Interface Vol. 23, No. 1, Spring 2014 by The Electrochemical Society

VOL. 23, NO. 1 Spring 2014

IN THIS ISSUE 3 From the Editors:

Writing New Chapters

7 Pennington Corner: Free the Science

9 ECS Launches

Author Choice Open Access

23 Special Section:

225th ECS Meeting Orlando, Florida

34 ECS Classics

Brian Conway Remembered

37 Currents: Reflections

on Chemistry and Electrochemistry after Fifty Years of Practice

43 Tech Highlights 45 Interfacial Electrochemistry of Ionic Liquids

Interfacial Electrochemistry of

Ionic Liquids Newest ECS Honorary Members John B. Goodenough

Allen J.Bard

47 Electrodeposition in Ionic Liquids

53 Vacuum Electrochemistry in Ionic Liquids

59 Influence of Molecular

Organization of Ionic Liquids on Electrochemical Properties

65 Interfaces between

Charged Surfaces and Ionic Liquids: Insights from Molecular Simulations

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

FROM THE EDITORS

Writing New Chapters

eginning with this issue, Interface embarks on writing some new chapters with not one, but two Editors leading the way. (See the winter 2013 issue for the story). Just a few short months on the job, and Petr Vanýsek and Vijay Ramani already have introduced some great ideas, which you’ll see in this, their first issue as Editors. Each Editor has a few words to say here (see below). In future issues they will alternate writing this column. Another new member of the Interface team is Annie Goedkoop, the Society’s Director of Publications. Annie will be Interface’s new Managing Editor, enabling me to leave that role and take up the job of Publisher in a more dedicated way: to develop content for all our publications, build support for ECS as one of the few remaining nonprofit publishers in our technical arena, and enable Open Access here at the Society, among other initiatives. Before joining the staff of ECS, I was brought in as a consultant to help turn the prototype into a full-fledged and robust members’ magazine; so I have been with Interface since “day one.” Over the years, I have worked with a series of remarkable Editors—Karrie Hanson (prototype, 1992), Paul Kohl (1992-94), Lee Hunt (interim, 1995), Jan Talbot (1995-99), and Krishnan Rajeshwar (1999-2013), or “Raj” as we all know him. To them, my thanks for bringing great things to the magazine—working with them has been one of the best parts of my job. To members of the ECS staff, thank you for playing a significant role in bringing off the enterprise—from contributing a great deal of news for and about our readers, to producing the magazine within short timeframes and selling advertisements to pay for its upkeep, to managing numerous tasks to ensure that Interface reaches its audience. To Raj, who has given nearly 15 years to Interface, and dealt with everything from recalcitrant authors to hurricanes with great humor and aplomb, go my deep and heartfelt thanks… I plan to “stay tuned” to your next episode with ECS.

Published by: The Electrochemical Society (ECS) 65 South Main Street Pennington, NJ 08534-2839, USA Tel 609.737.1902 Fax 609.737.2743 www.electrochem.org Co-Editors: Vijay Ramani, ramani@iit.edu; Petr Vanýsek, pvanysek@gmail.com Guest Editors: Andreas Bund, andreas.bund@tu-ilmenau.de; Frank Endres, frank.endres@tu-clausthal.de Contributing Editors: Donald Pile, donald.pile@gmail.com; Zoltan Nagy, nagyz@email.unc.edu Managing Editor: Annie Goedkoop, annie.goedkoop@electrochem.org Interface Production Manager: Dinia Agrawala, interface@electrochem.org Advertising Manager: Christie Knef, christie.knef@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 Electro-chemistry), Nick Wu (Sensor) Publisher: Mary Yess, mary.yess@electrochem.org

Mary Yess, ECS Deputy Executive Director & Publisher

About 15 odd years ago (Summer 1999 to be exact), the editorial in Interface was entitled “Transitions and Interfaces.” Now it is once again a time for transition. Interface has grown Vijay Ramani to new strengths under the guidance of Krishnan Rajeshwar. I am sure I speak for all of us as I express my gratitude to Raj for his outstanding stewardship, along with congratulations and very best wishes in his role as the Society’s newest Vice-President. Research progress in a given area often follows a trajectory akin to an autocatalytic reaction: a long induction time followed by exponential increase in rate and/or efficacy (hopefully the same is not true of new Interface editors!). A case in point is the field of ionic liquids, a truly versatile class of materials. Since the first “low melting point salt” was reported in 1914, there has been steady progress over the past century

Summing up research work for a professional journal and having it eventually published is one of the most satisfying events in a professional career. But sitting down and writing Petr Vanýsek the sentences describing the work does not come easily and even skilled and prolific authors will admit that writing is not always fun. The manuscript template is rigid and the customary style is restraining, with its use of passive voice, avoidance of synonyms, and guarded choice of words. And you should never use an exclamation mark in scientific writing! What a treat to have Interface to come alongside with the four ECS journals. The framework of Interface is defined and some of the items are standard and prescribed. But there is lot of flexibility in the way authors contribute and the style can be often quite lighthearted. An author celebrating the lifelong accomplishments of a former advisor

(continued on next page)

The Electrochemical Society Interface • Spring 2014

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 2014 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. 3 All recycled paper. Printed in USA.

FROM THE EDITORS Vanýsek (continued from previous page)

Ramani (continued from previous page)

can recall the fun times the research group had on an outing. Writing about science and including words such as “I,” “superlative,” or “cocktail” (though preferably not in the same sentence) can be rather liberating. And overseeing such writings being published is equally invigorating. I am truly honored to be chosen a co-editor of Interface and to be given the opportunity (a mandate, as I view it), to have fun while writing about science. I am looking forward to working with many of the members, who volunteer their time to contribute to our magazine. And I am looking forward to working with the staff, who through their dedication often volunteer their personal time to meet the deadlines and to accommodate the quirks of the authors and the editors. And thank you Raj, for passing on the magazine in such superlative shape!

that has now culminated in a period of exponential growth. Given their potential applicability in multiple electrochemical technologies (electrodeposition and energy conversion/storage, to name two), processes occurring at ionic liquid/electrode interfaces have piqued a lot of interest. This issue has four articles that present an excellent overview of the interfacial electrochemistry of ionic liquids from both a theoretical and experimental viewpoint. In closing, I must say that I am excited at this opportunity to work with Petr Vanýsek and the ECS staff in steering Interface through its third decade. I welcome your feedback and look forward to your contributions!

Petr Vanýsek, Interface Co-Editor

Vijay Ramani, Interface Co-Editor

Fall—W inter 2012 12

Summe r 2013

, NO. 2 VOL. 22 r 2 0 1 3 Summe

VOL. 2 F a l l – W1, NOS. 3-4 inter 2 012

IN THIS ISSUE

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the Editor: 3 From of The Law Growth al Sigmoid t: the Presidenfor ECS 7 From Point A Turning , ON, Canada hts Highlig 9 Toronto ECS Meeting G. S. Yuasas—The 35 Current 787 Li-ion Battery: ture Boeing a Low Tempera Test It at It Warm in Flight and Keep

IN THIS ISSUE

3 From the

Editor: Biomime tic or Bioinspir ed?

9 From the

President: Weatheri ng the Storm The Weston Corner: Legacy

Launche Network s ing and Research Site for Scientist s

17 Candida tes

for Society Office

Beginnin lating Electrop hts Tech Highlig

Fuels 41 Solar

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11 Penningt on

13 Redcat: ECS

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19 PRiME, Honolulu

, Highligh Hawaii: ts 58 Tech Highligh ts 61 Conducti ng and Their Polymers Applications 63 Novel MEMS Devices Based on Conductive Polymers Meeting

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Integrat the 43 An h to

Approac Solar ment of Develop ors Fuel Generat

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of Photoca for Solar ogies Technol aning, and Fuels, Self-Cle Cleanup mental Environ Water

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d Electrical ly-conduc ting Polymers for Nano-Micro Flexible Systems

Assay of GSTP1-re Sequence lated DNA for Prostrate Cancer Screening 88 ECS Summer Fellowship Reports .2

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107 San Francisco

Call for Papers, CA:

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Fro UE Sec m the ond Edi 7 Life tor: Fro for Liv m the Qu Fra ing in Presid icksilve me an r? 34 of Ref Acc ent: Tec h Hig ere elerat 35 nce ing hlig Lith hts ium 37 Ion A Ge Bat Ion neral tery Bat Saf 45 tery Discus ety Ho Saf sio ety n of Bat w Electro tery Li Saf lytes Bat ety Infl Qu tery Saf uen ce Rat alifica ety ing tion 57 s s for Sim Hu Beh ulation ma n Bat avior of Abu teri of 61 Lith se es The ium -Io Lith Role n ium of Sep 77 -Io 201 ara 1 Ann n Cel 115 l Saftors in ual Tor ety Rep Ca onto, ort ll for ON Pap , Canad ers a

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VOL. 21, NO. 3-4

Splitting Semicon ion of and Nitride s for Product Powder en Solar Hydrog ed Solar -Enhanc 63 PlasmonHarvesting Energy ion for a Fuel Product Future: 69 Solar ble Energy Sustaina of a Symposium Highlights ble Fuels from on Renewa Electricity and Sunlight

NO. 2 VOL. 22,

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They read Interface to find them! REQUEST an Interface Media Kit TODAY. Download Media Kit at http://www.electrochem.org/mediakit. Contact christie.knef@electrochem.org.

www.electrochem.org The Electrochemical Society Interface • Spring 2014

Vol. 23, No. 1 Spring 2014

Interfacial Electrochemistry of Ionic Liquids by Andreas Bund and Frank Endres

Electrodeposition in Ionic Liquids

Vacuum Electrochemistry in Ionic Liquids

by Adriana Ispas and Andreas Bund

by Oliver Höfft and Stefan Krischok

Corner: 7 Pennington Free the Science Launches 9 ECS Author Choice Open Access

13 Society News Section: 23 Special 225 ECS Meeting th

Influence of Molecular Organization of Ionic Liquids on Electrochemical Properties by Natalia Borisenko, Rob Atkin, and Frank Endres

the Editors: 3 From Writing New Chapters

Interfaces between Charged Surfaces and Ionic Liquids: Insights from Molecular Simulations by Vladislav Ivaništšev and Maxim V. Fedorov

Orlando, Florida

Classics 34 ECS Brian Conway Remembered

37 Currents: Reflections on Chemistry

and Electrochemistry after Fifty Years of Practice

40 People News 43 Tech Highlights 70 Section News 72 Awards 75 New Members 79 Student News On the cover . . .

In situ STM images of the Au(111) surface in different ionic liquids. (See related article on page 59.) Cover design by Dinia Agrawala. The Electrochemical Society Interface • Spring 2014

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+1-910-695-8884 The Electrochemical Society Interface • Spring 2014

PENNINGTON CORNER

Free the Science S

ince the dawn of modern science, the key to scientific advancement has been the exchange of knowledge in publications, meetings, and through other collaborations; and in the past decade we have experienced a significant change in the way this scientific exchange occurs. Digital information and the Internet have dramatically improved our ability to disseminate science on a worldwide scale and should lead to global advances at a pace never considered before. But there are obstacles because these technological advancements in the digital age have come at a high cost to scholarly publishing; not for producing scientific content but for the cost of dissemination incurred by users of the research and their institutions. The inexorable changes wrought by bringing publications activities into an electronic world have changed the entire publishing ecosystem. Just as the Internet has reshaped the music industry (among others), developments in technology have reconfigured the established morés of scholarly communication. This reconfiguration has advanced a natural consolidation in the publishing industry and has led to the systematic extinction of small scholarly publishers who are unable to compete on the scale achieved by commercial enterprises. Because societies cannot compete, they are often forced to strike agreements with commercial publishers that undermine or eliminate their scientific independence. Commercial publishers have learned that the subscription-based model could be played to their enormous benefit, placing a further cost on the scholarly publishing system. There has been a proliferation of new journals being added to subscription packages, burdening library budgets with additional journals and without providing reciprocal scientific value. This has been coupled with the excessively high prices being charged by many scientific publishers for the dissemination of technical knowledge, and collectively the money now being extracted from the process is stifling scientific advancement. In 2012 Elsevier, the world’s leading science publisher, posted profits of £780m from revenues of £2.1 billion for the payment of important knowledge in the scientific, technical, and medical fields.1 ECS - The Electrochemical Society is a global, nonprofit, scholarly society that has sustained a consistent and powerful mission to advance the science through dissemination of technical information. ECS continues to focus on its mission with even greater urgency because electrochemical processes can help to solve worldwide challenges in energy and clean water. These challenges have become two of the greatest

1. These figures were taken from “No Peeking…,” The Economist, January 11, 2014, p. 67. 2. The concept of Open Access as it is being used in scholarly publishing means that an article is freely available online to anyone who wishes to see it, so the reader doesn’t have to pay for it, nor does the reader have to belong to an institution that subscribes to the journal or publication in which the article appears.

The Electrochemical Society Interface • Spring 2014

burdens mankind is facing. It is this urgency for advancement that drives our compelling goal to—free the science—to drive its advancement so that scientists around the globe can exchange knowledge, without obstacles, to solve these imminent world challenges. ECS has had a reasonably stable existence for more than a century, and in that time has established itself as an important and reliable contributor to the exchange of information in its technical fields. The Society currently publishes four highlyregarded journals in the fields of electrochemistry and solid state science, but with the changing developments, its future and the future of the entire scholarly publishing world is unclear. What is clear is that an important part of the future is the increasing adoption of Open Access.2 Acknowledgment— and in some cases, the embracing of—this change is profoundly affecting the way that publishers, funders, institutions, and researchers approach their various functions. Meanwhile, institutional budgets are tightened, with subscriptions spending coming under increasing pressure, and competition from other publishers—both new and established—who are exploiting the opportunities an electronic-only environment delivers, continues to grow. In October 2013, the ECS Board of Directors boldly committed to an… ‟Open Access plan that would enable the dissemination of content from the ECS Digital Library at no cost to authors, readers, libraries, or funding agencies.” This requires that ECS move from the traditional subscriptionbased model of publishing to a platform where individuals and institutions can access the ECS Digital Library content without paying any fees (see OA article on page 9). The intended goal is to enable authors to reach readers without the for-profit selling of their work, and enable readers everywhere to access scholarly papers free from the burden of over-priced subscriptions charged by the profit-minded publishers. As a nonprofit publisher and steward of the science, ECS intends to maintain a high-quality peer review process, an editorial structure aimed at engaging the best content in our technical domain, and the platform necessary for the broadest and most useful dissemination of that content. Maintaining this editorial integrity, deep searchability, and content usability in an Open Access publishing environment will require ECS to create a new model for financial support and management of the ECS Digital Library. ECS is highly committed to Open Access and we have initiated a campaign to generate institutional and endowment type financial support for the ECS Digital Library. We need assistance from members, authors, institutions, and foundations to support this important new model of publication and create free dissemination of research and enable uninhibited scientific advancement.

Roque J. Calvo ECS Executive Director

CALL FOR NOMINATIONS for Technical Editor of the Batteries and Energy Storage Area of the Journal of The Electrochemical Society and ECS Electrochemistry Letters ECS (The Electrochemical Society) is seeking to fill the position of Technical Editor of the Batteries and Energy Storage Technical Interest Area for the Journal of The Electrochemical Society and ECS Electrochemistry Letters. The Batteries and Energy Storage (BES) Technical Interest Area (TIA) includes theoretical and experimental aspects of batteries, electrochemical capacitors, and redox flow batteries. Specific topics include design, modeling, and testing; electrode structures and characterization, including charge storage materials, binders, additives, membranes, electrolytes, conductivity enhancers, and current collectors. Also of interest are issues that pertain to safety, such as development and implementation of methods for its assessment. The Journal of The Electrochemical Society (JES) is the ECS flagship journal and has long been the premier international journal in the field of electrochemical science and technology.

The Society’s Technical Editors actively solicit manuscripts for their TIA through being involved in their technical community, engaging the ECS Divisions, and working with the staff to effectively communicate to their TIA’s stakeholders. Technical Editors ensure an efficient and fair peer review processing and minimize lag time of manuscript submissions. They work to recruit and select editorial reviewers. Technical Editors are required to adhere to policies and procedures for: (a.) manuscript submission and authorship criteria; (b.) peer review, evaluation of decisions regarding publication, and methods for reconsideration of rejected manuscripts; (c.) maintaining the scientific integrity and confidentiality of the peer review process; (d.) the identification and recommendation of theme issues and supplements; (e.) handling conflict of interest and disclosure issues; and (f.) handling allegations and findings of scientific misbehavior and misconduct. Technical Editors must clearly communicate publication guidelines and policies and oversee compliance. Technical Editors serve as members of their respective Editorial Boards and attend their biannual meetings. They work collaboratively with the Editors, the Publisher, and the Director of Publications to accomplish the objectives approved by the Publications Subcommittee and the Board of Directors. Nominees for the BES Technical Editor must possess and maintain scientific knowledge of the scope of the BES TIA (see http://ecsdl. org/site/ecs/tia_scopes.xhtml). Nominees must have qualities of leadership, technical breadth, creativity, motivation, and international reputation, and should be able to commit the necessary time. The Technical Editor oversees the review and disposition of manuscripts within his/her TIA, and works to develop content for the regular and special issues. A yearly honorarium is offered by the Society. Nominees must have published previously in a Society publication or other comparable scholarly journal. They must be skilled in the arts of writing, editing, critical assessment, negotiation, and diplomacy. 8

Published since 1902, JES is the only top peer-reviewed, archival journal still published by a nonprofit, scholarly society. ECS Electrochemistry Letters (EEL) is the newest ECS peer-reviewed journal to join JES. Along with the ECS solid state journals and ECS Transactions, JES and EEL provide unparalleled opportunities to disseminate basic research and technology results in electrochemical and solid state science and technology. JES and EEL each publish a minimum of 12 regular and special issues a year. All ECS journals offer Author Choice Open Access (http://www.electrochem.org/oa/). ECS maintains 13 TIAs (see http://ecsdl.org/site/ecs/tia_ scopes.xhtml), and there is one Technical Editor for each TIA, supported by Associate Editors and an Editorial Advisory Board. Technical Editors for the ECS journals ensure the publication of original, important, well-documented, peerreviewed articles that meet the objectives of the relevant journal, and are within the scope of the Society’s TIAs.

Technical Editors may not serve on the editorial boards of any nonECS peer-reviewed technical journal. Technical Editors will be expected to adhere to the Society’s Code of Ethics policies. A Technical Editor is appointed for a two-year term, renewable for additional terms, up to a maximum of eight years. The Publications Subcommittee will approve the appointment of the BES Technical Editor during the ECS meeting in Cancun (fall 2014). If selected as a finalist, candidates are expected to be available for face-to-face interviews with the Publications Subcommittee at the ECS meeting in Cancun (fall 2014). Self-nominations and third-party nominations are due no later than June 3, 2014. If you are interested in being considered for the position, or if you would like to recommend someone for the position, please send the information to ECS headquarters, to the attention of Mary Yess, ECS Deputy Executive Director & Publisher, mary. yess@electrochem.org. Full applications are due no later than July 3, 2014.Those interested should send a letter indicating their qualifications for the position, stating why they are interested in the position, giving their previous experience with peer-reviewed journals, and noting of their availability of their time to fulfill the duties of this position. Please also include a one-page résumé. Send all materials to ECS headquarters, to the attention of Mary Yess, ECS Deputy Executive Director & Publisher, mary.yess@electrochem.org. ECS • The Electrochemical Society 65 South Main Street, Bldg. D, Pennington, New Jersey 08534-2839, USA tel: 609.737.1902 • fax: 609.737.2743 The Electrochemical Society Interface • Spring 2014 www.electrochem.org

ECS Launches Author Choice Open Access by Mary Yess

art of the ECS mission is to disseminate the best research in our fields as widely as possible. In recent years ECS has been working on ensuring that the research published in our journals is truly at the cutting edge of our technical arenas, and that ECS publications have continued to focus on achieving quality through a high standard of peer-review. We are in the fortunate position of publishing four peer-reviewed titles that are among the most highly regarded in their areas. Now is the time to widen the focus and work on the second part of our mission: dissemination. The arrival of the Internet has changed so much about the way we work and communicate with each other, enabling scientists around the world to exchange ideas and build on each other’s work in ways that were unimaginable at the time of our establishment, over a century ago. The ECS leadership now sees that the models of communication and publication, which have served us so well for so long, are no longer fully meeting the spirit of our mission. It is time for ECS to change its publishing model, and move to embrace the brave new world of Open Access publishing. In May 2013, the ECS leadership approved the Society’s Open Access (OA) goals, which are as follows: (1.) To institute “hybrid” OA for the ECS journals as soon as possible. This allows authors to choose between making their articles OA (pay an Article Processing Charge or “APC” or use an article credit) or having their articles remain behind the paywall. (2.) To keep developing an OA plan to make our journals free and open to all: authors, readers, and libraries.

What Is Open Access?

ECS and Open Access

For those not already familiar with the concept, Open Access means that an article is freely available online to anyone who wishes to see it, so the reader doesn’t have to pay for it, nor does the reader have to belong to an institution that subscribes to the journal in which the article appears. Instead, the costs of publication are paid upfront before an accepted article is published (usually by funding institutions, employers, or authors, rather than afterward by readers or their institutions). Open Access is a move toward disseminating the results of important scientific work more widely through removing subscription barriers, and thereby making the outputs of research accessible to anyone with an Internet connection who may need or want to see them. (For those who would like a more comprehensive introduction to OA, Peter Suber’s article is a great place to start: http://legacy.earlham.edu/~peters/fos/overview.htm.)

It is, however, a big step for ECS. Up until the end of 2013, ECS funded its journal publications activities almost exclusively through subscriptions. Moving toward OA will require a change to the way we finance our journals. The challenge for us as a nonprofit society publisher is how to put the best OA business model in place for the future that will allow us to sustain excellence throughout our journals, while enabling Open Access. Our long-term goal is to move away from the subscriptions model entirely, and to truly free the science and allow totally unrestricted access to the important work that is going on in our fields. The research that ECS publishes has a direct impact on the sustainability issues facing our planet—energy supply, access to clean water, and other issues. The more widely this research can be accessed, the greater the likelihood of developments emerging that can make a difference in our world.

The Electrochemical Society Interface • Spring 2014

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(continued from previous page)

As a first step, ECS is embarking on its OA journey with a mixed funding model for enabling Open Access, currently including Article Processing Charges and subscriptions. As of the beginning of February, all of the ECS journals are now “hybrid” Open Access journals (Author Choice Open Access), where authors may choose whether or not to make their articles immediately available as Open Access.

How Does It Work? Authors who choose to make their article Open Access will either be levied an Article Processing Charge (APC) on acceptance, or they may use an article credit in place of the charge. For 2014 the APC will be USD $800, but ECS members, ECS meetings attendees, and subscribers will receive some automatic article credits. ECS members, both individual and institutional, will receive one Article Credit per member (or named member representative) for use in 2014. For any subsequent articles that a member wishes to make immediately available as Open Access that calendar year, and no other article credit exists, ECS is offering a discounted membership rate for the Article Processing Charge of USD $200 (for 2014). Authors belonging to an institution that subscribes to ECS journals are entitled to unlimited article credits in place of APCs for the duration of 2014, if they wish to publish their articles as Open Access. Attendees of the 225th ECS Meeting in Orlando, Florida (Spring 2014) and the 226th ECS Meeting in Cancun, Mexico (Fall 2014) will also receive one article credit (for use for up to 12 months after the meeting) for each meeting they attend. A screenshot of the Author Choice Open Access screen in the ECSxPress manuscript submission system. Currently ECS is not passing on the full costs of publication to the authors and hopes to be able to keep article processing charges at a moderate level. This policy will be Open Access and Copyright reviewed at the end of 2014. Articles that are immediately Open Access will be flagged as In the spirit of allowing maximum access to the outputs of research, freely available at the Table of Contents level (and in TOC alerts) and in an Open Access environment the standard copyright agreements at the abstract level in our Digital Library. The usage license under between authors, their publishers, and the end user no longer apply which they are made OA will also be visible. Readers can then follow in the same way. the link to the full text if they wish to, and will be able to download it In place of a copyright transfer, authors who wish to make their in its entirety regardless of their subscriber status. article Open Access are asked to sign an exclusive Open Access There are several reasons why authors would want to publish Publishing Agreement with ECS. Copyright will remain with the their articles Open Access. Authors may believe, as ECS does, that author; and the author will need to select a Creative Commons usage quality, peer-reviewed scientific research should be freely available license to attach to the work, which will define how the article may to anyone who wishes to read it. In addition, studies across academic be used by others. disciplines show that articles that are published as Open Access are downloaded more frequently. Finally, bodies that fund research are increasingly mandating that any output of that research is made Open Access as soon as it is published.

The Electrochemical Society Interface • Spring 2014

ECS offers authors a choice of two Creative Commons usage licenses. Some advocates of Open Access believe that CC BY, as the most liberal of the licenses, is the most appropriate license under which to publish Open Access content (see http://oaspa.org/why-ccby/), and in some cases, where funding bodies mandate Open Access publishing, they mandate a CC BY license. However, authors may wish to choose the CC BY-NC-ND license instead, which limits use to non-commercial use (-NC), and restricts others from creating derivative works (-ND). More information about the licenses can be found on the Creative Commons website (http://creativecommons. org/licenses/). Once an article is published, the author’s choice of Creative Commons license will be clearly marked at the abstract level, in the full text article, and will be embedded in the metadata. Copyright law does still apply to protect the work. Any breaches of a CC license would normally be seen as copyright infringements. If authors choose a CC BY-NC-ND license (non-commercial, no derivatives), ECS’s Open Access Publishing Agreement asks that ECS be granted rights they have always had in the traditional publishing model: others may not use the work for commercial purposes without getting permission from ECS, and the author grants to ECS the exclusive right to use the work for commercial purposes and to sublicense it to others. To find out more about the publishing agreement, go to http://www.electrochem.org/oa/publishing_ agreement/.

The Future of OA for ECS ECS ultimately aims to achieve full Open Access across its four peer-reviewed journals, but we have not yet determined the most appropriate business model. As a nonprofit society we need to consider many elements of the way we work, and how publishing fully-OA journals will change those. While we do further research and further modelling, we realize we need to be offering authors the option of making their articles Open Access right away. Author Choice Open Access satisfies the immediate needs of authors. Throughout the planning of our OA program, ECS has been collaborating with SPARC, the Scholarly Publishing and Academic Resources Coalition (www.sparc.arl.org). SPARC is a catalyst for action and collaborates with other stakeholders to stimulate new scholarly practices to ensure Open Access, and they have been tremendously helpful to, and supportive of ECS. “We are excited to see a major professional society make such a bold move toward open access,” said Heather Joseph, Executive Director of SPARC. “The Electrochemical Society’s plans will benefit the research community, universities, libraries, and the general public by making critical scientific findings more widely and rapidly available. The strategy ECS is pursuing is a critical development in the ongoing move toward open access within scholarly publishing. It demonstrates that professional societies can move boldly and decisively to increase the availability of important research.” During 2014 we will be working to put together a model for our future where every article we publish will be freely available to anyone who wishes to read it. We hope you will support us through these exciting and challenging times. Mary Yess is the Society’s Deputy Executive Director and Publisher; mary.yess@electrochem.org ORCID #: http://orcid.org/0000-0003-3909-6524

Join the Discussion on Redcat:

tinyurl.com/nkzvljo

The Electrochemical Society Interface • Spring 2014

CHORUS As part of the Society’s Open Access initiative, ECS is pleased to announce that it has become a signatory to the Clearinghouse for the Open Research of the United States. CHORUS, as it is known, is a nonprofit public-private partnership to increase public access to peer-reviewed publications that report on federally-funded research. CHORUS will provide a full solution for agencies to comply with the U.S. OSTP memo on public access to peer-reviewed scientific publications for federally-funded research. It will build on publishers’ existing infrastructure to enhance public access to research literature, avoiding duplication of effort, minimizing cost to the government, and ensuring the continued availability of the research literature. CHORUS utilizes current and developing tools, resources, and protocols for identification, discovery, access, preservation, and compliance (such as CrossRef, FundRef, and ORCID), ensuring continued innovation in the delivery of scholarly communication. In brief (when CHORUS is up and running), an author would identify his/her funding sources when submitting a paper for publication. Through CHORUS, publishers take care of everything else an author needs for compliance. By choosing a journal that uses CHORUS for compliance with their funding source, authors will not have to sort out complex requirements, manually deposit articles, or work through rules about versions and embargoes. Using CrossRef’s FundRef service, the selected article is tagged with the information, and the best available version (either the final, published version, or the author’s accepted manuscript) is made publicly available at no charge on the journal’s website at the appropriate time. CHORUS publishers arrange the archiving and preservation of research papers, and CHORUS offers a suite of tools to funding agencies to track and ensure compliance. CrossRef collects the data and CHORUS then uses this to enable access to articles reporting on federally funded research for text- and data-mining (TDM) purposes. Readers will be able to search for and view these articles in context, through the journals in which they are published. This allows for up-to-date information on any changes, corrections, or retractions that may have been added to the article, along with links to related articles, commentaries, or editorials. Readers can discover these publicly-available articles through their usual channels—Google, PubMed, and other sources. CHORUS is a cooperative effort involving publishers, federal agencies, resource partners, associations, and other organizations involved in scholarly publishing. Since the passage of the America COMPETES Act in 2010, the publishing community has been working closely with federal agencies that fund research to expand access to scholarly publications. CHORUS is an expression of this collaboration. Collectively, the more than 100 publishers (both commercial and nonprofit) that support CHORUS, produce the vast majority of the articles reporting on federally-funded research. CHOR, Inc., the organization behind CHORUS, is in the process of applying for 501(c)(3) not-for-profit status. Note: The information in this article was taken from the CHORUS website: http://chorusaccess.org/.

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ECS is proud to announce the establishment of the

Allen J. Bard Award in Electrochemical Science Award recipients will be honored for exceptional contributions to the fields of fundamental electrochemical science and recognized for exceptionally creative experimental and theoretical studies that have opened new directions in electroanalytical chemistry and electrocatalysis. The first award will be given in Chicago at the 227th ECS Meeting. Nominations are due April 15, 2014. For more information, please contact awards@electrochem.org.

Allen J. BArd is the Norman Hackerman-Welch Regents Chair in Chemistry in the Department of Chemistry at The University of Texas at Austin, and the Director of the Center for Electrochemistry.

Allen J. BArd

Among Dr. Bard’s many awards are The Electrochemical Society’s Carl Wagner Memorial Award (1981), Henry B. Linford Award for Distinguished Teaching (1986), and Olin Palladium Award (1987); Priestley Medal (2002), the Wolf Prize in Chemistry (2008). He was elected into the American Academy of Arts & Sciences in 1990. In 2013, Dr. Bard was awarded the National Medal of Science, one of the highest honors bestowed by the U.S. government upon scientists, engineers, and inventors.

Special thanks to the generous support of our donors and advertisers, especially:

CH Instruments ECS Physical and Analytical Electrochemistry Division

To help fund the award endowment and a continuing symposium in Dr. Bard’s honor, please donate online: 12

www.electrochem.org/bard

The Electrochemical Society Interface • Spring 2014

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Allen J. Bard and John B. Goodenough Receive ECS Honorary Membership

onorary ECS Memberships, recognized as one of the highest Society honors, were awarded to Allen J. Bard and John B. Goodenough on November 23, 2013 at a celebratory luncheon at The University of Texas Etter-Harbin Alumni Center. More than 80 colleagues, many who have studied with and been mentored by them, attended this extraordinary event, along with several ECS Past Presidents. ECS President Tetsuya Osaka, who was unable attend, recognized their achievements with the following note: “On behalf of The Electrochemical Society, it is my pleasure to congratulate Professors Bard and Goodenough on being selected as the 76th and 77th Honorary Members in the 111 year history of the Society. This recognition puts you in a group amongst some of the greatest scientists in history. We thank you for your contributions to the advancement of our science which in many ways has influenced the progress and quality of life for all of mankind.” Arumugam Manthiram, Director, Texas Materials Institute, Director, UT Materials Science & Engineering Program and Joe C. Walter Chair in Engineering, welcomed the attendees and served as emcees for the event. Roque Calvo, ECS Executive Director, recounted the history of Honorary Membership, noting the distinguished list of recipients. Roque also presented a 2013 ECS Student Chapter of Excellence Award to the University of Texas at Austin Student Chapter.

After introducing Allen Bard with a brief summary of his many accomplishments, Fernando Garzon, ECS Past President, presented an ECS Honorary Membership scroll. Allen J. Bard is the Norman Hackerman-Welch Regents Chair in Chemistry in the Department of Chemistry at The University of Texas at Austin, and the Director of the Center for Electrochemistry. He is considered the “father of modern electrochemistry” for his innovative work developing the scanning electrochemical microscope. This is an analytical tool used globally to find new materials for use in technology, as well as to explore the interior of cells. Dr. Bard has published over 800 peer-reviewed papers and other publications, and has more than 23 patents. He was editor-in-chief of the Journal of the American Chemical Society from 1982-2001. He has worked as a mentor and collaborator with more than 75 PhD students, 17 M.S. students, and 150 postdoctoral associates. Among Dr. Bard’s many awards are The Electrochemical Society’s Carl Wagner Memorial Award (1981), Henry B. Linford Award for Distinguished Teaching (1986) and Olin Palladium Medal (1987); Priestley Medal (2002), the Wolf Prize in Chemistry (2008). He was elected into the American Academy of Arts & Sciences in 1990. In 2013, Dr. Bard was awarded the National Medal of Science. (continued on next page)

The newest honorary members with current and past members of the ECS Board of Directors. From left to right are Roque Calvo, ECS Executive Director; Fernando Garzon, Past President; Johna Leddy, Former Secretary; Allen Bard; John Goodenough; Larry Faulkner, Past President and Honorary Member; Fred Strieter, Past President and Honorary Member; Krishnan Rajeshwar, 3rd Vice President. The Electrochemical Society Interface • Spring 2014

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Dr. Bard gave an insightful award lecture, extolling the societal benefits of scientific research, but urging a continued commitment to curiosity based research. Dr. Bard highlighted the fundamental research on magnetic resonance imaging, noting that early applications for funding could not have foreseen later applications like medical brain scans and detection of viruses such as prostate cancer and HIV. Dr. Bard emphasized that, “our scientific community, and our government, shouldn’t put too much constraint on scientific research, particularly if we want innovation.” Dr. Bard concluded by noting the importance of scientific societies like ECS and noting his concern about the explosive growth in the number of scientific journals for the purpose of generating profits. Krishnan Rajeshwar, ECS Vice President, presented an ECS Honorary Membership scroll after introducing John Goodenough, with a brief summary of his many accomplishments. John B. Goodenough is the Virginia H. Cockrell Centennial Chair in Engineering, in the Departments of Mechanical and Electrical & Computer Engineering at The University of Texas at Austin. A prominent solid-state physicist, he is credited for the identification and development of the Li-ion rechargeable battery as well as for developing the Goodenough-Kanamori rules for determining the sign of the magnetic superexchange in materials. Dr. Goodenough has authored more than 550 articles, 85 book chapters and reviews, and five books, including, Magnetism and the Chemical Bond (1963) and Les oxydes des metaux de transition (1973). He holds at least 16 U.S. patents. Dr. Goodenough is a member of the National Academy of Engineering, the National Academy of Sciences, and others. He has received numerous awards including the Von Hippel Award of The Materials Research Society (1989), the ECS Olin Palladium Award (1999), and is a co-recipient of the 2009 Enrico Fermi Award, one of the oldest and most prestigious given by the U.S. government. In 2010, he was elected a Foreign Member of the Royal Society. In 2013, Dr. Goodenough was awarded the National Medal of Science. During his award lecture, Dr. Goodenough shared his incredible life journey in science and concluded by emphasizing the need for alternative strategies for the development of sustainable energy. Dr. Goodenough noted the need for energy density increases and stated that, “new approaches like thin membrane block dendrites give us hope that we can make important steps toward sustainable energy supplies.” Dr. Bard and Dr. Goodenough were both recipients of the United States National Medal of Science in 2013. As ECS Past President Fernando Garzon stated at the time, “We honor their commitment to our science and embrace their inspiration.”

Fernando Garzon, ECS Past President, presenting Allen Bard with Honorary Membership.

Krishnan Rajeshwar, ECS 3rd Vice-President, presenting John Goodenough with Honorary Membership.

The Electrochemical Society Interface • Spring 2014

socie t y ne ws Guests were invited to attend a reception and luncheon, which included remarks from Larry Faulkner, ECS Past President, Honorary Member, and former President of the University of Texas at Austin. Dr. Faulkner noted that the body of knowledge of electrochemistry is impressive, particularly considering the inherent difficulty of the field. “There is an intrinsic elegance in what we already know,” Dr. Faulkner said, while making a strong case for additional research and development. “Thanks to science, particularly chemistry, life is incredibly better than just a few years ago.” Yet, he concluded by speaking to the urgency of our resource challenges, encouraging all present to help answer the question, “How can we wisely make use of Earth’s resources, fulfilling people’s wishes now and indefinitely into the future?” Ed. Note: Read the full text of Larry Faulkner’s talk in this issue’s “Currents” column on page 37. Read about this event from the students’ perspective in this issue’s “Student News” on page 84.

Larry Faulkner, ECS Past President, Honorary Member, and former President of the University of Texas at Austin speaks at the luncheon.

The Electrochemical Society Interface • Spring 2014

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ECS Names Digital Library Leadership Collections At the 223rd ECS Meeting in Toronto, the Board of Directors approved the renaming of the ECS Digital Library President’s Collection to the Leadership Collection, to better represent the donors that have already supported the Digital Library and encourage other former officers to sponsor additional collections. At the time, seven collections were named: The Charles W. Tobias Collection of 1971; The Ralph Brodd Collection of 1982; The Larry Faulkner Collection of 1992; The Wayne Worrell Collection of 1993; The Robert Frankenthal Collection of 1994; The James Amick Collection of 1995; The Battery Division Collection of 1999. Each of these leaders has supported ECS with a major gift to our publications endowment, and helped us digitize our scientific archives. The Frederick Strieter Collection of 1983 was recently added as our eighth addition to the Leadership Collection, thanks to a generous gift from Past President, Honorary Member, and ECS Fellow Frederick Strieter. With more than 100 years of scientific research published, there is still ample opportunity for naming collections within the ECS Digital Library! An annual collection may be renamed after a current or former ECS leader for $15,000. If you are interested in naming a collection in the ECS Digital Library after yourself or someone else, please contact Dan Fatton, Director of Development at 609.737.1902.

Silver/Silver Chloride

ECS Urges Constituents to Join ORCID ECS is pleased to announce that it recently became a member of the Open Researcher and Contributor ID (ORCID) registry. ORCID is an open, non-profit, community-based effort founded by academic institutions, professional bodies, funding agencies, and publishers to create and maintain a registry of unique researcher identifiers intended to remedy the systemic name ambiguity problem seen in scholarly research. ORCID resolves the confusion brought about by name changes, the cultural differences in name order presentation, and the inconsistent use of first-name and middle-name abbreviations on published research papers. The ORCID ID is a persistent digital identifier that distinguishes an author from every other researcher, and it follows an individual throughout his or her career. Similar to the Digital Object Identifiers (DOIs) used in the ECS journals to identify individual published papers, the ORCID ID is a 16-digit number which identifies the author and which can be published in electronic editions in the form of a Web address that leads to the researcher’s individual author profile. The ORCID record is controlled by the researcher, not by the organization, and individuals can manage their record of activities and search for others in the ORCID Registry at their convenience. ORCID IDs are free to obtain and use, and the one-time registration process has been integrated into the ECS journals submission site, ECSxPress (ExP) for convenience. Submitting authors can input their existing ORCID ID or register and secure an ID during the submission process via a built-in link to the ORCID site. Authors can also go directly to the ORCID website to obtain an ID and add it to their ExP profiles at their convenience. Once this process has been completed, the ExP system will recognize the ORCID ID and include it in all future submissions. When accepted papers are published, ECS will display the ORCID IDs of all registered authors on the article’s abstract and full-text views within the ECS Digital Library. Moving forward we will will be looking for ways to integrate ORCID IDs into our other systems and databases, such as those for the Meeting Abstracts and ECS Transactions. For more information about the ORCID ID registry, please visit the ORCID website at http://orcid.org, or contact ECS at publications@ electrochem.org.

Reference Electrode

Annual Business Meeting and Luncheon

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The Annual Society Business Meeting and Luncheon will take place on Tuesday, May 13, starting at 1215h. The President, Secretary, and the Treasurer will give brief reports on the current state of the Society.

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All members and meeting attendees are encouraged to participate in this event. Tickets are $27.00 by Early-Bird deadline, and $32.00 onsite. See page 23 for more information about the Orlando meeting, including how to register.

The Electrochemical Society Interface • Spring 2014

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Division News 12th IE&EE Division Outreach Program The Industrial Electrochemistry and Electrochemical

Engineering (IE&EE) Division of the Electrochemical Society (ECS) completed its twelfth Outreach Program at the 224th ECS Meeting in San Francisco, California. The outreach program is designed to bring awareness of electrochemical energy conversion devices to the future generations. The program aims to foster the younger generation’s interests in the fields of electrochemistry and electrochemical engineering. The outreach program has become a tradition in the IE&EE Division since its start at the 210th ECS Meeting (Cancun, Mexico, Fall 2006). Typically, the outreach programs have taken place at local schools. But, at the 224th meeting of the ECS, for the first time, the outreach program took place at the ECS site (the Hilton San Francisco Hotel), therefore, the participants of the program had ample opportunities to be exposed to electrochemistry and electrochemical engineering research. In addition to the outreach program, the participants attended the Energy Research Group Showcase & Poster Session of the Electrochemical Energy Summit that took place on Sunday evening, and learned about the hydrogen fuel cars while touring the exhibit during the conference. IE&EE members Gerardine Botte (Division Chair; Ohio University), John Staser (Ohio University), Elizabeth Biddinger (City College of New York), and E. Jennings Taylor (Division Secretary/ Treasurer; Faraday Technology, Inc.), along with graduate students Mike Shen of Washington University in St. Louis, Venkateshkumar, Prabhakaran of Illinois Institute of Technology, Nazrul Mojumder of University of Nevada, Reno, and Ohio University’s Luis A. Diaz, Ali Estejab, Fei Lu, Vedasri Vedharathinam, and Santosh Vijapur, conducted the outreach program. Seventy-seven high school students from two schools, Lowell High School and Galileo Academy of Science and Technology, along with their teachers, Bryan Cooley and Serena Chan, participated in the outreach program. The students represented a wide range of ethnic and cultural backgrounds. The event started with a keynote lecture from Dr. Botte explaining fuel cell and water electrolysis technologies, followed by a briefing on the fuel cell car competition to the students. The students were divided into 10 teams to compete in the race. The ECS outreach facilitators helped the students assemble the cars and explained technical details of fuel cells to the teams during the competition. Teams calculated the amount of hydrogen, produced by water electrolysis, required to fuel their cars to travel a fixed distance. The teams then competed with each other to make their car travel as close as possible to the assigned distance. Certificates

were presented to the winning team (the team that came closest to the assigned distance). Throughout the event, the student participants demonstrated great enthusiasm and curiosity about the model fuel cell car and each team strived to win. In accordance with custom, the model fuel cell cars were donated to the high schools to further carry out related education activities in the future. ECS and the IE&EE Division congratulate the winning teams “Lightning McQueen” from Lowell High School (Jianbert Calayag, Ahsan Sheikh, Justin Lee, and Ryan Chan) and “Gal’s Finest” from Galileo Academy of Science and Technology (Joshua Zhu, Lisa Li, Timothy Chung, Ariunaa Bat-Ochir, Lisa Au, Cassandra Chow, and Terry Cho), on their success, and offer a special thanks to all of the student participants and their teachers, Bryan Cooley and Serena Chan. We appreciate the time and effort spent by all the volunteers who helped with the organization and planning of the event: Shannon Bruce (Center for Electrochemical Engineering Research, Ohio University), Stacy Schlags (ECS meetings coordinator), Gerardine Botte (IE&EE Division Chair, Ohio University), Mary Yess (ECS Deputy Executive Director), and Ohio University’s ECS Student Chapter. We offer special thanks to Vijay Ramani of the Illinois Institute of Technology for purchasing the fuel cell cars and for supporting other parts of the outreach financially through his National Science Foundation CAREER Award. The outreach is an important part of the education component of The Electrochemical Society. It aims to inspire the future generation on the importance of electrochemical science, engineering, and technology on the solution of global problems related with the sustainability of energy and water. To date, members of the Industrial Electrochemistry and Electrochemical Engineering Division (IE&EE) of the Society have performed 12 outreach events (in the US as well as overseas). The program has been a success and has reached out to over 650 participants from middle and high schools. The participants learn by doing and having fun. It is exciting to see the students passionate about the program and eager to learn. The IE&EE Division looks forward to continued success in conducting this high impact educational outreach program at future meetings. If you have an interest in getting more involved in the activities of the division, please contact Gerardine Botte at botte@ohio.edu. Contributed by: Gerardine G. Botte, IE&EE Division Chair, and Ohio University ECS Student Chapter Faculty Advisor.

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. The Electrochemical Society Interface • Spring 2014

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 17

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Division Officer Slates Announced New officers for the 2014-2016 term have been nominated for the following Divisions. All election results will be reported in the summer 2014 issue of Interface.

Dielectric Science & Technology Division Chair Dolf Landheer, National Research Council – Canada

Chair R. Bruce Weisman, Rice University

Vice-Chair Yaw Obeng, NIST

Vice-Chair Slava V. Rotkin, Lehigh University

Secretary Vimal Desai Chaitanya, New Mexico State University

Secretary Hiroshi Imahori, Kyoto University

Treasurer Purushothaman Srinivasan, Global Foundries

Treasurer Dirk Guldi, University of Erlangen-Nurnberg

Awards Chair Peter Mascher, McMaster University, Canada

Members-at-Large (at least two to be elected) Jeff Blackburn, NREL Olga Boltalina, Colorado State University Francis D’Souza, University of North Texas Tatiana DaRos, University of Trieste Shunichi Fukuzumi, Osaka University Karl M. Kadish, University of Houston Prashant Kamat, University of Notre Dame Richard Martel, University of Montreal Nazario Martin, Universidad Complutense de Madrid Roberto Paolesse, University of Rome Tor Vergata Maurizio Prato, University of Trieste Tomas Torres, Universidad Autonoma de madrid Lon Wilson, Rice University Ming Zheng, NIST

Symposium Chair Mahendra Sunkara, University of Louisville Membership Chair Uros Cvelbar, Jozef Stefan Institute, Slovenia (IJS) Members-at-Large (up to 30 to be elected) Sacharia Albin, Norfolk State University Gautam Banerjee, Air Products and Chemicals, Inc. William Brown, University of Arkansas Zhi Chen, University of Electronic Science and Technology of China Toyohiro Chikyow, National Institute for Materials Science Stefan De Gendt, IMEC John Flake, Louisiana State University Reenu Garg, International Rectifier Dennis Hess, Georgia Institute of Tecnology Michel Houssa, University of Leuven Rashmi Jha, University of Toledo P.C. Joshi, Oak Ridge National Laboratory Samares Kar, Indian Institute of Technology Zia Karim, AIXTRON Paul Kohl, Georgia Institute of Tecnology Ana Londergan, Qualcomm Technologies G. Swami Mathad, S/C Tech Consulting USA Robert Mertens, University of Central Florida Durgamadhab Misra, New Jersey Institute of Technology Hazara S. Rathore R. Ekwal Sah, Fraunhofer-Institut Sudipta Seal, University of Central Florida Krishna Shenai, Argonne National Laboratory Kalpathy B. Sundaram, University of Central Florida John Susko Robin Susko Ravi M. Todi, Qualcomm, Inc.

Nanocarbons Division

Industrial Electrochemistry & Electrochemical Engineering Division Chair Venkat Subramanian, Washington University in St. Louis Vice-Chair E. Jennings Taylor, Faraday Technologies, Inc. Secretary/Treasurer (candidate not selected will become a member-at-large) John Staser, Ohio University Douglas P. Riemer, Hutchinson Technology Members-at-Large (at least three to be elected) James Fenton, University of Central Florida Trung Van Nguyen, University of Kansas Mark E. Orazem, University of Florida Robert Savinell, Case Western Reserve University John Weidner, University of South Carolina

The Electrochemical Society Interface • Spring 2014

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websites of note by Zoltan Nagy

Physical Properties of Ionic Liquids: Database and Evaluation

A comprehensive database on physical properties of ionic liquids, which was collected from 109 published sources spanning the period from 1984 through 2004. There are 1680 pieces of data on the physical properties for 588 available ionic liquids. From these the values for 276 kinds of cations and 55 kinds of anions were extracted. Contents: 1. The Classification of Ionic Liquids. Phase transition temperature: Melting point, Glass Transition Point, Decomposition Point, Freezing Point, and Clearing Point. 2. Density, Viscosity and Surface Tension. 3. Conductivity, Polarity, and Electrochemical Window. 43 pages. • S. Zhang, et al., Chinese Academy of Sciences • http://www.nist.gov/data/PDFfiles/jpcrd721.pdf

A Catalog of Commercially Available Ionic Liquids

Ionic liquids are ionic, salt-like materials that are liquid below 100 °C. Their use can be classified as process chemicals (e.g., solvents, separation media) and performance chemicals (e.g., electrolytes, lubricants). Ionic liquids tend to have appealing solvent properties and are miscible with water or organic solvents. Sigma-Aldrich offers a market-leading range of ammonium, imidazolium-, phosphonium-, pyridinium-, pyrrolidinium-, sulfonium, etc.-based ionic liquids. • Sigma-Aldrich • http://www.sigmaaldrich.com/chemistry/chemistry-products.html?TablePage=16255866

A Listing of Recent Publications on Ionic Liquids

The peer-reviewed articles on this ChemComm web themed issue highlight recent cutting edge achievements from prominent scientists working on all aspects of ionic liquid chemistry. Contributions range from new fundamental knowledge to novel applications of ionic liquids that take advantage of their unique attributes. The guest editors for this issue are Robin D. Rogers (University of Alabama), Douglas MacFarlane (Monash University) and Suojiang Zhang (Institute of Process Engineering). • Royal Society of Chemistry • http://pubs.rsc.org/en/journals/articlecollectionlanding?sercode=cc&themeid=d3759160-edca-4baf-871d-b8873930c974

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. He welcomes suggestions for entries; send them to nagyz@ email.unc.edu.

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ECS Sponsored Meetings for 2014 In addition to the regular ECS biannual meetings and ECS Satellite Conferences, ECS, its Divisions, and Sections sponsor meetings and symposia of interest to the technical audience ECS serves. The following is a list of the sponsored meetings for 2014. Please visit the ECS website for a list of all sponsored meetings. • 10th International Symposium on Electrochemical Micro & Nanosystem Technologies, November 5-8, 2014 – Okinawa, Japan • Fifth International Conference on Electrophoretic Deposition: Fundamentals and Applications (EPD-2014), October 5-10, 2014

— Hernstein, Austria

• 65th Annual Meeting of the International Society of Electrochemistry, August 31-September 5, 2014 — Lausanne, Switzerland • ACS Symposium on Fuel Cell Chemistry and Operation, August 10-14, 2014 – San Francisco, CA • Shechtman International Symposium on Sustainable Mining, Minerals, Metal and Materials Processing, June 28-July 4, 2014

— Cancun, Mexico

• 15th Topical Meeting of the International Society of Electrochemistry, April 27-30, 2014 — Niagara Falls, Canada • 14th Topical Meeting of the International Society of Electrochemistry, March 29-April 1, 2014 — Nanjing, China • China Semiconductor Technology International Conference 2014 (CSTIC 2014),March 16-17, 2014 — Shanghai, China To learn more about what an ECS sponsorship could do for your meeting, including information on publishing proceeding volumes for sponsored meetings, or to request an ECS sponsorship of your technical event, please contact ecs@electrochem.org.

In the

issue of • Highlights from the ECS Meeting in Orlando... Don’t miss all the photos and news from the ECS spring 2014 meeting in Orlando.

• Scanning Probe Microsopy will be featured in the summer 2014 issue. Guest edited by David Cliffel and Rob Calhoun, the featured articles include (tentative list): “Electrochemical Studies Using High Resolution AFM,” by Sergie Kalinin; “Advances in Biological Scanning Electrochemical Microsopy” by Shigueru Amemiya; “Electrode Tips for Nanoscale Scanning Electrochemical Microscopy,” by Michael Mirkin; and “Scanning Ion Conductance Microscopy,” by Lane Baker.

The Electrochemical Society Interface • Spring 2014

• 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 which gives readers a look at some little-known, but very useful sites.

Volume 61– O r l a n d o , F l o r i d a from the Orlando meeting, May 11—May 15, 2014

The following issues of ECS Transactions are from symposia held during the Orlando 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. 61 Ionic and Mixed Conducting Ceramics 9 No. 1 HC ........................... M $126.00, NM $157.00

Vol. 61 Wide Bandgap Semiconductor Materials and Devices 15 No. 4 HC ........................... M $130.00, NM $163.00

Vol. 61 Dielectrics for Nanosystems 6: Materials No. 2 Science, Processing, Reliability, and Manufacturing HC .........................M $111.00, NM $138.00

Vol. 61 Nanoscale Luminescent Materials 3 No. 5 HC.............................M $96.00, NM $119.00

Vol. 61 Silicon Compatible Materials, Processes, and Technologies for No. 3 Advanced Integrated Circuits and Emerging Applications 4 HC .........................M $96.00, NM $119.00

Vol. 61 More than Moore 2 No. 6 SC.............................TBD Vol. 61 Carbon Electronics: Interfaces to Metals, Dielectrics, and Electrolytes No. 7 SC.............................TBD

Forthcoming Issues ORL A1

Batteries and Energy Technology (General) – 225th ECS Meeting

ORL A2

Material and Electrode Designs for Energy Storage and Conversion

ORL A3

Mechanical-Electrochemical Coupling in Energy Related Materials and Devices

ORL A4

ORL H1

Physical and Analytical Electrochemistry (General) – 225th ECS Meeting

ORL H2

Symposium in Honor of Andrzej Wieckowski

ORL H3

Biofuel Cells 6

Stationary and Large Scale Electrical Energy Storage Systems 4

ORL H4

Charge Transfer: Electrons, Protons, and Other Ions 2

ORL B1

Sensors, Actuators, and Microsystems (General: Chemical and Biological Sensors) – 225th ECS Meeting

ORL H5

Physical Chemistry of Electrolytes

ORL B5

Future Prospects for Sensors: Commercialization, Practical Issues, and Ubiquitous Sensing

ORL H8

Spectroelectrochemistry 2

ORL H9

Symposium in Honor of Richard Buck

Corrosion (General) – 225th ECS Meeting

ORL M2

Carbon Nanostructures for Energy Conversion

Electrodeposition for Micro- and Nano- Battery Materials

ORL M3

Carbon Nanostructures in Medicine and Biology

ORL D2

Electroless Plating: Principles and Applications 3

ORL M4

Carbon Nanotubes - From Fundamentals to Devices

ORL E1

Industrial Electrochemistry and Electrochemical Engineering (General) – 225th ECS Meeting

ORL M5

Endofullerenes and Carbon Nanocapsules

ORL M6

Fullerenes - Chemical Functionalization, Electron Transfer, and Theory

ORL E2

Characterization of Porous Materials 6

ORL M7

Graphene and Related Structures

ORL E4

Electrolysis and Electrochemical Processes

ORL M8

Nanostructures for Energy Conversion

ORL E5

Materials for Low Temperature Electrochemical Systems

ORL M9

Porphyrins, Phthalocyanines and Supramolecular Assemblies

ORL F1

Characterization of Interfaces and Interphases

ORL P1

Chemical Mechanical Polishing 13

ORL F2

Computational Studies on Battery and Fuel Cell Materials

ORL Q1

Integrated Optoelectronics 7

ORL F5

Solar Fuels and Photocatalysts 3

ORL Z1

Student Posters (General) – 225th ECS Meeting

ORL F6

State-of-the-Art Tutorial on Durability in Low Temperature Fuel Cells

ORL Z2

Nanotechnology (General) – 225th ECS Meeting

ORL G2

Manuel Baizer Memorial Award Symposium in Organic Electrochemistry 11

ORL Z3

Solid State Topics (General) – 225th ECS Meeting

ORL C1 ORL D1

Ordering Information To order any of these recently-published titles, please visit the ECS Digital Library, http://ecsdl.org/ECST/ Email: customerservice@electrochem.org 22

The Electrochemical Society Interface • Spring 2014 02/24/14

225 ECS Meeting

ORLANDO, FL May 11-15, 2014 Hilton Orlando Bonnet Creek

Special Meeting Section

ORLANDO, FL May 11-15, 2014

225 ECS Meeting th

Hilton Orlando Bonnet Creek

Orlando, FL • Special Meeting Section

elcome to Orlando! What a great place to convene the 225th ECS Meeting – tropical weather, fun attractions, premier golfing and much more make this the perfect setting to complement your technical meeting experience. This major international conference will be located in the Hilton Orlando Bonnet Creek Hotel and will include more than 1,700 technical presentations, guest and award-winning lecturers, full-day short courses, professional development workshops, panels, and career opportunities, a dynamic technical exhibit, and the first-ever 5K Energy-Run-for-Fun, with proceeds benefitting the ECS Publications Endowment. Whether you’re running to symposia or receptions, or a part of the early morning race, enjoy the best that Orlando and the 225th ECS Meeting has to offer!

Featured Speakers and Lecturers The ECS Lecture Nanowires: From Nanocomputing to Nano-Bioelectronics by Charles M. Lieber Monday, May 12, 2014, 1700h Bonnet Creek Ballrooms VII & VIII Lobby Level Charles M. Lieber received his undergraduate degree from Franklin and Marshall College and carried out his doctoral studies at Stanford University, followed by postdoctoral research at the California Institute of Technology. He was an Assistant Professor at Columbia University, and now holds appointments in the Department of Chemistry and Chemical Biology as the Mark Hyman Professor of Chemistry, and the School of Engineering and Applied Sciences at Harvard University. Professor Lieber has pioneered the synthesis of a broad range of nanowire materials, the characterization of the fundamental properties of these materials, the development of methods of hierarchical assembly of nanowires, and applications of these materials in nanoelectronics, nanophotonics, and nanocomputing. He has pioneered the field of nano-bioelectronics with seminal contributions to sensing, the development of novel nanoelectronic cell probes, and cyborg tissues. Professor Lieber’s work has been recognized by many awards, including the IEEE Nanotechnology Pioneer Award (2013), Willard Gibbs Medal (2013), and Wolf Prize in Chemistry (2012). Lieber is an elected member of the National Academy of Sciences and the American Academy of Arts and Sciences. He is Co-Editor of Nano Letters, and has published over 350 papers (71,737 citations; H-index 121) and is the principal inventor on more than 35 patents.

Society Award Lecture – Vittorio de Nora Award Address On-Wire Lithography: An Electrochemical Approach to Controlling Nanoscale Architecture by Chad Mirkin Tuesday, May 13, 2014, 0805h B1 Sensors, Actuators, and Microsystems General Session Sarasota, Ground Level Chad Mirkin is the Director of the International Institute for Nanotechnology, and the George B. Rathmann Professor of Chemistry, Chemical and Biological Engineering, Biomedical Engineering, Materials Science and Engineering, and Medicine at Northwestern University. He is a chemist and nanoscience expert, who has authored over 550 manuscripts; he is an inventor on over 900 patent applications worldwide (243 issued). Professor Mirkin has won over 80 national and international awards, and he is a Member of the President’s Council of Advisors on Science & Technology (Obama Administration). He is one of only 15 scientists, engineers, and medical doctors to be elected to all three US National Academies (the Institute of Medicine, the Natl. Academy of Sciences, and the Natl. Academy of Engineering). He is the Founding Editor of Small, an Associate Editor of JACS, and the founder of multiple companies, including Nanosphere, AuraSense, and AuraSense Therapeutics. Professor Mirkin holds a BS from Dickinson College and a PhD from Penn State. He was an NSF Postdoc at MIT prior to becoming a Professor at Northwestern in 1991.

Nanoscience offers the promise of revolutionary advances in many areas of science and technology, ranging from electronics and computing to biology and medicine, yet the realization of this promise depends critically on the rational synthesis of unique functional nanoscale structures and their organization into welldefined devices, circuits and systems. Here we highlight the power of semiconductor nanowires as a platform material for exploring new science and technology. First, a brief review of the ‘chemical’

On-wire lithography (OWL) is a template-based, electrochemical process for forming one-dimensional solution dispersible arrays of nanorods with programmably synthesized nano- and micro-scale gaps. OWL provides excellent control over the nanowire diameter (from 30 to 360 nm depending on the membrane pore size), segment length (from 6 nm to a few microns), gap size (from 1 nm to a few microns), composition (e.g., Au, Ni, Ag, Pt, Pd, PEDOT, PTh, P3HT, PPY, PPV) of the different nanowire components. The versatility of this novel technique has allowed for the fabrication of a wide variety of structures with emergent and highly

(continued on next page)

The Electrochemical Society Interface • Spring 2014

Low Temperature Plasma Etching of Copper, Silver, and Gold Films by Dennis Hess Monday, May 12, 2014, 1540h P2 Silicon Compatible Materials, Processes and Technologies for Advanced Integrated Circuits and Emerging Applications 4 Flagler, Ground Level Dennis W. Hess is the Thomas C. DeLoach, Jr., Professor of Chemical & Biomolecular Engineering and Director of the NSF Materials Research Science and Engineering Center at the Georgia Institute of Technology. He received a B.S. in Chemistry from Albright College and M.S. and Ph.D. degrees in Physical Chemistry from Lehigh University. He was a Member of the Research Staff and Supervisor of Process Development at Fairchild Semiconductor from 1973 to 1977 where he worked for Bruce Deal. In 1977, he joined the Department of Chemical Engineering (ChE) at the University of California, Berkeley as an Assistant Professor. During his time at Berkeley, he served as Assistant Dean of the College of Chemistry (1982-1987) and Vice Chair of the ChE Department (19881991). From 1991-1996 Dr. Hess served as Chair of the ChE Department at Lehigh University. He joined the School of Chemical & Biomolecular Engineering at Georgia Tech in 1996. Dr. Hess served as Divisional Editor for Journal of The Electrochemical Society from 1978-1990 and Associate Editor for Chemistry of Materials from 1988-1996. From 2004-2012, he served as Editor for Electrochemical and Solid State Letters; currently, he is Editor of ECS Journal of Solid State Science and Technology and ECS Solid State Letters. He served as ECS President for the 1996-1997 term. He received the Thomas D. Callinan Award from the ECS Dielectric Science and Technology Division (1993), the Distinguished Alumnus Award from Albright College (1998), the Charles M. A. Stine Award from the Materials Engineering and Sciences Division of AIChE (1999), the ECS Solid State Science and Technology Award (2005), and The ECS Edward

Goodrich Acheson Award (2012). Dr. Hess is an ECS Fellow, a Fellow of the American Association for the Advancement of Science, the American Chemical Society and the American Institute of Chemical Engineers. Copper, silver and gold films have garnered considerable interest due to the numerous applications possible because of their unique electrical and optical properties. Low resistivity and good electromigration resistance make these films attractive as interconnect layers in integrated circuits and microelectronic devices, while nano structures of these metals can be used to form plasmonic devices. Fabrication of structures, devices and circuits with these metals requires etching or patterning methods. However, Group 11 metals are inherently difficult to reactively plasma etch at reasonable (<100 oC) temperatures because of the limited volatility of compounds that can be formed with these metals. As a result, additive processes (e.g., lift-off or electroplating followed by polishing) have been the preferred approach to generating patterns/ structures. In contrast, pattern formation by subtractive etching offers simplicity, consistency with the patterning processes used for other films in device manufacture, and in some cases may alleviate limitations in the fabrication of future generation devices. Etching of Cu, Ag, and Au in hydrogen-based plasmas at temperatures at or below room temperature has been demonstrated. Group 11 metal hydrides form readily in an H2 plasma, suggesting that these compounds are the likely etch products, despite their limited thermodynamic stability. Due to the low ion flux and momentum of hydrogen ions under the conditions used in the inductively-coupled plasma reactor system, sputtering alone cannot account for the etch rates observed (13, 33, and 26 nm/min respectively for Cu, Ag, and Au at 20 mTorr and 10oC in H2). In these cases, desorption of metal hydrides is promoted by ion, and likely photon, bombardment. Plasma etching with methane (CH4) plasmas is possible under the same plasma conditions as those for H2 plasmas. This etch gas displays Cu etch rates of 17 nm/min relative to that of H2 (13 nm/min) with no change in wall slope. These enhancements relative to H2 plasma etching appear to be due to the formation of etch products that have improved thermodynamic stability compared to copper hydrides (e.g., CH3Cu and CH3CuH-). Preliminary etch studies of Ag and Au films using CH4 plasmas demonstrate that chemical aspects of the etch process are important, since etch rates are not reduced although hydrocarbon deposition occurs during the etch process.

Charles M. Lieber (continued from previous page) synthesis of complex modulated nanowires will be highlighted as a central material in nanoscience for enabling the bottom-up paradigm. Second, we describe novel deterministic assembly methods that involve one initial patterning step with all subsequent steps registered to this initial pattern, including the assembly and interconnection of individual nanowire elements into complex circuits. Third, we will exploit these advances together with a novel architecture, to address the concept of assembling a nanocomputer, first introduced by Feynman in 1959, with the realization of a programmable nanoprocessor of unprecedented complexity. Last,

we will describe exciting complementary advances at the frontier between nanoelectronics and biology – “nano-bioelectronics” – including nanowire probes capable of intracellular recording and stimulation at scales heretofore not possible with existing passive electrical measurements, and an ‘out-of-the-box’ look at what the future might hold in terms of merging nanoelectronic circuits with cell networks in three dimensions to ‘synthesize’ cyborg tissues and cyborg organisms. The prospects for blurring the distinction between nanoelectronic circuitry, computation and living systems in the future will be highlighted.

Chad Mirkin (continued from previous page) functional properties that are advancing studies of SERS, plasmonics, and plexcitonics and forming the basis for novel molecular electronic, optoelectronic, encoding, and chemical and biological detection devices. synthesis of complex modulated nanowires will be highlighted as a central material in nanoscience for enabling the bottom-up paradigm. Second, we describe novel deterministic assembly methods that involve one initial patterning step with all subsequent steps registered to this initial pattern, including the assembly and interconnection of individual nanowire elements into complex circuits. Third, we will exploit these advances together with a novel architecture, to address the concept of assembling a nanocomputer, first introduced by Feynman in 1959, with the realization of a

The Electrochemical Society Interface • Spring 2014

programmable nanoprocessor of unprecedented complexity. Last, we will describe exciting complementary advances at the frontier between nanoelectronics and biology – “nano-bioelectronics” – including nanowire probes capable of intracellular recording and stimulation at scales heretofore not possible with existing passive electrical measurements, and an ‘out-of-the-box’ look at what the future might hold in terms of merging nanoelectronic circuits with cell networks in three dimensions to ‘synthesize’ cyborg tissues and cyborg organisms. The prospects for blurring the distinction between nanoelectronic circuitry, computation and living systems in the future will be highlighted.

Orlando, FL • Special Meeting Section

Society Award Lecture – Henry B. Linford Award for Distinguished Teaching

Short Courses Four Short Courses will be offered in Orlando on Sunday, May 11, 2014, from 0830h to 1630h. The registration fee for the Short Courses is $425 for ECS Members and $520 for Nonmembers. Students may register for a Short Course at a 50% discount—ECS Student Members: $212.50, and Nonmember Students: $260.

The registration fee for the course includes participation in the course, text materials, continental breakfast, luncheon, and refreshment breaks; the Short Course Registration fee does not include or apply to the general Meeting Registration, and it is not applicable to any other activities of the meeting. Pre-registration for Short Courses is required—the deadline is April 11, 2014

Short Course #1

Short Course #3

This course is intended for chemists, physicists, materials scientists, and engineers with an interest in applying electrochemical impedance techniques to study a broad variety of electrochemical processes. The attendee will develop a basic understanding of the technique, the sources of errors in impedance measurements, the manner in which experiments can be optimized to reduce these errors, and the use of graphical methods to interpret measurements in terms of meaningful physical properties.

This course is intended for chemists, physicists, materials scientists, and engineers to better understand the specific requirements for energy storage on the electric grid. The course will introduce students to the concepts associated with the “smart grid” and the demands that intermittent renewable power sources place on the grid from the perspective of distribution. We will then examine some of the key technologies under consideration for energy storage and the technical targets and challenges that must be addressed. Students will be brought up to date with the current state of the art, and review data from demonstration systems, experimental data from prototype designs, and some modeling and analysis.

Orlando, FL • Special Meeting Section

Basic Impedance Spectroscopy Mark E. Orazem, Instructor

Grid-Scale Energy Storage Jeremy P. Meyers, Instructor

Short Course #2

Fundamentals of Electrochemistry: Basic Theory and Thermodynamic Methods Jamie Noël, Instructor This course covers the basic theory and application of electrochemical science. It is targeted toward people with a physical sciences or engineering background who have not been trained as electrochemists, but who want to add electrochemical methods to their repertoire of research approaches. There are many fields in which researchers originally approach their work from another discipline but then discover that it would be advantageous to understand and use some electrochemical methods to complement the work that they are doing. The course has just been fully revised to include more practical examples and a more manageable volume of material. It complements a revised sister course, “Fundamentals of Electrochemistry: Basic Theory and Kinetic Methods”, to be offered by the same instructor at the ECS fall meeting. The two courses have different emphasis, and each is designed to be a stand-alone introduction to electrochemical fundamentals. If both courses are desired, they can be taken in either order. Short Course Refund Policy: Written requests for Short Course refunds will be honored only if received at ECS headquarters by May 5, 2014. All refunds are subject to a 10% processing fee and requests for refunds must be made in writing and e-mailed to customerservice@electrochem.org. Refunds will not be processed until AFTER the meeting. All courses are subject to cancellation pending an appropriate number of advance registrants.

Short Course #4

More-than-Moore Technologies: Device, Circuit and System Perspectives Yiyu Shi, Instructor This course is designed to be interdisciplinary, providing crossdomain knowledge in computer engineering, physics and chemistry. It is intended for chemists, physicists, materials scientists, and electrical/computer engineers with an interest in developing or utilizing More-than-Moore technologies. The course is best suited for an attendee who has little or no background in these technologies and wants to appreciate the overall picture. The attendee will develop basic understanding of fundamental mechanisms behind various More-than-Moore technologies, their pros and cons, their critical issues/open questions that need to be addressed, and their possible applications in computer circuit and system designs.

Before making any flight or hotel reservations, please check to make sure the Short Course that you have selected is being offered. Please visit the ECS website for full course descriptions and instructor biographies.

Panel of Professionals As part of the professional development series, ECS is pleased to present the inaugural Panel of Professionals at the 225th ECS Meeting in Orlando in May. Please join us on Monday, May 12th, 1800-1900h in Floridian Ballroom H, on the Lobby Level. Attendees will hear from three guest speakers, representing industry, academia, and government, each discussing the unique challenges and opportunities of pursuing a career in their chosen field.

Confirmed panelists: Hariklia (Lili) Deligianni, PhD, Thomas J. Watson Research Center, IBM Corporation Amy Marschilok, PhD, Research Associate Professor in Materials Science and Engineering Chemistry at Stony Brook University, SUNY Gabriel Veith, PhD, Senior Staff Scientist, Oak Ridge National Laboratory The session will be moderated by Kevin Rhodes of Ford Motor Company. There will be ample time for questions and answers. Students and early-career professionals are strongly encouraged to attend.

Award Winners Albert G. Baca is a Distinguished Member of the Technical Staff at Sandia National Laboratories. From 1985-1990 he worked at AT&T Bell Laboratories in GaAs-based microelectronics. Since 1990 he has been at Sandia National Laboratories where he has been responsible for the development of a number of compound semiconductor device technologies. Dr. Baca has led research efforts in the realization of compound semiconductor devices such as GaAs/AlGaAs heterostructure field effect transistors for high speed fiber optic communications, high voltage GaAs heterojunction bipolar transistors (HBTs), co-integration of sensors and GaAs electronics, low-power InP HBTs, novel InGaAsN HBTs, high power GaN/AlGaN high electron mobility transistors, and high voltage, high current photoconductive semiconductor switches. He has most recently engaged in reliability research in HBTs. This research has led both to research “firsts” as well as production worthy technology. He has co-authored more than 160 publications, holds eight US patents, and has also co-authored the book, Fabrication of GaAs Devices. He served on the honorary editorial board for Solid-State Electronics from 1998-2012. Dr. Baca received a BS degree in chemistry and mathematics from the University of New Mexico in 1979 and a PhD in chemistry from the University of California at Berkeley in 1985. He was selected fellow of the ECS in 2006. Among other Society activities, he served as chair of the Electronics and Photonics Division from 2007-2009, has coorganized multiple symposia for ECS meetings, and chaired the SolidState Subcommittee for selection of the Young Authors Award from 2002-2005. In 2003, he chaired the Subcommittee on Processing for the InP and Related Materials Conference. He also served on the IEEE GaAs IC Symposium Technical Program Committee from 1997-1999.

Supramanian Srinivasan Young Investigator Award of the Energy Technology Division Minhua Shao earned BS and MS degrees in chemistry from Xiamen University in China, and a PhD degree in materials science and engineering from Stony Brook University in 2006. Under the guidance of Radoslav Adzic, his doctoral research focused on understanding the reaction mechanisms of fuel cell reactions by surface enhanced infrared absorption spectroscopy (SEIRAS) and developing low cost electrocatalysts for oxygen reduction reaction (ORR) and small organic molecule oxidation. Dr. Shao joined UTC Power (now ClearEdge Power) in 2007 to lead the development of advanced catalysts and supports for proton exchange membrane fuel cell and phosphoric acid fuel cell. He was promoted to Technical Fellow for his outstanding technical contributions, strategic leadership and mentoring skills. In 2013, he joined Ford Motor Company to conduct research on lithium-ion batteries for the next generation electrified vehicles. He looks forward to starting his academic career at the Hong Kong University of Science and Technology this spring. He has published 50 peer-reviewed articles, 1 edited book and filed over 30 patent applications. He has also received a number of awards, including the ECS Student Achievement Award of the Industrial Electrochemistry and Electrochemical Engineering Division (2007), President’s Award to Distinguished Doctoral Students from Stony Brook University (2006), Chinese Government Award for Outstanding Self-Financed Students Abroad from China Scholarship Council (2006), and Dr. Mow Shiah Lin Award from Brookhaven National Laboratory (2006). Please see pages 24 and 25 for biographies of the Vittorio de Nora Award winner and the Henry B. Linford Award for Distinguished Teaching winner. For additional information and schedule for award presentations, please see the General Meeting Program on the Orlando page of the ECS web site: http://www.electrochem. org/meetings/biannual/225/. The Electrochemical Society Interface • Spring 2014

Research Award of the Energy Technology Division James M. Fenton is the Director of the University of Central Florida’s Florida Solar Energy Center (FSEC), where he leads a staff of 140 in the research and development of energy technologies that enhance Florida’s and the nation’s economy and environment and educate the public, students and practitioners on the results of the research. The US DOE is currently funding programs at FSEC in: “Building America” energy efficient homes, Photovoltaic Manufacturing, Hot-Humid PV testing of large-scale PV to show bankability, train-the-trainers education for solar installations, and programs to decrease the soft-costs of PV installation. Recently, DOE provided funding to UCF to manage a smart-grid education consortium for university power electrical engineering students (FEEDER), and the US DOT awarded to UCF the nation’s only University Electrical Vehicle Transportation Center (EVTC). Prior to joining FSEC, Dr. Fenton spent 20 years as a Chemical Engineering Professor at the University of Connecticut. He received his Ph.D. in Chemical Engineering from the University of Illinois in 1984 and his B.S. from UCLA in 1979. He has over 30 years’ experience in electrochemical energy devices and education topics which include: zinc/bromine, zinc/chlorine flow batteries, membrane durability, CO tolerance electrocatalysts, hydrogen purification processes, low-methanol crossover membranes, high temperature membranes, membranes needing no external humidification, selective oxidation catalysts, gas diffusion layer design, reversible PEM fuel cells, and biomass and landfill gas fuel processing. He is an Electrochemical Society Fellow and has strongly encouraged younger scientists and engineers in participating in The Electrochemical Society's, Energy Technology, and IEEE Division's technical symposia and in taking on service roles for the Society. He is the author of more than 120 scientific publications, a number of book chapters, and co-authored Experimental Methods and Data Analyses for Polymer Electrolyte Fuel Cells, and holds four patents. He led a 12-member university and industry research team on a $19 million U.S. Department of Energy research program to develop the next generation proton exchange membrane (PEM) fuel cell automobile engine that would operate at 120 ºC. He will be presenting “Membrane Electrode Assembly Fabrication from Membranes of the DOE High Temperature High Temperature Membrane Working Group,” as the award address for the Research Award of the Energy Technology Division.

Organic and Biological Electrochemistry Division Manuel M. Baizer Award Jun-Ichi Yoshida is a professor in the Department of Synthetic Chemistry and Biological Chemistry at Kyoto University, where he has been since 1994. He graduated from Kyoto University in 1975, where he received his doctor’s degree under the supervision of Prof. Makoto Kumada in 1981. In 1979, Dr. Yoshida joined the faculty at Kyoto Institute of Technology as an assistant professor. He was a visiting professor at the University of Wisconsin in 1982-1983, where he joined the research group of Prof. B. M. Trost. In 1985 he moved to Osaka City University, where he was promoted to an associate professor in 1992. Professor Yoshida has earned numerous awards, including the Progress Award of Synthetic Organic Chemistry, Japan (1987); the Chemical Society of Japan Award for Creative Work (2001); the Nagoya Medal Prize (Silver Medal) (2006); the Humboldt Research Award (2007); the Green Sustainable Chemistry Award (2010); the Ta-shue Chou Lectureship Award (2013); and the Chemical Society of Japan Award (2013). His research interests include integrated organic synthesis on the basis of reactive intermediates, organic electron transfer reactions, organometallic reactions, and microreactors. 27

Orlando, FL • Special Meeting Section

Electronics and Photonics Division Award

Technical Exhibit The ECS Technical Exhibit is always the talk-of-the-meeting—technical exhibits offer a popular networking opportunity as attendees gather together with colleagues and meet new contacts. The exhibitors in Orlando will showcase instruments, materials, systems, publications, and software, and other products and services, and many will provide demonstrations. Complimentary coffee breaks are scheduled on Tuesday and Wednesday at 0930h in the Exhibit Hall. In addition, the Poster Sessions and receptions will be held in the Exhibit Hall on Tuesday and Wednesday evenings, beginning at 1800h.

Exhibit Hours Grand Foyer, Lobby Level

Orlando, FL • Special Meeting Section

Monday, May 12 1900h–2300h ................................................. Exhibitor Move-In Tuesday, May 13 0900h–1400h.................................................... Technical Exhibit 0930h–1000h..................................Coffee Break in Exhibit Area 1800h–2000h................................................... Technical Exhibit, General & Student Poster Session* Wednesday, May 14 0900h–1400h.................................................... Technical Exhibit 0930h–1000h..................................Coffee Break in Exhibit Area 1800h–2000h........ Technical Exhibit & General Poster Session* 2030h–2330h................................. Technical Exhibit Tear Down * This event will host beer, soft drinks, and dry snacks

ECS welcomes our Exhibitors ALS CO., LTD. Booth 123 Katsunobu Yamamoto yamamoto@bas.co.jp www.als-japan.com Arbin Instruments Booth 138 Antony Parulian antony@arbinmail.com www.arbin.com Beijing Mikrouna / Vacuum Technology Inc. Booth 131 Sam Cai caiyuling@mikrouna.cn www.mikrouna.cn Biologic Booths 142, 143, 144 David Carey david.carey@bio-logic.us www.bio-logic.us ECS Booths 136, 137 Dan Fatton dan.fatton@electrochem.org www.electrochem.org

__________________________________

ESL Electro Science

Booth 124 Lauren Timko ltimko@electroscience.com www.electroscience.com Gamry Instruments

Horiba Scientific Booth 120 Diane Surine diane.surine@horiba.com www.horiba.com INFICON Booth 105 Tom Wilson tom.wilson@inficon.com www.inficon.com Ivium Technologies Booth 122 Pete Peterson info@ivium.us 800-303-3885 www.ivium.us MTI Corporation Booth 121 Mel Jiang mel@mtixtl.com www.mtixtl.com Nanoflex Booth 116 Camilla Hick cam.hick@nanoflex.com www.nanoflex.com PEC North America Inc. Booth 106 Peter Ulrix Peter.ulrix@peccorp.com www.peccorp.com Pine Research Instrumentation Booths 140, 141 Jenny Garry jgarry@pineinst.com www.pineinst.com/echem Princeton Applied Research/Solartron Analytical Booths 117, 118, 119 Ari Tampasis aritampasis@ametek.com www.princetonappliedresearch.com Redcat Booth 135 www.redcatresearch.org Scribner Associates, Inc. Booth 139 Jason Scribner jason@scribner.com www.scribner.com

Booths 112, 113 Wanda Dasch wdasch@gamry.com www.gamry.com 28

The Electrochemical Society Interface • Spring 2014

ECS thanks our

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for their generous support

Orlando, FL • Special Meeting Section

Gold Sponsor

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ECS Mobile APP! • Easy to download from the iTunes Store or Android Market. • Stay up-to-date with meeting activities 100% of the time. • Check it out—Plan events and presentations, manage your own schedule, stay in minute-by-minute contact with colleagues and other attendees, and more! • Tweet the word—Tell your friends and colleagues so everyone can stay on top and in touch at the 225th ECS Meeting! Use hashtag #ecs225.

The Electrochemical Society Interface • Spring 2014

Symposium Topics and Organizers A — Batteries, Fuel Cells, and Energy Conversion A1 — Batteries and Energy Technology Joint General Session (M-Th) – Y. Xing, V. Di Noto, J. Muldoon, A. Manivannan, S. Narayanan Battery Division, Energy Technology Division A2 — Material and Electrode Designs for Energy Storage and Conversion (M –Th) – J. Xiao, J. Wu, K. Zaghib, V. Kalra Battery Division, Energy Technology Division, Industrial Electrochemistry and Electrochemical Engineering Division A3 — Mechanical-Electrochemical Coupling in Energy Related Materials and Devices (M-W) – J. D. Nicholas, Y. Qi, P. Mukerjee, S. Bishop High Temperature Materials Division, Battery Division, Energy Technology Division A4 — Stationary and Large Scale Electrical Energy Storage Systems 4 (M-T) – S. Narayan, A. Weber, J. Meyers, B. Y. Liaw, G. Botte Energy Technology Division, Battery Division, Industrial Electrochemistry and Electrochemical Engineering Division

Orlando, FL • Special Meeting Section

B — Chemical and Biological Sensors B1 — Sensors, Actuators, and Microsystems General Session (Chemical and Biological Sensors) (T-W) – N. Wu, G. Hunter, L. Nagahara, A. Khosla, A. Simoniam, S. Mitra, Z. Aguilar Sensor Division, Battery Division, Energy Technology Division, High Temperature Materials Division B5 — Future Prospects for Sensors: Commercialization, Practical Issues, and Ubiquitous Sensing (M) – M. Carter, G. Hunter, V. Lvovich, J. Stetter, P. Hesketh, J. Li, S. Minteer, A. Khosla, S. C. Barton Sensor Division, Energy Technology Division, Physical and Analytical Electrochemistry Division, Interdisciplinary Science and Technology Subcommittee C — Corrosion Science and Technology C1 — Corrosion General Session (W-Th) – R. G. Buchheit Corrosion Division D — Electrochemical/Electroless Deposition D1 — Electrodeposition for Micro- and Nano-Battery Materials (T) – J. Rohan, J. Owen, S. Mukerjee, K. M. Abraham Electrodeposition Division, Battery Division, Energy Technology Division D2 — Electroless Plating: Principles and Applications 3 (M-T) – S. Djokic, N. Dimitrov, J. Stickney, L. Magagnin Electrodeposition Division E — Electrochemical Engineering E1 — Industrial Electrochemistry and Electrochemical Engineering General Session (T) – G. Botte, J. Weidner, H. Xu, E. J. Taylor Industrial Electrochemistry and Electrochemical Engineering Division, Battery Division, Electrodeposition Division, Energy Technology Division E2 — Characterization of Porous Materials 6 (T) – J. Staser, V. Birss, J. Gostick, J. Xiao Industrial Electrochemistry and Electrochemical Engineering Division, Battery Division, Energy Technology Division, Physical and Analytical Electrochemistry Division E4 — Electrolysis and Electrochemical Processes (W) – G. Botte, J. Weidner, K. Ayers Industrial Electrochemistry and Electrochemical Engineering Division, Energy Technology Division E5 — Materials for Low Temperature Electrochemical Systems (T-Th) – P. Pintauro, M. Shao, R. Wycisk, P. Atanassov, K. Karan, B. Lucht Industrial Electrochemistry and Electrochemical Engineering Division, Battery Division, Energy Technology Division, Physical and Analytical Electrochemistry Division F — Fuel Cells, Electrolyzers, and Energy Conversion F1 — Characterization of Interfaces and Interphases (T-W) – T. Nguyen, P. Atanassov, R. Kostecki, F.-Y. Zhang Energy Technology Division, Battery Division, Industrial Electrochemistry and Electrochemical Engineering Division, Physical and Analytical Electrochemistry Division F2 — Computational Studies on Battery and Fuel Cell Materials (in Honor of Professor Ishikawa Symposium) (M-W) – D. Chu, S. R. Narayan, E. M. Ryan, S. Meng Energy Technology Division, Battery Division, High Temperature Materials Division, Physical and Analytical Electrochemistry Division

F4 — Ionic and Mixed Conducting Ceramics 9 (M-Th) – M. Mogensen, T. Kawada, T. Armstrong, T. Gur, X.-D. Zhou, A. Manivannan, S. Gopalan, S. R. Narayan High Temperature Materials Division, Energy Technology Division F5 — Solar Fuels and Photocatalysts 3 (M-T) – N. Wu, V. Subramanian, A. Manivannan, P. Kulesza, D. Chu, H. Dinh, J. Fenton, H. Wang Energy Technology Division, Industrial Electrochemistry and Electrochemical Engineering Division, Physical and Analytical Electrochemistry Division F6 — State-of-the-Art Tutorial on Durability in Low Temperature Fuel Cells (T-W) – A. Weber, T. Zawodzinski, T. Schmidt, J. Fenton, R. Borup Energy Technology Division, Industrial Electrochemistry and Electrochemical Engineering Division, Physical and Analytical Electrochemistry Division (NOTE: Please refer to A3 for a related symposium) G — Organic and Bioelectrochemistry G2 — Manuel Baizer Memorial Award Symposium in Organic Electrochemistry 11 (M-T) – K. Chiba, D. Peters, S. Nishiyama Organic and Biological Electrochemistry Division H — Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry H1 — Physical and Analytical Electrochemistry General Session (M-T) – P. Kulesza Physical and Analytical Electrochemistry Division H2 — Symposium in Honor of Andrzej Wieckowski ( M-Th) – P. Zelenay, R. R. Adzic, S. Gottesfeld, J. Inukai, N. M. Markovic, S. Mukerjee, M. Neurock, A. Lewenstam, P. J. Kulesza, P. Atanassov, D. J. Myers Physical and Analytical Electrochemistry Division H3 — Biofuel Cells 6 (M-W) – P. Atanassov, S. C. Barton, N. Mano, S. Minteer Physical and Analytical Electrochemistry Division, Energy Technology Division, Organic and Biological Electrochemistry Division, Sensor Division H4 — Charge Transfer: Electrons, Protons, and Other Ions 2 (T-W) – S. Paddison, V. Di Noto Physical and Analytical Electrochemistry Division, High Temperature Materials Division H5 — Physical Chemistry of Electrolytes (M-W) – P. Trulove, P. J. Kulesza, P. Vanýsek, K. Gering Physical and Analytical Electrochemistry Division, Battery Division H8 — Spectroelectrochemistry 2 (T) – S. Mukerjee, V. Di Noto Physical and Analytical Electrochemistry Division H9 — Symposium in Honor of Richard Buck (M-T) – P. Vanýsek, A. Lewenstam Physical and Analytical Electrochemistry Division M — Carbon Nanostructures and Devices M1 — Carbon Electronics: Interfaces to Metals, Dielectrics, and Electrolytes (T-W) – M. Madou, A. Hoff, M. Carter, D. Landheer, R. Martel, R. Kostecki, C. Wang Dielectric Science and Technology Division, Battery Division, Electronics and Photonics Division, Nanocarbons Division, Sensor Division M2 — Carbon Nanostructures for Energy Conversion (M-T) – J. Blackburn, M. Arnold, K. Rajeshwar, R. Kostecki, R. Martel Nanocarbons Division, Energy Technology Division M3 — Carbon Nanostructures in Medicine and Biology (M) – T. DaRos, L. Wilson, R. Van Staden, D. Heller Nanocarbons Division, Sensor Division M4 — Carbon Nanotubes - From Fundamentals to Devices (T-W) – S. V. Rotkin, M. Zheng, S. Doorn, Y. Gogotsi, R. B. Weisman Nanocarbons Division M5 — Endofullerenes and Carbon Nanocapsules (W) – T. Akasaka, L. Echegoyen, S. Yang Nanocarbons Division M6 — Fullerenes - Chemical Functionalization, Electron Transfer, and Theory (T) – F. D’Souza, D. Guldi, S. Fukuzumi Nanocarbons Division, Physical and Analytical Electrochemistry Division M7 — Graphene and Related Structures (M-T) – H. Grebel, S. V. Rotkin, L. Huang, Y. Obeng Nanocarbons Division M8 — Nanostructures for Energy Conversion (T-W) – H. Imahori, P. Kamat, K. Murakoshi, V. Subramanian, J. Xiao Nanocarbons Division, Battery Division, Energy Technology Division

The Electrochemical Society Interface • Spring 2014

Symposium Topics and Organizers (continued)

N — Dielectric Science and Materials N2 — Dielectrics for Nanosystems 6: Materials Science, Processing, Reliability, and Manufacturing (M-W) – D. Misra, Y. Obeng, T. Chikyow, H. Iwai, Z. Chen, D. Bauza Dielectric Science and Technology Division, Electronics and Photonics Division N3 — More-than-Moore (M-W) – Y. Obeng, G. Banerjee, S. Datta, P. Hesketh, T. Hiramoto, P. Srinivasan, A. Hoff Dielectric Science and Technology Division, Electronics and Photonics Division, Sensor Division, Interdisciplinary Science and Technology Subcommittee P — Electronic Materials and Processing P1 — Chemical Mechanical Polishing 13 (T) – R. Rhoades, I. Ali, G. Banerjee, L. Economikos, D. Huang, Y. Obeng, B. Basim Dielectric Science and Technology Division P2 — Silicon Compatible Materials, Processes, and Technologies for Advanced Integrated Circuits and Emerging Applications 4 (M-W) – F. Roozeboom, E. P. Gusev, H. Iwai, K. Kakushima, V. Narayanan, P. J. Timans, Paul Kohl, O. M. Leonte Electronics and Photonics Division, Dielectric Science and Technology Division

Q — Electronic and Photonic Devices and Systems Q1 — Integrated Optoelectronics 7 (M-W) – M. J. Deen, Q. Fang, C. Jagadish, L. F. Marsal, K. Ohashi Electronics and Photonics Division, Dielectric Science and Technology Division Q2 — Wide Bandgap Semiconductor Materials and Devices 15 (M-Th) – F. Ren, D. Senesky, Y.-L. Wang, S. J. Pearton, E. B. Stokes, G. Hunter Electronics and Photonics Division, Sensor Division R — Luminescence and Display Materials, Devices, and Processing R1 — Nanoscale Luminescent Materials 3 (M-W) – P. Mascher, D. Lockwood Dielectric Science and Technology Division, Luminescence and Display Materials Division Z — General Z1 — General Student Poster Session (T) – V. Subramanian, V. Chaitanya, J. St-Pierre, C. Johnson, M. P. Foley, K. B. Sundaram All Divisions Z2 — Nanotechnology General Session (T-W) – W. Mustain, O. M. Leonte All Divisions, Interdisciplinary Science and Technology Subcommittee Z3 — Solid State Topics General Session (T-W) – K. Sundaram, O. M. Leonte, K. Shimamura, H. Iwai Dielectric Science and Technology Division, Electronics and Photonics Division, Energy Technology Division, Luminescence and Display Materials Division, Nanocarbons Division, Organic and Biological Electrochemistry Division, Sensor Division

SPECIAL OFFER! Purchase a hardcover copy of ECS Transactions Volume 61, Issues 1, 2, 3, 4, or 5 with your Orlando meeting registration and receive 10% off that issue’s list price! For ECS Members, the 10% discount will be on top of your regular Member discount for these issues. Any discounted books purchased must be picked up at the Orlando meeting. The discount does not apply to electronic editions of these issues. This discount is not valid on any other issues of ECST, Monographs, or Proceedings Volumes purchased at the meeting.

ECS Transactions – Forthcoming Issues In addition to those symposia that have committed to publishing an issue of ECS Transactions (ECST), all other symposia potentially will be publishing an issue of ECST approximately 16 weeks after the Orlando meeting. If you would like to receive information on any of these issues when they become available, please e-mail. Please include your name, e-mail address, and all issues in which you are interested. ECS Transactions (ECST) – Symposia with issues available “at” the meeting are labeled with this special icon. Hard-cover (HC) editions will be available for purchase and pick-up at the meeting; or you may pre-order on the meeting registration form or when registering online. Electronic (PDF) editions will be available ONLY via the ECS Digital Library (www.ecsdl.org). Electronic editions of the Orlando “at” meeting issues will be available for purchase beginning May 2, 2014. Please visit the ECS website for all issue pricing and ordering information for the electronic editions.

The Electrochemical Society Interface • Spring 2014

Orlando, FL • Special Meeting Section

M9 — Porphyrins, Phthalocyanines, and Supramolecular Assemblies (M-W) – K. Kadish, R. Paolesse, N. Solladie, T. Torres Nanocarbons Division, Physical and Analytical Electrochemistry Division

Reserve Hotel Accommodations Early Hotel discounts are available through April 11, 2014 or until the block sells out, whichever comes first!

Orlando, FL • Special Meeting Section

he 225th ECS Meeting will be held at the meeting headquarters hotel, the Hilton Orlando Bonnet Creek (14100 Bonnet Creek Resort Lane, Orlando, Florida 32821). We strongly encourage you to stay at this hotel to ensure an enjoyable and convenient meeting experience. Hotel reservations may be made online for the special discounted meeting rate of $205 which includes the mandatory $22 resort fee, Internet access and free shuttle service to Disney attractions. The deadline for reservations is April 11, 2014, or until the block sells out, whichever comes first. Reservations placed after April 11 will be accepted on a space and rate availability basis only.

Travel Companions— Nontechnical Registrants Travel companions of attendees are invited to register for the 225th ECS Meeting as a “Nontechnical Registrant.” The nontechnical registrant registration Early-Bird fee of $25 (increases to $35 after April 11) includes admission to non-ticketed social events; use of an exclusive Get-together Lounge with beverage service and light refreshments, Monday through Thursday, 0800-1000h; and a special “Welcome to Orlando” orientation presented by Visit Orlando on Monday, May 12 at 0900h in the lounge. Please note that online registration is not available for Nontechnical Registrants.

Registration Information Registration Hours Saturday, May 10............................................................. 1600–1900h Sunday, May 11................................................................ 0700–1900h Monday, May 12.............................................................. 0700–1900h Tuesday, May 13.............................................................. 0700–1730h Wednesday, May 14......................................................... 0800–1600h Thursday, May 15............................................................ 0800–1200h Registration Fees—ALL PARTICIPANTS AND ATTENDEES ARE REQUIRED TO PAY THE APPROPRIATE REGISTRATION FEE LISTED BELOW. Payment can be made by cash, check, or travelers’ checks in U.S. funds drawn on a U.S. bank. Visa, MasterCard, American Express, or Discover are also accepted. The deadline for Early-Bird Registration is April 11. 2014. Regular registration rates are in effect online after April 11, 2014 and at the meeting. Early-Bird (through April 11)

Regular Rate (April 12 and after)

ECS Member.............................................$475...........................$575 Nonmember...............................................$635...........................$735 ECS Student Member...............................$170...........................$270 Student Nonmember.................................$205...........................$305 One Day ECS Member.............................$290...........................$390 One Day Nonmember...............................$380...........................$480 Nontechnical Registrant..............................$25.............................$35 ECS Emeritus or Honorary Member....... Gratis......................... Gratis Information for Students –All students must present a current, dated student ID card, or for postdocs, a letter from a professor stating that you are a full or part-time student, when you pick up your registration materials at the meeting. 32

ECS Meeting Abstracts—are always right at hand—and as always, are FREE with registration. Registrants may easily access them through wireless Internet, which will be available at the meeting; view them on the ECS Meeting App; or download them directly from the 225th ECS Meeting website. Paper editions of meeting abstracts are no longer distributed; attendees who require paper should download the abstracts and print them in advance of the meeting. Financial Assistance—Financial assistance is 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. Individuals requiring an official letter of invitation should write to the ECS headquarters office; such letters will not imply any financial responsibilities of ECS.

General Meeting Information Key Locations in the Hilton Orlando Bonnet Creek Hotel Meeting Registration..................................Grand Foyer, Lobby Level Information/Message Board........................Grand Foyer, Lobby level ECS Headquarters Office...............................Bradford, Ground Level ECS and Redcat.........................................Grand Foyer, Lobby Level AV Tech Table.................... Located outside select symposium rooms Technical Exhibit.......................................Grand Foyer, Lobby Level

Refund Policy Refund requests for Meeting Registration or Short Course Registration (separate fees) must be requested in writing and will be accepted only if received by May 5, 2014. All refunds are subject to a 10% processing fee. Requests for refunds should be e-mailed to customerservice@electrochem.org. Refunds will not be processed until AFTER the meeting.

Photography & Recording

By attending the ECS meeting, you agree that you will not record any meeting-related REC activity, without the express, written consent from ECS. Recording means any audiovisual or photographic methods. Meeting-related activity means any presentation (oral or poster) or social event directly related to the meeting. You may photograph your own personal, non-meeting related activity, but you must obtain permission from all involved parties before photographs can be taken of other people or displays at the meeting or exhibit. Press representatives must receive media credentials and recording permission from the ECS Headquarters Office. If you violate this policy, you will be removed from the meeting. Your registration will be revoked and you will lose all access to the meeting. In this case, you will not receive a refund of the registration fees. ECS also reserves the right to deny your attendance at future ECS or ECS sponsored meetings. Thank you for your consideration.

ADA Accessibility

Special accommodations for disabled attendees will be handled on an individual basis provided that adequate notice is given to the ECS Headquarters Office. The Electrochemical Society Interface • Spring 2014

Author Choice Open Access ECS is very pleased to announce the launch of Author Choice Open Access across its four peer-reviewed journals: Journal of The Electrochemical Society, ECS Journal of Solid State Science and Technology, ECS Electrochemistry Letters, and ECS Solid State Letters. If you are attending the 225th ECS Meeting in Orlando, Florida you will also receive one Article Credit, which may be used for up to 12 months after the meeting. (See story on page 9.) If you have questions, please visit our Open Access page on the ECS website or contact oa@electrochem.org for personal assistance.

The 225th ECS Meeting 5K ENERGY-RUN-FOR-FUN Claim your space at the starting line of the inaugural 5K EnergyRun-For-Fun and enjoy the scenery of the Hilton Orlando Bonnet Creek during a fresh morning run! Plus, the top three finishers will receive award medals. The 5K Energy-Run-For-Fun is a ticketed event within the 225th ECS Meeting, with proceeds benefitting the ECS Publications Endowment. Bring your shoes and join us for a memorable activity to jog your mind, as well as your body.

The Electrochemical Society 65 South Main Street, Pennington, New Jersey 08534-2839, USA Tel: 609.737.1902 l Fax: 609.737.2743 E-mail: ecs@electrochem.org

www.electrochem.org

When: Monday, May 12, starting time of 0730h Where: Signature Island Cost: • Early-Bird rate until April 11, 2014...........$15 • Between April 12 and May 11, 2014.........$20 • Event day sign-up......................................$25 To register for this exciting event, please add it to your meeting registration.

Meeting Events-at-a-Glance Note: For a list of Committee Meetings, please visit the Orlando meeting page: http://www.electrochem.org/orlando.

SUNDAY, MAY 11

TUESDAY, MAY 13

0830h ��Short Courses 1400h ��Professional Development Series: Essential Elements for Employment Success

0800h ��Technical Sessions* 0800h ��Professional Development Series: Resume Review 0810h ��Vittorio de Nora Award Address: On-Wire Lithography: An Electrochemical Approach to Controlling Nanoscale Architecture by Chad Mirkin 0900h ��Technical Exhibit 0930h ��Technical Session Coffee Break in Exhibit Hall 1215h ��Annual Society Business Meeting & Luncheon; non-refundable ticketed event 1700h ��ECS Publications–Author Information Session 1800h ��Technical Exhibit and General and Student Poster Session

MONDAY, MAY 12 0730h ��5K Energy-Run-For-Fun 0800h ��Technical Sessions* 0800h ��Professional Development Series: Essential Elements for Employment Success 0930h ��Technical Session Coffee Break 1200h ��Professional Development Series: Resume Review 1540h ��Henry B. Linford Award for Distinguished Teaching Address: Low Temperature Plasma Etching of Copper, Silver, and Gold Films by Dennis Hess 1700h ��The ECS Lecture— Nanowires: From Nanocomputing to Nano-Bioelectronics by Charles M. Lieber 1800h ��Professional Development Series: Panel of Professionals 1900h ��Student Mixer (By invitation only; contact sponsorship@electrochem.org for details)

WEDNESDAY, MAY 14 0800h ��Technical Sessions* 0800h ��Professional Development Series: Resume Review 0900h ��Technical Exhibit 0930h ��Technical Session Coffee Break in Exhibit Hall 1800h ��Student Poster Award Presentation in Exhibit Hall 1800h ��Technical Exhibit and General Poster Session

THURSDAY, MAY 15 0800h ��Technical Sessions* 0930h ��Technical Session Coffee Break The Electrochemical Society Interface • Spring 2014

* Check Technical Program for exact time

ECS Classics Brian Conway Remembered by Barry R. MacDougall

along with the many important contributions he made to the field of hen I was asked to electrochemical science and technology. write a retrospective Conway began his career at Imperial College, London University, on the life and career in the group of John O’M. Bockris (recently deceased) in 1946 at age of Brian E. Conway, I thought 21. That early research with Bockris led to seven major publications, a lot about what it was that dealing mainly with electrocatalysis of the hydrogen evolution reaction made Brian a truly unique (HER) on different metals, and the role of solution and surface figure in the field of physical impurities on the kinetics and mechanism of the reaction. While it is electrochemistry. Besides the probably hard to believe these days, not that much was known about obvious fact that he was a very the detailed kinetics and mechanism of such processes ~ 70 years ago. major force in advancing the John considered Brian to be a superlative physical electrochemist (in his field during his nearly 60-year own words), and had immense respect for his mind and wisdom. During career, I realized that it was due my years at University of Ottawa (U of O), Bockris visited Brian on at least in part to his equally many occasions for stimulating, in-depth scientific discussions as well strong contributions to both as reminiscing about British culture and values (Brian would confide the “electrodics” and “ionics” to us), something I found hard to understand as a young student from sides of electrochemistry. [For Brian Conway Nova Scotia. They spent a lot of time working on Modern Aspects of those not familiar with these Electrochemistry, as well as joint papers and projects; I always thought terms, the former refers to heterogeneous processes occurring at that John loved being in Ottawa, and having direct scientific exchanges the interface between the solid electrode and the solution, while the with Brian. It must have been hard to put-up with John sometimes, but latter deals with mainly homogeneous phases and ions in solution.] Brian was always able to handle it with grace and style. Both are critical for electrochemistry, and Brian was a master in both areas over all those years. This is something that is rarely, if ever, the case today (and was even unusual in the field when Brian started in 1946). As one of his former students from the electrodics side of the house about 40 years ago, I can personally attest to Brian’s being one-of-a-kind in the physical sciences, and a master at devising ways to understand why things happen in solution and at electrodes during electrochemical processes (and utilize that knowledge and understanding). To provide that picture, I will follow Brian’s scientific career from its beginnings in the mid-40s to his last accomplishments in mid-2005. I will use personal stories of Brian-the-person (garnered from many of his colleagues, as well as his wife Nina Conway and close colleague Halina Kozlowski, both of whom still live in Ottawa), The “Gang” at Imperial College, London, 1947/48, with B. Conway in the front row, second from right; J. Bockris, R. Parsons, M. Fleischmann, H. Rosenberg are also present.

The Electrochemical Society Interface • Spring 2014

Before leaving Brian’s early career days at Imperial College, I want years can be divided into 4 distinct periods, namely 1956-1966, 1967to cite the considerable influence of the very first Discussions of the 1978, 1979-1989, and 1990-2005. I will now give just a few highlights Faraday Society, held in London in 1947, on the 22 year-old BEC. from these different periods to illustrate the contribution and impact of He was able to attend with John and others from the Imperial group, BEC at U of O, which resulted in nearly 450 publications. and met J. A. V. Butler there; as well, he was exposed for the first Conway’s initial 10 years at U of O, 1957-1966, were an active time to the work of the famous group of Russian electrochemists. That period in numerous wide-ranging areas of electrochemistry, including group included A. N. Frumkin, B. V. Ershler, B. Levich, P. Dolin, B. the Kolbe reaction, battery materials and processes, identifying Kabanov, and others. During the depression years of the 1930s and pseudo-capacitance as related to electrode surface coverage, polymer then WW 2, the west had little access to the cutting-edge research in thermodynamics, ion hydration/electrostriction/other ionics issues, electrochemistry being conducted in the USSR, so this meeting was H/D separation factors, adsorption of organics, etc. Brian produced an important one, and for Brian it took place at the start of his very ~80 papers during the period, working with students like Gileadi, long career in the field. Others at that meeting included N. F. Mott, A. Kozlowski, Gilroy, Vijh, Barradas, Salomon, Marincic, Rudd, and Hickling, J. J. Lingane, T. P. Hoar, J. E. B. Randles, W. F. K. Wynne- many others. I believe that Conway was fortunate in being able to Jones, J. Heyrovský, to name but a few. For Brian, it must have been attract such talented students worldwide in this early period in incredible to have been there. Canada, and it helped cement his reputation as a pre-eminent physical After obtaining his PhD at Imperial, Brian joined the Chester electrochemist in Canada and abroad. Beatty Cancer Research Institute in London, staying from 1949 to In the second phase, 1967-1978, Brian’s research expanded to 1954 as a staff member. There he worked with the famous J. A. V. include fuel cell processes, oscillatory kinetics, partial molal volumes, Butler (of Butler-Volmer equation fame). His research with Butler, compressibility of salts, ellipsometry, RDE at high temperatures, whom he admired and respected greatly as a gentleman and scholar, etc. Co-workers like Gottesfeld, Wojtowiaz, Perkins, Sattar, Currie, concerned in part the influence of electrochemically-generated free LaLiberte were but a few during that period. About 114 publications radicals and ionizing radiation on DNA-type species in the body, with a view to assisting in the treatment of certain cancers. While this is in no way my area of expertise, I would imagine that using valid electrochemical phenomena to fight cancer-causing cells was quite novel 60+ years ago. I have the feeling that his years with Butler (and the associated 15+ publications in respected journals) had a profound influence on Brian, and helped set-the-stage for his long, distinguished career in electrochemistry. In 1954, Bockris convinced Brian to leave his mother country for the possibly greener shores of America, where John had taken up a position at the University of Pennsylvania in 1953; Brian joined him as a PDF and stayed for 2 years. During that time, a number of very significant research papers were published by the two, covering subjects like the mechanism and kinetics of proton transfer in solution, the HER on different metals taking into consideration A. N. Frumkin and a young B. E. Conway in Frumkin’s Lab, Moscow, 1950s. the M-H bond strengths and the metal d-band characters, and the detailed mechanism of metal deposition processes themselves. Those were active, fruitful years for both of them, and set-the-stage for the next resulted from that very productive decade for Brian. The next 2 phases major move in Brian’s career. This revolved around an invitation from from 1979 to 2005 resulted in an additional 250 publications in such the University of Ottawa, via Prof. K. J. Laidler, who saw the need areas as electrochemical supercapacitors (on which Brian wrote a for a strong school of electrochemistry at U of O. The invitation was classic reference book), temperature dependence of both the Tafel accepted, and Brian remained there for the subsequent 49 years of his slope “b” and the symmetry factor beta, electrosorption valency of career. anions and its influence on surface oxidation, the fluorine and chlorine Brian’s research record at the U of O shows the breadth and depth evolution reactions, ion hydration in the double-layer, single crystal of his accomplishments, covering electrodics and ionics, polymer and alloy electrodes, and many more. Indeed, Conway’s range thermodynamics, high and low temperature work, fundamental and and depth of subjects covered continued to be vast until the end of industrial research, environmental and energy research, etc. To this his life; he never did slow down. In these last two phases, dozens day, I am amazed by the scope of his research, and the fact that he of researchers worked with Brian and I can obviously only name a clearly understood in detail all aspects of the work carried out over the few: Tilak, Harrington, Wilkinson, Birss, Tessier, Bai, Liu, Mozota, decades in his laboratory and by his researchers. He knew all aspects Barnett, Hamelin. A complete listing of all the students, colleagues of his reported research that appeared in papers, book chapters, books, and co-authors who worked with Brian over his almost 60-year career reports, conference presentations and proceedings, etc; indeed, this is simply outside the scope of this article. was a source of great pride for Brian. He was a superlative research What I personally remember from my PhD years in Brian’s director and teacher who was always available to his students and laboratory was his enormous “discussion” ability with all those who collaborators; he had no sense of time-for-himself – his life was worked with him, which I understand pervaded all of his 49 years at U his work and electrochemistry. Students like myself of course did of O. His knowledge, memory and powers of reasoning were legendary not realize how lucky we were at the time this was happening. This however became quite clear to us as the years passed. Those U of O (continued on next page) The Electrochemical Society Interface • Spring 2014

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in the scientific community, as all who interacted with him will know. On a more personal side, he expected his students to be at work on Saturday, and Sunday if possible; he was certainly there on both days if he was in town. In those longgone days we students were only too pleased to be present since he had time to meet and discuss with us. It was a time when he was free from his many weekly administrative and teaching duties, and Brian was free to “let his hair down” and show us just what a superlative glassblower he was. Indeed, he could have easily been a “master glassblower” if he had had the time needed to devote to it; he loved the challenge of forming complex internal seals with, e.g., Luggin capillaries. With pieces of thin glass shavings in his hair, Brian would discuss scientific and research issues with his students who stood and admired his glassblowing abilities. Lunch at Brian’s favorite local restaurants (Chinese or Brian Conway in his laboratory in the 1990s sitting in front of a SEM with X-ray analysis Italian) over the weekend was anticipated by us capabilities. students, and more in-depth scientific discussions ensued. I’m certain that none of us realized all those years ago how fortunate we were to have a supervisor/mentor scientific phenomena and observations. Conway was a complete like Brian Conway, who was always more concerned with the desire scientist and professor (teacher) in the truest sense of the words. My for understanding and knowledge than he was with himself. That era only “mild” criticism of Brian and his approach was that he sometimes produced some of the giants of electrochemistry; besides Conway, understated and downplayed his very considerable achievements and a few I personally recall are: Uhlig, Hackermann, Tobias, Kruger, scientific abilities. He always showed a lot of self-restraint in making Pourbaix, Gerisher, Bruce Wagner, Newman, Heller, Yeager, Rapp, low-key scientific statements regarding what he considered should be Alkire, Hashimoto, Epelboin. Like Conway himself, many of these obvious to everyone in the field. Conway was always a gentleman trailblazers had very strong associations with ECS over very long and scholar, whose ego never interfered with his strong desire to periods of time, and in many capacities. further the understanding and appreciation of science, in particular Conway received scores of awards and honors during his long electrochemistry. I found him to be something of a rare individual distinguished scientific career. Two in particular were very important indeed, and The Electrochemical Society (and electrochemistry itself) for him, both ECS Society awards. The first was the Henry B. Linford were most fortunate to have had such a person as one-of-their-own for Teaching Award in 1984; indeed, Brian is the only Canadian to have the second half of the last century, and a bit beyond. so far received this award. Secondly, the Olin Palladium Award in 1989; I know that he was very proud to be included with such other About the Author recipients as Carl Wagner, U. R. Evans, A. N. Frumkin and A. J. Bard. Only one other Canadian, the late Morris Cohen of NRC, has received Barry R. MacDougall completed his PhD with B. E. Conway this award during its 65-year existence. Those, and many other in 1972, and remained in close touch with him during the next 33 awards and honors from numerous societies, never inflated Brian’s years (both being in Ottawa). MacDougall was President of ECS in ego or changed his openness and willingness to discuss science and 2007/2008, and became an adjunct Professor at the University of technology with anyone. He was always a down-to-earth person Ottawa in 2006. He continues to give what were previously Conway’s driven by an insatiable curiosity and desire to understand and explain graduate courses at the University.

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currents Reflections on Chemistry and Electrochemistry after Fifty Years of Practice by Larry R. Faulkner Ed. Note: These comments were presented at the ceremony commemorating Honorary Membership in The Electrochemical Society for Allen J. Bard and John B. Goodenough, University of Texas at Austin, Texas, November 23, 2013. See related articles in this issue on pages 13 and 84.

et me begin simply by congratulating our two awardees today. As a former president of this university and of the Society, as one of the graduates of the University and an Honorary Member of the Society, indeed, even as a student of one of the awardees, and as a friend of both, I take a special pride in this particular recognition of their marvelous achievements, manifested over sterling careers. Science enjoys few like either of them. Congratulations, John. Congratulations, Al. And let me add a note of welcome to everyone in the audience. There are, of course, colleagues here from across the University, but others have come from outside the institution, even from elsewhere in the country. For our visitors, I will just say that this is an exciting university with marvelous assets and energy. I hope you can experience some of its qualities while you are here. Electrochemical science and technology have been among its strengths for many decades, in substantial measure because of the powerful intellects and the fostering collegiality of Allen Bard and John Goodenough. Just about exactly fifty years ago – this month, as I recall – I walked into the office of the chemistry department chairman at SMU and asked to become a chemistry major. It was among my better decisions. The fit has proven to be perfect. I have loved the science and its history. I have loved its relevance to the world at large. I have even loved the fact that chemists are workaholics. It’s notable, in fact, that when I went to see the department chairman back in 1963, it was about eight o’clock in the evening. The light was on in his office, as it was practically every night. While he didn’t warmly welcome my interruption, he still helped me – and Professor Harold Jeskey became an important mentor and a lifelong friend. Given the convergence of this anniversary with my duties of the moment, I would like to take this time to offer some reflections on the present and future of our field – on the urgencies and obligations before it. The word “chemistry” will be used as a label for the field, but I mean to include all of chemical science and technology. In these last fifty years, I have watched chemistry change tremendously – in scale and application, certainly in the catalogue of knowledge, but also in public perception. The DuPont motto back in the early 60s was “Better Living Through Chemistry,” and the public had every confidence that it rang true. The word “chemistry” was a synonym for “magic.” But there was not yet much understanding of environmental impact. That was still around the corner, awakening broadly in the very late 60s and early 70s. The 70s showed us both edges of the chemical

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sword, just as we came to see two edges to quite a few other blades. We were naïve back then about many things, from the powers of science to the powers of presidents. Naïveté took a real beating from the late 1960s through the 1970s. Words and phrases that had generally evoked common pride, trust, and optimism – like “government,” “the presidency,” and “military service” – became much more neutral, or even negative, in the public perception. The words “chemical” and “scientific” were casualties of the times, too. DuPont found a different motto. But just as naïveté gave way to alarm and suspicion, they, in turn, have gradually given way over decades to something more mature. Even though our national life – or really now, our global life – is subject to ridiculous fads of favor and disfavor, responsible citizens seem mostly to have learned that anything of real power – anything that can yield great benefits – also carries serious risk. There is always a negative side requiring attention and mitigation. While the ignorance of long ago might have given us a bit of bliss, this fuller perception of our science girds us and our leaders for the challenges that lie all around. Realism about both benefits and risks provides a basis for truly responsible exercise of the power inherent in our knowledge. The public view of chemistry matters enormously, for chemistry is the science by which people manage their use and stewardship of the material world. And this issue – the use and stewardship of the material world – is the great challenge of our time. It will remain so beyond the time given to any of us here. Global population has more than doubled over the 50 years since 1963, from just over 3 billion to 7 billion, and a much larger fraction has been brought from poverty into fair prosperity. Earth is groaning under the strain of legitimate hopes of individuals in every society. Here is the big question: How can we wisely make use of the Earth’s resources to provide fulfilling, secure lives for the Earth’s people, now and indefinitely into the future? All of the words are important: “wisely make use,” “fulfilling, secure lives,” “for the Earth’s people,” “now,” “indefinitely into the future.” This is surely a challenge of policy and politics, and of economics and business, but it is without doubt a challenge of chemistry wherever the material world is actually touched. How can we intelligently and efficiently extract, transform, preserve, and reuse resources? How can we understand environmental impact comprehensively and manifest well-chosen mitigations? How can we use less of critical materials in the interest of serving more of the globe – or serving it longer? How can we find synthetic substitutes to a larger spectrum of natural resources in short supply? Embedded in these questions are chemical problems for generations of scientists and engineers. And we can be sure that relevant problems will not cease to arise. No one is going to solve the global material challenges with any single breakthrough or (continued on next page)

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policy. The thing to do is to be ever conscious of those challenges, to roll up our sleeves, and to try to make a serious contribution as ideas and opportunities present themselves. But by no means should we allow ourselves to be overwhelmed. Thanks to science, especially to chemistry, life is tremendously better for most of the people on Earth than it was even a few decades ago. Spreading prosperity has created problems, of course; but the answer is to address them. History shows that humankind is enormously resourceful. Faced with problems, people find solutions. Science is a great and powerful tool for doing just that, perhaps the greatest and most powerful ever devised. And as long as the use and stewardship of the material world remains the central global issue, chemistry will be the central science. Although I have opened here with an emphasis on the big scene, on the grand exigency, on the utility of our science and its responsibilities to humankind, I don’t want to neglect the art of chemistry. It remains important to find out why and how chemistry happens and why molecular systems function as they do. As the science advances, our global understanding and our capabilities move forward, too, sometimes with great leaps, sometimes in the recognition that we used to be operating with wrong ideas altogether. There are at least three reasons for carrying forward with a healthy program of fundamental chemical research: First, the science is lovely and captivating. The very art of it justifies effort. But just as important, the art is what first draws students in. Second, we cannot afford just to keep on not knowing what we don’t know. After all, this is the core science behind the physical well-being and viability of humankind. Third, we can identify matters that we do not yet understand, but that we can clearly perceive to be central to capabilities of enormous, lasting importance. Many relate to energy conversion, certainly including the elusive secrets of electrocatalytic reduction of oxygen to water or electrocatalytic oxidation of simple fuels other than hydrogen. Self-repair in chemical systems is another mystery with great leverage on future technology. You can make a list of your own, I’m sure. In matters like these, fundamental science is the only way to lay a foundation that can really support the eagerly-sought capabilities (as well as other benefits that we have not yet imagined). Inside chemistry, there is, of course, electrochemistry, a special domain to everyone here. Its historical roots are deep, extending almost to the boundary between alchemy and the beginning of the true science. The earliest discoveries of Volta, Galvani, and Davy are now more than two centuries back ... and we have been working on batteries and fuel cells ever since! Since electrochemical science and technology is the area where practically everyone in this room is most likely to make contributions, let me dwell specially on it for a moment. Anyone who has worked in electrochemistry knows that electrochemical systems are composed, in roughly equal measures, of elegance and exasperation. We have chosen to study the incredibly difficult, to be sure. If electrochemical systems were not so important, many fewer investigators would have worked on them these past two centuries. The systems are intrinsically complex, both spatially and dynamically; moreover, the most important processes take place in tiny portions of the total space, where observation and characterization are so difficult.

But with sometimes stunning ingenuity, investigators have probed and learned. The body of knowledge and theory surrounding electrochemical phenomena is remarkably elaborate, given the intrinsic difficulty of the research. There is considerable elegance in what we already know. And there remains inspiring elegance in the very idea that electrochemistry affords control and observation of the most fundamental chemical act: the addition or subtraction of electrons, one-by-one, to molecules, ions, and atoms. If only we had a better view! But over my fifty years in science, the view has dramatically improved. Tools of great power have been invented, and still better ones must be on the way. Despite the exasperation, keep probing in electrochemistry. The payoff can be very large – in terms of art, in terms of scientific understanding of broad significance, in terms of technology, in terms of this century’s central issue: the use and stewardship of the material world. This year marks another anniversary: the 200th of Sir Humphry Davy’s finest discovery: the great Michael Faraday, who began his long career at the Royal Institution in 1813 as Davy’s assistant. Faraday was a bookbinder’s apprentice before that. Although Davy was himself a historic, groundbreaking scientist, his preeminent contribution was, by far, finding and developing Michael Faraday. It’s a lesson to all of us who teach and develop younger talent. And that brings us back to these men whom we honor today. They are known everywhere as decent, generous, and collegial, and I believe that those qualities are great amplifiers of their influence. Science, in the end, is a social enterprise. Many outside seem to perceive science as wholly built on intellect and logic, perhaps by automatons without souls. The truth is that scientific progress depends in very great measure on softer attributes of worthy individuals and organizations, such as trust, instinct, communication, and motivation. To be sure, scientific insight is indispensable, both to discovery and to the construct of understanding. But broad influence in science – the ability to promulgate ideas in the community – expands immeasurably for scientists of great insight who also manifest humanity and humility. No better exemplars will be found than these two honorees. John Goodenough and Allen Bard, we are enormously proud of you at the University of Texas – and with these Honorary Memberships, the Electrochemical Society expresses pride on behalf of your electrochemical colleagues at large. Everyone in this room wishes each of you deep satisfaction, not just from your scientific achievements, but also from your long careers of worthy contribution, throughout which you have taught, aided, and inspired countless colleagues. Thank you all for listening today.

About the Author Larry R. Faulkner is President Emeritus of The University of Texas at Austin and retired President of Houston Endowment. He previously served on the chemistry faculties of Harvard University, the University of Illinois, and the University of Texas. He is a former president of the Society and is both an Acheson Awardee and Honorary Member. He was a doctoral student of Allen Bard and later co-authored Electrochemical Methods with Professor Bard.

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226th Meeting of The Electrochemical Society XXIX Congreso de la Sociedad Mexicana de Electroquímica 7th Meeting of the Mexico Section of The Electrochemical Society

2014 ECS and SMEQ

CANCUN

Joint International Meeting

Mexico October 5-10, 2014 Moon Palace Resort

General Topics • • • • • • • •

Batteries and Energy Storage 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 and Processing Electronic and Photonic 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 all-inclusive hotel rates start at $249 and are now available at the meeting headquarters hotel, the Moon Palace Resort. The early-bird reservation deadline is September 5, 2014 or until the block sells out, whichever comes first!

Important Deadlines . . . • Early-bird registration opens in June 2014 – Deadline is September 5, 2014. • Travel grants are available for student attendees and young professional (early career and

faculty) attendees. Please use the online submission system which may be found by visiting http://www.electrochem.org/sponsorship/travel_grants.htm Applications are due July 1, 2014.

• Early-bird registration and hotel discounts are available until September 5, 2014 or until the block sells out! Reserve early!

More . . . • Extend the advantage of attending the ECS meeting by signing up for a one-day Short Course on

•

Sunday, October 5. Just some of the topics are: impedance spectroscopy, polymer electrolyte fuel cells, fundamentals of electrochemistry, and more. Listen to what some of past attendees have to say… “Great opportunity to learn from someone at the forefront of the topic.” (from a master’s degree student); and “This course fulfilled my expectations.” (from an R&D scientist at electroplating company). Check the ECS website for the final list of courses offered at the ECS meeting in Cancun. Full papers presented at ECS meetings will be published in ECS Transactions. Visit the ECS website for more details.

Please visit the Cancun Meeting page for more information:

www.electrochem.org/cancun

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Faraday Technology Inc. Receives the Presidential Green Chemistry Challenge Award

he 2013 recipient of the Small Business category of the Presidential Green Chemistry Challenge Award was Faraday Technology, Inc. (Clayton, Ohio). The award was for Functional Chrome Coatings Electrodeposited from a Trivalent Chromium Plating Electrolyte. Chromium remains top choice material for surface coatings in many highly demanding applications for industrial applications for military and commercial markets. The usual plating baths rely on solutions of hexavalent chromium, although Cr(VI) is the most toxic form of chromium due to its carcinogenic properties. Replacement of chromium by other material is a possibility, but so far no satisfactory alternative exists. However, Faraday Technology, Inc. developed a process in which the Cr(VI) is replaced by less toxic and non-carcinogenic trivalent form of chromium. The process relies on programmed electroplating from Cr(III) bath, in which a reductive cathodic pulse is followed by an anodic pulse, and then a relaxation period. This approach allows for thicker coatings and the structure of properties of the coating can be adjusted as well. The patented FARADAYIC® TriChrome Plating Process could eliminate about 13 million pounds of hexavalent chromium waste in year in the United States alone and as much as 300 million pounds worldwide. The Presidential Green Chemistry Challenge Awards promote environmental and economic benefits of developing and using novel green chemistry. The award was established by the Environmental Protection Agency in 1996 and the EPA Office of Chemical Safety and Pollution Prevention sponsors the Presidential Green Chemistry Challenge Awards in partnership with the American Chemical Society Green Chemistry Institute® and other members of the chemical community including industry, trade associations, academic institutions, and other government agencies. Through 2013, EPA presented awards to 93 winners in categories of Greener Synthetic Pathways, Greener Reaction Conditions, The Design of Greener Chemicals, and Business and Academia. Faraday Technology was founded in 1991 to develop and commercialize novel electrochemical technology. The company core competency lies in the management of the innovation process from concept to pilot-scale. It provides its government and commercial clients with applied electrochemical engineering technology development from bench-scale through pilot or pre-production levels. In support of its electrical mediation approach, Faraday also markets “first production” rectification equipment and effluent decontamination reactor hardware.

Adam Weber Receives Outstanding Early Career Scientist Award

dam Weber, Chair of the ECS Energy

Technology Division was bestowed a Presidential Early Career Award for Scientists and Engineers, the highest honor bestowed by the United States Government on science and engineering professionals in the early stages of their independent research careers. The awards, established by President Clinton in 1996, are coordinated by the Office of Science and Technology Policy within the Executive Office of the President. Adam Weber Awardees are selected for their pursuit of innovative research at the frontiers of science and technology and their commitment to community service as demonstrated through scientific leadership, public education, or community outreach. To learn more about the award and this year’s recipients, please visit: http://www.whitehouse.gov/the-press-office/2013/12/23/presidentobama-honors-outstanding-early-career-scientists. Dr. Weber holds BS and MS degrees from Tufts University, and earned his PhD at University of California, Berkeley in chemical engineering under the guidance of John Newman. His dissertation work focused on the fundamental investigation and mathematical modeling of water management in polymer-electrolyte fuel cells. Dr. Weber continued his study of water and thermal management in polymer-electrolyte fuel cells at Lawrence Berkeley National Laboratory, where he is now a staff scientist. He has authored over 40 peer-reviewed articles on fuel cells, flow batteries, and related electrochemical devices, developed many widely used models for fuel cells and their components, and has been invited to present his work at various international and national meetings. Dr. Weber has been the recipient of a number of prestigious awards including a Fulbright scholarship to Australia, the 2008 Oronzio and Niccolò De Nora Foundation Prize on Applied Electrochemistry of the International Society of Electrochemistry, and the 2012 Supramaniam Srinivasan Young Investigator Award of the ECS Energy Technology Division. His current research involves understanding and optimizing fuel-cell performance and lifetime; understanding flow batteries for grid-scale energy storage; and analysis of solar-fuel generators.

Lubomyr T. Romankiw Elected a Foreign Associate to NAE

Lubomyr T. Romankiw

ational Academy of Engineering (NAE) announced on February 6, 2014 election of new members and foreign associates. L. T. Romankiw, an IBM Fellow (IBM, Yorktown Height, NY) was elected as a Foreign Associate for “innovation of thin-film magnetic head structures and electrochemical process technologies for microelectronics device fabrication.”

Members (U.S. citizens) or foreign associates (non-U.S. citizens) are elected to NAE membership by their peers. Election to membership is one of the highest professional honors accorded an engineer. Members have distinguished themselves in business and academic management, in technical positions, as university faculty, and as leaders in government and private engineering organizations. The current membership is 2,250 U.S. members and 214 foreign associates.

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Enrico Fermi Award Bestowed on Long-Time ECS Member Allen Bard

ebruary 3, 2014 was a festive day for science in Washington DC. Two prestigious scientists received The Enrico Fermi award. The two men honored were Allen J. Bard and Andrew Sessler. In the early afternoon the winners were introduced to President Obama in the Oval Office by the Director of the Office of Science and Technology Policy John Holdren. The formal ceremony took place later that day at the U.S. Department of Energy Headquarters in Washington, DC. The Fermi Award honors the memory of the Nobel Laureate Enrico Fermi and it has been presented to outstanding scientists since 1956. It is one the oldest honors in science and technology given by the U.S. Government and it is also very prestigious. The Fermi Award is administered on behalf of the White House by the Office of Science of the U.S. Department of Energy. Although in some years there were multiple recipients, some years the award was not even awarded. The purpose of the The Enrico Fermi Award recipients Allen J. Bard (left) and Andrew Sessler (right) meet in the Oval Office award is to encourage and recognize with President Barack H. Obama on February 3, 2014. (Photo by P. Souza, reprinted with permission of The excellence in research, leadership, White House Photo Office.) and service in energy science and Allen Bard described to Petr Vanýsek for Interface his reflection technology. A Fermi Award winner receives a citation signed by the on receiving the award: President of the United States and the Secretary of Energy, a medal bearing the likeness of Enrico Fermi, and an honorarium. “I’m very pleased that this Enrico Fermi award for energy Dr. Bard’s citation reads: “For international leadership research is an acknowledgment of the important contributions in electrochemical science and technology, for advances in of electrochemistry of all types to the energy field. Thus I think photoelectrochemistry and photocatalytic materials, processes, and it represents an award to the field of electrochemistry as much devices, and for discovery and development of electrochemical as it does to me personally. I am very thankful to members of methods including electrogenerated chemiluminescence and scanning my research group and many colleagues who have contributed electrochemical microscopy.” so much to the research that this award recognizes. Indeed Dr. Bard joined the University of Texas at Austin in 1958, and my biggest contribution has been in helping to train new although he was on several sabbaticals as a visiting professor or generations of scientists who will make important contributions lecturer at various institutions, he remained at UT for his entire career. of their own.” Allen Bard is known to many generations of students as a co-author (with Larry Faulkner) of the textbook Electroanalytical Methods. To The co-recipient of the Award this year was Andrew Sessler, who those practicing electrochemistry, he is known on many levels, for his worked extensively in the field of energy efficiency at the Atomic own publications, for editing the series Electroanalytical Chemistry Energy Commission and the Energy Department and later he served (21 volumes) and the Encyclopedia of the Elements (16 volumes) as the Director of the Lawrence Berkeley National Laboratory. Dr. and for the reference/monograph Standards Potentials in Aqueous Sessler’s citation is “For advancing accelerators as powerful tools of Solutions. He was also the editor-in-chief of the Journal of the scientific discovery, for visionary direction of the research enterprise American Chemical Society from 1982 to 2001. The Electrochemical focused on challenges in energy and the environment, and for Society recognized his accomplishments by awarding him the Olin championing outreach and freedom of scientific inquiry worldwide.” Palladium Medal in 1987. In 2013 he became an Honorary Member This is the second time a prominent ECS member received this of ECS. Award. John Goodenough was the 2009 recipient of this award.

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

from the ECS Toronto meeting, May 12—May 16, 2013

The following issues of ECS Transactions are from symposia held during the Toronto 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 hard-cover or soft-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.) Please contact customerservice@electrochem.org with any questions or to place an order.

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Vol. 53 Porphyrin and Supramolecular Assemblies No. 37 SC..............................M $34.00, NM $43.00 PDF............................M $18.07, NM $22.59 The Electrochemical Society Interface • Spring 2014 10/22/13

tech highlights Examination of Mechanisms for Liquid-AirInterface Corrosion of Steel in High Level Radioactive Waste Simulants

The tanks used to store nitrate- and nitrite-rich alkaline waste are susceptible to liquid-airinterface (LAI) corrosion. While this attack has been insufficient to perforate tank walls, it does adversely impact the chemistry within the tank. A variety of mechanisms related to local chemistry changes at the LAI have been proposed to explain this phenomenon. However, no conclusive data has been produced to support any of them. In this work, in situ Raman spectroscopy, combined with local pH measurements, was employed to probe the concentration of key electrolyte species (e.g., nitrate, nitrite, hydroxyl) at the actual LAI, establishing whether any deviations from the bulk chemistry preceded corrosion initiation. However, both the nitrate and nitrite concentrations (as well as their relative ratio) were found to remain stable prior to corrosion initiation. Similarly, local pH measurements indicated that the pH at the LAI did not deviate from that of the bulk until well after corrosion had been initiated, indicating that local acidification was also not a likely cause of the corrosion attack. The authors conclude that the mechanism of LAI corrosion initiation may be similar to crevice corrosion and that it may be associated with a local pH decrease due to metal ion hydrolysis, but at a length scale below that resolvable by the techniques employed in this study. From: J. Electrochem. Soc., 160, C521 (2013). Graphene Oxide Fuel Cell

Graphene oxide (GO), the oxidized form of graphene, is an electronic insulator due to the presence of randomly allocated nonconductive sp3 carbon in its structure. Following their preliminary report of GO’s high proton conductivity (J. Am. Chem. Soc. 2013, 135, 8097), a group of researchers from Kumamoto University in Japan recently described the use of GO as the membrane electrolyte for H2/O2 fuel cells. The authors prepared GO suspension by oxidizing graphite powder by the Hummer’s method. The suspension was then processed into a paper-like film through filtration. With a thickness of about 10-60 µm, the GO paper exhibited proton conductivities in the range of 10−5-10−4 S/cm at low humidity (< 20%) and room temperature. In addition, the GO paper was also shown to be nonpermeable to H2 and O2. By directly sputtering platinum metal or casting commercial Pt/C catalyst on both sides of the GO paper, simple membrane electrode assemblies (MEAs) were constructed. A non-noble metal oxygen reduction electrode was also prepared on the GO paper. An interesting finding amongst the cell performance results obtained with these

The Electrochemical Society Interface • Spring 2014

MEAs was that the Pt/C electrode on GO showed better performance than that on a 150μm Nafion membrane. From: J. Electrochem. Soc., 160, F1175 (2013). Resistive Switching: A Solid-State Electrochemical Phenomenon

In recent years, the memristor, in particular the resistive switcher, has been the subject of many papers. Some descriptions explaining this already known behavior of resistive switching have resulted in misinterpretations of the phenomenon. A scientist at Universität Stuttgart has written a paper to describe the underlying set of electrochemical equilibria of species involved in the processes, and the conditions for the resultant functioning of a resistive switcher. The resistive switcher is based on a mixed ionic-electronic conductor (MIEC) solid electrolyte galvanic cell under load, in which one electrode is under ionblocking operation mode. Variation in the voltage-induced change in n- and p-type electronic conductivity across the solid electrolyte ultimately gives rise to the observed lagging of resistance behind the voltage change. Because the cause-action relation described is based on idealized conditions, the author discusses additional effects that occur in the behavior of a resistive switcher in practice. Two types of switchers, unipolar and bipolar, are provided with explanations of their differing current-voltage behaviors. To address how this solid-state electrochemistry understanding differs from the explanations prevailing in the literature, the author also provides a critical discussion of those experimental observations and interpretations. From: ECS J. Solid State Sci. Technol., 2, P423 (2013). Electrodeposition of Cu-Ni Alloy Electrodes with Bimodal Porosity

Porous electrodes are widely used in industrial electrochemical systems because they facilitate enhanced mass transport and overall electrochemical reaction rates. Among the numerous applications for porous electrodes are batteries, fuel cells, supercapacitors, and water desalination. Cattarin and coworkers at the Istituto per l’Energetica e le Interfasi in Italy recently reported a preparation method for porous Cu-Ni alloy electrodes that offers advantages over traditional methods such as dealloying or electrodeposition within rigid templates. They demonstrated that electrodeposition of Cu-Ni alloy electrodes at high current densities (3 A/cm2) from an acidic solution containing copper and nickel sulfate produced alloys with a unique bimodal porosity, due in part to the copious hydrogen evolution that accompanies the

alloy deposition. The alloy microstructure consists of pores with dimensions in the tens of microns along with submicron-sized dendrites and other high surface-area features. The authors showed that this porous alloy electrode has excellent performance characteristics for cathodic reduction of nitrate (a common pollutant in water and wastewater streams) with lower overvoltages and dramatically higher peak currents compared to compact electrodes of identical composition. Due to these attributes, along with the relatively low cost of these porous alloys, the authors propose that these electrodes offer great promise in water and wastewater treatment. From: ECS Electrochem. Lett., 2, D58 (2013). Electrochemically Induced p-Type Conductivity in Carbon Nanotubes

The ability to control the conduction characteristics of single wall carbon nanotubes (SWNTs) is crucial for any application in electronics. Recent exciting work has shown that vacuum-annealed n-type SWNTs can transform to p-type when exposed to ambient air. The process can be reversed after annealing, and no underlying mechanism has been proposed that accounts for this marked change in conduction character. However, transfer doping that causes n-type to p-type conduction changes can also be facilitated electrochemically. Researchers at Case Western Reserve University in collaboration with the University of Louisville demonstrated that indeed, electrochemical control of conduction type in SWNTs is possible in humid air. By allowing a surface water film to form on SWNTs, a form of surface transfer doping was made possible by relative shifting of the Fermi level energy according to the Nernst equation. Specifically, the researchers showed that considerable reduction in resistance and a corresponding improvement in Seebeck coefficients could be achieved for a film composed of SWNTs in humid air, as compared to deoxygenated or dry air environments. The authors posited that such effects should be considered when studying SWNTs in humid air and that certain changes in the electrical properties of graphene and multi-walled nanotubes can be explained by this electrochemical phenomenon. From: ECS Solid State Lett., 2, M57 (2013).

Tech Highlights was prepared by Zenghe Liu of Google Inc., David Enos and Mike Kelly of Sandia National Laboratories, Colm O’Dwyer of University College Cork, Ireland, and Donald Pile of Nexeon Ltd. Each article highlighted here is available free online. Go to the online version of Tech Highlights, in each issue of Interface, and click on the article summary to take you to the full-text version of the article. 43

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Interfacial Electrochemistry of

Ionic Liquids by Andreas Bund and Frank Endres

onic liquids (ILs), which were in their infancy about 15 years ago, have today been accepted as versatile materials in various fields of chemistry. There is now an overwhelming number of publications dealing with ILs. In comparison to molecular liquids, they show certain remarkable properties. For one, they are an extraordinarily disparate class of materials. Millions of different ILs can potentially be synthesized by combination of various cations and anions. Since even slight changes in the side group of an anion or cation can lead to considerably altered properties of the resultant IL, a wide matrix of ILs with tailored properties can be envisaged. Currently there are about 1000 ILs commercially available. They have wide thermal windows, i.e., most of them can be handled between 0 and 200 °C, which closes the gap between conventional solvents and high temperature molten salts.1 This property, together with their wide electrochemical windows, makes ILs interesting candidate materials for the electrodeposition of refractory metals like tantalum and niobium that in the past could only be deposited from high temperature molten salts. From selected ILs, these metals can now be deposited in thin crystalline layers at temperatures between 150 and 200 °C. However, there seem to be limits to the use of ILs for metal electrodeposition, for example the electrodeposition of titanium remains quite challenging. The composition of the IL plays an important role in the electrochemical process. These interesting aspects are addressed in the article contributed by Ispas et al. in this issue. Apart from their wide thermal and electrochemical windows, most of the ILs have negligible vapor pressures at room temperature, which allows studies to be performed even in an ultrahigh vacuum. This allows researchers to monitor species that are generated during an electrochemical process using techniques such as photoelectron spectroscopy. In a low temperature plasma, electrochemistry can be performed at the IL/plasma interface. Metal and semiconductor nanoparticles (e.g., Si and Ge) can also be obtained via this plasmasynthesis route. Höfft et al. summarize these aspects in their article. The focus of electrochemists vis-à-vis ILs has hitherto been on their electrochemical window, which in some cases can be as wide as ±3 V vs NHE. But the electrochemical window in itself does not explain certain phenomena, for example, obtaining microcrystalline metal deposits in one IL medium, but nanocrystalline deposits in a slightly different one under comparable conditions. The first advances toward resolving these were made about seven years ago in papers showing that ILs formed solvation layers at interfaces. These solvation layers were so strongly adsorbed that they could be probed with an atomic force microscope. Shortly afterwards, it was shown that ILs were also adsorbed on metal surfaces and that the adsorption and orientation of the liquids varied with the electrode potential. Thus, it is likely that ILs can strongly influence electrochemical reactions.2 Borisenko et al. summarize these aspects of ILs in their contribution in this issue. Meanwhile these experimental observations on the electrochemical aspects of ILs have been well supported by theory and computer simulations. Interfacial properties can already be predicted to a good extent, and there has been remarkable progress on the theoretical chemistry front, as discussed by Ivaništšev and Fedorov in this issue. It is evident that theory is an important tool to understand the complicated

The Electrochemical Society Interface • Spring 2014

interfacial electrochemistry of ILs. In our opinion there must be a focus on these aspects in the future, as a deep understanding of the interfacial electrochemistry is needed to develop viable technical processes that lie at the confluence of electrochemistry and ILs.

About the Authors Andreas Bund studied Chemistry at the University of Saarland during 1989-1995. His PhD (1999, summa cum laude) was on the application of piezoelectric quartz crystals for rheological and microgravimetric in-situ measurements. In 1999 he moved to Dresden University of Technology where he did his habilitation thesis in 2004. The habilitation thesis was on tribological, rheological, and magnetohydrodynamic effects at electrochemical interfaces. In 2005 he was awarded the renowned Heisenberg fellowship of the Deutsche Forschungsgemeinschaft. During the time of his fellowship he was twice a visiting scientist at the University of Utah where he worked with Henry S. White on electrochemical magnetohydrodynamics and the numerical simulation of electrochemical processes. From 2009 to 2010 he held a visiting professorship at TU Munich, Faculty of Physics, Chair Interfaces and Energy Conversion. In August 2010 he was appointed full professor at Technische Universitaet Ilmenau, group of Electrochemistry and Electroplating. Andreas Bund has about 90 ISI refereed journal articles. He may be reached at Andreas.Bund@tu-ilmenau.de. Frank Endres studied chemistry at the Saarland University (Saarbrucken, Germany) from 19881993 and graduated there in 1993 with a diploma in Chemistry. He got his Dr. rer. nat. (PhD) degree in 1996 at the same university and moved subsequently to the University of Karlsruhe where he got his habilitation for physical chemistry in 2002. In the same year he was appointed by the Clausthal University of Technology as Professor and became in 2012 the founding director of the new Institute of Electrochemistry there. His interests comprise the physical chemistry of surfaces and interfaces, ionic liquid electrochemistry and materials science. He may be reached at frank.endres@tu-clausthal.de.

References 1. F. Endres, S. Zein El Abedin, Acc. Chem. Res., 40, 1106 (2007). 2. F. Endres, O. Höfft, N. Borisenko, L. H. S. Gasparotto, A. Prowald, R. Al-Salman, T. Carstens, R. Atkin, A. Bund, and S. Zein El Abedin, Phys. Chem. Chem. Phys., 12, 1724 (2010).

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Electrodeposition in Ionic Liquids by Adriana Ispas and Andreas Bund

N +

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−

S O

−

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P F CF2 F CF 2 CF3

−

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− F P F F F F

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alcohol. Popular DES are based on the mixture of choline chloride with urea, or with ethylene glycol, glycerol or propylene glycol. Compared to real ILs, DES are much cheaper but have more limited thermal and electrochemical stabilities.3 In the spring 2007 edition of Interface there were a series of articles from Keith E. Johnson, Tetsuya Tsuda and Charles L. Hussey that discussed the properties of ILs and their possible applications in electrochemical process: as electrolytes in lithium ion batteries; in supercapacitors; for treatment of nuclear wastes; in dyesensitized photoelectrochemical cells, to mention a few. However, one important aspect of ILs is that they can concomitantly serve both as solvents and supporting electrolytes, a fact that make them an attractive alternative to organic or toxic solvents in the electroplating industry. The choice of salt used is very important for electrodeposition in ILs. From some precursor salts it is possible to precisely electrodeposit the target element, while the choice of other precursor salts preclude total reduction to metal (Fig. 2). To improve the deposition rates and plating process efficiency, special ILs have been designed that contain the metal species to be plated.11

which makes them interesting alternatives to high temperature molten salts. Some ILs are stable up to several hundred degrees Celsius and have an electrochemical window of up to 4-5 V. Furthermore some precursors for the deposition of reactive elements are either not soluble or decompose in water, but are highly soluble and stable in ILs. On the flip side, one drawback of ILs is their relatively low electrical conductivity compared to aqueous systems — a direct consequence of their high viscosity. However due to their good thermal stability, IL based electrolytes can be operated at elevated temperatures, thereby somewhat alleviating this problem. The aforementioned useful physicalchemical properties make ILs interesting candidates for the electrodeposition of reactive metals, semiconductors and polymers that cannot be plated from aqueous baths. Possible applications include electrorefining, decoration, corrosion protection or other functional surface finishings.1,2 One subclass of ILs that has garnered interest are deep eutectic solvents (DES). They are eutectic mixtures of two components: one, a simple quaternary ammonium halide, and the other, an inorganic metal salt or an organic hydrogenbound donor, such as an amide or an

n practice, the electrodeposition of most metals and alloys is almost exclusively performed from aqueous solutions. Chromium, nickel, zinc, copper, silver and gold are some of the metals that are largely used in various technical applications. They can be obtained from aqueous solutions that in some cases are based on toxic components (e.g., cyanide) and using processes that have rather low current efficiencies (e.g., chromium). There are a number of metals with a Nernst potential well below that of water decomposition and that therefore cannot be electroplated from aqueous baths (e.g. aluminum, magnesium, tantalum and others). Ionic liquids (ILs) have now caught the attention of electroplaters, hitherto mostly in the research labs. ILs consist of an organic cation (e.g. pyrrolidinium, imidazolium, ammonium) and an inorganic or organic anion (e.g. chloride, bromide, tetrafluoroborate, triflate). They have a wide range of solubilities and miscibilities; for example, some of them are hydrophobic, while others are hydrophylic (Fig 1). ILs do not readily evaporate and most ILs are nonflammable and nontoxic, thereby providing key environmental advantages when compared to organic solvents. ILs are liquid at temperatures far below 100°C,

−

O O

cations

anions

Fig. 1. Structures of cations and anions of commonly used ILs. Theoretically, 1012 to 1018 possible combinations between the cations and anions are possible. However, not all of these envisaged ILs will have good conductivity and electrochemical windows that make them useful for electrochemical applications. The Electrochemical Society Interface • Spring 2014

Ispas and Bund

(continued from previous page)

With such ILs, very high current densities can be employed, which can considerably reduce plating times and thus costs. An important book on electrodeposition in ILs appeared in 2008.2 However, the first reviews on the various materials (metals, semiconductors or conducting polymers) that can be plated from ionic liquids, on the physico-chemical properties of ILs, and on the challenges of conducting electrochemistry in ILs appeared starting from 2002.1,4-10 Most reviews have hitherto focused on the type of metals/alloys/semiconductors or polymers that one can deposit in ionic liquids. The above mentioned reviews discuss recipes for plating metals and alloys from ILs, such as Al, Pd, In, Sb, Te, Cd, Cu, Ag, Ni, Co, Zn, Sn, Ga, Ge, Si, Ta and many more. This short overview will focus on some other aspects, namely on the use of additives, co-deposition, and pulse plating in ILs.

Use of Additives for Electrodeposition from ILs Additives added to the plating bath can be adsorbed chemically or physically on the surface to be coated. In the case of chemisorption, there can be partial transfer of electrons between the substrate and adsorbate, while for physisorption, electrostatic or van der Waals forces are prevalent.12 The additives act both on kinetics of the electrodeposition and on the growth mechanism. Plating in the presence of additives generally yields deposits with a better morphology and improved mechanical or electrochemical properties. Some additives reduce the internal stress within the deposits, some facilitate bright surfaces or reduce the roughness of the deposits. All

(a)

these beneficial properties of additives have been observed for layers electrodeposited in aqueous solutions. The brightness of deposits (e.g. Fe, Co, Ni) and their grain size can be increased by increasing the plating bath temperature even in the absence of additives in ILs.13-15 This is due to the stronger adsorption of cations on the electrode surface at lower temperatures, which hinders the nucleation and growth of the deposits and results in grain refining.16 In passing, we note that ionic liquids themselves can be used as additives during plating from aqueous electrolytes, e.g. for grain refining.17-20 However, this application of ILs in aqueous baths is beyond the scope of this article. There is not much literature to be found on the effect of additives in deposition from ILs. Herein, some studies are presented wherein additives have been used in ILs to improve the properties of electrodeposited layers. This issue of Interface also contains articles by Fedorov and Ivaništšev, Borisenko, Atkin, and Endres where the structure and dynamics of the IL/electrode interface is discussed. One important point discussed in those contributions is that the double layer in ILs is different from that in aqueous solutions. In the following paragraph, we present a simple description of cation adsorption on the electrode surface to describe the role of additives during electrochemical plating. In the absence of additives, the cations of an IL will accumulate near the electrode surface when it is negatively polarized. The reduction of metal cations is expected to occur slowly, through the adsorbed layer of cations (for example, the 1-butyl-1methylpyrrolidinium cation, [BMP]+). As a consequence, the reduction of the metal ions is hindered. In the presence of additives, a cationic complex of the metal ions with the

additive can be formed, and this can partly compensate for the electrostatic barrier at the interface by facilitating charge transfer to the metal ions. Other mechanisms can be based on the adsorption of the additives on the electrode surface. By replacing some of the bulky adsorbed IL cations, the additive molecules can induce a more facile electrode reaction. As a consequence, a smoother and shinier surface is obtained in the presence of additives (such as acetonitrile, coumarin, thiourea, benzotriazole or acetone)11,14,21 with better adhesion on the substrate also observed in the case of coumarin.13,22 For example, acetonitrile has been added as an additive during Fe deposition from1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide, [BMP][TFSA], containing Fe(TFSA)2.13 Acetone,14,21 coumarin22 and thiourea21,22 have been added during Co and Ni electrodeposition from [BMP][TFSA], containing Co(TFSA)2 or Ni(TFSA)2. Changes in the coordination environment in the presence of thiourea,22 acetonitrile and acetone are higher (the coordination number of acetonitrile or acetone is 14) compared to those induced by the [TFSA]- anion (coordination number 7).13 The changes in the coordination environment indicated the formation of a complex product between the metal ions and the additives, which could facilitate the reduction of the Co2+. However, the coordination was not affected when coumarin was used in Co deposition from [BMP][TFSA] ILs containing Co(TFSA)222 suggesting that no complex of Co2+ ions with coumarin was formed. In this latter case, the reduction of cobalt occurred from the divalent cobalt species [Co(TFSA)3]-. When nicotinamide was used as additive during Al electrodeposition from AlCl3 in 1-butyl-3-methylimidazolium chloride23 an inhibition of Al deposition was observed,

(b)

Fig. 2. (a) Silicon layer (thickness ca 180 nm) deposited from 1 M SiCl4 in [BMP][TFSA] at room temperature (25°C) and E=-2.3 V on Au electrodes. The counter and reference electrodes used were Pt wires. The presence of elemental Si is supported by the mass charge balance via in-situ microgravimetry. (b) Si-containing layer (thickness ca. 300 nm) deposited from 1 M SiI4 in [BMP][TFSA] at room temperature (25°C) and E=-2.3V on Au electrodes. In-situ microgravimetry indicated that the deposited layer did not consist solely of elemental Si. 48

The Electrochemical Society Interface • Spring 2014

but, at the same time, highly uniform and smooth surfaces were obtained. This example shows that additives can have opposing contributions to the various important parameters in a plating process (time, quality etc.). Zinc electrodeposition from DES (1:2 choline chloride: urea and 1:2 choline chloride: ethylene glycol) in the presence of acetonitrile, ethylene diamine and ammonia has been studied in Abbott et al.24 The use of ammonia promoted mass transport, enhanced deposition rates and engendered a specific morphology. The addition of ethylene diamine inhibited the reduction of Ni but favored the reduction of Zn. Brighter deposits could be obtained in the presence of either ethylene amine or ammonia. Acetonitrile had a negligible effect on the electrochemical deposition of Zn from ILs. Additives can also be used in lithiumion batteries to improve the cycling ability of lithium in ILs.25,26 Propylene carbonate27,28 and ethyl alcohol27 have been used in the electrodeposition of Co and Zn-Co from ILs and toluene. LiCl has been used in Al electrodeposition29 and LiF in Ta electrodeposition.30 In all these studies, it was shown that the grain size and morphology of the deposits, and the electrochemical behavior could be altered by addition of suitable additives to the ILbased plating baths. This area remains of considerable interest and it is in theory possible to tune the properties of the plating bath for any metal by choosing a suitable combination of IL solvent and additive.

Codeposition Electrocodeposition implies the simultaneous deposition of a metal matrix (e.g., Ni, Cu, Zn) or a polymeric matrix (PEDOT) and of nano or micro sized particles. The nanoparticles to be deposited can be oxides (Al2O3, TiO2, SiO2, ZrO2, CeO2), carbon based materials (Cr3C2, SiC, WC, diamond, carbon nanotubes), magnetic particles (Fe3O4, Co) or insulating particles (Teflon). Usually the aim is to obtain codeposits with better mechanical, optical, magnetic properties or corrosion resistance than the matrix itself. Therefore, in some industrial applications (e.g. automotive or aerospace industry), codeposited materials have already replaced pure metals.12,31 Hitherto electrocodeposition has mostly been performed in aqueous baths. Reports on electrocodeposition in ILs are very scarce. Abbott and co-workers have reported the electrocodeposition of Cu and Cr from DES in the presence of Al2O3 and SiC particles.32,33 The stability of the DES based suspensions with various particles such as Si3Ni4, SiC, BN, Al2O3 and diamond was reported to be quite good: 1 µm Al2O3 particles sedimented within 24 h from the suspension, while 50 nm particle suspensions were stable for more than 1

The Electrochemical Society Interface • Spring 2014

Fig. 3. Cyclic voltammograms (scan rate = 10 mV/s) in 0.5 M TaF5 in [BMP][TFSA], obtained on Au electrodes, at 25 and 120°C. Platinum wires were used as counter and reference electrodes. Wave C1 is attributed to a partial reduction of TaV, and C2 to the deposition of a Ta0 rich layer.

week.32,33 The codeposition of Cu-Al2O3 and Cu-SiC films from DES was shown to be different compared to codeposition from aqueous solutions, in terms of deposition thermodynamics and kinetics, or in terms of the complexing mechanisms of the metal ions. This will remain an area of interest in the future.

Pulse Plating in ILs Most electrodeposition from the ILs is performed in constant current or constant potential mode. In some studies, cyclic voltammetry is also used as a deposition technique. Pulsed electrodeposition is a powerful technique widely used by the plating industry to improve the morphology (e.g., finer grains) or the throwing power (e.g., covering through holes in printed circuit boards by pulse reverse plating). Pulsed electrodeposition can also improve the adhesion of the deposit to the substrate, and, in the case of alloy deposition, it can be used to tailor the composition of the electrodeposit. Pulse plating (PP) implies a splitting of the Nernst-Diffusion layer into two regions, a pulsating and a stationary diffusion layer.12 The concentration of the active species that will be reduced in the pulsating layer varies with the frequency of the pulsating current. A short review on pulse plating from ILs can be found in Ispas and Bund.34 Most papers are on Al electrodeposition35-42 and its alloys with Co, Cu, Sb or Ni.43-46 Other alloys that have been obtained by pulse plating from ILs and deep eutectic solvents, respectively, are In-Sn47 and BiSbTe.48 Some conducting polymers have also been synthesized by pulse plating in ILs.49,50 Most of the

studies have focused on the morphological aspects of the deposited layers, i.e., these studies describe the improvement in the morphology of the deposits, in the adhesion of the deposited layers on different substrates, and the reduction of the grain size of the deposits when compared to the layers obtained by direct plating. Moreover, no surface pretreatment was necessary to obtain an adherent and structured Al film on Al36 electrodes when pulse plating was used. Another powerful application of pulse plating is alloy deposition. Different alloy compositions can induce varied physicochemical properties in the resultant films. For example, by varying the alloy composition, magnetic properties can be altered,43 the morphology can be improved44,45 or the electronic properties can be modulated.45 Sometimes, contamination of the deposited layers with impurities from the bath, or with species that arise from the partial decomposition of electrolytes has been observed in the deposited layers obtained from IL-based baths. However, this contamination can be reduced if pulse plating is used instead of dc plating.44 Selectivity in terms of crystalline phases can also be achieved using pulse plating in ILs. For example, a single phase of Al-Ni alloy (Ni3Al) can be obtained by pulse plating, while multiple intermetallic phases are usually detected in the dc plated deposits.46 There are metals for which the reduction process is quite complex as it involves the transfer of many electrons, e.g. tantalum or niobium (Fig. 3). The electrodeposition of Ta using potentiostatic pulses in ILs produces smoother and more compact (continued on next page)

Ispas and Bund

(continued from previous page)

layers when compared to dc plating at elevated temperatures.34,51 At the same time, potentiostatic pulses favor the electrodeposition of Ta at room temperature52 (Fig. 4). Hard magnetic layers (Co-Sm) can also be obtained by using the pulse plating technique in ILs.53

Outlook Electrochemistry is an economic technique for obtaining coatings on substrates of complicated geometrical shape (e.g. screws, springs). Deposits with smooth surfaces, good resistance against corrosion and high hardness, and low levels of contamination with foreign species are usually desired for specific functional coatings. For layers that cannot be deposited from aqueous baths, ILs are the media

of choice. If ILs are to be employed for electrodeposition on a larger (industrial) scale, it is highly probable that additives in conjunction with pulse plating techniques will be used. We anticipate intensive research on optimizing deposition processes in ILs in the presence of additives, or under different plating conditions. Another key aspect that should be kept in mind is the effect of impurities. These could be byproducts arising from the synthesis of ILs (such as Li) or traces of water. Some effects of the impurities have been addressed in the literature2,5,7 and therefore are not detailed here. When one implements an IL-based plating process on an industrial scale, minimization of impurities will be essential. The precursors that one can use in the deposition process are also very important, as well as the anion/cation combination employed. We envision that an important role will be played by tailored ILs in this context.11

(a)

(b)

(c)

(d)

About the Authors Adriana Ispas studied physics at the “Alexandru I. Cuza” University in Iasi, Romania, where she obtained her MSc in applied physics in 2001. In 2003 she moved to Germany to the Dresden University of Technology, in the department for Electrochemistry and Physical Chemistry, where in 2007 she obtained her PhD. The PhD thesis was on magnetic field effects during electrodeposition of Ni and Ni-Fe alloys. Since 2007 she works on electrodeposition of metals, semi-conductors and conducting polymers from ionic liquids. Presently she works at the Institute of Materials Engineering at Technische Universitaet Ilmenau. In 2013 she was awarded a Postdoctoral Carl-Zeiss fellowship. She may be reached at adriana.ispas@tuilmenau.de.

Fig. 4. Scanning electron micrographs of layers electrodeposited from ILs: (a) 0.5 M TaF5 in 1-methyl-3-propyl-imidazolium bis(trifluromethylsulfonyl)amide, [PMIm][TFSA]: at 130°C and E=-1.6V; (b) 0.5 M TaF5 in [PMIm][TFSA], 1 s at E=-0.8 V and 1 s at E=-1.7 V; (c) 0.5 M NbF5 in [PMIm][TFSA]: 130°C and E=-1.3V; (d) 0.5 M NbF5 in [PMIm][TFSA]: at 25°C, 1 min at E=-2.5 V and 1 min at E=-1.0 V, Working electrode was Au, counter and reference electrodes were Pt wires. 50

The Electrochemical Society Interface • Spring 2014

Andreas Bund studied Chemistry at the University of Saarland during 1989-1995. His PhD was on the application of piezoelectric quartz crystals for rheological and microgravimetric in situ measurements. He obtained his PhD in 1999 with summa cum laude. In 1999 he moved to Dresden University of Technology where he did his habilitation thesis in 2004. The habilitation thesis was on tribological, rheological and magnetohydrodynamic effects at electrochemical interfaces. In 2005 he was awarded the renowned Heisenberg fellowship of the Deutsche Forschungsgemeinschaft. During the time of his fellowship he was twice a visiting scientist at the University of Utah where he worked with Henry S. White on electrochemical magnetohydrodynamics and the numerical simulation of electrochemical processes. From 2009 to 2010 he held a visiting professorship at TU Munich, Faculty of Physics, Chair Interfaces and Energy Conversion. In August 2010 he was appointed full professor at Technische Universitaet Ilmenau, group of Electrochemistry and Electroplating. Andreas Bund has about 90 ISI refereed journal articles. He may be reached at Andreas.Bund@tu-ilmenau.de.

References 1. Y. Katayama, in Electrochemical Aspects of Ionic Liquids, 2nd ed., H. Ohno, Editor, John Wiley and Sons Inc., New York (2011). 2. F. Endres, A. P. Abbott, and D. R. MacFarlane, Electrodeposition from Ionic Liquids, Wiley-VCH, Weinheim (2008). 3. A. P. Abbott, D. Boothby, G. Capper, D. L. Davies, R. K. Rasheed, J. Am. Chem. Soc. 126, 9142 (2004). 4. F. Endres, ChemPhysChem 3, 144 (2002). 5. M. C. Buzzeo, R. G. Evans, R. G. Compton, ChemPhysChem 5, 1106 (2004). 6. A. P. Abbott, K. J. McKenzie, Phys. Chem. Chem. Phys. 8, 4265 (2006). 7. P. Hapiot, C. Lagrost, Chem. Rev. 108, 2238 (2008). 8. C. Larson, Trans. Inst. Met. Finish. 86(4) (2008), special issue on “Plating from Ionic Liquids.” 9. W. Simka, D. Puszczyk, G. Nawrat, Electrochim. Acta, 54, 5307 (2009). 10. A. P. Abbott, G. Frisch, K. S. Ryder, Annu. Rev. Mater. Res., 43, 335 (2013).

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11. S. Schaltin, N. R. Brooks, L. Stappers, K.Van Hecke, L. Van Meervelt, K. Binnemans, J. Fransaer, Phys. Chem. Chem. Phys., 14, 1706 (2012). 12. M. Schlesinger and M. Paunovic, Modern Electroplating, 4th ed., John Wiley & Sons, New York (2000). 13. Y.-L. Zhu, Y. Katayama, T. Miura, J. Electrochem. Soc., 159, D699 (2012). 14. Y. Katayama, R. Fukui, T. Miura, J. Electrochem. Soc., 154, D534 (2007). 15. Y.-L. Zhu, Y. Kozuma, Y. Katayama, T. Miura, Electrochim. Acta., 54, 7502 (2009). 16. S. Zein El Abedin, E. M. Moustafa, R. Hempelmann, H. Natter, F. Endres, Chem. Phys. Chem., 7, 1535 (2006). 17. V. S. Vidhya, J. Vatsala Rani, A. Ratheesh Kumar, R. Thangamuthu, K. R. Murali, M. Jayachandran, Mater. Sci.: Mater. Electron., 22, 1460 (2011). 18. Q.-B. Zhang, Y.-X. Hua, Y.-X. Ren, L.-Y.Chen, J. Cent. South Univ., 20, 2096 (2013) 19. Q. Zhang, Y. Hua, C. Liyuan, Adv. Mater. Res., 634-638, 140 (2013). 20. M.H. Allahyarzadeh, B. Roozbehani, A. Ashrafi, S. R. Shadizadeh, A. Seddighian, E. Kheradmand, J. Electrochem. Soc., 159, D473 (2012). 21. Y.-L. Zhu, Y. Katayama, T. Miura, Electrochim. Acta., 85, 622 (2012). 22. R. Fukui, Y. Katayama, T. Miura, Electrochim. Acta, 56, 1190 (2011). 23. Q. Zhang, Q. Wang, S. Zhang, X. Lu, J. Solid State Electrochem, DOI 10.1007/ s10008-013-2269-y. 24. A. P. Abbott, J. C. Barron, G. Frisch, K. S. Ryder, A. F. Silva, Electrochim. Acta, 56, 5272 (2011). 25. G. H. Lane, A.S.Best, D. R. MacFarlane, M. Forysyth, A. F. Hollenkamp, Electrochim. Acta, 55, 2210 (2010). 26. M. Egashira,T. Kiyabu, I. Watanabe, S. Okada, J.-I. Yamaki, Electrochemistry, 71(12), 1114 (2003). 27. N. Koura, T. Endo, Y. Idemoto, J. NonCrys. Solids, 205, 650 (1996). 28. P.-Y. Chen, I-W., Electrochimica Acta, 46, 1196 (2001). 29. A. P. Abbott, F. Qiu, H. M. A. Abood, M. R. Ali, K. S. Ryder, Phys. Chem. Chem. Phys., 12, 1862 (2010). 30. S. Zein El Abedin, U. Welz-Biermann, F. Endres, Electrochem. Commun., 7, 941 (2005). 31. A. K. Vijh, in Modern Aspects of Electrochemistry, No. 17, J. O’M. Bockris, B. E. Conway, and R. E. White, Editors, Plenum Press, New York-London (1986).

32. A. P. Abbott, K. El Ttaib, G. Frisch, K. J. McKenzie, K. S. Ryder, Phys. Chem. Chem. Phys., 11, 4269 (2009). 33. A. Abbott, J. C. Barron, M. Elhadi, G. Frisch, S. J. Gurman, A. R. Hillman, E. L. Smith, M.A. Mohamoud, K. S. Ryder, ECS Trans., 16(36), 47 (2009). 34. A. Ispas, A. Bund, Trans. Inst. Met. Finish., 90, 298 (2012). 35. M. Ueda, Y. Tabei and T. Ohtsuka, ECS Trans., 33(7), 563 (2010). 36. C. Lecoeur, J.-M. Tarascon and C. Guery, J. Electrochem. Soc., 157, A641 (2010). 37. J. Tang and K. Azumi, Electrochim. Acta, 56, 1130 (2011). 38. C.-C. Yang, Mater. Chem. Phys., 37, 355 (1994). 39. B. Li, Y. Chen, L. Yan and J. Ma, Electrochemistry, 78, 523 (2010). 40. B. Li, C. Fan, Y. Chen, J. Lou and L. Yan, Electrochim. Acta, 56, 5478 (2011). 41. G. Oltean, L. Nyholm and K. Edström, Electrochim. Acta, 56, 3203 (2011). 42. H. Natter and R. Hempelmann, Z. Phys. Chem., 222, 319 (2008). 43. M. Rostom Ali, A. Nishikata and T. Tsuru, Electrochim. Acta, 42, 1819 (1997). 44. Q. Zhu and C. L. Hussey, J. Electrochem. Soc., 149, C268 (2002). 45. T. Gandhi, K. S. Raja and M. Misra, Electrochim. Acta, 53, 7331 (2008). 46. M. Rostom Ali, A. Nishikata and T. Tsuru, J. Electroanal. Chem., 513, 111 (2001). 47. M. Noda, M. Morimitsu and M. Matsunaga, ECS Trans., 3(35), 249 (2007). 48. F. Golgovici, A. Cojocaru, L. Anicai and T. Visan, Mater. Chem. Phys., 126, 700 (2011). 49. D. Zane, C. Bianchini, G. B. Appetecchi, A. Curulli and S. Passerini, ECS Trans., 25(32), 63 (2010). 50. D. He, Y. Guo, Z. Zhou, S. Xia, X. Xie and R. Yang, Electrochem. Commun., 11, 1671 (2009). 51. A. Ispas, B. Adolphi, A. Bund, F. Endres, Phys. Chem. Chem. Phys., 12, 1793 (2010). 52. N. Borisenko, A. Ispas, E. Zschippang, Q. Liu, S. Zein El Abedin A. Bund, F. Endres, Electrochim. Acta, 54, 1519 (2009). 53. A. Ispas, M. Buschbeck, S. Pitula, A. Mudring, M. Uhlemann, A. Bund, F. Endres, ECS Trans., 16(45), 119 (2009).

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The Electrochemical Society Interface â&#x20AC;˘ Winter 2013 1

Vacuum Electrochemistry in Ionic Liquids by Oliver Höfft and Stefan Krischok

n recent years, ionic liquids (IL) have been introduced as new electrolytes in electrochemistry.1 Their physical and chemical properties facilitate new and exciting applications for electrochemical processes. For example, ILs are characterized by their large electrochemical windows, which permit the electrodeposition of metals like aluminium and even semiconductors like silicon.2,3 Furthermore, through careful selection of the IL, one can influence and tune the electrodeposition process. The electrodeposition of aluminum is a good example, nanocrystalline aluminum deposits can be synthesized from AlCl3 in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py 1,4] Tf2N), whereas microcrystalline deposits can be obtained in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([EMIm] Tf2N), although the Al species are virtually identical.4 The reasons for this behaviour are different adsorption structures (“solvation layers”) of the cations and anions on the electrode.5 [Please refer to article by Ipsas et al. in this issue for more details of electrodeposition in ILs – Ed.]. Furthermore, the interaction processes between ionic liquids and interfaces (in particular the adsorption of the IL ions on electrode materials) have been extensively studied using in-situ scanning tunnelling microscopy (STM), atomic force microscopy (AFM) and spectroscopic techniques like sum frequency generation and X-ray diffraction.6-9 [Please refer to article by Borisenko et al. in this issue for further details – Ed.]. The (usually) very low vapor pressure of ILs, which range between 10−9 and 10−8 Pa at or near room temperature and between 10−4 and 10−2 Pa, at 100 °C, opens up many additional approaches for the investigation of ILs. In particular, it is possible to apply vacuum-based methods to study ILs. X-ray photoelectron spectroscopy (XPS) has proven to be a powerful technique to study IL interfaces in a controlled environment.10-14 Due to the fact that monolayer of ILs can be prepared by evaporation in ultra high vacuum (UHV), adsorption structures can readily be analysed with XPS and monitored with STM.15,16 The logical next step is to study the electrochemistry of IL-electrode interfaces directly in vacuum. Kuwabata et al. developed an in situ electrochemical scanning electron microscope (ECSEM) for the monitoring of electrodeposition processes.17 Figure 1 shows their first electrochemical cell design. With this cell they studied the oxidation and reduction of a poly(pyrrole) film on The Electrochemical Society Interface • Spring 2014

platinum in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([BMIm] Tf2N). It was clearly visible that the film thickness decreased and increased, respectively, during oxidation and the reduction. In addition, with in situ EDX measurements, the doping of the poly(pyrrole) film with potassium ions was investigated. With a new cell, produced from fluorine doped tin oxide-coated glass (FTO), Kuwabata et al. imaged silver electrodeposition in [BMIm]Tf2N.18 With the ECSEM, they observed a dendritic growth of silver on FTO. These measurements were accompanied by in situ EDX studies. Such observations have helped to close the gap between the in situ STM/AFM experiments at the nanoscale and the ex situ SEM measurements of thicker, micro-scale deposits. Precise fabrication and accurate filling of the cell are necessary to image the electrode surface, because a thick IL film on top of the surface can hinder the penetration of the secondary electrons (used for imaging) through the liquid film to obtain proper image. Such requirements become especially important for in situ XPS measurements, as the inelastic mean free path of electrons excited by the x-ray radiation is only a few nanometers. Electrochemical cells for in situ XPS were introduced by the groups of Licence, Compton and Kötz.19-21 Taylor et al.19 studied the electrochemical reduction of iron in an [EMIm] EtOSO3 and [BMIm] FeCl4

mixture, whereas Kötz et al21 analyzed the boundary between a Pt anode and an [EMIm] BF4 electrolyte. Wibowo et al.20 investigated potassium electrodeposition from [Py1,4] Tf2N onto a nickel mesh. This field presents many promising avenues for investigation of the IL-electrode interface and of electrochemical processes using ILs.

Synthesis of Materials in Vacuum The synthesis of nanoparticles is a hot topic in the field of IL research. The synthesis of a variety of nanoparticles from ILs in vacuum is possible by different methods, such as sputter deposition or physical vapor deposition of metals onto surfaces of the liquids in vacuum, reduction with free electrons in a scanning electron microscope and plasma electrochemical approaches.22 The advantage of using ILs as a medium for nanoparticle synthesis is that the derived nanoparticles can be stabilized without the presence of any adventitious stabilizing agent.23 An overview on the different methods to produce nanoparticles in ILs and their applications can be found in three recent reviews.23-25 With respect to the electrochemical route for nanoparticle synthesis in ILs, Dupont and Scholten have stated in their review, “Electrochemical reductions of metal compounds in ILs are likely the cleanest methods for preparing metal NPs since only electrons are (continued on next page)

Fig. 1. Electrochemical cell by Kuwabata et al.17 Figure from Kuwabata et al.13 (Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission.) 53

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involved.”23 One can extend this statement, since the entire process takes place in the highly controlled environment of a vacuum chamber. The synthesis approaches involving scanning electron microscopes and scanning Auger electron microscopes were introduced by Roy et al.26 and Imanishi et al.27 Here, the electrons were used both for the reduction of precursor to yield the nanoparticles and for monitoring the process. In this context one has to be aware that the electrons might not only induce the desired precursor reduction but might also interact with the IL medium, leading to their decomposition. The plasma approach is different since the electrons for the reduction are provided from a plasma, which is in direct contact with the IL. Consequently, electrons are able to reduce dissolved metal or semiconductor compounds directly at the IL/plasma interface. Generally speaking, the idea of using free electrons for precursor reduction is not new, as Gubkin used a plasma in conjunction with an aqueous solution of silver nitrate more than hundred years ago28 to synthesise silver at the water surface. Nowadays atmospheric-pressure microplasmas or plasma jets are available to provide electrons to aqueous interfaces for precursor reduction.29,30 With these techniques, the high vapor pressure of water can be circumvented. The low vapor pressure of ILs further facilitates obtaining a stable plasma above the interface. The ignition of such a plasma can be achieved with different systems.22,31 One of the easiest ways is to use DC plasma reactors. In Fig. 2, a sketch of such a reactor is shown. It consists of a glass cell with two metal electrodes, which are connected to a DC power supply. The cell is pumped using a rotary pump and the gas flow for the plasma can be regulated using a vacuum valve. Argon is usually used as the plasma gas. A typical experiment starts by filling the reactor with the IL electrolyte containing the desired metal precursor. Thereafter, the electrolyte is carefully outgassed at a pressure of 10-3 mbar. The plasma gas is then fed into the cell, a pressure of around 1 mbar is maintained, and a voltage between 500 and 1000 V is applied between the electrodes. The exact parameters depend on the distance between the electrodes and on the electrolyte used. When the upper electrode acts as the cathode, the electrons move towards the electrolyte and the gas ions move towards the counter electrode. At the plasma/IL interface, the electrons can react with the dissolved metal ions and particles are formed. In Fig. 3 a typical temporal evolution of the plasma electrochemical experiment is shown, with reference to the generation of copper nanoparticles from a [EMIm] Tf2N/ Cu Tf2N solution.32 It is clear that the reaction starts directly at the plasma/ 54

Fig. 2. Sketch of a plasma reactor. Figure from Meiss, et al.36 Copyright Wiley-VCH Verlag GmbH & Co. KGaA. (Reproduced with permission.)

Fig. 3. Temporal evolution of the plasma electrochemical reduction (30 min) of Cu+ in [EMIm]Tf2N. Figure from Brettholle, et al.32 (Reproduced by permission of the PCCP Owner Societies.)

IL interface and, with time, a dark cloud grows in the downward direction in the cell, whereas the rest of the liquid remains clear. Some small bubbles are formed at the anode, likely due to the decomposition of the IL at this electrode. Plasma electrochemistry using DC reactors was divided into two modes (A and B mode) by Hatakeyama et al.33 These modes depend on the polarisation of the electrodes. Nanoparticles can, in principle, be synthesised in both modes. In the A-mode, where the cathode is immersed in

the liquid, secondary electrons, created due to the interaction of the plasma gas ions with the IL interface, act as the reducing agents. In the B-mode, where the cathode is above the liquid, the primary electrons in the plasma reduce the dissolved species. Another DC plasma reactor concept was introduced by Liu et al., wherein no electrode is immersed in the liquid (both electrodes are in the gas phase). The electrolyte is placed in a quartz crucible and is located at the “positive column” of the glow discharge.34 In addition Liu et al., The Electrochemical Society Interface • Spring 2014

showed that a sub-atmospheric dielectric barrier discharge (SADBD) plasma can also act as a reducing agent.35 Radio frequency discharge plasma setups have also been used for plasma electrochemistry.36 With these approaches, the generation of silver, gold, platinum, palladium and copper nanoparticles in different ILs have been reported22,31-34 The particle sizes have been determined by transmission electron microscopy (TEM) and, in the case of ILs, this can be done directly with the particles in the IL. Thus, secondary reactions induced during separation of the particles from the IL, and the resultant convolution in particle size data, can be avoided. This is especially important for the particles made from reactive metals. However, this approach also has a possible disadvantage in that a detailed analysis of the particle structure is rendered difficult by the presence of an IL film around the particles. In general, all particles thus synthesized and reported in the literature were found to exhibit sizes well below 100 nm. No correlation between IL physical properties (like surface tension) and particle size has hitherto been conclusively established. The particles synthesised in ILs have mostly been equivalent or larger in size compared to the particles generated with the chemical reduction method or the sputtering technique. For example the copper nanoparticles produced by physical vapor deposition in [BMIm]Tf2N and [BMIm]PF6 exhibit particles sizes around 3 nm.37 By chemical reduction, comparable particle sizes were observed.38 The copper nanoparticles produced in [BMIm]dca were also in this size regime, while the Cu particles in [EMIm]Tf2N and [Py1,4]Tf2N were larger.52 A comparison of the particle dimensions achieved from plasma electrochemistry in ILs consisting of imidazolium cations and different anions, with the particles generated by reduction with low-energy electrons in a SEM yielded similar size regimes.39 Interestingly, Kuwabata et al. found that the anion plays an important role on the particle size, whereas the change of the alkyl chain length of the cation has a minor influence on the particle size.39 Here, the particles derived from imidazolium liquids containing the [Tf2N] anion were around a factor of two larger compared particles derived from imidazolium ILs containing the [PF6] anion. This is in good agreement with our own observations. Due to the very low vapor pressure of ILs, XPS can be used as a powerful tool for characterization. It provides detailed insights into the surface stoichiometry, possible surface enrichments, and the chemical state of the detected elements. Thus, it is possible to investigate the original chemical state of the dissolved species, to perform the characterization of the synthesized material, including, e.g., the oxidation state (valence) of the produced material, and to analyse the residuals from the ILs. The Electrochemical Society Interface â&#x20AC;˘ Spring 2014

Using more sophisticated experimental setups, it is even possible to obtain direct insights into the electrochemical mechanisms in play.19-21 As an example of XPS studies on salts dissolved in ILs and the characterization of electrodeposited materials, data for the TaF5/[PMIm]Tf2N system are shown in Fig. 4 (for more details see Krischok, et al.40). In Fig. 4a the influence of the Ta salt concentration on the N 1s signal is shown. The Tf2N related signal at about 399 eV decreases with respect to the PMIm related N-signal at about 402 eV (from the expected 1:2 ratio) with increasing amounts of TaF5. Obviously

the cation:anion ratio of the IL at the surface is strongly modified by the Ta salt. In Fig. 4b the obtained Ta spectra are shown. The Ta signal is different for the dissolved Ta salt in the IL, the Ta near the surface of the deposited Ta film after short sputtering (note that in this particular case the sample was exposed to ambient conditions after film production), and the Ta after longer sputtering. The data for the electrodeposited film show that the surface is oxidized (see signal after 20 min sputtering). With increasing sputtering time, an additional metallic Ta component appears. Moreover, the XPS of the as prepared film reveals the (continued on next page)

(a)

(b)

Fig. 4. (a) Changes of the N1s XPS core level spectra of [PMIm] Tf2N in dependence of the dissolved Ta-salt concentration. The shown spectra have been normalized and the binding energy was adjusted by shifting the PMIm related signal to 401.7 eV for charge compensation. (b) Ta signal for the dissolved salt and for the deposited film after short and longer sputtering time. The spectra have been normalized and a vertical offset was added for better visualisation. All XPS spectra were recorded using monochromatized Al Ka radiation. 55

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presence of large amounts of IL residuals. Similar studies have also been performed for the production of Cu nanoparticles from ILs by plasmaelectrochemical methods.32 But what is the advantage of the plasma electrochemical approach in combination with ionic liquids compared to the other methods? One advantage might be that this technique opens the way to the generation of semiconductor particles like germanium and silicon. Kareem and Kaliani were able to produce ZnS nanoparticle in [BMIm]BF4 with plasma electrochemistry,41 therefore the synthesis of other semiconductor compounds should also be feasible. Endres et al. have shown by electrodeposition experiments that nanoscale silicon and germanium films can be easily made from different SiCl4 and GeCl4 containing IL solutions.42,43 Not too surprisingly, the first attempts to reduce SiCl4 and GeCl4 by plasma electrochemistry failed as the precursors were simply pumped off due to too high vapor pressures. Then, a solid GeCl2·dioxane complex (GeCl2C4H8O2) was selected as germanium source.44 Compound particles with sizes smaller than 50 nm have been obtained using this solid. With XPS, the chemical composition of the solution before and after the plasma treatment has been analyzed. At the electrode-solution interface, germanium can be detected in both cases. The detailed spectrum of the Ge 2p region shows, for the untreated solution, only germanium in the Ge2+ oxidation state. After the plasma interaction, an additional component is visible in the spectrum, which can be attributed to a lower oxidation state of Ge. This demonstrates that the plasma process leads to germanium reduction via Ge2+ and Ge+ to Ge0. For attempts to produce silicon particles, SiI4 was chosen, a solid that cannot be pumped off from the reactor. An electrodeposition experiment performed by Bund et al. revealed that from SiI4/ [Py1,4]Tf2N solutions, elemental Si could not be obtained, but rather subvalent SixIy compounds were produced. Nevertheless, these first results showed that SiI4 can be reduced electrochemically.44 XPS investigation of silicon electrodepositon from ILs has not been successful until now. As there are only a few Si precursors available, we have developed a new reactor design that permits the use of high vapor pressure precursors in future.45 A further application for plasma electrochemistry using ILs is the direct functionalization of materials with metal particles. Hatakeyama et al. impregnated carbon nanotubes with gold and palladium salts, followed by plasma treatment.46 They observed the formation of metal particles between the bundles of the carbon nanotubes. They expected that this

resulted in the formation of more uniform particles because the small spaces inside the nanotubes inhibited particle agglomeration.46 Obviously, plasma electrochemistry in ILs can also be used for the production of hybrid materials as described above. Finally, a possible “disadvantage” of vacuum electrochemistry has to be addressed. In all presented cases, the ILs interact with high-energy electrons or photons in the case of SEM or XPS experiments, and with low energy electrons in the plasma experiments. Thus the IL might degrade. For example, from pulse radiolysis measurements it is known that aromatic cations, especially imidazolium cations, serve as electron trapping centers during radiolysis, resulting in the formation of neutral radicals and radical ions.47,48 These radicals can activate secondary reactions in the system. Additionally we have shown that there is an influence of non-monochromated AlKa X-rays and electron beams on the surface composition of the IL [EMIm] Tf2N.49 In plasma experiments Hatakeyama et al. have observed strong color change in an IL containing an imidazolium cation.33 With optical emission spectroscopy, methylidyne radicals (CH) in the plasma could be detected,33,46 arising from a loss of an alkyl chain from the imidazolium cation. Such radicals can also act also as reducing agents in solution, thereby convoluting the electrochemical process.

Conclusions and Outlook Ionic liquids have created a pathway for performing electrochemistry under vacuum. The electrons from electron microscopes or from a plasma can be used directly as reducing agents in such a process/ experiment. One can monitor and investigate electrochemical processes at the IL/vacuum interface and at the IL/electrode interface in classical electrochemical cells using SEM or photoelectron spectroscopy, provided the precursors used have a low vapor pressure. The need for low vapor pressure precursors is one of the disadvantages of vacuum electrochemistry. However, with an optimized cell design, such challenges can be overcome. Some interesting preliminary results that demonstrate the possibility to produce even compound semiconductors by plasma electrochemistry have been presented. Moreover, electrochemistry in the monolayer regime might be possible since the production of very thin layers of ILs in UHV by evaporation or other deposition methods is possible and not too difficult. This might lead to a deeper understanding of electrochemical processes at the atomic scale. In closing, ILs enable a versatile platform for fundamental electrochemical studies in vacuum, as well as processes of interest, such as nanoparticle synthesis. These areas are poised for growth.

About the Authors Oliver Höfft studied physics at the University of Marburg and at the University of Technology Clausthal, where he received his diploma in 2002. In 2006 he got his Dr. rer. nat. (PhD) degree at the TU Clausthal. In the same year he joined the group of Frank Endres as a Postdoctoral Researcher, where he is currently working on his habilitation thesis His research interests include plasma electrochemistry and surface science on ionic liquid interfaces. He may be reached at oliver.hoefft@tuclausthal.de. Stefan Krischok studied Physics at the Clausthal University of Technology (Germany) from 19911997 and graduated there in 1997 with a diploma in Physics. He got his Dr. rer. nat. (PhD) degree in 2001 at the same university and moved subsequently to the Technische Universität Ilmenau (Germany) where he got his habilitation for experimental physics in 2007. Currently he is leading an independent research group. His interests are in the field of surface and interface science. At present, semiconductor materials (group III-nitrides), ionic liquids and materials for sensor applications are of particular interest. He may be reached at stefan.krischok@tuilmenau.de.

References 1. F. Endres, S. Zein El Abedin, Phys. Chem. Chem. Phys., 8, 2101 (2006). 2. F. Endres, A. P. Abbott, and D. MacFarlane, Electrodeposition from Ionic Liquids, Wiley-VCH, Weinheim (2008). 3. H. Ohno, Electrochemical Aspects of Ionic Liquids, John Wiley & Sons, Inc., New York (2005). 4. P. Eiden, Q. X. Liu, S. Zein El Abedin, F. Endres, I. Krossing, Chem.–Eur. J. 15, 3426 (2009). 5. F. Endres, O. Höfft, N. Borisenko, L. H. Gasparotto, A. Prowald, R. Al-Salman, T. Carstens, R. Atkin, A. Bund, S. Zein El Abedin, Phys. Chem. Chem. Phys., 12, 1724 (2010). 6. R. Atkin, S. Zein El Abedin, R. Hayes, L. H. S. Gasparotto, N. Borisenko, F. Endres, J.Phys Chem.C, 113, 13266 (2009). 7. R. Atkin, G. G. Warr, J. Phys. Chem. C, 111, 5162 (2007).

The Electrochemical Society Interface • Spring 2014

8. S. Baldelli, Acc. Chem. Res., 41, 421 (2008). 9. M. Mezger, H. Schröder, H. Reichert, S. Schramm, J. S. Okasinski, S. Schroder, V. Honkimäki, M. Deutsch, B. M. Ocko, J. Ralston, M. Rohwerder, M. Stratmann, H. Dosch, Science, 322, 424 (2008). 10. K. R. J. Lovelock, I. J. Villar-Garcia, F. Maier, H.-P. Steinrück, Chem. Rev., 110, 5158 (2010). 11. E. Smith, I.V. Garcia, D. Briggs, P. Licence, Chem. Commun., 5633 (2005). 12. S. Caporali, U. Bardi, A. Lavacchi, J. Electron. Spectrosc. Relat. Phenom., 151, 4 (2006). 13. O. Höfft, S. Bahr, M. Himmerlich, S. Krischok, J. A. Schaefer, V. Kempter, Langmuir, 22, 7120 (2006). 14. H.-P. Steinrück, Surf. Sci., 604, 481 (2010). 15. T. Cremer, M. Killian, J. M: Gottfried, N. Paape, P. Wasserscheid, F. Maier, H. P. Steinrück, ChemPhysChem, 9, 2185 (2008). 16. T. Waldmann, H.-H. Huang, H. E. Hoster, O. Höfft, F. Endres, R. J. Behm Chem Phys Chem., 12, 2565 (2011). 17. S. Arimoto, D. Oyamatsu, T. Torimoto, S. Kuwabata, ChemPhysChem., 9, 763 (2008). 18. S. Arimoto, H. Kageyama, T. Torimoto, S. Kuwabata, Electrochem. Comm., 10, 1901 (2008). 19. A. W. Taylor, F. Qiu, I. J. Villar-Garcia, P. Licence, Chem. Commun., 5817 (2009). 20. R. Wibowo, L. Aldous , R. M. J. Jacobs, N. S. A. Manan, R. G. Compton, Chem. Phys.Lett., 509, 72 (2011).

21. D. Weingarth, A. Foelske-Schmitz, A. Wokaun, R. Kötz, Electrochem. Comm., 13, 619 (2011). 22. O. Höfft, F. Endres, Phys. Chem. Chem. Phys., 13, 13472 (2011). 23. J. Dupont, J. D. Scholten, Chem. Soc. Rev., 39, 1780 (2010). 24. T. Torimoto, T. Tsuda, K. Okazaki, S. Kuwabata, Adv. Mater., 22, 1196 (2010). 25. K. Richter, P. S. Campbell, T. Baecker, A. Schimitzek, D. Yaprak, and A.-V. Mudring, Phys. Status Solidi B, 2013, DOI 10.1002/pssb.201248547. 26. P. Roy, R. Lynch, P. Schmuki, Electrochem. Comm., 11, 1567 (2009). 27. A. Imanishi, M. Tamura, S. Kuwabata, Chem. Commun., 1775 (2009). 28. J. Gubkin, Ann. Phys., 268, 114 (1887). 29. C. Richmonds, R. M. Sankaran, Appl. Phys. Lett., 93, 131501 (2008). 30. D. Mariotti, J. Patel, V. Svrcek, P. Maguire, Plasma Process. Polym., 9, 1074 (2012). 31. K. Baba, T. Kaneko, R. Hatakeyama, Appl. Phys. Express, 2, 035006 (2009). 32. M. Brettholle, O. Höfft, L. Klarhöfer, S. Mathes, W. Maus-Friedrichs, S. Zein El Abedin, S. Krischok, J. Janek, F. Endres, Phys. Chem. Chem. Phys., 12, 1750 (2010). 33. T. Kaneko, K. Baba. T. Harada, R. Hatakeyama, Plasma Process. Polym., 6, 713 (2009). 34. Y. B. Xie, C. J. Liu, Plasma Process. Polym., 5, 239 (2008). 35. Z. Wie, C. L. Liu, Materials Lett. 65, 353 (2011). 36. S. A. Meiss, M. Rohnke, L. Kienle, S. Zein El Abedin, F. Endres, J. Janek, ChemPhysChem., 8, 50 (2007).

37. K. Richter, A. Birkner, A.-V. Mudring. Phys. Chem. Chem. Phys., 13, 7136 (2011). 38. P. Arquillière, P. H. Haumesser, C. C. Santini, Microelectron. Eng., 92, 149 (2012). 39. A. Imanishi, S. Gonsui, T. Tsuda, S. Kuwabata, K. Fukui, Phys. Chem. Chem. Phys., 13, 14823 (2011). 40. S. Krischok, A. Ispas, A. Zühlsdorff, A. Ulbrich, A. Bund, F. Endres, ECS Trans. 50(11), 229 (2012). 41. T. A. Kareem, A. A. Kaliani, Ionics, 2013, DOI 10.1007/s11581-013-08772. 42. F. Endres, S. Zein El Abedin, Phys. Chem. Chem. Phys., 4, 1649 (2002). 43. S. Zein El Abedin, N. Borisenko, F. Endres, Electrochem. Commun., 6, 510 (2004). 44. A. A. Aal, R. Al-Salman, M. AlZoubi, N. Borissenko, F. Endres, O. Höfft, A. Prowald S. Zein El Abedin, Electrochimica Acta, 56, 10295 (2011). 45. N. Spitczok von Brisinski, O. Höfft, F. Endres, J. Mol. Liquids, 2013, DOI 10.1016/j.molliq.2013.09.017. 46. T. Kaneko, K. Baba, R. Hatakeyama, Plasma Phys. Contr. F., 51, 124011 (2009). 47. I. A. Shkrob, S. D. Chemerisov, J. F. Wishart, J. Phys. Chem. B, 111, 11786 (2007). 48. I. A. Shkrob, J. F. Wishart, J. Phys. Chem. B, 113, 5582 (2009). 49. A. Keppler, M. Himmerlich, T. Ikari, M. Marschewski, E. Pachomow, O. Höfft, W. Maus-Friedrichs, F. Endres, S. Krischok, Phys. Chem. Chem. Phys., 13, 1174 (2011).

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Influence of Molecular Organization of Ionic Liquids on Electrochemical Properties by Natalia Borisenko, Rob Atkin, and Frank Endres

to study the structure and dynamics of onic liquids (ILs) are pure salts with layers. The tip deflection is transformed ILs.22-24 Theoretical descriptions of the melting points typically less than 100°C. to a normal force (F) by via Hooke’s Law, ILs exhibit several advantages over using the cantilever spring constant. As the IL/electrode interface using molecular conventional molecular liquids in disparate tip moves towards the surface, it encounters dynamics and Monte Carlo simulations,25-35 applications because of their remarkable the first layer (at d3). The force experienced and mean field theory,36,37 have predicted physical properties, which include wide increases as the tip pushes against this layer, “bell-” and “camel-” shaped capacitance electrochemical stability windows, high until sufficient force is reached to rupture curves and oscillating ion density profiles ionic conductivity and negligible vapor the layer (Fig. 1a, blue curve). The tip at the electrode surface, consistent with pressure. IL applications, either already then jumps into contact with the next layer experimental results. However, a proper realized or currently under development, (at d2) and the process is repeated until theoretical model of the electrified IL/solid encompass many diverse areas such as the tip reaches the innermost layer (at d1). interface does not yet exist and further analytics, catalysis, chemical synthesis, The force now increases markedly because experimental studies are required for better separation technologies, electrochemistry, the structuring in the innermost layer is the understanding the IL/electrode interfacial capacitors, batteries, fuel cells, solar cells, most robust due to the attractive interactions structure. and tribology. Many of these applications between the IL ions and the surface. When During the last decade, in situ atomic involve reactions at the IL/solid interface. the tip pushes through this layer, it comes force microscopy (AFM) and scanning Hence, a detailed understanding of the into contact with either the substrate surface tunneling microscopy (STM) have been structure of this interface is important and or a layer of ions that are so strongly bound extensively used to probe the IL structure at cannot be overstated. to the substrate that the tip cannot displace the IL/solid interface.1,5,8,38-50 The mechanism ILs exhibit behavior that is very different it. The positions of the steps in the force of operation of the AFM experiment is from common molecular liquids. As ILs are curve are related to the separation (or spatial presented schematically in Fig. 1. The composed entirely of charged species, they distribution) of the layers near the surface. solid electrode substrate and the AFM tip usually exhibit a more pronounced structure The retraction curve can look quite different and cantilever are completely immersed in the bulk and at surfaces than molecular (Fig. 1a, red curve), most likely either due within the IL (Fig. 1a). The layers close liquids.1 ILs are subject to a range of cohesive to attractive interactions between the tip and to the surface are shown schematically as the surface or interfacial layers, or due to single (blue) layers. As the AFM tip moves interactions (Coulombic, van der Waals, fluid dynamics effects. towards the surface, it is deflected away due hydrogen bonding and solvophobic forces), to the forces imparted by the interfacial IL resulting in a well-defined nanostructure (continued on next page) both in the bulk and at interfaces.2 The nanostructure of ILs evolves as a consequence of electrostatic interactions between charged groups that produce polar domains. Cation alkyl chains are solvophobically repelled3 from these charged domains and cluster together to form apolar regions, that in turn produce a sponge-like phase-separated nanostructure.4 This spongelike structure present in the bulk changes immediately adjacent to a smooth solid surface. Atomic force microscopy (AFM) force curves5,6 and reflectivity experiments7 both reveal the formation of discrete ion or ion pair layers immediately adjacent to the solid surface. This layered surface structure decays to the bulk sponge morphology over a length-scale of a few nanometers.8 The IL/solid interface has been the subject of extensive experimental and theoretical studies. Various spectroscopic and scattering methods have been applied to examine this interface.7,9-21 Electrochemical Fig. 1. (a) Schematic view of an AFM tip approaching a solid surface in the presence of IL with the corresponding impedance spectroscopy (EIS) force versus distance profile below. (b) Schematic view of a STM tip probing the solid surface immersed within an IL measurements have been used and the real STM-image recorded. The Electrochemical Society Interface • Spring 2014

Borisenko, Atkin, and Endres (continued from previous page)

In the (in situ) electrochemical STM experiment, the surface and the STM tip are immersed in the IL (Fig. 1b). The typical distance between the STM tip and the surface is about 1 nm, implying that there is at least one layer between the tip and the sample. The IL ions adsorbed onto the surface participate in the tunneling process, and the STM tip must move through these adsorbed layers during the scanning process. The STM tip either pushes away the layers that are not strongly adsorbed or images them (Fig. 1b). From AFM results, one can conclude that ILs are strongly adsorbed onto solid surfaces and that several IL layers are present adjacent to the surface.1,5,6,8,39-41,51 The distance between the layers is the same as the size of an ion pair. The strength of interactions between the innermost layer and the substrate is dependent on the surface, cation and anion type.6,39 Ion arrangements vary Fig. 2. (a, d) In situ STM images of the Au(111) surface in [Py1,4 ]FAP, (b, e) [EMIM]FAP, and (c, f) [HMIM]FAP. significantly as a function of applied potential, with more pronounced surface structure can be observed (Fig. 2f). At a potential of the surface is consistent with an innermost detected at more positive or more negative -1.0 V, an ion pair sized step is detected in layer enriched in [Py1,4]+. The next spacing potentials. The interfacial layer is enriched the second layer, as opposed to an anion (0.9 nm) is consistent with the size of the by counter-ions strongly bound to the sized step (Fig. 3f). [Py1,4]FAP ion pair dimension. Furthermore, surface. Such strong, specific adsorption These in situ STM and AFM results at -1.0 V the width of the ion layer in contact will influence electrochemical reactions show that the IL cation has a strong with the gold becomes thinner (0.25 nm in occurring at the surface.52 influence on the structure and composition Fig. 3d), indicating that the cation adopts In situ STM experiments confirm that ILs of the interface. With the same anion, an orientation that renders it more parallel adsorbed at an electrode surface do influence the Au(111) surface undergoes the (22 x to the surface, which in turn induces the electrochemical processes. However, the √3) reconstruction with [Py1,4]+, but with Au(111) (22 x √3) reconstruction (seen in underlying mechanisms are not yet fully Fig. 2d). [EMIM]+ and [HMIM]+ the herringbone understood. A potential-dependent longIn the case of [EMIM]FAP, the formation superstructure is not obtained. This can range reconstruction of electrode surfaces of an interaction ion “layer” at the OCP perhaps be due to specific cation/surface, has been clearly elucidated, along with the (-0.2 V vs. Pt) results in unclear images cation/anion and cation/cation interactions, formation of anion/cation adsorption layers (Fig. 2b). The roughness of this “layer” which are strongly dependent on the type at the electrode surface.8,38,40,43-49,53 increases at more negative electrode of the functional groups (pyrrolidinium or The strong influence of the cation on potentials (Fig. 2e).54 Two small steps, imidazolium ring and the length of the alkyl the IL/electrode interface structure can chains), and therefore will be different for 0.3 nm and 0.5 nm wide, are detected that be clearly seen from in situ STM and various cations. It is likely that the different likely correspond to cation (0.3 nm) and AFM results obtained for ILs with the cations have different orientations in the anion (0.5 nm) sublayers (Fig. 3b). Their tris(pentafluoroethyl)trifluorophosphate (FAP) interfacial layer depending on their chemical sum (0.3 nm + 0.5 nm) gives the [EMIM] anion and 3 different cations, namely 1-butylstructure and the applied electrode potential. FAP ion pair dimension (0.83 nm).39 At a 1-methylpyrrolidinium ([Py1,4]+), 1-ethyl-3This in turn induces different surface potential of -1.0 V, instead of an anion layer methylimidazolium ([EMIM]+) and 1-hexylstructures (c.f. Fig. 2). Thus, a particular adsorbed at the surface, an ion-pair sized 3-methylimidazolium ([HMIM]+).8,38,54 In situ geometrical configuration of [Py1,4]+ at step is detected in the second layer (Fig. 3e). STM images show that the appearance of the Both in situ STM and AFM results show a potential of -1.0 V causes the Au(111) Au(111) surface differs for each IL (Fig. 2). In that multiple ionic liquid interfacial layers (22 x √3) reconstruction shown in Fig. 2d, the case of [Py1,4]FAP, the Au(111) surface is form at the Au(111) electrode interface in while [EMIM]+ and [HMIM]+ do not seem subjected to a restructuring / reconstruction.8 [HMIM]FAP.38 At the OCP (-0.05 V vs. Pt) to favor the herringbone superstructure. At the open circuit potential (OCP) (-0.2 V Solutes dissolved in ionic liquids also the STM images show a wormlike surface vs. Pt) the typical Au(111) surface is influence their interfacial structure. For structure with ~0.3 nm deep vacancies obtained (Fig. 2a). However, in the cathodic instance, AFM experiments reveal that (Fig. 2c). The AFM data reveals a weakly regime, the Au(111) surface undergoes a interfacial layering is markedly weaker when bound, cation-rich interfacial layer covered (22 x √3) surface reconstruction leading to LiCl in added to an IL43,55 and in situ STM by an anion rich layer (Fig. 3c). If the a herringbone superstructure (Fig. 2d). The electrode potential is reduced to -1.0 V, measurements show that, unlike for the pure AFM measurements reveal that at the OCP, at islands of ca. 0.2-0.4 nm in height (which IL (Fig. 4a), the “reconstruction” of the gold least 4 IL layers are present at the interface correlates well with the size of the cation) surface is different in the presence of LiCl (Fig. 3a). A small (0.35 nm) step closest to 60

The Electrochemical Society Interface • Spring 2014

Fig. 3. (a, d) Typical force versus distance profile for an AFM tip approaching a Au(111) surface in [Py1,4 ]FAP, (b, e) [EMIM]FAP, and (c, f) [HMIM]FAP.

(Fig. 4b). At negative electrode potentials, both [Py1,4]+ and Li+ ions will interact with the gold surface. Therefore, at a potential of -1.2 V, the adsorption of the [Py1,4]+ will induce the Au(111) (22 x √3) reconstruction, while the adsorption of Li+ will reduce the interfacial structure hindering the (22 x √3) reconstruction. These two competing effects will lead to the structure presented in Fig. 4b, where Au(111) undergoes an incomplete herringbone reconstruction.

Outlook Ionic liquids exhibit a remarkably diverse interfacial chemistry, with multiple interfacial layers present at the IL/solid interface. The adsorption strength of ILs onto solid surfaces is much higher than for typical organic solvents or water. The structure and composition of the interfacial layer can be tuned by varying the surface potential and the ionic structure, and by addition of solutes. This allows us to envision that IL interfacial properties can be readily matched to a particular application once the required fundamental understanding is elucidated. Further studies of the IL/electrode interface, both in pure ILs, and in the presence of solutes, are required to fulfil this vision. The Electrochemical Society Interface • Spring 2014

Fig. 4. In situ STM images of the Au(111) surface in (a) [Py1,4]FAP and (b) [Py1,4]FAP containing 0.1 M LiCl.

About the Authors Natalia Borisenko studied electrochemistry and physical chemistry at the St. Petersburg State Polytechnical University (St. Petersburg, Russia) from 1997-2003 and got her Masters degree there in 2003. In

the same year she joined the group of Endres (Clausthal University of Technology, Clausthal, Germany) where she obtained her Dr. rer. nat (PhD) degree in 2006. Currently she is working at the same university in the group of Prof. Endres. Her main interests cover the electrochemistry of ionic liquids, the processes at the ionic liquid / solid interfaces, and the electrodeposition of (continued on next page) 61

Borisenko, Atkin, and Endres (continued from previous page)

metals and semiconductors from ionic liquids. She may be reached at natalia. borissenko@tu-clausthal.de. Rob Atkin is an Australian Research Council Future Fellow and Associate Professor at the University of Newcastle, Australia. After completing a PhD in 2003 focused on the mechanism of surfactant adsorption at the solid liquid interface, he completed postdoctoral work at Bristol University (UK) in Brian Vincent’s laboratory studying microencapsulation. In 2005 he was awarded an Australian Research Council Postdoctoral Fellowship to study surfactant self-assembly in ionic liquids at the University of Sydney, then in 2007 he received a University of Newcastle Research Fellowship. His research is centered on bulk and interfacial ionic liquid structure, and associated properties, and he leads the Newcastle Ionic Liquid group. He may be reached at rob. atkin@newcastle.edu.au. Frank Endres studied chemistry at the Saarland University (Saarbrucken, Germany) from 19881993 and graduated there in 1993 with a diploma in Chemistry. He got his Dr. rer. nat. (PhD) degree in 1996 at the same university and moved subsequently to the university of Karlsruhe where he got his habilitation for physical chemistry in 2002. In the same year he was appointed by the Clausthal University of Technology as Professor and became in 2012 the founding director of the new Institute of Electrochemistry there. His interests comprise the physical chemistry of surfaces and interfaces, ionic liquid electrochemistry and materials science. He may be reached at frank.endres@tu-clausthal.de.

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26. J. Vatamanu, O. Borodin, and G. D. Smith, J. Am. Chem. Soc., 132, 14825 (2010). 27. J. Vatamanu, O. Borodin, and G. D. Smith, J. Phys. Chem. B, 115, 3073 (2011). 28. S. A. Kislenko, I. S. Samoylov, and R. H. Amirov, Phys. Chem. Chem. Phys., 11, 5584 (2009). 29. S. K. Reed, O. J. Lanning, and P. A. Madden, J. Chem. Phys., 126, 084704 (2007). 30. M. V. Fedorov, and A. A. Kornyshev, J. Phys. Chem. B, 112, 11868 (2008). 31. M. V. Fedorov, and A. A. Kornyshev, Electrochim. Acta, 53, 6835 (2008). 32. G. Feng, J. S. Zhang, and R. Qiao, J. Phys. Chem. C, 113, 4549 (2009). 33. S. Wang, S. Li, Z. Cao, and T. Yan, J. Phys. Chem. C, 114, 990 (2009). 34. N. Georgi, A. A. Kornyshev, and M. V. Fedorov, J. Electroanal. Chem., 649, 261 (2010). 35. A. I. Frolov, K. Kirchner, T. Kirchner, and M. V. Fedorov, Faraday Discuss., 154, 235 (2012). 36. A. A. Kornyshev, J. Phys. Chem. B, 111, 5545 (2007). 37. K. B. Oldham, J. Electroanal. Chem., 613, 131 (2008). 38. T. Carstens, R. Hayes, S. Zein El Abedin, B. Corr, G. B. Webber, N. Borisenko, R. Atkin, and F. Endres, Electrochim. Acta, 82, 48 (2012). 39. R. Hayes, N. Borisenko, M. K. Tam, P. C. Howlett, F. Endres, and R. Atkin, J. Phys. Chem. C, 115, 6855 (2011). 40. R. Atkin, S. Zein El Abedin, R. Hayes, L. H. S. Gasparotto, N. Borisenko, and F. Endres, J. Phys. Chem. C, 113, 13266 (2009). 41. R. Hayes, S. Zein El Abedin, and R. Atkin, J. Phys. Chem. B, 113, 7049 (2009). 42. D. Wakeham, R. Hayes, G. G. Warr, and R. Atkin, J. Phys. Chem. B, 113, 5961 (2009). 43. F. Endres, N. Borisenko, S. Zein El Abedin, R. Hayes, and R. Atkin, Faraday Discuss., 154, 221 (2012). 44. L. G. Lin, Y. Wang, J. W. Yan, Y. Z. Yuan, J. Xiang, and B. W. Mao, Electrochem. Commun., 5, 995 (2003). 45. Y.-Z. Su, Y.-C. Fu, J.-W. Yan, Z.-B. Chen, and B.-W. Mao, Angew. Chem., Int. Ed. 48, 5148 (2009). 46. G.-B. Pan, and W. Freyland, Chem. Phys. Lett., 427, 96 (2006). 47. Y.-Z. Su, J.-W. Yan, M.-G. Li, Z.-X. Xie, B.-W. Mao, and Z.-Q. Tian, Z. Phys. Chem., 226, 979 (2012). 48. M. Gnahm, T. Pajkossy, and D. M. Kolb, Electrochim. Acta, 55, 6212 (2010).

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52. F. Endres, O. Höfft, N. Borisenko, L. H. Gasparotto, A. Prowald, R. Al-Salman, T. Carstens, R. Atkin, A. Bund, and S. Zein El Abedin, Phys. Chem. Chem. Phys., 12, 1724 (2010). 53. M. Gnahm, C. Berger, M. Arkhipova, H. Kunkel, T. Pajkossy, G. Maas, and D. M. Kolb, Phys. Chem. Chem. Phys., 14, 10647 (2012).

49. F. Endres, S. Zein El Abedin, and N. Borissenko, Z. Phys. Chem., 220, 1377 (2006). 50. J. J. Segura, A. Elbourne, E. J. Wanless, G. G. Warr, K. Voitchovsky, and R. Atkin, Phys. Chem. Chem. Phys., 15, 3320 (2013). 51. H. Li, M. W. Rutland, and R. Atkin, Phys. Chem. Chem. Phys., 15, 14616 (2013).

54. N. Borisenko, S. Zein El Abedin, and F. Endres, ChemPhysChem, 13, 1736 (2012). 55. R. Hayes, N. Borisenko, B. Corr, G. B. Webber, F. Endres, and R. Atkin, Chem. Commun., 48, 10246 (2012).

226th Meeting of The Electrochemical Society

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ECS Future Meetings 2014 ECS and SMEQ

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October 5-10, 2014 Moon Palace Resort

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www.electrochem.org/meetings The Electrochemical Society Interface • Spring 2014

î&#x20AC;&#x201A;e Electrochemical Society Series

Interfaces between Charged Surfaces and Ionic Liquids: Insights from Molecular Simulations by Vladislav Ivaništšev and Maxim V. Fedorov

Molecular-Scale Interfacial Structure in Ionic Liquids It has been shown in a number of experimental, modeling and theoretical studies that ionic liquids undergo structural changes at a molecular level upon charging of the solid-liquid interface. This has direct effects on mass and charge transfer phenomena occuring at the interface7 as well as on the differential capacitance (Cdiff) dependence on the electrode potential (U)8–10 and temperature.11,12 Changes in the interfacial structure of ionic liquids at charged surfaces also influence their lubrication properties.13,14 Thus, from a practical point of view, the response of the interfacial ionic liquid structure to changes of the surface charge determines the performance of these interfaces in a variety of applications such as supercapacitors, batteries and electrocatalysis.1–3 For recent reviews on experimental studies in this area we refer the reader to Refs. 15–17; for an overview of molecular modeling studies, please see Ref. 18. Many independent experimental studies that have used different techniques (highenergy X-ray reflectivity, nuclear magnetic resonance, surface apparatus, and atomic force microscopy (AFM)) have reported the formation of multilayered structures of ionic liquids at charged interfaces with alternate layers of cations and anions (see e.g., Refs. 19–22). Similar multilayered The Electrochemical Society Interface • Spring 2014

interfacial structures in ionic liquids have also been found in a number of Molecular Dynamics (MD) studies that have used different simulation methods (force fields and simulation conditions), ionic liquid models (coarse-grained and atomistic) as well as electrode models (carbon material, structure-less charged surface, metal, etc).18 It has been shown that charging of the electrode surface affects the magnitude of the ion layering at the interface.8,9,13,14,23,24 Recent AFM studies have shown that the molecular-level structure and, consequently, interfacial properties of ionic liquids at charged surfaces can be changed by varying the surface potential.13,14 It has also been shown in these studies that the interfacial structure can be changed by varying chemical composition of the ionic liquids, i.e. varying the length of alkyl chains of organic cations or anion type, etc. However, we note that a multilayerlike structure is not the only possible arrangement of ions at the interface. Indeed, monolayer-like interfacial structures of ionic liquids at charged surfaces has been reported for several ionic liquids systems.25 Critical analysis of several studies applying the sum frequency generation spectroscopy technique have led the authors to the conclusion that ions at the solid–liquid interface in ionic liquids are organized into

essentially one ionic layer – a structure that resembles the classical Helmholtz picture of an ionic monolayer at a charged surface,26 where the structural correlations between the ions beyond this layer resemble the bulk liquid structure.25 In trying to resolve the apparent contradiction between the different views on the interfacial structure of ionic liquids at charged surfaces, Kirchner et al. have recently performed an MD study of structural reorganization in ionic liquids upon surface charging using a wide scale of surface charges.6 The authors of Ref. 6 used a coarse-grained model of ionic liquids that was previously developed in Refs. 8, 9. The results of this work have shown that by varying the surface charge, one can observe both multilayer structure and monolayer structure in ionic liquids. Although the conclusions were derived from a rather crude model that describes ionic liquid cations and anions as charged Lennard-Jones spheres, we believe that similar arguments can be applied when analyzing interfacial properties of more complex models and real systems. Figure 1 schematically presents two main types of the molecular-scale structure of an electrified electrode–ionic liquid interface (continued on next page)

σ = −8 μC/cm2 1

σ = −16 μC/cm2

κCation = 0.5

κCation = 1.0

0 −1

φ(z) / V

nterfacial effects in (room temperature) ionic liquids at charged surfaces are very important for ionic liquids applications in electrochemistry,1 energy storage,2 catalysis3 and other areas (e.g., lubrication4,5). However despite the many articles published on this subject (several hundred papers just in 2013) there is still no general agreement in the literature about the main factors that govern the structure and properties of ionic liquids at charged interfaces. This is mainly due to a large number of available combinations of ionic liquids (and their mixtures) and different surfaces. In this article, we make an attempt to rationalize recent experimental and computational findings on structural transitions in ionic liquids at charged interfaces. Herein, we present a critical (qualitative) analysis of available molecular modeling and experimental data using a recently developed concept of surface charge compensation that allows one to compare results for different ionic liquids on the same methodological footing.6

−2 −3 −4 −5 −6 0

z / nm

10 0

z / nm

Fig. 1. Electrostatic potential φ(z) across two model interfaces representing multilayer (LEFT) and monolayer (RIGHT) structures in a model ionic liquid. For the sake of simplicity, here both anions and cations are represented by spherical particles of the same size. In the underlying simulation snapshots the electrode, cations and anions are depicted as gray, red and blue spheres, respectively. The opacity level of the snapshots is adjusted proportionally to the variation of the amplitude of φ(z). 65

Ivaništšev and Fedorov

Surface Charge Compensation Phenomena

(continued from previous page)

that can be formed in a model ionic liquid: the multilayer structure (LEFT) and the monolayer structure (RIGHT).27 The multilayer structure in Fig. 1:LEFT is characterized by segregation of ions into cationic and anionic layers; this type of interfacial structure is related to the overscreening phenomena in ionic liquids.8–10,28 Overscreening implies that the innermost layer contains more charge than is needed to compensate the surface charge (σ). The excess of charge in the innermost layer (λ1, see the definition below) is compensated by subsequent ionic liquid layers in the transition region. The interfacial layering of ionic liquid particles is reflected in the oscillations of the electrostatic potential (φ(z) in Fig. 1), ionic number density (ρN in Fig. 2a), and ionic charge density and its derivatives, like the excess of charge in the i-th layer (λi in Fig. 2c). Thus, in the multilayer regime, the molecular-scale structure of ionic liquid at a charged interface can be divided into three regions: (i) the innermost layer of counterions in direct contact with the surface, (ii) the transition zone, several nanometers thick, that consists of alternating ion layers, and (iii) the bulk-like structured ionic liquid at larger distances from the surface. We note that, in contrast to the multilayer regime, there is no transition zone in the case of the monolayer structure. Consequently there are no oscillations in the electrostatic potential (Fig. 1: RIGHT) – the innermost layer coexists directly with the bulk-like structured ionic liquid.

κIon=

σ max θIon

Figure 2 illustrates the relationships between the structure of the transition region and packing of the innermost layer of counter-ions for different electrode charge densities.27 Figure 2a shows the

number density contour map

Molecular-Scale Structural Reorganization For the sake of comparison of molecular organization in ionic liquids for the two regimes (multilayer vs monolayer), Fig. 2b shows anions (blue) and cations (red) within 1.7 nm from the charged surface at κCation = 0.5 (TOP) and κCation = 1 (BOTTOM). As can be seen from this figure, already at κCation = 0.5 the innermost layer is dominated by the electrode counter-ions. In previous studies, observations of similar structures were associated with the lattice saturation effect and the maximum of the differential capacitance curve (Cdiff vs. U).30 However, Fig. 2 shows that within a distance of 1.7 nm from the electrode, there are also co-ions coordinated with several (2 to 4) counter-

C 16

0.5

Cation

0.5

8 0 8

/ C cm 2

Anion

To perform a quantitative analysis of structural transitions in the interfacial region, we introduce a parameter θmax that corresponds to the maximum charge density that can be stored in a monolayer for a selected type of ionic liquid ions (that would correspond to a densely packed monolayer of ions at physically possible maximum of ion packing density).6 By its definition, for a given ionic liquid θmax depends only on the ion charge and geometric parameters of the selected ion type (size and shape). The essential features of the monolayer structure are – (i) a linear electrostatic potential drop across the interface;29 (ii) the charge density stored in the monolayer equals to θmax; (iii) the electrode counterions that form the monolayer completely compensate the surface charge, i.e. σ = θmax. Due to the fact that θmax depends only on the charge and geometry of the ions, one can use the surface charge renormalized by θmax to compare different ionic liquid systems on the same universal footing. The dimensionless surface charge compensation parameter (κ) is then defined as:

dependency of the ion number density (ρN) on the distance from the electrode (z) and the renormalized surface charge density – in the form of a contour map of ρN(z, κ). As seen from this figure, vertical valleys divide the interface into the distinct regions discussed above: the innermost layer, the transition region and the bulk ionic liquid. We note that the number of layers in the transition region (within ∼1 to ∼4 nm from the surface for the coarse-grained model) depends on the κIon. It increases with increasing the surface charge until κIon ≈ 0.5 and then decreases revealing a bare monolayer at κIon = 1. The horizontal valleys on the density contour map (Fig. 2a) at κIon = 1 confirm the coexistence of the monolayer with bulk-like ionic liquid.

1 0

z / nm

0.1

0.1 0.2

Fig. 2. (a) Left: Dependency of anion (dark, blue) and cation (light, red) number density (ρN) on the distance from the electrode (z) and renormalized surface charge density (κIon). Dashed lines divide the interface into the innermost, transition and bulk regions. The contour interval equals to ρbulk, the first contour starts at 1.5ρbulk, and the ρN(z,κIon) peaks are cut at 7.5ρbulk to facilitate the visual analysis. (b) Middle: The top subfigure shows dislocation of anions (blue) and cations (red) within 1.7 nm from the surface (gray) at σ = −8 µC cm−2 and κCation = 0.5. The bottom subfigure shows dislocation of ions within 1.7 nm from the surface (gray) at σ = −16 µC cm−2 and κCation = 1. (c) Right: Excess of charge in the first (λ1, filled marks) and in the second (λ2, empty marks) interfacial layers. The κIon values of 1 correspond to ±16 µC cm−2 on the σ-scale shown on the left. Areas corresponding to the multilayer and monolayer structures are highlighted in color and with dotted lines. 66

The Electrochemical Society Interface • Spring 2014

175 150

Cs+

125

C2MIm+ N1114+

50 25 0

25 50

C4Pyr+ C4MIm+ + C10MIm (C6)3C14P+ TFSA PF6

where zi corresponds to an extremum (or a step height) of |cnQ(z)/σ| on the interval that defines the i-th layer. , where and A is a unit area. Thus the electrostatic potential φ(z) Sas well as ρQ(z), cnQ(z) and λi are all derived from the ion number densities at the interface. We note that the screening factor (|cnQ(z)/ σ|) as well as similar conceptions of the excess charge magnitude and the normalized surface charge density have been employed in several previous studies on ionic liquids at charged interfaces.8,34–36 The increase of the absolute charge excess in the interfacial layers with increasing κIon from 0 to 0.5 manifests the transition from the disordered to the multilayer structure, while the further decrease of the charge excess after κIon= 0.5 indicates the vanishing of the multilayer structure towards exposure of the monolayer structure at κIon = 1. The λi vs. κIon dependence represents an analog of dimensionless “reaction coordinate” for the reorganization process. On the larger κ-scale, the monolayer structures in the coarse-grained models are formed at integer values of κIon (adjusted for the compressibility of ions),37 similar to the one-dimensional lattice Coulomb gas model (with lower fugacity).38 An exact solution for the latter model also indicates that the maximal charge layering happens at renormalized surface charge densities of 0.5. The presented results reveal that similar effects can happen in three-dimensional ionic liquids models. In the recent atomistic MD simulations of Paek et al. and Hu et al. there is evidence supporting monolayer formation in the case of more complex atomistic ionic liquid models (see Table II in Ref. 34 and Fig. 4 in Ref. 39). Therefore, in our opinion, the κ-scale can be used for rationalizing general trends in realistic systems. Figure 3 shows the relationship between the size of ions and the maximum packing charge density The Electrochemical Society Interface • Spring 2014

PF6

100

max / C cm 2

ions. Thus, we believe that the correlations between cations and anions actually define the distance between the counter-ions in the innermost layer at κIon = 0.5. The packing density of ions at the interface can be further increased upon surface charging without crowding up to the monolayer structure formation (from κIon = 0.5 to κIon = 1.0). To our best knowledge, the corresponding regime of electrostriction has not been previously described in the literature, although similar effects have been discussed before in terms of the Cdiff vs. |U| dependence.28,31–33 The transition from the multilayer structure to the monolayer structure is illustrated using the charge excess in the i-th layer (λi) in Fig. 2c. The parameter λi is defined through the cumulative charge density as follows:

FAP ESO4 BF4 NO3

100

125

Br Cl

150

0.2

0.3

C4Pyr+

FAP

(C6)3C14P+ 0.4

r / nm

0.5

0.6

1 nm

Fig. 3. Left: Dependence of sterically determined maximum charge density (θmax) on ionic radius (r). Dashed lines denote a range of surface charge densities commonly used in electrochemical experiments with ionic liquids. For complex ions the radii were estimated from their molecular volumes taken from Refs. 47, 48 assuming (as a first approximation) that ions are spherical in shape. The radii of halogenide anions and alkali metals cations were taken from Ref. 49. Right: ball-and-stick models of chosen ions amplified relative to the presented scale.

in the ion monolayer θmax (that corresponds to κIon = 1). As a first approximation, it is assumed here that the ions are nearly round and are non-polarizable (we note that the former assumption is practically true for the alkali, halogenide and, perhaps, PF6− and BF4− ions). However, it should be noted that the presented θmax values are quite approximate and can be adjusted by considering compressibility and specific packing of the ions. According to the approximate ionθmax relationship presented on Fig. 3, the formation of the monolayer structure both in the cathodic and anodic regimes can be expected at realistic electrode charge densities (~±35 μC/cm2)24,26 for a number of relatively large ions such as CnMIm+ and CnMPyr+ with n ≥ 4, TFSA−, FAP−, etc. These ions are electrochemically stable due to the presence of stabilizing functional groups and larger contact distances from the electrode40,41 and, therefore, relatively high electrode charge densities necessary for the formation of the monolayer structures can be achieved experimentally in these systems. We note that the curve presented on Fig. 3 should be taken only as a qualitative guide because it does not take into account effects of complex geometric shapes of (some) ions, specific interionic interactions and (partial) charge transfer between the ions and the

charged surface. These effects may change the specific conditions of the monolayer formation in realistic systems. Overall, the ideas discussed above require further development and an extensive validation by direct experiments and more sophisticated molecular models. Nevertheless, we note that a number of characteristic structures at electrochemical conditions have been observed experimentally that could serve as partial evidence of monolayer formation in real ionic liquid systems. For example, formation of ordered ionic adlayers has been observed via scanning tunneling microscopy;42–44 a “monolayer” to “bilayer” restructuring induced by confinement has been observed by surface forces apparatus45 and solid-like multilayers in ionic liquids have been recently reported.22,46

Conclusions MD simulations of ionic liquid–electrode interfaces show that a transition from a multilayer ion structure to an ordered monolayer structure can be observed at certain values of the surface charge density. Upon this transition, a distinct change in the surface charge excess in the first two interfacial layers can be seen as a function of the renormalized surface charge density 67

Ivaništšev and Fedorov

(continued from previous page)

(on the κ-scale). The degree of ordering in the innermost ion layer increases upon increasing the surface charge density, while the transition region exhibits systematic transformations upon surface charging. The point of maximum layering in the transition region depends on the density of the ionic liquid as well as on the ion-ion and ion–electrode interactions. For the coarsegrained ionic liquids models from Refs. 6, 8, 9 the point of the maximum layering is typically situated at κIon ≈ 0.5. This range of κIon corresponds to frequently used surface charge densities in experimental and simulation studies on ionic liquids (see Fig. 3 as a guide) and this may explain the fact that multilayered structures in ionic liquids have often been reported in the experimental and modeling literature.15-18 However, upon further increase of the charge density, the multilayer structure gradually transforms to a monolayer structure while approaching an integer value of κIon. Herewith integer κIon values serve as transition points for the structural reorganization processes happening in both regions. We suggest that the surface charge densities that correspond to κIon ≈ 1 (and consequently to the regime of monolayer formation) can be used as “landmark” points for qualitative and quantitative comparison of theoretical, simulations and experimental data on ionic liquids structure at charged surfaces.

Acknowledgments We are grateful for computer time at the EPSRC funded ARCHIE-WeSt High Performance Computer (www.archie-west. ac.uk, EPSRC grant no. EP/K000586/1) and for the supercomputing support from the von Neumann-Institut für Computing, FZ Jülich (Project ID ESMI11). We thank Kathleen Kirchner, Tom Kirchner, Andrey Frolov, Alexei Kornyshev and Ruth LyndenBell for useful discussions.

About the Authors Vladislav Ivaništšev is a Research Associate in the Department of Physics, the University of Strathclyde in Glasgow, UK (the Department is a part of the Scottish Universities Physics Alliance, SUPA). He received his PhD for his work on “Double layer structure and adsorption kinetics of ions at metal electrodes in room temperature ionic liquids” from the University of Tartu in 2012. His current research focuses on electrochemistry of ionic liquids and employs computer modeling. He may be reached at vladislav.ivanistsev@strath.ac.uk. 68

Maxim V. Fedorov is SUPA2 Professor (Chair) at the Department of Physics of the University of Strathclyde in Glasgow, UK (the Department is a part of the Scottish Universities Physics Alliance, SUPA). He received his PhD (2002, Biophysics) and DSc (2007, Physical Chemistry) degrees from the Russian Academy of Sciences. He moved to the University of Strathclyde in 2011 from the Max Planck Institute for Mathematics in the Sciences in Leipzig (Germany) where he was a research group leader. Since 2012 he is also Director of the West of Scotland Academia-Industry Supercomputer Centre (aka ARCHIEWeST) in Glasgow (located at the University of Strathclyde). In 2012 he received the Helmholtz Award from the International Association of the Properties of Water and Steam (IAWPS) for his work on theoretical physical chemistry of liquids. His research interests focus on modeling of ionic liquids at electrified interfaces, ion effects on (bio) macromolecules and nano-objects, and molecular-scale theories of solvation interfaces. More details of his research can be found at http://bcp.phys.strath.ac.uk/ molecular-theory-and-simulations/profmaxim-fedorov. He may be reached at maxim.fedorov@strath.ac.uk.

References 1. M. Armand, F. Endres, D. R. MacFarlane, H. Ohno, and B. Scrosati, Nat. Mater., 8, 621 (2009). 2. D. R. MacFarlane, N. Tachikawa, M. Forsyth, J. M. Pringle, P. C. Howlett, G. D. Elliott, J. H. Davis, M. Watanabe, P. Simon, and C. A. Angell, Energy Environ. Sci., 7, 232 (2014). 3. P. Hapiot and C. Lagrost, Chem. Rev., 108, 2238 (2008). 4. J. Sweeney, F. Hausen, R. Hayes, G. B. Webber, F. Endres, M. W. Rutland, R. Bennewitz, and R. Atkin, Phys. Rev. Lett., 109, 155502 (2012). 5. O. Werzer, E. D. Cranston, G. G. Warr, R. Atkin, and M. W. Rutland, Phys. Chem. Chem. Phys., 14, 5147 (2012). 6. K. Kirchner, T. Kirchner, V. Ivaništšev, and M. Fedorov, Electrochim. Acta, 110, 762 (2013). 7. F. Endres, O. Höfft, N. Borisenko, L. H. Gasparotto, A. Prowald, R. Al-Salman, T. Carstens, R. Atkin, A. Bund, and S. Z. El Abedin, Phys. Chem. Chem. Phys., 12, 1724 (2010). 8. M. V. Fedorov and A. A. Kornyshev, Electrochim. Acta, 53, 6835 (2008). 9. M. V. Fedorov and A. A. Kornyshev, J. Phys. Chem. B, 112, 11868 (2008). 10. M. Z. Bazant, B. D. Storey, and A. A. Kornyshev, Phys. Rev. Lett., 106, 046102 (2011).

11. M. Drüschler, N. Borisenko, J. Wallauer, C. Winter, B. Huber, F. Endres, and B. Roling, Phys. Chem. Chem. Phys., 14, 5090 (2012). 12. J. Vatamanu, O. Borodin, and G. D. Smith, J. Am. Chem. Soc., 132, 14825 (2010). 13. H. Li, M. W. Rutland, and R. Atkin, Phys. Chem. Chem. Phys., 15, 14616 (2013). 14. H. Li, F. Endres, and R. Atkin, Phys. Chem. Chem. Phys., 15, 14624 (2013). 15. R. Hayes, G. G. Warr, and R. Atkin, Phys. Chem. Chem. Phys., 12, 1709– 1723 (2010). 16. S. Perkin, Phys. Chem. Chem. Phys., 14, 5052 (2012). 17. R. Atkin, N. Borisenko, M. Drüschler, F. Endres, R. Hayes, B. Huber, and B. Roling, J. Mol. Liq., IN PRESS (2014). 18. C. Merlet, B. Rotenberg, P. A. Madden, and M. Salanne, Phys. Chem. Chem. Phys., 15, 15781 (2013). 19. M. Mezger, H. Schröder, H. Reichert, S. Schramm, J. S. Okasinski, S. Schöder, V. Honkimäki, M. Deutsch, B. M. Ocko, J. Ralston, M. Rohwerder, M. Stratmann, and H. Dosch, Science, 322, 424 (2008). 20. Y. Yokota, T. Harada, and K.-I. Fukui, Chem. Commun., 46, 8627 (2010). 21. F. Endres, N. Borisenko, S. Z. E. Abedin, R. Hayes, and R. Atkin, Faraday Discuss., 154, 221 (2012). 22. M. R. Castillo, J. M. Fraile, and J. A. Mayoral, Langmuir, 28, 11364 (2012). 23. R. M. Lynden-Bell, A. I. Frolov, and M. V. Fedorov, Phys. Chem. Chem. Phys., 14, 2693 (2012). 24. H. Zhou, M. Rouha, G. Feng, S. S. Lee, H. Docherty, P. Fenter, P. T. Cummings, P. F. Fulvio, S. Dai, J. McDonough, V. Presser, and Y. Gogotsi, ACS Nano, 6, 9818 (2012). 25. S. Baldelli, J. Phys. Chem. Lett., 4, 244 (2013). 26. W. Schmickler and E. Santos, Interfacial Electrochemistry, 2nd ed., Springer, New York, (2010). 27. The simulation setup for the MD simulations and the model parameters are described in details in Refs. 6, 8, 9. The model systems consist of two smooth charged surfaces (11 nm×11 nm) and a variable number of ionic pairs (up to 1050).6,8,9,37 Simulations were carried out using molecular dynamics at temperatures from 250 to 500 K, in an NVT ensemble. The results shown in Fig. 1 and 2 are drawn for the symmetric ionic liquid model with a bulk number density of 0.32 ions per nm3 and ionic radii of 0.5 nm. 28. N. Georgi, A. A. Kornyshev, and M. V. Fedorov, J. Electroanal. Chem., 649, 261–267 (2010). 29. As Fig. 1 shows, in the case of the multilayer structure the total potential drop (in terms of its absolute values) is smaller than the drop in the first layer. The Electrochemical Society Interface • Spring 2014

30. Y. Lauw, M. D. Horne, T. Rodopoulos, V. Lockett, B. Akgun, W. A. Hamilton, and A. R. J. Nelson, Langmuir, 28, 7374 (2012). 31. A. A. Kornyshev, J. Phys. Chem. B, 111, 5545 (2007). 32. Y. Lauw, M. D. Horne, T. Rodopoulos, and F. A. M. Leermakers, Phys. Rev. Lett., 103, 117801 (2009). 33. Y. Lauw, M. D. Horne, T. Rodopoulos, A. Nelson, and F. A. M. Leermakers, J. Phys. Chem. B, 114, 11149 (2010). 34. E. Paek, A. J. Pak, and G. S. Hwang, J. Electrochem. Soc., 160, A1 (2013). 35. G. Feng, J. Huang, B. G. Sumpter, V. Meunier, and R. Qiao, Phys. Chem. Chem. Phys., 13, 14723 (2011). 36. J. Wu, T. Jiang, D.-E. Jiang, Z. Jin, and D. Henderson, Soft Mat., 7, 11222 (2011). 37. V. Ivaništšev, K. Kirchner, T. Kirchner, and M. Fedorov, Phys. Rev. Lett., SUBMITTED (2014). 38. V. Démery, D. S. Dean, T. C. Hammant, R. R. Horgan, and R. Podgornik, J. Chem. Phys., 137, 064901 (2012). 39. Z. Hu, J. Vatamanu, O. Borodin, and D. Bedrov, Phys. Chem. Chem. Phys., 15, 14234 (2013). 40. G. H. Lane, Electrochim. Acta, 83, 513 (2012). 41. S. Fletcher, V. J. Black, I. Kirkpatrick, and T. S. Varley, J. Solid State Electrochem., 17, 327 (2013). 42. Y. Su, J. Yan, M. Li, M. Zhang, and B. Mao, J. Phys. Chem. C, 117, 205 (2013). 43. Y. Z. Su, Y. C. Fu, J. W. Yan, Z. B. Chen, and B. W. Mao, Angew. Chem. Int. Edit., 48, 5148 (2009). 44. G.-B. Pan and W. Freyland, Chem. Phys. Lett., 427, 96 (2006). 45. A. M. Smith, K. R. J. Lovelock, N. N. Gosvami, P. Licence, A. Dolan, T. Welton, and S. Perkin, J. Phys. Chem. Lett., 4, 378 (2013). 46. S. Bovio, A. Podesta, C. Lenardi, and P. Milani, J. Phys. Chem. B, 113, 6600 (2009). 47. A. J. L. Costa, M. R. C. Soromenho, K. Shimizu, I. M. Marrucho, J. M. S. S. Esperança, J. N. C. Lopes, and L. P. N. Rebelo, ChemPhysChem, 13, 1902 (2012). 48. M. Součková, J. Klomfar, and J. Pátek, Fluid Phase Equilibr., 333, 38 (2012). 49. D. R. Lide, Editor, CRC Handbook of Chemistry and Physics, 90th ed., CRC Press, New York (2009).

THE ELECTROCHEMICAL SOCIETY

Monograph Series

The following volumes are sponsored by ECS, and published by John Wiley & Sons, Inc. They should be ordered from: ECS, 65 South Main St., Pennington, NJ 08534-2839, USA or www.electrochem.org/dl/bookstore.htm.

Lithium Batteries: Advanced Technologies and Applications Edited by B. Scrosati, K. M. Abraham, W. van Schalkwijk, and J. Hassoun (2013) 392 pages. ISBN 978-1-18365-6 Fuel Cells: Problems and Solutions (2nd Edition) by V. Bagotsky (2012) 406 pages. ISBN 978-1-1180-8756-5 Uhlig's Corrosion Handbook (3rd Edition) by R. Winston Revie (2011) 1280 pages. ISBN 978-0-470-08032-0 Modern Electroplating (5th Edition) by M. Schlesinger and M. Paunovic (2010) 736 pages. ISBN 978-0-470-16778-6 Electrochemical Impedance Spectroscopy by M. E. Orazem and B. Tribollet (2008) 524 pages. ISBN 978-0-470-04140-6 Fundamentals of Electrochemical Deposition (2nd Edition) by M. Paunovic and M. Schlesinger (2006) 373 pages. ISBN 978-0-471-71221-3 Fundamentals of Electrochemistry (2nd Edition) Edited by V. S. Bagotsky (2005) 722 pages. ISBN 978-0-471-70058-6 Electrochemical Systems (3rd Edition) by John Newman and Karen E. Thomas-Alyea (2004) 647 pages. ISBN 978-0-471-47756-3 Atmospheric Corrosion by C. Leygraf and T. Graedel (2000) 368 pages. ISBN 978-0-471-37219-6 Semiconductor Wafer Bonding by Q. -Y. Tong and U. Gösele (1998) 320 pages. ISBN 978-0-471-57481-1 Corrosion of Stainless Steels (2nd Edition) by A. J. Sedriks (1996) 464 pages. ISBN 978-0-471-00792-0

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

www.electrochem.org The Electrochemical Society Interface • Spring 2014

t ech SEC TION highligh NE WS ts Canada Section On November 23, 2013, the fall meeting of the ECS Canada Section took place in the University of Quebec at Montreal (UQAM), Montreal, Canada. This one-day event was organized by Steen B. Schougaard, a university professor in the Department of Chemistry of the UQAM, and coordinated by Reza B. Moghaddam, a postdoctoral researcher in Schougaard’s group. The meeting, Diversity of Electrochemistry in the 21st Century, was aimed at attracting cutting edge research in various fields of electrochemistry. Daniel Scherson, the 2nd Vice-President of The Electrochemical Society, was invited as the keynote speaker of the meeting. He delivered an interesting lecture, entitled “Wireless Communication by an Autonomous Self-powered Cyborg Insect,” on conversion of the chemical energy to electrical energy through a biofuel cell inside a Blaberus discoidalis which was further converted to audible signals that could be sensed and processed by a receiver. Following that, the meeting enjoyed lectures by several widely known speakers who presented their recent

Drew Higgins received Canada Section Student Award; left to right Bradley Easton (University of Ontario), Daniel Scherson (Case Western Reserve University), Drew Higgins (University of Waterloo), and Janine Mauzeroll (McGill University), Canada Section Chair.

Daniel Scherson giving a lecture on Wireless Communication by an Autonomous Self-powered Cyborg Insect.

The Electrochemical Society Interface • Spring 2014

t ech SEC TION highligh NE WS ts findings on energy conversion systems, electrochemiluminescence, molecular electronic devices, sensors, and corrosion. The Canada Section Student Award was also presented at this meeting. Drew Higgins, a PhD student in the Department of Chemical Engineering of the University of Waterloo, received his award from Janine Mauzeroll, ECS Canada Section president. Mr. Higgins was also one of the invited speakers who lectured on “Advanced Cathodic Catalysts for PEM Fuel Cells.” Of many high quality poster presentations, three were selected for the best poster prizes. Matthew Genovese (University of Toronto), Philippe Ducharme (McGill University), and Mathieu Saulnier (UQAM) whose poster presentations were ranked 1st, 2nd, and 3rd will receive prizes of $250, $150, and $100, respectively. Bathium Canada Inc., London Scientific Ltd., Heka Electronics Inc., and SnowHouse Solutions Inc., as well as NanoQAM, the Department of Chemistry, and Faculty of Science of the University of Quebec at Montreal generously sponsored this meeting.

The poster session at the ECS Canada Section meeting.

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We welcome the opportunity to share with our membership, the scientific advances and activity news from your Section. Send your news to: ecs@electrochem.org

Visit www.electrochem.org The Electrochemical Society Interface • Spring 2014

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. Award nomination materials should be sent to: (Award Name), c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534; Phone: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. If you have questions, 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 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 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 The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534; Phone: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by April 15, 2014. 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; Phone: 1.609.737.-1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by April 15, 2014. 72

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; Phone: 1.609.737.1902; e-mail: awards@electrochem. org. Electronic submission of nomination packets is preferred. Materials are due by October 1, 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 ECS Life membership, 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; Phone: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by October 1, 2014.

The Electrochemical Society Interface • Spring 2014

NE W AWA MEMBERS RDS

Division Awards The Thomas D. Callinan Award of the Dielectric Science and Technology Division was established to promote interest and activity in the field of dielectric science and technology among the engineers and scientists. The award carries a citation scroll and a prize money of $1,500. The next award will be presented at the ECS spring meeting in Chicago, Illinois, May 24-28, 2015. Nominations along with two letters of recommendation should be sent to Callinan Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534; Phone: 1.609.737.1902; e-mail: awards@ electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by August 1, 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. Nominations and supporting documents should be sent to Electrodeposition Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534; Phone: 1.609.737.1902; e-mail: awards@electrochem. org. Electronic submission of nomination packets is preferred. Materials are due by April 1, 2014. The Electronics and Photonics Division Award was established in 1968 to encourage excellence in electronics research and outstanding technical contribution to the field of electronics science. The award consist of a scroll, a prize of $1,500, and expenses up to $1,000 or payment of Life Membership in the Society. 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 Electronics & Photonics Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534; Phone: 1.609.737.1902; e-mail: awards@ electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by August 1, 2014. The Research Award of the Energy and Technology Division was established in 1992 to encourage excellence in energy related research. The award consists of a scroll, a prize of $1,500, and membership in the Energy Technology Division as long as a member of ECS. 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 Energy Technology Research Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534; Phone: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by September 1, 2014. The Supramaniam Srinivasan Young Investigator Award of the Energy Technology Division was established in 2011 to recognize and reward an outstanding young researcher in the field of energy technology. Such early recognition of highly qualified scientists is intended to encourage especially promising researchers to remain active in the field. The award is named after the cofounder of the Energy Technology Division, Supramaniam Srinivasan. The award shall consist of a scroll, a prize of $1,000, and free meeting registration costs to help the recipient attend the ECS meeting at which the presentation is made The next award will be presented at the ECS spring meeting in Chicago, Illinois, May 24-28, 2015.

The Electrochemical Society Interface • Spring 2014

Nominations and supporting documents should be sent to Energy Technology Srinivasan Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534; Phone: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by September 1, 2014. The Richard Smalley Research Award of the Nanocarbons Division was established in 2006 to recognize outstanding contributions to the understanding and applications of fullerenes in a broad sense. The award consists of a scroll, a prize of $1,000, and travel assistance up to $1,500. 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 Nanocarbons Smalley Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534; Phone: 1.609.737.1902; e-mail: awards@ electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by September 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, multi-disciplinary, inter-functional efforts to commercialize new electrochemical technology within the past 10 years and consists of a commemorative plaque with appropriate inscription presented to the sponsoring organization and 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 to IEEE N.E.T. Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534; Phone: 1.609.737.1902; e-mail: awards@electrochem. org. Electronic submission of nomination packets is preferred. Materials are due by May 1, 2014.

Travel Grants Many of the Society’s Divisions offer travel assistance to students and young professionals presenting papers at ECS meetings. For details about travel grants for the 226th ECS meeting in Cancun, Mexico, please see the Cancun 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 prior to completing the online application. You must submit your abstract and have your abstract confirmation number in order to apply for a travel grant. Apply for travel grants using the online submission system (links found on the travel grant web page). If you have any questions, please email travelgrant@electrochem.org. The deadline for submission for fall 2014 travel grants is July 1, 2014.

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 • Karim Zaghib, IREQ, Canada

The Meeting Venue The site of the meeting is the Villa Erba (www.villaerba.it), which is set magnificently on the lake shore on the edge of the 15th century villa in Como, Italy. 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 registration and accomodation details. IMLB 2014 is sponsored and managed by ECS (www.electrochem.org).

NE W MEMBERS ECS is proud to announce the following new members for October, November, and December 2013.

Active Members Desmond Adair, Astana, Kazakhstan Valeri Afanasiev, Leuven, Belgium Joel Ager, Berkeley, CA, USA Hosang Ahn, Goyang, South Korea Saif Almheiri, Abu Dhabi, United Arab Emirates Abdullah Al-Musa, Riyadh, Saudi Arabia Naoya Aoki, Soka, Japan Abdelhafid AQIL, Liege, Belgium Takuto Araki, Yokohama, Kanagawa, Japan Fevzi Arkun, San Carlos, CA, USA Michael Auinger, Duesseldorf, Germany Loic Baggetto, Oak Ridge, TN, USA Majid Bahrami, Surrey, BC, Canada Chuannan Bai, Parsippany, NJ, USA Luciana Bava, Atlanta, GA, USA Enrico Bellandi, Agrate Brianza, Italy Paul Berger, Columbus, OH, USA Marco Bettinelli, Verona, Italy Manuela Bevilacqua, Sesto Fiorentino (Firenze), Italy Pratim Biswas, Chesterfield, MO, USA Tom Blomberg, Helsinki, Finland Agustin Bolzan, La Plata, Argentina Damien Boyer, Aubiere, France Patrick Campbell, Livermore, CA, USA Veronique Carron, Grenoble, France Geneviève Chadeyron, Aubiere, France Ramanan Chebiam, Hillsboro, OR, USA Chi-Liang Chen, Taipei, Taiwan Xiaomei Chen, Kyoto, Kyoto, Japan Qian Cheng, Tsukuba, Ibaraki, Japan Mahito Chiba, Wako-shi, Saitama, Japan Kye Hyun Cho, Gyeong San Gyeongbuk, South Korea Kyu Taek Cho, Berkeley, CA, USA Yoong-Kee Choe, Tsukuba, Ibaraki, Japan Ivan Ciofi, Leuven, Belgium Hushan Cui, Beijing, P. R. China Yanhua Cui, Mianyang, Sichuan, P. R. China Yanjie Cui, Lemont, IL, USA Nazila Dadvand, Mechanicsburg, PA, USA Kehua Dai, Berkeley, CA, USA Zhenhua Dan, Sendai, Miyaki Ken, Japan Rytis Dargis, Palo Alto, CA, USA Prateek Dasgupta, Brandon, FL, USA Sankar Dasgupta, Mississauga, ON, Canada Shadi Dayeh, La Jolla, CA, USA Michael Deschamps, Orleans, France Ruvini Dharmadasa, Louisville, KY, USA Nikolaus Dietz, Atlanta, GA, USA Fulya Dogan, Argonne, IL, USA Chung-Li Dong, Hsinchu, Taiwan Michael Dudley, Stony Brook, NY, USA David Durkin, Annapolis, MD, USA Zhi Chang Ee, Singapore, Singapore The Electrochemical Society Interface • Spring 2014

Eric Eisenbraun, Albany, NY, USA Moshe Eizenberg, Haifa, Israel Yossef Elabd, Philadelphia, PA, USA Jens Eller, Zürich, ZH, Switzerland Andrzej Ernst, Grodzisk Mazowiecki, Poland Zhiyong Fan, Hong Kong, Hong Kong Sam Farhat, Glendale, CA, USA Bonnie Fernandez-Fenaroli, Davis, CA, USA Alexander Forse, Cambridge, Cambridgeshire, United Kingdom Michel Foure, Berkeley, CA, USA Michel Frei, Palo Alto, CA, USA Stefan Gadomski, South Lake Tahoe, CA, USA Selvarani Ganesan, East Lansing, MI, USA Feng Gao, Wilmington, DE, USA Alberto Garcia, Derio Bizkaia, Spain Enrique Garcia - Quismondo, Móstoles, Spain Raynald Gauvin, Montreal, QC, Canada Hugh Geaney, Kildimo, Limerick, Ireland Thomas Gennett, Golden, CO, USA Kevin Glasgow, Brookfield, WI, USA Andreas Gluesen, Juelich, Germany Gene Goebel, Grover Beach, CA, USA Linda Gonzalez, Pedro Escobedo, Mexico Elena Gonzalo, Miñano, Spain Dimitrios Gournis, Ioannina, Greece Todd Grinsteinner, Rocklin, CA, USA Frank Grosse, Berlin, Germany Robert Gruar, Oxford, Oxfordshire, United Kingdom Hamid Gualous, Cherbourg, France Alicia Lei Gui, Oldenburg, Germany James Guidry, Broussard, LA, USA Rolando Guzman Blas, San Juan, PR, USA Sang-hyeon Ha, Daejeon, South Korea Gary P. Halada, Stony Brook, NY, USA Joseph Han, San Jose, CA, USA Xiaofei Han, Tempe, AZ, USA Chris Han-Adebekun, Allentown, PA, USA Greg Haugen, St. Paul, MN, USA Hidekazu Hayashi, Yokkaichi, Mie, Japan Tetsutaro Hayashi, Niihama, Ehime, Japan Guangli He, Beijing, P. R. China Jaeyeong Heo, Gwangju, South Korea Oliver Hilt, Berlin, BE, Germany Peter Hing, Bandar Seri Begawan, Brunei Hiroo Hongo, Moriya, Ibaraki, Japan Mikihiro Hori, Toyota, Aichi, Japan Frances Houle, Berkeley, CA, USA Gregory Houzet, Le Bourget du Lac, France John Hryn, Argonne, IL, USA Brian Huffman, Zionsville, IN, USA Belinda Hurley, Columbus, OH, USA Chikara Iwasawa, Haga-gun, Tochigi, Japan Jordi Jacas Biendicho, Oxford, United Kingdom Nadine Jacobs, Oldenburg, Germany

Ho Won Jang, Seoul, South Korea Alexander Jansen, Santa Clara, CA, USA Angelique Jarry, Berkeley, CA, USA Abirami Jeyaprakash, Singapore, Singapore Xiao Jie, Tsukuba, Ibaraki, Japan Hong Jin, Beijing, P. R. China Sean Joo, Santa Clara, CA, USA Sung-Hoon Jung, Phoenix, AZ, USA Thomas Kadyk, Burnaby, BC, Canada Bhalchandra Kakade, Kattankulathur, Tamil Nadu, India Hiroyuki Kanesaka, Kawasaki City, Kanagawa, Japan Frederic Kanoufi, Paris, France Marcin Karbarz, Warsaw, Poland Riki Kataoka, Ikeda, Japan Fotios Katsaros, Athens, Greece David Kelley, Merced, CA, USA Peter Khalifah, Stony Brook, NY, USA Daejoong Kim, Seoul, South Korea Eui Tae Kim, Daejon, South Korea EungSoo Kim, San Jose, CA, USA Hyunuk Kim, Daejeon, South Korea Jong Kyu Kim, Pohang, Gyeongbuk, South Korea Jong won Kim, Hwaseong si Gyeonggi do, South Korea Jongwon Kim, Cheongju, South Korea Kenny Kim, Phoenix, AZ, USA Namsu Kim, Gyeonggi-do, South Korea Yong-Gu Kim, Uiwang-Si, South Korea Ikuya Kinefuchi, Tokyo, Japan Axel Kirste, Ludwigshafen, Germany Akinori Kita, Koriyama-shi, Fukushima, Japan Kenji Kiyohara, Ikeda, Osaka, Japan Jessica Koehne, Moffett Field, CA, USA Brian Koeppel, Richland, WA, USA Kazutoshi Kojima, Tsukuba, Ibaraki, Japan Toshikatsu Kojima, Ikeda City, Osaka, Japan Tatyana Konkova, Hitachi-shi, Ibaraki, Japan Hideki Koyanaka, Oita-city, Oita, Japan Kei Kubota, Shinjuku, Tokyo, Japan Akihiro Kushima, Cambridge, MA, USA Joshua Lamb, Albuquerque, NM, USA Arnulf Latz, Ulm, BW, Germany Andreas Laumann, Moosburg, BY, Germany Darren LeClere, Toyohashi, Aichi, Japan Eunseok Lee, Berkeley, CA, USA Hyung-Joo Lee, Iksan Jeonbuk, South Korea Christophe Lethien, Villeneuve d’ascq, France Pieter Levecque, Rondebosch, South Africa Kalle Levon, Brooklyn, NY, USA Jiang Li, Yokohama, Japan Jianling Li, Beijing, P. R. China Seongsu Lim, Yongin-si Gyunggi-do, South Korea (continued on next page) 75

NE W MEMBERS (continued from previous page)

Ning Liu, Erlangen, BY, Germany Tianbiao Liu, Richland, WA, USA Wenjuan Liu, Midland, MI, USA Aranzazu Maestre Caro, Hillsboro, OR, USA Bryan McCloskey, Campbell, CA, USA Joanna McKittrick, La Jolla, FL, USA Dean Miller, Argonne, IL, USA Hamish Miller, Sesto Fiorentino, Italy Kota Miyoshi, Yokohama, Kanagawa, Japan Liliana Mogni, Bariloche Rio Negro, Argentina Swomitra Mohanty, Salt Lake City, UT, USA Takashi Mohri, Obu-shi, Aichi, Japan Ashley Moore, Bedford, MA, USA MuMu Moorthi, Plano, TX, USA Kenta Motobayashi, Sapporo, Sapporo, Japan David Muller, Ithaca, NY, USA Rajaram Nagarale, Austin, TX, USA Shinji Nakanishi, Susono, Shizuoka, Japan Hideki Nakayama, Susono, Shizuoka, Japan Eduard Nasybulin, Richland, WA, USA Patrick Ndungu, Durban, South Africa Hai Nguyen, Bern, Switzerland Donald Nicoll, Niskayuna, NY, USA Kazunori Nishio, Tsukuba, Ibaraki, Japan Masafumi Nose, Susono, Shizuoka, Japan Takasumi Ohyanagi, Tsukuba, Ibaraki, Japan Jeffrey Ortega, Camarillo, CA, USA Mayuko Osaki, Susono-city, Shizuoka, Japan Feng Pan, Shenzhen GongDong, P. R. China Jing Pan, Wuhan, P. R. China Lawrence Pan, Newark, CA, USA Mu Pan, Wuhan, P. R. China Gu-Gon Park, Daejeon, South Korea Hyo Gyung Park, Ulji-Gun, Ulsan, South Korea Kyusung Park, Austin, TX, USA Young-Bog Park, Seoul, South Korea Andrew Pascall, Livermore, CA, USA Catarina Pereira-Nabais, Hagondange, Moselle, France Nicholas Pieczonka, Windsor, ON, Canada Edwin Piner, San Marcos, TX, USA Olivier Pollet, Grenoble, France Aswini Pradhan, Norfolk, VA, USA Shane Prestegar, Kin Kora, Queensland, Australia Michael Procter, Burnaby, BC, Canada Daniel Ramirez, Valparaiso, Chile Justin Richards, Wolfsburg, NI, Germany Confesol Rodriguez, Waterbury, CT, USA Jelena Rubesa, Graz, Austria Benjamin Rupert, Menlo Park, CA, USA Young-Gyoon Ryu, Cambridge, MA, USA Toshiyuki Sanada, Hamamatsu, Shizuoka, Japan Christine Sanders, Sugarloaf Key, FL, USA Park Sangjin, Uiwang-Si, Gyeonggi-do, South Korea 76

Keith Scott, Newcastle Upon Tyne, United Kingdom Steven Selverston, San Jose, CA, USA Junjie Shen, Hangzhou Zhejiang Province, P. R. China Randhir Singh, Victoria, BC, Canada Brian Sisk, Milwaukee, WI, USA Kyle Smith, Cambridge, MA, USA Jungmin Song, Gyeonggi-do, South Korea Tighe Spurlin, Portland, OR, USA Chris Storment, Santa Rosa, CA, USA Olivier Sudre, Thousand Oaks, CA, USA Soon Sung Suh, Gyeonggi-do, South Korea Ying Sun, Yorktown Heights, NY, USA Yuki Tachibana, Southfield, MI, USA Yuki Takei, Minoh city, Osaka, Osaka, Japan Satoshi Tanimoto, Yokohama, Kanagawa, Japan Carina Terkelsen, Lyngby, Denmark Ranjit Thapa, Kattankulathur, Tamil Nadu, India Sobi Thomas, Daegu, South Korea Sophie Tintignac, Goteborg, Sweden Toshiaki Tsuchiya, Matsue, Shimane, Japan Mark Uebergang, Nailsworth, Australia Yoshihiro Uozumi, Yokkaichi, Mie, Japan Jon Ustarroz, Brussels, Belgium Gregorio Vargas, Saltillo, Coahuila, Mexico Grigory Vazhenin, Berlin, Germany Jiajun Wang, Upton, NY, USA Zhihui Wang, Berkeley, CA, USA Shin Watanabe, Tsukuba, Ibaraki, Japan Eric Webb, Camas, WA, USA Lei Wen, Haidian District, Beijng, P. R. China Jeffrey Wetzel, Austin, TX, USA Manuel Wieser, Marcoola, Queensland, Australia Benjamin Wilson, Aalto, Finland Bingxi Wood, Cupertino, CA, USA Marcus Worsley, Livermore, CA, USA Hsing-Chen Wu, Zhudong Town Hsinchu County, Taiwan Chunchuan Xu, Dearborn, MI, USA Tomokazu Yamane, Yokosuka-shi, Kanagawa, Japan Akihiro Yamano, Ikeda, Japan Dongfang Yang, London, ON, Canada Xiao Yang, Kyoto, Kyoto, Japan Thomas Yersak, La Jolla, CA, USA Shun Yokoyama, Sendai, Japan Sunghoon Yu, Daejeon, South Korea Weibo Yu, Albany, NY, USA Changzhou Yuan, Maanshan Anhui, P. R. China Weiyong Yuan, Bentley, Perth, Australia Wen Yuan, Berkeley, CA, USA Jong-Il Yun, Yuseong gu Daijeon, South Korea Ewelina Zabost, Warsaw, Poland Christopher Zalitis, Reading, Berkshire, United Kingdom Zhenhua Zeng, West Lafayette, IN, USA Yinghe Zhang, Tokyo, Japan

Member Representatives Sebastien Benoit, Claix, France D. J. Black, Knoxville, TN, USA Jean-Paul Diard, Claix, France Arnold Forman, Palo Alto, CA, USA Thierry Kauffmann, Claix, France Abe Krebs, Warminster, PA, USA Daniel Lonsdale, Knoxville, TN, USA David Loveday, Warminster, PA, USA Belen Molina-Concha, Knoxville, TN, USA Nicolas Murer, Claix, France Mohammed Reffass, Claix, France Rob Roberts, Knoxville, TN, USA Patrick Romanet, Claix, France Aaron Todd, Warminster, PA, USA Burak Ulgut, Warminster, PA, USA Karim Zaghib, Varennes, QC, Canada

Student Members Christopher Alexander, Gainesville, FL, USA Ashley Allen, Seattle, WA, USA Josh Aller, Bozeman, MT, USA Ahmed Alomary, Olaya Riyadh, Saudi Arabia Stephen Ambrozik, Johnson City, NY, USA Shannon Anderson, Talahassee, FL, USA Nadia Aoun, Clausthal-Zellerfeld, NI, Germany Margarita Arcila-Velez, Clemson, SC, USA Burcu Arslan, Ankara, Turkey Mary Anitha Arugula, Auburn, AL, USA Mohammad Asadikiya, Miami, FL, USA Yasser Ashraf Gandomi, Knoxville, TN, USA Ryan Austin, Scarborough, ON, Canada Antonio Baclig, Stanford, CA, USA Suresh Kannan Balasingam, Ulsan, South Korea Heather Barkholtz, DeKalb, IL, USA John Barnes, Kokomo, IN, USA Bastien Bartheleny, Namur, Belgium Stephanie Bellinger Buckley, Arlington, MA, USA Federico Bertasi, Padova, PD, Italy Abihimanyu Bhat, Austin, TX, USA Erika Biserni, Milan, Italy Preetika Biswas, Chennai, Tamil Nadu, India Daniel Bittinat, Golden, CO, USA Jacob Blickensderfer, Cleveland, OH, USA Kiran Bnao, Clayton, Vic, Australia Zeynep Bolukoglu, Ankara, Turkey David Branagan, Maynooth, Co. Kildare, Ireland Trevor Braun, Seattle, WA, USA Matthew Brier, Troy, NY, USA Michae Brilz, Darmstadt, HE, Germany Junfu Bu, Stockholm, Sweden Aaron Burkey, Athens, OH, USA Theodore Burye, Haslett, MI, USA Zeyuan Cao, Newark, DE, USA The Electrochemical Society Interface â&#x20AC;˘ Spring 2014

NE W MEMBERS Sophie Carenco, Paris, France Salvador Carmona, Iztapalapa, Distrito Federal, Mexico Christian Carvajal Rossainz, Virginia Beach, VA, USA Matthew Casey, Nashville, TN, USA Adrian Cavazos Sepulveda, Thuwal Makkah, Saudi Arabia Hansen Chang, Yokohama, Kanagawa, Japan Chunhui Chen, Miami, FL, USA Guangyu Chen, Upton, NY, USA Jamie Chen, Madison, WI, USA Shuru Chen, University Park, PA, USA Yan Chen, Cambridge, MA, USA Chieh Cheng, Hsinchu City, Taiwan Lei Cheng, Berkeley, CA, USA Tai-Chin Chiang, Taipei City, Taiwan Ladislav Chladil, Brno, Czech Republic Woohyung Cho, Seoul, South Korea Yujin Cho, Jangan-gu Suwon, Gyeonggi-do, South Korea Nadim Chowdhury, Dhaka, Bangladesh Matthew Conway, Charlotte, NC, USA David Crisostomo, Nashville, TN, USA Kevin Daniels, Columbia, SC, USA Timo Danner, Offenburg, BW, Germany Nicholas Day, Portland, OR, USA Aoife Delaney, Kilcullen Co Kildare, Ireland Francisco Delgadillo, Guadalajara, Mexico Igor Derr, Berlin, Germany Stephen DeWitt, Haverhill, MA, USA Oscar Diaz Morales, Leiden Zuid Holland, Netherlands Safak Dogu, Chandler, AZ, USA Sean Doris, San Francisco, CA, USA Soren Dresp, Berlin, Germany Dauphin Ducharme, Montreal, QC, Canada Chelsea Ehlert, Queensbury, NY, USA Oyidia Elendu, Tallahassee, FL, USA Javier Espinoza-Vergara, Santiago, Chile Jeffrey Ethier, Orange City, FL, USA Brian Fane, Knoxville, TN, USA Bren Mark Felisilda, Cagayan de Oro City, Philippines Julien Ferrand, Crolles, France Sarah Flick, Vancouver, BC, Canada Tania Frade Costa, Lisbon, Takanori Fukuda, Yokohama, Kanagawa, Japan Mehdi Ghaffari, State College, PA, USA Mahdi Ghelichi, Burnaby, BC, Canada Manuel Giraldo, Orlando, FL, USA Ram Gona, Chennai, Tamil Nadu, India Arindom Goswami, Denton, TX, USA Aravind Chenrayan Govindaraju, Chennai Tamil Nadu, India Vinicius Graciano, São Paulo, SP, Brazil Liya Guo, Birmingham, W Mids, United Kingdom Tianyi Guo, Hamilton, ON, Canada Joshua Hammons, Lemont, IL, USA The Electrochemical Society Interface • Spring 2014

Lei Han, Lexington, KY, USA Lu Han, Dayton, OH, USA Chia-Kan Hao, Hsinchu city, Taiwan Morgan Harding, Gainesville, FL, USA Katherine Harry, Berkeley, CA, USA Mitsuhisa Hasegawa, Hatoyama Saitama, Japan Lindsay Hastings, Rehoboth, MA, USA Marta Hatzell, State College, PA, USA Steve He, Stanford, CA, USA Thomas Hellstern, Palo Alto, CA, USA Karen Herdman, Maynooth Co., Kildare, Ireland Steffen Hess, Ulm, BW, Germany Chenyao Hu, Nanjing, P. R. China Mao-Chia Huang, Jhongli City, Taiwan Tai-Wei Hwang, Notre Dame, IN, USA Danish Iqbal, Dusseldorf, Germany Kousuke Ito, Sendai, Japan Amory Jacques, Namur, Belgium Reza Jafari Jam, Lund, Sweden MinSu Jeon, Seoul, Seongdong-gu, South Korea Changheum Jo, Seoul, South Korea Erlendur Jonsson, Goteborg, Sweden Durst Julien, Munich, BY, Germany Prakasha K. R., Chennai, Tamil Nadu, India Berhanu Kacha, Taipei, Taiwan Mahmoud Kamal Ahmadi, Buffalo, NY, USA Ho-Young Kang, Seoul, South Korea Wenjing Kang, Cincinnati, OH, USA Seiya Kato, Noda, Chiba, Japan Hannes Kerschbaumer, Mainz, Germany Kriangsak Ketpang, Dalseong-Gun Daegu, South Korea Anushree Khandale, Nagpur Maharashtra, India Piyush Khullar, Charlottesville, VA, USA Hyungsub Kim, Ansan-si, South Korea Youngmin Kim, Gwangju, South Korea John Kirtley, Bozeman, MT, USA Takashi Kitamura, Kyoto, Kyoto, Japan Ah Reum Koh, Seoul, South Korea Avinash Kola, Cambridge, MA, USA Vinaykumar Konduru, Houghton, MI, USA Dhrubajit Konwar, Lawrence, KS, USA Katrin Kortsdottir, Stockholm, Sweden John Krause, Charlotte, NC, USA Karl Kreder, Austin, TX, USA Dhanjai Kumar, Gwalior, Madhya Pradesh, India Rafael Kuwertz, Clausthal-Zellerfeld, NI, Germany Donghoon Kwon, Pohang Gyeongbuk, South Korea Jeffrey Landgren, Iowa City, IA, USA Daniel Lardizabal, Chihuahua, Mexico Sampson Lau, Ithaca, NY, USA Hung-Fan Lee, Chung Li, Taiwan Hyoung Rae Lee, Seoul, South Korea

Minoh Lee, Ulsan, South Korea Vincent Lee, Hamilton, ON, Canada Sandeep Lele, Sunnyvale, CA, USA Bin Li, Boston, MA, USA Ta-Jen Li, Taipei, Taiwan Yiyang Li, Stanford, CA, USA Zhiyun Li, Hamilton, ON, Canada Hong-Gang Liao, Berkeley, CA, USA Ching-Chang Lin, Hsinchu City, Taiwan Qingfeng Lin, Hong Kong, Hong Kong Jianfeng Liu, Fukuoka, Fukuoka, Japan Weiling Liu, Singapore, Singapore Laura Loaiza, Salento, Quindio, Colombia Francisco Lopez Morales, Iztapalapa, Distrito Federal, Mexico Han-Wei Lu, Taipei, Taiwan Yingying Lu, Ithaca, NY, USA Francisco Lucas, São Carlos, SP, Brazil Chuze Ma, La Jolla, CA, USA Takashi Mabuchi, Sendai, Miyagi, Japan Lauren MacEachern, Halifax, NS, Canada Pablo Mancheno-Posso, Tucson, AZ, USA Jevgenija Manerova, Sheffield, South Yorkshire, United Kingdom Madison Martinez, Lafayette, CO, USA Tatsuya Masuda, Hachioji, Japan Krzysztof Mech, Ocieka, Poland John Mefford, Austin, TX, USA Lingkuan Meng, Chaoyang District, Beijing, P. R. China Desalegn Alemu Mengistie, Taipei, Taiwan Cedric Michelet, La Haye-Fouassiere, France Hyeongjoo Moon, El Dorado Hills, CA, USA David Morris, Montreal, QC, Canada Rahim Munir, Thuwal-Jeddah Makkah, Saudi Arabia hyunwoong Na, Incheon, Seoul, South Korea Ieva Narkeviciute, Palo Alto, CA, USA Craig Neal, Orlando, FL, USA Emanuela Negro, Delft, Netherlands William Nelson, Hamilton, OH, USA Christian Nowak, Troy, NY, USA Sean Ogden, Cohoes, NY, USA Salawu Omotayo, Thuwal Jeddah Province, Saudi Arabia Livia Palma, Ribeirao Preto, SP, Brazil Abhilash Paneri, Gainsville, FL, USA Archishman Panja, Chennai, Tamil Nadu, India Enrique Paz, Tampa, FL, USA Darja Pecko, Ljubljana, Slovenia Jacob Phipps, Mesa, AZ, USA Ainsley Pinkowitz, Troy, NY, USA David Pleha, Brno, Czech Republic Surya Narayana Chennai, Tamil Nadu, India Bikash Prajapat, Dhemaji, Assam, India Sriram Prakash, Chennai, Tamil Nadu, India Tomasz Rapecki, Warsaw, Poland Thomas Rebbecchi, Troy, NY, USA (continued on next page) 77

NE W MEMBERS (continued from previous page)

Dennis Ribbe-Soranno, Vienenburg, NI, Germany Stefan Rudi, Berlin, BE, Germany Meer Safa, Miami, FL, USA Taiga Sagisaka, Noda, Chiba, Japan Vishal Sahore, Fayetteville, AR, USA Jakkid Sanetuntikul, Daegu, South Korea Anthony Santamaria, Davis, CA, USA Alexander Schoekel, Berlin, Germany Nobuyuki Serizawa, Yokosuka Kanagawa, Japan Mehrdad Shahabi-Navid, Gothenburg, Vastra Gotaland, Sweden Feifei Shi, Albany, CA, USA Akihiro Shinohara, Nagakute, Aichi, Japan Mahsa Sina, Piscataway, NJ, USA Brian Sneed, Brighton, MA, USA Min-Kyu Song, Emeryville, CA, USA Myeongjun Song, Incheon, South Korea Camillo Spoeri, Berlin, BE, Germany Marco Spreafico, Rho Lombardia, Italy Juliana Steter, Sao Carlos, Sao Paulo, Brazil Kodi Summers, Sparks, NV, USA

Bing Sun, Uppsala, Sweden Hongtao Sun, Troy, NY, USA Mohammad Takmeel, Gainesville, FL, USA Nanako Tanaka, Stuttgart, BW, Germany Maureen Tang, San Francisco, CA, USA Casey Thurber, Denton, TX, USA Mukul Tikekar, Ithaca, NY, USA Anton Tokranov, Providence, RI, USA Xiaodong Tong, Bejing, P. R. China Bradley Trembacki, Austin, TX, USA Anthony Tsikouras, Dundas, ON, Canada Natalie Tzap, Mount Laurel, NJ, USA Md. Aman Uddin, Storrs, CT, USA Fulya Ulu, Ankara Çankaya, Turkey Surya Teja Vala, Chennai Tamil Nadu, India Mario Valvo, Uppsala, Sweden Kandasamy Vignarooban, Mesa, AZ, USA Quan Vo, Houston, TX, USA Wandi Wahyudi, Thuwal Makkah, Saudi Arabia Fang Wang, Bejing, P. R. China Huanhuan Wang, Stony Brook, NY, USA Qi Wang, Troy, NY, USA Xiao Wang, Cincinnati, OH, USA Yongjie Wang, Merced, CA, USA

Ethan Wappes, Bloomington, IN, USA Yiying Wei, Sydney, NSW, Australia Curtis White, II, Norfolk, VA, USA Brandon Wood, Berkeley, CA, USA Chenghao Wu, Berkeley, CA, USA Kevin Wujcik, Berkeley, CA, USA Jing Xu, Cleveland, OH, USA Natsuki Yakabe, Noda, Chiba, Japan Litao Yan, Columbia, MO, USA Sarah Yang, Sparks, NV, USA Tanghong Yi, Albany, CA, USA Gizem Yilmaz, Boston, MA, USA Litao Yin, Beijing, P. R. China Chan-Yeop Yoo, Seoul, South Korea Zhiyuan Zeng, Berkeley, CA, USA Yubo Zhai, Shanghai, P. R. China Sanliang Zhang, Davis, CA, USA Tian Zhang, Osaka, Osaka, Japan Bijuan Zheng, Wuhan, P. R. China Bin Zhou, Mesa, AZ, USA Dehua Zhou, Dupage, IL, USA Yue Zhou, State college, PA, USA Xiuping Zhu, State College, PA, USA Yakun Zhu, Salt Lake City, UT, USA

Benefits of ECS Student Membership Annual Student Membership Dues Are Only $25 w Student Grants and Awards

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65 South Main Street, Building D, Pennington, New Jersey 08534-2839 USA • Tel 609.737.1902 • Fax 609.737.2743 78

The Electrochemical Society Interface • Spring 2014

t ST ech UDENT highligh NE WS ts Energy Technology Division Graduate Student Award Thomas Dursch earned his BS from the Department of Chemical and Biomolecular Engineering at the University of Pennsylvania. Currently, he is a fifth year PhD student in the Department of Chemical and Biomolecular Engineering at the University of California, Berkeley, co-advised by Clayton Radke (U.C. Berkeley) and Adam Weber (Lawrence Berkeley National Laboratory). His thesis title is “IceCrystallization Kinetics During Cold-Start of a Proton-Exchange-Membrane Fuel Cell.” Aside from his doctoral work, Mr. Dursch’s current research interests also include synthesis and characterization of polyelectrolyte copolymer hydrogels with application to drug delivery and soft contact lenses. Mr. Dursch has published five peer-reviewed publications in the Journal of The Electrochemical Society, Langmuir, Biomaterials, and the International Journal of Heat and Mass Transfer; he also has three ECS Transactions articles. In addition, he has received several awards, including the U.C. Berkeley Dissertation Year Fellowship in 2013, the ACS Langmuir Student Award in 2012, and the ACS Award (U. Penn.) in 2009. He may be reached at tdursch@berkeley.edu. James Radich was born and raised along the Mississippi Gulf Coast, growing up a lover of the outdoors. The wide variety of experiences in nature throughout his life spawned his passion for natural sciences and engineering. After graduating high school with special honors, Radich pursued a Bachelor’s degree in chemical engineering at Mississippi State University, graduating cum laude with additional real-world experience earned through cooperative education program. Following graduation, Radich worked for two years as an environmental assessment/remediation regulator for the Mississippi Department of Environmental Quality, after which he took a position as Engineering Manager at a commercial bioenvironmental research laboratory working on developing sensor and in situ remediation technologies for some of the most challenging environmental contaminants. In 2007, Radich pursued a Master’s degree at Mississippi State University working on microbial influences on seafloor gas hydrates. After graduating with his Master’s degree in 2009, Radich finally followed his passion for energy research to the University of Notre Dame, where he currently works with Prashant Kamat on graphenebased energy conversion and storage applications. Radich was also awarded the Jana and Patrick Eilers Graduate Fellowship for Sustainable Energy Research and the Bayer Environmental Research Fellowship, both in 2013-2014 academic year. Radich will graduate in May 2014 with his PhD and intends to continue research into relevant photo- and electrochemical systems.

Industrial Electrochemistry & Electrochemical Engineering Division H. H. Dow Memorial Student Achievement Award Matthew Ward Brodt received a BS in Chemical Engineering from the University of Virginia (UVa) in 2010 and is a PhD candidate in the Peter Pintauro group in the Chemical and Biomolecular Engineering Department at Vanderbilt University. His undergraduate research included the evaluation of bimetallic nanoparticle catalysts for the production of ethanol from synthesis gas under the guidance of Robert Davis. He also participated in the Naval Research Enterprise Internship Program (NREIP) at Indian Head, MD during the summers of 2009 and 2010 where he implemented and tested a method to quickly characterize metal fuel particles for energetic applications. Brodt’s present research at Vanderbilt involves electrospinning nanofiber nonwoven electrode mats that function as cathodes and anodes in high-performance membrane electrode assemblies (MEAs) for PEM hydrogen/air fuel cells. He is focused on lowering the platinum loading in MEAs while increasing power output and electrode durability. With industry collaboration, he hopes to engineer state-of-the-art electrodes that make an important impact on fuel cell vehicle commercialization. Brodt has enjoyed contributing to the scientific community and was a founding member and editor of UVa’s first engineering journal, the Spectra Engineering and Applied Science Research Journal. The Spectra reports exciting new research performed by undergraduates at UVa and is distributed to high schools in Virginia to spark students’ interest in science and engineering. He has also participated in the Vanderbilt Student Volunteers for Science, an organization that gives science demonstrations to local elementary and middle schools.

Industrial Electrochemistry & Electrochemical Engineering Division Student Achievement Awards Paul Northrup is currently finishing up his PhD in Chemical Engineering at Washington University in St. Louis (Wash U) under Venkat Subramanian. During his time at Wash U, Northrup has worked on a variety of projects related to the modeling and simulation of electrochemical systems. His reformulation of the porous electrode pseudo 2D (P2D) model using orthogonal collocation has allowed for the use of physics based models in optimization and parameter estimation routines, which require numerous simulation runs to find a solution, and to include more complex phenomena, such as thermal effects and multi-cell stacks. Furthermore, efficient battery simulation permits the inclusion of first-principle based models into battery management systems (BMS) and is part of an ARPA-E funded initiative to include the P2D model into model predictive control (MPC) schemes for improved performance in electric vehicles. Northrup has also developed a kinetic Monte Carlo (KMC) model to study the growth and heterogeneity of the solid electrolyte interface (SEI) layer during battery charging. In addition to his battery work, (continued on next page)

The Electrochemical Society Interface • Spring 2014

t ST ech UDENT highligh NE WS ts (continued from previous page)

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Northrup has modeled supercapacitor performance and estimated parameters using experimental data, allowing for life studies to be performed and to examine causes of failure. Northrup has contributed to finding numerical solutions to elliptic partial differential equations using a perturbation modification to the method of false transients, resulting in a method that is more robust and can capture more solutions than traditional approaches. Prior to his doctoral studies, Northrup graduated summa cum laude with a BS in Chemical Engineering from Wash U. Vedasri Vedharathinam is currently pursuing her PhD in the Department of Chemical and Biomolecular Engineering at Ohio University, Ohio, under the guidance of Gerardine G. Botte. Vedharathinam’s doctoral research focuses on developing a mechanism for the electrochemical oxidation of urea on Ni catalyst in alkaline medium. Her project involved various electrochemical and in situ spectroscopic techniques to determine the reaction kinetics and intermediates during the electrochemical oxidation of urea. Apart from her doctoral research, Vedharathinam is involved in the recovery of Ni-Co bimetallic catalyst from spent NiMH batteries and its application as anode catalyst in urea electrolysis for H2 production. It is an original research work in which she wrote the proposal and won the Student Enhancement Award from Ohio University, 2011. Vedharathinam received her master’s degree from the Department of Chemistry at University of Calgary, Canada and obtained her bachelor’s degree in chemical and electrochemical engineering from the Central Electrochemical Research Institute (CECRI), India. Her MSc research focused on investigating possible solutions to the mechanical degradation of Ni-YSZ anode in Solid Oxide Fuel Cell (SOFC) due to redox cycling. Vedasri has published four peer reviewed journal articles and two ECS transactions. She has organized various scholarly activities in the field of electrochemistry. Vedasri took initiative and founded the “Ohio University ECS Student Chapter” and served as the President of the organization. She has successfully organized IEEE outreach programs in ECS meetings and has invited electrochemistry experts to present seminars at the departmental seminar on behalf of OU chapter. Venkata Raviteja Yarlagadda is currently pursuing his PhD in the Department of Chemical & Petroleum Engineering at University of Kansas, Lawrence, Kansas, under the guidance of Trung Van Nguyen. He received his Bachelor degree in chemical engineering from Osmania University, India, and his masters degree from the Department of Chemical & Petroleum Engineering at University of Kansas, Lawrence (KS). Yarlagadda’s masters thesis involved measuring the conductivities of molten metal oxide electrolytes and evaluating them in a Direct Carbon Fuel Cell. Yarlagadda’s PhD dissertation involves modeling and experimentally characterizing a regenerative hydrogen-bromine fuel cell system. He is currently working on developing high surface area carbon electrodes to achieve the best bromine electrode configuration in a hydrogen-bromine fuel cell. Yarlagadda has given seven oral presentations and two poster presentations in international conferences (three of the oral presentations were given at the ECS meetings), and received a travel grant from ECS to present in the 224th meeting held at San Francisco. He has also won the best presentation award in the 4th annual Global - Center of Excellence (G-COE) international forum held at Honolulu, Hawaii. Yarlagadda can be contacted by e-mail at raviteja27@ku.edu. The Electrochemical Society Interface • Spring 2014

t ST ech UDENT highligh NE WS ts Drexel University Student Chapter The ECS Student Chapter at Drexel University, in conjunction with the Academy of Natural Sciences of Drexel University in Philadelphia, Pennsylvania, volunteered at STEM career days for middle school students across Philadelphia on November 8 and 15, 2013. Chapter president Kelsey Hatzell, along with ECS student members and members of the Drexel Nanotechnology Institute, Boris Dyatkin, Joseph Halim, Amanda Pentecost, and Katie Van Aken, helped to organize the event, which was part of a broader STEM initiative across Philadelphia. Over a two-week period the event drew in over 1000 middle school students from the Philadelphia public, charter and parochial schools.

Boris Dyatkin (background) and Joseph Halim (front) help Philadelphia high school students measure the voltage output from a lemon, and assemble a series “battery” composed of limes, lemons, and potatoes.

The middle schoolers learned about the fundamental working principles of batteries through a hands-on lemon (and a lime/potato) voltaic experiment. The demonstration emphasized how the lemon battery (lemon juice and zinc and copper metal) changes chemical energy to electrical energy, as well as the primary components of a battery. The participants were able to compare different fruit and vegetable “electrolytes” by comparing lemons, limes, and potatoes. They learned about the scientific process used every day in research and were encouraged to develop their own hypotheses about voltage change when lemons were connected in series with each other or in series with limes and potatoes. The high school students learned how to make measurements with a multimeter, and ended up estimating how many potatoes they would have to carry around to replace one AAA battery (about four or five!).

Seventh graders from Eugenio Maria De Hostos Charter School in North Philadelphia use a multimeter to measure voltages in a potato.

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 • Spring 2014

t ST ech UDENT highligh NE WS ts Auburn University Student Chapter The Auburn University Student Chapter grew this year to 14 members strong. The chapter held an election of new officers on January 24, 2014 with following results: President - Hyejin Park, Vice President - Samir Paul, Treasurer - Yoonsung Chung, and Secretary - Sangjun Fan. The faculty adviser is Jeff Fergus.

The Chapter is planning for two research presentations this semester given by member students, plus a faculty seminar, and a poster presentation. Membership in the chapter is free to ECS student members.

The Auburn University Student Chapter members, with their advisor Jeff Fergus (standing), during the organizational meeting in January 2014.

University of Maryland Student Chapter The University of Maryland (UMD) Student Chapter organized that learning about the combination of historical background and local lab tours during the 224th ECS meeting in San Francisco, current cutting-edge science at the lab was a uniquely rewarding experience. California. Initiated by Chapter president Colin Gore, the Chapter Immediately following the ALS tour, Steve Visco, CEO took advantage of the meeting proximity to Berkeley, CA and set up and CTO of PolyPlus Battery Company and former ECS High opportunity to see the Advanced Light Source (ALS) on the campus Temperature Materials Division Chair, arranged for a demonstration of Lawrence Berkeley National Lab (LBL), as well as visit PolyPlus Battery Company on the afternoon of October 30th. Students from the University of Virginia Student Chapter, the National Capital Section of ECS, and the Colorado School of Mines Chapter were invited to participate as well. Twelve students in all participated in the tours. Doug Taube, Chemistry Laboratory Manager of the ALS, generously led the group on a tour of the facility. He began by chronicling the history of the lab and its founder, Nobel Laureate Ernest Lawrence, who invented the cyclotron in the 1930s. He closed the introductory material by describing the eventual repurposing of the facility as a synchrotron source (currently the brightest soft x-ray source in the US) in the 1980s, after its cyclotrons were decommissioned. The tour group was then led around the synchrotron and its 43 beam lines, hearing highlights of the breakthrough research occurring at several of the end stations, from surface science of advanced fuel cells at ambient pressure to 3D tomography of the xylem Ashley Maes (CSM Chapter President), Melissa Vandiver, Colin Gore (UMD Chapter in drought-tolerant grape vines. Students agreed President), Ye Liu, Ying Liu, and William Gibbons (left to right) at PolyPlus Battery Company. 82

The Electrochemical Society Interface â&#x20AC;˘ Spring 2014

t ST ech UDENT highligh NE WS ts of his company's technology to the students at the PolyPlus offices only a few blocks away. The company specializes in new primary and rechargeable Li-Air, Li-Water, and Li-Sulfur battery technologies that have accumulated commendable support, including multiple ARPA-E awards. Thomas Conry, in charge of New Business Development, described the unique PolyPlus “protected Li electrode” technology and its implementation in each of their devices. As a followup of the group visit at Berkeley, Dr. Visco reciprocated by visiting UMD in November, where he gave a talk entitled “Roadmap to NextGeneration Batteries.” The group then caught BART back from Oakland to San Francisco to return to the conference center for the student poster sessions later that evening.

The UMD Student Chapter tour group poses under a massive electromagnet from the retired cyclotron, mimicking a photograph (top right) of Ernest Lawrence and Lab scientists from over half a century ago.

Montana State University Student Chapter

The new Student Chapter of ECS at Montana State University is very excited for the semester ahead. United in a passion for science, pizza at meetings, engineering, and electrochemistry, the Chapter has organized three key committees: Fundraising, Outreach, and Recruitment. In February, the Chapter had a booth at the MSU Engineerathon and exhibited a bicycle-powered light demonstration and a fruit-battery demonstration.

The Electrochemical Society Interface • Spring 2014

t ST ech UDENT highligh NE WS ts University of Texas – Austin Student Chapter Ed. Note: See related articles in this issue on pages 13 and 37. The Electrochemical Society recognized Professors Allen J. Bard and John B. Goodenough with Honorary Memberships on November 23, 2013 at their home institution, The University of Texas at Austin. Many scientific colleagues, including former graduate students and postdoctoral associates of the awardees, traveled long distances to celebrate the occasion. Professors Bard and Goodenough are now recognized as the 76th and 77th members of an exclusive group made up of some of the most prominent names in electrochemical and solid state science dating back to the late 19th century. Arumugam Manthiram, Director of the Texas Materials Institute and Joe C. Walter Chair in Engineering, served as the host for the awards ceremony. Roque Calvo, ECS The UT-Austin Student Chapter officers with current and previous ECS officers. From left to right: Josephine Executive Director, presented Cunningham, Daniel Redman, Fred Strieter, Roque Calvo, and Fernando Garzon. the ECS Student Chapter at The University of Texas at Austin with a 2013 ECS Student Chapter of Excellence Award and also discussed the history of the ECS Honorary Membership. Former ECS President Fernando Garzon and current ECS Vice-President Krishnan Rajeshwar presented the awards to Professors Bard and Goodenough, respectively. Both recipients delivered inspiring lectures upon reception of the award. In his lecture, Professor Bard conveyed his philosophy on the importance of fostering curiosity-driven science, rather than exclusively supporting research for a target application. He discussed three exemplary research initiatives that were conceived out of pure scientific curiosity without any foreseeable benefits to society at the time, which eventually developed into major thriving fields with tremendous societal impact. The first two examples he discussed were nuclear magnetic resonance (NMR) and light amplification by stimulated emission of radiation (the laser). Since the time of their theoretical establishment, the ongoing research and development in these fields has undoubtedly brought about great technological change. Professor Bard also discussed how the investigation of electrogenerated chemiluminescence (ECL) by his research group UT-Austin ECS student members with Allen Bard with the ECS Student and his colleagues was motivated by curiosity, since the fundamental Chapter of Excellence award. From left to right: Craig Milroy, Allen Bard, understanding of the ECL system was of utmost concern, rather than Josephine Cunningham, and Preethi Mathew. its societal impact. He stated that if someone had asked him during the early stages of the work whether or not ECL would ever have taking a notorious 32-hour qualifying exam, written in part by Enrico practical use in a clinical setting, he would have certainly answered Fermi at The University of Chicago, he decided not to pursue nuclear “no” based on the understanding of the system at the time. ECL has physics, but rather to study solid-state physics under the supervision since been developed for use in biomedical assays as a very sensitive of Clarence Zener. He described the inspirational beginnings of his and practical method of detection, which is now heavily adopted in career at the Lincoln Laboratory at MIT, developing ferrimagnetic clinical applications throughout the world. metal oxides for magnetic memory. His success in this research Professor Goodenough shared his incredible life journey beginning paved the way for him to focus on fundamental investigations and when he was a young undergraduate majoring in mathematics and eventually develop the concepts of cooperative orbital ordering, also reading a considerable amount of poetry and philosophy, “searching known as a cooperative Jahn-Teller distortion, and the Goodenoughfor his calling” in life. He recalled one particular work, Alfred Kanamori rules for magnetic interactions. Despite the fact that he had Whitehead’s Science in the Modern World, as highly influential during very little formal education in chemistry, Professor Goodenough’s his service in World War II as an Army Air Force meteorologist: “I groundbreaking fundamental research had been recognized by came to the conclusion that, if I were ever to come back from the war the Inorganic Chemistry Department at the University of Oxford, and if I were to have the opportunity to go back to graduate school, offering him a position as the Head of the Department. He shared I should study physics.” Professor Goodenough explained how upon 84

The Electrochemical Society Interface • Spring 2014

tech ST UDENT highlights NE WS that the decision to accept Oxford’s invitation, among many other tempting offers, was facilitated by his wife, Irene. It turned out to be the right decision. At Oxford, Professor Goodenough’s group experimentally identified lithium cobalt oxide as the cathode material for the Li-ion rechargeable batteries, capable of achieving high energy density without using metallic lithium as an anode. This discovery brought about the first commercialized rechargeable Liion batteries by Sony Corporation, used in modern handheld electronics today. Professor Goodenough concluded his lecture by stressing the urgency for developing sustainable energy and highlighted some recent findings by his group at The University The audience during the ECS Honorary Membership Induction. First row, from left to right: John Goodenough, of Texas at Austin regarding the Allen Bard, Fernando Garzon, Roque Calvo, and Krishnan Rajeshwar. Second row, from left to right: Josephine Cunningham, Donald Robinson, Alex Boika, Jeffrey Dick, Ki Min Nam, Byungkwon Kim, and development of thin membranes Matthew Beaudry. that block anode dendrites from reaching the cathode and allow for the alternative design of higher capacity cells. The final speech was delivered by Larry R. Faulkner, a former graduate student of Allen Bard, past President of The Electrochemical Society (1991-1992), and past President of the University of Texas at Austin (1998-2006). Dr. Faulkner reflected on the past 50 years of electrochemistry and chemistry in general, highlighting that the greatest challenge for chemists is to manage the use and stewardship of the material world. He asked the big question, “How can we wisely make use of Earth’s resources, to provide fulfilling, secure lives for the Earth’s people, now and indefinitely into the future?” Dr. Faulkner concluded by noting that this year marks the 200th anniversary of Sir Humphrey Davy’s greatest discovery, UT-Austin ECS student members and past officers at the Honorary Membership luncheon. From left to right: Alex Michael Faraday. The two honored Boika, Karen Scida, Netzahualcoyotl Arroyo Curras, Preethi Mathew, Craig Milroy, and Jeffrey Dick. professors, Bard and Goodenough, have undoubtedly adopted this important lesson of Humphrey Davy toward developing younger talent and shaping the future of electrochemistry and solid state science. As a student at The University of Texas at Austin, I can personally attest to Dr. Faulkner’s comments on Professors Allen J. Bard and John B. Goodenough by observing their impact on my peers and on me as I begin my own scientific journey. I am honored to have the opportunity to be in their presence and I am fortunate to be conducting my research in an environment cultured by these great men who hold such a strong devotion to science and commitment to the prosperity Nominations due April 15, 2014. of future generations.

Allen J. Bard Award in Electrochemical Science

This notice was prepared by Donald Robinson, Vice-President, UT-Austin ECS Student Chapter. The Electrochemical Society Interface • Spring 2014

CH Instruments

t ST ech UDENT highligh NE WS ts 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 Energy Technology Division Graduate Student Award was established in 2012 to recognize and reward promising young engineers and scientists in fields pertaining to the Division. The awards are intended to encourage the recipients to initiate or continue careers in this field. Up to two recipients chosen will receive an appropriately worded certificate as well as an amount of $1,000, payable to the recipient. In addition, the recipient will receive a waiver of student registration, and un-reimbursed travel expenses to attend the Spring ECS meeting, an amount not to exceed $1,000 in order to accept the award. 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 Energy Technology Student Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534; Phone: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by September 1, 2014. The H. H. Dow Memorial Student Award of the Industrial Electrochemistry and Electrochemical Engineering Division was established in 1990 to recognize promising young engineers and scientists in the fields of electrochemical engineering and applied electrochemistry. The award consists of a scroll and a prize of $1,000 for educational purposes. 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 IEEE Dow Student Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534; Phone: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by September 15, 2014. The Student Achievement Award of the Industrial Electrochemistry and Electrochemical Engineering Division was established in 1989 to recognize promising young engineers and scientists in the field of electrochemical engineering and to encourage the recipients to initiate careers in this field. The award consists of a scroll and a prize of $1,000 for educational purposes. The award consists of a scroll and a prize of $1,000 for 86

educational purposes. 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 IEEE Dow Student Award, c/o The Electrochemical Society, 65 S. Main Street, Building D, Pennington, NJ 08534; Phone: 1.609.737.1902; e-mail: awards@electrochem.org. Electronic submission of nomination packets is preferred. Materials are due by September 15, 2014.

Student Travel Grants Many of the Society’s Divisions offer travel assistance to students and early career professionals presenting papers at ECS meetings. For details about travel grants for the 226th ECS meeting in Cancun, Mexico, please see the Cancun 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 prior to completing the online application. You must submit your abstract and have your abstract confirmation number in order to apply for a travel grant. Apply for travel grants using the online submission system (links found on the travel grant web page). If you have any questions, please email travelgrant@electrochem.org. The deadline for submission for fall 2014 travel grants is July 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/ membership/student.htm. The Electrochemical Society Interface • Spring 2014

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 • Spring 2014

Date: _________________________________

ECS Institutional Members

(Number in parentheses indicates years of membership)

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

Benefactor

Asahi Kasei E-Materials Corporation (6) Chiyoda-Ku, Japan Bio-Logic USA Knoxville, TN, USA, Bio-Logic SAS (6) Claix, France Duracell (57) Bethel, CT, USA Gelest Inc. (5) Morrisville, PA, USA Hydro-Québec (7) Varennes, Canada Industrie De Nora S.p.A. (31) Milano, Italy

Patron

Saft Batteries, Specialty Battery Group (32) Cockeysville, MD, USA AMETEK – Scientific Instruments (33) Oak Ridge, TN, USA

IBM Corporation (57) Yorktown Heights, NY, USA

Dow Chemical Company (73) Midland, MI, USA

Panasonic Corporation (7) Osaka, Japan

Energizer (69) Westlake, OH, USA

Faraday Technology, Inc. (8) Clayton, OH, USA

Scribner Associates Inc. (18) Southern Pines, NC, USA

Gamry Instruments (7) Warminster, PA, USA

Technic, Inc. (18) Providence, RI, USA

Axiall Corporation (19) Monroeville, PA, USA

Sponsoring

Ballard Power Systems, Inc. (30) Burnaby,

Sustaining

Pine Research Instrumentation (8) Durham, NC, USA

El-Cell (1) Hamburg, Germany

Lawrence Berkeley National Lab (10)

Quallion, LLC (14) Sylmar, CA, USA

Berkeley, CA, USA

Sandia National Laboratories (38) Albuquerque, NM, USA

BC, Canada

Medtronic, Inc. (34) Minneapolis, MN, USA

C. Uyemura & Co., Ltd. (18) Osaka, Japan

Metrohm Autolab (8) Utrecht, Netherlands

Central Electrochemical Research Institute (21) Tamilnadu, India

TDK Corporation, Device Development Center (21) Narita, Japan

Metrohm USA (8) Westbury, NY, USA

Teledyne Energy Systems, Inc. (15)

EaglePicher Technologies, LLC (7) Joplin, MO, USA

Next Energy EWE – Forschungzentrum (6) Oldenburg, Germany

Sparks, MD, USA

TIMCAL Ltd. (27) Bodio, Switzerland Toyota Central R&D Labs., Inc. (34) Nagoya,

Electrosynthesis Company, Inc. (18)

Nissan Motor Co., Ltd. (7) Yokosuka, Japan

Lancaster, NY, USA

Occidental Chemical Corporation (72)

GS-Yuasa International Ltd. (34) Kyoto, Japan

Dallas, TX, USA

Yeager Center for Electrochemical Sciences (16) Cleveland, OH

Honda R&D Co., Ltd. (7) Tochigi, Japan

Permascand AB (11) Ljungaverk, Sweden

ZSW (10) Ulm, Germany

3M Company (25) St. Paul, MN, USA

International Lead Zinc Research Organization (35) Durham, NC, USA

Japan

Kanto Chemical Co., Inc., (2) Soka City, Saitama,

PEC North America (10) Boca Raton, FL, USA

Co-Operative Plating Company, (3) St. Paul, MN, USA General Motors Research Laboratories (62) Warren, MI, USA

Giner, Inc./GES (27) Auburndale, MA, USA

Japan

Leclanche SA (29) Yverdon, Switzerland Los Alamos National Laboratory (6) Los Alamos, NM, USA

Japan

Mitsubishi Heavy Industries, Ltd. (1) Nagasaki,

Reagent (2) Runcorn, Cheshire, England SolviCore GmbH & Co. KG (1) Hanau-Wolfgang, Germany

Please help us continue the vital work of ECS by joining as an institutional member today. To join or discuss institutional membership options please contact Christie Knef, Development Manager, at 609.737.1902 ext. 121 or christie.knef@electrochem.org. 02/12/2014

The Electrochemical Society Interface • Spring 2014

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