reprinted with permission from AAAS with the condition that readers may view, browse, and/or download this figure for temporary copying purposes only, provided these uses are for noncommercial personal purposes. Except as provided by law, this material may not be further reproduced, distributed, transmitted, modified, adapted, performed, displayed, published, or sold in whole or in part, without prior written permission from the publisher. The Electrochemical Society Interface • Winter 2013

fabrics, and other hydrocarbons derivatives. Another intriguing possibility is to perform these chemical conversions directly within an SOEC with the aid of specially designed catalysts and the control over chemical driving forces, chemical reaction pathways, and reaction product selectivity that can be exerted by an electrical polarization.

SOFC and SOEC Operating Principles

Progress Over the past decade, the SOFC/SOEC community has achieved major advances in realizing the promise of these devices by reducing SOFC operating temperatures from ~1000°C to ~600°C,7,8,21 demonstrating areaspecific SOFC power densities in excess of 1W/cm2 above 600°C,7,22 increasing SOFC lifetimes into the tens of thousands of hours range,23 and reducing installed SOFC costs to the $6-8/Watt range.13,14 (These costs are similar to those that were encountered by the solar industry a decade ago, and it is only now, with the help of the ~$300 million/year DOE Sun Shot program, that solar is starting to encounter widespread adoption as it moves from its current $3.50/Watt installed capacity price to an anticipated $1/ Watt cost by 2017.)15,24 While installed costs of $4/W have been projected for scaled-up 100kW SOFC systems,14 the SOFC-PPP workshop participants concluded that before SOFC/SOEC technology can move toward widespread practical application, progress on the critical scientific and engineering issues summarized in Table II must be made to reduce costs and/or improve device functionality, performance, and stability.

Priorities Research and Development Priorities.— A list of critical scientific and engineering issues, an explanation why they are being researched, and recent developments impacting the need to, or likelihood of, solving these issues are summarized in Table II. Achieving progress on these issues was determined to be critical for placing SOFCs and SOECs on lower cost learning curve trajectories. Policy Priorities.—The SOFC-PPP workshop participants agreed that U.S. SOFC funding of ~$100 million/year would be needed to make significant progress in solving the critical scientific and engineering issues summarized in Table II. This amount of funding could easily be offset by SOFC/ SOEC efficiency-induced cost-savings in the $550 billion/year9 energy business. Further, this amount of funding would place per capita U.S. SOFC R&D funding levels at $0.33/year, making them similar to the per capita commitments of other countries. Germany, for instance, funds SOFC R&D efforts at a per capita level of $1.50/year.25,26 If U.S. SOFC funding levels were to be increased, several workshop participants expressed the opinion that a greater emphasis should be placed on fundamental research, compared to past efforts. The Electrochemical Society Interface • Winter 2013

SOFCs are electrochemical mass and energy conversion and storage devices. Like all fuel cells, SOFCs utilize spatially separated redox reactions to drive ionic species through an electrolyte and electronic current through an external circuit. However unlike other types of fuel cells, SOFCs utilize solid-state materials with high oxygen vacancy (VO••) conductivities and low interfacial oxygen exchange resistances. As shown above, this facilitates the transport of oxygen vacancies from the anode, where lattice oxygen (OOx ) leaves the lattice to oxidize a fuel (or energy-carrier) and produce electrons (e') via the reaction: Fuel (Energy Carrier)(g)+(OOx )(s)→Oxidized Fuel(Energy Carrier)(g)+VO••(s)+2e'(s) to the cathode, where oxygen vacancies and electrons are consumed as oxygen enters the lattice via the reaction:

VO••(s)+2e'(s)+½O2(g)→(OOx )(s)

Thus, as long as fuel/energy-carrier and oxidant are applied to the anode and cathode, respectively, electrons flow through the external circuit joining the anode and cathode (producing electricity). SOFCs purpose-built to operate in a reverse mode, where fuel (energy carrier) and oxidant are produced when oxidized fuel (energy carrier) and electricity are provided, are referred to as Solid Oxide Electrolysis Cells.

Workshop participants also suggested that greater efforts be made to educate the public, policy-makers, and the broader scientific community on the unique benefits of SOFCs, and to eliminate the misconception that all fuel cells have to be associated with the hydrogen economy. To this end, the development of widespread, highly visible SOFCs for niche applications (similar to the solar powered calculators of the 1970s or the current polymer electrolyte membrane-powered forklifts) was identified as a priority. To support industry, it was also suggested that an unbiased, independent laboratory be set up to promote confidence in SOFC manufacturer performance claims. Workshop participants also suggested that NSF and/or the Department of Energy (DOE) Basic Energy Sciences (DOE-BES) division consider whether the establishment of high-temperature electrochemistry programs aimed at bringing together ion transport, electro-catalysis, electrodics, nanostructures, and interfacial chemistry fuel cell/battery/chemical work together, would help advance their missions.

The workshop participants also called upon greater coordination between the various government agencies funding SOFC research and development. Opinions on the appropriate degree of coordination included: • The creation of a National Fuel Cell Development Project (akin to the National Nanotechnology Initiative (NNI) and described more fully in Behling27) that would support basic research and product development activities on all fuel cell types and be led by a highly experienced manager with access to the nation’s most senior leadership. • The creation of a “Sun Shot” type program for fuel cells focusing on the most efficient use of currently available domestic hydrocarbon fuels. As was done for solar cells, this program would focus on overcoming barriers to commercialization with specific cost, efficiency, and durability goals, across all federal stakeholder agencies. It (continued on next page) 51

Nicholas

(continued from previous page) Table II. Critical SOFC/SOEC Scientific and Engineering Issues. Research Area

Critical Scientific & Engineering Issues

What’s New?

Expand SOFC/SOEC operating conditions by researching/developing: Stable, highperformance, low temperature SOFC materials Strain and/or interface engineered SOFC materials

Improved fuel flexible, high temperature anodes

Anodes that catalyze CH4 oxidation below 500oC

• Identifying the rate-limiting mechanisms for oxygen reduction, transport, and evolution • Exploring structures with new ionic conduction mechanisms • Developing new materials with higher ionic conductivity, lower oxygen surface exchange resistances, and higher catalytic activity • Understanding the relationship between performance, surface structure, stress/strain, catalytic activity, defect thermodynamics, defect kinetics, electronic structure, etc. under actual SOFC temperature, atmospheric, and electrochemical polarization conditions • Understanding how interface engineering can be used to alter materials properties and performance under SOFC operating conditions • Understanding the activation of molecular structures and the impact of inorganic impurities when using fuels other than H2 or CH4 (such as direct carbon, biogas, JP-8, etc.) • Developing new materials and concepts for fuel flexible anodes • Developing techniques to recycle fuel in small scale systems • Eliminating costly external reforming by achieving internal reforming • Understanding and resolving chemical processes at catalytic time scales • Identifying materials that have fast oxygen exchange kinetics and catalyze CH4 oxidation below 500oC

New oxygen and/or proton conducting materials, computational modeling, in situ testing capabilities, etc. 29-36 Both strain37 and interface effects38-40 have recently been shown to enhance ionic transport and/or surface exchange kinetics. The projected emergence of natural gas as the most-used domestic fuel by 203011 adds to the importance of this research area. Much work has been done on methane oxidation heterogeneous catalysis under open-circuit conditions, but almost none has been done under polarized SOFC operating conditions.

Give SOFCs/SOECs new functionalities by researching/developing: Reversible SOFCs/ SOECs for energy storage SOFCs/SOECs for chemical synthesis

• Understanding high overpotential effects on material performance and stability SOECs are a new research area, with the number of papers increasing by • Understanding pore formation in the electrolyte 1500% over the past six years.41 • Understanding delamination at oxygen electrode – electrolyte interfaces • Developing materials that are stable in both oxygen-rich and oxygen-deficient environments • Developing strategies for extracting value from the chemical conversion capability of SOFCs • Understanding high overpotential effects on catalysis performance, stability, and selectivity

Improve SOFC/SOEC manufacturability by researching/developing: New processes for tailored microstructures

• Developing novel processes such as self-assembly, spinodal decomposition, multi-step infiltration, etc. to obtain new, desirable hierarchical microstructures • Developing interfacial mechanisms for increasing densification rate in low-cost processing • Understanding materials interactions and the effect on defects in co-processing • Leveraging domestic microelectronics expertise to produce micro-SOFCs • Developing materials that are easily scaled to manufacturing level processes and can be used with existing cell fabrication methods

The collaborative culture that has developed between academic and industrial members of the domestic SOFC community (as demonstrated by the participation of both groups in the SOFC-PPP workshop and the successful completion of joint DOESECA program projects), means that academic SOFC/SOEC advances can be quickly transferred to industry. (Table II continued on next page)

would utilize a three-tiered, integratedactivity approach that would (1) build on the successes of both the DOE Solid State Energy Conversion Alliance (SECA) and DOE Energy Efficiency and Renewable Energy (EERE) Hydrogen and Fuel Cell programs, (2) utilize the DOE Advanced Research Projects Agency-Energy (ARPA-E) program to invest in new high-risk/high-reward material sets and technologies, and (3) expand the amount of fundamental fuel cell research funded by NSF and DOEBES. • Using groups like the Interagency Power Group (https://iapginfo.org/) to increase coordination between federal programs currently funding SOFC research.

Lastly, the workshop participants suggested that a National Academy of Sciences study be commissioned to aid policy-makers in how to best structure U.S. fuel cell policy and/or identify the best technologies (fuel cell or otherwise) for the clean utilization of hydrocarbon fuels in the context of a future U.S. energy mix with a variety of renewable energy sources.

Conclusions As summarized in this report, SOFCs and SOECs offer a unique opportunity to reduce the environmental impact of today’s hydrocarbon based economy while simultaneously providing the infrastructure for a CO2-neutral economy utilizing biofuels, solar fuels or hydrogen. It is therefore alarming that U.S. SOFC programs, such as the DOE SECA program have been zeroed out in the DOE FY2012 and FY2013 budget requests.28

As members of the scientific community and our respective countries, we have the power to shape future SOFC/SOEC policy, and SOFC/SOEC policy has the power to shape our future. Both need our investment.

Disclaimer The opinions expressed here are those of the academic, industrial, and public-policy SOFC-PPP workshop participants, and do not represent those of the National Science Foundation, the Department of Energy, the U.S. Government, or any other organization.

Acknowledgments The SOFC-PPP Workshop was made possible through the generous support of the NSF Catalysis and Bio-catalysis Program under Award Number 1326996. Additional The Electrochemical Society Interface • Winter 2013

Table II. Critical SOFC/SOEC Scientific and Engineering Issues. (continued) Research Area

What’s New?

Critical Scientific & Engineering Issues

Improve SOFC/SOEC performance and durability by researching/developing: Redox stable anodes • Understanding the influence electronic and geometric structure have on catalytic activity • Understanding interfacial phase formation and segregation Sulfur tolerant anodes

• Understanding the sulfur poisoning mechanisms • Eliminating the need for an external desulfurizer by developing sulfur tolerant anodes

New in situ/in operando techniques for studying behavior under SOFC operating conditions, etc.36,42-44 New computational modeling, in situ characterization techniques, strain engineering,31,43 etc. The projected emergence of natural gas as the most-used domestic fuel by 203011 adds to the importance of this research area.

Cr-controlled metallic • Understanding alloy oxidation mechanism to develop low electrical resistance protective scales interconnects • Identifying Cr-free alloys suitable for use in SOFCs • Developing Cr mitigation materials/solutions that allow low-cost steel interconnects

Recent advances in developing low temperature electrodes and electrolytes will mitigate these problems by allowing additional materials/coatings to be considered.

On-board diagnostics

• Developing on-board diagnostics that allow real-time efficiency, maximizing balance of plant This area remains largely unexplored, adjustments to short-term load changes and long term cell degradation making it a rich area for advancement.

Thermo-mechanochemical predictive capabilities

• Understanding and mitigating the effects that gradients in temperature, composition, and defect chemistry have on stress-strain deformation behavior and mechanical failure • Performing basic materials property (i.e., elastic property, thermodynamic property, etc.) measurements to support SOFC commercialization efforts

• Understanding microstructure-property-performance relationships in electrodes to link Quantitative intrinsic thin film measurements to porous thick film electrode performance Performance/ Design Models • Developing computational methods to predict phase equilibria • Developing atomic level computational methods sensitive to materials criticality to discover new materials with desirable electrochemical and catalytic properties • Developing predictive multi-physics simulations to link atomic processes to cell-level performance, and cell-level performance to stack-level performance • Developing better/new open-source economic-technology models to identify niche applications, and incorporate them into stack and reformer design models • Developing the tools, models, and designs necessary to reduce balance of plant (blowers, reformers, etc.) costs Reliable degradation models

• Understanding the factors controlling microstructural (e.g., nanoscale coarsening) and compositional (e.g., Cr poisoning, surface segregation, etc.) degradation mechanisms • Connecting degradation to atomistic models, and validating these models in real systems to eliminate the gap between lab scale testing and real system degradation • Developing science-based accelerated testing protocols

participant travel funds were provided by The Electrochemical Society High Temperature Materials Division. The author wishes to thank all the SOFC-PPP workshop participants for their contributions to this work. The author is especially grateful to committee chairmen Scott Barnett, Jeff Fergus, Masaru Tsuchiya, and Eric Wachsman for their assistance in organizing the SOFC-PPP workshop.

About the Author Jason Nicholas is an Assistant Professor in the Chemical Engineering and Materials Science Department at Michigan State University. His present research interests lie in utilizing the interplay between stress, microstructure, processing and materials properties to improve the performance of chemical-to-electrical energy conversion/ storage devices (fuel cells, chemical separators, pseudo-capacitors, batteries, The Electrochemical Society Interface • Winter 2013

etc.) and environmentally-aware devices (electro-chromic coatings, chemical sensors, chemical actuators, etc.). Updates on his work can be found at https://www.egr.msu. edu/nicholasgroup/.

References 1. K. W. Bedringas, I. S. Ertesvag, S. Byggstoyl, and B. F. Magnussen, Energy, 22, 403 (1997). 2. S. H. Chan, C. F. Low, and O. L. Ding, J. Power Sources, 103, 188 (2002). 3. EG&G Technical Services, Fuel Cell Handbook, U.S. Department of Energy, Office of Fossil Energy, Washington, DC (2004). 4. K. Hosoi and M. Nakabaru, ECS Transactions, 25, 11 (2009). 5. Hexis Inc., http://www.hexis. com/sites/default/files/media/ publikationen/130524_hexis_ broschuere_galileo_e_web.pdf (2014).

Advances in high-throughput combinatorial materials science, and increased attention between mechanical, electrical, and chemical coupling in the SOFC community.32,45-48 Advances in nondestructive 3D microstructural reconstructions,49-51 finite element/finite difference modeling of reconstructed SOFC geometries,52,53 thermodynamic modeling of SOFCrelevant materials,54 etc. With recent advances in stack technologies, balance of plant costs are the largest expense for large scale (i.e., greater than ~15 kW) SOFC systems.14 Thin film materials degradation testing,55 nondestructive 3D microstructural reconstructions,49-51 computational modeling of surface evolution,44 etc.

6. Ceres Power Holdings PLC, http:// w w w. c e r e s p o w e r. c o m / s t o r e / files/218-Ceres%20Power%202010_ interactive-V2.pdf (2010). 7. E. D. Wachsman and K. T. Lee, Science, 334, 935 (2011). 8. B. C. H. Steele and A. Heinzel, Nature, 414, 345 (2001). 9. Energy Information Administration, http://www.eia.gov/forecasts/ieo/ pdf/0484(2013).pdf (2013). 10. Energy Information Administration, http://www.eia.gov/forecasts/steo/ realprices/ (2013). 11. International Energy Association, World Energy Outlook 2012, OECD Publishing, Paris, France (2012). (continued on next page)

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12. National Fuel Cell Research Center, http://www.nfcrc.uci.edu/2/ F U E L _ C E L L _ I N F O R M AT I O N / MonetaryValueOfFuelCells/Fuel_ Cell_Value-Methodology_2011_ FINAL_072411_Large-Units_Final. pdf (2011). 13. W. G. Colella and S. P. Pilli, ASME J. Fuel Cell Science Technology, in print (2013). 14. B. D. James, A. B. Spisak, W. G. Colella, Manufacturing Cost Analysis of Stationary Fuel Cell Systems, report for the U.S. DOE EERE FCT Program, http://www.sainc.com/service/SA%20 2012%20Manufacturing%20Cost%20 Analysis%20of%20Stationary%20 Fuel%20Cell%20Systems.pdf (2012). 15. R. Smith and C. Sweet, The Wall Street Journal, http://online.wsj.com/article/ SB1000142412788732490630457903 6721930972500.html (2013). 16. A. G. Association (2013). 17. M. A. Laguna-Bercero, S. J. Skinner, and J. A. Kilner, J. Power Sources, 192, 126 (2009). 18. A. Hauch, S. D. Ebbesen, S. H. Jensen, and M. Mogensen, J. Mater. Chem., 18, 2331 (2008). 19. S. F. J. Flipsen, J. Power Sources, 162, 927 (2006). 20. C. Schlitzberger, N. O. Brinkmeier, and R. Leithner, Chemical Engineering & Technology, 35, 440 (2012). 21. N. Oishi, A. Atkinson, N. P. Brandon, J. A. Kilner, and B. C. H. Steele, J. Am. Ceramic Soc., 88, 1394 (2005). 22. T. Suzuki, Z. Hasan, Y. Funahashi, T. Yamaguchi, Y. Fujishiro, and M. Awano, Science, 325, 852 (2009). 23. L. Blum, U. Packbier, I. C. Vinke and L. G. J. de Haart, Fuel Cells, 13, 646 (2012). 24. U.S. Department of Energy, http:// www1.eere.energy.gov/solar/sunshot/ pdfs/dpw_white_paper.pdf (2010). 25. OECD, Better Policies to Support Ecoinnovation, OECD Publishing (2011).

26. E. D. Wachsman, C. A. Marlowe, and K. T. Lee, Energ. Environ. Sci., 5, 5498 (2012). 27. N. Behling, Issues in Science and Technology, Spring 2013, 83 (2013). 28. U.S. Department of Energy, Past and Present EERE Budget Database- http:// www1.eere.energy.gov/office_eere/ bo_budget_archives.html, in, Office of Energy Efficiency and Renewable Energy Editor, Washington, DC (2013). 29. E. Nikolla, J. Schwank, and S. Linic, J. Catalysis, 250, 85 (2007). 30. J. H. Wang and M. L. Liu, Electrochem. Commun., 9, 2212 (2007). 31. Z. H. Cai, Y. Kuru, J. W. Han, Y. Chen and B. Yildiz, J. Am. Chem. Soc., 133, 17696 (2011). 32. Q. Yang, T. E. Burye, R. R. Lunt, and J. D. Nicholas, Solid State Ionics, 249250, 123 (2013). 33. R. Moreno, P. GarcĂa, J. Zapata, J. Roqueta, J. Chaigneau, and J. Santiso, Chemistry of Materials (2013). 34. M. B. Pomfret, J. C. Owrutsky, and R. A. Walker, in Annual Review of Analytical Chemistry, Vol 3, E. S. Yeung and R. N. Zare Editors, p. 151, Annual Reviews, Palo Alto (2010). 35. T. Norby, Solid State Ionics, 125, 1 (1999). 36. W. C. Chueh, A. H. McDaniel, M. E. Grass, Y. Hao, N. Jabeen, Z. Liu, S. M. Haile, K. F. McCarty, H. Bluhm, and F. El Gabaly, Chemistry of Materials, 24, 1876 (2012). 37. M. Kubicek, Z. H. Cai, W. Ma, B. Yildiz, H. Hutter, and J. Fleig, ACS Nano, 7, 3276 (2013). 38. M. Sase, K. Yashiro, K. Sato, J. Mizusaki, T. Kawada, N. Sakai, K. Yamaji, T. Horita, and H. Yokokawa, Solid State Ionics, 178, 1843 (2008). 39. N. Sata, K. Eberman, K. Eberl, and J. Maier, Nature, 408, 946 (2000). 40. T. Norby, MRS Bull., 34, 923 (2009). 41. Web of Science, http://thomsonreuters. com/web-of-science/ (2013).

42. B. J. Ingram, J. A. Eastman, K.-C. Chang, S. K. Kim, T. T. Fister, E. Perret, H. You, P. M. Baldo, and P. H. Fuoss, App. Phys. Lett., 101, 051603 (2012). 43. Z. H. Cai, M. Kubicek, J. Fleig, and B. Yildiz, Chemistry of Materials, 24, 1116 (2012). 44. H. Jalili, J. W. Han, Y. Kuru, Z. H. Cai and B. Yildiz, J. Phys. Chem. Lett., 2, 801 (2011). 45. A. Chroneos, B. Yildiz, A. Tarancon, D. Parfitt, and J. A. Kilner, Energy Environ. Sci., 4, 2774 (2011). 46. S. R. Bishop, K. L. Duncan, and E. D. Wachsman, Acta Materialia, 57, 3596 (2009). 47. D. Marrocchelli, S. R. Bishop, H. L. Tuller, and B. Yildiz, Adv. Funct. Mater., 22, 1958 (2012). 48. H. L. Tuller and S. R. Bishop, Annual Review of Materials Research, 41, 369 (2011). 49. K. Yakal-Kremski, J. S. Cronin, Y. C. K. Chen-Wiegart, J. Wang, and S. A. Barnett, Fuel Cells, 13, 449 (2013). 50. J. R. Izzo, A. S. Joshi, K. N. Grew, W. K. S. Chiu, A. Tkachuk, S. H. Wang, and W. B. Yun, J. Electrochem. Soc., 155, B504 (2008). 51. P. R. Shearing, J. Golbert, R. J. Chater, and N. P. Brandon, Chemical Engineering Science, 64, 3928 (2009). 52. N. S. K. Gunda, H. W. Choi, A. Berson, B. Kenney, K. Karan, J. G. Pharoah, and S. K. Mitra, J. Power Sources, 196, 3592 (2011). 53. J. D. Nicholas and S. A. Barnett, J. Electrochem. Soc., 156, B458 (2009). 54. K. Hilpert, D. Das, M. Miller, D. H. Peck, and R. Weiss, J. Electrochem. Soc., 143, 3642 (1996). 55. M. Kubicek, A. Limbeck, T. Fromling, H. Hutter, and J. Fleig, J. Electrochem. Soc., 158, B727 (2011). 56. General Electric, Inc.http://www. geaviation.com/engines/marine/pdfs/ datasheet_lm6000.pdf (2013). 57. J. Peirs, D. Reynaerts, and F. Verplaetsen, J. Micromech. Microeng., 13, S190 (2003).

The Electrochemical Society Interface â&#x20AC;˘ Winter 2013

Reversible Solid Oxide Fuel Cell Technology for Green Fuel and Power Production by Nguyen Q. Minh and Mogens B. Mogensen

reversible solid oxide fuel cell (RSOFC) is a device that can operate efficiently in both fuel cell and electrolysis operating modes. Thus, in the fuel cell mode, an RSOFC functions as an SOFC, generating electricity by electrochemical combination of a fuel (hydrogen, hydrocarbons, alcohols, etc.) with air (oxygen in the air). In the electrolysis mode, an RSOFC functions as an electrolyzer (in this case, referred to as a solid oxide electrolysis cell or SOEC), producing hydrogen (from water) or chemicals such as syngas (from mixtures of water and carbon dioxide) when coupled with an energy source (fossil, nuclear, renewable). Figure 1 illustrates the operating principles of the RSOFC. The RSOFC has the following attractive features (demonstrated or potential): compatibility (environmentally compatible with reduced CO2 emissions in power generation mode), flexibility (fuel flexible and suitable for integration with any type of energy sources), capability (useful for different functions), adaptability (suitable for a variety of applications and adaptable to local energy needs), and affordability (competitive in costs).1 The RSOFC thus possesses all the desired characteristics to serve as a technology base for green, flexible, and efficient energy systems in the future (Fig. 2). Sustainable energy systems based on the RSOFC for the future is feasible. An example of such a system is shown schematically in Fig. 3. In this system, the RSOFC, operating in the electrolysis mode, uses a renewable energy supply (e.g., solar, wind, hydro) to produce hydrogen (from H2O)

or syngas (H2+CO) (from mixtures of H2O and CO2). The chemicals produced can be used to generate power by the same RSOFC operating in the fuel cell mode or can be stored or converted to other chemicals/fuels for subsequent uses. Similarly, the RSOFC can generate power from biomass-derived fuels and the electricity generated can then be used for a variety of power generation applications. The RSOFC is both the SOFC and SOEC incorporated in a single unit. Since the SOEC is the SOFC operated in reverse mode and traditionally derived from the SOFC, the RSOFC being developed is typically based from the more technologically advanced SOFC. Thus, materials for the RSOFC are those commonly used in the SOFC, i.e., yttria stabilized zirconia (YSZ) for the electrolyte, perovskites (such as lanthanum strontium manganese oxide or LSM, lanthanum strontium cobalt iron oxide or LSCF) for the oxygen electrode, nickel/YSZ cermet for the hydrogen electrode and for stacking, conductive oxides (such as lanthanum strontium chromium perovskite or LSC) or stainless steels for the interconnect (depending on the operating temperature). Like the SOFC, the RSOFC operates in the temperature range of 600o-1000oC. Specific operating temperature depends on cell/stack designs and selected materials.2,3

Solid Oxide Fuel Cell Technology The RSOFC is fundamentally and technologically based on SOFC technology. In the past 20 years, the SOFC has received significant attention as a clean and efficient energy conversion technology for a variety

of practical fuels and has been under development for a broad spectrum of power generation applications. The key features of the SOFC are its all solid state construction (ceramic and metal) and high operating temperature (600o-1000oC). The combination of these features leads to a number of distinctive and attractive attributes for the SOFC including cell and stack design flexibility, multiple fabrication options, multi-fuel capability, and operating temperature choices. SOFC cells can be configured to be self supporting (electrolyte-supported, anodesupported, cathode-supported) or external supporting (interconnect-supported, substrate-supported). Stack designs being developed for the SOFC include the tubular design, the segmented-cells-in-series design, the monolithic design, and the planar design, with the planar design currently being the most common. These design options permit flexibility to shape the SOFC into a structure having the desired electrical and electrochemical performance along with required thermal management, mechanical integrity, and dimensional constraint (if any) to meet operating requirements of specified power generation applications.4 A wide range of fabrication processes have been investigated for making SOFC cells. Fabrication processes developed for the SOFC include conventional ceramic processing methods (e.g., tape casting, tape calendering, screen printing, and extrusion) and deposition techniques (e.g., plasma spraying, spin coating, dip coating, electrochemical vapor deposition, electrophoretic deposition).4 The key step in any selected process is the fabrication of (continued on next page)

Fig. 1. Operating Principles of an RSOFC (written for hydrogen fuel in SOFC mode and steam electrolysis in SOEC mode). The Electrochemical Society Interface â&#x20AC;˘ Winter 2013

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dense electrolytes and the fabrication process selected depends on the configuration of the cells in the stack. One of the key attributes of the SOFC is its multi-fuel capability. For fuels other than pure hydrogen, the SOFC can operate on reformates (via external reformation) or on hydrocarbons and other fuels (via internal reforming or direct utilization).5 The operating temperature of the SOFC can be varied by modifying electrolyte material and/or electrolyte thickness. Examples include operating temperatures of 900o-1000oC for thick (>50 micrometers) YSZ electrolytes,2 700o-800oC for thin (<15 micrometers) YSZ electrolytes2 or doped lanthanum gallate electrolytes,6 500o-600oC for thin doped ceria electrolytes,7 and 400o-500oC for thin doped ceria/bismuth oxide bilayer electrolytes.8 The SOFC has been considered for a broad spectrum of power generation applications and markets. Applications include power systems ranging from watt-sized devices to multimegawatt power plants and potential markets for the SOFC cover portable, transportation, and stationary sectors. Many of the applications for the SOFC have progressed to hardware demonstration and prototype/ pre-commercial stages while several applications, especially those with large power outputs, are at the conceptual/design stage (Fig. 4). Significant advancements have been made in the past few years in several technological areas critical to the development and commercialization of the fuel cell: performance, fabrication scale-up and miniaturization, fuel utilization, and performance degradation and durability. Performance.—SOFC single cells have exhibited peak power densities as high as 2 W/cm2 at temperatures as low as 650oC (with hydrogen fuel and air oxidant, low fuel and air utilizations).8 SOFC stacks have demonstrated electrochemical performance under operating conditions appropriate for practical uses. For example, a 96-cell planar stack shows a power density of about 0.3 W/ cm2 (voltage of about 0.82 V per cell at 0.364 A/cm2), 715oC on air (15% air utilization), and fuel containing 25.2% H2- 22.4% N2-14.5% natural gas (NG)-37.8% H2O (68% fuel utilization).9 For state-of-the-art SOFC single cells (having minimal ohmic resistance contributions from the components), cathode (oxygen electrode) polarization is generally the major contribution to cell performance losses. Thus, many cathode studies have been conducted to obtain a better understanding of the oxygen reduction reaction mechanisms and develop approaches to improve cathode performance.10,11 One major development in recent cathode R&D work is the demonstration of infiltration as a potent means for electrode performance enhancement.12,13 For example, infiltration 56

Fig. 2. Characteristics of a future energy system.

Fig. 3. An example of an RSOFC-based sustainable energy system.

of yttria-doped ceria (YDC) into LSM/YSZ cathode increased peak power density from 208 to 519 mW/cm2 at 700oC and power density at 0.7V from 135 to 370 mW/cm2.12 Infiltration of active components as dispersed particles or connected nanoparticulate networks to form nanostructures enhances cathode performance by modifying catalytic activities and/or conduction pathways of the electrode. Use of nanostructures has also been shown to improve anode performance.14 The main issue is the stability of the nanostructure over extended periods of time at high operating temperatures. Operating

the SOFC at reduced temperatures (e.g., <600oC) or stabilizing the nanostructure are potential approaches to maintain sufficient long-term stability.12,15 In SOFC stacks, especially planar stacks with metallic interconnects, contact resistance between the electrodes, especially the cathode, and the metallic interconnect is the major factor in stack performance losses16 and long-term performance degradation. The contact between the ceramic cathode and the metallic interconnect tends to change due to thermodynamic driving forces and other operating characteristics The Electrochemical Society Interface • Winter 2013

Fig. 4. SOFC power systems (hardware demonstrators, prototypes and pre-commercial systems up to 200 kW, concepts at 1MW and above).

such as temperature distribution, thermal expansion mismatch as operation proceeds. These factors can lead to degradation in long-term operation. It is highly possible that during long-term operation, chemical interaction develops and electrical contact between the cathode and the interconnect evolves, ohmic resistance increased and contact area reduced, resulting in higher ohmic losses and thus degradation (Fig. 5). Conductive contact pastes have been used in planar stacks to minimize contact resistance; however, stability of such contact pastes over long duration is questionable. Fabrication scale-up and miniaturization.—Tubular SOFC cells (typical diameters of >15 mm) have been fabricated in full active length (e.g., 150 cm) and tubular cell stacks of up to 100 kW have been assembled.4 Planar SOFC cells, especially anode- (hydrogen electrode-) supported cells, have recently been scaled up to sizes having active areas (e.g., 500-1000 cm2) suitable for uses in large power systems. Manufacture of planar cells as large as 1200 cm2 in total area has been demonstrated17 and planar SOFC stacks of up to 15 kW have been built and operated for thousands of hours. Segmented-cells-in-series SOFCs has been made into practical assembly/ stack sizes (e.g., 60-cell assemblies of 60 W output18). These assemblies can be stacked and bundled to form modules of appropriate power levels. For example, 20 kW modules The Electrochemical Society Interface • Winter 2013

Fig. 5. Cathode (oxygen electrode)/metallic interconnect contact evolution.

suitable for 1 MW systems have been constructed from five strips of 12 parallel bundles of six 60-cell assemblies.18 SOFC stacks based on the monolithic design have been scaled up to 30 kW sizes.19 In addition to fabrication scale-up for large power systems, the SOFC has also been scaled down for certain applications such as consumer electronics devices and compact portable powers.20 Miniature SOFCs being developed to date include micro-tubular (diameters of <5 mm) cells,20 thin-film cells micro-fabricated on silicon wafers20 and single-chamber SOFCs.21

The development of practical units based these miniature cells has made significant technical and commercialization progress with recent introduction of pre-commercial products, such as 5 V, 2.5 W mobile power,22 12-24 V, 1-375 W portable power,23 and 1.2 V, 4000 mAh SOFC charger.24 Fuel utilization.—The SOFC can operate directly on fuels other than hydrogen (e.g., hydrocarbons, alcohols) via internal reforming (on fuel feeds with significant amounts of water) or direct utilization (on (continued on next page) 57

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fuel feeds with no water). Internal reforming using on-anode reformation is well known and has been demonstrated for the SOFC. Instead of complete (100 percent) internal reforming, it is possible to have a portion of the fuel reformed in an external reformer (referred to as a pre-reformer) and the resulting reformate plus the remaining fuel are fed to the SOFC where the fuel is internally reformed (via steam reforming) within the fuel cell. An example is the demonstration of operation of a 5 kW SOFC system with an auto-thermal reformation reformate containing about 7 volume% methane slip.25 This pre-reforming/internal reforming option has been employed to use the endothermic reforming reactions to reduce cooling requirements in thermal management of the SOFC. The SOFC has been shown in recent years to have the capability for direct utilization of different types of fuel.26 For direct fuel utilization operation, the anode material has been modified to address the carbon deposition issue associated with nickel commonly used in the anode composition (e.g., Cu/ceria instead of Ni/YSZ27). With modified anodes, high electrochemical performance can be achieved for direct SOFCs. For example, a peak power density of about 400 mW/cm2 at 800oC was obtained with 7.3% ethanol balance He fuel and air oxidant for an anode-supported SOFC with a dual layer anode consisting of a CuCeO2 impregnated Ni/YSZ support outer layer and a Ni/YSZ electroactive inner layer (Fig. 6).28 Long-term performance stability of direct SOFCs without significant carbon deposition, however, remains to be demonstrated.

Performance degradation and durability.â&#x20AC;&#x201D;SOFC single cells, when properly prepared with conventional highpurity materials and operated on clean fuels and air, show minimal performance degradation for extended periods of time. For example, tubular cells were electrically tested for times as long as eight years and showed satisfactory performance with less than 0.1% per 1000 h degradation.4 SOFC cells, however, can experience significant performance degradation in realistic environments, depending on several factors such as gas input purities and component materials used in the stack/system.29 Sulfur is the most prevalent fuel impurity in many practical fuels and its poisoning effects on the Ni/YSZ anode are well known.3 It has also been shown that silicon impurities present in the fuel (originated from, for example, stack glass sealants or silica containing insulations in the system) can also poison the Ni/YSZ anode.30 On the cathode side, presence of significant amounts of water or carbon dioxide in air can have deleterious effects on cell performance.31-33 Most of recent R&D activities on performance degradation have been focused on the chromium poisoning issue in long-term operation of planar stacks having metallic interconnects. Chromium present in the metallic interconnect can migrate to cathode reactive sites and interact with the cathode, poisoning the electrode thereby increasing cathode polarization with time. At present, the most common mitigating approach is to use conductive coatings (e.g., Co-Mn spinel) on the metallic interconnect to minimize the chromium transport and migration.34 SOFC stacks and systems have been operated for tens of thousands of hours and durability has been demonstrated recently

Fig. 6. Performance at 800oC with 7.3% ethanol balance He fuel and air oxidant for an anodesupported SOFC (with a dual layer anode consisting of a Cu-CeO2 impregnated Ni/YSZ support outer layer and a Ni/YSZ electroactive inner layer). (Type 2 and 3 indicates different thermal treatments of infiltrated anodes).28 58

with low performance degradation rates under specified operating conditions. For example, a short planar SOFC stack (with uncoated metallic interconnects) has been in operation at 700oC for more than five years with the overall voltage degradation of about 1% per 1000 h35. With coated metallic interconnects, a stack has been tested for more than 14000 h with a reduced degradation rate of about 0.12% per 1000 h.35 Figure 7 is an example of performance of a 96-cell stack showing 1.3% voltage degradation per 1000 h (with internal reforming).9

Solid Oxide Electrolysis Cell Technology The RSOFC functions as a SOEC when operated in electrolysis mode. The RSOFC thus can be used to produce hydrogen from H2O,36 syngas from mixtures of H2O and CO2,37 and oxygen from CO2.38 The SOEC is the only electrolysis cell having this capability. The SOEC operating at high temperatures has the advantage that the electrical energy required for the electrolysis decreases as temperature increases and the unavoidable Joule heat is used in the water and/or carbon dioxide splitting process. Thus, the SOEC can work under the socalled thermoneutral condition, i.e., at the thermoneutral voltage (Vtn), the electricity input exactly matches the total energy demand of the electrolysis reaction. In this case, the electrical-to-hydrogen conversion efficiency is 100%. At cell operating voltages <Vtn, heat must be supplied to the system to maintain the temperature and the conversion efficiency (based only on the electrical input) is above 100%. At cell operating voltages >Vtn, heat must be removed from the system and the efficiency is below 100%. SOEC single cells have been shown to have the ability to perform well for hydrogen production from steam. For example, a cell voltage of 1.1V (below Vtn) has been obtained for a Ni/YSZ supported SOEC cell of 45 cm2 active area at a current density of about 1.4A/cm2, 900oC, 93% H2O balance H2.39 Figure 8 summarizes data on current densities at the thermoneutral voltage reported in the literature for steam electrolysis between 500o and 900oC. Current density variations for the same material systems are due to starting material characteristics, processing, absolute humidity input, and flow rates. At higher temperatures (>900oC), extraordinarily high current densities have been reported, e.g., about 3 A/cm2 at 1.3V, 950oC.37 SOECs have been shown capable of CO2 electrolysis37,40 and syngas production by inputs of H2O+CO2 at similar current density ranges to steam electrolysis41 although the area specific resistance (ASR) for electrolysis of CO2 is generally higher than that of H2O.42 The mechanism for the CO2 reduction is not well determined and may depend on the detailed structure of the electrode. In The Electrochemical Society Interface â&#x20AC;˘ Winter 2013

Fig. 7. Long-term performance of 96-cell planar stack.9

the case of H2O+CO2, it is possible that only H2O is involved in the electrochemical reaction and the CO2 in the mixture reacts with H2 of the reaction products via a reverse water gas shift reaction. SOEC cells are commonly derived from cells developed for fuel cell operation. In general, such cells can operate stably

in electrolysis mode with no or minor modifications. However, an oxygen electrode that works stably in SOFC mode may experience rapid performance decay in electrolysis mode due to electrode delamination caused by oxygen evolution at the electrode/electrolyte interface.43 This type of degradation has been observed for

Fig. 8. Current densities at thermoneutral voltage reported for SOECs between 500o and 900oC (the bars show the range of values). The Electrochemical Society Interface â&#x20AC;˘ Winter 2013

oxygen electrodes based on predominantly electronic conducting oxides (e.g., LSM) when not designed to minimize oxygen pressure built-up at the interface during operation. For oxygen electrodes based on mixed ionic electronic conducting oxides (e.g., LSCF) with similar microstructures, electrode delamination may occur but at higher current densities (because of lower electrode overvoltage due to the spreading of triple phase boundary active sites on the mixed conducting surface). Long-term degradation of SOEC cells is generally higher than that obtained for similar cells in fuel cell mode.44 Root causes for this difference, however, are not fully understood. SOEC single cells and multi-cell stacks have been operated and hydrogen/syngas production (from H2O/H2O+CO2) has been demonstrated in laboratory scale. To date, planar cells as large as 20 cm x 20 cm size, stacks as tall as 60-cell height and a 15 kW laboratory facility have been fabricated and hydrogen production rates as high as 5.7Â Nm3/h have been achieved.42 SOECs have been tested up to 2500 h and performance degradation is typically in the order of 5-10% per 1000 h. A recent SOEC work reports low degradation (<1% per 1000 h) for electrolysis of H2O+CO2 at current densities below 0.7 A/cm2 (Fig. 9).45 The SOEC has been considered for hydrogen production from steam36,46 at distributed plant (e.g., 1,500 kg H2/day) (continued on next page) 59

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Fig. 9. Voltage as function of time for 1 kW 10-cell sStack of 12 cm x 12 cm footprint. Temperature = 850oC, gas input = 10% H2-45% H2O-45% CO2.45

and central station (e.g., 150,000 kg H2/ day) sizes,43 syngas production for industrial uses,47 and oxygen generation/recovery for space applications.48,49 Integration of SOEC systems with nuclear50 and renewable energy resources such as solar energy51 has been envisioned. Figure 10 shows a concept of a SOEC-based hydrogen production central system coupled with high-temperature gascooled nuclear reactors.52 Figure 11 is an example of a concept combining SOECs with biomass based plant.53 In this concept, oxygen produced in the SOEC unit can be used for the gasification of biomass, and steam for the SOEC can be generated in the gasification plant. The SOEC generates hydrogen that is needed for conversion of all the carbon in the biomass to chemicals such as methanol (MeOH), dimethyl ether (DME), gasoline, and synthetic natural gas (SNG). This concept also includes a method of upgrading digested biogas using co-electrolysis of CO2 (present) and steam (added) in biogas.

Reversible Solid Oxide Fuel Cell Technology An RSOFC must operate efficiently in both SOFC and SOEC modes. Thus, two key requirements for RSOFCs, addition to those specified for SOFC/SOEC operation, are (1) acceptable electrode performance reversibility and stability, and (2) efficient and stable cyclic operation. Electrode performance reversibility and stability for reversible operation.— In general, the hydrogen electrode shows performance reversibility (symmetry) between fuel cell and electrolysis modes. The oxygen electrode, on the other hand, shows 60

Fig. 10. Concept for large-scale centralized nuclear hydrogen production.52

performance reversibility at low current densities but may exhibit irreversibility at higher current densities in electrolysis mode depending on a number of factors such as electrode microstructure, material and operating parameter.43 Performance stability of the electrodes is very much dependent on electrode microstructures. Oxygen electrode microstructures must be designed to circumvent oxygen pressure build-up at electrode/electrolyte interfaces during electrolysis. Hydrogen electrode microstructures must be engineered to facilitate both water and hydrogen transport to and from reaction sites. Efficient and stable cyclic operation.— RSOFC single cells and multi-cell stacks have been built and tested and their cyclic operation has been demonstrated. Cell and stack performance in electrolysis mode

typically shows higher degradation rates than those in fuel cell mode.43,54,55 Figure 12 shows an example of a 10-cell RSOFC stack and its performance (in terms of ASR) in operation for more than 1000 h (operating alternately between internal reforming fuel cell mode and steam electrolysis mode).16 This stack showed an initial power density of 480 mW/cm2 at 0.7V, 800oC with 64% H2 - 35% N2 as fuel and 80% fuel utilization in fuel cell mode and produced about 6.3 standard liter per minute of hydrogen at 1.26 V cell voltage, 0.62 A/cm2 with 30% H2 - 70% H2O and steam utilization of about 54%. The RSOFC is at its early stage of development and to date, only limited work, mainly in laboratory scale, has been conducted on this technology. Advancements in RSOFCs will continue to leverage The Electrochemical Society Interface • Winter 2013

Fig. 11. Concept combining SOEC, biomass gasifier, and biomass digester.53

Fig. 12. Photograph of 10-cell stack (cell active area of 142 cm2) and stack ASR in methane internal reforming fuel cell mode and steam electrolysis mode (fluctuations seen in steam electrolysis due to instability of steam generation and delivery).16

progress in SOFC/SOEC technology. However, certain R&D is required to address several critical issues specific to the RSOFC, such as oxygen electrode performance and reversibility, a set of materials, cell/stack designs and operating parameters suitable for reversible operation, and system design and integration to demonstrate the feasibility of the technology. This will serve as a basis for further development to advance the technology toward practical applications.

The Electrochemical Society Interface â&#x20AC;˘ Winter 2013

About the Authors Nguyen Q. Minh is currently Associate Director, Center for Energy Research at the University of California, San Diego. Previously he was Chief Scientist and Manager, Fuel Cells at GE and Honeywell/ AlliedSignal. His experience covers a full spectrum of SOFC research and product R&D areas, ranging from technology assessment, strategy/roadmap formulation,

fundamental/engineering study to materials/ processes/manufacturing development, system design/operation, and prototype demonstration. He may be reached at nminh@ucsd.edu. Mogens B. Mogensen has been employed at Risoe National Laboratory since April 1980. He has had several duties as project manager, section head, group leader, and center leader in parallel to his engagement (continued on next page) 61

Minh and Mogensen

(continued from previous page)

in energy research. He became Research Professor June 2003, and he withdrew from personnel management in 2006 to devote all time to R&D. His main research area since 1989 has been solid oxide fuel cells and electrolyzer cells. He has over 225 papers registered by Web of Science (h-index 44); and more than 600 registered by Google Scholar (h-index 51). Almost all of his research has been carried out in close cooperation with industry. He may be reached at momo@dtu.dk.

References 1. N. Q. Minh, in 10th European SOFC Forum, Paper A1106, Lucerne, Switzerland (2012). 2. N. Q. Minh and T. Takahashi, Science and Technology of Ceramic Fuel Cells, Elsevier Science, Amsterdam, The Netherlands (1995). 3. S. C. Singhal and K. Kendall, Editors, High Temperature Solid Oxide Fuel Cells: Fundamentals, Design and Applications, Elsevier, Oxford, UK (2003). 4. K. Kendall, N. Q. Minh, and S. C. Singhal, in High Temperature Solid Oxide Fuel Cells: Fundamentals, Design and Applications, S. C. Singhal and K. Kendall, Editors, p. 197, Elsevier, Oxford, UK (2003). 5. N. Q. Minh, in Fuel Cell Science and Engineering, Materials, Processes, Systems and Technology, Vol. 2, D. Stolten and B. Emonts, Editors, p. 963, Wiley-VCH, Weinheim, Germany (2012). 6. T. Akbay, in Perovskite Oxide for Solid Oxide Fuel Cells, T. Ishihara, Editor, p. 183, Springer, New York, NY (2009). 7. M. C. Tucker, J. Power Sources, 195, 4570 (2010). 8. E. D. Wachsman and K. T. Lee, Science, 334, 935 (2011). 9. H. Ghezel-Ayagh, in 13th Annual SECA Workshop, www.netl.doe.gov/ publications/proceedings/10/seca/ index.html (2012). 10. National Energy Technology Laboratory, Recent Solid Oxide Fuel Cell Cathode Studies, Report DOE/ NETL-2013/1618 (2013). 11. J. Hayd, L. Dieterle, U. Guntow, D. Gerthsen, and E. Ivers-Tiffée, J. Power Sources, 196, 7263 (2011). 12. T. Z. Sholklapper, C. P. Jacobson, S. J. Visco, and L. C. De Jonghe, Fuel Cells, 5, 303 (2008). 13. J. M. Vohs and R. J. Gorte, Adv. Mater., 21, 943 (2009).

14. C. Ding, H. Lin, K. Sato, T. Kawada, J. Mizusaki, and T. Hashida, Solid State Ionics, 181, 1238 (2010). 15. Y. Gong, D. Palacio, X. Song, R. L. Patel, X. Liang, X. Zhao, J. B. Goodenough, and K. Huang, Nano Lett., DOI: 10.1021/nl402138w (2013). 16. N. Q. Minh, J. Korean Ceram. Soc., 47, 1 (2010). 17. M. J. Day, S. L. Swartz, and G. B. Arkenberg, ECS Trans., 35(1), 385 (2011). 18. R. Goettler and T. Ohm, in 11th Annual SECA Workshop, www.netl.doe.gov/ publications/proceedings/10/seca/ index.html (2010). 19. w w w. m h i . c o . j p / e n / t e c h n o l o g y / business/power/sofc/development_ situation.html 20. E. Traversa, Interface, 49 (Fall 2009). 21. M. Kuln and T. W. Napporn, Energies, 3, 27 (2010). 22. www.nectarpower.com 23. www.ezelleron.eu 24. www.pointsourcepower.com 25. GE Hybrid Power Generation Systems, Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program, Final Report (2006). 26. S. Park, J. M. Vohs, and R. J. Gorte, Nature, 404, 265 (2000). 27. S. McIntosh and R. J. Gorte, Chem. Rev., 104, 4845 (2004). 28. E. N. Armstrong, J.-W. Park, and N. Q. Minh, Electrochem. Solid-State Lett., 15, B75 (2012). 29. H. Yokokawa, K. Yamaji, M. E. Brito, H. Kishimoto, and T. Horita, J. Power Sources, 196, 7070 (2011). 30. Y. L. Liu, S. Primdahl, and M. Mogensen, Solid State Ionics, 161, 1 (2003). 31. S. H. Kim, T. Ohshima, Y. Shiratori, K. Itoh, and K. Sasaki, in MRS Proceedings, Volume 1041, V. Pthenakis, A. Dillon and N. Savage, Editors, 1041-R03-10, Materials Research Society, Warrendale, PA (2007). 32. A. Hagen, K. Neufeld, and Y. L. Liu, J. Electrochem. Soc., 157, B1343 (2010). 33. W. Zhou, F. Liang, Z. Shao, and Z. Zhu, Scientific Reports, 2:327, DOI: 10.1038/srep00327 (2012). 34. N. Q. Minh, S. C. Singhal, and M. C. Williams, ECS Trans., 17(1), 211 (2009). 35. L. Blum, U. Packbier, I. C. Vinke, and L. G. J. de Haart, Fuel Cells, 13, 646 (2013). 36. A. Hauch, S. D. Ebbesen, S. H. Jensen, and M. Mogensen, J. Mater. Chem., 18, 2331 (2008). 37. S. H. Jensen, P. H. Larsen, and M. Mogensen, Int. J. Hydrogen Energy, 32, 3253 (2007).

38. J. Guan, R. Doshi, G. Lear, K. Montgomery, E. Ong, and N. Minh, J. Am. Ceram. Soc., 85, 2651 (2002). 39. A. Brisse, J. Schefold, and M. Zahid, Int. J. Hydrogen Energy, 33, 5375 (2008). 40. S. D. Ebbesen and M. Mogensen, J. Power Sources, 193, 349 (2009). 41. J. Hartvigsen, L. Frost, and S. Elangovan, www.fuelcellseminar.com/ media/51332/sta44-4.pdf (2012). 42. C. M. Stoots, J. E. O’Brien, K. G. Condie, and J. J. Hartvigsen, Int. J. Hydrogen Energy, 35, 4861 (2010). 43. GE Hybrid Power Generation Systems, High Performance Flexible Reversible Solid Oxide Fuel Cell, Final Technical Report (2008). 44. A. Hauch, S. H. Jensen, S. D. Ebbesen, and M. Mogensen, in Energy Solutions for Sustainable Development Proceedings, Risø Energy International Conference 2007, Risø-R-1608 (EN), L. S. Petersen and H. Larsen, Editors, p. 327, Risø National Laboratory Technical University of Denmark, Roskilde, Denmark (2007). 45. S. D. Ebbesen, J. Høgh, K. A. Nielsen, J. U. Nielsen, and M. Mogensen, Int. J. Hydrogen Energy, 36, 7363 (2011). 46. B. Yu, W. Q. Zhang, J. Chen, J. M. Xu, and S. R. Wang, Sci. China Ser. B-Chem., 51, 289 (2008). 47. Q. Fu, in Syngas: Production, Applications and Environment Impact, A. Indarto and J. Palgunadi, Editors, p. 209, Nova Science Publishers, Hauppauge, NY (2011). 48. K. R. Sridhar and R. Foertner, J. Propul. Power, 16, 1105 (2000). 49. D. Weng and S. Yates, AIAA Paper 2010-8675, American Institute of Aeronautics and Astronautics, Reston, VA (2010). 50. R. Rivera-Tinoco, C. Mansilla, C. Bouallou, and F. F. Werkoff, Int. J. Nuclear Hydrogen Production and Applications, 1, 249 (2008). 51. J. Padin, T. N. Veziroglu, and A. Shabin, Int. J. Hydrogen Energy, 25, 295 (2000). 52. J. E. O’Brien, X. Zhang, C. R. O’Brien, and G. Tao, www.fuelcellseminar.com/ media/9066/hrd34-5.pdf (2011). 53. M. Mogensen, S. H. Jensen, S. D. Ebbesen, A. Hauch, C. Graves, J. V. T. Høgh, X. Sun, S. Das, P. V. Hendriksen, J. U. Nielsen, A. H. Pedersen, N. Christiansen, and J. B. Hansen, in 2012 World Gas Conference, Kuala Lumpur, Malaysia (2012). 54. G. Tao and A. V. Virkar, www1.eere. enery.gov/hydrogenandfuelcells/pdfs/ rev_fc_wkshp_tao.pdf (2011). 55. C. Brown, www1.eere.energy.gov/ hydrogenandfuelcells/pdfs/rev_fc_ wkshp_brown.pdf (2011).

The Electrochemical Society Interface • Winter 2013

Design of Materials for Solar-Driven Fuel Production by Metal-Oxide Thermochemical Cycles by Mark D. Allendorf, James E. Miller, and Anthony H. McDaniel

lthough mounting evidence indicates that climate change is anthropogenic,1-5 demand for energy continues to increase, particularly in developing countries. The U.S. Energy Information Administration predicts in their 2013 outlook that world energy demand will increase 56 percent from 2010 to 2040, driven largely by non-OECD Asia.6 As seen in Fig. 1, liquid fuels constitute the largest portion of this consumption and are projected to remain so, in spite of expected rising prices. Nearly two thirds of the predicted 38% increase by 2040 in consumption of liquid fossil fuels is due to the transportation sector. This trend will be very difficult to reverse for numerous reasons, including factors such as the structure of cities, relative unavailability of public transportation, reluctance of governments to adopt climate-friendly transportation policies, and historical behavior patterns. Consequently, liquid transportation fuels likely will remain in use for the foreseeable future, particularly since the infrastructure for transporting and delivering liquid fuels to its points of use will be extremely expensive to replace. Development of carbon-neutral routes to liquid fuels is thus a must if the impacts of climate change are to be mitigated and ultimately reversed. Production of fuel by synthetic means is not a new problem. During World War II, Germany produced hydrocarbon fuels using Fischer-Tropsch chemistry and coal as a carbon source. However, methods of producing carbon-neutral liquid fuels are, for the most part, largely in the realm of research. Even first-generation biofuels (e.g. ethanol) are arguably not carbon-neutral.7 Approaches receiving considerable attention currently include advanced biofuels (e.g. algal biodiesel production and cellulosic ethanol),8 artificial photosynthesis,9 and solar-driven electrolysis (solar cell + electrolyzer).10 The latter provides a useful tool for benchmarking new fuel production technologies, since both electrolyzers and solar-electric power are well-understood technologies. Average annual solar-to-fuel efficiencies (AASFE) as high as 18% for production of hydrogen are predicted to be achievable by this approach.11 An alternative approach is to use thermochemical cycles that divide the energetically unfavorable thermolysis of water or carbon dioxide (temperatures >3000°C) into two or more reactions that have much more appealing thermodynamics. Many such cycles have been proposed, including hybrid sulfur, sulfur-iodine, zinc The Electrochemical Society Interface • Winter 2013

oxide, and various other metal oxides. Of these, metal oxides are attractive due to typically low material cost, lack of hazardous or toxic products or intermediates, relative simplicity, and importantly, the potential to achieve high AASFE. A generic two-step metal oxide cycle is as follows: at T = TTR

(1; thermal reduction)

at T = TCDS or TWS

(2; CO2 or H2O splitting)

(3; CO2 or H2O thermolysis)

Accounting for thermochemical, collection, and processing efficiencies, solar thermochemical fuel production (STFP) cycles of this type using “non-volatile” metal oxides could achieve AASFE in excess of 25% using a dish solar collector, assuming the development of an advanced working metal oxide substrate.

Guidelines for Material Selection A large number of diverse metal oxides have been proposed for STFP,12 including stoichiometric compounds such as ferrites and other transition metal spinels, zinc oxide, Nb2O5/NbO2, CdO/Cd, In2O3/In, WO3/W, SnO2/Sn, ceria and doped cerias, and most recently, perovskites. Many of these are no longer under consideration for a variety of reasons, including cost, reduction temperature, and conversion efficiency. These oxides fall into two basic categories: non-volatile and volatile. Those within the latter class produce a volatile metal, such as In or Zn, that exists in the gas phase at the required thermal reduction temperature. Volatile oxides are less attractive from a processing point of view because the metal product must be quenched (cooled, condensed, and separated from the O2 product) to prevent the oxide from reforming via the reverse of reaction 1. Consequently, the most actively investigated materials currently are the non-volatile oxides ferrites and ceria. It is tempting to conclude that, given this relatively small number of oxides, identifying an “ideal” metal oxide would be relatively straightforward. Unfortunately, such is not the case; a large number of material- and (continued on next page)

Fig. 1. World energy demand (in quadrillion Btu) until 2010, with projections to 2040. Data obtained from USEnergyInfoAdmin 2013 Energy Outlook.6 63

Allendorf, Miller, and McDaniel (continued from previous page)

process-specific factors can have a strong effect on the performance of a given metal oxide couple, as shown schematically in Fig. 2. Material-specific properties of concern include reaction thermodynamics, volatility (in spite of the appellation “nonvolatile,” even a material as refractory as ceria has a finite, and potentially corrosioninducing, vapor pressure), transport and reaction kinetics, and microstructure. Alternatively, process-specific aspects such as operating temperature, oxygen partial pressure, radiation loss, and reactor materials impact choices for the active metal oxide material and ultimately determine not only the AASFE, but also reactor construction cost and lifetime. In a detailed examination of many of these factors, we concluded that the concept of an ideal material must be considered in the context of the entire process, and not on the basis of, for example, thermodynamics alone.13 Fortunately, it is possible to estimate boundaries for material properties based on efficiency and operational targets.13 The resulting “design guidelines,” which are summarized in Table I, simplify the task of identifying an optimal material. Note that the properties listed are both intrinsic (e.g., melting point) and extrinsic (e.g., thickness) characteristics, but also include aspects of process design that are influenced by factors other than the properties of the active material. The rationale for each of these is summarized briefly below; a more detailed discussion is available elsewhere.13 Operating temperature window.— This parameter is determined by a set of interacting factors, including reaction thermodynamics, target efficiency, and durability of reactor materials. Nevertheless, thermodynamics and basic engineering considerations allow us to establish approximate upper (TTR = Tmax, Reaction 1) and lower temperature (TGS or CDS = Tmin, Reaction 2) limits. Almost certainly, TTR will not exceed ~ 1500°C in a practical system due to concerns with materials of construction and challenges in minimizing thermal losses as the temperature is increased. On the oxidation side of the cycle, TGS should ideally be as close to 25°C as possible, to maximize the thermodynamic driving force (possible extent) of the reaction. In this case, however, the kinetics of the gas splitting reaction will almost certainly require higher operating temperatures. The activation energy for reoxidizing zirconia-supported cobalt ferrite using steam, for example, is 141 kJ mol-1 and significant H2 production rates are not observed until temperatures of 900°C are reached.14 An additional, less obvious, concern is that the greater the temperature swing the greater the amount of sensible heat required to heat the oxide from TCDS to TTR. Coupling this sensible heat load to that needed for heating the carbon dioxide from TCDS or TWS to the reaction temperature, and taking into consideration the effectiveness 64

Fig. 2. Phenomena and material properties that must be considered in developing an optimal material for an STFP cycle. Table I. Properties and considerations for an “ideal” STFP working oxide. Property

Boundary

Comments

Region of thermodynamic favorability

Reduction (R1): 800 ≤ TTR ≤ 1500°C Gas splitting (R2): 25 ≤ TGS ≤ 400°C

Max eff. for TTR = 800 and TGS = 25, (1500, 400) = 72%

Vapor pressure @ TTR

< 2 x 10-5 Pa

Langmuir equation estimates loss <0.1 mm/y

Melting Point

> 3275°C

Microstructure stability, unlikely to be met.

Geometry/Structure

Thermal and mass diffusion length ≥ characteristic dimension. Macrostructure scale consistent with thermal stresses in implementation.

Maximize utilization of active material. Avoid breakage and degradation.

Reaction kinetics

Chemical flux matched to solar energy flux.

100% eff ≈ 3.5 mmol CO/s-Watt, TGS > 400°C likely required.

at which heat can be recuperated within the cycle between TTR and TCDS, the actual gas splitting temperature should be expected to exceed 500°C with an optimal temperature difference during operation (TTR-TCDS) of less than 500°C. Reaction thermochemistry.—The ideal constraint on the thermodynamics of Reactions 1 and 2 is that both must be spontaneous under operating conditions, i.e., the Gibbs free energy ΔG must be negative within the operating temperature window. To the extent that they are not, additional work, e.g. pump work, must be added to the system to drive the reaction. This is an important consideration since the temperature separation between the regions of thermodynamic favorability are likely to be larger than the 500°C suggested above (Table 1). Meredig and Wolverton (MW) developed an analytical framework for assessing the suitability of a given material, reducing the thermodynamics to a form in which only the material-specific properties are considered. These authors illustrated

their method using various stoichiometric reactions for known thermochemical cycles (e.g., Fe3O4 → 3FeO + 0.5O2).15 Subsequently, we extended their approach to non-stoichiometric materials, such as ceria, doped ceria, and partial reduction of ferrites. Not surprisingly, the range of favorable thermodynamic values is a complex function of operating conditions and the extent of reduction. Both the temperatures of thermal reduction and gas splitting have a strong influence. The O2 partial pressure during the reduction step is also important; practical considerations (pump work, equipment size, the energy losses and heat loss associated with a diluent gas) suggest that a practical P(O2) lower limit is 100 Pa. Nevertheless, one can define regions of thermodynamic favorability in which the range of acceptable enthalpy of thermal reduction values is a function of the entropy of reduction. The example data plotted against the MW analysis in Fig. 3 show that complete reduction of NiFe2O4 to an overall stoichiometry of NiFe2O3.0 is achievable The Electrochemical Society Interface • Winter 2013

Fig. 3. Regions of thermodynamic favorability for metal-substituted ferrites, assuming thermal reduction at 1773 K, various O2 partial pressures during the reduction step, and a range of gas splitting temperatures (shown here for CO2 splitting). Closed symbols correspond to increasing values of δ in equations 1 and 2. Open symbols correspond to the specific reactions in the legend. See Ref. 13 for additional information

only if P(O2) is reduced to 10-3 atm (greenshaded region), well below the practical limit. However, within the blue-shaded region (P(O2) = 10-6 atm) these ferrites can be reduced to NiFe2O3.7. In neither case is complete reoxidation feasible; the rightmost data point corresponding to NiFe2O3.99 lies outside both the green- and blue-shaded regions. Vapor pressure of working oxide.— Although many oxides considered for STFP are considered “non-volatile,” at the high reaction temperatures required, even materials as refractory as ceria have a nonnegligible vapor pressure. Consequently, long exposure to flowing gas can vaporize the material and reduce fuel production capacity or result in downstream contaminationrelated operational failures. In general, oxides containing transition metals will form diatomic oxides (e.g., FeO, NiO, etc.) under thermal reduction conditions and much more volatile metal hydroxides in the presence of water vapor. An estimate of the evaporative loss rate can be obtained from the Langmuir sublimation model, with knowledge of the material’s vapor pressure as a function of temperature.16 This model will likely overpredict the mass loss rate, but nevertheless provides a useful guide and can provide estimates of maximum operating temperatures needed to maintain an acceptable mass loss rate. Losses <0.1 mm/year are predicted if the vapor pressure above the oxide is less than ~ 2x10-5 Pa. For ferrites, temperatures (TTR) <1270 °C are required to avoid possible mass loss rates The Electrochemical Society Interface • Winter 2013

greater than 10 mm/year (considered severe in this application). Ceria, in contrast, forms CeO and CeO2, but due to their much lower vapor pressures the Langmuir model predicts that at temperatures up to 1500°C the vaporization rate is less than ~ 1 mm/yr. The lower temperatures possible for reoxidation using ceria also favor low mass loss rates. These results illustrate how factors beyond the thermochemistry of the reaction must be evaluated to develop effective materials for STFP. Microstructural stability.—The high temperatures necessary for STFP will also increase mass transport rates, causing sintering of particles and closure of porosity. Previous investigators have seen reductions in capacity and decreased reaction rates for ferrites as a result of rapid mass transport, requiring the use of supports to stabilize the material.14,17-19 Empirical observations from high-temperature materials science provide guidelines for selecting materials that will be reasonably stable during STFP over many cycles. The Tamman (0.5Tmp; bulk-to-surface migration) and Hüttig (0.33Tmp; 2-d mobility, agglomeration on surfaces) temperatures, in conjunction with the melting point (Tmp), allow one to assess the microstructural stability. Sintering and creep become significant at ~0.4Tmp. Based on these criteria, if Thigh is 1500°C then Tmp must be at least 3300°C, a value possessed by very few materials. Some qualitative conclusions can therefore be reached. First, conventional approaches to increase the rates of surface-limited reactions cannot be

employed as micro-porosity is unlikely to be maintained. Similarly, stationary packed beds of fine particulates can be expected to eventually sinter and densify into a single solid mass possibly impeding gas transport or leading to other operational difficulties. Therefore, from a durability standpoint, STFP materials are probably limited to larger length scales and/or to systems that account for a regeneration of the physical form. Reaction kinetics.—The rates of Reactions 1 and 2 are among the least well characterized aspects of thermochemical cycles. In the absence of kinetic data, however, it can be stated that achieving high AASFE requires that energy consumption of the reactions (i.e., endothermic reduction), and hence the reaction rates, be matched to the solar flux entering the system. To the extent that these are not matched, heat must be rejected, which decreases the efficiency. Although the temperatures used are very high, kinetic data we obtained for ferrites and perovskites (see below) show that both Reactions (1 and 2) are thermally activated. The gas splitting step (Reaction 2) is not typically at equilibrium, for example.14,20 Additional energy to surmount the activation barrier of the reaction is required to drive it at an acceptable rate.

Assessment of Current Materials Ferrites and other spinels.—Ferrites (AxFe3-xO4) have received considerable attention because of their favorable thermodynamics, which enable deep reduction. Thermal reduction of ferrites leads to wüstite (FexO in the case of Fe3O4 x ≤ 1.0), a non-ideal solution phase that is hyperstoichiometric in oxygen. The use of Fe3O4 for solar fuel production is well studied but not practical because of the relatively low melting point of FeO (liquid-phase products present material handling issues for STFP cycles). However, metal-substituted ferrites, including those with A = Mg, Mn, Co, Ni, and Zn, are more attractive because the wüstite product phase has a higher melting point. Examples of thermodynamic cycles for splitting both CO2 and water have been reported.12,13 Thermodynamic analysis predicts that the theoretical efficiency of the reaction step (accounting only for the endotherm of Reaction 1) can exceed 70% for NiFe2O4 and CoFe2O4 if the ferrite is thermally reduced to an overall composition of MFe2O3.5 (50% of the maximum, assuming full reduction to wüstite). This requires reducing the O2 partial pressure to below 100 Pa.13 Another material involving a spinel structure is the so-called hercynite cycle, in which a metal-substituted ferrite, such as CoFe2O4, reacts with Al2O3 to form CoAl2O4 and FeAl2O4 (hercynite). An advantage of this reaction is that the onset of reduction occurs at 940°C, ~ 150°C lower than other (continued on next page) 65

Allendorf, Miller, and McDaniel (continued from previous page)

ferrites due to the thermodynamic driving force provided by the formation of alumina. However, the thermodynamics of H2O + FeAl2O4 reaction are not as favorable as with FeO; H2O splitting is not spontaneous, requiring an out-of-equilibrium condition (e.g., a sweep gas) to drive the reaction to products. Both isobaric21 and isothermal22 water splitting cycles based on this reaction have been proposed. Unfortunately, some serious impediments arise with ferrites. First, the relatively low melting point makes sintering fast on the timescale of the reactions, leading to poor cycling behavior. This can be remedied by supporting or solubilizing the ferrite on/into a material such as yttria-stabilized zirconia (YSZ), but this reduces the gravimetric and volumetric capacity. Second, the oxidation reaction involves an initial fast surfacelimited phase, but the reaction quickly evolves to one controlled by mass diffusion. This occurs because the ferrite product layer forms a shell around the reduced (wüstite) phase through which oxygen transport is very slow.14,23 Finally, the wüstite phase is relatively volatile and volatile hydroxides can form in the presence of water vapor (see above). This may be somewhat less of a problem for the hercynite cycle; since the reduction can occur at lower temperatures, volatile iron hydroxides can still form and may limit the durability of this material as well. Ceria and doped ceria.—Ceria is a nonstoichiometric oxide that loses oxygen at high temperatures by forming vacancies and corresponding Ce3+ ions and corresponding Ce3+ ions. Because of its high electron and oxygen ion mobility, it has been considered as an electrode material or the electrolyte in solid oxide fuel cells.24 Consequently, no phase change occurs, which minimizes potential problems with mechanical stresses for example. This oxide is, however, extremely refractory, having a P(O2) < 10-8 atm at 1300°C, more than five orders of magnitude lower than NiFe2O4. At the limits of realistic operating conditions, which we consider to be P(O2) = 100 Pa (10-3 atm) and 1500°C thermal reduction temperature, ceria can only be reduced to ~ CeO1.98. This realistically limits process efficiencies to values that are too low for practical commercial use; for example, Furler et al. recently reported an average efficiency of only 1.73% when operating at ~ 1600°C.25 Doped cerias initially offered some hope that the reduction temperature could be reduced. Transition-metal dopants are thought to provide the greatest lattice destabilization (and thus, the largest increase in P(O2)), but many lanthanide-doped materials are known as well. Unfortunately, thermodynamic analyses indicate that little or no improvement is to be expected.13,26 Experimental results are consistent with these predictions. Although all dopants reduce the enthalpy of reduction, this 66

benefit is offset by a concomitant decrease in entropy. Transition-metal dopants also suffer reversibility problems, due either to permanent reduction of their oxidation state or the formation of stable product phases. It is therefore unlikely that either ceria or doped ceria will be of practical use for STFP. Perovskites.—Recently, a novel class of perovskites (general formula ABO3) was reported that provides considerably higher H2 and CO yields than ceria. Based on the hypothesis that a perovskite stable under both the reducing and oxidizing steps of a thermochemical cycle, such as LaAlO3, could be doped with Mn on the B site and Sr on the A site to create a redox-active material that is phase-stable upon oxygen depletion. The resulting material, SrxLa1MnyAl1-yO3-δ, produces up to nine-fold x higher H2 and six-fold higher CO yield when reduced at 1350°C and reoxidized at 1000°C (Fig. 4).20 Oxygen evolution begins 300°C lower than undoped ceria and at comparable reaction rates (see discussion below). Cycling experiments indicate that this capacity is maintained over at least 80 cycles, a considerable improvement over metal-substituted ferrites. Conceivably, perovskite compositions with even better performance may exist, but discovering these is complicated by the large composition space that can adopt the perovskite structure. Notably, a related perovskite, (La, Sr)

MnO3-δ, recently investigated by Scheffe et al., can also be used for STFP. Somewhat lower, but still favorable, reduction extents relative to ceria were obtained.27

Measurement of Gas-splitting Kinetics Rates of thermal reduction and gas splitting are largely unknown for the conditions relevant to STFP. Recently, we developed a unique, optically-accessible stagnation flow reactor (SFR) (Fig. 5) that enables these rates to be measured under realistic STFP conditions. This instrument is equipped with a 500 W continuouswave NIR diode laser for sample heating enabling rapid screening of reaction rates across a range of temperatures and pressures encountered during STFP operation (such as high heating rates (> 100°C/s) at solar concentrations equivalent to 5000 suns). Gas compositions exiting the SFR are measured by mass spectrometry. An important attribute that distinguishes the fluid dynamics of the SFR from flow tube reactors, packed bed reactors, or thermogravimetric analyzers (TGA), which are commonly used to measure kinetic data, is that the gas-phase region above the sample is an ideal 1-D flow field governed by diffusive transport. This creates a well-controlled environment for characterizing kinetic behavior.

Fig. 4. H2 (top) and CO (bottom) production rates as a function of time for a Sr- and Mn-doped LaAlO3, measured during oxidation in 40 vol% H2O or CO2 at 1000 °C (green open symbols), compared to CeO2 (gray open symbols). STFP materials were thermally reduced at 1350 °C in He. The total amount of H2 or CO produced in mmoles per g material is shown in parentheses. Solid lines are the results of kinetic modeling. The Electrochemical Society Interface • Winter 2013

Fig. 5. Schematic of the Sandia laser-heated SFR. Graph inset shows O2 uptake and release for a perovskite oxide in a constant background pressure of O2 heated and cooled at 16Â°C/s.

The inset to Fig. 5 illustrates how this approach has been used to resolve the O2 uptake and release kinetics of a perovskite oxide. In this case, the sample is exposed to a constant partial pressure of O2 during heating and cooling. As the material heats up, O2 is liberated from the solid until a new equilibrium is established at the higher temperature (positive O2 production rate in figure inset). Upon cooling, the solid reabsorbs O2 from the ambient, which is shown as a negative production rate in the graph. The area under the uptake and release curves measures redox capacity, while the temporal characteristics contain rate information and mechanistic insight. We employed the SFR to measure the kinetics of gas splitting for CeO2, Sr- and Mn-doped LaAlO3, and mixed metal ferrite-zirconia composite materials. As mentioned previously, the redox kinetics largely determine the reaction extents and efficiencies that may be realized in practice, and are an important consideration in the reactor design. This is because the AASFE will suffer if the reaction rates are not well-matched to the solar flux. To the extent they are not, then the slower process will hinder reactor throughput unless a mitigating strategy, such as decoupling the residence times in each reaction zone,

is used to balance the production of O2 and CO (or H2). This tradeoff demonstrates the importance of considering reactor design and material chemistry within the context of redox kinetics.

Topics for Future Research It is clear that the properties of the active material, including not only the thermodynamics, but also the reactivity, microstructural stability, and volatility, must be understood to develop efficient and economical STFP processes. There is considerable need for additional research concerning all of these properties. In general, there is a broad palette of potential materials of interest that have not been studied at the temperatures required for thermal reduction, creating a major gap in the understanding of their behavior under processing conditions. Future work to develop accurate thermodynamic models, determine reaction kinetics, and predict the evolution of material properties during high-temperature cycling will therefore be essential. Given the large composition space of materials of interest, computational screening will be an invaluable tool, as will high-throughput, automated, synthesis and characterization. Despite these challenges,

the scientific and engineering data now available are highly encouraging that STFP can be a viable technology for producing carbon-neutral transportation fuels.

Acknowledgments This work was supported by the U.S. Department of Energy Fuel Cell Technologies Program as part of the production technology development area and by the Laboratory Directed Research and Development Program at Sandia National Laboratories. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energyâ&#x20AC;&#x2122;s National Nuclear Security Administration under Contract DE-AC04-94AL85000.

About the Authors Mark D. Allendorf is a Senior Scientist at Sandia National Laboratories and holds a PhD in inorganic chemistry from Stanford University. He leads efforts to develop novel material solutions to energy- and national security-related problems, involving both fundamental science and applications development. In addition to his work in high-temperature chemistry, he conducts (continued on next page)

The Electrochemical Society Interface â&#x20AC;˘ Winter 2013

Allendorf, Miller, and McDaniel (continued from previous page)

interdisciplinary research to develop metalorganic frameworks for applications such as chemical sensing, radiation detection, hydrogen storage, gas separations, and charge transfer. He is President Emeritus and Fellow of The Electrochemical Society and has won multiple Sandia awards for leadership and teamwork. His research involves postdoctoral fellows, students, and Sandia technical staff members and has more than 140 publications. He may be reached at mdallen@sandia.gov. James E. Miller has been involved in catalysis and chemical processing research at Sandia National Laboratories for over 20 years, most recently serving as the principal investigator of the laboratories’ Sunshine to Petrol (S2P) effort. The goal of S2P is the efficient and cost effective production of hydrocarbon fuels from sunlight, carbon dioxide, and water via chemical means. Dr. Miller has been involved in all multiple aspects of the project including prototype design development and demonstration, materials development, and systems studies. He holds degrees in chemical engineering from Texas A&M University (BS) and the University of Texas at Austin (PhD). He may be reached at jemille@sandia.gov. Anthony McDaniel is a member of the technical staff at Sandia National Laboratories and holds degrees in chemical engineering from the University of Colorado (Boulder, BSc) and the University of California (Los Angeles, PhD). His current research is focused on thermochemistry and electrochemistry of materials critical to developing sustainable energy technologies. These include complex oxides used in water and carbon dioxide splitting, solid oxide fuel cells, lithium ion batteries, and super ionic conductors. He also leads a program funded by the Department of Energy to develop a solar-thermochemical reactor for the efficient production of hydrogen from concentrated sunlight. He may be reached at amcdani@sandia.gov.

References 1. L. Comte, L. Buisson, M. Daufresne, and G. Grenouillet, Freshwater Biology, 58, 625 (2013). 2. M. Forsius, S. Anttila, L. Arvola, I. Bergstrom, H. Hakola, H. I. Heikkinen, J. Helenius, M. Hyvarinen, K. Jylha, J. Karjalainen, T. Keskinen, K. Laine, E. Nikinmaa, P. Peltonen-Sainio, K. Rankinen, M. Reinikainen, H. Setala, and J. Vuorenmaa, Current Opinion in Environmental Sustainability, 5, 26 (2013). 3. S. Jenouvrier, Global Change Biology, 19, 2036 (2013). 4. M. Koch, G. Bowes, C. Ross, and X. H. Zhang, Global Change Biology, 19, 103 (2013). 5. C. Rosenzweig and P. Neofotis, Wiley Interdisciplinary Reviews-Climate Change, 4, 121 (2013). 6. International Energy Outlook 2013; U.S. Energy Information Administration (2013). 7. T. D. Searchinger, S. P. Hamburg, J. Melillo, W. Chameides, P. Havlik, D. M. Kammen, G. E. Likens, R. N. Lubowski, M. Obersteiner, M. Oppenheimer, G. P. Robertson, W. H. Schlesinger, and G. D. Tilman, Science, 326, 527 (2009). 8. V. Menon and M. Rao, Progress in Energy and Combustion Science, 38, 522 (2012). 9. N. S. Lewis, Interface, 22, 41 (2013). 10. J. Ivy, National Renewable Energy Laboratory Report NREL/MP (2004). 11. N. P. Siegel, J. E. Miller, I. Ermanoski, R. B. Diver, and E. B. Stechel, Industrial & Engineering Chemistry Research, 52, 3276 (2013). 12. T. Kodama and N. Gokon, Chem. Rev., 107, 4048 (2007). 13. J. E. Miller, A. H. McDaniel, and M. D. Allendorf, Adv. Energy Mater., DOI: 10.1002/aenm.20130046. 14. J. R. Scheffe, A. H. McDaniel, M. D. Allendorf, and A. W. Weimer, Energy & Environmental Science, 6, 963 (2013).

15. B. Meredig and C. Wolverton, C. Phys. Rev. B, 80, 245119 (2009). 16. Lafferty, J. M. Scientific Foundations of Vacuum Technique; 2nd ed.; Wiley: New York, 1962. 17. N. Gokon, T. Minno, Y. Nakamuro, and T. Kodama, J. Sol. Energy Eng.-Trans. ASME, 130, 011018, (2008). 18. T. Kodama, N. Gokon, and R. Yamamoto, Sol. Energy, 82, 73 (2008). 19. J. R. Scheffe, M. D. Allendorf, E. N. Coker, B. W. Jacobs, A. H. McDaniel, and A. W. Weimer, Chem. Mater., 23, 2030 (2011). 20. A. H. McDaniel, E. C. Miller, D. Arifin, A. Ambrosini, E. N. Coker, R. O’Hayre, W. C. Chueh, and J. H. Tong, Energy & Environmental Science, 6, 2424 (2013). 21. J. R. Scheffe, J. H. Li, and A. W. Weimer, Int’l. J. Hydrogen Energy, 35, 3333 (2010). 22. C. L. Muhich, B. W. Evanko, K. C. Weston, P. Lichty,X. Liang, J. Martinek, C. B. Musgrave, and A. W. Weime, Science, 341, 540 (2013). 23. E. N. Coker, J. A. Ohlhausen, A. Ambrosini, and J. E. Miller, J. Mater. Chem., 22, 6726 (2012). 24. M. Mogensen, N. M. Sammes, and G. A. Tompsett, Solid State Ionics, 129, 63 (2000). 25. P. Furler, J. R. Scheffe, and A. Steinfeld, Energy Environ. Sci., 5, 6098 (2012). 26. J. R. Scheffe and A. Steinfeld, Energy Fuels, 26, 1928 (2012). 27. J. R. Scheffe, D. Weibel, and A. Steinfeld, Energy Fuels, 27, 4250 (2013).

The Electrochemical Society Interface • Winter 2013

High Temperature Materials Corrosion Challenges for Energy Conversion Technologies by Elizabeth Opila

What Is High Temperature Corrosion? High temperature corrosion is the chemical attack of solid functional or structural materials resulting in degradation of the desired properties. Typically the material reacts with a gaseous environment consuming the material of interest, often forming undesirable reaction products. Carl Wagner developed the theory elucidating the electrochemical nature of high temperature corrosion whereby continued formation of reaction products occurs by transport of electronic and ionic species in the solid state product phase.1 The definition of “high temperature” can begin at temperatures as low as 300 to 500°C, where water is present as a vapor rather than liquid (cf. aqueous corrosion), but can vary with material systems. For example zirconium nuclear fuel cladding oxidation is a catastrophic problem at 1200°C whereas oxidation of SiC is minimal at this temperature. High temperature corrosion scientists attempt to understand the driving forces for the corrosion processes as well as the rate at which corrosion occurs. Thus corrosion mechanisms are described in terms of the thermodynamics and kinetics of reactions. Which products will form and at what rate? Thermodynamic stability of corrosion products are typically calculated using free energy minimization techniques now easily conducted with commercially available software (FactSage,2 Thermocalc,3 Pandat4). Accuracy of these results relies on complete thermochemical databases, which are not available for all material systems. Ab initio Density Functional Theory is a valuable method to calculate thermodynamic The Electrochemical Society Interface • Winter 2013

data where none are available; however, experimental validation may still be required, especially for transition metal oxides where theory is still maturing.5 The relative stability of oxide corrosion products are shown on an Ellingham-Richardson diagram as shown in Fig. 1. Oxides shown lower on the plot have a larger negative free energy of formation and are thus more stable. Understanding kinetics of high temperature reactions requires characterization of changes in the complex phase assemblages of both reactants and products found in most energy applications. The rate of the corrosion reaction can be limited by surface chemical reactions, solid state diffusion through corrosion products in which condensed phase defect chemistry dominates, liquid phase diffusion, or gas phase transport processes. Figure 2 shows the relative solid state diffusion rate of dominant diffusing species6 for a number of technologically relevant oxides. The formation of liquid or gaseous corrosion products must also be considered since these reactions can be dominated by diffusion processes that are much faster than solid state transport considered above.

-200

The formation of liquid corrosion products from salts and slags can result in dissolution of protective solid oxides. The continued dissolution and precipitation of reaction products in liquid films existing in chemical potential gradients results in a continuous fluxing process that rapidly consumes the underlying structural material.7 Many energy conversion technologies including combustion processes (Brayton, Rankine cycles) or electrochemical conversion of hydrogen (SOFC) produce high temperature water vapor products. Water vapor is especially reactive and can degrade both metals and oxides by the formation of gaseous metal hydroxides. Knowledge of stable gaseous metal hydroxides as well as the rate at which they form is essential to predicting material degradation in many energy conversion applications, as recently summarized.8 The challenge of predicting and increasing thermochemical lifetimes of complex material systems in complex environments is to understand the interplay between the formation of equilibrium phases predicted by thermodynamics (Fig. 1) versus the reaction kinetics (Fig. 2). Materials systems for high (continued on next page)

increasing oxide stability

= 2NiO O2(g) + i N 2 eO (g) = 2F 2Fe + O2

-300 -400

∆Gof (kJ/mol)

nergy conversion processes are often employed at high temperatures to increase thermodynamic efficiencies or to provide enhanced kinetics for electrochemical processes. While high temperature operation offers these benefits, the thermodynamic driving force and kinetics of any accompanying high temperature corrosion processes are also increased. In this paper, corrosion issues relevant to energy conversion by Rankine cycle, Brayton cycle turbines, nuclear power, solid oxide fuel cells, high temperature thermoelectric systems, and solar concentrator systems are discussed. Corrosion mechanisms, component life prediction, and strategies for mitigating high temperature corrosion specific to each energy technology are addressed.

-500

/3 g) = 2 + O2( r C 3 4/

-600

Cr 2O3

SiO2 (g) = Si + O2

-700

l O3 2/3 A 2 g) = ( O l+ 2 4/3 A

-800 -900

ZrO2 (g) = O 2 + r Z

-1000 0

200

400

600

800

1000

1200

1400

1600

Temperature (°C) Fig. 1. Ellingham diagram portraying relative stability of oxides relevant to high temperature corrosion. Data from FactSage Pure Substance data base.2 69

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1E-8

Cr in

1E-9

1E-11 1E-12

Cr 2O

Ni in

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700

1E-10

1E-14

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1E-7

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900

O in

O Cr 2

Diffusion Coefficient (cm2/sec)

1E-6

O3 Al 2 in

1000

Conventional coal-fired power plants generate power via the Rankine cycle in which the combustion process is used to heat water to produce steam that powers a turbine, generating electricity. The fireside and steam side of chromia-forming ferritic steels typically used for the heater tubes present different corrosion problems.9 Coal has a wide variety of chemistries10 that result in varying amounts of sulfur and chlorine in the combustion environment as well as widely varying oxide ash compositions containing Al, Si, Ca, Fe, K, Na, and Mg oxides. Challenges for predicting the corrosion reactions on the fireside of the boiler include the formation of nonequilibrium phases as combustion products and as condensates (such as sulfides and sulfates) in cooler portions of the boiler tubes. Corrosion by HCl(g) and rapid corrosion when low melting temperature sulfates form are major concerns. Degradation on the steam side of the heater tubes is related to the high water vapor contents and its effect on oxide morphology, oxide adherence, and oxide volatility.11 Coal can also be gasified to form syngas (CO(g) + H2(g)) in an integrated combined cycle, using heat to power a conventional steam turbine and employing the syngas in a Brayton cycle gas-fired turbine. Water vapor attack is again the prime concern in the gas-turbine environment where the higher temperatures can necessitate the use of Ni-base alloys rather than steel.

1E-5

1200

Power Generation by Rankine or Brayton Cycles

Temperature (°C) 1600 1400

temperature applications should be designed so that slow growing reaction products are thermodynamically stable and allowed to establish protective diffusion barriers. For example in aluminum-containing Ni-base superalloys the thermodynamically stable oxidation product is Al2O3 whereas NiO, being a more defective oxide, grows more rapidly. Alloy designers have identified the critical levels of aluminum in Ni-base superalloys required to establish slow growing Al2O3 scales rather than faster forming NiO scales. In some cases, highly stable corrosion products can form with rapid reaction kinetics, e.g., ZrO2 formation from Zr oxidation, or liquid and gaseous products can form making mitigation of high temperature corrosion challenging. The following sections explore high temperature corrosion issues important for a series of energy conversion technologies. This discussion is not exhaustive but highlights critical degradation issues in high temperature energy technologies. When available, strategies for mitigating the high temperature corrosion reactions are also described.

NiO

O in S iO

0.7

0.8

0.9

1.0

1.1

-1

1000/T (K ) Fig. 2. Diffusion coefficients in oxides relevant to high temperature corrosion. Data from Introduction to Ceramics.6

Efforts to increase efficiency and/or more effectively capture carbon include using oxygen instead of air (oxyfiring) or increasing the steam temperature from about 600°C to 760°C (Advanced UltraSupercritical).9 The increased temperatures and high steam contents will result in more rapid material degradation and the need for higher-temperature Ni-base alloys. Natural gas is an alternative fuel to coal which is used in a combined cycle (Rankine plus Brayton). The gas-fired turbines operate at higher temperatures, thus alloy/ coating system life is limited due to more rapid diffusion and oxidation rates. Just as for coal-fired power generation, the desire to increase efficiencies and lower emissions drives the search for higher temperature materials. Significant efforts to replace fossil fuels with biomass are being made, especially in Europe. Biomass (e.g., straw and grass) typically contains higher alkali and chlorine contents than coal, but lower sulfur.12 Chlorine can result in the formation of stable gaseous metal chlorides such as FeCl3(g), non-adherent oxide layers, and low-melting phases, all of which accelerate the consumption of the underlying alloy. Improved material performance is sought for all conditions by developing higher temperature alloys or more corrosion resistance coatings, typically containing more Cr or Al. These solutions are expensive, so significant increases in efficiencies, longer lifetimes, or reduced emissions are required.

Nuclear Power Nuclear power plants typically use fissile 235UO2 as fuel. Fission results in the release of thermal energy that is used to heat pressurized water. The pressurized water flows through heat exchanger tubes, heating secondary water to produce steam which drives a turbine using the Rankine cycle. Under normal operating conditions, aqueous corrosion of reactor components is the degradation mode of concern. Aqueous corrosion is outside the scope of this review. However, under Loss of Coolant Accident (LOCA) conditions, temperatures rapidly increase and high temperature corrosion reactions control the reactor failure and radioactive product release. These mechanisms recently achieved notice in light of the reactor failures at the Fukushima Daiichi power plant after the magnitude 9.0 earthquake and resulting tsunami.13 Three high temperature reaction mechanisms during LOCA are of particular note. First, the zirconium alloy (Zircaloy) fuel cladding reacts with steam. Due to the exothermic nature of Reaction 1 Zr + 2H2O(g) = ZrO2 + 2H2(g)

(1)

oxidation proceeds at a runaway rate at temperatures above about 1200°C generating large amounts of hydrogen.14 The high levels of hydrogen can result in explosions which damage the reactor containment systems. Second, volatile fission products are released from the fuel The Electrochemical Society Interface • Winter 2013

matrix, react with the steam/hydrogen gas mixture flowing through the reactor core and can be released into the environment through the damaged containment.15 Finally, the high temperature fuel reacts with reactor vessel and structural materials forming a molten mixture. Subsequent injection of water can result in dissolution of the reacted fuel mixture which can be released to the environment with subsequent cooling water leaks.16 Of these three, issues, the oxidation of zirconium alloys is most well understood.14,17 Current research focuses on developing alternative fuel cladding materials to replace zirconium alloys with more slowly oxidizing materials. Figure 1 shows that SiO2, Al2O3, and Cr2O3 are all stable oxides, and more importantly, Fig. 2 shows that oxygen transport through these oxides is significantly slower than that through ZrO2. Thus Si-, Al-, and Cr- containing materials are all candidates for fuel cladding with better oxidation performance in LOCA. Cheng et al. examined the oxidation rates of alternative cladding materials and concluded that SiC, high Cr (>20 wt%) alloys or Al-forming alloys all show significantly improved oxidation resistance at high temperature LOCA conditions. The oxide scale thickness generated in 8 h at 1200°C in 1 MPA steam for candidate cladding materials are compared to Zircaloy-2 in Fig. 3. The oxide scale thickness is a relative measure of the oxidation rate, and thus the amount of hydrogen generated in reactions similar to reaction 1. Further evaluation of these candidate fuel cladding materials, including their response to radiation exposure, is needed. A second area of concern during LOCA, is the release of fission products during vaporization reactions. Short lived fission products including 131I and 137Cs are of interest due to their radioactive danger. Vapor species such as Cs(OH) and CsI are expected to form in amounts greater than the metal vapor partial pressures, increasing transport rates out of the hot

core. Cubicciotti15 has calculated the equilibrium partial pressures of these and many other fission vapor products as a function of temperature, H2O/H2 ratio and pressure under LOCA-relevant conditions. Equilibrium calculations are expected to be relevant due to the high temperatures of interest. In addition, Cubicciotti18 also calculated vapor transport rates based on his equilibrium thermodynamic calculations. Many of the calculations use estimated thermochemical data, demonstrating the need for more accurate thermochemical measurements and calculations. Finally, consideration of reactions occurring during reactor core melting are of importance. Melted fuel will react with concrete,18 stainless steel reactor vessel components and zirconium alloy fuel cladding as well as other structural components of the reactor.16 The resulting phase assemblage is expected to be very complex16 with long-term environmental hazards due to potential radioactive material release if complete isolation of contaminated water is not maintained. Development of more oxidation resistant fuel cladding and improved thermochemical data for gas, liquid, and solid phases formed during LOCA events are needed.

Solid Oxide Fuel Cells Solid Oxide Fuel Cells (SOFC) offer increased efficiencies relative to combustion by the direct electrochemical conversion of hydrogen and other more complex fuels to electricity. Because SOFCs operate at intermediate (500-700°C) or high (700900°C) temperatures relative to PEM fuel cells, they offer the advantages of fuel flexibility and lower cost catalysts. The advantages of operation at elevated temperatures, however, also results in high temperature materials degradation issues. SOFCs are complex systems typically consisting of (La,Sr)MnO3 (LSM) cathodes, Y2O3-stabilized ZrO2 (YSZ)

electrolytes, Ni-YSZ anodes, ferritic FeCr interconnects as well as glass sealants. Thermochemical degradation mechanisms include (1) poisoning of active surfaces by species resulting from fuel impurities or volatilization of SOFC components, and (2) solid state interdiffusion and reaction between various cell components. Yokokawa has recently assessed material degradation mechanisms that affect durability and reliability of SOFCs.19 Research needs for increased thermochemical durability of SOFCs are also cited in a companion article in this issue.20 One important degradation reaction is the paralinear oxidation of Fe-Cr interconnect materials to form Cr2O3 with simultaneous volatilization of the oxide by the following reaction: ½ Cr2O3 + H2O(g) + ¾ O2(g) = CrO2(OH)2(g)

(2)

The formation of the CrO2(OH)2 gaseous species results in Cr-poisoning of the cathode. Thermodynamics for Reaction 2 have recently been established allowing for more accurate prediction of poisoning rates.21,22 This problem has been somewhat mitigated by the development of interconnect alloys that oxidize to form less volatile oxides, or oxides that do not result in cathode poisoning.23 An example of solid state interdiffusion and reaction is the formation of La2Zr2O7 from reaction of the LSM cathode and YSZ electrolyte.19 Alternative cathode and electrolyte compositions are being investigated with the goal of sufficient electrochemical activity at lower temperatures where diffusion is less of a problem. Materials under investigation include lanthanum strontium cobaltite cathodes and lanthanum strontium gallium magnesium oxide electrolytes. Movement to intermediate temperature oxide fuel cells can reduce both the thermodynamic driving force and the kinetics for degradation reactions. (continued on next page)

Fig. 3. Oxides formed on Zircaloy 2, 317 stainless steel and SiC (left to right) after exposure at 1200°C in 1 MPa steam for 8 hours.17 The Electrochemical Society Interface • Winter 2013

Opila

(continued from previous page)

Thermoelectric Energy Conversion Thermoelectric devices convert heat directly to electrical energy based on the Seebeck effect. Charge carriers, electrons, and holes, diffuse in a temperature gradient from the hot side to the cold side leading to measurable current flow. Thermoelectric materials have been used for deep space probes and are now proposed for waste heat recovery from conventional Rankine and Stirling power generation technologies as well as other industrial processes and transportation systems.24 The efficiency of thermoelectric materials depends on a high electrical conductivity decoupled from a low thermal conductivity as measured by a figure of merit ZT. Most thermoelectric research focuses on increasing this figure of merit.24-26 The best thermoelectric materials are narrow band gap semiconductors, limiting property optimization strategies. Thermal conductivity is reduced through the choice of complex crystal lattices or introduction of nanoscale grain or phase boundaries that scatter phonons. Electrical conductivity is increased via doping. The theoretical efficiency of thermoelectric devices can also be improved by increasing the temperature difference between the hot-side and coldside of the thermoelectric thus driving the move to higher temperature materials. Many of the highest ZT materials are antimonides and tellurides, which suffer from high sublimation rates and poor oxidation resistance.27 For example, antimony vaporizes to form Sb, Sb2, Sb3, Sb4 species that can reach very high partial pressures and result in rapid consumption of the solid thermoelectric device.27 In addition, antimony is very reactive with typical metallic contact materials, so that diffusion barrier layers are likely needed to prevent degradation of interconnects. The high temperature durability of thermoelectrics is a research area that is somewhat neglected, though vital for application of thermoelectrics to waste heat recovery. Some research is being conducted on half Heusler intermetallic compounds25 or even oxide thermoelectric materials28 that would be significantly more stable in high temperature oxidizing conditions. The identification, characterization, and development of earth-abundant, nontoxic, moderately efficient thermoelectric materials for waste heat recovery is an area of interest that warrants additional research effort.

Concentrated Solar Power Concentrated Solar Power (CSP) conversion to heat is an energy technology currently receiving substantial interest, as in the U.S. Department of Energy Sun 72

Shot Initiative announced in 2011 (http:// www1.eere.energy.gov/solar/sunshot/ csp.html). CSP offers advantages over photovoltaic electricity generation in the use of broad-spectrum sunlight and potential for hybridization with other technologies to store and convert heat to shift power generation from peak sunlight times. CSP collector concepts include parabolic troughs, heliostat fields, linear Fresnel reflectors, and parabolic dish concepts.29 Each concept offers potential advantages in interfacing with heat storage, as well as installation and operational cost. In addition, operating temperatures vary from 300 to 2000°C, which affects materials degradation mechanisms and rates. Thermochemical degradation of solar receiver tubes, cavity receivers, or particle receiver materials is an area of concern, especially for heliostat fields and associated tower receivers that operate at the highest temperatures. Heliostat field collectors have a low level of technology maturity, and thus research in the area is just beginning. Solar collectors must be matched to appropriate heat storage concepts. Heat storage can be accomplished via sensible heat (heating a material), latent heat (phase change), or chemical heat (reversible chemical reaction).30 Molten salts such as NaNO3 and KNO3 can be used as Heat Transfer Fluids (HTF) or phase change materials due to their high sensible and latent heats in the temperature range of 100 to 600°C. LiF and alkali carbonates have potential as phase change materials at temperatures up to about 900°C. Reversible metal–metal oxide reactions are another method to store heat. In many cases molten salt or molten metals are envisioned as components of the heat storage concept. Corrosion of storage tanks in contact with molten salts or metals is a concern for long term application of solar concentrators. Molten salts are already used in the chemical and metals industries providing an experience base for corrosion issues.30 Some concepts would employ particles as heat transfer materials, thus eliminating liquid phase corrosion problems. Concentrated solar power can also be directly employed to produce hydrogen by high temperature water splitting as described in a companion paper in this issue.31 High temperature water vapor interactions with the active materials then become a concern as previously described for combustion and SOFC environments.

Summary Many energy conversion technologies operate at high temperatures where oxidation/corrosion driving forces can be large and degradation reaction kinetics are fast. Thermodynamics and kinetics of reactions between components and environments within the energy conversion system must be considered to predict system lifetimes. Common aspects of materials

development and materials choices exist across conventional Rankine cycle, Brayton cycle, nuclear power, solid oxide fuel cell, thermoelectrics, and concentrated solar power. High temperature materials with slow growing stable oxide phases are most desirable. Molten corrosion products or heat transfer fluids can increase degradation rates. Sublimation and volatilization reactions can form gaseous products at very rapid rates and must be accounted for. Thermochemical data are needed to predict material lifetimes in the extreme environments of high temperature energy conversion technologies.

About the Author Elizabeth J. Opila is an Associate Professor of Materials Science and Engineering at the University of Virginia (Charlottesville, VA). She obtained her PhD in materials science from the Massachusetts Institute of Technology. Dr. Opila has six patents and over 90 publications on topics such as oxidation of ceramics and composites, stability of oxides in water vapor, and oxide defect chemistry. She is a past Chair of the High Temperature Materials Division and has co-organized the long-running ECS symposium “High Temperature Corrosion and Materials Chemistry” since its inception in 1998. She is a Fellow of ECS. She may be reached at opila@virginia.edu.

References G. Y. Yurek, “Mechanisms of DiffusionControlled High-Temperature Oxidation of Metals,” pp. 397-446 in Corrosion Mechanisms, Edited by F. Mansfeld. Marcel Dekker, Inc., New York, 1987. 2. C. W. Bale, P. Chartrand, S. A. Degterov, G. Eriksson, K. Hack, R. Ben Mahfoud, J. Melançon, A. D.Pelton, and S. Petersen, Calphad, 26, 189 (2002). 3. J. Andersson, T. Helander, L. Höglund, P. Shi, and B. Sundman, Calphad, 26, 273 (2002). 4. S. Chen, S. Daniel, F. Zhang, Y. A. Chang, X.-Y. Yan, F.-Y. Xie, R. Schmid-Fetzer, and W. A. Oates, J. Chem. Phys., 136, 150901 (2012). 6. W. D. Kingery, H. K. Bowen, and D. R. Uhlmann, Introduction to Ceramics; p. 240, John Wiley & Sons, New York, 1976. 7. R. A. Rapp, Metallurgical and Materials Transactions A, 31A, 2105 (2000). 8. P. J. Meschter, E. J. Opila, and N. S. Jacobson, Ann. Rev. Mater. Res., 43, 559 (2013). 9. B. Pint, JOM, 65, 1024 (2013). 10. S. C. Kung, Oxidation Metals, 77, 289 (2012). 1.

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11. S. R. J. Saunders, M. Monteiro, and F. Rizzo, Progress in Materials Science, 53, 775 (2008). 12. H. P. Nielsen, F. J. Frandsen, K. DamJohansen, and L. Baxter, Progress in Energy and Combustion Science, 26, 283 (2000). 13. R. Pool, Engineering & Technology, 6, 32 (2011). 14. F. Tanabe, J. Nucl. Sci. Technol., 49, 18 (2012). 15. D. Cubicciotti and B. R. Sehgal. Nucl. Technol., 65, 266 (1984). 16. P. C. Burns, R. C. Ewing, and A. Navrotsky, Science, 335, 1184 (2012). 17. T. Cheng, J. R. Keiser, M. P. Brady, K. A. Terrani, and B. A. Pint, J. Nucl. Mater., 427, 396 (2012).

18. D. Cubicciotti, Pure Appl. Chem., 57, 1 (1985). 19. H. Yokokawa, T. Horita, K. Yamaji, H. Kishimoto, and M. Brito, J. Kor. Cer. Soc., 49, 11 (2012). 20. J. Nicholas, Interface, 22(4), 49 (2013). 21. E. J. Opila, D. L. Myers, N. S. Jacobson, I. M. B. Nielsen, D. F. Johnson, J. K. Olminsky, and M. D. Allendorf, J. Phys. Chem. A, 111, 1971 (2007). 22. M. Stanislowski, E. Wessel, K. Hilpert, T. Markus, and L. Singheiser, J. Electrochem. Soc., 154, A295 (2007). 23. J. W. Fergus, Materials Science and Engineering: A, 397, 271 (2005). 24. J. Fleurial, JOM, 61, 79 (2009). 25. J. R. Sootsman, D. Y. Chung, and M. G. Kanatzidis, Agnew. Chem. Int. Ed., 48, 8616 (2009).

26. T. M. Tritt, Ann. Rev. Mater. Res., 41, 433 (2011). 27. J. A. Nesbitt, E. J. Opila, and M. V. Nathal, J. Electron. Mater., 41, 1267 (2012). 28. J. W. Fergus, J. Eur. Cer. Soc., 32, 525 (2012). 29. D. Barlev, R. Vidu, and P. Stroeve, Solar Energy Mater. Solar Cells, 95, 2703 (2011). 30. A. Gil, M. Medrano, I. Martorell, et al., Renewable and Sustainable Energy Reviews, 14, 31 (2010). 31. M. D. Allendorf, Interface, 22(4), 63 (2013).

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The Electrochemical Society Interface • Winter 2013

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t ech SEC TION highligh NE WS ts Japan Section

The ECS Japan Section awarded the Young Researcher Award at the AMFPD’13 to Aya Hino (left) of Kobe Steel, Ltd., shown here with Hiroki Hamada (right), the AMFPD’13 Organizing Committee Chair.

Solid state devices have been key components or systems in today’s information and communication society and will be more and more important for creating a more comfortable and safer society, for example, in the fields of medical treatment, inspection, monitoring, and social infrastructure. There are a lot of exciting and challenging issues in the research on future solid state devices. The ECS Japan Section co-sponsored several international meetings concerning with those technical fields this year. The 2013 International Conference on Solid State Devices and Materials (SSDM 2013) was held September 24-27, 2013, in Fukuoka. The program was consisted of three plenary talks, 55 invited papers, 289 contributed oral papers, 241 posters, and 35 late news papers. The attendance was approximately 1,000. The 20th International Workshop on Active-Matrix Flat Panel Displays and Devices (AM-FPD’13) was held July 2-5, 2013, in Kyoto. This year marked the twentieth anniversary event in the workshop series. Since its inception in 1994, the workshop has been providing important opportunities for people engaged in the research and development of systems, devices and processes, materials for FPDs, related physical phenomena and novel electronics systems such as thin-film transistors, photovoltaics, and thin-film materials and devices. The ECS Japan Section selected a winner for the ECS Japan Section Young Researcher Award of this year. The recipient was Aya Hino of Kobe Steel, Ltd. for the distinguished paper in the AMFPD’12. The workshop on Future Trend of Nanodevices and Photonics (IEEE ED WIMNACT 37) was held February 18, 2013, at the Tokyo Institute of Technology. This workshop provided young researchers, a great opportunity for information exchange and discussions at the forefront of the research on nanodevices and photonics. The international workshop on Nanodevices Technologies 2013 was held March 5, 2013, at Hiroshima University. This workshop consisted of three plenary talks, three invited talks, a panel discussion, and aposter session. The panel discussion was organized by A. Triumi of the University of Tokyo. Throughout the workshop, nanodevice technologies for microelectronics and novel biomedical applications were discussed. In collaboration with the seven local sections and special committees of the Electrochemical Society of Japan, one symposium, one summer school, five subsection academic meetings were co-organized.

The International Workshop on Nanodevices Technologies 2013 was held March 5, 2013, at Hiroshima University.

The workshop on Future Trends of Nanodevices and Photonics (IEEE ED WIMNACT 37) was held February 18, 2013, at the Tokyo Institute of Technology. 74

The Electrochemical Society Interface • Winter 2013

t ech SEC TION highligh NE WS ts Taiwan Section The annual electrochemical training course took place at the National Taiwan University of Science and Technology, Taipei, Taiwan on July 11 and 12. The annual activity was organized by the ECS Taiwan Section and focused on the theory, analytical practices, and case studies of electrochemistry used in various applications. The topics covered from the fundamentals of electrochemistry, impedance spectroscopy, to the application for energy conversion and storage devices, as well as passivity and electrochemical deposition. The attendee who

successfully completes the 12-hour lectures receives a certificate. The one-and-half day event has attracted nearly 200 attendees, including researchers, scholars, graduate, and undergraduate students from different institutions and universities. The new members of the ECS Taiwan Section are: Chang Lun Wang, Chair; Hsisheng Teng, Vice-Chair; Nie-Lih Wu, Councilor; Bing Joe Hwang, Chi-Chao Wa, and Jim Cherng, Incumbent Councilors; Shawn D. Lin, Treasurer; and Wei-Nien Su, Secretary.

Scenes from the ECS Taiwan Sectionâ&#x20AC;&#x2122;s annual electrochemical training course.

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Visit www.electrochem.org The Electrochemical Society Interface â&#x20AC;˘ Winter 2013

NE W AWA MEMBERS RDS

Call for Nominations For details on each award, including a list of requirements for award nominees, and in some cases, a downloadable nomination form, please go to the ECS website (www.electrochem.org) and click on the “Awards” link. This will take you to a general page that will then lead to the individual awards. The awards are grouped in one of four categories: Society Awards, ECS Division Awards, Student Awards, and ECS Section Awards. Click on one of these sub-links to find the individual award. Please see each for information about where nomination materials should be sent; or you may contact the ECS headquarters office by using the contact information on the awards Web page. For student awards, please see the Student News Section in this issue.

Visit www.electrochem.org and click on the “Awards” link. ECS 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, wall plaque, life membership in the Society, complimentary meeting registration at the meeting to accept the award, and a prize of $10,000. The next award will be presented at the ECS fall meeting in Cancun, Mexico, October 5-10, 2014. Nominations and supporting documents should be sent to Acheson Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by January 15, 2014. The Olin Palladium Award (in Basic Electrochemistry and Corrosion Science) was established in 1950 for distinguished contributions to the field of electrochemical or corrosion science. The award consists of a palladium medal, a plaque, life membership in the Society, complimentary meeting registration at the meeting to accept the award, and a monetary prize of $7,500. The next award will be presented at the ECS fall meeting in Phoenix, Arizona, October 11-16, 2015. Nominations and supporting documents should be sent to Palladium Medal, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by October 1, 2014. 76

The Gordon E. Moore Medal for Outstanding Achievement in Solid State Science and Technology was originally established in 1971 (as the Solid State Science and Technology Award) for distinguished contributions to the field of solid state science. The award consists of a silver medal, a wall plaque, life membership in the Society, complimentary meeting registration at the meeting to accept the award, and prize of $7,500. The next award will be presented at the ECS spring meeting in Chicago, Illinois, May 24-28, 2015. Nominations and supporting documents should be sent to Moore Medal, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by April 15, 2014. The Allen J. Bard Award in Electrochemical Science was established in 2013 to recognize distinguished contributions to electrochemical science. The award is named in honor of Allen J. Bard, in recognition of his outstanding advancements in electrochemical science. The award consists of a wall plaque, life membership in the Society, complimentary meeting registration at the meeting to accept the award, and a prize of $7,500. The first Bard award will be presented at the ECS spring meeting in Chicago, Illinois, May 24-28, 2015. Nominations and supporting documents should be sent to Bard Award, c/o ECS, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; Tel: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by April 15, 2014. The Electrochemical Society Interface • Winter 2013

NE W AWA MEMBERS RDS 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 solidstate science and technology by a young scientist or engineer. The award consists of a certificate, a prize of $5,000, ECS Life Membership, and travel assistance to the meeting of the award presentation (up to $1,000). The next award will be presented at the ECS fall meeting in Cancun, Mexico, October 5-10, 2014. Nominations and supporting documents should be sent to Tobias Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by January 15, 2014. The Carl Wagner Memorial Award was established in 1980 to recognize mid-career achievement and excellence in research areas of interest of the Society, and significant contributions in the teaching or guidance of students or colleagues in education, industry, or government. The award consists of an life membership in the Society, a certificate, a silver medal, and travel assistance to the meeting of the award presentation (up to $1,000). The next award will be presented at the ECS fall meeting in Phoenix, Arizona, October 11-16, 2015. Nominations and supporting documents should be sent to Wagner Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by October 1, 2014. The award of ECS Fellows was established in 1989 for individual contribution and leadership in the achievement of science and technology in the area of electrochemistry and solid-state sciences and current active participation of the affairs of ECS, and consists of a scroll, lapel pin, and announcement in a Society publication. The next Fellows will be presented at the ECS fall meeting in Cancun, Mexico, October 5-10, 2014. Nominations and supporting documents should be sent to Fellows Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by February 1, 2014.

Division Awards The Battery Division Research Award was established in 1958 to recognize outstanding contributions to the science and technology of primary and secondary cells and batteries and fuel cells. The award consists of a scroll, a prize of a $2,000, travel assistance to the meeting if required, and membership in the Battery Division for as long as the winner is an ECS member. The next award will be presented at the ECS fall meeting in Cancun, Mexico, October 5-10, 2014. Nominations and supporting documents should be sent to Battery Research Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by March 15, 2014.

The Electrochemical Society Interface • Winter 2013

The Technology Award of the Battery Division was established in 1993 to encourage the development of battery and fuel cell technology. The award consists of a scroll, prize of $2,000, travel assistance to the meeting if required, and membership in the Battery Division for as long as the winner is a Society member. The next award will be presented at the ECS fall meeting in Cancun, Mexico, October 5-10, 2014. Nominations and supporting documents should be sent to Battery Technology Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by March 15, 2014. The Electrodeposition Division Research Award was established in 1979 to recognize recent outstanding achievement or contribution in the field of electrodeposition. The award consists of a scroll and a prize of $2,000. The next award will be presented at the ECS fall meeting in Cancun, Mexico, October 5-10, 2014. Submit nominations in a letter detailing the accomplishments of the nominee accompanied by a list of supporting publications with titles to Electrodeposition Research Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; fax: 1.609.737.2743; e-mail: travelgrant@ electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by April 1, 2014. The New Electrochemical Technology (NET) Award of the Industrial Electrochemistry and Electrochemical Engineering Division was established in 1998 to recognize significant advances in industrial electrochemistry. The award recognizes collaborative, multidisciplinary, inter-functional efforts to commercialize new electrochemical technology within the past ten years and consists of a commemorative plaque with appropriate inscription presented to the sponsoring organization; commemorative scrolls presented to up to six key contributors as well, as identified by the sponsoring organization. The next award will be presented at the ECS spring meeting in Chicago, Illinois, May 24-28, 2015. Nominations and supporting documents should be sent in a single electronic PDF document to IE&EE NET Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; fax: 1.609.737.2743; e-mail: travelgrant@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by April 15, 2014. The Centennial Outstanding Achievement Award of the Luminescence and Display Materials Division was established in 2002 to encourage excellence in luminescence and display materials research and outstanding contributions to the field of luminescence and display materials science. It consists of a scroll and a prize of $1,000. The next award will be presented at the ECS fall meeting in Cancun, Mexico, October 5-10, 2014. Nominations and supporting documents should be sent to LDM Outstanding Achievement Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by January 1, 2014. (continued on next page)

NE W AWA MEMBERS RDS The Max Bredig Award in Molten Salt and Ionic Chemistry of the Physical and Analytical Electrochemistry Division sponsored by ARCO Metals Company and the Aluminum Company of America, was established in1984 in order to recognize excellence in molten salt and ionic liquid chemistry research and to stimulate publication of high quality research papers in this area in the Journal of The Electrochemical Society. The award consists of a scroll and a prize of $1,500. The next award will be presented at the ECS meeting in San Diego, California, May 29-June 3, 2016. Nominations and supporting documents should be sent to PAED Bredig Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by March 15, 2014. The Outstanding Achievement Award of the Sensor Division was established in 1989 to recognize outstanding achievement in the science and or technology of sensors and to encourage excellence of work in the field. It consists of a scroll and a prize of $1,000. The next award will be presented at the ECS fall meeting in Cancun, Mexico, October 5-10, 2014. Nominations and supporting documents should be sent to Sensor Outstanding Achievement Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due

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by March 1, 2014. The Young Faculty Travel Grants of the Battery Division were established to recognize promising faculty members at colleges and universities who are in the first five years of their appointments and engaged in research in the science and engineering of electrochemical energy storage and conversion. The grants shall be given for a single meeting. The grant award consists of a check in an amount not exceeding $1,000 payable to the recipient at the time of the meeting and a waiver of registration for that meeting as well as one-year membership in the Society. The next grant will be presented for the ECS spring meeting in Orlando, Florida, May 11-16, 2014. Nominations and supporting documents should be sent to Battery Division Young Faculty Travel Grant, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; fax: 1.609.737.2743; e-mail: travelgrant@ electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by January 1, 2014. The Early Career Faculty Travel Grants of the High Temperature Materials Division were established to assist postdoctoral associates, junior faculty, or other young investigators below the age of 35, who are both members of the High Temperature Materials (HTM) Division and are presenting papers at symposia sponsored or co-sponsored by the HTM Division at ECS meetings. The grant award consists of a check in an amount not exceeding $1,000 payable to the recipient at the time of the meeting. The next grant will be presented for the ECS spring meeting in Orlando, Florida, May 11-16, 2014. Nominations and supporting documents should be sent to HTM Early Career Travel Grant, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; e-mail: travelgrant@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by January 1, 2014.

Section Awards The Allesandro Volta Medal of the Europe Section was established in 1998 to recognize excellence in electrochemistry and solid-state science and technology research, and consists of a silver medal and a check for $500. The next award will be presented at the ECS fall meeting in in Cancun, Mexico, October 5-10, 2014. Nominations and supporting documents should be sent to Europe Section Volta Medal, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by March 15, 2014.

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The Electrochemical Society Interface • Winter 2013

NE W MEMBERS ECS is proud to announce the following new members for July, August, and September 2013.

Active Members Wim Aarts, Portland, OR, USA Ahmed Abdo, Kuwait, Kuwait Atsushi Aoki, Nagoya, Aichi, Japan Shigetoshi Aono, Okazaki, Japan Sofiya Babanova, Albuquerque, NM, USA Sandeep Bahl, Santa Clara, CA, USA Viorel Balan, La Buisse, France Uri Banin, Jerusalem, Israel Sibel Barisci, Kocaeli, Turkey El Mehdi Bazizi, Dresden, Germany Leonard Berlouis, Glasgow, Scotland, UK Patrick Bernard, Bordeaux, France Jan Besser, Chemnitz Saxony, Germany Martin Bettge, Lemont, IL, USA Fredrik Bjorefors, Uppsala,Sweden David Boldridge, Aurora, IL, USA Christopher Bonino, Durham, NC, USA Mikhail Brik, Tartu, Estonia Wen-Bin Cai, Shanghaihai, P. R. China Renata Camillo-Castillo, Essex Junction, VT, USA Umberto Celano, Heverlee, Belgium Fardad Chamran, Mountain View, CA, USA Peter Chaplin, Osborne, Australia Santanu Chaudhuri, Spokane, WA, USA Katharine Chemelewski, Ithaca, NY, USA Shengli Chen, Wuhan Hubei, P. R. China Chin-Chang Cheng, Taoyuan Hsien, Taiwan Wooni Choi, Livermore, CA, USA Henry Choque, ILO, Moquegua, Peru Karin Chumbimuni-Torres, Orlando, FL, USA Philip Cox, Cocoa Beach, FL, USA Craig Dawson, Cheshire, United Kingdom Hendrik Dekkers, Leuven, Belgium Mickael Dolle, Pessac, France Eric Donsky, Austin, TX, USA Mikael Dumortier, Lausanne, VD, Switzerland Sune Ebbesen, Roskilde, Denmark Ubong Eduok, Dhahran, Saudi Arabia David Finkelstein, Varennes, QC, Canada Jason Forster, Berkeley, CA, USA Keith Friedman, Austin, TX, USA David Fritz, Duesseldorf, NW, Germany Min-Rui Gao, Newark, DE, USA Byron Gates, Burnaby, BC, Canada Jeffrey Glass, Durham, NC, USA Tobias Glossmann, Redford, MI, USA Daniel Goodman, Billerica, MA, USA Sanketh Gowda, Lemont, IL, USA Jan Grym, Prague, Czech Republic Zhenxing Han, Tucson, AZ, USA S. Harinipriya, Jodhpur, India Stefan Harrer, Carlton, Vic, Australia Frederic Hasche, Garching, BY, Germany Bahman Hekmatshoar, Yorktown Heights, NY, USA Mark Hintze, Charlotte, NC, USA Tetsuro Hirasaki, Sugro-guh, Shizuoka, Japan Frank Holsteyns, Heverlee, Belgium Lewis Hom, Mountain View, CA, USA Tsuyoshi Hoshino, Mito-City, Ibaraki, Japan Maolin Hu, Wenzhou, Zhejiang, P. R. China Barbara Hughes, Golden, CO, USA The Electrochemical Society Interface • Winter 2013

Ioannis Ieropoulos, Bristol, UK Seongil Im, Seoul, South Korea Hirokazu Ishitobi, Kiryu, Gunma, Japan Kohei Ito, Fukuoka, Japan Shiho Iwanaga, Hayward, CA, USA Marvin Jaime-Vasquez, Alexandria, VA, USA JinNyoung Jang, Sejong City, South Korea Martin Johnson, Piedmont, CA, USA Shinji Jomori, Susono, Shizuoka, Japan Nicolas Jourdan,Brabant Leuven, Belgium Akihisa Kajiyama, Sanyo-onoda, Yamaguchi, Japan Yijin Kang, Naperville, IL, USA Sudhakaraprasad Kariate, Stillwater, OK, USA Hiromichi Kataura, Tsukuba, Ibaraki, Japan Abdel-Nasser Kawde, Dhahran Eastern Provience, Saudi Arabia Joohoon Kim, Seoul, South Korea Sang-Woo Kim, Suwon, South Korea Laurie King, Laramie, WY, USA Hidayat Kisdarjono, Camas, WA, USA Nitin Kumar, Albuquerque, NM, USA Eisuke Kuraya, Nago, Japan Castro Laicer, Watertown, MA, USA Michal Leskes, Cambridge, Cambridgeshire, UK Suiqiong Li, Newark, CA, USA Yongfu Lian, Harbin, P. R. China Nathan Lien, Winona, MN, USA Ruben Lieten, Heverlee, Belgium Feng Lin, Berkeley, CA, USA Lin Liu, Lawrence, KS, USA Shi Liu, Fremont, CA, USA Carlos Lledo-Fernandez, Aberdenshire, UK Daniel Lowy, College Park, MD, USA Peng Lu, Troy, MI, USA Christopher Lueth, Bellevue, WA, USA Bradley Lundahl, San Clemente, CA, USA Zeeshan Mahmood, Darmstadt, He, Germany Kranthi Maniam, Vellore, Tamil Nadu, India William Maskell, London, United Kingdom Chad Mason, Singapore, Singapore John Mason, Pittsburgh, PA, USA Pierre-Eric Melchy, Burnaby, BC, Canada Boris Merinov, Pasadena, CA, USA Robert Messinger, Orleans, France Artur Motheo, Sao Carlos, Sao Paulo, Brazil Bruno Moura, Rio de Janeiro, Brazil Yoshiharu Mukouyama, Saitama, Japan Yuzo Nagumo, Seikacho, Japan Hiroki Nara, Tokyo, Japan Toshio Nishi, Shimotsuke-shi, Tochigi, Japan Junjie Niu, Cambridge, MA, USA Yoshihiro Oka, Himeji, Hyogo, Japan Yoshifumi Oshima, Ibaraki, Osaka, Japan Frank Osterloh, Davis, CA, USA Jos Oudenhoven, Eindhoven, Netherlands Antoine Pacco, Heverlee, Belgium Murat Peksen, Julich, Germany Kristin Persson, Berkeley, CA, USA Mihaela Popovici, Leuven, Belgium Maurizio Prato, Trieste, Italy Anthony Pullen, Tucson, AZ, USA Jing Qi, Storrs, CT, USA Iuliana Radu, Heverlee, Belgium Venkat Raja, Kitchener, ON, Canada

Dorthe Ravnsbaek, Cambridge, MA, USA Kafil Razeeb, Shanakiel, Cork, Ireland Steven Reece, Cambridge, MA, USA Zhiyong Ren, Boulder, CO, USA Jessy Rivest, Berkeley, CA, USA Isadora Rodrigues, Foz do Iguaçu, Parana, Brazil Maria Luz Rodriguez-Mendez, Valladolid, Spain Gayatri Sahu, Oak Ridge, TN, USA Bulent Sarlioglu, Madison, WI, USA Bjoern Schimmoeller, Billerica, MA, USA Ruediger Schweiss, Munchen, Germany Ben Schweitzer, Chicago, IL, USA Hiroyuki Shimada, Kanagawa, Japan Paul Short, Albuquerque, NM, USA Richard Soltis, Dearborn, MI, USA Sun-Ju Song, Gwangju Chonnam, South Korea Joshua Spurgeon, Pasadena, CA, USA Thomas Stephenson, Albuquerque, NM, USA Aslihan Sumer, Spokane, WA, USA Jin Suntivich, Ithaca, NY, USA Takahiro Suzuki, Chiba, Japan Tsunehisa Suzuki, Yamagata, Japan Konrad Swierczek, Krakow, Poland Kuniharu Takei, Osaka, Japan Yohei Tanaka, Tsukuba, Japan Yoshiaki Tazaki, Hoosick Falls, NY, USA Xiaowei Teng, Durham, NH, USA Eric Yeow Hwee Teo, Singapore, Singapore Takayuki Toshima, Koshi City, Japan Panuporn Udompansa, Hayward, CA, USA Dennis Van Dorp, Heverlee, Belgium Guy Vereecke, Leuven, Belgium Virginie Viallet, Amiens, France Vishal Vijay, Hayward, CA, USA Toshimasa Wadayama, Miyagi, Japan Weining Wang, Clayton, MO, USA Ana Wati, Hachioji, Tokyo, Japan Tzu Chien Wei, Hsinchu, Taiwan Adam Weisenstein, Columbia Falls, MT, USA Brandon Wood, Livermore, CA, USA Qingzhong Wu, Sugar Land, TX, USA Xiaodong Xu, Seattle, WA, USA Wanli Yang, Berkeley, CA, USA Huseyin Yildiz, Karaman, Turkey Ho Yeon Yoo, Amherst, NY, USA Jinsong Yu, Valparaiso, IN, USA Roswitha Zeis, Ulm, BW, Germany Xintong Zhang, Changchun Jilin Province, P. R. China Jiefang Zhu, Uppsala, Sweden Ye Zhu, Palos Hills, IL, USA

Member Representatives Takao Fukumizu, Tochigi, Japan Thomas Greszler, Honeoye Falls, NY, USA Tatsuya Hatanaka, Aichi, Japan Hiroko Kato, Aichi, Japan Kazuo Kawahara, Ann Arbor, MI, USA Kensaku Kodama, Nagakute, Aichi, Japan Savidra Lucatero, Clayton, OH, USA (continued on next page) 79

NE W MEMBERS (continued from previous page)

Matthew Marinella, Albuquerque, NM, USA Hideaki Oka, Aichi, Japan Bogdan Petrescu, Claix, France Makoto Sato, Hirakata, Osaka, Japan Stephen Snyder, Clayton, OH, USA Shohei Toyota,Tochigi, Japan

Students Syed Sulthan A. A. H. Rashid, Makkah Province, Saudi Arabia Mohammed Hussain Abdul Jabbar, College Park, MD, USA Pablo Acosta, Grenoble, France Serkan Akbulut, Nashville, TN, USA Eric Allcorn, Austin, TX, USA Ayar Al-zubaidi, Nagoya City, Aichi, Japan Seong Jin An, Pittsburgh, PA, USA Sune Andreasen, Kongens Lyngby, Denmark Ronnie Anseth, Porsgrunn, Norway Georgina Armendariz Vidales, Querétaro, Mexico Samvel Avagyan, San Diego, CA, USA Muratahan Aykol, Evanston, IL, USA Nasim Azimi, Bolingbrook, IL, USA Sirigineedi Babu, Cookeville, TN, USA Ramalingam Balavinayagam, Columbia, MO, USA Marya Baloch, Minano, Spain Abbas Barfidokht, Sydney, NSW, Australia Aadil Benmayza, Chicago, IL, USA Chaparral Berry, Bozeman, MT, USA Snehasis Bhakta, Storrs, CT, USA Peter Bleith, Villigen PSI, Switzerland Karen Bollenbach, Virginia Beach, VA, USA James Bridgewater, Scottsdale, AZ, USA Benjamin Britton, Burnaby, BC, Canada Michael Burkholder, Pittsburgh, PA, USA Pongkarn Chakthranont, Stanford, CA, USA Ya Yun Chan, Singapore, Singapore Ju-Hung Chao, State College, PA, USA Muddit Chaudhary, Chennai, Tamil Nadu, India Chen Las Cruces, NM, USA Pushpa Chhetri, Reno, NV, USA Jae Ik Choi, La Jolla, CA, USA Jae-Yong Choi, Cheonan Chungnam, South Korea Moon-Bong Choi, Gwangju, South Korea Yun-Il Choi, Nagoya, Aichi, Japan Tsung Chou, Taipei, Taiwan Ane Christiansen, Roskilde, Denmark Andre Clayborne, Jyvaskyla Suomi, Finland Isvar Cordova, Durham, NC, USA Timothy Crowtz, Halifax, NS, Canada Chunhua Cui, Berlin, Germany Daniel Cuypers, Heverlee, Belgium Aarit Dabral, Uttar Pradesh, India James Daubert, Raleigh, NC, USA Paul DeGregory, Austin, TX, USA Bala Devadas, Taipei, Taiwan Badrinath Dhakal, Auburn Hills, MI, USA Kryssia Diaz-Orellana, Clemson, SC, USA Abdoulaye Djire, Ann Arbor, MI, USA Peter Doyle, Beaver Falls, PA, USA David Eisenberg, Austin, TX, USA 80

Soumia El Khakani, Montreal, QC, Canada Ismaila Emahi, Saint Louis, MO, USA Stephanie Essig, Freiburg, Germany Dan Fang, Los Angeles, CA, USA Jung-Ying Fang, Hsinchu, Taiwan Te-Hua Fang, Kaohsiung City, Taiwan Xin Fang, Los Angeles, CA, USA Ling Fei, Las Cruces, NM, USA Hamid Feyzizarnagh, Toledo, OH, USA Juan Flores Segura Pachuca de Soto, Hidalgo, Mexico Stephen Fosdick, Austin, TX, USA Kevin Frankforter, Madison, WI, USA Kan Fu Storrs, Mansfield, CT, USA Ruchi Gakhar, Reno, NV, USA Dora Garcia Osorio, Temixco, Morelos, Mexico Ramona Georgescu, Bucharest, Romania Timon Geppert, Muenchen, BY, Germany Carol Glover, Swansea, United Kingdom Christoph Grimmer, Graz, Austria Pengfei Guo, Singapore, Singapore Xiaoguang Hao, Ann Arbor, MI, USA Hima Haridevan, Alappuzha, India Bronwyn Harrod, Davis, CA, USA Kelsey Hatzell, Philadelphia, PA, USA Quanzhi He, Chicago, IL, USA Christopher Hendricks, Rockville, MD, USA Jake Herb, Princeton, NJ, USA Yaovi Holade, Poitiers, France Yu-Ping Hsiao, Taichung, Taiwan Yanyan Hu, Cambridge, Cambridgeshire, UK Yoon Hwa, Seoul, South Korea Imgon Hwang, Incheon Nam-ku, South Korea Yuya Ichikawa, Sakai City, Osaka, Japan Ha Ni Im, Gwangju, South Korea Rene Jakelski, Munster, Germany Soghra Jalil Pour Kivi, Orrawa, ON, Canada Sang-Yun Jeon, Gwangju, South Korea Bin Jiang, Tokyo, Tokyo, Japan Kun Jiang, Shanghai, P. R. China Young Soo Joung, Cambridge, MA, USA Youngwon Ju, Dongdaemun-gu Seoul, South Korea Young Hwa Jung, Daejeon, South Korea Yuhong Kang, Blacksburg, VA, USA Pejman Kazempoor, Golden, CO, USA Asim Khan, Sydney, NSW, Australia Ashish Khandeparker, Gainesville, FL, USA Guyeon Kim, Halifax, NS, Canada Sang Woo Kim, Cheonan Chungnam, South Korea Yeoju Kim, Gyunggi-do, South Korea Joachim Langner, Karlsruhe, BW, Germany Michael Lazar, Niantic, CT, USA DongHyeok Lee, Sejong, South Korea Kyoungmoo Lee, Kitami Hokkaido, Japan Soonbo Lee, Seoul, South Korea Tae Hee LEE, Seoul, South Korea Jessica Leon, San Luis Potosi, Mexico Longjun Li, Austin, TX, USA Na Li, Storrs, CT, USA Sheng Li, QLD, Australia Sirong Li, Halifax, NS, Canada Yubai Li, State College, PA, USA Dae-Kwang, Lim Gwangju, South Korea Vipawee Limsakoune, Merced, CA, USA Chi-Chou Lin, College Station, TX, USA

Min Ling, Berkeley, CA, USA Chao Liu, Charlottesville, VA, USA Jia Liu, Uppsala, Sweden Ying Liu, Greenbelt, MD, USA Fa Sain Lo, Chung Li City, Taiwan Peter Lobaccaro, Berkeley, CA, USA Valentino Longo, Eindhoven, Netherlands Eric Lopez, San Diego, CA, USA Pin Lu, El Cerrito, CA, USA Dongni Ma, Tucson, AZ, USA Jia Ma, Columbus, OH, USA Sichao Ma, Urbana, IL, USA Natalia Macauley, Vancouver, BC, Canada Alireza Mahdavifar, Atlanta, GA, USA Mohamed Mahmoud, Tempe, AZ, USA Feixiong Mao, Albany, CA, USA Naveenkumar Marati, Uttar Pradesh, India Michael Marshak, Cambridge, MA, USA Anthony Matasso, Fort Worth, TX, USA Meghan McCormick, Bloomington, IN, USA Amal Mehrotra, Fremont, CA, USA Lis Melo, Hamilton, ON, Canada Augustus Merwin, Reno, NV, USA Thomas Mittermeier, Garching, BY, Germany Masahiro Miura, Yamaguchi, Japan Nazrul Mojumder, Reno, NV, USA Miguel Angel Munoz, Minano, Spain Kishore Anand Narayana, Lexington, KY, USA Akira Nordmeier, Reno, NV, USA Ji-Won Oh, Anyang-si, Gyeonggi-do, South Korea Hector Ortiz, Mexico Gilbert Osayemwenre, Alice Eastern Cape, South Africa Cagla Ozgit-Akgun, Cankaya Ankara, Turkey Monica Padilla, Albuquerque, NM, USA Jie Pan, Lexington, KY, USA Ankit Pande, Chennai, Tamil Nadu, India Raghvendra Pandey, Varanasi, India Suman Parajuli, Reno, NV, USA An Pham, San Diego, CA, USA Mark Poyner, Tulsa, OK, USA Leonie Przewieslik, Berlin, BE, Germany Xin Qi, Muenster, NW, Germany Jingxia Qiu, Parkwood, Australia Raj Kumar R., Tamil Nadu, India Ananthakumar Ramadoss, Jeju, South Korea Arun Deepak Ramalingom Pillai, Virginia Beach, VA, USA Vijaya Rana, Pradesh, India Michelle Rasmussen, Salt Lake City, UT, USA Nadya Rauff-Nishtar, Lancaster, UK Sanjeev Rayaprolu, Reno, NV, USA Maria Reiner, Villach, Austria Derek Rife, Saint Louis, MO, USA Karen An Ronquillo, San Diego, CA, USA Aaron Roy, Albuquerque, NM, USA Ashley Ruth, Jessup, MD, USA Swagotom Sarkar, Reno, NV, USA Andrew Scheuermann, Stanford, CA, USA Kjell Schroder, Austin, TX, USA Uta Schwenke, Garching, Bavaria, Germany Ieuan Seymour, Cambridge, United Kingdom Matthew Shaner, Pasadena, CA, USA Mike Kuan-Yu Shen, Richmond Heights, MO, USA Kazuma Shinozaki, Lakewood, CO, USA The Electrochemical Society Interface • Winter 2013

NE W MEMBERS Shantanu Shukla, Edmonton, AB, Canada Armin Siebel, Munchen, Germany Gustav Sievers, Greifswald, Germany Rakesh Sihag, Hanumangarth, Rajasthan, India David Simpson, Potsdam, NY, USA David Snydacker, Evanston, IL, USA Junyoung Song, Seoul, South Korea Hassan Srour, Villeurbanne, France Maksim Starykevich, Aveiro, Portugal Malcolm Stein, Cypress, TX, USA Stephen Stewart, Santa Fe, NM, USA Mie Moeller Storm, Roskilde, Denmark Sarah Straub, Plainfield, IL, USA Fiona Strobridge, Cambridge, UK Kohei Suda, Tokyo, Kanagawa, Japan Yifei Sun, Edmonton, AB, Canada Yu Sun, Hsinchu, Taiwan Graeme Suppes, Burnaby, BC, Canada Ann-Marie Suriano, Rapid City, SD, USA Atefeh Taheri, Davis, CA, USA Madhavi Tangirala, Norfolk, VA, USA Jacob Tarver, Gaithersburg, MD, USA Ahmet Tezel Trondheim, Sor Trondelag, Norway

Ryosuke Todo, Kitami Hokkaido, Japan Naoto Todoroki, Sendai, Miyagi, Japan Raghu Tomar, Alwar Rajasthan, India Binh Tran, Hsinchu, Taiwan, Taiwan Sandy Tran, La Palma, CA, USA Phong Trinh, Los Angeles, CA, USA Pierrre Celestin Urisanga, Saint Louis, MO, USA Honorio Valdes Espinosa, Seattle, WA, USA Joquel Vasquez, San Diego, CA, USA Codruta Vlaic, Ilmenau, Thuringia, Germany Guilei Wang, Beijing, P. R. China Jiarui Wang, Davis, CA, USA Lei Wang, Hong Kong Xiaofeng Wang, Storrs, CT, USA Wei Wei, Uppsala, Sweden Michael Weiss, Karlsruhe, BW, Germany Stuart Whitman, Moscow, ID, USA Teguh Widodo, Koto-ku, Tokyo, Japan Nicholas Williard, College Park, MD, USA Dominica Wong, Chapel Hill, NC, USA Ka Hung Wong, Surrey, BC, Canada Michael Workman, Albuquerque, NM, USA Dongjun Wu, Houston, TX, USA

Fei Wu, Saint Louis, MO, USA Dahai Xia, Edmonton, AB, Canada Junheng Xing, Guangzhou, P. R. China Wenting Xing, Cambridge, MA, USA Xiuhui Xu, Singapore, Singapore Nansi Xue, Ann Arbor, MI, USA Ashutosh Yadav, Chennai, Tamil Nadu, India Shuhei Yamamoto, Saitama, Japan Chenguang Yang, Arcadia, CA, USA Ting Yang, Tempe, AZ, USA Yao-Yue Yang, Shanghai, P. R. China Yoji Yasuda, Yokohama, Kanagawa, Japan Yu-Ting Yen, Hsinchu, Taiwan Mesut Yilmaz, Nashville, TN, USA Tomohiro Yoshida, Ube, Yamaguchi, Japan Mengqi Zhang, Knoxville, TN, USA Qing Zhang, Newark, DE, USA Zhuoxiang Zhang, Villigen, AG, Switzerland Jianqing Zhao, Baton Rouge, LA, USA Jie Zheng, Newark, DE, USA Lushan Zhou, Bloomington, IN, USA Liangzhu Zhu, Salt Lake City, UT, USA Chenxi Zu, Austin, TX, USA

DNV Roger W. Staehle Designated Professorship Fontana Corrosion Center Department of Materials Science and Engineering The Ohio State University The Fontana Corrosion Center and the Department of Materials Science and Engineering at The Ohio State University (mse. osu.edu) invite applications for the DNV Roger W. Staehle Designated Professorship. This position is a regular tenure-track faculty appointment in the Department of Materials Science and Engineering in the area of corrosion science and engineering. Appointment is anticipated at the rank of Assistant or Associate Professor and tenure will be possible based on experience and accomplishment. Appointment at the rank of Professor will also be considered. The Strategic Plan of the Department of Materials Science and Engineering at Ohio State (http://mse.osu.edu/department/ strategic-plan) articulates an ambitious course of discovery and learning that enhances the impact made by our signature research thrusts. The successful applicant will be expected to deepen and complement existing strengths in corrosion, materials characterization and computational materials science to develop compelling teaching and research programs. These new programs are expected to have strong links to industry needs and provide essential training to the next generation of corrosion scientists and engineers.Â Research leadership is implicit in this designated professorship and the successful applicant will be expected to attract significant federal funding and industrial partnerships to sustain a vibrant research program. Additionally, the candidate will possess the ability to work cooperatively and collegially to advance research and teaching programs with greatest efficiency and highest impact. In view of our aspirations and the nature of this opportunity, we seek candidates who are ardent discoverers, passionate teachers and mentors, committed stewards of our discipline and proven collaborators. For the best candidate, we offer a vibrant research environment at one of the largest, best equipped and best connected academic research platforms in North America. Candidates must have an earned doctoral degree in materials science and engineering or in a closely related field. The successful candidate will be expected to develop and sustain active sponsored research programs, teach core undergraduate and/or graduate courses and be an active participant in the international corrosion science community. The anticipated start date for this position is September 2014. Screening of applicants will begin immediately and will continue until the position is filled. Interested candidates should submit a complete curriculum vitae, separate 2-3 page statements of research and teaching goals, and the names, addresses, and e-mail addresses of at least five references electronically to the following email address: fcc@osu.edu. The Ohio State University is an affirmative/equal opportunity employer. Women, minorities, and people with disabilities are encouraged to apply and build a diverse workplace. Columbus is a thriving metropolitan community, and the University is responsive to the needs of dual career couples.

The Electrochemical Society Interface â&#x20AC;˘ Winter 2013

NE W AWA MEMBERS RDS

Volume 53 – T o r o n t o , C a n a d a

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2013 ECS Summer Fellowship Reports 2013 Summer Fellowship Committee

Summer Fellowships Each year ECS gives up to five Summer Fellowships to assist students in continuing their graduate work during the summer months in a field of interest to the Society. Congratulations to the five Summer Fellowship recipients for 2013. The Society thanks the Summer Fellowship Committee for their work in reviewing the applications and selecting five excellent recipients. Applications for the 2014 Summer Fellowships are due January 15, 2014 (see http://www.electrochem.org/awards/student/ student_awards.htm#n).

Vimal Chaitanya, Chair New Mexico State University

Jeffrey Fergus Auburn University

Christopher Apblett Sandia National Laboratories

Jeffrey W. Long U.S. Naval Research Lab

Bryan Chin Auburn University

Kalpathy Sundaram University of Central Florida

The 2013 Edward G. Weston Summer Research Fellowship – Summary Report Assessment of Magnesium Alloy Corrosion Using Potentiometric Mode of Scanning Electrochemical Microscopy by Philippe Dauphin Ducharme agnesium remains a very reactive material. Different alloying, elemental composition, and casting methods can be employed to enhance corrosion properties.1 In spite of its poor corrosion behavior, magnesium’s mechanical and lightweight properties draw the attention of the automotive industry toward its addition in car components to improve fuel efficiency. The complexity of the corrosion mechanism in magnesium alloys and the size of the anodic/cathodic sites responsible for microgalvanic corrosion requires high-resolution in situ and ex situ characterization to get a proper understanding of the alloys’ corrosion behavior.2 Scanning electrochemical microscopy (SECM) can achieve high-resolution in situ imaging while recording both surface reactivity and topography. When magnesium alloys are immersed, different electrochemical fluxes in solution can be recorded with SECM. The Mg alloy corrosion reaction proceeds following Eq. 3.

Mg  Mg2+ + 2e2H2O + 2e-  H2 + 2OHMg + H2O  H2 + Mg2+ + 2OH-

micron-sized quartz capillary, pulled using a P-2000 CO2 laser (Sutter Instrument), is tip filled with a polymeric cocktail containing an ionophore selective towards Mg2+ (ETH 7025),4 as observed in Fig. 1c. The capillary is then back filled with a constant activity MgCl2 solution where an Ag|AgCl wire can then be inserted (Fig. 1a). The reference electrode enables the measurement of the junction potential difference at the tip. A calibration curve is created using standards solutions of different Mg2+ activities ranging from 10-7 is 10-1. A linear behavior is measured between 10-5 and 10-1

(Fig. 2a). The potentiometric sensor is then placed over a graphite cast AM50 Mg alloy (of interest for industrial applications), which has been polished following an established procedure,5 at a tip-to-substrate distance of 1 mm using shear force.6 Upon immersion in a 50 µL drop of 1.6 wt. % NaCl solution, the potential is recorded while the potentiometric sensor is scanned across the surface. Figure 2b illustrates a 6 x 8 mm area scanned to locate corrosion initiation sites. Using the calibration curve, the potentials are transformed into activity units (Fig. 2a). The measured activities lie (continued on next page)

(a)

(b)

(c)

(1) (2) (3)

Equation 1 describes the main anodic reaction, where the Mg alloy dissolves and generates Mg2+ ions. Through the detection of this ionic flux at a specific position over the Mg alloy surface, it would be possible to obtain local corrosion rate information. The potentiometric mode of SECM, initially developed in the laboratory of Allen Bard,3 enables the measurement of ionic fluxes using an ion-selective electrode. A The Electrochemical Society Interface • Winter 2013

Fig. 1. (a) Schematic representation of the sensor where the black region represents the ion-selective membrane, the light grey, the constant activity MgCl2 solution and the darker grey the Ag|AgCl reference wire; (b) and (c) are respectively SEM micrographs of the potentiometric sensor from bottom up and the tip. 83

Ducharme

(continued from previous page)

(a)

in the linear domain of the calibration curve and are therefore analytically valid. The areas of larger Mg2+ activity are currently believed to correlate with the α-Mg rich phase, which is considered an anodic site in the microgalvanic process. Future experiments will consist in correlating the initiation sites observed in SECM with their morphology and elemental composition measured by scanning electron microscopy (SEM). The measurement of Mg2+ ion fluxes also enables the ability to numerically simulate alloy corrosion to predict their outcome.

Acknowledgments

(b)

The author thanks ECS for funding the Summer Fellowship as well as Janine Mauzeroll for her guidance through the project. Mohsen Danaie and Gianluigi Botton are acknowledged for SEM characterization of the sensor. Robert Matthew Asmussen, Pellumb Jakupi and David Shoesmith are also thanked for their participation in this collaborative effort.

About the Author Philippe Dauphin Ducharme is a third year graduate student in the Chemistry Department at McGill University, Canada. He is currently a PhD candidate under the supervision of Janine Mauzeroll. Ducharme’s thesis concentrates on monitoring Mg alloys corrosion using Scanning Electrochemical Microscopy while concomitantly developing a numerical method to predict Mg corrosion for their industrial applications. He may be reached at philippe.dauphinducharme@ mail.mcgill.ca.

References

Fig. 2. (a) Calibration curve of the potentiometric sensor. The linear regression equation between aMg2+ = 10-5 to 10-1 is y = 25.3x + 47.2 with a R2 = 0.9825 ; B) Mg2+ activity map recorded in SECM on top of a graphite cast AM50 Mg alloy surface when positioned at 1 mm from the surface recorded at 1 mm/s. A Ag|AgCl and Pt wires are used as a reference and counter electrodes.

1. K. B. Deshpande, Corrosion Sci., 52 2819 (2010). 2. D. Sachdeva, Corrosion Sci., 60 18 (2012). 3. B. R. Horrocks, M. V. Mirkin, D. T. Pierce, A. J. Bard, G. Nagy, and K. Toth, Analytical Chem., 65 1213 (1993). 4. E. Malinowska, A. Manzoni, and M. E. Meyerhoff, Analytica Chim. Acta, 382, 265 (1999). 5. D. Trinh, P. Dauphin Ducharme, U. Mengesha Tefashe, J. R. Kish, and J. Mauzeroll, Analytical Chem., 84 9899 (2012). 6. A. Hengstenberg, C. Kranz, and W. Schuhmann, W., Chemistry – A European Journal, 6, 1547 (2000).

The Electrochemical Society Interface • Winter 2013

The 2013 Colin G. Fink Summer Research Fellowship – Summary Report Developing Operando Cells for Confocal Raman Spectroelectrochemistry by Gabriel G. Rodríguez-Calero he electrification of transportation and the need to store energy from renewable, but intermittent sources, has generated a great deal of interest in the study of electrode materials for electrochemical energy storage technologies.1 It is not sufficient to study materials in situ because additional system components can give rise to deviations of the electrochemical reactions from the expected performance. In most cases, the interactions of the complete system are often underestimated. However, it is important to understand these complex interactions of the components of the system if we expect to incorporate new materials into traditional battery configurations and expect them to work as intended. Conducting polymers represent attractive materials for electrochemical energy storage technologies. 2 Their electrochemical reactions are well understood and have been studied by Raman spectroelectrochemistry.3 Even though these model systems (i.e., in situ experiments) offer information about the changes undergone by the electrode during electrochemical cycling, factors such as film thickness, electrochemical charging/

discharging rate (C-rate), and cell geometry are different in real operating conditions. To better understand how these factors affect the electrochemical reactions of the electrode material, we have developed an electrochemical cell (Fig. 1) that contains Mylar windows by which we can measure Raman spectra of electrode materials while the cell is in operando conditions. As a case study we chose poly-3,4ethylenedioxythiophene (PEDOT); a conducting polymer film electropolymerized on current collectors. The current collector employed was gold-coated aluminum foil. We proceeded to assemble a 2 electrode cell, similar to a coin cell, in which the negative electrode was Li metal, the electrolyte was lithium hexaflourophosphate in propylene carbonate, and a polymer separator, Celgard, was employed. Electrochemical cycling at 1 mV/s for this half cell (Fig. 2c) was performed and Raman spectra were collected at 2.5 V and 4.2 V vs Li/Li+ (Fig. 2a and 2b, respectively). The reaction scheme is presented in the inset to Fig. 2c. The Raman spectroelectrochemistry in the operando cell exhibits the typical Raman spectrum observed in in situ experiments.

When the polymer is in the neutral undoped state, sharper peaks for the Raman shifts around 1300 cm-1 can be observed. The peaks are then broader when the polymer is electrochemically oxidized from the neutral to the highly doped cationic state. The change is attributed to the quinoid-type bonding that the polymer undergoes when oxidized. In this particular case the electrode material was not found to be influenced by the presence of Li metal, the Celgard separator, or the overall cell configuration. The film thickness appears to cause some resistive behavior as evidenced by the slope in the LSV. However, there are no indications in the Raman spectra in the region studied that the polymer is being affected by the other components of the system. In conclusion, We have effectively fabricated an opernando Raman spectroelectrochemical cell and effectively studied a PEDOT electrode material during electrochemical cycling. Most importantly We found that the other components of the system do not affect the electrochemical reactions of PEDOT as evidenced by the similarities between the in situ and operando experiments. (continued on next page)

Fig. 1. Schematic of operando Raman spectroelectrochemical cell.

The Electrochemical Society Interface • Winter 2013

Rodríguez-Calero

(continued from previous page)

Fig. 2. Raman spectra of a PEDOT film on a gold coated aluminum current collector obtained at (a) 2.5 V vs Li/Li+ and (b) 4.5 V Li/Li+. (c) LSV of a PEDOT film on a gold coated aluminum current collector in 1 M LiPF6/PC electrolyte using a 2 electrode configuration with a sweep rate of 1mV/s.

Acknowledgments

About the Author

References

I would like to thank ECS for honoring me with the Colin Garfield Fink Summer Fellowship, and my advisor, Prof. Héctor D. Abruña, for his guidance and support on the work presented herein.

Gabriel G. Rodríguez-Calero is a fifth year graduate student in the Department of Chemistry and Chemical Biology at Cornell University. He completed his undergraduate studies in the Department of Chemistry at the University of Puerto Rico, Río Piedras Campus. His thesis work has focused on the investigation of organic materials for electrochemical energy storage technologies. He may be reached at gr235@ cornell.edu.

1. J.-M. Tarascon and M. Armand, Nature, 414, 359 (2001). 2. S. Conte, G. G. Rodríguez-Calero, S. E. Burkhardt, M. A. Lowe, and H. D. Abruña, RSC Advance, 3, 1957 (2013). 3. M. Lapkowski and A. Pron, Synthetic Metals, 110, 79 (2000).

The Electrochemical Society Interface • Winter 2013

The 2013 Joseph W. Richards Summer Research Fellowship – Summary Report Microsegregation Effects on the Thermal Conductivity of Silicon-Germanium Alloys by Yongjin Lee ue to increased need for renewable energy sources in recent years, a significant number of both experimental and theoretical efforts have been undertaken to find effective ways to enhance the performance of thermoelectric (TE) energy conversion. Since the 1960s, SiGe alloys have received much attention as one of the promising candidates for TE materials, due to their low thermal conductivity (κ), as compared to pure Si and Ge. Earlier studies1,2 demonstrated that the low κ is mainly attributed to phonon scattering as a result of the mass difference between Si and Ge atoms (the so-called alloy scattering). While the strength of alloy scattering is a strong function of the Si/Ge ratio, previous experiments3 also showed evidence that Si and Ge atoms often remain locally segregated in bulk SiGe samples prepared by mechanical alloying. However, no research has been reported regarding the microsegregation effect on κ. As a part of the ECS summer project, we performed a computational analysis to explore how the local atomic arrangement affects thermal transport in bulk SiGe; some results of this work are presented herein. To investigate the microsegregation effect, we prepared several Si0.8Ge0.2 samples by embedding spherical Ge particles of different sizes (ranging from 5 to 293 atoms) in the Si matrix. As illustrated in Fig. 1, embedded Ge particles were randomly positioned but not allowed to overlap each other. A nonequilibrium MD (NEMD) method4 with the Stillinger-Weber (SW) potential model5 was used to calculate the κ of SiGe alloys at 300 K, while the SW parameters were modified using the first-principles-based force-matching method.6 For each of the Si1-xGex systems considered, five independent NEMD simulations were performed with different atomic arrangements and initial velocity distributions. All NEMD simulations were performed using LAMMPS (Large-Scale Atomic and Molecular Massively Parallel Simulator)7 with a time step of 1 fs; a detailed description of the simulation steps can be found in Ref. 8 and 9. Figure 2 shows the variation of κ for the Si0.8Ge0.2 samples as a function of Ge particle diameter (De); here, De is approximated by (6NGeVGe/π)1/3, where NGe is the number of Ge atoms in the particle and VGe is the volume per atom for Ge (= 0.0238 nm3 from our DFT-GGA calculation). The κ is predicted to monotonically increase with

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Fig 1. The various Si0.8Ge0.2 configurations show a random distribution of Si and Ge atoms (random) and embedded Ge particles with different diameters (De = 0.91, 1.58, and 2.37 nm) in the Si matrix. Green (black) balls and yellow lattices represent Ge and Si atoms, respectively.

Fig 2. Predicted variation of the relative thermal conductivity with respect to the random alloy (κ/κ/) as a function of the diameter (De) of Ge particles embedded in Si0.8Ge0.2 (see Fig. 1); note that the predicted κ/ for the randomly distributed Si0.8Ge0.2 sample is about 1.25 Wm-1K-1. 87

Lee

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De; note that κ = 4.18 Wm-1K-1 at De = 2.37 nm is about 3.3 times greater than κ = 1.25 Wm-1K-1 for the random alloy. Given that mass disorder is mainly responsible for the reduction of κ in the SiGe alloy, single and paired Ge atoms may act mainly as scattering centers when they are atomically dispersed. On the other hand, when Ge atoms remain locally segregated, scattering by the mass difference would occur at Ge particle-Si matrix interfaces. Therefore, such Ge segregation will reduce the number of scattering centers, thereby increasing phonon transport, compared to when Ge atoms are homogeneously distributed in the Si0.8Ge0.2 matrix. Our results clearly highlight that the local segregation (microsegregation) of alloying elements, along with composition, can be a critical factor in determining the κ of alloys. The increase of κ with microsegregation suggests that the minimum κ would be achieved when Si and Ge atoms are randomly distributed.

Acknowledgments The author thanks The Electrochemical Society for the Joseph W. Richards Summer Fellowship as well as Gyeong S. Hwang for his guidance. We also acknowledge the Texas Advanced Computing Center for use of their computing resources.

About the Author Yongjin Lee is a PhD candidate in the McKetta Department of Chemical Engineering at the University of Texas at Austin under the supervision of Gyeong S. Hwang. He may be reached at yongjin@ utexas.edu.

References 1. B. Abeles, D. S. Beers, G. D. Cody, and J. P. Dismukes, Phys. Rev., 125, 44 (1962); A. Skye, and P. K. Schelling, J. Appl. Phys., 103, 113524 (2008); J. Garg, N. Bonini, B. Kozinsky, and N. Marzari, Phys. Rev. Lett., 106, 045901 (2011). 2. G. Joshi, H. Lee, Y. Lan, X. Wang, G. Zhu, D. Wang, R. W. Gould, D. C. Cuff, M. Y. Tang, M. S. Dresselhaus, G. Chen, and Z. Ren, Nano Lett., 8, 4670 (2008); C. B. Vining, W. Laskow, R. R. Van der Beck, and P. D. Gorsuch, J. Appl. Phys., 69, 4333 (1991); J. P. Dismukes, L. Ekstrom, E. F. Steigmeier, I. Kudman, and D. S. Beers, J. Appl. Phys., 35, 2899 (1964); M. C. Steele, and F. D. Rosi, J. Appl. Phys., 29, 1517 (1958).

3. J. S. Lannin, Solid State Commun., 19, 35 (1976); K. Owusu-Sekyere, W. A. Jesser, and F. D. Rosi, Mater. Sci. Eng., B3, 231 (1989); X. W. Wang, H. Lee, Y. C. Lan, G. H. Zhu, G. Joshi, D. Z. Wang, J. Yang, A. J. Muto, M. Y. Tang, J. Klatsky, S. Song, M. S. Dresselhaus, G. Chen, and Z. F. Ren, Appl. Phys. Lett., 93, 193121 (2008). 4. F. Muller-Plathe, J. Chem. Phys., 106, 6082 (1997). 5. F. H. Stillinger and T. A. Weber, Phys. Rev. B, 31, 5262 (1985). 6. Y. Lee and G. S. Hwang, Phys. Rev. B, 85, 125204, (2012). 7. S. Plimpton, J. Comput. Phys., 177, 1 (1995). 8. Y. Lee, S. Lee, and G. S. Hwang, Phy. Rev. B, 83, 125202 (2011). 9. Y. Lee and G. S. Hwang, J. Appl. Phys., Submitted.

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The 2013 F. M. Becket Summer Research Fellowship – Summary Report Bilirubin Oxidase-based Cathode for Microbial Fuel Cell (MFC) Applications: The Effects of Bacterial/Pollutants’ Presence on Enzyme Stability by Carlo Santoro icrobial fuel cells (MFCs) are promising bioelectrochemical systems with the potential for treating organic compounds and simultaneously generating electricity.1 MFCs have been intensively studied in the last decades, but performances remain still low. One of the reasons is that the cathodes are directly exposed to the aqueous solution containing bacteria and various chemical compounds, which leads to cathode flooding and poisoning, and finally lowers the current output. In contrast, enzymes (e.g., laccase and bilirubin oxidase2) are capable of catalyzing oxygen reduction reaction (ORR), and have been used as cathodic catalysts showing high open circuit potential (OCP), very low overpotentials, and high activity, especially in the range where MFCs work3. However, the main problem with enzymatic cathodes is long-term stability. In this report, we extensively characterize the trends of OCP, current density achieved at 0.25V and the polarization behavior of bilirubin oxidase (BOx) based cathode over a period of 12 days.

A single chamber (volume 130 ml) was used as the half electrochemical cell4 (Fig. 1). The voltages expressed in this report were referred to sat. Ag/AgCl (+0.197V vs. SHE). The enzymatic cathode (geometric area 2.25 cm2) was prepared as described previously.5 The electrolyte used was phosphate buffer solution (PBS, 100 mM) with or without the addition of activated sludge (AS, 40ml). The AS was used as bacterial/pollutants source to evaluate the enzymatic degradation due to bacterial contamination. The cathodes were poised at 0.3V for the first two days, 0.2V during the following two days, and 0.1V in the remaining time of the tests. At the beginning, the OCPs were slightly higher than 0.5 V for the PBS solution and the PBS/AS solution (Fig. 2a), as previously showed.5 Over time the OCPs decreased and after 12 days, the cathode facing PBS had an OCP of 0.415 V while the one in the PBS/AS solution had a low OCP (0.3 V), which was the typical OCP achieved by the material only without enzymes addition, underlining the probable complete deactivation/ poisoning of the enzymes. At the same time,

the current density generated at a constant potential of 0.25V showed the advantage of the cathode performance in absence of bacteria (Fig. 2a). The enzymatic activity decreased much faster in the presence of bacteria/pollutants in the AS solution. The current generated on day 12 was still relatively high (≈200 μA/cm2) in the PBS solution and but was only ≈50 μA/cm2 in the PBS/AS solution (Fig. 2a). A general view of the cathode’s performance over time was showed by the polarization curves, with two arrows pointing the decrease of OCP and current (Fig. 2b). The presence of bacteria/ pollutants in the PBS/AS solution lowered the current output and reduced the enzymatic activity faster than the natural occurring deactivation in the PBS solution. The interaction between bacteria/pollutants and enzymes, and the enzymes protection (e.g., silica encapsulation) to prolong the lifetime of BOx based cathodes should be further investigated for more practical applications. (continued on next page)

Fig 1. The half electrochemical cell configuration and cathode detailed design.

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Santoro

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(a)

Acknowledgments The author thanks ECS for funding the summer fellowship as well as Plamen Atanassov, Sofia Babanova and Baikun Li for their extraordinary guidance through the entire project that has been helpful for achieving important results and open new interesting scientific explorations and scenarios.

About the Author

(b)

Carlo Santoro is a PhD candidate in the Department of Civil and Environmental Engineering at the University of Connecticut. He is pursuing his degree under the guidance of Baikun Li in the School of Engineering. His thesis concentrates on the optimization of the cathode in microbial fuel cells and particularly the improvement of the cathode structure, the decrease of catalyst loading, and the study of platinum-free cathodes (e.g. biocathodes and enzymatic-based cathodes). He may be reached at carlo.santoro830@ gmail.com.

References

Fig. 2. The trend of OCP and current density during a 12-day test period (a). The changes of polarization curves during a 12-day test (b). (Solid line indicates the PBS solution, and broken line indicates the presence of bacteria in the PBS/AS solution).

1. A. Rinaldi, B. Mecheri, V. Garavaglia, S. Licoccia, P. Di Nardo, and E. Traversa, Energy Environ. Sci., 1, 417 (2008). 2. P. Atanassov, C. Apblett, S. Banta, S. Brozik, S. Calabrese Barton, M. Cooney, B. Yann Liaw, S. Mukerjee, and S. D. Minteer, Electrochem. Soc. Interface, 16, 28 (2007). 3. S. Babanova, K. Artyushkova, Y. Ulyanova, S. Singhal, and P. Atanassov, J. Power Sources, 245, 389 (2014). 4. C. Santoro, A. Stadlhofer, V. Hacker, G. Squadrito, U. SchroĚ&#x2C6;der, and B. Li, J. Power Sources, 243, 499 (2013). 5. C. Santoro, S. Babanova, P. Atanassov, B. Li, I. Ieropoulos, and P. Cristiani, J. Electrochem. Soc., 160, H720 (2013).

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The 2013 H. H. Uhlig Summer Research Fellowship – Summary Report Temperature-dependent Electrodeposition of Crystalline Si Prepared by an Electrochemical Liquid-Liquid-Solid Growth Process

rystalline group IV semiconductor materials are essential components in microelectronics, solar cells, and sensor applications.1 Conventional largescale production of crystalline Si relies on energy-demanding processes necessary to chemically reduce precursors at elevated temperatures.2 Exploration of alternative non-energy-intensive synthetic methods is thus critical to reduce the massive energy input in the currently available production strategies. Electrochemical deposition provides a scalable, easy-to-access option for producing semiconductor materials. Reports have demonstrated the utilization of electrodeposition in preparation of group IV semiconductors from molten salts3 or non-aqueous solvents,4 yet the challenges remain due to high crystallization barriers of covalent semiconductors to yield crystalline group IV semiconductor as-deposited at low temperature.5 Our group has recently demonstrated an electrochemical liquid-liquid-solid (ecLLS) process to electrochemically deposit crystalline Si nanocrystals under benchtop conditions at temperatures compatible with aqueous and organic solvents.6 As depicted in Fig 1a, the key innovation in

by Junsi Gu our strategy involves the use of liquid Ga electrodes functioning both as conventional cathodes and crystallization solvents for crystal growth. In our approach, elemental Si is first electrochemically reduced from its high-valence precursor SiCl4 at the liquid Ga surface, followed by dissolution into the liquid metal to form a Si-Ga alloy. Continuous reduction and dissolution cause the alloy to reach supersaturation, leading to phase segregation that yields Si nano-crystals. In such a process, the temperature dictates both the nucleation and crystal growth steps by affecting the alloy saturation point and crystal growth kinetics. This report will test the hypothesis that growth temperature has a primary influence on crystallite size and deposit morphology. Figure 1b shows the cyclic voltammetric response of Ga(l) electrodes at room temperature in a propylene carbonate (PC) solution of 0.05 M SiCl4 and 0.2 M tetrabutylammonium chloride (TBAC), highlighting the cathodic wave that indicates the reduction of SiCl4 at -2.0 V vs. Pt quasireference electrode (QRE) before the onset of solvent decomposition at ca. -3.2 V. No such feature was observed with the absence of dissolved SiCl4.

Temperature-dependent electrodeposition was carried out potentiostatically at -2.5 V vs. Pt QRE at 120, 140, and 160 °C, respectively in the PC solution of 0.05 M SiCl4 and 0.2 M TBAC. For Si deposits obtained at 120 and 140 °C, the scanning electron micrographs (Fig. 2a, 2b) show that the morphology was dominated by faceted nanocrystals, indicating the crystalline nature of the product. Statistics analysis (N = 50) of the crystal sizes (Fig. 2c) reveals an increase in the average crystal size from 0.25 to 0.36 μm2 and broadening in the distribution as the growth temperature increases. Further increase in the growth temperature to 160 °C results in the emergence of high-aspect-ratio morphology (Fig. 2d). Elemental analysis based on energy dispersive X-ray spectroscopy (Fig. 2e) indicates the deposit contains primarily Si with a small contribution from Ga and O. The results collectively indicate that growth temperature influences not only the crystallite size but also the deposit morphology. Further study is required to understand the driving forces for different growth morphology to provide better control of the products through ec-LLS. (continued on next page)

Fig. 1. (a) Schematic depiction of the electrochemical liquid-liquid-solid process. (b) Cyclic voltammetric response of liquid Ga electrodes at room temperature in a propylene carbonate solution containing 0.2 M tetrabutylammonium chloride with (red) and without (black) dissolved 0.05 M SiCl4.

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Fig. 2. Scanning electron micrograph of Si prepared by ec-LLS process at (a) 120 °C and (b) 140 °C. (c) Histogram showing size distribution of Si crystallites observed in (a) and (b). (d) Scanning electron micrograph of Si prepared by ec-LLS process at 160 °C. (e) Energy dispersive X-ray spectrum of the deposits observed in (d). All electrodeposition was performed in a propylene carbonate solution containing 0.2 M tetrabutylammonium chloride and 0.05 M SiCl4 at -2.5 V vs. Pt QRE for 1 hr. Scale bar: 2 μm.

Acknowledgments

About the Author

References

The author sincerely thanks the financial support from the ECS Summer Fellowship and the guidance of Stephen Maldonado. Additional support provided by American Chemical Society Petroleum Research Fund (51339-DNI5) is also gratefully acknowledged. The FEI Nova SEM instrument used in this work is maintained by University of Michigan Electron Microbeam Analysis Laboratory through NSF grant (DMR-0320740).

Junsi Gu is a PhD student in the Chemistry Department at University of Michigan under the supervision of Stephen Maldonado. Gu focuses on the development of low temperature electrodeposition methods for preparing crystalline semiconductor nanomaterials. He may be reached at junsigu@umich.edu.

1. K.-Q. Peng and S.-T. Lee, Adv. Mater., 23, 198 (2011). 2. C. S. Tao, J. Jiang, and M. Tao, Sol. Energy Mater., 95, 3176 (2011). 3. S. K. Cho, F.-R. F. Fan, and A. J. Bard, Angew. Chem., Int. Ed., 51, 12740 (2012). 4. Y. Nishimura and Y. Fukunaka, Electrochim. Acta, 53, 111 (2007). 5. U. Köster, Physica Status Solidi (A), 48, 313 (1978). 6. J. Gu, E. Fahrenkrug, and S. Maldonado, J. Am. Chem. Soc., 135, 1684 (2013).

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San Francisco Student Poster Session Award Winners

ECS President Tetsuya Osaka presented awards to the winners of the Student Poster Session competition. From left to right are: Kelsey Hatzall (First Place, Electrochemical Science & Technology, Poster #107); Kristy Jost (First Place, Solid State Science & Technology, Poster #53); Vimal Chaitanya (organizer); Tobias Placke, Paul Meister, and Sergej Rothermel (Second Place, Electrochemical Science & Technology, Poster #11); Kalpathy Sundaram (organizer); ECS President Tetsuya Osaka; Takashi Suda (Second Place, Solid State Science & Technology, Poster #14); Olga Fromm (Second Place, Electrochemical Science & Technology, Poster #11); Oana Leonte (judge); and Raluca Stefan-van Staden (judge).

he Society’s general Student Poster Session in San Francisco received 148 submissions, giving the organizers and judges a full evening’s work. After all the reviewing and scoring was completed, the following were announced as the winning posters. Applied Materials (www.appliedmaterials.com/) very generously provided the cash prizes that were presented along with the award certificates. First Place – Electrochemistry, Poster #107: “Optimization of Flowable Electrodes for Electrochemical Flow Capacitors,” by Mohammed Boota, Kelsey B. Hatzall, and Christopher R. Dennison, all from Drexel University. Second Place, Electrochemical Science & Technology, Poster #11: “X-ray Diffraction Studies of the Electrochemical Interaction of Bis(trifluoromethanesulfonyl) Imide Anions into Graphite,” by Tobias Placke, Guido Schmuelling, Richard Kloepsch, Olga Fromm, Sergej Rothermel, and Paul Meister, all from MEET Battery Research Center, University of Muenster. First Place, Solid State Science & Technology, Poster #53: “Knitted Electrochemical Capacitors for Applications in Smart Garments,” by Kristy Jost and John McDonough, both from Drexel University. Second Place, Solid State Science & Technology, Poster #14: “Synthesis of Intermetallic Nanoparticles as Co-Catalyst on Anatase TiO2 and Its Photocatalytic Activity,” by Takashi Tsuda and Masanari Hashimoto, both from Kanagawa University.

The Electrochemical Society Interface • Winter 2013

The Society cannot run the General Student Poster Session without the hard work of the organizers. In San Francisco, Venkat Subramanian, Vimal Chaitanya, Kalpathy Sundaram, Matt Foley, and Pallavi Pharkaya, all contributed their time and energy to making the session a success. The session also requires the intense efforts of the judges, which, in San Francisco included Candace Chan, Paul Gannon, Frederic Hasche, Wesley Henderson, Andy Herring, Peter Hesketh, Durst Julien, Oana Leonte, Torsen Markus, Stefeno Meini, Yaw Obeng, Elizabeth Podlaha Murphy, Alice Suroviec, EJ Taylor, Raul van Staden, Philippe Vereecken, and Yang Chaun Xing.

Arizona State University Student Chapter The Arizona State University Student Chapter Members (ECS@ASU) have had a busy summer and fall, since its founding in May 2013. Members promoted the chapter at a welcome event, held their first general meeting, visited a museum, and started a monthly journal club, where each member provides a technical review and contributes to the lively discussion. The Chapter conducted a community outreach program on October 5. The program was presented at the Teleos Preparatory Academy in the Eastlake Park Neighborhood in Phoenix, Arizona. The program is an original design and was funded by the Ironmen Network of the Pilgrim Rest Campus and ebike sponsorship by The Battery Bike Co.

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ECS@ASU Officers (from left to right) are William Bowman, Community Outreach Coordinator; Iolanda Klein, Secretary; Tylan Watkins, Recruitment Coordinator; and Telpriore “Greg” Tucker, President— all preparing for the Chapter’s first Community Outreach Program.

The outreach program focused on the fundamental chemistries of emerging renewable energy sources and identification of known fossil fuels. The call-and-response presentation compared/ contrasted these energy sources areas of electrochemical processes, thermodynamic efficiencies, electricity production, devices, U.S. energy consumption, anthropogenic pollution, household usage, local companies, recent news events, important persons in history, careers in chemistry, and more. Supplemental video animations of solar power and battery function were featured and a survey was taken by the students. In the Solar Module, the group leader explained the concept of photovoltaics to the students. They exposed the amorphous silicon solar cells to direct sunlight and measured the open circuit potential with a multi-meter. Afterward they arranged the solar panel sets into a series circuit and sought the optimal angle to produce enough voltage to power an LED light bulb. The students were able to examine large outdoor 45W solar panels in application of recharging a 12V lead-acid battery.

Candace Chan, Graduate Advisor and Chair of the local professional chapter, the Arizona Section, opened the first general meeting of the ECS@ASU.

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Fellow ASU Student Chapter members had a chance to take a well-deserved break from their research and the lab. They visited the latest exhibit, “The Art of Video Gaming,” at the Phoenix Art Museum during First Friday Artwalk in midtown Phoenix, AZ.

Later they learned the how dc voltage was transferred to an inverter to create ac electricity for a standard household 110V outlet or a charger USB outlet. In the Battery Module, students learned about the concept of electrochemical redox properties of everyday common materials for an experiment. They put zinc-coated screws (anodic electrodes) and copper pennies (cathodic electrodes) into lemons and limes (acidic electrolytes). They used alligator clips to connect these newly-made battery cells in serial and parallel circuit arrangements, which they measured the difference in voltage with a multi-meter. Lastly, the students compared the measured potentials of their semi-organic cells to standard 9V, AA, AAA, and coin cell batteries. In the Ebike Module, the group leader explained the electrochemical processes of lead-acid and Li-ion battery systems for everyday devices. Electrical bikes (ebikes) are a form of green transportation and are now considered a disruptive technology. The ebikes used in the session enabled the students to experience a real world application and provided a little more fun to the already excitement-filled day. (continued on next page)

ECS@ASU Members and the Ironmen Network, Life Coaches, at the Chapter’s 2013 Outreach Program.

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Students from the Teleos Preparatory Academy learned about photovoltaics at the ECS@ASU Chapter’s outreach program.

The Teleos Preparatory Academy students learned about batteries at the ECS@ASU Chapter’s outreach program.

ECS@ASU Chapter’s closed out their outreach program with a fun ride on some ebikes. 96

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t ST ech UDENT highligh NE WS ts Montréal Student Chapter The 3rd ECS Montréal Student Symposium took place on June 28 at Université du Québec à Montréal (UQÀM) in collaboration with UQÀM and the NanoQAM research center. Following the 2nd Symposium, the Montréal ECS Student Chapter continued its success and reached more than 70 participants from five universities in Montréal and Québec City, as well as a national research center. The attendees enjoyed 16 talks and 17 posters, including the two invited presentations of Mario Leclerc (Laval University) and Karim Zaghib (Hydro-Québec Research Institute IREQ). Prof. Leclerc’s talk, entitled “Plastic Solar Cells,” summarized the major breakthroughs of his research in the past years toward the development of polymers for light harvesting applications. This was followed by the talk of Dr. Zaghib, entitled “Li-Ion and Beyond Li-Ion for Energy Storage: Challenges and Opportunities,” which discussed the research progresses at the Hydro-Québec Research Institute related to safety and characterization of different materials employed in Li-ion batteries. Prizes for the best oral and best poster presentations were awarded to David Polcari from McGill University for his talk on “Quantification of Multidrug Resistance in Human Cancer Cells Using Scanning Electrochemical Microscopy” and Mary Hanna from Université du Québec à Montréal for her poster on the “Colloidal Synthesis and Characterization of Cu1.0(In1.05-x,Alx)S2.1 Semiconducting Particles.” Further information about the ECS Montréal Student Chapter can be found at http://ecsmontreal.blogspot.com or visit us on Facebook.

Students in discussions during the poster session of the Montréal Student Chapter’s 3rd symposium.

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The 3rd ECS Montréal Student Symposium of the Montréal Student Chapter attracted more than 70 students and staff from Montréal and Québec universities and research centers.

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The Electrochemical Society Interface • Winter 2013

Netzsch Instruments................................................... 30 Ohio State University..................................................81 Princeton Applied Research.................................... 1, 6 Scribner Associates Inc.............................................. 28 Solartron Analytical/Ametek............ inside back cover Texas A&M University.............................................. 27

t ST ech UDENT highligh NE WS ts University of Texas at Austin Student Chapter The ECS Student Chapter at the University of Texas at Austin (UTAustin) was first established in 2007. Since then, the organization has carried out its mission of providing an environment where students over a wide range of academic disciplines can network and discuss their research in electrochemistry and solidstate sciences. The current officers are Josephine Cunningham (President), Donald Robinson (Vice-President), Daniel Redman (Treasurer), and Matthew Beaudry (Secretary). The faculty adviser is Arumugam Manthiram. The Chapter presently has 17 registered student members from the Cockrell School of Engineering and the College of Natural Sciences at UT. Additionally, many unregistered students and faculty members participate in activities held by the Chapter. The Chapter introduced a new type of event this year, the ECS Student Chalk Talk series. A chalk talk is a casual chalkboard presentation whereby audience members are encouraged to participate and interrupt the speaker at any time with questions to stimulate discussion about the research topic. The host of the talk is a graduate student who leads the discussion based on his/ her research. The first Chalk Talk featured Jacob Goran, a PhD candidate from the UT chemistry department, who presented his research in bioelectrochemistry on nitrogendoped carbon nanotubes.

The Chapter held a second Chalk Talk this summer presented by William Hardin, a PhD candidate in the materials science program. Hardin presented his research on platinum-free electrocatalysts for oxygen reduction and oxygen evolution. Due to the success and popularity of these interactive presentations, the Chapter has decided to

adopt multiple Student Chalk Talks into its yearly activities and further implement them as a means to showcase the work of exceptional graduate students and recruit more ECS members. The Chapter was fortunate to have Guihua Yu, a new assistant professor in the mechanical engineering department at

The UT-Austin Student Chapter officers with Will Hardin after the summer 2013 Student Chalk Talk. From left to right are Daniel Redman, Donald Robinson, Will Hardin, Matthew Beaudry, and Josephine Cunningham.

The UT-Austin Student Chapter hosted a Student Chalk Talk, given by PhD candidate Will Hardin on platinum-free electrocatalysts for oxygen reduction and evolution. 98

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UT, as the presenter for the summer faculty seminar. Dr. Yu presented his research on investigating nanostructured conductive polymer hydrogels as electrode materials for electrochemical capacitors and as anode material supports for lithium ion batteries. The Chapter continues to grow in membership and is currently planning next year’s seminars and chalk talks along with outreach activities for science education. More information about the ECS Student Chapter at the University of Texas at Austin can be found at utelectrochem.org.

The UT-Austin Student Chapter officers and presenter, Dr. Yu. From left to right: Matthew Beaudry, Daniel Redman, Donald Robinson, and Guihua Yu.

Students on the

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 The Electrochemical Society Interface • Winter 2013

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Student Awards

For details on each award— including a list of requirements for award nominees, and in some cases, a downloadable application form—please go to the ECS website (www. electrochem.org) and click on the “Awards” link. Awards are grouped in the following sub-categories: Society Awards, ECS Division Awards, Student Awards, and ECS Section Awards. Please see the individual award call for information about where nomination materials should be sent; or contact ECS headquarters.

Call for Nominations Visit

www.electrochem.org and click on the “Awards” link.

The ECS Summer Fellowships were established in 1928 to assist students during the summer months in pursuit of work in the field of interest to ECS. The next fellowships will be presented in 2013. Nominations and supporting documents should be sent to ECS Summer Fellowships, c/o ECS, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; e-mail: awards@ electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by January 15, 2014. The Student Research Award of the Battery Division was established in 1962 to recognize promising young engineers and scientists in the field of electrochemical power sources and consists of a scroll, a prize of $1,000, waiver for the meeting registration, travel assistance to the meeting if required, and membership in the Battery Division as long as a Society member. The next award will be presented at the ECS fall meeting in Cancun, Mexico, October 5-10, 2014. Nominations and supporting documents should be sent to Battery Student Award, c/o ECS, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; e-mail: awards@electrochem. org. Electronic submission of nomination packets is preferred. Materials are due by March 15, 2014. The Canada Section Student Award was established in 1987 for a student pursuing, at a Canadian University, an advanced degree in any area of science or engineering in which electrochemistry is the central consideration. The award consists of consists of a monetary award determined by the Section Executive Committee not to exceed $1,500 (U.S.). The next award will be presented at a meeting of the Canada Section in 2014. Nominations and supporting documents should be sent to Canada Section Student Award, c/o ECS, 65 S. Main Street, Building D, Pennington, NJ 08534, USA; tel: 1.609.737.1902; e-mail: awards@ electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by February 28, 2014. 100

Student Travel Grants Several of the Society’s Divisions offer travel assistance to students and young faculty members presenting papers at ECS meetings. For details about travel grants for the 225th ECS meeting in Orlando, Florida, USA, please see the Orlando, Florida, Call for Papers; or visit the ECS website: www. electrochem.org/student/travelgrants.htm. Please be sure to click on the link for the appropriate Division as each Division requires different materials for travel grant approval. Complete the online application (preferred) or download the PDF application and send to travelgrant@electrochem.org, indicating of which Division a travel grant is being requested. The deadline for submission for the spring 2014 travel grants is January 1, 2014.

Awarded Student Memberships Available ECS Divisions are offering 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). Postdoctoral students are not eligible. Awarded memberships are renewable for up to four years; applicants must reapply each year. Memberships include article pack access to the ECS Digital Library, and a subscription to Interface. To apply for an Awarded Student Membership, use the application form on the next page or refer to the ECS website at: www.electrochem.org/ awards/student/student_awards.htm#a.

The Electrochemical Society Interface • Winter 2013

tech ST UDENT highlights NE WSApplication Awarded Student Membership

ECS Divisions are offering Awarded Student Memberships to qualified full-time students. To be eligible, students must be in their final two years of an undergraduate program or be enrolled in a graduate program in science, engineering, or education (with a science or engineering degree). Postdoctoral students are not eligible. Awarded memberships are renewable for up to four years; applicants must reapply each year. Memberships include article pack access to the ECS Digital Library and a subscription to Interface.

Divisions (please select only one):

Personal Information Name:

________________________________________________________ Date of Birth:__________________

Home Address:

_______________________________________________________________________________________

 Battery  Corrosion  Dielectric Science & Technology  Electrodeposition  Electronics and Photonics  Energy Technology  High Temperature Materials

Phone:____________________________________ Fax:________________________________________

 Industrial Electrochemistry & Electrochemical Engineering  Luminescence & Display Materials

Email:__________________________________________________________________________________

 Nanocarbons  Organic & Biological Electrochemistry

School Information School:

_______________________________________________________________________________________

(please include Division and Department)

Address:

_______________________________________________________________________________________

Undergraduate Year (U) or Graduate Year (G) - circle one:

Major Subject:

__________________________ Grade Point Average: _______________ out of possible:

Have you ever won this award before?

YES

 Physical and Analytical Electrochemistry  Sensor

If yes, how many times?______

Signatures

Student Signature: _____________________________________________________________________________

Date:

Faculty member attesting to eligibility of full time student:

Faculty Member: ___________________________________________________________ Dept.: ______________________________________________________

E-mail Address:

_____________________________________________________________________________

The Electrochemical Society Interface • Winter 2013

Date: _________________________________

101

Volumes 32, 34, 37, 39, 40, 42, 43, 44, 46, 47, 49, 51, 52, 54, 57 from ECS Co-Sponsored Meetings

The following issues of ECS Transactions are from conferences co-sponsored by ECS. All issues are available in electronic (PDF) editions, which may be purchased by visiting http://ecsdl.org/ECST/. Some issues are also available in hard-cover, soft-cover, or CD-ROM 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 Volumes Volume 57

Solid Oxide Fuel Cells 13 (SOFC-XIII) Okinawa, Japan, October 6 - 11, 2013 Vol. 57 Solid Oxide Fuel Cells 13 (SOFC-XIII) No. 1 CD-ROM...............................M $215.00, NM $269.00 PDF.......................................M $195.59, NM $244.49

Volume 54

2013 International Conference on Semiconductor Technology for Ultra Large Scale Integrated Circuits and Thin Film Transistors Villard-de-Lans, France, July 7 - 12, 2013 Vol. 54 2013 International Conference on Semiconductor Technology No. 1 for Ultra Large Scale Integrated Circuits and Thin Film Transistors (ULSIC vs. TFT 4) Soft-cover.............................M $98.00, NM $122.00 PDF.......................................M $88.87, NM $111.09

Volume 52

China Semiconductor Technology International Conference 2013 (CSTIC 2013) Shanghai, China, March 19 - 21, 2013 Vol. 52 China Semiconductor Technology International Conference No. 1 2013 (CSTIC 2013) Soft-cover.............................M $205.00, NM $256.00 PDF.......................................M $186.06, NM $232.57

Volume 51

2012 Fuel Cell Seminar & Exposition Uncasville, Connecticut, November 5 - 8, 2012 Vol. 51 Fuel Cell Seminar 2012 No. 1 Soft-cover.............................M $92.00, NM $117.00 PDF.......................................M $79.67, NM $99.59

Volume 49

27th Symposium on Microelectronic Technology and Devices Brasília, Brazil, August 30 - September 2, 2012 Vol. 49 Microelectronics Technology and Devices - SBMicro 2012 No. 1 Hard-cover...........................M $146.00, NM $183.00 PDF......................................M $132.78, NM $165.97

Volume 47

China Semiconductor Technology International Conference 2012 (CSTIC 2012) Shanghai, China, March 18 - 19, 2012 Vol. 47 China Semiconductor Technology International Conference No. 1 2012 (CSTIC 2012) Soft-cover.............................M $212.00, NM $265.00 PDF.......................................M $192.39, NM $240.49

Volume 46

Proceedings of the Workshop on Knudsen Effusion Mass Spectrometry Juelich, Germany, April 23 - 25, 2012 Vol. 46 18º Simpósio Brasileiro de Eletroquímica e No. 1 Eletroanalítica (XVIII SIBEE) Hard-cover...........................M $88.00, NM $110.00 PDF......................................M $75.66, NM $94.57

Volume 44

China Semiconductor Technology International Conference 2012 (CSTIC 2012) Shanghai, China, March 18 - 19, 2012 Vol. 44 China Semiconductor Technology International Conference No. 1 2012 (CSTIC 2012) Soft-cover.............................M $212.00, NM $265.00 PDF.......................................M $192.39, NM $240.49

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Volume 43

XVIII Simposio Brasileiro de Electroquimica e Eletroanalitica Bento, Gonçalves, Brazil,August 28 - September 1 , 2011 Vol. 43 18º Simpósio Brasileiro de Eletroquímica e No. 1 Eletroanalítica (XVIII SIBEE) Soft-cover.............................M $127.00, NM $159.00 PDF.......................................M $115.29, NM $144.11

Volume 42

2010 Fuel Cell Seminar & Exposition Orlando, Florida, October 31 - November 3, 2011 Vol. 42 Fuel Cell Seminar 2010 No. 1 Soft-cover.............................M $100.00, NM $125.00 PDF.......................................M $90.60, NM $113.25

Volume 40

Advanced Batteries, Accumulators and Fuel Cells (ABAF 12) Brno, Czech Republic, September 11 - 24, 2011 Vol. 40 Advanced Batteries, Accumulators and Fuel Cells (ABAF 12) No. 1 Soft-cover.............................M $98.00, NM $122.00 PDF.......................................M $88.87, NM $111.09

Volume 39

26th Symposium on Microelectronics Technology and Devices Joao Pessoa, Brazil, August 30 - September 2, 2011 Vol. 39 Microelectronics Technology and Devices - SBMicro 2011 No. 1 Hard-cover............................M $138.00, NM $173.00 PDF.......................................M $125.58, NM $156.98

Volume 37

Semiconductor Technology for Ultra Large Scale Integrated Circuits and Thin Film Transistors III Hong Kong, China, June 26 - July 1, 2011 Vol. 37 2011 International Conference on Semiconductor No. 1 Technology for Ultra Large Scale Integrated Circuits and Thin Film Transistors (ULSIC vs. TFT) Soft-cover............................M $88.00, NM $110.00 PDF......................................M $75.66, NM $94.57

Volume 34

China Semiconductor Technology International Conference 2011 (CSTIC 2011) Shanghai, China, March 13 - 14, 2011 Vol. 34 China Semiconductor Technology International Conference No. 1 2011 (CSTIC 2011) Soft-cover............................M $212.00, NM $265.00 PDF......................................M $192.39, NM $240.49

Volume 32

Advanced Batteries, Accumulators and Fuel Cells (ABAF 11) Brno, Czech Republic, September 19 - 23, 2010 Vol. 32 Advanced Batteries, Accumulators and Fuel Cells (ABAF 11) No. 1 Soft-cover............................M $92.00, NM $115.00 PDF......................................M $79.67, NM $99.59

Ordering Information To order any of these recently-published titles, please visit the ECS Digital Library, http://ecsdl.org/ECST/ Email: customerservice@electrochem.org 10/25/13

The Electrochemical Society Interface • Winter 2013

2014 ECS and SMEQ Joint International Meeting

226th Meeting of The Electrochemical Society

XXIX Congreso de la Sociedad Mexicana de Electroquímica

7th Meeting of the Mexico Section of The Electrochemical Society

Call for

Papers CANCUN

Mexico October 5-10, 2014 Moon Palace Resort

The Electrochemical Society Interface • Winter 2013

103

2014 ECS and SMEQ Joint International Meeting

CANCUN, Mexico

October 5-10, 2014

For the full Cancun, Mexico, Call for Papers, see the ECS website: www.electrochem.org/meetings/biannual/226/. General Information

he 2014 ECS and SMEQ (Sociedad Mexicana de Electroquímica) Joint International Meeting with the will be held from October 5-10, 2014. This major international conference offers a unique blend of electrochemical and solid-state science and technology; and serves as a major forum for the discussion of interdisciplinary research from around the world through a variety of formats, such as oral presentations, poster sessions, exhibits, and tutorial sessions.

Abstract Submission and Deadlines Abstracts are due no later than March 28, 2014. Note: Some abstracts may be due earlier than March 28, 2014. Please carefully check the symposium listings for any alternate abstract submission deadlines. For complete details on abstract submission and symposia topics, please see www.electrochem.org. Submit one original meeting abstract electronically via www.electrochem. org, no later than March 28, 2014. Faxed abstracts, e-mailed abstracts, and late abstracts will not be accepted. In June 2014, all presenting authors will receive an e-mail from ECS headquarters office notifying them of the date, time, and location of their presentation. Only presenting authors with nonU.S. addresses will receive a hardcopy acceptance letter. Other hardcopy letters will be sent only upon request to abstracts@electrochem.org. Meeting abstracts should explicitly state objectives, new results, and conclusions or significance of the work. Regardless of whether you submit as a poster or an oral presentation, it is at the Symposium Organizers’ discretion whether it is scheduled for an oral or poster presentation. Programming for this meeting will occur in April-May 2014. Check the ECS website for further program details.

Paper Presentation

All authors selected for either oral or poster presentations will be notified in June 2014. Oral presentations must be in English. Both LCD projectors and laptops will be provided for oral presentations. Presenting authors MUST bring their presentation on a USB flash drive to be used with the laptop that will be provided in each technical session room. If a presenting author would like to use his/her own laptop for presentation, we strongly suggest that the author verify laptop/projector compatibility in the presentation room prior to the start of the session or all other presentations. Speakers requiring additional equipment must make written request to the ECS headquarters office at least one month prior to the meeting and appropriate arrangements will be worked out, subject to availability, and at the expense of the author. Poster presentations should be displayed in English, on a board approximately 3 feet 10 inches high by 3 feet 10 inches wide (1.17 meters high by 1.17 meters wide), corresponding to the abstract number and day of presentation in the final program.

Manuscript Publication

ECS Meeting Abstracts—All meeting abstracts will be published on the ECS website, copyrighted by ECS, and all abstracts become the property of ECS upon presentation. ECS Transactions—all full papers presented at ECS meetings are eligible for submission to the online proceedings publication, ECS Transactions (ECST). Each meeting is represented by a “volume” of ECST, and each symposium is represented by an “issue.” Some symposia will publish their issue to be available for sale “AT” the meeting. Please see each individual symposium listing in this Call for Papers to determine if there will be an “AT” meeting issue. In the case of “AT” meeting symposia, submission to ECST is mandatory, and required in advance of the meeting. Some symposia will publish their issue to be available “AFTER” the meeting, and all authors are encouraged to submit their full papers. To determine acceptance in ECST, all submitted manuscripts will be reviewed, either by the symposium organizers or by the ECST Editorial Board. After the meeting, all accepted papers in ECST will be available for sale, either individually, or by issue. Please visit the ECST website (ecsdl.org/ECST/) for additional information, including overall guidelines, deadlines for submissions and reviews, author and editor instructions, a manuscript template, and much more. Authors presenting papers at ECS meetings, and submitting to ECST, are encouraged to submit to the Society’s technical journals: the Journal of The Electrochemical Society, ECS Journal of Solid State Science and Technology, ECS Electrochemistry Letters, or ECS Solid State Letters. Although there is no hard deadline for the submission of these papers, it is considered that six 104

months from the date of the symposium is sufficient time to revise a paper to meet the stricter deadlines of the journals. “Instructions to Authors” are available from the ECS headquarters office, the journals, or the ECS website. If publication is desired elsewhere after presentation, written permission from ECS is required.

Financial Assistance

Financial assistance is very limited and generally governed by the symposium organizers. Individuals may inquire directly to the symposium organizers of the symposium in which they are presenting their paper to see if funding is available.

Letter of Invitation

Individuals requiring an official letter of invitation should write to the ECS headquarters office; such letters will not imply any financial responsibility of ECS. Students seeking financial assistance should consider awarded travel grants listed elsewhere in this Call for Papers.

Hotel Reservations l Deadline September 5, 2014

The 2014 ECS and SMEQ Joint International Meeting will be held at the allinclusive Moon Palace Resort, Carretera Cancun-Chetumal Km. 340, Cancun, Quintana Roo, CP. 77500, Mexico. Please refer to the meeting website for the most up-to-date information on hotel availability and information about the block of rooms where special rates have been reserved for participants attending the meeting. The hotel reservation deadline is September 5, 2014. Please refer to the ECS website (www.electrochem.org) for rates and reservations.

Meeting Registration

All participants—including authors and invited speakers—are required to pay the appropriate registration fees. Hotel and meeting registration information will be posted on the ECS website (www.electrochem.org) as it becomes available. The deadline for discounted early-bird registration is September 5, 2014.

Short Courses

A number of short courses will be offered on Sunday, October 5, 2014 from 8:30 AM-4:30 PM. Short Courses require advance registration and may be cancelled if enrollments are too low. As of press time, the following Short Courses are planned for the meeting: Basic Impedance Spectroscopy; Fundamentals of Electrochemistry: Basic Theory and Thermodynamic Methods; Grid Scale Energy Storage; and More than Moore Technologies: Device, Circuit, and System Perspectives. Please check the ECS website for the final list of offerings.

Technical Exhibit

The 2014 ECS and SMEQ Joint International Meeting will also include a Technical Exhibit, featuring presentations and displays by over 40 manufacturers of instruments, materials, systems, publications, and software of interest to meeting attendees. Coffee breaks are scheduled in the exhibit hall along with evening poster sessions. Please see the ECS website for further details.

Sponsorship Opportunities

ECS biannual meetings offer a wonderful opportunity to market your organization through sponsorship. Sponsorship opportunities include unparalleled benefits and provide an extraordinary chance to present scientific products and services to key constituents from around the world. Sponsorship allows exposure to key industry decision makers, the development of collaborative partnerships, and potential business leads. ECS welcomes support in the form of general sponsorship at various levels: Platinum: $10,000+, Gold: $5,000, Silver: $3,000, and Bronze: $1,500. Sponsors will be recognized by level in Interface, the Meeting Program, meeting signage, on the ECS website, and in the mobile app. In addition, sponsorships are available for the plenary and keynote talks and other special events. These opportunities include additional recognition, and may be customized to create personalized packages. Special event sponsorships will be assigned by the Society on a first-come, first served basis. Advertising opportunities—in the Meeting Program as well as in Interface—are also available. Please contact Christie Knef at 1.609.737.1902, ext. 121, or see the ECS website for further details.

Contact Information

If you have any questions or require additional information, contact ECS, 65 South Main Street, Pennington, New Jersey, 08534-2839, USA, tel: 1.609.737.1902, fax: 1.609.737.2743, e-mail: meetings@electrochem.org; Web: www.electrochem.org. The Electrochemical Society Interface • Winter 2013

2014 ECS and SMEQ Joint International Meeting

CANCUN, Mexico

October 5-10, 2014

Symposium Topics A — Batteries and Energy Storage

H4 — Electrode Processes 9

A1 — Batteries and Energy Technology Joint General Session

H5 — Liquid–Liquid Electrochemical Interfaces

A2 — Batteries Beyond Lithium Ion

H6 — Molten Salts and Ionic Liquids 19

A3 — Electrochemical Capacitors: Fundamentals to Applications

H7 — Oxygen Reduction Reactions

A4 — Electrochemical Interfaces in Energy Storage Systems

H8 — Systems Electrochemistry

A5 — Lithium-Ion Batteries A6 — Nano-architectures for Next-Generation Energy Storage Technologies A7 — Nonaqueous Electrolytes A8 — Solar Fuels and Photocatalysts 4 A9 — Stationary and Large-Scale Electrical Energy Storage Systems 4 B — Chemical and Biological Sensors

M — Carbon Nanostructures and Devices M1— Nanocarbon Fundamentals and Applications: From Fullerenes to Graphene N — Dielectric Science and Materials N1 — Thermal and Plasma CVD of Nanostructures and Their Applications P — Electronic Materials and Processing P1 — Atomic Layer Deposition Applications 10

B1 — Chemical Sensors 11. Chemical and Biological Sensors and Analytical Systems

P2 — Electrochemistry in Organic Electronic Materials: Synthesis, Analysis, and Applications

B2 — Microfabricated and Nanofabricated Systems for MEMS/NEMS 11 (Chemical and Biological Sensors)

P3 — High Purity and High Mobility Semiconductors 13

C — Corrosion Science and Technology

P4 — Plasma Processing 20

C1 — Corrosion General Session

P5 — Processing Materials of 3D Interconnects, Damascene, and Electronics Packaging 6

C2 — Electrochemical Techniques and Corrosion Monitoring

P6 — Semiconductor Wafer Bonding 13: Science, Technology, and Applications

C3 — High Resolution Characterization of Corrosion Processes 4

P7 — SiGe, Ge, and Related Compounds: Materials, Processing, and Devices 6

C4 — High Temperature Corrosion

P8 — Thermoelectric and Thermal Interface Materials

D — Electrochemical/Electroless Deposition D1 — Electrodeposition for Energy Applications 3 D2 — Electrochemical Science and Technology: Challenges and Opportunities in the Path from Invention to Product D3 — Magnetic Materials, Processes, and Devices 13 D4 — Surface Treatments for Biomedical Applications 4 E — Electrochemical Engineering E1 — Characterization of Electrochemical Reactors: Fluid Dynamics and Current Distribution

P9 — Transparent Conducting Materials for Electronic and Photonics Q — Electronic and Photonic Devices and Systems Q1 — Emerging Nanomaterials and Devices Q2 — Fundamentals and Applications of Microfluidic and Nanofluidic Devices 2 Q3 — GaN and SiC Power Technologies 4 Q4 — Low-Dimensional Nanoscale Electronic and Photonic Devices 7 Q5 — Nonvolatile Memories Q6 — Photovoltaics for the 21st Century 10

E2 — Electrochemical Treatments for Organic Pollutant Degradation in Water and Soils

Q7 — Semiconductors, Dielectrics, and Metals for Nanoelectronics 12

E3 — Symposium in Honor of Professor Ralph E. White

Q9 — State-of-the-Art Program on Compound Semiconductors 56 (SOTAPOCS 56)

F — Fuel Cells, Electrolyzers, and Energy Conversion F1 — Thermal Energy Harvesting F2 — Solid State Ionic Devices 10 F3 — Polymer Electrolyte Fuel Cells 14 (PEFC 14) G — Organic and Bioelectrochemistry G1 — Bioelectroanalysis and Bioelectrocatalysis 2 H — Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry

Q8 — Solid-State Electronics and Photonics in Biology and Medicine

Q10— Thin Film Transistors 12 (TFT 12) R — Luminescence and Display Materials, Devices, and Processing R1 — Luminescence and Display Materials: Fundamentals and Applications (in Honor of Hajime Yamamoto) S — Physical Sensors S1 — Microfabricated and Nanofabricated Systems for MEMS/NEMS 11 (Physical Sensors) Z — General

H1 — Physical and Analytical Electrochemistry General Session

Z1 — Student Poster Session

H2 — Chemically Modified Electrodes

Z2 — Energy Water Nexus

H3 — Electrochemistry in Nanospaces 2

Z3 — Nanotechnology General Session

The Electrochemical Society Interface • Winter 2013

105

Student Travel Grant Application

Cancun, Mexico

The Society’s, Battery, Corrosion, Dielectric Science & Technology, Electrodesposition, Electronics and Photonics, Energy Technology, High Temperature Materials (HTM), Industrial Electrochemistry & Electrochemical Engineering (IE&EE), Nanocarbons, Organic and Biological Electrochemistry (O&BE), Physical and Analytical Electrochemistry, and Sensor Divisions offer travel grants to students presenting papers at the Society’s next meeting in Cancun, Mexico, October 5-10, 2014. To apply, complete this application and send it along with a copy of your transcript and a letter from an involved faculty member attesting both to the quality of the student’s work and financial needs, and a copy of the student’s meeting abstract. For additional information please send an email to travelgrant@electrochem.org. Please note the specific division in your inquiry, as requirements might differ between Divisions. Meeting Site: Name: School Address: Email: Phone #: Undergraduate Year (U) or Graduate Year (G) - circle one:

Major Subject: Grade point average:

out of possible:

(please provide a letter of recommendation from your faculty advisor and a copy of your transcript)

Symposium Title (#): Title of paper to be presented at the meeting: Are you an ECS Student Member of the Society?

q yes

q no

(if not, please additionally submit the Awarded Student Membership application)

Estimated meeting expenditures: $ Signature: Date: Check only one Division. (Applications made to multiple Divisions will be rejected.) q Battery q Corrosion q Dielectric Science & Technology q Electrodeposition q Electronics & Photonics q Energy Technology q High Temperature Materials q Industrial Electrochemistry and Electrochemical Engineering q Nanocarbons q Organic and Biological Electrochemistry q Physical and Analytical Electrochemistry q Sensor Please send materials to: Attn: (Division Name) Student Travel Grant, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534; Phone: 609-737-1902; Fax: 609-737-2743; e-mail: travelgrant@electrochem.org. Electronic submission of nomination packets is preferred.

Applications for Travel Grants for the Cancun, Mexico, meeting must be received no later than July 1, 2014.

w w w. e l e c t r o c h e m . o r g / s p o n s o r s h i p / t r a v e l _ g r a n t s . h t m 106

The Electrochemical Society Interface • Winter 2013

Young Professionals Travel Grant Application

Cancun, Mexico

The Society’s Battery, Energy Technology, High Temperature Materials (HTM), and Physical and Analytical Electrochemistry Divisions offer travel grants to postdoctoral associates, junior faculty, and other young investigators presenting papers at the Society’s meeting in Cancun, Mexico, October 5-10, 2014. To apply, complete this application and send it along with a copy of your CV and a letter of recommendation from an established researcher attesting both to the quality of the applicant’s work and financial needs, and a copy of the applicant’s meeting abstract. For additional information please send an email to travelgrant@electrochem.org. Please note the specific division in your inquiry, as requirements might differ between Divisions.

Meeting Site: Name: Organization: Address: Email: Phone #:

Symposium Title (#): Title of paper to be presented at the meeting:

Estimated meeting expenditures: $

Signature: Date:

Check only one Division. (Applications made to multiple Divisions will be rejected.) q Battery q Energy Technology q High Temperature Materials q Physical and Analytical Electrochemistry Please send materials to: Attn: (Division Name) Young Professionals Travel Grant, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534; Phone: 609-737-1902; Fax: 609-737-2743; e-mail: travelgrant@electrochem.org. Electronic submission of nomination packets is preferred.

Applications for Travel Grants for the Cancun, Mexico, meeting must be received no later than July 1, 2014.

w w w. e l e c t r o c h e m . o r g / s p o n s o r s h i p / t r a v e l _ g r a n t s . h t m The Electrochemical Society Interface • Winter 2013

107

The Electrochemical Society Monograph Series

The definitive volume on corrosion— now expanded and completely updated

Praise for The second ediTion

“An excellent sourcebook on a wide range of corrosion topics.” —Chemical Engineering Research and Design

Continuing a legacy that began with the classic 1948 edition comes this long-awaited, fully revised Third Edition of the authoritative guide on corrosion. A thorough and timely compilation, Uhlig’s Corrosion Handbook, Third Edition explores, in eighty-eight chapters, a multitude of subjects important to understanding the methods for controlling the degradation of materials. It includes updates of all information along with many new chapters including corrosion monitoring; principles of accelerated corrosion testing; failure analysis; composite materials; diagnosing, measuring, and monitoring microbiologically influenced corrosion; and high-temperature oxidation of metals and alloys. In addition, this new Third Edition: • Gives a solid summary of the scientific background of all the types of corrosion in a comprehensive and well-organized way • Includes new coverage of many important corrosion topics, including nuclear waste containment, CO2 corrosion of steel, ethanol-induced stress corrosion cracking, dealloying, shape memory alloys, nanocrystals, and corrosion of electronics • Features information on the standards for corrosion testing, microbiological corrosion, and electrochemical noise • Presents both scientific and practical approaches, making it extremely useful for all materials science professionals

ECS MEMbERS will receive a discount!

R. WINSTON REVIE CANMET Materials Technology Laboratory in Ottawa, Canada

978-0-470-08032-0 • 1,200 pages • Hardcover • October 2010 $195.00 US / CAN $234.00 / £133.00 / =C172.00

Valuable contributions from internationally renowned authors once again help distinguish Uhlig’s Corrosion Handbook, Third Edition as a leading resource in the field as each page builds on the book’s longstanding reputation as an indispensable companion for engineers, scientists, students, and others concerned with the use of materials in applications where integrity, reliability, and resistance to corrosion are critical. aBoUT The aUThor R. WINSTON REVIE has had a career of more than thirty years at the CANMET Materials Technology Laboratory in Ottawa, Canada, where he is a Senior Research Scientist and Program Manager. Currently, he is President of the NACE Foundation of Canada, a registered educational charity. He is also past director of the Northern Area of NACE International; a past chairman of the ASM Canada Council and of the Electrochemical Society Canadian Section; and a past president of the Metallurgical Society of the Canadian Institute of Mining, Metallurgy and Petroleum. Dr. Revie coauthored the third and fourth editions of Corrosion and Corrosion Control, a widely used textbook, and was the editor of the second edition of Uhlig’s Corrosion Handbook. Dr. Revie is a Fellow of NACE International, ASM International, and the Canadian Institute of Mining, Metallurgy and Petroleum.

TO ORDER CALL 609.737.1902 OR VISIT THE ECS WEbSITE AT WWW.ELECTROCHEM.ORG

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