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Quantifying Quality
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Making a Case for Battery Modeling
PRiME 2020 Highlights
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Cold Sintering for High-Temperature Electrochemical Applications
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FROM THE EDITOR
I
Welcome to Day 196
think I speak for everyone when I say that I have serious virus fatigue. Everybody is getting a bit grumpy at times. (Of course, no one in my house.) The times in which we are living seem to be conspiring to tax everyone’s patience and better angels. At least here in the U.S., some appear to interpret the wearing of a mask as an in-your-face political statement as opposed to an on-your-face public health action. My neighbors had four lawn signs supporting political candidates stolen. People were setting up cameras to catch the perpetrators. Note that this is a neighborhood where the last big scandal was when someone didn’t mow their lawn often enough. You cannot imagine that horror. Am I glad U.S. presidential elections are held every four years! For some bizarre reason, this behavior reminded me of the challenges that can arise during peer review. I mentioned the importance of peer review in my last editorial for vetting scientific studies, but it can have a dark side. Blind peer review provides anonymity to the reviewer in order to encourage frank assessments of the manuscript. Unfortunately, that same anonymity can lead some reviewers to take on an attitude that goes beyond critical into insulting. The problem with such an attitude is not that it might hurt the author’s feelings; it is that it creates a barrier to progress. The goal of peer review is not only to sort the wheat from the chaff but also to improve manuscripts that will be accepted by providing an independent appraisal of the methods, results, and most importantly, the discussion. Suggestions for improvements, additions, and subtractions are critical to a good review. A critical eye is necessary, but not sufficient. Communicating the assessment and suggestions in a way that is clear but devoid of snarky comments provides the best chance to have a constructive dialogue. We can disagree agreeably. Doing so does not lessen the impact of the critique in any way. Instead, it urges an in-kind reply, and it therefore focuses on the quality of both the scientific arguments and the communication of those arguments. I am no fan of being criticized, but I can say that every paper that I have written has been improved by the review process. The reviews make me think more deeply. I am alerted to text that is perfectly clear to me but not to others. The technical editors do yeoman’s work in making sure that the review process is fair: both the reviewers and the authors get their say. They are clearly working off a lot of bad karma. We as scientists are not separate from our culture. We see the same lack of civility due to anonymity play out on vast areas of the Internet, particularly in the Comments section. The shield of anonymity leads some to try to work out some self-image issues by trolling—an association that is unfair to all the actual trolls that I know. Before the Internet (yes, younger readers, there was a time before the Internet, but after dinosaurs), such anonymity was hard to find. I am certain people had the same thoughts, but they rarely made their way out, and when they did, they did not receive hundreds of likes. Maybe we can lead our fellow global citizens out of the darkness. The next time you review a manuscript, reread aloud your review before submitting it. Then edit out the unnecessary sharp edges. Only then should you submit. You may have noticed that Interface has been only available in a digital format for the last couple of issues. The Interface Advisory Board made the decision to do so in order to both contribute to the Society’s cost savings and to allow us to reach those of you who have been shut out of your paper versions because of COVID-19 restrictions, including restrictions on mailing. I hope those who love the tactile experience of magazines have been able to make the transition. I am sure that dedicated readers of this column (now down to one) are waiting anxiously for an update on Bubba the Whippet. In short, he is back, and badder than ever. Frisbees and tennis balls are, once again, living a perilous existence. He is still building his stamina, but when chasing a ball, he is hell on wheels once again. In protest, his sister killed a vole, adding to her impressive kill list of squirrels, birds (including a hummingbird), chipmunks, and a snake. Yes, a snake, but that is a story for a different time. Until next time, be safe and happy.
Rob Kelly Editor rgk6y@virginia.edu https://orcid.org/0000-0002-7354-0978
Published by: The Electrochemical Society (ECS) 65 South Main Street Pennington, NJ 08534-2839, USA Tel 609.737.1902, Fax 609.737.2743 www.electrochem.org Editor: Rob Kelly, rgk6y@virginia.edu Guest Editors: Sean Bishop, srbisho@sandia.gov; Jianhua (Joshua) Tong, jianhut@clemson.edu Contributing Editors: Donald Pile, Donald.Pile@gmail. com; Alice Suroviec, asuroviec@berry.edu Director of Publications: Beth Craanen, Beth.Craanen@electrochem.org Production Editor: Mary Beth Schwartz, MaryBeth.Schwartz@electrochem.org Print Production Manager: Dinia Agrawala, interface@electrochem.org Staff Contributors: Frances Chaves, Beth Craanen, Genevieve Goldy, Mary Hojlo, Christopher J. Jannuzzi, John Lewis, Anna Olsen, Jennifer Ortiz, Shannon Reed, Beth Schademann, Mary Beth Schwartz, Francesca Spagnuolo, Keerthana Varadhan Advisory Board: Brett Lucht (Battery), Dev Chidambaram (Corrosion), Durga Misra (Dielectric Science and Technology), Philippe Vereecken (Electrodeposition), Jennifer Hite (Electronics and Photonics), Mani Manivannan (Energy Technology), Cortney Kreller (High-Temperature Energy, Materials, & Processes), John Weidner (Industrial Electrochemistry and Electrochemical Engineering), Jakoah Brgoch (Luminescence and Display Materials), Hiroshi Imahori (Nanocarbons), Jim Burgess (Organic and Biological Electrochemistry), Andrew Hillier (Physical and Analytical Electrochemistry), Ajit Khosla (Sensor) Publications Subcommittee Chair: Turgut Gür Society Officers: Stefan De Gendt, President; Eric Wachsman, Senior Vice President; Turgut Gür, 2nd Vice President; Gerardine Gabriela Botte, 3rd Vice President; Marca Doeff, Secretary; Gessie Brisard, Treasurer; Christopher J. Jannuzzi, Executive Director & CEO 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
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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 is part of membership service; subscription to nonmembers is available; see the ECS website. Single copies $10.00 to members; $19.00 to nonmembers. © Copyright 2020 by The Electrochemical Society. *“Save as otherwise expressly stated.” Periodicals postage paid at Pennington, New Jersey, and at additional mailing offices. POSTMASTER: Send address changes to The Electrochemical Society, 65 South Main Street, Pennington, NJ 08534-2839. The Electrochemical Society is an educational, nonprofit 501(c)(3) organization with more than 8,500 scientists and engineers in over 75 countries worldwide who hold individual membership. Founded in 1902, the Society has a long tradition in advancing the theory and practice of electrochemical and solid state science by dissemination of information through its publications and international meetings. Cummings Printing uses 100% recyclable low-density polyethylene (#4) film in the production of Interface.
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Advanced Manufacturing for High-Temperature Materials by Sean R. Bishop and Jianhua Tong
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Manufacturing Techniques of Thin Electrolyte for Planar Solid Oxide Electrochemical Cells by Wuxiang Feng, Wei Wu, Congrui Jin, and Dong Ding
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Aerosol Jet Deposition for Structured Materials by Lok-Kun Tsui, John Plumley, and Fernando H. Garzon
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Cold Sintering for HighTemperature Electrochemical Applications by Zane Grady, Joo-Hwan Seo, Kosuke Tsuji, Arnaud Ndayishimiye, Sarah Lowum, Sinan Dursun, Jon-Paul Maria, and Clive A. Randall
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Advanced Manufacturing of Intermediate-Temperature Protonic Ceramic Electrochemical Cells by Shenglong Mu, Zeyu Zhao, Hua Huang, Jincheng Lei, Fei Peng, Hai Xiao, Kyle S. Brinkman, and Jianhua (Joshua) Tong
Vol. 29, No. 4 Winter 2020
the Editor: 3 From Welcome to Day 196 the President: 7 From O Tempora! O Mores!
8 Quantifying Quality 2020 10 PRiME MeetingHighlights 14 Candidates for Society Office 18 Society News 30 Free Radicals 35 People News 37 Looking at Patent Law 43 Tech Highlights 74 Section News 75 Awards Program 78 New Members 2020 Summer 81 ECS Fellowship Reports 89 Student News 94 SOFC-XVII Call for Papers On the Cover: Lok-kun Tsui, Research Assistant Professor, University of New Mexico–Center for Micro-Engineered Materials, used his Sony camera to capture a close-up photo of the print head of the Integrated Deposition System “Nanojet” aerosol jet printer. The image also can be found in the feature, “Aerosol Jet Deposition for Structured Materials.” Image courtesy of Lok-kun Tsui. Cover design by Dinia Agrawala.
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The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
FROM T HE PRESIDENT
O Tempora! O Mores!
T
spring and plans to expand our publication portfolio in the his Latin phrase, spoken by Cicero around 70 BC, months to come. All this demonstrates how ECS positions translates to “Oh the times, oh the customs.” These itself—providing many opportunities for individuals not just to words are more than appropriate for the current be members, but also to become part of a research community worldwide crisis and how we react to it. When I wrote the active in a broad domain summer Interface editorial, I of scientific and technical hoped that society could look areas with global relevance. forward to resuming life as ECS offers its members usual. However, the COVID-19 opportunities to engage in pandemic keeps forcing us symposium participation and to adapt our customs in all Looking back at PRiME 2020, the organization, to become active aspects of societal behavior volunteer leadership and ECS staff made participants in one of our rapidly. This also affects The scientific divisions, to publish Electrochemical Society, its the impossible possible. Last summer, who and review scientific papers, members, leadership, and staff. would have thought that we as a community and most importantly, to meet Looking back at PRiME would manage to convert our flagship and socialize with peers and 2020, the volunteer leadership conference from an in-person meeting to quickly become friends. and ECS staff made the So, do not wait to become impossible possible. Last to a successfully virtual meeting in less part of the next generation summer, who would have than four months? of ECS membership and thought that we as a community leadership. More than ever would manage to convert in these changing times, ECS our flagship conference from is where you count, and we an in-person meeting to a count on you. successfully virtual meeting In summary, reflecting on the concluding words of my in less than four months? Thanks to the innovative format, summer editorial, with our members and stakeholders’ level of PRiME was free for registrants—a true example of Free the engagement, professionalism, and voluntarism, I am confident Science, a key mission of The Electrochemical Society. The that ECS is ready more than ever for future challenges and to success was visible in the live events honoring the Society’s adapt to changing times and customs. Nobel laureate members, ECS Fellows, and recipients of division, section, and Society awards. Even more notably, we maintained almost 80 percent of the originally submitted abstracts as content for the digital meeting. PRiME attained a record number of just under 7,000 attendees. What is less visible is the enormous background work done by volunteers and staff to create a framework that allows us going forward to Stefan De Gendt address and organize virtual meetings with content and adapt ECS President quickly to changing situations. Significant new initiatives have president@electrochem.org evolved in other domains where ECS is active—specifically, https://orcid.org/0000-0003-3775-3578 the webinar and training opportunities launched since the
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Quantifying Quality by E. Jennings Taylor and Chris Jannuzzi n recent years, scientific publishing has seen consistent increases in terms of both the number of manuscripts published, roughly 4% year-over-year, as well as the number of journal titles that exist. As of mid-2018, there were over 42,000 active scholarly peer-reviewed titles publishing over three million articles annually.1 With such an enormous corpus of titles and literature, across a host While JIF does provide a useful metric for showing the average of technical disciplines and domains, one can appreciate the need to number of citations received for recently published articles in a define clear metrics to assess both the quality of a given title and to particular journal, there are limitations in terms of its ability to provide the technical publishing community at large—librarians and accurately assess journal quality or prestige on a wide scale. Vincent corporate subscription managers as well as authors and readers—with Larivière, a professor of information science at the University of a useful, practical means of comparing and ranking titles against each Montreal, led a 2015 study to assess the utility and validity of JIF. The other. Researchers looking to share their latest groundbreaking results study’s findings pointed to two major limitations with JIF. The first is want to publish in the most respected journals and are under enormous the opacity and inconsistency of the data being used to calculate JIF. pressure to do so, especially as it relates to promotion (e.g., tenure) Clarivate Analytics, the organization that manages JIF calculations decisions and proposal funding allocations. and publishes Journal Citation Reports (JCR) Librarians need to spend precious financial in which Impact Factors appear annually, does resources wisely and subscribe to the vital not share the data used to drive JIF calculations, journals in their field. Publishers, commercial so it is not possible to reproduce the JIF for and non-profit alike, who are competing for a given title. In addition, given the many Their analysis further revealed authors and readers, need a simple means of variances in how journals format, display, and that compared to the 10 top distinguishing themselves within their crowded abbreviate reference information, it is difficult to “electrochemical” journals technical domains. However, is it possible to consistently track citation information across the (when ranked by impact reduce something as abstract and subjective as thousands of journals in the JCR.3 factor in the Materials the quality or the prestige of a journal to a single The second concern the study found with JIF Science and Electrochemistry number? is how a few highly cited articles can dramatically categories) JES is by far the In sports, it is a straightforward process to skew the JIF for a given title. According to the most cited in patent literature, determine who ran the faster 100-meter sprint, study, for some titles, up to 75% of the articles further calling into questions or who jumped over the highest bar. Moreover, in a given journal had lower citation counts the value of IF, or any single while sophisticated tools are necessary to than the journal’s published JIF, greatly calling measure the often-infinitesimal differences to question the JIF’s predictive capabilities of metric, in terms quantifying a between the first and second place in a race, a particular journal title. As the study’s authors journal’s stature. the rubric for determining who the winner is concluded, “we hope that this analysis helps to simple, clear. However, consider the judging expose the exaggerated value attributed to the of a figure skating routine or gymnastics floor JIF and strengthens the contention that it is an program. Such sports require a multidimensional inappropriate indicator for the evaluation of rating scheme that accounts for and assesses research or researchers.4” athletic performance and other intangible elements such as creativity, Other indicators, similar or related to JIF, have been developed to artistry, and aesthetic sense. Similarly, trying to judge or rate a journal’s help provide additional quantitative measures of journal prestige. The stature and quality is a complicated, nuanced, and ultimately, more Eigenfactor Score (ES) is another metric used to measure journal difficult task. quality and influence. Although also based on citation information from The most widely used metric to determine journal prestige is the Clarivate’s Web of Science, ES differs from JIF in several ways. Most Journal Impact Factor (JIF), also known simply as Impact Factor important of these differences is that ES is based on the total number (IF). JIF was developed by linguist and entrepreneur Eugene Garfield, of citations, irrespective of the number of articles published. Therefore, and although the current JIF is only calculated for works published a journal that publishes 1,000 articles will have double the ES of a from 1975 onward, the initial concept dates back to the mid-1950s and journal that publishes 500 articles, assuming all articles receive the evolved throughout the 50s and 60s into the methodology that is used same number of citations. In addition, the ES citing period is five years, today.2 A journal’s JIF is the number of citations generated during the more than double the citing period for JIF. One of the critiques of ES is target year for articles (or citable items) that the journal published in the that it very strongly correlates to the raw number of citations a journal preceding two years, divided by the number of citable items published receives, suggesting the weighting ES employs does not significantly in the previous two years. For example, if a journal generated 3,000 impact the Eigenfactor Score.5 However, an additional metric related citations in 2019 for the 1,000 articles it cumulatively published in to ES is the Article Influence Score, which divides the number of 2017 and 2018, the JIF would be 3,000/1,000 = 3. The presumption is citations in the ES calculation by the number of citable items. that the more citations a journal receives for the articles it publishes, the more significant both the published articles and the journal are. J. Bohannon, “Hate Journal Impact Factors?”, AAAS ScienceMag.org, https://www.sciencemag.org/news/2016/07/hate-journal-impact-factorsnew-study-gives-you-one-more-reason. 4 V. Larivière and V. Kiermer, et. al, bioRxiv, “A Simple Proposal for the Publication of Journal Citation Distributions,” https://academic.oup.com/ rev/article-abstract/24/4/343/1518234. 3
R. Johnson, A. Watkinson, and M. Mabe, The STM Report: An Overview of Scientific and Scholarly Publishing, 25 (2018). 2 E. Garfield, JAMA, 90(295), 1 (2006). 1
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The Scimago Journal Rank (SJR) also attempts to quantify journal quality and impact. SJR differs from JIF in that it considers citations received for articles over a three-year, as opposed to a twoyear period. Also, rather than considering citation references from the Web of Science, the SJR is based solely on what is reported in the Scopus database. Lastly, as is the case with ES, SJR assigns weighting to the value of the publication in which the citation appears. However, although considered a “sophisticated alternative” to the basic JIF, issues of transparency and replicability, as detailed in an article published by Oxford University Press, call into question its overall usefulness as a quantitative measure of quality.6 Although there are limitations to each of the evaluation methods described above, the fact is that these metrics are widely publicized and used to some degree by most technical publishing stakeholder groups. Therefore, to a publisher like The Electrochemical Society (ECS), these statistics matter. The good news for ECS is that the Society’s journals are of high quality and that quality is consistently reflected in the scores received for the metrics schemes just described. The Journal of the Electrochemical Society (JES) has a 3.721 JIF and is ranked 5th in the Materials Science Coatings and Films technical area and 12th in the Electrochemical technical area. For a small, independent publisher like ECS, these are no doubt strong metrics. However, digging a little deeper into the data reveals other metrics that possibly better reflect ECS’s long-standing commitment to publishing excellence. One area in which ECS publications outperform other titles in our space is in terms of the Cited Half-Life. The Cited Half-Life describes the median age of the articles that were cited in a journal in a given year. For example, if a journal has a Cited Half-Life of 5.2, half of the articles cited in a given year are more than 5.2 years old, and half are less than 5.2 years old. For JES, the Cited Half-Life published by Clarivate is 10.4. Further mining the data reveals that JES has the highest Cited Half-Life of the top 10 Journals (as ranked by impact factor) in the Materials Science Coatings and Films category, and the second-highest Cited Half-Life for the top 10 Journals in the Electrochemistry category. This means that a majority of the cites received by JES fall outside of the citing period for the traditional JIF calculation, suggesting that the content published in JES has longer period of impact and relevance than many journals with much higher JIFs. When asked to share his thoughts on why this was, JES Editor Robert Savinell of Case Western Reserve University said, “The research published in JES more often addresses fundamentals of electrochemical processes and materials, presenting new insights in electrochemical foundations that have lasting impact. In addition to groundbreaking research, JES also publishes work that has a high degree of utility, such as critical advances in electrochemical measurements, data analysis, and electrochemical systems modeling. This type of content often has lasting value to the research community, for a longer period of time than is captured by traditional impact factor measures, hence the reports of the long cited half-life of articles published in JES.” This combination of publishing research that is both new and novel, as well as foundational and practical, may well be the driver behind ECS’s success in a different, often overlooked citation venue: patent literature. More specifically, during the examination of patent applications, the United States Patent & Trademark Office (USPTO) consider prior art to make a patentability assessment.7 Specifically, patentable inventions must be novel and non-obviousness in view of the prior art. Journal articles published represent an important subset of the prior art considered during the examination of patent applications.8 Recently, ECS Past President Johna Leddy, working with her PhD student Daniel Parr IV, studied data from the USPTO to see how often ECS journals, particularly JES, were cited in patent applications relative to other journals in our technical field. Using patent citation information available from the USPTO9, they compared how often each of the over 7,250 science and engineering journals codified by The University of British Columbia’s Woodward Library10 was cited. What their analysis revealed is astounding. P. Davis, The Scholarly Kitchen, “Eigenfactor,” (2008). J. Mañana-Rodríguez, Research Evaluation, “A Critical Review of SCImago Journal & Country Rank,” 24(4), pp. 343-354, https://doi. org/10.1093/reseval/rvu008 (2015).
As Prof. Leddy herself describes, “The innovation inherent in ECS journals is readily apparent on even casual inspection of the patent literature. Daniel Parr IV queried the patent databases for ECS journal citations. The outcomes of the search are startling. Of the 7,279 journals queried in patents in all content domains, 5% of the citations are to ECS journals. ECS journals rank 3rd, behind Chemical Communications and Langmuir. Clearly, ECS journal content is the bedrock for innovation in science and technology. The impact of ECS journals in innovation warrants acknowledgment.” Their analysis further revealed that, compared to the 10 top “electrochemical” journals (when ranked by impact factor in the Materials Science and Electrochemistry categories), JES is by far the most cited in patent literature, further calling into question the value of IF, or any single metric, in terms of quantifying a journal’s stature. The frequency with which research published in JES is cited in patent literature, coupled with its long cited half-life metric, supports the assertion that content published in the journal has a high degree of utility as well as a long period of relevance, far longer than most of the other titles publishing in ECS’s technical domains. Of course, as has been pointed out with respect to other indicators discussed in this piece, it is difficult to judge the true quality and prestige of a journal by any one metric. Therefore, rather than relying on a single such measure, it is important to consider a wide array of metrics (and to have a basic understanding of how each is derived and what its limitations are) in order to form a holistic understanding of the overall quality and prestige of a given journal. © The Electrochemical Society. DOI: 10.1149.2/2.F01204IF.
About the Authors E. Jennings Taylor is the founder of Faraday Technology, Inc., a small business focused on developing innovative electrochemical processes and technologies based on pulse and pulse reverse electrolytic principles. Taylor leads Faraday’s patent and commercialization strategy and has negotiated numerous via field of use licenses as well as patent sales. In addition to technical publications and presentations, Taylor is an inventor on 40 patents. Taylor is admitted to practice before the United States Patent & Trademark Office (USPTO) in patent cases as a patent agent (Registration No. 53,676) and is a member of the American Intellectual Property Law Association (AIPLA). Taylor has been a member of ECS for 38 years and is a fellow of ECS. He may be reached at jenningstaylor@ faradaytechnology.com. https://orcid.org/0000-0002-3410-0267 Chris Jannuzzi, ECS Executive Director/ Chief Executive Officer. Chris comes to ECS from IEEE in Piscataway, NJ, where he was executive director of the Electron Devices Society for over six years and executive director of the Photonics Society for the last four years. Prior to joining IEEE, he was senior director of member services at The College Board. He is a graduate of New York University and holds an MA from Teachers College, Columbia University, in organization and leadership. With a proven ability to lead volunteer-driven technical societies, and a passion for advancing science and technology, Chris strives to maintain and enhance ECS’s preeminence in the field of electrochemical and solid state engineering. He may be reached at chris.jannuzzi@electrochem.org. https://orcid.org/0000-0002-7293-7404
E. J. Taylor and M. Inman, Electrochem. Soc. Interface, 26(3), 39 (2017). E. J. Taylor and M. Inman, Electrochem. Soc. Interface, 27(3), 33 (2018). 9 http://patft.uspto.gov/netahtml/PTO/search-adv.htm) 10 https://woodward.library.ubc.ca/research-help/journal-abbreviations/#A
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PRiME 2020 Highlights
2020
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he PRiME 2020 digital meeting registered a record 6,892 participants from around the world, surpassing 2016 PRiME’s record attendance and making this the highest meeting registration in PRiME (and ECS) history! 2020 registration included 4,451 digital participants and 2,441 digital presenters—including 1,199 student presenters. Participants could choose from 3,996 presentation files composed of 1,635 slides, 1,980 videos, and 381 posters, covering 2,547 individual presentations. In addition, 19 symposia convened 75 hour-long live sessions in which presenters and participants engaged and exchanged ideas. Of course, it wouldn’t have been a PRiME meeting without keynote events throughout the week!
Opening Ceremony
The opening ceremony kicked off the online meeting. Introductory remarks were given by Susumu Kuwabata, ECSJ President; Woonsup Shin, KECS President; and Stefan De Gendt, ECS President, who welcomed attendees to the first-ever, exclusively online PRiME 2020 event and provided an overview of the week ahead.
Hua University Department of Materials Science Engineering, Taiwan; and our contributing meeting sponsor MDPI. Prof. Dr. Nam-Gyu Park of Sungkyunkwan University delivered this year’s PRiME Lecture, “Perovskite Solar Cells: Past 10 Years and Next 10 Years.” Dr. Park developed the first stable, 9.7 percent efficient solid state perovskite solar cell (PSCs), leading to an explosion in perovskite research. In 2017, he was named a Citation Laureate scientist worthy of a Nobel Prize. Dr. Park, a pioneer in the perovskite field, addressed the efficiency, materials, upscaling, and stability Nam-Gyu Park, of PSCs, considered a promising area for nextPRiME 2020 lecturer. generation photovoltaics. Dr. Kai Zhu, a senior scientist in the Chemistry and Nanoscience Center at the National Renewable Energy Laboratory (NREL), whose research covers both basic and applied research on perovskite solar cells, moderated Prof. Park’s talk. Online participants had the opportunity to ask questions in a Q&A session following Dr. Park’s lecture. Lastly, Jannuzzi thanked all meeting sponsors Kai Zhu, plenary session moderator. and ECS’s institutional members again for their continued support and commitment to PRiME 2020.
The Electrochemical Energy Summit (E2S): The Electrification of Transportation Susumu Kuwabata, ECSJ President.
Woonsup Shin, KECS President.
Stefan De Gendt, ECS President.
Plenary Session ECS CEO and Executive Director Christopher Jannuzzi welcomed attendees to the meeting during the plenary session, an event that featured the meeting’s PRiME Lecture. Jannuzzi thanked PRiME 2020’s general meeting sponsors, particularly those celebrating milestone institutional membership anniversaries through ECS’s Leadership Circle Awards, including: Platinum meeting sponsor SK Innovation; gold meeting sponsor Samsung SDI; silver meeting sponsors Ion Power, Inc., LG Chem, and Scribner; bronze meeting sponsor National Tsing
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The Electrochemical Energy Summit (E2S) brings together policy makers and researchers who shared information on the critical issues of energy needs and pivotal research in electrochemical energy addressing societal needs. For the 2020 topic E2S focused on “The Electrification of Transportation,” and examined the growing role that electrochemistry and solid state science play in providing sustainable solutions for global transportation systems. “Since 2011, E2S has been a fixture of every PRiME and ECS fall meeting,” said ECS CEO and Executive Director Christopher Jannuzzi. “Tonight we continue that tradition by addressing one of the most important of these challenges: the electrification of transportation.” A panel of esteemed scientists, researchers, and practitioners led the discussion moderated by Bor Yann Liaw, a Directorate Fellow in the Energy and Environmental Science and Technology Group at the Idaho National Laboratory and member of the PRiME OrgaThe Electrochemical Society Interface • Winter 2020 • www.electrochem.org
nizing Committee. Featured speakers included Hidetaka Nishikori, of the New Energy and Industrial Technology Development Organization (NEDO), presenting “R&D Acti-vities of Next Generation Batteries in National ProjBor Yann Liaw Hidetaka Nishikori ects of NEDO”; Chang Hwan Kim, from Hyundai Motor Company, presenting “The Journey towards a Sustainable Mobility: Electrification”; and Sunita Satyapal, at the United States Department of Energy, presenting “U.S. DOE Hydrogen and Fuel Chang Hwan Kim Sunita Satyapal Cell Technologies Office E2S discussion panel. Perspectives.” Throughout the presentations, panelists responded to online participants’ questions using a digital Q&A feature.
Research Conference on Solid State Ionics. She reflected on how her work in battery research has evolved since then, particularly in nonconventional (safe) electrolytes. Nobel laureates Whittingham and Yoshino gave presentations each describing their careers, and journeys leading to the 2019 Nobel Prize in Chemistry. The online audience then participated in Shirley Meng Yang Kook Sun a live Q&A session with the speakers. The Legends of Battery Science moderators. Nobel laureates were asked what advice they’d give the newest Nobel Chemistry laureates. “What I felt most since receiving the Nobel Prize is that every one of my words now has a great impact on people. This is true of government officers, academic societies, and also industry leaders. But I felt it especially for children. The Nobel Prize is a big dream for children. After receiving the prize, I gave many lectures to school students in Japan. I was gratified that students listened to my words with their eyes shining. They saw the very great joy of receiving the award. So to this year’s laureates, I say, please give children dreams,” said Yoshino.
Legends of Battery Science: A Celebration with M. Stanley Whittingham and Akira Yoshino This very special event celebrated Prof. Dr. M. Stanley Whittingham and Prof. Dr. Akira Yoshino, pioneers of the lithium ion battery, who shared the 2019 Nobel Prize in Chemistry. Dr. Shirley Meng, M. Stanley Akira Yoshino, newly-elected Chair Whittingham, recipient of the of the ECS Battery recipient of the 2019 Nobel Prize Division and the Zable 2019 Nobel Prize in Chemistry. Chair Professor in in Chemistry. Energy Technologies in the Department of NanoEngineering at the University of California, San Diego, and Dr. Yang Kook Sun, Professor at Hanyang University in South Korea, served as moderators. The event began with a surprise video of Whittingham’s friends, colleagues, and students wishing him a very happy birthday. Featured speakers included Maria Forsyth of Deakin University, presenting “Future Electrolyte Systems for Safer, High Energy Density Batteries”; and Jun Liu of Pacific Northwest National Laboratory, presenting “Leading the Path for Energy Storage.” Liu described his friendship with Whittingham and praised his admirable character: beloved teacher, excellent role model, gentleman, true friend, family man, and much more. Forsyth also spoke Jun Liu Maria Forsyth about Whittingham and how they first met Legends of Battery Science featured speakers. in 1990 at the Gordon
Legends of Battery Science event speakers answer online participants’ questions in a Q&A session.
Whittingham reflected on the impact of the current global pandemic on the Nobel ceremony. “It’s difficult for us to give them advice because Akira and I had this great experience in Stockholm and after. (I am) not sure there will be a Stockholm experience this year, so their life will be very different from ours. But ours is something we will never forget—from the moment we got on the plane in New York, to when we got back home, and everything that’s happened since. I am not sure how they are going to do anything this year; it is going to be very difficult.” Lastly, ECS CEO and Executive Director Christopher Jannuzzi closed the night by awarding ECS Honorary Memberships to Whittingham and Yoshino. “Honorary membership in the ECS was established in 1919 to recognize seminal contributions to The Electrochemical Society. Thomas Edison was one of the first ECS Honorary Members. Since then the list has slowly grown to include other luminaries in our (continued on next page)
ECS CEO and Executive Director Christopher Jannuzzi presents Prof. Dr. M. Stanley Whittingham and Prof. Dr. Akira Yoshino with ECS Honorary Memberships.
The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
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field such as Prof. John B. Goodenough, co-recipient of the 2019 Nobel Prize for Chemistry. As we have heard tonight, the careerlong contributions of Prof. Whittingham and Dr. Yoshino are as vital and impactful as any in the 20th or 21st centuries, and there is no doubt they too have earned the highest honor ECS can bestow on its members,” said Jannuzzi. “Therefore, on behalf of the ECS Board of Directors and all the Society’s members, it is my great pleasure to confer on you both Honorary Membership in The Electrochemical Society!”
Awards and Recognition
• The Battery Division Technology Award was presented to Yong Yang of Xiamen University. • The Battery Division Technology Award was presented to Jie Xiao of Pacific Northwest National Laboratory. • The Battery Division Research Award was presented to Hubert Gasteiger of the Technical University of Munich. • The Battery Division Postdoctoral Associate Research Award Sponsored by MTI Corporation and the Jiang Family Foundation was presented to Marco-Tulio F. Rodrigues of Argonne National Laboratory. • The Battery Division Postdoctoral Associate Research Award Sponsored by MTI Corporation and the Jiang Family Foundation was presented to David Hall of the University of Cambridge. • The Battery Division Student Research Award Sponsored by Mercedes-Benz Research & Development was presented to Julian Self of the University of California, Berkeley. • The Battery Division Student Research Award Sponsored by Mercedes-Benz Research & Development was presented to Matthias Künzel of Helmholtz Institute Ulm and Karlsruhe Institute of Technology. • The Corrosion Division H. H. Uhlig Award was presented to Nick Birbilis of the Australian National University. • The Corrosion Division Morris Cohen Graduate Student Award was presented to Chao (Gilbert) Liu of Shell Technology Center. • The Electrodeposition Division Research Award was presented to Daniel Josell of the National Institute of Standards and Technology. • The Electrodeposition Division Early Career Investigator Award was presented to Trevor Braun of the National Institute of Standards and Technology. • The Energy Technology Division Supramaniam Srinivasan Young Investigator Award was presented to Christopher Hahn of SLAC National Accelerator Laboratory. • The High Temperature Materials Division Outstanding Achievement Award was presented to Mogens Mogensen of DTU Energy, Technical University of Denmark. • The Industrial Electrochemistry and Electrochemical Engineering Division Student Achievement Award was presented to Saket Bhargava of the University of Illinois at Urbana-Champaign. • The Industrial Electrochemistry and Electrochemical Engineering Division H. H. Dow Memorial Student Achievement Award was presented to Zhongyang Wang of the Illinois Institute of Technology.
Photo: Eric de Vries
ECS celebrated researchers’ great achievements in electrochemistry and solid state science by recognizing Society award winners, including PRiME Student Poster Awards, as well as ECS Society, Division, Section, and Chapter Awards, Toyota Fellowships, and more. Five Society awards were presented. The Charles W. Tobias Young Investigator Award—established in 2003 to recognize a young scientist or engineer's outstanding scientific and/or engineering work in fundamental or applied electrochemistry or solid state science and technology—was presented to Bryan McCloskey, Associate Professor and Vice Chair of Graduate Education in the Department of Chemical and Biomolecular Engineering at the University of California, Berkeley, U.S., for his work on “Understanding Reactivity at ElectrodeElectrolyte Interfaces in Li-O2 and Li-ion Batteries.” The Edward Goodrich Acheson Award—established in 1928 to recognize distinguished contributions to the advancement of any of the objects, purposes, or activities of ECS—was presented to Esther Takeuchi, SUNY Distinguished Professor and William and Jane Knapp Chair in Energy and the Environment at Stony Brook University, U.S., for her work on “From Medical Applications to the Environment: The Important Role of Electrochemical Energy Storage.” The Vittorio de Nora Award—established in 1971 to recognize distinguished contributions to the field of electrochemical engineering and technology—was presented to Hubert Gasteiger, Appointed Chair of Technical Electrochemistry at the Technical University of Munich, Germany, for his work on “Analysis of the Catalyst Requirements with Regards to Catalyst Structure and Catalyst Durability Studies for PEM Water Electrolysis.” The Norman Hackerman Young Author Award—for the best paper published in the Journal of The Electrochemical Society (JES) by a young author or co-authors for the volume year preceding the award—was presented to Takanori Akita, PhD student at the Tokyo University of Science, Japan, for his paper, “Behavior of Additives in Copper Electroplating Using a Microfluidic Device.” The Bruce Deal & Andy Grove Young Author Award—established in 2013 to recognize the best paper published in the ECS Journal of Solid State Science and Technology (JSS) by a young author or co-authors for the volume year preceding the award—was presented to Takashi Matsumae, PhD in Engineering from the University of
Tokyo, Japan, for his paper, “Direct Bonding of an Electroformed Cu Substrate and Si Chip at Room Temperature in Atmospheric Conditions.” Twenty division awards and section awards were presented over the course of the meeting:
Bryan McCloskey, recipient of the Charles W. Tobias Young Investigator Award.
Esther Takeuchi, recipient of the Edward Goodrich Acheson Award.
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Hubert Gasteiger, recipient of the Vittorio de Nora Award.
Takanori Akita, recipient of the Norman Hackerman Young Author Award.
Takashi Matsumae, recipient of the Bruce Deal & Andy Grove Young Author Award.
The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
• The Luminescence and Display Materials Division Centennial Outstanding Achievement Award was presented to Kazuyoshi Ogasawara of Kwansei Gakuin University. • The Physical and Analytical Electrochemistry Division Max Bredig Award In Molten Salt and Ionic Liquid Chemistry was presented to Sheng Dai of Oak Ridge National Laboratory. • The Sensor Division Outstanding Achievement Award was presented to Shekhar Bhansali of Florida International University. • The Sensor Division Outstanding Achievement Award was presented to Nianqiang (Nick) Wu of the University of Massachusetts Amherst. • The Europe Section Alessandro Volta Medal was presented to Martin Winter of the Institute of Physical Chemistry at the University of Münster.
General Student Poster Session The General Student Poster Session included 237 posters. The session’s award winners are: 1st Place: $1,500 cash award–Jong Hwa Kim, Kyung Hee University “Feasibility of LiNbO3 Surface Coating on High-Ni Layered Cathode Materials for Lithium Ion Batteries” 2nd Place: $1,000 cash award–Ryota Takai, Kyoto University “Molybdenum Electroplating Using Concentrated Chloride Aqueous Solution” 3rd Place: $500 cash award–Yuya Takekuma, Tokyo University of Science “Increased Light Harvesting in Photosystem 1-Based Biophotovoltaics with Artificial Antenna” ECS thanks the following individuals who served as judges for the PRiME 2020 Z01 General Student Poster Session: • Alice Suroviec, Berry College • Adriana Ispas, Technische Universität Dresden • Colm O’Dwyer, University College Cork • Chengcheng Fang, Michigan State University • Feng Lin, Virginia Polytechnic Institute and State University • Futoshi Matsumoto, Kanagawa University • Sadagopan Krishnan, Oklahoma State University • Masanori Hara, Toyota Technological Institute • Andrew C. Hillier, Iowa State University • Hisakage Funabashi, Hiroshima University • Yoshinao Hoshi, Nagoya Institute of Technology • Hiroshi Imahori, Kyoto University • Shinsuke Inagi, Tokyo Institute of Technology • Etsuro Iwama, Tokyo University of Agriculture and Technology • Yoshiyuki Kuroda, Yokohama National University
First Place Z01 General Student Poster Session award winner, Jong Hwa Kim.
Second Place Z01 General Student Poster Session award winner, Ryota Takai.
• Masanobu Matsuguchi, Ehime University • Masanori Hayase, Tokyo University of Science • Masatsugu Morimitsu, Doshisha University • Kohei Miyazaki, Kyoto University • Kazuyoshi Ogasawara, Kwansei Gakuin University • Azusa Ooi, Tokyo Institute of Technology • Yuji Okuyama, University of Miyazaki • Petr Vanýsek, Northern Illinois University • Michelle A. Rasmussen, Lebanon Valley College • Shinji Nohara, University of Yamanashi • Soshi Shiraishi, Gunma University • Hitoshi Takamura, Tohoku University • Tetsu Tatsuma, University of Tokyo • Toshiki Nokami, Tottori University • Tsuyoshi Tanaka, Tokyo University of Agriculture and Technology • Tetsuya Tsuda, Osaka University • Vito Di Noto, Università degli Studi di Padova • Wu Xu, Pacific Northwest National Laboratory • Yong-Tae Kim, Pohang University of Science and Technology • Taeeun Yim, Incheon National University
Sponsors and Exhibitors Special thanks to the meeting’s sponsors and exhibitors, whose support and participation directly contributed to the success of the meeting. Thank you for developing the tools and equipment driving scientific advancement, sharing your innovations with the electrochemical and solid state communities, and providing generous support for PRiME 2020. PRiME 2020 – General Meeting Sponsors Platinum SK innovation Gold Samsung SDI Silver Ion Power, Inc. LG Chem Scribner Bronze National Tsing Hua University Contributing MDPI – Publisher of Open Access Journals Chemosensors Sensors Materials
Third Place Z01 General Student Poster Session award winner, Yuya Takekuma.
The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
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CA NDIDAT ES FOR SOCIE T Y OFFICE The following are biographical sketches and candidacy statements of the nominated candidates for the annual election of ECS officers.
Candidate for President
Candidates for Third Vice President
Eric Wachsman is Maryland Energy Innovation Institute Director and the Crentz Centennial Chair in Energy Research with appointments in both the materials science and chemical engineering departments at The University of Maryland. Prior to Maryland, he was the Rhines Chair Professor in Materials Science at the University of Florida and a senior scientist at SRI International. He received his PhD in materials science from Stanford University in 1990, and MS and BS degrees in chemical engineering from Stanford and the University of California, Berkeley, respectively. His research is focused on solid ion-conducting materials and electrocatalysts, including the development of solid state batteries, solid oxide fuel cells and electrolysis cells, ion-transport membranes, and solid state gas sensors, with over 270 publications and 35 patents/ patent applications, and to date, three companies have been founded based on these technologies. Dr. Wachsman has contributed to the next generation of electrochemists, having graduated 34 PhD and 30 MS students, supervised 38 postdocs and research scientists, and mentored several junior faculty, of which three have gone on to receive ECS awards. His involvement with students includes founding and serving as faculty advisor for ECS student chapters at both the University of Florida and The University of Maryland, with the Maryland chapter winning Outstanding ECS Student Chapter Awards in 2013 and 2017, and ECS Student Chapter of Excellence in 2014, 2015, and 2016. He is a fellow of The Electrochemical Society (2008) and The American Ceramic Society (2012) and an elected member of the World Academy of Ceramics (2017). He is the recipient of the 2017 Carl Wagner Memorial Award (ECS), the 2014 Sir William Grove Award (IAHE), the 2014 Pfeil Award (IOM3), the 2012 Fuel Cell Seminar & Energy Exposition (FCS&E) Award, and the 2012 High Temperature Materials Division Outstanding Achievement Award (ECS). Dr. Wachsman joined ECS as a graduate student in 1989 to present a paper for the first
Peter Mascher obtained a PhD in engineering physics in 1984 from the Technische Universität Graz (TUG) in Austria and in 1989 joined McMaster University in Hamilton, Ontario, Canada. He is a professional engineer and a professor in the Department of Engineering Physics and chaired the department from 1994 to 2000. From 2003 to 2014, he served as Associate Dean (Research and External Relations), Faculty of Engineering, and since 2014 he is overseeing McMaster’s international portfolio as Vice-Provost, International Affairs. He is a fellow of The Canadian Academy of Engineering and The Electrochemical Society. Mascher holds the William Sinclair Chair in Optoelectronics and leads active research groups involved in the fabrication and characterization of thin films for optoelectronic applications, the development and application of silicon-based nanostructures, and the characterization of defects in solids by positron annihilation spectroscopy. His research work has been continuously funded for more than 30 years by the Natural Sciences and Engineering Research Council of Canada (NSERC) and has drawn funding from the Canada Foundation for Innovation (CFI), several federal and provincial Centres of Excellence, and industry, for a lifetime total surpassing $25M. He has supervised more than 85 graduate students and postdoctoral fellows, has authored or co-authored close to 250 publications in peer-reviewed journals and conference proceedings, and has presented many invited lectures at international conferences and workshops. From 2003 to 2007, he served as the program director of the Ontario Photonics Consortium, at the time the largest ever Ontario-funded project. I have been an active member of ECS for the past 30-plus years, initially as a participant and presenter at the biannual ECS meetings. Over the years, I have organized and co-organized close to 20 topical symposia and initiated in 2010 (together with David Lockwood) the International
Colm O’Dwyer is a professor of chemical energy in the School of Chemistry at the University College Cork (UCC) in Ireland, and principal investigator at Tyndall National Institute, the Environmental Research Institute, and the Advanced Materials and BioEngineering Research Centre. He received his PhD with Prof. D. Noel Buckley in 2003 on semiconductor electrochemistry and physics and conducted postdoctoral research on ultracold atom cooling and surface science in Toulouse, France. Since 2008 a Science Foundation Ireland Stokes Lecturer on Nanomaterials, he now (2012-present) leads a multidisciplinary research group at UCC developing 3D printed batteries, energy storage materials, optoelectronic materials and processes, and photonic structures. His current research interests include 3D printed energy storage devices and real-time photonics for examining optoelectronic materials and battery materials. He is a fellow of the Institute of Physics. In 2017, he was one of the recipients of the Bell Labs Prize. With talented students, postdocs, and collaborators, Prof. O’Dwyer has coauthored over 230 peer-reviewed articles (27 in JES/JSS), numerous book chapters, and 60 ECS Transactions articles over the years, covering most of the technical interest areas of the Society. O’Dwyer has been an ECS member for nearly 20 years. It began in 2001 after attending the 199th ECS Meeting in Washington, D.C., as a graduate student. Since that meeting, he has served ECS continuously in many roles. He has organized or co-organized over 35 ECS symposia in electrochemical and solid state topics since 2007, and through the Interdisciplinary Science & Technology Subcommittee, helped deliver new mega-symposia across several ECS divisions. He has served the Electronics and Photonics Division as an Executive Committee Member for over 12 years, and more recently, as First Vice-Chair and then as Division Chair. He has served the Society on several key committees and as a member of the Board of Directors. As an award-winning advocate of open access publication, he has also guest edited four special focus
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Statement of Candidacy
The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
Eric Wachsman (continued from previous page)
International Symposium on Solid Oxide Fuel Cells (SOFC-I), and quickly became active in ECS, organizing 16 symposia and serving on numerous ECS committees. (He currently is lead organizer for SOFCXVII, July 2021.) He rose through the ECS High Temperature Materials Division (now H-TEMP) Executive Committee, chairing the division in 2006, and continued to chair society committees, including the Interdisciplinary Science & Technology Subcommittee, through to his election as ECS Vice President in 2018. As a result, he served on the ECS Board of Directors in 2006-2007 and continually from 2013 through today.
Statement of Candidacy
I have been an active member of ECS at both the division and society levels and am proud to have served multiple terms on the Board of Directors. My involvement has given me an understanding of the Society’s operations, successes, and the challenges ahead. Importantly, it has also provided me with an understanding of ECS’s role in supporting its members, the advancement of science, and our contributions to society at large. We live in a rapidly changing world with major societal issues, such as the availability of affordable and sustainable energy, clean water and air, food, and in this last year especially, health. The solutions to these issues are at the nexus of science and technology and becoming more electrochemical in nature. As such, developing symposia that address these grand challenges has been the focus of my efforts as Interdisciplinary Science & Technology Subcommittee Chair and since my election in 2018 as ECS Vice President. ECS as a scientific society also faces challenges of the uncertainty of hosting live meetings, declining membership, competition for our publications, and many of our members face challenges in obtaining adequate research funding, which could be exacerbated by the economic impact of COVID-19. Therefore, if elected ECS President, my goals would be to continue to expand ECS participation in addressing major societal issues, but also to provide the best possible benefits to our members. We as a scientific society need to not only Free the Science but also partner with our sister societies to Stand Up for Science. We are not policymakers, but we should make every effort to ensure that policymakers base their decisions utilizing the best available science. Wearing a mask and social distancing under the current pandemic, while an inconvenience, should be a societal norm and not a political issue. Moreover, we should invite more policymakers and funding agency
representatives to ECS meetings to provide an opportunity for dialogue and an opportunity for our members to learn of new funding opportunities and trends. We need to continue to increase the impact and maintain the reputation for quality of ECS publications, and give greater free access as a membership benefit. Moreover, our student members are the future of our society, and every effort must be made for them to decide, such as I did over 30 years ago, to make ECS their scientific home. Peter Mascher (continued from previous page)
Symposium on Nanoscale Luminescent Materials, now in its seventh edition. In 2005, I joined the governing body of the DS&T division, became Awards Chair in 2010, and then moved through Secretary to Vice-Chair, and, currently, Division Chair. Since 2017, I have served as a technical editor for the ECS Journal of Solid State Science and Technology (JSS). I greatly value the strong multi- and interdisciplinary flavor of the ECS meetings. If elected, I would work with the ECS Board to preserve the wide range of topics while exploring avenues to streamline the meeting programs. The current COVID-19 pandemic has forced us to implement dramatic changes to how meetings are conducted. We need to make sure that we remain open to adopting new modalities of scientific interaction even in a post-pandemic environment. One of the drivers undoubtedly will be considerations of the environmental footprint of largescale travel. New hybrid modalities also will allow us to expand the reach of our meetings to non-traditional and under-represented constituencies, thereby addressing a key aspect of the drive towards equity, diversity, and inclusion. Input and feedback from the wider ECS membership will be critical in accomplishing this task. ECS meetings also are highly international, which makes them very attractive for graduate students and early career researchers, as they provide a forum for information exchange, the development of collaborations, and gaining greater global awareness. It will be important to continue to provide support for students to participate in the meetings and to highlight their accomplishments. Throughout the years, I have always looked forward to adjudicating the student poster competitions and have tremendously enjoyed my conversations with the presenters. In my function as one of the technical editors of JSS, I have come to appreciate the often extraordinarily high quality of the submissions to the journal, which is reflected in the steadily increasing impact factors. If elected, I would remain interested in enhancing the quality of ECS
The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
publications and work with the board and the journal editors on the establishment of new thematically focused journals. In the current climate of science skepticism, even greater emphasis needs to be placed on the Free the Science initiative to maintain and enhance ECS’s societal impact. In summary, I would be honored to serve as ECS Vice President, in a collegial and inclusive manner and with a strong focus on attracting new members from among early career researchers, students, and underrepresented groups. This, together with highly interdisciplinary biannual meetings and strong and widely accessible journals, will ensure a vibrant and relevant society for years to come. Colm O’Dwyer (continued from previous page)
issues for JES and JSS on semiconductor electrochemistry, thermoelectrics, and 2D materials and devices.
Statement of Candidacy
One of ECS’s many strengths is the diversity in the community we see at each meeting, committee, division, and in the pages of our journals, magazine, blog, and social networks. Our meetings each year showcase the multidisciplinarity and collegiality that makes this Society a premier venue to advance electrochemical and solid state science and technology. ECS is a non-profit organization that exists for its members and the wider community to disseminate the advances that so many people make for the sake of a better, healthier, safer, and greener future. Disseminating this know-how is a keystone of our mission. The Free the Science initiative is a visionary approach to open access publication, and ECS set the bar in accessibility for authors and readers. My commitment to all members is to lead ECS to maximize accessibility to all authors across academia and industry R&D, especially early career researchers, industry professionals, and underrepresented groups, so that the science and technology showcased by ECS is diverse beyond standard metrics. Our world changed in 2020 due to the COVID-19 pandemic, and the way our community interacts, works, and shares knowledge may have changed forever in some ways. The success of the online element of our PRiME Meeting in 2020 was very encouraging and provided ECS with wonderful opportunities to broaden accessibility and engagement, especially where meeting attendance is difficult for many. If elected as ECS Vice President, I am committed to lead ECS with your support, to adapt our engagement to a larger community worldwide. We often say our children’s future (continued on next page) 15
CAFOR NDIDAT ES T FOR SOCIE (continue T Y OFFICE CA NDIDAT ES SOCIE Y OFFICE d) Colm O’Dwyer (continued from previous page)
motivates everything, and it takes a village to raise a child. This is true within ECS, and my responsibility as part of the leadership is to provide the platform for our younger colleagues. In disseminating knowledge and core values, I plan to put in place strategies to boost social media interactions and the methods of communication of our student
members, who are the future leaders in our Society and society in general. As vice president, I will advocate for programs to elevate our STEM education and outreach in all its forms, science communication, and the attractiveness of our journals, that mesh with the professional culture of our younger members and established members alike. If elected as our vice president, I pledge to engage with our divisions, other societies, funding agencies, policymakers, and our
student chapters to ensure the diversity in our people and programs grow and thrive. It is an honor to be nominated, and if elected, my professional and personal pledge is to serve ECS and the interest of all divisions, you, the members, and our wider community to bolster engagement and governance so that we are resilient in the coming few years. Thank you for considering my candidacy.
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ORCID
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Join ORCID today and become part of the solution. The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
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SOCIE T Y NE WS
ECS Implements Single Sign-On With the completion of the year-long project to implement Single Sign-On (SSO), the electrochemical and solid state community can now log in to the ECS website with just one set of credentials and have access to all ECS-approved applications and websites without having to log in again. SSO simplifies username and password management while improving identity protection, decreasing “password fatigue.” A critical step in the project was integrating ORCID iD across ECS platforms, ScholarOne, and ECSarXiv. Members can now link their ORCID iD—the platform researchers use to share information on a global scale—to their membership profile. While accessing ORCID requires an additional sign in, the same credentials as their ECS My Account can be used. ScholarOne—IOPP’s article submission system—uses ORCID as a sign-on option, so including ORCID as part of a members’ profile eliminates having to remember multiple login names/passwords. “Implementing SSO provides our community with the kinds of critical linkages that help make work more efficient and effective—a crucial service provided by the Society—and helps ECS as an organization continues to ‘punch above our weight,’” said Chris Jannuzzi, ECS Executive Director and CEO. “As of January 2, 2020, Society members gained instant access to ECS content when they joined or renewed their membership. No more waiting! In addition, members no longer need to use tokens to use their 100 free downloads. After logging on, no extra steps are required to visit various articles. This is a great step forward for our community,” said Shannon Reed, ECS Director of Community Engagement. “ORCID has become an important aspect of the scholarly publishing digital infrastructure in providing researchers with a persistent identifier globally. The importance of ORCID is evident, with the organization closing in on the milestone of 10 million ORCID iDs and key stakeholders across scholarly research embracing integration into their systems and workflow. I’m thrilled that we executed a broader integration within the Society and use of ORCID across ECS’s platforms,” said Beth Craanen, Director of Publications. In addition, only one name/password is required for ECS volunteer leaders and staff to access symposia planning, travel grants, awards,
and membership applications. The same is true for job seekers and employers accessing the ECS Career Center. Login for PRiME 2020 was also integrated with The Conference Exchange Online & Onsite Event Management Software (Confex), allowing for single sign-on.
How ECS SSO Works • Go to www.electrochem.org and click “Login” at the top of the screen. • This takes you to the new Login screen. Enter your email and password. • The SSO system checks whether you have been authenticated. • If yes, you are given access to the site. • If you are new to the SSO system, click “ALLOW” to log in to your ECS My Account. • This takes you to your ECS My Account page, where you can access and/or update any of your account information. • Click “Link my ORCID Account” to go to ORCID and link ORCID to your My Account page. • Meanwhile, the SSO system is requesting authentication from the identity provider or authentication system. • When your identity is verified, SSO passes your authentication data to the website and returns you to that site. • Alternatively, you can select items from the Resources menu. You are now approved for SSO login and do not need to log in again. • After the initial authenticated login, the site passes authentication verification data with you as you move through the site, verifying that you are authenticated each time you go to a new page—without you having to reinput your login information. Please contact customerservice@electrochem.org regarding difficulties with the SSO login process.
Early Career Membership Pilot Program Postgraduate work early career professionals, or those coming from non-traditional fields, are a critical component of the ECS community. In May 2020, the Individual Membership Committee approved a pilot Early Career Membership program to help them transition smoothly into careers and ECS membership. Early Career Membership will be offered at only $70, almost half the cost of regular membership. The value that the Society brings to early career members does not stop at ECS meetings. Members access the following resources that help build long lasting, successful careers. • ECS Digital Library with more than 160,000 articles and abstracts—and 100 free downloads. • ECS Career Center, which connects job seekers with employers and great jobs. • Education programs affordably priced and tailor-made to sharpen employment skills. • Honors, Awards, Fellowships, & Travel Grants that recognize excellence—and enhance resumes.
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• Deep discounts on ECS biannual meetings, educational programming, products and services, and publications such as Monographs and ECS Transactions. • Publication assistance, including a 75 percent discount on each open access Article Processing Charge (APC), ScholarOne (a comprehensive workflow-management system for scholarly journals), editorial feedback, and more.
William Mustain, Professor of Chemical Engineering at the University of South Carolina and Chair of the Individual Membership Committee, said about the pilot program, “One of the things that our committee is most passionate about is engaging with young professionals and showing them how ECS and ECS members like us can be an invaluable resource as they start their careers. I personally could not imagine where my career would be without this community.” The committee will collect data on the pilot program through the year. After that, a recommendation will be sent to the board about whether the Early Career Membership program should become permanent. The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
SOCIE T Y NE WS
The ECS Toyota Young Investigator Fellowship The ECS Toyota Young Investigator Fellowship is a partnership between The Electrochemical Society and Toyota Research Institute of North America (TRI-NA), a division of Toyota Motor Engineering & Manufacturing North America, Inc. (TEMA). Through this program, ECS and Toyota promote innovative and unconventional technologies borne from electrochemical research. The fellowship encourages young professors and scholars to pursue innovative electrochemical research in green energy technology. Almost $900,000 in fellowships has been awarded to 19 scientists since the program was founded in 2014. ECS thanks Toyota for its support and visionary investment in green energy technology innovations.
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This fellowship enables the Hall group to utilize fundamental science for creating a greener world.
”
—A. Shoji Hall, PhD
The ECS Toyota Young Investigator Fellowship Recipients 2020-2021 A. Shoji Hall Assistant Professor, Johns Hopkins University “Engineering of Electrified Platinum/Ionic Liquid Interfaces Enables High Performance Oxygen Reduction Electrocatalysis”
Piran Ravichandran Kidambi Professor, Vanderbilt University
Haegyeom Kim Lawrence Berkeley National Laboratory
“Atomically Thin Membranes for Advanced Next-Generation Fuel Cells”
“Development of New Nitrides-Based Lithium Conductors for All-SolidState Batteries”
2019-2020
Nemanja Danilovic Lawrence Berkeley National Laboratory
Neil Dasgupta Professor, University of Michigan
Kelsey Hatzell Professor, Vanderbilt University
“Emerging Interfacial Phenomena at Pt@C/ ionomer Interface at 120C and Anhydrous Conditions”
“Multi-Modal Operando Analysis of LithiumSolid Electrolyte Interfaces”
“Tracking Ion Transport Pathways and Hybrid Solid Electrolytes”
Jennifer L. Schaefer Professor, University of Notre Dame
Zhenhua Zeng Research Scientist, Purdue University
“Use of Liquid-Free, Deformable Electrolytes in Lithium Metal Batteries with Porous Anodes”
“Towards Overcoming Scaling Rules and Durability Challenges of Low-PGM ORR Catalysts”
APPLICATIONS FOR THE 2021-2022 TOYOTA FELLOWSHIP ARE DUE BY JANUARY 31, 2021. For more information, please contact Mr. Shannon C. Reed, MBA, ECS Director of Community Engagement, via email at Shannon.Reed@electrochem.org. The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
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ECS Journals Current and Upcoming Focus Issues Journal of The Electrochemical Society (JES)
READ ONLINE
NOW IN PRODUCTION
2D Layered Materials: From Fundamental Science to Applications
International Meeting on Chemical Sensors (IMCS) 2020 – Volume One
Organic and Inorganic Molecular Electrochemistry
Selected Papers of Invited Speakers to IMLB 2020
Technical Editor: David Cliffel Guest Editors: Wolfram Jaegermann, Zia Karim, Yaw Obeng, Colm O’Dwyer
Technical Editor: Janine Mauzeroll Collaborating Technical Editor: John Harb Guest Editors: Jean-Paul Lumb, Song Lin, Sylvain Canesi, Matthew Graaf
Technical Editor: Ajit Khosla Guest Editors: Peter Hesketh, Steve Semancik, Udo Weimar, Yasuhiro Shimizu, Joseph Stetter, Gary Hunter, Joseph Wang, Xiangqun Zeng, Sheikh Akbar, Muthukumaran Packirisamy, Rudra Pratap Technical Editor: Doron Aurbach Associate Editors: Thierry Brousse, Scott Donne, Brett Lucht, Venkat Srinivasan, Nae-Lih (Nick) Wu
Proton Exchange Membrane Fuel Cell & Proton Exchange Membrane Water Electrolyzer Durability Technical Editor: Xiao-Dong Zhou Guest Editors: Jean St-Pierre, Deborah Myers, Rodney Borup, Katherine Ayers
ACCEPTING SUBMISSIONS Characterization of Corrosion Processes in Honor of Philippe Marcus
Recent Advances in Chemical and Biological Sensors & Micro-Nanofabricated Sensors and Systems
Molten Salts and Ionic Liquids II
Future of Intercalation Chemistry for Energy Storage and Conversion in Honor of M. Stanley Whittingham
Technical Editor: Gerald S. Frankel Guest Editors: Dev Chidambaram, Koji Fushimi, Vincent Maurice, Vincent Vivier Deadline: January 6, 2021 Technical Editor: David Cliffel Guest Editors: David P. Durkin, Paul C. Trulove, Robert A. Mantz Deadline: January 13, 2021
UPCOMING Solid Oxide Fuel Cells (SOFCs) and Electrolysis Cells (SOECs) Technical Editor: Xiao-Dong Zhou Guest Editors: Eric Wachsman, Subash Singhal Submissions Open: April 8, 2021 Deadline: July 29, 2021
18th International Meeting on Chemical Sensors (IMCS) – Volume Two
Technical Editor: Ajit Khosla Associate Editors: Michael Adachi, Netz Arroyo, Thomas Thundat Deadline: February 17, 2021
Technical Editor: Doron Aurbach Associate Editor: Brett Lucht Guest Editors: Louis Piper, Shirley Meng Deadline: March 3, 2021
Visit
www.electrochem.org/focusissues • Calls for upcoming JES and JSS focus issue papers • Links to published issues • Future focus issue proposals
Technical Editor: Ajit Khosla Guest Editors: Peter Hesketh, Steve Semancik, Udo Weimar, Yasuhiro Shimizu, Joseph Stetter, Gary Hunter, Joseph Wang, Xiangqun Zeng, Sheikh Akbar, Muthukumaran Packirisamy, Rudra Pratap Submissions Open: May 6, 2021 Deadline: August 4, 2021 20
The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
ECS Journals Current and Upcoming Focus Issues ECS Journal of Solid State Science and Technology (JSS)
READ ONLINE 2D Layered Materials: From Fundamental Science to Applications
Solid-State Materials and Devices for Biological and Medical Applications II
Technical Editor: Fan Ren Guest Editors: Yu-Lin Wang, Toshiya Sakata, Zong-Hong Lin, Wenzhuo Wu
Technical Editor: Peter Mascher Guest Editors: Wolfram Jaegermann, Zia Karim, Yaw Obeng, Colm O’Dwyer
NOW IN PRODUCTION
Porphyrins, Phthalocyanines, and Supramolecular Assemblies in Honor of Karl M. Kadish
Technical Editor: Fan Ren Associate Editor: Meng Tao Guest Editors: Hiroki Hamada, Thad Druffel, Jae-Joon Lee
Technical Editor: Francis D’Souza Guest Editors: Dirk Guldi, Robert Paolesse, Tomas Torres
Photovoltaics for the 21st Century
ACCEPTING SUBMISSIONS Solid State Reviews
Technical Editors: Ajit Khosla Contributing Technical Editors: Jennifer Bardwell, Francis D’Souza, Peter Mascher, Kailash C. Mishra, Fan Ren Associate Editors: Michael Adachi, Netz Arroyo, Thomas Thundat, Meng Tao Guest Editors: Sheng-Joue Young, Zhenhuan Zhao, Sandeep Arya, Sajjad Husain Mir, Kumkum Ahmed, MD Nahin Islam Shiblee Deadline: December 30, 2020
4D Materials and Systems + Soft Robotics
Technical Editor: Ajit Khosla Associate Editors: Michael Adachi, Netz Arroyo Guest Editors: Hidetmisu Furukawa, Koh Hosoda, Sheng-Joue Young, Zhenhuan Zhao, Tsukasa Yoshida, Yoon Hwa, Sathish K. Sukumaran, Masahiro Shimizu, Jessica E. Koehne Deadline: February 3, 2021
Visit
www.electrochem.org/submit • JES manuscript submissions • JSS manuscript submissions
Photovoltaics for the 21st Century II
Technical Editor: Fan Ren Associate Editor: Meng Tao Guest Editors: Jae-Joon Lee, Doo-Hyun Ko, Yoonmook Kang, Hyeok Kim Deadline: March 10, 2021
Semiconductor Wafer Bonding: Science, Technology, and Applications Technical Editor: Jennifer Bardwell Guest Editors: Roy Knechtel, Chuan Seng Tan, Tadatomo Suga, Helmut Baumgart, Frank Fournel, Mark Goorsky, Karl D. Hobart Deadline: March 17, 2021
UPCOMING Solid State Electronic Devices and Materials
Technical Editor: Fan Ren Guest Editors: Chao-Sung Lai, Chia-Ming Yang, Yu-Lin Wang Submissions Open: January 28, 2021 Deadline: April 28, 2021
www.electrochem.org/focusissues The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
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Institutional Member
spotlight New 2020 Institutional Member The Electrochemical Society welcomes Pacific Northwest National Laboratory (PNNL) to the elite group of ECS Institutional Members.
Institutional Members: It’s time to renew! To ensure that your benefits and community support continue uninterrupted, renew your membership before the end of 2020. Don’t lose your discounts on print and digital advertising, and sponsoring and exhibiting at ECS biannual meetings—along with providing academic, government, and industry partners with access to critical research and the ECS community. Over 300 ECS institutional member representatives enjoy all individual member benefits, including access to the ECS Digital Library and member pricing.
The Pacific Northwest National Laboratory is a U.S. Department of Energy multidisciplinary national laboratory with distinctive strengths in several research areas, including chemistry, earth sciences, and data analytics. PNNL’s research enables foundational scientific discovery, energy resiliency, and national security with objectives that include creating a secure and resilient electric power grid, reinventing chemical catalysts and catalytic processes, and accelerating scientific discovery via data analytics and simulation at extreme scales. (www.pnnl.gov)
Be the Next Leader Contact Anna.Olsen@electrochem. org to inquire about the benefits of institutional membership for your organization.
CONTACT
Anna.Olsen@electrochem.org today to renew your institutional membership or learn about institutional membership benefits for your organization.
For more information you also can visit:
www.electrochem.org/leadership-circle
UPCOMING ECS SPONSORED MEETINGS In addition to the ECS biannual meetings and ECS satellite conferences, ECS, its divisions, and sections sponsor meetings and symposia of interest to the technical audience ECS serves. The following is a partial list of upcoming sponsored meetings. Please visit the ECS website (www.electrochem.org/upcoming-meetings/) for a list of all sponsored meetings.
2021 • 239th ECS Meeting with the 18th International Meeting on Chemical Sensors (IMCS) May 30-June 3, 2021, Hilton Chicago, Chicago, IL https://imcs2021.gatech.edu • 17th International Symposium on Solid Oxide Fuel Cells (SOFC-XVII) July 18-23, 2021, The Brewery Conference Center, Stockholm, Sweden
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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 sponsorship@electrochem.org.
The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
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Division News Battery Division Celebrates Award Winners Prof. Roseanne Warren from The University of Utah is the 2020 recipient of the National Science Foundation (NSF) CAREER award. This award is presented by the NSF in support of junior faculty who exemplify the role of teacher-scholars through research and education and the integration of these endeavors in the context of their organizations’ missions. The award includes a federal grant for research and education activities for five consecutive years. Prof. Shirley Meng from the University of California San Diego is the 2020 recipient of The Faraday Medal from the Royal Society of Chemistry (RSC). Named after scientist Michael Faraday, the medal is awarded by the Electrochemistry Group of the RSC to honor distinguished mid-career electrochemists working outside of the United Kingdom and the Republic of Ireland for their research advancements.
Battery Division Presents Early Career Award The Battery Division is pleased to announce a new award: the ECS Battery Division Early Career Award Sponsored by Neware Technology Limited. This award recognizes and supports the development of talent and future leaders in battery and fuel cell science and technology among early-career professionals and is to encourage excellence among early career professionals in battery and fuel cell research. Candidates must be ECS members and have obtained his/her PhD within 10 years of the nomination deadline date. The 10-year timeline may be extended for special reasons (childbirth, military service, long-term illness, etc.), to be considered on a case-by-case basis. The award prize consists of an appropriately worded scroll, a $2,000 check (USD), complimentary meeting registration at the designated meeting, and the recipient may receive up to $2,000 toward travel expenses to attend the meeting. Neware Technology Limited is a leading battery testing system provider headquartered in Shenzhen, China. They have been committed to providing high-performance battery testing system since 1998.
Publisher’s Note In the summer 2020 issue of Interface, on page 26, 2020-2021 ECS Committees, Nominating Committee, featured a misspelled name. The name should read Colm O’Dwyer. ECS regrets this error.
Industrial Electrochemistry and Electrochemical Engineering Division New EIS Measurement Model Program IE&EE Division member Prof. Dr. Mark Orazem (Department of Chemical Engineering, University of Florida) and student William Watson have made their new impedance spectroscopy measurement model program available at no cost (for non-commercial use) through ECSarXiv, The Electrochemical Society’s free online service for preprints and other preliminary communications, Mark Orazem at https://ecsarxiv.org/kze9x/. Orazem began working on the program in the early 1990s. His undergraduate student, William Watson, provided the final key—using Python—to make distribution of the program viable. The measurement model is used to analyze electrochemical impedance spectroscopy (EIS) data. The measurement model installation file works with the MS Windows operating system. The program makes it possible to identify the stochastic error structure of measurements used to weight further regressions; determine what part of a measurement is inconsistent with the KramersKronig relations; and estimate capacitance and William Watson ohmic resistance, from which the characteristic frequency above which the geometry of the electrode may cause frequency dispersion can be identified. The easy-to-use program allows users to fit custom models to their data. A 130+-page reference manual, reached from the Help Tab, provides links to sample data, custom models, and Python code.
Sensor Division UNC Selected for Editors’ Choice An article by student members of the ECS Sensor Division was chosen as an American Chemical Society Editors’ Choice selection. “μ-MIP: Molecularly Imprinted Polymer-Modified Microelectrodes for the Ultrasensitive Quantification of GenX (HFPODA) in River Water” by Matthew W. Glasscott, Kathryn J. Vannoy, Rezvan Kazemi, Matthew D. Verber, and their professor, Jeffrey Dick Jeffrey E. Dick, of The University of North Carolina at Chapel Hill, was published in May 2020. They report on developing a robust, sensitive, and inexpensive sensing modality to detect the earliest onset of the contamination of surface water by per- and polyfluoroalkyl substances (PFAS)—hazardous environmental micropollutants. The article is Matthew W. available at https://pubs.acs.org/doi/abs/10.1021/ Glasscott acs.estlett.0c00341.
www.electrochem.org/ecsarxiv The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
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New Division Officer Slates New officers for the spring 2021–spring 2023 term have been nominated for the following divisions. All election results will be reported in the summer 2021 issue of Interface.
Mercury Oxide Reference Electrode Battery Development Electrochemistry in Alkaline Electrolyte All plastic construction for use where glass is attacked Stable, Reproducible Alkaline & Fluoride Media
www.koslow.com “Fine electrochemical probes since 1966”
Electronics and Photonics
Chair Jennifer Hite, Naval Research Laboratory Vice-Chair Qiliang Li, George Mason University 2nd Vice-Chair Vidhya Chakrapani, Rensselaer Polytechnic Institute Secretary Zia Karim, Yield Engineering Systems Treasurer Erica A. Douglas, Sandia National Laboratories Energy Technology
Chair William Mustain, University of South Carolina Vice-Chair Katherine Ayers, Nel Hydrogen Secretary Minhua Shao, The Hong Kong University of Science and Technology Treasurer Ahmet Kusoglu, Lawrence Berkeley National Laboratory Hui Xu, Giner, Inc. Iryna Zenyuk, University of California at Irvine Organic and Biological Electrochemistry
DID
YOU KNOW?
You can belong to more than one primary division! Join Additional Primary Divisions!
www.electrochem.org/divisions
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Chair Sadagopan Krishnan, Oklahoma State University Vice-Chair Song Lin, Cornell University Secretary/Treasurer Jeffrey M. Halpern, University of New Hampshire Physical and Analytical Electrochemistry
Chair Andrew Hillier, Iowa State University Vice-Chair Stephen Paddison, University of Tennessee Knoxville Secretary Anne Co, Ohio State University Treasurer Svitlana Pylypenko, Colorado School of Mines
The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
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ECS Division Contacts High-Temperature Energy, Materials, & Processes
Battery
Y. Shirley Meng, Chair University of California San Diego shirleymeng@ucsd.edu • 858.822.4247 (US) Brett Lucht, Vice-Chair Jie Xiao, Secretary Jagjit Nanda, Treasurer Doron Aurbach, Journals Editorial Board Representative Corrosion
James Noël, Chair University of Western Ontario jjnoel@uwo.ca • 519.661.2111 (ext. 88029) (CA) Dev Chidambaram, Vice-Chair Eiji Tada, Secretary/Treasurer Gerald Frankel, Journals Editorial Board Representative Dielectric Science and Technology
Peter Mascher, Chair McMaster University mascher@mcmaster.ca • 905.525.9140 (ext. 24963) (US) Uros Cvelbar, Vice-Chair Sreeran Vaddiraju, Secretary Zhi David Chen, Treasurer Peter Mascher, Journals Editorial Board Representative Electrodeposition
Philippe Vereecken, Chair IMED philippe.vereecken@imec.be • +32.4.741.73.110 (BE) Natasa R. Vasiljevic, Vice-Chair Luca Magagnin, Secretary Andreas Bund, Treasurer Takayuki Homma, Journals Editorial Board Representative Electronics and Photonics
Junichi Murota, Chair Tohoku University murota@riec.tohoku.ac.jp • +81.22.217.3913 (JP) Yu-Lin Wang, Vice-Chair Jennifer Hite, 2nd Vice-Chair Qiliang Li, Secretary Robert Lynch, Treasurer Fan Ren, Journals Editorial Board Representative Jennifer Bardwell, Journals Editorial Board Representative Energy Technology
Vaidyanathan Subramanian, Chair University of Nevada Reno ravisv@unr.edu • 775.784.4686 (US) William Mustain, Vice-Chair Katherine Ayers, Secretary Minhua Shao, Treasurer Xiao-Dong Zhou, Journals Editorial Board Representative
Paul Gannon, Chair Montana State University pgannon@montana.edu • 406.994.7380 (US) Sean Bishop, Sr. Vice-Chair Cortney Kreller, Jr. Vice-Chair Xingbo Liu, Secretary/Treasurer Raymond Gorte, Journals Editorial Board Representative
Industrial Electrochemistry and Electrochemical Engineering
Shrisudersan Jayaraman, Chair Corning Incorporated jayaramas@corning.com • 607.974.9643 (US) Maria Inman, Vice-Chair Paul Kenis, Secretary/Treasurer John Harb, Journals Editorial Board Representative Luminescence and Display Materials
Jakoah Brgoch, Chair University of Houston jbrgoch@central.uh.edu • 713.743.6233 (US) Rong-Jun Xie, Vice-Chair Eugeniusz Zych, Secretary/Treasurer Kailash Mishra, Journals Editorial Board Representative Nanocarbons
Hiroshi Imahori, Chair Kyoto University imahori@scl.kyoto-u.ac.jp • +81.75.383.2566 (JP) Jeffrey Blackburn, Vice-Chair Ardemis Boghossian, Secretary Slava V. Rotkin, Treasurer Francis D’Souza, Journals Editorial Board Representative Organic and Biological Electrochemistry
Diane Smith, Chair San Diego State University dksmith@mail.sdsu.edu • 619.594.4839 (US) Sadagopan Krishnan, Vice-Chair Song Lin, Secretary/Treasurer Janine Mauzeroll, Journals Editorial Board Representative Physical and Analytical Electrochemistry
Petr Vanýsek, Chair Northern Illinois University pvanysek@gmail.com • 815.753.1131 (US) Andrew Hillier, Vice-Chair Stephen Paddison, Secretary Anne Co, Treasurer David Cliffel, Journals Editorial Board Representative Sensor
Jessica Koehne, Chair NASA Ames Research Center jessica.e.koehne@nasa.gov • 650.604.6818 (US) Larry Nagahara, Vice-Chair Praveen Kumar Sekhar, Secretary Dong-Joo Kim, Treasurer Ajit Khosla, Journals Editorial Board Representative The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
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2020-2021 ECS Committees Executive Committee of the Board of Directors
Stefan De Gendt, Chair.......................................................................................President, Spring 2021 Eric Wachsman...............................................................................Senior Vice President, Spring 2022 Turgut Gur..................................................................................... Second Vice President, Spring 2023 Gerardine Botte.................................................................................Third Vice President, Spring 2024 Marca Doeff.......................................................................................................Secretary, Spring 2024 Gessie Brisard ...................................................................................................Treasurer, Spring 2022 Christopher Jannuzzi................................................................................... Term as Executive Director
Audit Committee
Christina Bock, Chair................................................................Immediate Past President, Spring 2021 Stefan De Gendt.................................................................................................President, Spring 2021 Eric Wachsman...............................................................................Senior Vice President, Spring 2021 Gessie Brisard.................................................................................................... Treasurer, Spring 2022 Robb Micek....................................................................Nonprofit Financial Professional, Spring 2022
Education Committee
James Nöel, Chair.............................................................................................................. Spring 2021 Svitlana Pylypenko............................................................................................................. Spring 2024 Paul Gannon...................................................................................................................... Spring 2024 Keryn Lian.......................................................................................................................... Spring 2021 David Hall.......................................................................................................................... Spring 2021 Vimal Chaitanya................................................................................................................. Spring 2022 Takayuki Homma................................................................................................................ Spring 2022 Walter Van Schalkwijk........................................................................................................ Spring 2023 Tobias Glossman................................................................................................................ Spring 2023 Amin Rabieri...................................................................................................................... Spring 2023 Fen Zhang.......................................................................................................................... Spring 2021 Marca Doeff.......................................................................................................Secretary, Spring 2024 William Mustain...............................................Chair, Individual Membership Committee, Spring 2023
Ethical Standards Committee
Christina Bock, Chair ...............................................................Immediate Past President, Spring 2021 Johna Leddy.................................................................................................. Past Officer, Spring 2023 Paul Natishan ................................................................................................ Past Officer, Spring 2021 Marca Doeff.......................................................................................................Secretary, Spring 2024 Gessie Brisard....................................................................................................Treasurer, Spring 2022
Finance Committee
Gessie Brisard, Chair ........................................................................................Treasurer, Spring 2022 E. Jennings Taylor.............................................................................................................. Spring 2023 Bruce Weisman.................................................................................................................. Spring 2023 Peter Foller........................................................................................................................ Spring 2022 Robert Micek...................................................................................................................... Spring 2022 Marca Doeff.......................................................................................................Secretary, Spring 2024 Tim Gamberzky............................................................................Chief Operating Officer, Term as COO
Honors and Awards Committee
Shelley Minteer, Chair ....................................................................................................... Spring 2023 Vimal Chaitanya................................................................................................................. Spring 2024 Mikhail Brik....................................................................................................................... Spring 2024 Diane Smith....................................................................................................................... Spring 2024 Viola Birss......................................................................................................................... Spring 2021 Francis d’Souza.................................................................................................................. Spring 2021 Scott Calabrese Barton....................................................................................................... Spring 2021 Viola Birss......................................................................................................................... Spring 2021 Shelley Minteer.................................................................................................................. Spring 2021 Scott Calabrese Barton....................................................................................................... Spring 2021 Junichi Murota................................................................................................................... Spring 2022 Dev Chidambaram............................................................................................................. Spring 2022 Wei Tong............................................................................................................................ Spring 2022 Nianqiang Wu.................................................................................................................... Spring 2023 John Flake......................................................................................................................... Spring 2023 Fernando Garzon................................................................................................................ Spring 2023 Stefan De Gendt.................................................................................................President, Spring 2021
Institutional Engagement Committee
Marion Jones, Chair.......................................................................................................... Spring 2022 Hemanth Jaganathan.......................................................................................................... Spring 2023 Thomas Barrera.................................................................................................................. Spring 2023 David Carey....................................................................................................................... Spring 2023 Jie Xiao.............................................................................................................................. Spring 2021 Christopher Beasley........................................................................................................... Spring 2021 Florika Macazo................................................................................................................... Spring 2021 Alex Peroff......................................................................................................................... Spring 2022 Alok Srivastava.................................................................................................................. Spring 2022 Craig Owen........................................................................................................................ Spring 2022 William Mustain...............................................Chair, Individual Membership Committee, Spring 2023 Gessie Brisard....................................................................................................Treasurer, Spring 2022
Technical Affairs Committee
Eric Wachsman, Chair.....................................................................Senior Vice President, Spring 2021 Stefan De Gendt.................................................................................................President, Spring 2021 Christina Bock..........................................................................Immediate Past President, Spring 2021 Yue Kuo.......................................................................Second Immediate Past President, Spring 2021 Gerardine Botte................................................................ Chair, Meetings Subcommittee, Spring 2021 Turgut Gur................................................................... Chair, Publications Subcommittee, Spring 2021 E. Jennings Taylor..................................................................... Chair, IST Subcommittee, Spring 2021 Christopher Jannuzzi.............................................................................Executive Director, Term as ED
Publications Subcommittee of the Technical Affairs Committee
Turgut Gur, Chair........................................................................... Second Vice President, Spring 2022 Gerardine Botte, Vice Chair...............................................................Third Vice President, Spring 2022 Krishnan Rajeshwar..........................................................................................JSS Editor, 12/31/2021 Robert Savinell...................................................................................................... JES Editor, 6/3/2021 Jeffrey Fergus..............................................................................ECS Transactions Editor, 12/31/2020 Robert Kelly.................................................................................................Interface Editor, 5/31/2022 Kang Xu............................................................................................................................. Spring 2022 Cortney Kreller................................................................................................................... Spring 2022 Christina Roth.................................................................................................................... Spring 2021 Hui Xu................................................................................................................................ Spring 2021
Meetings Subcommittee of the Technical Affairs Committee
Gerardine Botte, Chair.......................................................................Third Vice President, Spring 2023 Turgut Gur, Vice Chair................................................................... Second Vice President, Spring 2023 Jianlin Li............................................................................................................................ Spring 2023 Thomas Schmidt ............................................................................................................... Spring 2021 Paul Truelove..................................................................................................................... Spring 2022
Interdisciplinary Science and Technology Subcommittee of the Technical Affairs Committee
E. Jennings Taylor, Chair.................................................................................................... Spring 2022 Alice Suroviec ................................................................................................................... Spring 2023 Uros Cvelbar...................................................................................................................... Spring 2023 Jennifer Hite....................................................................................................................... Spring 2023 Scott Calabrese Barton....................................................................................................... Spring 2023 Alok Srivastava.................................................................................................................. Spring 2021 Diane Smith....................................................................................................................... Spring 2021 Jessica Koehne.................................................................................................................. Spring 2021 Juan Peralta Hernandez...................................................................................................... Spring 2021 John Vaughey.................................................................................................................... Spring 2022 Nick Birbilis....................................................................................................................... Spring 2022 Sean Bishop....................................................................................................................... Spring 2022 Jeff L. Blackburn................................................................................................................ Spring 2022 Natasa Vasiljek................................................................................................................... Spring 2022
Symposium Planning Advisory Board of the Technical Affairs Committee
William Mustain, Chair ..................................................................................................... Spring 2023 Alice Suroviec.................................................................................................................... Spring 2023 Neal Golovin...................................................................................................................... Spring 2023 Toshiyuki Nohira................................................................................................................ Spring 2021 Chi-Chang Hu.................................................................................................................... Spring 2021 James Burgess................................................................................................................... Spring 2022 Luis A. Diaz Aldana............................................................................................................ Spring 2022 Mohammadreza Nazemi..................................................................................................... Spring 2022 Seyyedamirhossein Hosseini............................................................................................. Spring 2021 Marion Jones................................................................... Chair, Sponsorship Committee, Spring 2022 Marca Doeff.......................................................................................................Secretary, Spring 2024
Gerardine Botte, Chair.......................................................................Third Vice President, Spring 2023 Shirley Meng .................................................................................... Chair, Battery Division, Fall 2023 Jamie Noel.................................................................................... Chair, Corrosion Division, Fall 2023 Jessica Koehne..................................................................................Chair, Sensor Division, Fall 2023 Junichi Murota ............................................... Chair, Electronics and Photonics Division, Spring 2021 Vaidyanathan Ravi Subramanian.................................Chair, Energy Technology Division, Spring 2021 Diane Smith ............................. Chair, Organic and Biological Electrochemistry Division, Spring 2021 Peter Vanýsek ...........................Chair, Physical and Analytical Electrochemistry Division, Spring 2021 Phillipe Vereecken..............................................................Chair, Electrodeposition Division, Fall 2021 Paul Gannon......................................................Chair, High Temperature Materials Division, Fall 2021 Jakoah Brgoch.................................... Chair, Luminescence and Display Materials Division, Fall 2021 Peter Mascher.................................... Chair, Dielectric Science and Technology Division, Spring 2021 Hiroshi Imahori .................................................................. Chair, Nanocarbons Division, Spring 2021 Shrisudersan Jayaraman..................................Chair, Industrial Electrochemistry and Electrochemical Engineering Division, Spring 2021 E. Jennings Taylor.......... Chair, Interdisciplinary Science and Technology Subcommittee, Spring 2022
Nominating Committee
Other Representatives
Individual Membership Committee
Christina Bock, Chair................................................................Immediate Past President, Spring 2021 Colm O’Dwyer.................................................................................................................... Spring 2021 Dennis Hess....................................................................................................................... Spring 2021 Graham Cheek................................................................................................................... Spring 2021 Gerardine Botte.................................................................................Third Vice President, Spring 2021
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Society Historian Roque Calvo.................................................................................................................. Spring 2021 American Association for the Advancement of Science Christopher Jannuzzi................................................................................ Term as Executive Director Science History Institute Yury Gogotski.................................................................................Heritage Councilor, Spring 2021 National Inventors Hall of Fame Shelley Minteer.................................................... Chair, Honors & Awards Committee, Spring 2023 The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
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Websites of Note Suggested for you by Alice Suroviec.
Energy2D Host: The Concord Consortium Site: http://energy.concord.org Energy2D is an interactive multiphyics NSF-funded free simulation program that models all three modes of heat transfer and their coupling with particle dynamics. The software runs on most computers and allows the user to design experiments to test hypotheses quickly. The results should be considered qualitative, but it is an excellent way to start testing a hypothesis or use in class when teaching about these topics.
Introduction to High-Temperature Materials Host: Indian Institute of Technology Kharagpur Sites: https://youtu.be/mwyZ-U6x0h0 and https://youtu.be/ RE8T512N0mo Introduction to High-Temperature Materials is a short twovideo series hosted by the Indian Institute of Technology Kharagpur. For those new to the area or would like a quick refresher on the content, these videos cover the introductory materials.
MatWeb
Total Materia
Host: MatWeb, LLC Site: http://matweb.com
Host: Key to Metals AG Site: https://www.totalmateria.com
MatWeb is a searchable online database of engineering materials. The site has a collection of over 140,000 datasheets. In addition, there are search tools based on such material properties as composition, manufacturer, and trade name. This database is quite extensive and continually being updated.
Total Materia is both a paid website and Android app that contains over 350,000 metallic alloys with a range of unique additional modules to meet different research needs. The site includes global information from thousands of standards, updated monthly, connected through international crossreference tables. There is the option for a free one-month trial for users that would like to see what information is available on this database. © The Electrochemical Society. DOI: 10.1149.2/2.10.1149.2/2.F02204IF.
(Please note that certain apps might not be available depending on the end user’s region or country. The features of some apps also can vary.)
About the Author
Alice Suroviec is a professor of bioanalytical chemistry and dean of the College of Mathematical and Natural Sciences at Berry College. She earned a BS in chemistry from Allegheny College in 2000. She received her PhD from Virginia Tech in 2005 under the direction of Dr. Mark R. Anderson. Her research focuses on enzymatically modified electrodes for use as biosensors. She is currently associate editor of the PAE Technical Division for the Journal of The Electrochemical Society. She can be reached at asuroviec@berry.edu and is always looking for new app/website suggestions. https://orcid.org/0000-0002-9252-2468
The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
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SOCIE T Y NE WS ECS Transactions Errata ECS Transactions is the official conference proceedings publication of The Electrochemical Society. In Volume 98, Issue 10, PRiME 2020: Molten Salts and Ionic Liquids 22, there were two errors. The first was a spelling error for one of the editor’s names. The name should read Paul C. Trulove. The second was the omission of Dr. Sheng Dai’s photograph. Dai received the 2020 Physical and Analytical Dr. Sheng Dai Electrochemistry Division Max Bredig Award in Molten Salt and Ionic Liquid Chemistry. ECS regrets these errors.
Staff News Celebrating 10 Years with ECS Anna Olsen celebrated 10 years with The Electrochemical Society on November 29. During her time at ECS, her role has evolved to touch almost all aspects of the Society, from membership and publications to meetings. A team player, Anna was involved in constituent and member services, moved to senior content associate and library liaison, and then to her current position as corporate programs manager. “The rich history of the Society is a great fit with my love of science,” said Anna. “Anna’s enthusiasm and dedication continue to shine and serve as valuable assets to the Society,” stated Shannon Reed, ECS Director of Community Engagement. Anna holds a BA from Holy Family University. She is married to her best friend, loves her fur baby, and enjoys traveling, reading, and cooking.
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Francesca Spagnuolo joined ECS in September 2020 as a meetings program specialist. In this role, she will play a large part in the planning, organization, and execution of ECS meetings, with specific management responsibilities for the development of the technical programs. Francesca will work closely with ECS division leaders, symposium organizers, session chairs, and authors of technical papers to ensure the value of the ECS meetings and promote successful planning, all while providing the highest level of customer service. Francesca attended Johnson & Wales University and studied hospitality management with a focus on event management. She has worked in the hospitality industry for almost 10 years in various roles, most recently as a catering sales manager for The Westin Princeton at Forrestal Village. While working within the hospitality industry, Francesca built a strong foundation in her program and event coordination skills, which will make her a great asset to ECS. Francesca prides herself on her ability to build and maintain strong client relationships and is excited to implement her skills and experience through her work at ECS. “We are very excited to have Francesca join the ECS Meetings Team,” said John Lewis, ECS Director of Meetings. “She has extensive event management experience and is very intelligent and intuitive, all of which will serve her well in this position. In her short time with ECS, she has already proven to be a valuable addition to the Society. It is a pleasure to welcome her to the ECS family, and I wish her great success in this new role.”
INTERESTED IN PUBLISHING WITH ECS? Visit the ECS website to learn more about the book publishing process, information on preparing a proposal, and helpful advice on how to get your book published. Questions? If you have questions or are ready to take the next step, reach out to ECS staff at publications@electrochem.org. 28
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SOCIE T Y NE WS In the NEXT ISSUE of
• The spring 2021 issue of Interface will mark the 30th Volume of the publication and feature the theme: Solid State Aspects of Energy Conversion. Paul Maggard, Associate Professor, Department of Chemistry, NC State University, will be the guest editor. We will have articles on the role of synthesis for energy storage materials, a discussion of tailoring the properties of inorganic semiconductors for efficient and stable storage of sunlight, and the challenges of 3D electrodeposited anode architectures for sodium ion rechargeable batteries.
• There will be a sneak peek of the upcoming 239th ECS Meeting with the 18th International Meeting on Chemical Sensors (IMCS). Learn about symposia, lectures, and more for the meeting, which takes place May 30-June 3, 2021, in Chicago, Illinois. • But wait, there’s more! Vol. 30, No.1, Spring 2021, also will include a special Free Radicals feature, the 2020 Year in Review, the 2020 Class of Highly Cited Researchers, Editorial Board Appointments, and Pennington Corner from ECS Executive Director/CEO Christopher J. Jannuzzi.
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Introduction
Continuum modeling of electrochemical systems goes back to at least the 1960s, athematical modwith seminal work on porous eling to understand electrodes by Newman and battery performance Tobias4 opening up a rich has a history of research stream that continues more than 50 years. today. This has produced The essence of modeling is to models for many different make predictions, as is the case by David A. Howey, Scott A. Roberts, batteries, including lead-acid,5 across all scientific disciplines; nickel/metal hydride,6 lithiumVenkatasubramanian Viswanathan, indeed, we can think of modion,7 lithium-oxygen,8 and els as hypotheses or theories to Aashutosh Mistry, Martin Beuse, others. Particle-scale models be tested against experimental seek to provide additional Edwin Khoo, Steven C. DeCaluwe, data. Models allow us to interinsight, numerically resolving and Valentin Sulzer polate between and extrapolate the physics within particles from points in data; without individually, rather than them, a new experiment would volume averaging.9 Recently, need to be run for every use advances in X-ray imaging have enabled image-based mesoscale case of a battery. However, the characteristics of battery models models,10 while others have focused on predicting the electrode vary widely depending on the applications of interest, from quanstructure through detailed manufacturing simulations11,12 or tum chemical calculations of material properties, through conresolving the role of conductive binders.13 The phase-field method tinuum performance models, and to techno-economic analysis of has also been successfully applied to describe electrochemical markets. This breadth can be confusing, and despite the apparent reactions14–17 at electrode/electrolyte interfaces (typically success and a sizable modeling community, we feel there remains solid/liquid or solid/solid interfaces) involved in complicated skepticism in some quarters about the utility of battery modeling; phenomena such as phase separation and dendrite formation. the near-term benefits are not always clear to those working to For the last several decades, electrical and control engineers build better cells and packs on the ground. In this short article, have also turned to battery modeling for the purpose of we discuss the history, impact, and frontiers of battery modeling, estimation of metrics such as state of charge (e.g., Aylor, Thieme, aiming to demonstrate the significance and benefit that state-ofand Johnson18), generally using equivalent circuit models. These the-art approaches bring to battery development. models, of course, have a long history in general electrical engineering and in the context of impedance spectroscopy (e.g., Cole and Cole19). However, work on circuit models using feedback control techniques for state estimation was accelerated We take a broad view of battery modeling (Fig. 1), categorizing in the late 1990s and early 2000s by university and industry the models into (i) atomistic models, used to discover and optimize groups (e.g., Bergveld, Kruijt, and Notten,20 Plett21), and research materials; (ii) continuum electrochemical engineering models, efforts in these areas have grown substantially over the past often based either on porous electrode theory or interface/particle/ decade. mesoscale formulations, used to understand manufacturing and Techno-economic modeling comes in many forms, but in its predict device performance; (iii) electrical circuit models, used essence, it is about combining engineering with an economic to fit impedance data and estimate states in control systems; (iv) perspective on a problem. Such models always have to walk techno-economic models, used to understand cost and lifecycle the tightrope between being sufficiently accurate whilst keeping impacts. A fifth sub-field, data-driven models, has also recently complexity tractable. Arguably, top-down cost models go back emerged; this cuts across all areas and has been demonstrated in to Theodore Wright, who in 1936 observed a power law for cost the context of materials discovery and lifetime estimation. An decrease versus cumulative production.22 Since then, this concept alternative but complementary perspective, which captures the has been applied widely, including for battery technologies,23 multiscale nature of the tools available, considers that models although it is seen more as a tool for longer-term assessments can be used to (a) predict properties from structure, (b) predict rather than short-term decision-making.24 Another well-known performance from properties, or (c) make decisions off the basis formulation is Moore’s Law, establishing such a relationship of predicted performance. for time rather than production. Similarly, many bottom-up The atomistic design of battery materials requires an engineering cost models have been developed for batteries, understanding of multicomponent phase diagrams, and historically with the open-source BatPaC model from the Argonne National leveraged the cluster expansion methodology combined with firstLaboratory being one of the most prominent.25 principles calculations developed for metal alloys.1 This method Given the huge complexities of modeling battery physics from led to the first set of electrodes designed using atomistic modeling the bottom up, it was inevitable that data-driven techniques would in 1998,2 and subsequently, including the development of the also be applied in this domain. For example, in recent years, work Materials Project,3 it has become relatively routine to calculate has emerged using various regression techniques for data-driven trends in open-circuit voltages for battery materials accurately. health prediction.26,27 Machine learning has also played a role in supporting mesoscale modeling, including image-segmentation and phase identification.28
M
Making a Case for Battery Modeling
Background
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estimators (called observers) for metrics such as state of charge,35 power capability,36 hotspot temperature,37 and state of health.38 In these approaches, a model typically predicts a measured quantity, such as voltage; the error between the measured and predicted quantities is calculated and fed back to the model as an additional input; this feedback is used to drive the model states (and/or parameters) towards the real battery states. When correctly applied, this overcomes a lack of knowledge of initial conditions and uncertainty in model structure, parameters, and measurements. The impact of these techniques is evident in a number of ways, such as control of fast charging, accurate Fig. 1. The spectrum of battery modeling. Models address one of four “why” questions using appropriate paradigms—the electric vehicle range “how.” Length and timescales of interest are associated with each corresponding paradigm; sometimes, these are (somewhat estimation, improved subjectively) also categorized into micro, meso, and macroscale. Each of these paradigms can be implemented using physicsbased and/or data-driven techniques. performance and safety, fault detection, and preventative maintenance. More broadly, state of health and lifetime prediction, an emerging area of research, could have a strong impact on understanding the costs of insurance and warranties, asset depreUnderstanding, Discovery, and Design ciation, and related issues. Perhaps the most traditional application of battery modeling is to Use-cases and Deployment understand behavior and discover new designs and usage scenarios. Models have been used for decades to understand material properties Batteries have become a general-purpose technology with uses and performance-limiting processes (e.g., transport and kinetics). across many sectors. Modeling elucidates innovation opportunities, As model-based numerical experiments can be performed cheaply product fit, and deployment cases. First, understanding current and and quickly, it is often more efficient to study wide parametric future costs is an important part of the development cycle for emerging spaces numerically, allowing optimization and focusing physical products (e.g., grid storage, electrified trucks, and aircraft). Cost experiments on the most beneficial regimes. models can help to assess competitiveness for particular applications. Some modeling studies identify battery designs (component, cell, Investors increasingly use bottom-up models to assess the viability of and pack parameters) to optimize efficiency and longevity for specific improvements in battery technology, such as those recently proposed applications. This might include particle sizes, manufacturing steps, by companies. Second, lifecycle analysis provides estimates of cell geometry (electrode thickness, number of layers, etc.), tab environmental impacts. Trusted models are required to understand placement, and size, among other factors. This can be achieved by degradation and identify control measures and appropriate use varying design parameters in a validated simulation tool or by fitting cases. Third, batteries rely on a complex supply chain, and system8,11 data in order to identify rate-limiting steps in physical experiments. dynamic models enable the assessment of interdependent variables. Other models help accelerate the materials discovery process. For example, after a battery is retired from use in an electric vehicle, By identifying and understanding limiting phenomena, models it might be used in stationary applications, which delays availability can provide insight and feedback to materials chemists regarding for recycling, reduces the need to buy a new battery, and thereby 12,29–31 required properties for performance breakthroughs. Moreover, influences raw material demand. Fourth, use-case analysis integrates multiscale simulations can couple these continuum-level insights performance and cost together to understand key levers to enable with first-principles calculations to directly identify new materials market penetration and has enabled the identification of critical suband material combinations with the required properties.32 Harnessing component targets for different market segments. machine-learning techniques can further accelerate the screening and identification process.33 Finally, it is increasingly common to combine advanced in situ and operando characterization with atomistic and mesoscale modeling to tease out design rules for performance.34
Benefits of Battery Modeling
Opportunities, Challenges, and Next Steps
Estimation and Control Real-time models are a critical aspect of batteries in use. The most common example of this is in battery management systems, where model-based techniques from control engineering are used to build
Parametrization and Validation
As model fidelity and complexity increase, so do the number of parameters required. While it may be straightforward to calibrate simple models from experimental data, the potential insight of identifying rate-limiting steps may be compromised when multiple (continued on next page)
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parameters are calibrated from the same data. Although common parameter sets are available in the literature, their applicability is often questionable and can lead to repeated mistakes and propagation of inappropriate assumptions. These kinds of identifiability issues have been studied more widely and occur in other subjects, such as control engineering and biological modeling.39 The battery modeling community could beneficially adopt tools and techniques developed in these fields. The challenge of experimental measurements for parameterization and validation is similarly difficult. For example, while it may be easy to use thermocouples to measure surface temperatures, reference electrode measurements to separate anode vs. cathode kinetics are often challenging.40 Obtaining experimental data with sufficient breadth and specificity such that the intended parameters are identifiable is a non-trivial issue.
Data-Driven Approaches Integrating physics-based models with recently developed machine learning tools enables some exciting opportunities to improve performance whilst maintaining transparency. Data-driven approaches offer flexible techniques for fitting functions, and the integration of this with physics models41,42 presents a new frontier that could enable approaches that are more accurate, generalizable, and interpretable.
Multiphysics
As capabilities and computational speed improve, there is an opportunity to build increasingly complex models that incorporate different physics (e.g., coupled mechanical-electrochemical behavior), bridge scales, or model new and poorly understood mechanisms or devices (e.g., long-term battery degradation, metal-air or multi-valent batteries). However, such advances must be critically assessed, as new phenomena can add significant complexity that may not be matched by model performance gains. This is particularly true
if complexity increases computational cost and reduces usability (i.e., prevents broad use by non-experts). Effort should be made to include the minimum set of physics that represents the modeled system and the features of the credible data available to populate that model.
Interdisciplinarity
Communication between different modeling communities also presents a unique challenge. Connecting across length-scales (e.g., atomistic to continuum, cell to pack level), combining battery science with machine learning and data-driven approaches, or collaborating between divergent fields such as battery chemistry and controls engineering will require coordination and efforts to explain jargon and motivation. Different fields must learn to bridge divides on nomenclature, conventions, and best practice. While challenges exist, the benefits to such interdisciplinary efforts are obvious, including the sharing of insights, acceleration of new discoveries, and avoiding duplicate efforts.
Openness The success of porous electrode models can, in part, be attributed to the open sharing of the original Dualfoil code.43 In this spirit, the modeling community should strive to make well-documented and tested software openly available.44–46 This will improve the sharing and reproducibility of models as well as encourage their adoption by non-modelers.
Outlook We hope we have made a convincing case that battery modeling has a long and interesting history and supports breakthroughs in battery science and engineering. Modeling adds rationality to battery research, development, and deployment. In order to achieve the ambitious goals set forth here, there is a need for broad community engagement across domains. The authors welcome feedback on these topics. The Battery Modeling Webinar Series (BMWS) community47
About the Authors David A. Howey, Associate Professor, Department of Engineering Science, University of Oxford. Howey leads a group focused on modeling and control of energy storage systems. He is a Samsung GRO Award winner and is the recipient of recent funding from EPSRC, InnovateUK, UKRI, Faraday Institution, Continental AG, and Siemens. Howey is also co-founder of Brill Power Ltd., a company spun out of his lab in 2016 to commercialize novel BMS technology. You can read more about David on http://howey.eng.ox.ac.uk/. He may be reached at david.howey@eng.ox.ac.uk. https://orcid.org/0000-0002-0620-3955
Venkatasubramanian Viswanathan, Associate Professor of Mechanical Engineering, Carnegie Mellon University. Viswanathan’s research interests are on technologies that can accelerate the transition to sustainable transportation, aviation, and chemicals. He is a recipient of numerous awards, including the MIT Technology Review Innovators Under 35, Office of Naval Research (ONR) Young Investigator Award, Alfred P. Sloan Research Fellowship in Chemistry, and National Science Foundation CAREER award. More details about his research can be found at http://cmu.edu/me/ venkatgroup. He may be reached at venkvis@cmu.edu. https://orcid.org/0000-0003-1060-5495
Scott A. Roberts, Principal Research and Development Chemical Engineer, Engineering Sciences Center, Sandia National Laboratories. Scott’s research interests are in coupled multiphysics simulations using high-performance computing. He has recently developed MLenabled image-based simulation technologies, applying them to multi-physics simulations of battery electrodes. Roberts may be reached at sarober@sandia.gov. https://orcid.org/0000-0002-4196-6771
Aashutosh Mistry, Postdoctoral Appointee, Chemical Sciences and Engineering Division, Argonne National Laboratory. Mistry’s research interest is understanding mechanisms that limit electrochemical systems. He combines physicsbased analysis, data-driven predictions, and controlled experiments to probe such mechanisms. Mistry may be reached at amistry@anl.gov. https://orcid.org/0000-0002-4359-4975
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is a step in this direction, with speakers and engagement across the different sub-disciplines discussed here. This article is in itself evidence that bringing together a combined modeling perspective is essential to enable batteries to become the platform technology for decarbonization.
Acknowledgements
SNL is managed and operated by NTESS under DOE NNSA contract DE-NA0003525. A.M. gratefully acknowledges support from Argonne National Laboratory. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357. A.M. appreciates Daniel Juarez Robles’s assistance in creating the module subfigure in Fig. 1. © The Electrochemical Society. DOI: 10.1149.2/2.F03204IF.
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Martin Beuse, PhD Candidate, Energy Politics Group, ETH Zurich. Beuse also works as a strategy consultant in the field of distributed energy and batteries. His research interest is in techno-economic modeling, using methods from engineering and economics to answer questions of investors, industry, and public policy. He may be reached at mbeuse@ethz.ch. https://orcid.org/0000-0002-1475-5696 Edwin Khoo, Research Scientist, Institute for Infocomm Research, Agency for Science, Technology, and Research (A*STAR), Singapore. Khoo applies machine learning and deep learning techniques to various domains and applications of industrial interest, such as battery modeling, semiconductor manufacturing, materials discovery, drug discovery, polymer coating formulation, and food security. He may be reached at edwin_khoo@i2r.a-star.edu.sg. https://orcid.org/0000-0002-3171-7982
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39. D. V. Raman, J. Anderson, and A. Papachristodoulou, Phys. Rev. E, 95, 032314 (2017). 40. Y. Li, X. Han, X. Feng, Z. Chu, X. Gao, R. Li, J. Du, L. Lu, and M. Ouyang, J. Power Sources, 481, 228933 (2021). 41. J. Willard, X. Jia, S. Xu, M. Steinbach, and V. Kumar, Integrating Physics-Based Modeling with Machine Learning: A Survey. arXiv:2003.04919 [physics, stat] 2020, arXiv: 2003.04919. 42. A. Aitio and D. Howey, ‟Combining non-parametric and parametric models for stable and computationally efficient battery health estimationˮ. ASME Dynamic Systems and Control Conference 2020 43. K. E. Thomas, M. Doyle, and J. Newman, Introduction to Dualfoil. 2002; http://www. cchem.berkeley.edu/jsngrp/fortran_ files/dualfoilfaq.pdf. 44. Z. Hong and V. Viswanathan, ACS Energy Lett., 5, 3254 (2020). 45. S. C. DeCaluwe, Electrochem. Soc. Interface, 28, 47 (2019). 46. V. Sulzer, S. G. Marquis, R. Timms, M. Robinson, S. J. Chapman, Python Battery Mathematical Modelling (PyBaMM) ECSarXiv (2020). 47. J. A. Baker, M. Beuse, S. C. DeCaluwe, L. W. Jing, E. Khoo, S. Sripad, U. Ulissi, A. Verma, A. A. Wang, Y. T. Yeh, N. Yiu, D. A. Howey, and V. Viswanathan, ACS Energy Lett., 5, 2361 (2020).
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SOCIE PEOPLE T Y NE WS Savinell Awarded Hovorka Prize
Innovation Award for Akolkar
R
obert Savinell, Distinguished University Professor, Case Western Reserve University, has received the 2020 Frank and Dorothy Humel Hovorka Prize from Case Western Reserve University—an award presented annually to an active or emeritus faculty member whose exceptional achievements in teaching, research, and scholarly service have benefited the community, nation, and world. Savinell’s accomplishments also Robert Savinell extend to The Electrochemical Photo: Case Western Society. Since 2013, he has been Reserve University editor of the Journal of The Electrochemical Society, where he focuses on continuing the tradition of rigorous review, enhancing timeliness of decision and publication, while transitioning JES to full open access. In 2000, he became an ECS Fellow. Today Savinell’s work is chronicled in 155-plus peer-reviewed publications and nine patents.
R Rohan Akolkar
ohan Akolkar has received the 2020 Innovation Award for his work with Lam Research to commercialize e-ALD technology developed in his lab at Case Western Reserve University. This process produces atomically thin metal layers for use in the semiconductor industry. Akolkar is a professor of chemical and biomolecular engineering at Case Western Reserve University. He also is an associate editor of the Journal of The Electrochemical Society.
SEARCHING FOR PEOPLE NEWS Interface is searching for People News for our upcoming spring issue. If you have news you would like to share with the ECS Society about a promotion, award, retirement, or other event, please email it to MaryBeth.Schwartz@electrochem.org.
In Memoriam ...
Edward McCafferty 1937 – 2020
Edward McCafferty was born on November 28, 1937, in Wilkes-Barre, PA, and passed away on September 21, 2020. He grew up in Pennsylvania coal country and lived in Wilkes-Barre until graduating from Wilkes College with a BS in chemistry in 1959. Ed joined Bethlehem Steel Corporation as a research engineer after graduation. He also began pursuing an MS in chemistry with Prof. A. C. Zettlemoyer at Lehigh University and earned his MS in 1964. He continued with Prof. Zettlemoyer as a NASA Fellow and earned his PhD in chemistry in 1968. The importance of Ed’s contributions and impact on the understanding of surface interactions started while still a graduate student where he studied the interaction of water vapor with α-ferric oxide. He was one of the earliest to show that adsorbed water molecules are structured at surfaces and that a network of hydrogen-bonded ice-like layers forms enroute to the build-up of liquid-like layers. Two of his papers on this research still are cited today. After graduation, Ed went on to The University of Texas as a Robert A. Welch Postdoctoral Fellow in Chemistry, where he worked under Prof. Norman Hackerman. One of Ed’s papers from this time, “Double-layer capacitance of iron and corrosion inhibition with polymethylene diamines,” published in the Journal of The
Electrochemical Society, is still cited today. He then joined the U. S. Naval Research Laboratory in 1970, where his contributions and pioneering efforts expanded into the areas of inhibitors, surface modification techniques (ion beam and laser), mathematical modeling of corrosion processes, surface analysis, and passivity and its breakdown. Ed’s interest in mathematical explanations lead him to pursue and earn an MS in applied math from Johns Hopkins University in 1996. In 1972, Ed joined The Electrochemical Society, and became an ECS Emeritus Member in 2016. He showed great leadership in the scientific community, particularly with his long-standing service and support of the Corrosion Division and The Electrochemical Society. He began his service to ECS as the chair of the Young Authors’ Award Subcommittee in 1979 and went on to serve on numerous committees, including Honors and Awards (Chair), Corrosion Monograph (Chair), an officer of the Corrosion Division Executive Committee and Chair from 1985 to 1986, and served as a Journal Divisional Editor. He also organized many symposia and edited numerous proceedings volumes for the division. Ed’s innovative research, integrity, and passion for science were the hallmarks of his career. He was one of the more creative and unique thinkers in the field of corrosion science. Ed always pushed the envelope and often questioned the conventional wisdom. His ideas and approaches generated much discussion. He was truly a gifted and dedicated scientist. Ed’s research was internationally respected, as evidenced by the over 4,700 citations of his 111 papers, his many invited lectures at major meetings and universities, invitations to (continued on next page)
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SOCIE PEOPLE T Y NE WS (continued from previous page)
be a panelist, and the awards he received. Among his numerous awards and recognitions are the 1971 Victor K. LaMer Award from the Division of Colloid and Surface Chemistry of the American Chemical Society, the 1992 NRL Sigma Xi Award for Pure Science, ECS Fellow in 1996, the Corrosion Division H. H. Uhlig Award in 2007, the 1982 William Blum Award and the 2003 R. T. Foley Award from the National Capital Section of The Electrochemical Society, and the 2003 Jerome Kruger Award in Corrosion Science from the Baltimore-Washington Chapter of NACE International. He was a very creative person, whose passions went beyond science to teaching, playing and watching baseball, poetry, and his family. Ed was a published poet and was named the Corrosion Division Poet Laureate after writing and delivering a poem in honor of Jerry Kruger at the symposium celebrating Jerry’s 70th birthday. He used to love to read his poetry at events, and his poems have been published in such literary magazines as The Fountain, Glassworks, Poet Lore, Gargoyle, Potomac Review, WordWrights, and Scribble. Ed also wrote the book, Audrey & I Stride Forth, published by Argonne House Press (2002). Ed also loved to teach, whether to a freshly minted PhD or to an undergraduate being exposed to corrosion electrochemistry for the first time. He was a professorial lecturer at The George Washington
University for 10 years. The notes for his Introduction to Corrosion course became the basis for his Introduction to Corrosion Science textbook (2010), which serves as a rigorous introduction to corrosion for advanced undergraduate/first-year graduate-level instruction at many universities. Ed authored another textbook, Surface Chemistry of Aqueous Corrosion Processes, a combined chemistry/ physical chemistry approach toward the study of aqueous corrosion processes (2015). While Ed’s research was respected globally, perhaps more importantly, he was also respected internationally for the person he was. He had a wonderful sense of humor and loved to joke. He would often say something that appeared quite serious, and then he would wink or smile. We have received countless emails from around the world expressing appreciation for Ed, the scientist, and Ed, the man. Someone once said, “You are either a great researcher or a great person. It is rare for someone to be both.” Ed was both. He was a mentor and friend; he enriched our lives and made the world a better place. Ed will be missed. Ed is survived by his wife, Mary, his two children, two grandchildren, and a sister. This notice was contributed by Paul Natishan and Douglas Hansen.
In Memoriam ...
Jean-Michel Savéant 1933 – 2020
Jean-Michel Savéant, Emeritus Professor at the Université de Paris, France, and former research director at the Centre national de la recherche scientifique (CNRS), passed away on August 16, 2020, at the age of 86. He was a giant of electrochemistry, combining a strong personality with extreme rigor and elegance in his work, deep creativity, and a communicative enthusiasm for ceaselessly exploring the frontiers of knowledge and chemical sciences. Savéant’s scientific career is the story of the founding and development of molecular electrochemistry. He pioneered and developed most aspects of the field, from instrumentation to theoretical aspects and practical applications. In a conceptual and practical effort to solve contemporary energy challenges, Savéant pioneered an enormous body of knowledge, tools, and models to develop highly original and key contributions towards various subfields of chemistry and biochemistry, including electron and proton transfer chemistry, modeling of chemical reactivity, chemistry of free radicals, chemistry of metal complexes, photochemistry, physical chemistry of solids, enzymology, and catalytic activation of small molecules such as CO2 and H2O. “Jean-Michel Savéant belonged to a glorious era of electrochemistry when science was guided by a curiosity for understanding the world better, and scientists were colorful personalities. He leaves an enormous scientific legacy with hundreds of papers reflecting his enormous impact. Electrochemistry and science as a whole have lost a giant and many of us will miss a friend and a mentor,” said Christian Amatore, Cyrille Costentin, and Marc Robert. 36
Born in 1933, Savéant received his undergraduate degree from the Ecole Normale Supérieure, Agrégation des Sciences Physiques (1954-1958), France, then did predoctoral work at l’Istituto di Chimica Fisica dell’ Università di Padova (1959), Italy. After performing his military service (1960-1962), Savéant completed his PhD at the Ecole Normale Supérieure (1966), where he then served as vice director of the chemistry department. In 1971, he became professor at the Université Paris Denis Diderot, France. Savéant was named research director of the Centre National de la Recherche Scientifique in 1985. From 1988-1989, Savéant was a distinguished Fairchild Scholar at the California Institute of Technology. Among the many honors bestowed on Savéant are the Bruno Beyer Award of the Royal Australian Chemistry Institute (2005), ECS Organic and Biological Electrochemistry Division Manuel M. Baizer Award (2002), ECS Olin Palladium Award (1993), and Faraday Medal of the Royal Chemical Society (1983). He became a member of the Académie des sciences (French Academy of Sciences) in 2000, and a foreign associate of the National Academy of Sciences, U.S., in 2001. Author of over 400 peer-reviewed articles, Savéant applied for and/ or received at least 10 patents. The author (with Cyrille Costentin) of Elements of Molecular and Biomolecular Electrochemistry, Savéant was Oskar K. Rice Distinguished Lecturer at The University of North Carolina, Chapel Hill (1995); Nelson Leonard Distinguished Lecturer at the University of Illinois (1999); and George Fisher Baker Lecturer at Cornell University (2002). Savéant presented frequently at ECS meetings, delivering invited lectures when he received the ECS Olin Palladium and Manuel M. Baizer Awards. With special thanks to Christian Amatore, Cyrille Costentin, and Marc Robert for their personal tributes to Jean-Michel Savéant. © 2020 The Author(s). Published by The Electrochemical Society.
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Looking at Patent Law:
Patenting a Methane Conversion Process – A Case Study by E. Jennings Taylor and Maria Inman
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I
n this installment of the ‟Looking at Patent Lawˮ articles, we present a case study of an elevated temperature methane conversion process. We have chosen this invention to align with the focus of this issue of Interface on the High-Temperature Energy, Materials, & Processes (H-TEMP) Division of The Electrochemical Society. Recall from our previous article,1 the prosecution (examination) history of a patent application is publicly available in the file wrapper on the U.S. Patent & Trademark Office (USPTO) Patent Application Information Retrieval (PAIR) system.2 With the USPTO PAIR system as the primary source of information for this case study, we illustrate the prosecution “events” encountered during the examination of U.S. Patent No. 10,525,407, “Systems, Methods, and Devices for Direct Conversion of Methane.”3 The ‘407 patent was issued on January 7, 2020, with co-inventors Eric D. Wachsman and Dongxia Liu. Eric Wachsman is a professor at the University of Maryland with dual appointments in the Department of Materials Science & Engineering and the Department of Chemical Engineering. Eric is also the director of the Maryland Energy Innovation Institute. Eric was elected a fellow of ECS in 2008 and currently serves as senior vice president of ECS. Dongxia Liu is an associate professor at the University of Maryland in the Department of Chemical and Biomolecular Engineering. Dongxia is a member of the Maryland Energy Innovation Institute. The ‘407 patent is generally directed towards a method for converting methane to value-added products, such as hydrogen, hydrocarbons, and aromatics. The method utilizes a reactor incorporating an ion-conducting perovskite-type oxide membrane operating at ~1,000°C. The technology is more fully described in a recent publication,4 and was the subject of the Carl Wagner Memorial Award address, “Mixed Protonic-Electronic Membrane Reactors; Converting Hydrocarbon Resources and CO2 to Fuels,” presented at the 232nd meeting of The Electrochemical Society in National Harbor, MD.5
Patent Applications The events leading to the filing of the utility patent application are presented in Table I and summarized herein. Two U.S. provisional patent applications titled “Systems, Methods, and Devices for Direct Conversion of Methane” were filed in the U.S. The provisional patent applications were filed by attorneys on behalf of co-inventors Eric D. Wachsman and Dongxia Liu. Both were and are professors at the University of Maryland. The provisional patent applications, 62/238,474 and 62/300,338, were filed on October 7, 2015, and February 26, 2016, respectively. While we did not consider the provisional patent applications, we presume the second added clarity to the first provisional patent application. Subsequently, a foreign patent application under the Patent Cooperation (PCT) was filed October 6, 2016. The PCT filing was within one year of the filing dates of the earliest provisional patent filing date and thereby maintained the priority date (October 7, 2015) of the earliest provisional patent application.6 The PCT patent application designated the United States as well as other jurisdictions (foreign countries). Interestingly, the applicants chose to file a PCT patent application, followed by a national stage request for examination in the U.S. This strategy could have coincided with a stronger interest in foreign markets for the subject invention or to delay examination/issuance of the U.S. patent application/patent. A “national stage” U.S utility patent application or a “request for U.S. examination” of the PCT patent application was filed on April 4, 2018, at the USPTO.7 The U.S. utility, as well as other patent (continued on next page)
Table I. U.S. and PCT Patent Applications Associated with Direct Methane Conversion Invention.
APPL. TYPE
APPL. NO.
TITLE
FILING DATE
U.S. Provisional
62/238,474
Systems, Methods & Devices for Direct Conversion of Methane
Oct. 7, 2015 (Priority Date)
U.S. Provisional
62/300,338
Systems, Methods & Devices for Direct Conversion of Methane
Feb. 26, 2016
PCT International
PCT/055818
Systems, Methods & Devices for Direct Conversion of Methane
Oct. 6, 2016 (<12 months from earliest provisional application)
U.S. Utility (National Stage)
15/765,820
Systems, Methods & Devices for Direct Conversion of Methane
Apr. 4, 2018 (<30 months from earliest provisional application)
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Fig 1. Basic Flow Under the Patent Cooperation Treaty (adapted from the USPTO Manual of Patent Examination Procedure.
Taylor and Inman
(continued from previous page)
applications, have to be filed within 18 months of the PCT patent application in order to benefit from the filing date of the PCT patent application. A generalized flow schematic illustrating the sequence of events, which maintained the priority date of the filing date of the earliest provisional patent application, is presented in Fig. 1.8 In this case, “file local application” is equivalent to the “earliest provisional patent application.” The PCT was filed within 12 months of filing the earliest provisional patent application, consistent with the required flow of events. The international search report is completed at approximately 16 months from the earliest provisional patent application (see below). The PCT patent application was published 18 months from the earliest provisional patent application filing date. Finally, the national phase entry occurs within 18 months of the PCT filing date. By filing a PCT patent application prior to filing a U.S. utility patent application, the applicants are able to 1. review the international search report for unanticipated prior art and revise their U.S. prosecution strategy, and/or 2. delay U.S. prosecution. In either case, prosecuting the PCT application first followed by the U.S. application or prosecuting the U.S. application first followed by the PCT, the priority date of the earliest provisional patent application remains the same. Figure 2 illustrates a cross-sectional view of the packed-bed tubular membrane reactor (300) for the methane conversion method of the subject invention. The tubular membrane reactor (300) consists of a porous support tube (304) coated with a hydrogenpermeable membrane (306). The porous support tube (304) is filled with a methane conversion catalyst (324). A methane gas stream is introduced through inlet (312) to the first gas volume (302), where it is in contact with a methane conversion catalyst (324). The reaction products, with the exception of hydrogen, exit the packed-bed tubular membrane reactor (300) through outlet (314). The hydrogen reaction product selectively permeates through the membrane (306) into the second gas volume (310). An inert sweep gas such as helium is introduced via inlet (316) to the second gas volume (310) and carries the hydrogen out of the reactor through the exit (318). In order to establish a filing date, a utility patent application must include the following. 1. Specification9 “…a written description of the invention, and the manner and process for making it…to enable any person skilled in the art…to make and use [the invention]…” 2. Minimum of one claim10 “…particularly pointing out… the subject matter…as the invention…” 3. Drawings11 “…where necessary for understanding the subject matter…to be patented…”
In order to maintain the filing date, the following additional criteria are required. 1. Filing fee in accordance with the current USPTO fee schedule12 2. Inventor oath or declaration asserting13 a. The patent application was authorized by the inventor(s), b. The inventor(s) believe he/she is the original inventor, or they are the original joint inventors. The specification included a description of the prior art, problems within the prior art, a summary of the invention describing various embodiments of the invention addressing the prior art problems, and a 38
File local patent application 0 month
12 month
Provisional patent application
PCT patent application
International search report
International publication
Enter national phase
16 month
18 month
30 month
U.S. ‘820 patent application
Fig 1. Basic flow under the Patent Cooperation Treaty. (Adapted from the USPTO Manual of Patent Examination Procedure.)
detailed description of the invention regarding the packed-bed tubular membrane reactor (300) for methane conversion. The meaning of the terms used in the written description of the invention are defined by their use in the specification. Consequently, in this scenario, the U.S. utility has to be filed within 30 months of the provisional patent application to benefit from the provisional patent application. The utility patent application contained amended claims directed towards one statutory patent class, a method (of converting methane).14 The original PCT patent application included both method and apparatus claims directed towards the methane conversion invention. Presumably, after reviewing the international search report, the inventors decided the apparatus claims could not overcome the prior art, or they were not required for business reasons. The sole independent claim15,16 from the patent application (as amended from the PCT patent application) is reproduced as: Claim 1. A method of converting methane, the method comprising: flowing methane in a first volume so as to contact a catalyst in a reactor while heating the reactor to an elevated temperature; transporting H2 from the first volume to a second volume in the reactor via a membrane supported within the reactor; and removing products from the first volume, wherein the products comprise C2 hydrocarbons and/or aromatics. Dependent Claim 7 was not amended from the PCT patent application and is reproduced as: Claim 7. The method of Claim 1, wherein the methane comprises a perovskite-type oxide having a formula of M’Ce1-x-yZrx M’’yO3-δ, where M’ is at least one of Sr and Ba; M’’ is at least one of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, W, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb; x is between 0.1 and 0.2, inclusive; and y is between 0.1 and 0.3, inclusive. The declaration included an assertion by the inventors stating, “…I believe I am the original, first and joint inventor with the other named inventor(s) of the subject matter which is claimed…” Please note that the “named inventors” must be correctly represented on a U.S. patent application.17 Specifically, the inclusion of a colleague as a co-inventor who did not participate in the conception of the invention is known as a misjoinder and invalidates an otherwise valid patent. Similarly, the exclusion of a co-inventor who participated in the conception is known as a nonjoinder and invalidates an otherwise valid patent. If an inventor is erroneously omitted or erroneously included as an inventor, the misjoinder/ nonjoinder may be corrected, and the patent remains valid.18 The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
prior art from the international search report associated with the PCT patent application. The USPTO encourages applicants to carefully examine22 “Prior art cited in search reports of a foreign patent office in a counterpart application…” The IDS is the submission of relevant background art or information to the USPTO by the applicant. The “Duty of Candor” requires that the inventor submit an IDS within a reasonable time of submission of the patent application disclosing23 “…to the Office [USPTO] all information known to that individual to be material to patentability…”
Fig 2. Figure 3A from ‘704 patent depicting a cross-sectional view of an exemplary methane conversion membrane reactor according to one or more embodiments of the subject invention.
As detailed above, the subject patent application included a specification, claims, drawings, inventor oath as well as the appropriate filing fee. Consequently, the requirements to establish and maintain a filing date were met in the U.S. utility patent application. On July 11, 2018, the USPTO issued a filing receipt and the utility patent application was assigned number 15/765,820 with a filing date of April 4, 2018. A power of attorney appointed registered patent practitioners from the firm Klarquist Sparkman, LLP.
The “Duty of Candor” is specific to any existing claim and requires that the IDS be continually updated while the claim is pending. The “Duty of Candor” ceases only when the claim is allowed, and the patent issue fee is paid. The “Duty of Candor” extends to any individual associated with the filing of the patent application, including the following. 1. Inventor(s) 2. Patent Counsel 3. Persons who are substantially involved in the preparation or prosecution of the patent application.
“…prosecute this application and to transact all business in the United States Patent and Trademark office connected therewith…”
Substantial involvement could include technical assistants, collaborators, or colleagues. Substantial involvement would generally not extend to clerical workers. Furthermore, the inclusion of a reference in an IDS24
Assignment, March-in Rights, and Small Entity Status
“…is not taken as an admission that the reference is prior art against the claims.”
As noted above, the inventors were professors and employees of the University of Maryland. Consequently, the inventors assigned their patent rights to the University of Maryland. The assignments were recorded with the USPTO. The work leading to the subject invention was supported under two grants from the National Science Foundation (NSF) Chemical, Bioengineering, Environmental, and Transport Systems (CBET) Division within the Directorate for Engineering. As stipulated in the Bayh-Dole Act, the patent application included the following statement19 “This invention was made with government support under CBET 1264599 and CBET 1351384 awarded by the National Science Foundation (NSF). The government has certain rights in the invention.” Regarding march-in rights, a key policy objective of the BayhDole Act is20 “…to ensure that the Government obtains sufficient rights in federally supported inventions to meet the needs of the Government and protect the public against nonuse or unreasonable use of inventions…” To our knowledge, the government has never exercised BayhDole march-in rights in any invention. Finally, the patent included a statement asserting “small entity” status as a nonprofit university.21 The small entity status entitled the applicants to reduced filing, issue, and maintenance fees.
Information Disclosure Statement On June 15, 2018, the attorneys for the applicants submitted a supplemental “Information Disclosure Statement” (IDS) in accordance with US patent laws. The supplemental IDS included
If a finding of a violation of the “Duty of Candor” resulting in “inequitable conduct” regarding any claim in a patent is determined, then all the claims of the subject patent are rendered invalid.25 Finally, in spite of the requirement of the “Duty of Candor,” the applicant is cautioned not to “bury” the examiner with a long list of non-material references in hopes that the examiner will not notice the relevant material references.26 The guidance from the USPTO is to27 “…avoid the submission of long lists of documents if it can be avoided…If a long list is submitted, highlight those documents which have specifically brought to the applicant’s attention and/or are known to be of most significance.”
Non-Final Office Action (NFOA) The utility patent application was preceded by an international PCT patent application as well as provisional patent applications. The timing of the filing of the provisional, PCT, and utility patent applications maintained the priority date of the provisional patent application. Consequently, for purposes of prior art searching, the priority date for the ‘820 patent application is the filing date of the earliest provisional patent application, 62/238,474 filed October 7, 2015. On September 25, 2018, the USPTO issued a NFOA containing 1. a list of references cited by the applicant and considered by the examiner, 2. an examiner’s search strategy for the subject patent application, 3. a list of references cited by the examiner, and 4. a non-final rejection of the subject patent application. The claims associated with the patent application were rejected as being either anticipated28 or obvious29 in view of the prior art. On October 18, 2018, the USPTO issued a notice of publication of the U.S. utility patent application. Normally, U.S. utility patent applications are published 18 months after their priority date,
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Taylor and Inman
(continued from previous page)
which in this case is the filing date of the earliest provisional patent application, October 7, 2015, (refer to Table I). However, the U.S. utility patent application was filed subsequent to the PCT international patent application and 30 months after the filing date of the provisional patent application. Per USPTO procedure, the U.S. utility patent application was published30 “…promptly after the expiration of a period of eighteen months from the earliest filing date…”
Response to NFOA On January 18, 2019, the applicants responded to the NFOA and presented arguments regarding the anticipation and obviousness rejections along with amended claims.31 The applicant attempted to overcome the rejections by 1. Stipulating the catalyst operates at the same temperature at which the membrane transports hydrogen, and 2. Incorporating the limitations of dependent Claim 7 into independent Claim 1. Specifically, Claim 1 was amended (underlined content) in response to the NFOA as follows Claim 1. A method of converting methane, the method comprising: flowing methane in a first volume so as to contact a catalyst in a reactor while heating the reactor to an elevated temperature; transporting H2 from the first volume to a second volume in the reactor via a membrane supported within the reactor; and removing products from the first volume, wherein the products comprise C2 hydrocarbons and/or aromatics, a composition of the catalyst is selected such that the catalyst catalyzes conversion of methane into said products at a same operating temperature at which the membrane transports H2, and the membrane comprises a perovskite-type oxide having a formula of M’Ce1-x-yZrx M’’yO3-δ, where: M’ is at least one of Sr and Ba; M’’ is at least one of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, W, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb; x is between 0.1 and 0.2, inclusive; and y is between 0.1 and 0.3, inclusive.
Claim 1. A method of converting methane, the method comprising: flowing methane in a first volume so as to contact a catalyst in a reactor while heating the reactor to an elevated temperature; transporting H2 from the first volume to a second volume in the reactor via a membrane supported within the reactor; and removing products from the first volume, wherein the products comprise C2 hydrocarbons and/or aromatics, a composition of the catalyst is selected such that the catalyst catalyzes conversion of methane into said products at a same operating temperature at which the membrane transports H2, and the membrane comprises a perovskite-type oxide having a formula of M’Ce1-x-yZrx M’’yO3-δ, where: M’ is at least one of Sr and Ba; M’’ is at least one of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, W, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb; x is between 0.1 and 0.2, inclusive; y is between 0.1 and 0.3, inclusive, the catalyst comprises Fe(c)SiO2, the method further comprises forming the catalyst by fusing ferrous metasilicate with quartz, and the ferrous metasilicate is formed by a sol-gel method employing a mixture of toluene, methanol, FeCl2, NaOC2H5, tetraethyl orthosilicate (TEOS), and NaOH. During the prosecution of the ‘820 patent application, the USPTO examiner expressed confusion regarding the term “(c)” in Fe(c)SiO2. The applicant’s clarified the meaning of the term by pointing to the specification where the applicant stated “…preferably Fe(c)SiO2, where (c) denoted confinement.” Recall, the inventors are permitted to be their own lexicographer.32 “An applicant is entitled to be his or her own lexicographer… [even by] setting forth a definition of the term that is different from its ordinary and customary meaning(s).” The amendment to independent Claim 1 included extensive limitations to avoid the prior art resulting in a claim of limited scope but also a stronger claim in terms of validity. More specifically, to quote Court of Appeals for the Federal Circuit (Patent Court) Judge Giles S. Rich:33
Final Rejection
“…a patent that is strong in that it contains broad claims which adequately protect the invention so that they are hard to design around is weak in that it may be easier to invalidate in court…a patent with narrow claims…is weak as protection and as incentive to invest but strong in that a court will not likely invalidate.”
“Applicants arguments filed 01/18/2019 have been fully considered but they are not persuasive.”
On August 30, 2019, the USPTO issued a notice of allowance for the U.S. utility patent application with the amended claims associated with the invention. After payment of the issue fee, the 15/765,820 patent application issued as U.S. Patent No. 10,525,407 on January 7, 2020.
On April 22, 2019, the USPTO issued a final office action rejecting the amended independent claim and all of the claims in the patent application. The final rejection was based on obviousness and stated the following.
Response to Final Rejection On August 21, 2019, the applicants responded to the final office action and presented arguments regarding the obviousness rejection along with amended claims. The amended independent claim included additional limitations by specifying the methane conversion catalyst and its method of preparation. Specifically, Claim 1 was amended (underlined content) in response to the final office action as follows 40
Allowance of Patent Application
Summary
In this installment of our “Looking at Patent Law” series, we present a case study of the prosecution of U.S. Patent No. 10,525,407, “Systems, Methods, and Devices for Direct Conversion of Methane,” co-invented by professors Eric D. Wachsman and Dongxia Liu of
The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
the University of Maryland. This case was chosen to coincide with the focus of this issue of Interface on the High-Temperature Energy, Materials, & Processes (H-TEMP) division of The Electrochemical Society. The case study begins with a brief synopsis of the background of the invention followed by 1) request to begin U.S. examination of an international patent application filed under the Patent Cooperation Treaty (PCT), 2) submission of amended claims and Information Disclosure Statements (IDS) based on the PCT preliminary patentability search report, 3) nonfinal and final rejections of the utility patent application based on novelty and obviousness from the prior art, 4) applicant’s strategy for overcoming the prior art rejections by amending the independent claim with limitations from the dependent claims, and 5) allowance of the patent. Interestingly, the applicants chose to file a PCT patent application, followed by a national stage request for examination in the U.S. This strategy could have coincided with a stronger interest in foreign markets for the subject invention or to delay examination/issuance of the U.S. utility patent application/patent. With this case study, we hope to demystify the patent prosecution process and better prepare electrochemical and solid state scientists, engineers, and technologists to interact with their patent counsel regarding their inventions. © The Electrochemical Society. DOI: 10.1149.2/2.F04204IF.
About the Authors E. Jennings Taylor is the founder of Faraday Technology, Inc., a small business focused on developing innovative electrochemical processes and technologies based on pulse and pulse reverse electrolytic principles. Taylor leads Faraday’s patent and commercialization strategy and has negotiated numerous via field of use licenses as well as patent sales. In addition to technical publications and presentations, Taylor is an inventor on 40 patents. Taylor is admitted to practice before the United States Patent & Trademark Office (USPTO) in patent cases as a patent agent (Registration No. 53,676) and is a member of the American Intellectual Property Law Association (AIPLA). Taylor has been a member of ECS for 38 years and is a fellow of ECS. He may be reached at jenningstaylor@faradaytechnology.com. https://orcid.org/0000-0002-3410-0267 Maria Inman is the research director of Faraday Technology, Inc., where she serves as principal investigator on numerous project development activities, and manages the company’s pulse and pulse reverse research project portfolio. In addition to technical publications and presentations, she is competent in patent drafting and patent drawing preparation and is an inventor on seven patents. Inman is a member of ASTM and has been a member of ECS for 21 years. Inman serves ECS as a member of numerous committees. She may be reached at mariainman@faradaytechnology.com. https://orcid.org/0000-0003-2560-8410
6. 35 U.S.C. §111 Application. 7. 35 U.S.C. §371 National Stage: Commencement. 8. Manual of Patent Examination Procedure (MPEP) §1842 Basic Flow Under the PCT. 9. 35 U.S.C. §112(a) Specification/In General. 10. 35 U.S.C. §112(b) Specification/Conclusion. 11. 35 U.S.C. §113 Drawings. 12. https://www.uspto.gov/learning-and-resources/fees-andpayment/uspto-fee-schedule#Patent%20Fees 13. 35 U.S.C. §115(b)(1)(2) Inventor’s Oath or Declaration/ Required Statements. 14. 35 U.S.C. §101 Inventions Patentable. 15. E. J. Taylor and M. Inman, Electrochem. Soc. Interface, 26(3), 44 (2017). 16. 35 U.S.C. §112(c) Specification/Form. 17. E. J. Taylor and M. Inman, Electrochem. Soc. Interface, 26(2), 45 (2017). 18. Manual of Patent Examination Procedure (MPEP) §1481.02 Correction of Named Inventor. 19. 35 U.S.C. §203 March-in Rights. 20. 35 U.S.C. §200 Policy and Objective. 21. 37 CFR §1.27(a)(3)(ii)(A) Definition of small entities and establishing status as a small entity to permit payment of small entity fees; when a determination of entitlement to small entity status and notification of loss of entitlement to small entity status are required; fraud on the Office. 22. 37 CFR §1.56(a)(1) Duty to Disclose Information Material to Patentability. 23. 37 CFR §1.56(a) Duty to Disclose Information Material to Patentability. 24. Riverwood Int’l. Corp. v. R. A. Jones & Co., 324 F.3d 1346, 135455, 66 USPQ2d 1331, 1337-38 (Fed Cir. 2003). 25. Manual of Patent Examination Procedure (MPEP) §2016 Fraud, Inequitable Conduct, or Violation of Duty of Disclosure Affects All Claims 26. R. B. Taylor, Mich. Telecomm. & Tech. Law Rev., 99, 19 (2012). 27. Manual of Patent Examination Procedure (MPEP) §2004.13 Aids to Comply with Duty of Disclosure. 28. 35 U.S.C. §102 Conditions for Patentability; Novelty. 29. 35 U.S.C. §103 Conditions for Patentability; Non-Obviousness Subject Matter. 30. 37 CFR § 1.211 Publication of Applications. 31. 37 CFR § 1.111 Reply by applicant or patent owner to a nonfinal Office action. 32. Manual of Patent Examination Procedure (MPEP) §2111.01 Applicant May Be Own Lexicographer. 33. G. S. Rich, Geo. Wash. L. Rev., 35, 641 (1967).
References 1. E. J. Taylor and M. Inman, Electrochem. Soc. Interface, 26(4), 57 (2017). 2. USPTO Patent Application Information Retrieval (PAIR) https:// portal.uspto.gov/pair/PublicPair 3. E.D. Wachsman and D. Liu, U.S. Patent No. 10,525,407 issued Jan. 7, 2020. 4. M. Sakbodin, Y. Wu, S. Oh, E. Wachsman, and D. Liu, Angew. Chem. Int. Ed., 55, 16149 (2016). 5. E. Wachsman, “Mixed Protonic-Electronic Membrane Reactors: Converting Hydrocarbon Resources and CO2 to Fuels,” Carl Wagner Award address, Presented at the 232nd Electrochemical Society Meeting, Oct. 3, 2017; https://www.electrochem. org/232/society-awards
Have you missed any of these educational articles by Taylor and Inman? Visit the complete collection!
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T ECH HIGHLIGH T S Origin of Capacity Degradation of High-Voltage KVPO 4F Cathode Potassium ion-battery (KIB) is one of the next-generation rechargeable batteries beyond lithium-ion and shows great potential for grid-level electrochemical energy storage application due to its low cost and high operational voltage (>4V). Particularly, potassium vanadium fluorophosphate (KVPO4F) is one of the most promising cathode candidates and possesses superior properties, such as higher specific capacity and structural stability, as well as cheaper cost compared to the layered potassium transition metal oxide. However, fast capacity decay remains a big issue for KVPO4F. Kim et al. incorporated the previous work in literature and dived deeper into the origin of capacity degradation of this high-voltage cathode material. The tests were conducted using KVPO4F/K coin cell configuration with one of four different solutions. Through ex-situ XRD, EDS, and XPS, the authors showed that the capacity degradation originated from the formation of passive layer on the cathode through electrolyte decomposition at the interface at high voltage (>4.5V vs. K/ K+), with barely any structural deformation. They also showed that the cell using ethylene carbonate/propylene carbonate solvent maintained the highest capacity retention (~63%) between 5.0-2.5V after 200 cycles owing to the highest oxidation stability validated by linear scanning voltammetry (LSV). From: H. Kim, Y. Tian and G. Ceder, J. Electrochem. Soc., 167, 110555 (2020).
An RDE Approach to Investigate the Influence of Chromate on the Cathodic Kinetics on 7XXX Series Al Alloys under Simulated Thin Film Electrolytes The excellent intrinsic properties of the 7XXX series of aluminum (Al) alloys, including their high strength-to-weight ratio, make them desirable for use in many applications, such as aerospace and defense. However, these alloys are susceptible to localized corrosion, when the Cu-rich intermetallic particles that form during precipitation hardening preferentially corrode with respect to the Al matrix in a chloride-containing environment. Much research has focused on the role of chromate in the corrosion protection of AA2XXX alloys, with limited studies on AA7XXX alloys. To that end, researchers at the University of Virginia have investigated the influence of chromate on the cathodic kinetics on AA7XXX alloys through electrochemical and surface characterization of these alloys in simulated atmospheric environments. They demonstrated through rotating disk electrode experiments that the oxygen reduction reaction (ORR) was greatly suppressed with the addition of chromate, with a higher rotation rate and thinner diffusion layer, as well as decreased Cu content increasing the effects. Lastly, surface
characterization confirmed hypotheses based on previous AA2XXX studies that a Cr3+ rich film formed on the surface of AA7XXX alloys and of platinum, selected as an exemplar material, impedes the ORR, thereby offering corrosion protection. From: U.-E. Charles-Granville, C. Liu, et al., J. Electrochem. Soc., 167, 111507 (2020).
Recycling of Gold Using Anodic Electrochemical Deposition from Molten Salt Electrolyte With the concentration of gold in electronic devices at 400 ppm, about 10X of that found in the highest grade of ore, gold recycling makes sense from both sustainability and economic viewpoints. Today’s process utilizes the combination of pyro and hydrometallurgy techniques, which involves steps requiring lengthy process times and produces hazardous liquid waste. It is in this context that researchers from the University of Tokyo have come up with a novel approach based on three factors: a) alloying gold with an alkaline metal, such as sodium, b) dissolving the alloy in a molten salt containing the same alkaline metal cation, and c) anodically depositing gold. This approach avoids the hydrometallurgy step altogether. The alloying alkaline metal is deposited on the cathode and is thus recovered. The research team carried out electrochemical characterization using cyclic voltammetry and identified the potential at which gold can be oxidatively deposited. Gold separation was carried out potentiostatically at 0.6V vs. Na/Na+ reference electrode. The authors confirmed the purity of gold obtained using SEM, EDS, and XRD. This work provides a great starting point for developing an environmentally friendly, sustainable gold recycling process. From: T. Ouchi, S. Wu and T.H. Okabe, J. Electrochem. Soc., 167, 123501 (2020).
Communication–Detection of Salivary Cortisol Using Zinc Oxide and Copper Porphyrin Composite Using Electrodeposition and PlasmaAssisted Deposition The gold standard for detecting salivary cortisol levels is an enzyme-linked immunosorbent assay (ELISA). A research team led by Florida International University investigators is aiming to develop a simpler electrochemical test based on a copper chlorophyllin (CuPP) complex loaded on ZnO nanostructures, which would allow disposable sensors to be used for point of care health monitoring. The researchers deposited the ZnO-CuPP onto carbon electrodes in two ways: (1) nano-ZnO electrodeposition followed by chemical incorporation of CuPP, and (2) deposition with an atmospheric low-temperature plasma jet. Amperometric detection of cortisol in standard solutions showed a 3X higher sensitivity in the plasmadeposited electrodes due to formation of a more effective ZnO and CuPP composite. In following experiments, measurement of
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cortisol concentrations in 50 salivary samples showed a close match between ELISA readings and the plasma-deposited ZnOCuPP electrodes, which also demonstrated good repeatability. This suggests a multi-use and personalized cortisol sensor could be used to monitor stress-related problems in patients. This paper was featured in the JSS Focus Issue on Porphyrins, Phthalocyanines, and Supramolecular Assemblies in Honor of Karl M. Kadish. From: A. Sonawane, S. Nasim, P. Shah, et al., J. Solid State Sci. Technol., 9, 061022 (2020).
Structure and Photocatalytic Properties of TiO2 Coated Multi-Walled Carbon Nanotubes Prepared by Solvothermal Method Water pollution has become an even more pressing matter in recent decades due to unrestrained flow of wastewater from various industries, as well as poorly planned urbanization. In response to this pollution problem, photocatalytic degradation of sewage has become a hot topic in the field of wastewater treatment. TiO2 is one of the most commonly researched photocatalytic materials due to its high photocatalytic activity. However, TiO2 has a relatively wide bandgap, which limits its application, and photogenerated holes and electrons are easily recombined, thus reducing its photocatalytic efficiency. In an effort to overcome these issues, researchers from Yangzhou University have developed a simple and efficient onestep solvothermal method for the preparation of TiO2 coated multi-walled carbon nanotubes (MWCNTs). TiO2-MWCNTs nanocomposites demonstrate a reduced bandgap of ~3.0 eV compared to ~3.2 eV for pure TiO2. Through analysis of photoluminescence spectra, the researchers demonstrate that TiO2-MWCNTs nanocomposites offer improved electron transfer performance compared to pure TiO2. The effects of MWCNTs/TiO2 mass ratio on the optical and photocatalytic properties of the nanocomposites were also investigated. The facile method presented in this work is a promising route to overcome the limitations of TiO2 as a photocatalytic material for water treatment. From: D. Li, W. Zhang, et al., ECS J. Solid State Sci. Technol., 9, 063001 (2020).
Tech Highlights was prepared by Joshua Gallaway of Northeastern University; Mara Schindelholz of Sandia National Laboratories; David McNulty of Paul Scherrer Institute; Chao (Gilbert) Liu of Shell; Chock Karuppaiah of Vetri Labs; and Donald Pile. 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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Advanced Manufacturing for High-Temperature Materials by Sean R. Bishop and Jianhua Tong
A
dvances in manufacturing are largely driven by reducing cost and energy use and taking advantage of materials and designs to unlock new device properties. Energy conversion and storage is a key electrochemistry application in the high-temperature energy, materials, and processes (H-TEMP) Division. For example, the solid oxide fuel and/or electrolysis cell uses a thin, dense oxide ion (or proton) conducting membrane sandwiched between thin, porous electrodes to convert fuel to electricity and vice versa at ~>500oC. Furthermore, due to their high-temperature stability, ceramics are typically used. Developments in advanced manufacturing are thus directed towards making thinner, dense electrolytes and microstructurally optimized, multi-phase electrodes. Other high-temperature electrochemical applications requiring similar manufacturing developments include semi-conductor gas sensors, catalytic membrane reactors, heterogeneous catalysis, and thermal and corrosion barriers. The first article in this issue, “Manufacturing Techniques of Thin Electrolyte for Planar Solid Oxide Electrochemical Cells,” is written by W. Wu and D. Ding (Idaho National Laboratory), W. Feng (Binghamton University), and C. Jin (University of NebraskaLincoln). This feature breaks up manufacturing processes into those that require high-temperature sintering (sintering-engaged), such as screen printing and tape casting, and those that do not (sinteringfree), such as physical and chemical vapor deposition. As the authors describe, sintering-engaged processes are typically low cost, but result in thicker electrolytes and less control over composition and discrete phase formation, as compared to sintering-free processes. The second article, “Aerosol Jet Deposition for Structured Materials,” is by L. Tsui, J. Plumley, and F. H. Garzon, all from the University of New Mexico. This feature focuses on a technique to create mesoscopic architectures of electrochemical functional materials. The aerosol jet technique generates an aerosol of droplets that are deposited on a substrate to create unique microstructures with higher resolution and greater substrate roughness tolerance while using higher viscosity (e.g., higher solids loading) inks as compared to inkjet-based deposition. The third article, “Cold Sintering for High-Temperature Electrochemical Applications,” is written by a team of authors from Pennsylvania State University. Z. A. Grady, J. H. Seo, K. Tsuji, A. Ndayishimiye, S. Lowum, S. Dursun. J. P. Maria, and C. A. Randall describe a new method to reduce the cost of conventional sintering by lowering the temperature required for densification. Typically, powder interface chemistry is modified using dry or wet “solvents” to promote a dissolution/precipitation process, reducing ceramic densification to ~100–300oC from ~1,000–1,500oC. The lower temperature process may open doors to achieving nano-scale, high electrochemical activity electrode microstructures, which typically coarsen during high-temperature processing. The final article, “Advanced Manufacturing of IntermediateTemperature Protonic Ceramic Electrochemical Cells,” comes from Clemson University. S. Mu, Z. Zhao, H. Huang, J. Lei, F. Pang, H. Xiao, K. S. Brinkman, and J. Tong briefly review the exciting developments in the manufacturing of protonic ceramic electrochemical devices in recent years. The conventional sintering techniques for protonic ceramics are briefly summarized as a baseline. After that, the state-of-the-art solid state reactive sintering technique is discussed for demonstrating promising device performance. Finally, the newly-developed rapid laser reactive sintering and integrated additive manufacturing techniques for advanced manufacturing of protonic ceramics with desired crystal structures, microstructures,
and complicated geometries are briefly introduced, making it possible to rapidly and cost-effectively manufacture protonic ceramic electrochemical devices. It is worth noting that this issue only covers a small part of the advances in the manufacturing of high-temperature materials. For example, further improvements in nano-structuring electrodes and electrolytes with atomic layer deposition are expected. Additionally, understanding the role solid state ionics (e.g., ionic migration) has in electrically assisted sintering processes (e.g., flash sintering, current assisted hot pressing, or spark plasma sintering) is expected to lead to their broader use. Lastly, advances in computation are playing a role in improving manufacturing processes through, for example, rapid response and adaptability of process control methods and understanding the physics of complicated processes. © The Electrochemical Society. DOI: 10.1149.2/2.F05204IF.
Authors’ Note This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government.
About the Authors Sean Bishop is a scientist at Sandia National Laboratories in Albuquerque, NM, returning after having been a student intern 15 years earlier. Sean was a principal engineer at Redox Power Systems, USA (2016-2019), a research scientist at the Massachusetts Institute of Technology, USA (2014-2016), and an assistant professor at Kyushu University, Japan (20112014). Sean has been characterizing and processing high-temperature ceramics for two decades. He received his PhD at the University of Florida on characterizing the point defect chemistry of solid oxide fuel cell materials in 2009. He is currently the senior vice-chair of the ECS H-TEMP Division. He may be reached at srbisho@sandia.gov. Jianhua (Joshua) Tong is an associate professor of materials science and engineering at Clemson University. Before joining Clemson in 2016, he was a research assistant/associate professor at the Colorado School of Mines. At Clemson, Dr. Tong manages the Sustainable Clean Energy Laboratory. He has published more than 80 peer-reviewed papers and six book chapters, and filed 15 patents. His publications have been cited over 5,200 times, and his h-index is greater than 33. He received his PhD from the Dalian Institute of Chemical Physics, CAS. In addition, he received extensive researcher/ JSPS fellow/postdoc training on catalytic membrane reactors and solid oxide fuel cells at the Research Institute of Innovative Technology for the Earth, the National Institute of Advanced Industrial Science and Technology, the University of Cincinnati, and the California Institute of Technology. He may be reached at jianhut@ clemson.edu. https://orcid.org/0000-0002-0684-1658
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REVIEWS FROM PREVIOUS EDITIONS
Manufacturing Techniques of Thin Electrolyte for Planar Solid Oxide Electrochemical Cells by Wuxiang Feng, Wei Wu, Congrui Jin, and Dong Ding
S
Introduction
olid oxide electrochemical cell (SOC) technology, such as solid oxide fuel cells (SOFC) for distributed power generation and solid oxide electrolysis cells (SOEC) for hydrogen production, increasingly attracts interest from the research community due to its advantages of efficient direct conversion of energy and environmentally benign operation. The conventional SOCs using oxygen-ion conducting electrolytes suffer from many challenges associated with high operating temperature (typically above 750°C), which not only results in fast degradation but also problems, such as expensive refractory materials in the system components, less competitive cost, slow start-up, and burden on thermal insulation.1 The trend of research on SOCs has shifted from high-temperature to intermediate-temperature. To compensate for the ionic conductivity loss of electrolyte material at lower temperatures, strategies include exploring new proton conducting electrolyte materials with higher conductivity and decreasing the thickness of electrolytes. Because the new protonic ceramic electrolyte development is still at an early stage,2,3 the research emphasis was placed on thin electrolyte manufacturing using an electrode-supported configuration and has decreased the operating temperature of SOCs from 800-1,000°C to around 700°C without compromising performance.4 In the electrode-supported SOCs, the electrode support, acting as a supporting layer by providing sufficient mechanical strength, was fabricated before introducing the thin electrolyte. It has a thickness in the range of a few hundred microns and is predominantly formed by extrusion, tape casting, and dry pressing, which can be manufactured readily with much fewer defects as observed. In contrast, manufacturing the thin electrolyte is paramount and complicated. The electrolyte with a thickness at the range of 10-20 microns or less plays a critical role in reducing ohmic resistance. A well-manufactured electrolyte needs to be 1.) thin, 2.) gas-tight and pinhole-free, 3.) chemically pure, 4.) well contacted with electrodes, 5.) near to bulk conductivity, and 6.) cost-efficient. These properties put stringent requirements on and present challenges to the development of manufacturing techniques and processes. Generally, an electrolyte layer was fabricated on a pre-sintered or as-prepared electrode support layer (ESL), referred to as a white body or green body, respectively, by either sintering-engaged processes or sinteringfree processes. Sintering-engaged processes involve two steps: coating and subsequent sintering. Briefly, the processes are depositing a green body electrolyte layer on ESL followed by debinding and co-sintering. The coating step uses techniques, such as tape casting, screen coating, wet powder spray, electrophoretic deposition, dip coating, spin coating, slip coating, and additive manufacturing, etc. The sintering step involves technologies, such as solid state sintering, spark plasma sintering, microwave sintering, selective laser sintering, and flash light sintering, etc. The sintering-free processes form a dense and very thin electrolyte layer on the ESL in one step using thermal spray technologies or gas phase deposition technologies that do not need high-temperature sintering, such as thermal plasma spray, chemical, or physical vapor deposition. Sintering-engaged processes are more cost-efficient compared with sintering-free processes. However,
they can have drawbacks, such as inaccurate stoichiometric control, mismatch of shrinkage behavior, and relatively large thickness of electrolyte. In this article, we review the process of manufacturing thin electrolytes in electrode-supported planar SOCs by categorizing them as sintering-engaged or sintering-free processes. Manufacturing technologies are expected to play an increasingly important role in helping SOC technology move forward for the market penetration by reducing the processing cost and ultimate electricity and hydrogen cost. This short review illustrates the sophisticated technical characteristics mostly linked to performance-driven metrics for reduced temperature operation and general economic feasibility considerations.
Overview of Sintering-Engaged Processes Electrolyte Coating Techniques Screen Printing (SP) Screen printing (SP) is the most widely used coating technique in planar SOC fabrication. It has been proven to be able to fabricate dense electrolyte layers as thin as ~2.5µm, and as large as 33×33 cm2.2,5,6 In the SP process, a viscous electrolyte ceramic paste with viscosity in the range of few Pa·s is forced through the open meshes of a screen using a squeegee.7 (See Fig. 1(a).) The paste is preferred to have a so-called pseudo-plastic rheological behavior to ensure the dimensional accuracy of the printing layer.7 One concern for SP is that the thickness of dense electrolyte is usually in the range of 10-20µm,8– 13 which is relatively thick and should be optimized for lower ohmic resistance. Another concern for SP is that multiple printing passes and drying time in between them are usually necessary to produce a gastight electrolyte, which not only increases production time but also results in larger thickness. However, two recent publications showed the feasibility of <5µm-thick dense electrolytes and a single printing cycle. In 2018, An et al. reported a 5×5 cm2 cell with a <5µm-thick electrolyte with excellent performance of an open circuit voltage (OCV) of 1.056V and a power density of 1.3 W/cm2 at 600°C.14 They proposed that the high performance for the large cell was resulted from the improvement of the mismatch of thermal shrinkage between anode and electrolyte layer. In 2019, Choi et al. reported a columnar structural 2.5-µm thick BCZY3 electrolyte yielding a power density of 960 mW/cm2 and an OCV of 1.052 V at 600oC. The electrolyte was obtained with only a single printing pass. Wet Powder Spray (WPS) Electrolyte deposition by wet powder spray (WPS), also known as spray coating or suspension spray, is a process in which spraying a colloidal electrolyte suspension is used to form an electrolyte coating. (See Fig. 1(b).) The coating ink was sprayed over heated anode support along a meandering path. The requirements for powder used in WPS are 1.) high-quality starting powder with a homogeneous particle size distribution and 2.) no large amount of aggregates. WPS is a scalable technology that can deposit thin electrolyte cost-efficiently and has been applied in the fuel cell industry in the manufacturing
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(continued on next page) 47
Feng et al.
(continued from previous page)
of electrolyte, cathode, and protective coating of interconnects.15–17 A unique advantage of WPS is its capability of coating electrolytes on non-uniform or non-planar geometries.7 Studies on WPS usually use a pressurized spray gun to produce the gas-tight electrolyte layer with thickness commonly in a range of 10-30µm.18–25 Pressurized spray guns are widely used in industry but suffer from overspray, which affects coating efficiency and production cost.7 Recently, more and more researchers employ ultrasonic spray systems, with much less overspray, to produce a thinner electrolyte layer (<10µm) resulted from smaller and more uniform suspension droplets in the spray mist produced via ultrasonic atomization. For example, Taillades et al. produced a cell of 4µm-thick BZCYYb electrolyte producing an OCV of 1.105V and a power density of 418 mW/cm2 at 600°C.26 Electrophoretic Deposition (EPD) Electrophoretic deposition (EPD) is a process of depositing electrolyte powder on a substrate coated with a thin conductive layer in organic media by electrophoresis. (See Fig. 1(c).) Previous
studies showed EPD could deposit gas-tight electrolyte film in anode-supported SOCs with thickness in the range of 4-30 µm.27–29 It is reported that the deposition rate can be as high as 1µm/min, and EPD is capable of depositing multiple layers sequentially.30 No report has shown its applications in the fuel cell industry so far. It has disadvantages such as 1.) the production of crack-free sintered films with 5-10µm thickness in one cycle is difficult, it is necessary to use multiple EPD cycles to heal pores and defects, and 2.) a need for a graphite layer to be coated on the substrate to ensure better conductivity. Thus, adhesion of the coatings to substrate is not always as good as required.27 Tape Casting (TC) Tape casting (TC) was first introduced in 1947 by Howatt et al.31 and has been widely used in SOC anode and electrolyte manufacturing. In the process of tape casting, a slurry containing the electrolyte ceramic powder, referred to as slip, is degassed under agitation at the vapor pressure of the media to remove air bubbles. (See Fig. 1(d).) Subsequently, the slip is extruded through a blade on a polyester film. The blade, referred to as a doctor blade, can control the thickness of the casted slip. The tape is dried on a heated bed to remove part of
Fig. 1. Schematics of coating techniques in sintering-engaged processes: (a) screen printing, (b) wet power spray, (c) electrophoretic deposition, (d) tape casting and lamination, (e) spin coating, (f) slip casting, and (g) inkjet printing. Fig.1(c) is reproduced from the John H. Glenn Research Center.47 48
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the media and shift it from a semi-solid to solid. Unlike SP and WPS mentioned above, TC is a film manufacturing technique that needs subsequent lamination or calendaring to combine with ESL and form the green body of half-cells. As reported by previous literatures,32–35 it is hard to fabricate an electrolyte layer thinner than 10µm by the conventional TC process. To further decrease the thickness, Moon and Hyun et al. reported the use of a novel tape caster called a lip coater using a slip with low viscosity (200-500 mPa·s) to produce a gas-tight yttria-stabilized zirconia (YSZ) electrolyte of 5µm in thickness36. Another drawback of TC is the need for lamination or calendaring to form a green body half-cell decreases production efficiency. To solve this problem, Schmidt et al. proposed co-casting by using several doctor blades for casting a ceramic slurry of different compositions in a single pass.37 Liu et al. reported sequential TC by casting slip on a premade tape to form a multi-layer structure.38 In our group, we developed a rollto-roll process to manufacturing SOCs as large as 10 ×10 cm2 cells by tape casting and are working on utilizing spray coating to further elevate our efficiency.39 Spin Coating Spin coating or spin casting (SC) uses an electrolyte ceramic slurry or sol-gel suspension deposited onto a smooth, flat substrate, which is subsequently spun at a high velocity to centrifugally spread the solution over the substrate. (See Fig.1(e).) The speed at which the solution is spun and the viscosity of the slurry or sol determine the ultimate thickness of the deposited film. Repeated depositions can be carried out to increase the thickness of films as desired. SC has potential for industrialization but is harder to incorporate into a production line compared with SP, TC, and WPS. Han et al. reported 5 × 5 cm2 cells with an 1µm gas-tight YSZ electrolyte fabricated by dip coating a YSZ nanosuspension followed by spin coating the polymeric sol onto a tape-cast anode.40 Kang et al. used an electrolyte ceramic slurry for spin coating and engineered a 7.6µm-thick porous, yet gas-tight, BZCYYb electrolyte on porous ASL, which led to an OCV higher than 1V.41 Slip Casting Slip casting, and especially vacuum slip casting (VSC), is a coating technique for planar or tubular porous substrates. During VSC, a wet powder slurry is applied on ESL support, and the liquid part is pumped out through the porous structure by vacuum applied on the other side of the ESL. (See Fig. 1(f).) In this way, a uniform powder layer is formed. Thin, flat layers of electrolyte with thicknesses ranging from 1 to 30µm can be produced.7,42,43 Owing to the vacuum-assisted filtration and sedimentation, the green particle density is relatively high and thus ensures good gas-tightness after sintering. Despite its advantages, it is not widely used, and only a few researchers report its application on SOC fabrication. Additive Manufacturing Additive manufacturing, referring to a variety of techniques that manufacture using the scheme of material addition throughout a three-dimensional work envelope under automated control, has been gaining popularity over last two decades. There are five commercially available additive manufacturing technologies: inkjet printing (IJP), selective laser sintering (SLS), fused deposition modeling (FDM), stereolithography (SLA), and laminated object manufacturing (LOM). Although all of them are capable of manufacturing ESL,44,45 only inkjet printing has been reported for depositing thin electrolyte films in anode-supported SOC due to its high vertical resolution. The schematic of inkjet printing technology is shown in Fig. 1(g). Recently, Han et al. fabricated a fully inkjet-printed SOC with 0.8µm thick YSZ electrolyte using an HP printer, achieving an ohmic resistance of approximately 0.05 Ω cm2, an OCV of 1.12 V, and a maximum power density of 730 mW/cm2 at 650°C.14 Large-area inkjet printing of YSZ layers is also possible as presented by Esposito et al. They deposited thin, gas-tight, 1.2µm thick YSZ electrolyte layers of an area of 16 cm2 on NiO-YSZ tape casted anode supports by using colloidal inks with nanometric powders and obtaining a close-to-theoretical OCV of 1.07-1.15 V.46 The drawback of inkjet
printing is the deposition rate, which is much lower than conventional methods such as tape casting, screen coating, and wet powder spray, but has the potential for great improvement through the employment of multiple inkjet nozzles simultaneously during printing.
Sintering Technologies Solid State Sintering (SSS) Solid state sintering (SSS) is a conventional and the most frequently used sintering technique in which half-cells are sintered using a conventional resistance furnace at a target temperature for several to tens of hours without applied pressure. It is a low-cost technique in terms of apparatus and highly industrially established. However, due to the high target temperature and long annealing time needed for densification and grain growth, side reactions and element evaporation are frequently observed, leading to undesired stoichiometry variations and degraded bulk and grain boundary conductivities.48–55 A process called two-step sintering was proposed to mitigate such issues by exposing the half-cell to a peak temperature for few minutes to achieve critical density followed by rapid cooling to a lower temperature than the target temperature used in the conventional SSS process to promote further grain growth.56 A modification of SSS technique is solid state reactive sintering (SSRS), which combines phase formation and sintering in a single step. In the SSR method, the stoichiometric mixtures of precursors are mixed, formed in the desired dimension, and then fired in a single process, which reduces the overall cost of fabrication and processing time. That said, the feasibility of producing phase-pure samples by SSRS route at high temperature has been expressed as a concern in some studies.57,58 Spark Plasma Sintering (SPS) Spark plasma sintering (SPS) is a technology that applies external pressure and an electric field simultaneously in a controlled atmosphere to enhance the densification of ceramic compacts. The electric field-driven densification supplements sintering with a form of hot pressing, to enable lower temperatures, less time, and less energy consumption than SSS. (See Fig. 2(a).) For example, Bu et al. produced a 500µm BZCY pellet that was sintered by SPS for around 5 min with near full density (98%). Park et al. also reported a highly dense (98%) BZY8 ceramic prepared with sintering nano-powder at 1,400-1,500°C for 5 min. Usually, SPS only sinters for a few minutes at a lower temperature than that used in SSS, thus minimizing grain growth (generally nano-sized grains are expected), and most importantly, for the proton-conducting perovskite, avoidance of BaO evaporation.34,56 It is interesting to note that Hulbert et al.59 showed that, despite the name, a spark plasma does not actually exist during SPS, so SPS is also known as “Field Assisted Sintering Technique” (FAST) or “Electric Field Assisted Sintering” (EFAS) in the sintering community.60,61 Microwave Sintering (MS) Microwave sintering (MS) heats the material internally rather than via surface radiative heat transfer from an external heat source. (See Fig. 2(b).) Due to the higher heating efficiency by microwaves, less time is needed to reach the sintering temperature. Additionally, greater densification of powder sintered by a microwave furnace can be reached compared with conventional SSS, as reported by Goldstein.62 Jiao et al. reported a comparison of two cells sintered by a microwave furnace and a resistance furnace.63 The cell sintered in a microwave furnace for 5 min produced a higher performance electrolyte, suggested to be due to finer and sharper particles and higher TPB densities in the anode. Ng et al. also reported a study comparing cells fabricated by MS (at 1,300-1,350°C) and SSS (at 1,300-1,500°C).64 It was found that the grain size of conventional sintered cells varied from 2.9 to 9.8µm, whereas that of the MSsintered cells was below 2µm. In addition, they found MS-sintered cells have higher ionic conductivity than SSS-sintered cells at 800°C. More studies are necessary to reveal the full benefits of microwave sintering technology.
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Fig. 2. Schematics of sintering techniques in sintering-engaged processes: (a) spark plasma sintering and (b) microwave sintering. Fig. 2(a) is reproduced from Yushin et al.65 Fig. 2(b) is reproduced from Demirskyi et al.66
Overview of the Sintering-Free Thin Electrolyte Manufacturing Process Physical Vapor Deposition (PVD)
Physical vapor deposition (PVD) consists of a variety of vacuum deposition methods, which can be used to produce thin films. PVD is characterized by a process in which the material goes from a condensed phase to a vapor phase and then back to a thin film condensed phase. (See Fig. 3(a).) Its subcategories include cathode arc deposition, electron-beam PVD, evaporation deposition, closespace sublimation, pulsed laser deposition, sputter deposition, pulsed electron deposition, and sublimation sandwich method. PVD is capable of depositing a submicron thin film but requires a smooth surface of the substrate to facilitate the effective deposition.67 If a substrate with a porous or rough surface is used for directional PVD, such as evaporation, sputtering, and pulsed laser deposition (PLD), a realistic situation is that the sidewall of the pores will not be covered. Thus, voids in electrolyte will be formed.68 Hence, a surface modification layer of the porous ESL substrate is usually required, which inevitably increases production time. Also, the surface modification layer should be prudently designed and treated by annealing to mitigate Ni coarsening after reduction.69,70 Noh et al. reported an anode supported SOC with 1um-thick YSZ and 200nm-thick Gd-doped ceria (GDC) thin films deposited on an anode functional layer with controlled surface quality by pulsed laser deposition (PLD) producing an OCV higher than 1V and a power density of ~500 mW/cm2 at 500°C.71
Chemical Vapor Deposition (CVD)
Chemical vapor deposition (CVD) is a process in which the substrate is exposed to one or more volatile precursors, which react and/or decompose on the substrate surface to produce the desired thin film deposit. (See Fig. 3(b).72)It includes many subcategories as in PVD, such as plasma-enhanced CVD (PECVD), aerosol assisted CVD (AACVD), atomic-layer CVD (ALCVD), and metal-organic CVD (MOCVD). Among all electrolyte manufacturing technologies, CVD is the only one that forms materials at a molecular level and hence, not only provides a very thin, nanoscale layer, but also can deposit thin films on complex substrate surfaces or selected areas.73 However, due to the molecular level resolution, its deposition rate is relatively slow (~200-2500 A/min72), and the fabrication cost of the sophisticated apparatus is relatively high, as compared with other methods. A variety of novel CVD technologies has been developed to mitigate the drawbacks and to broaden its applicability. Jang et 50
al. reported a cell with a fully dense 1-µm thick aerosol-assisted CVD YSZ electrolyte producing a stable OCV greater than 1V at a temperature ranging from 450-600°C and a power density of 600 mW/cm2 at 600°C.74
Thermal Plasma Spray (TPS)
With thermal plasma spray (TPS), the electrolyte feedstock is introduced into and melted by a plasma jet (with a temperature between 7,000K and 20,000K75) propelled towards a substrate surface where the molten droplets flatten, rapidly solidify, and form a film. (See Fig. 3(c).) It is often used for the development of metal-supported SOCs. TPS can be categorized into atmospheric, vacuum, low-pressure, and suspension plasma spray. Its high deposition rate makes it a promising technique for mass production of SOCs.However, it has difficulty manufacturing < 20 μm electrolytes with high compactness up to date. This technology is still under development. Soysal et al. reported a 35 µm 8 mol% YSZ electrolyte with good gas-tightness fabricated with vacuum TPS.76 In combining such plasma-sprayed electrolytes with improved plasma sprayed electrodes, power densities of ~800 mW/ cm2 at 800°C for small single cells (12.56 cm2), of ~400 mW/cm2 at 800°C for 80 cm2 cells, and >300 mW/cm2 at 0.7V in a 250 W stack made of 10 cells were successfully demonstrated.
Summary and Perspective SOCs using a thin electrolyte layer are a development trend of IT-SOC technology. Various manufacturing techniques have been developed and applied in the past decades to increase cell performance and boost production efficiency by effectively minimizing the thickness of the electrolyte layer. The electrolyte manufacturing process can be divided into sintering-engaged or sintering-free processes. Sintering-free processes like CVD and PVD are relatively expensive technologies in terms of equipment cost and have lower production efficiency compared with the sinteringengaged processes, although they are capable of producing very thin, highly compact, and structurally-designed electrolyte formed at temperatures much lower than those required in sintering-engaged processes. In contrast, thermal plasma spray has unique advantages, such as rapid manufacturing and low cost, but faces a great challenge on minimizing film thickness and porosity. As a result, the sinteringengaged processes will remain more widely used compared with sintering-free processes, although suffering from problems such as sintering-caused side reactions, mismatch of shrinkage behavior, and high energy consumption. It is envisioned that advanced The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
Wei Wu is a staff material scientist at the Idaho National Laboratory (INL), specializing in the development of electrochemical technologies, such as electrochemical upgrading of light alkanes, steam electrolysis, and fuel cells. Dr. Wu has extensive industry and research institute experience in the design, fabrication, and evaluation of advanced electrocatalysts and solid state devices. Prior to joining INL, he was a postdoctoral researcher at the University of Maryland Energy Research Center (UMERC), where his effort was focused on scale-up of bi-electrolyte layer solid oxide fuel cells. Dr. Wu received his doctorate in material science from the Chinese Academy of Sciences. He may be reached at wei.wu@inl.gov. https://orcid.org/0000-0003-2067-7361 Congrui Jin joined the Department of Civil and Environmental Engineering at the University of Nebraska-Lincoln in the spring of 2020. She received her PhD in mechanical engineering with a minor in applied mathematics from Cornell University. Prior to joining the University of Nebraska-Lincoln, she was an assistant professor at the Department of Mechanical Engineering at The State University of New York at Binghamton. Dr. Jin’s research contribution is documented in more than 40 peer-reviewed journal publications, two book chapters, and one book. Her research interest is in the broad area of theoretical and applied mechanics motivated by practical applications in electrochemical systems, additively manufactured materials, and construction materials. She may be reached at cjin5@ unl.edu. https://orcid.org/0000-0003-0606-5318
Fig. 3. Schematics of sintering-free techniques: (a) CVD, (b) PVD, and (c) TPS. Fig. 3(a) is reproduced from Zhang et al.77 Fig. 3(b) is reproduced from Faraji et al.78 Fig. 3(c) is reproduced from Wang et al.79
manufacturing technologies, enabled by automation and artificial intelligence, will provide more technical opportunities for process intensified SOC manufacturing with significant cost reduction. © The Electrochemical Society. DOI: 10.1149.2/2.F06204IF.
About the Authors Wuxiang Feng is a PhD candidate in mechanical engineering at Binghamton University. He obtained his MS in mechanical engineering from Binghamton University in 2018. He is currently conducting research in electrochemistry as an intern at the Idaho National Laboratory under the supervision of Dong Ding, Congrui Jin, and Wei Wu. His research efforts focus on advanced manufacturing and scale-up of solid oxide electrochemical cells (SOCs) and SOC stacks by using technologies such as solid oxide additive manufacturing, HT roll-to-roll, rapid sintering, and ultrasonic spray. He may be reached at wuxiang.feng@inl.gov.
Dong Ding is a senior materials scientist/ engineer at the Idaho National Laboratory and a group manager for the chemical processing group. Dr. Ding has over 100 co-authored peerreviewed publications and holds three U.S. patents and multiple patent applications. He is a principal investigator for multiple projects, including direct funded and laboratory directed research and development. He is a technical lead of HydroGEN of Energy Materials Network under the U.S. Department of Energy. Dr. Ding serves as an executive committee member in the H-TEMP Division for The Electrochemical Society, and an editorial board member for the Journal of Power Sources Advances. Dr. Ding is a recipient of the Asian American Most Promising Engineer of the Year 2020, and Federal Laboratory Consortium Far West Awards in the category of Outstanding Technology Development in 2019. His current research interests include natural gas upgrading, high-temperature electrolysis, advanced manufacturing, CO2 conversion, ammonia electrosynthesis, and fuel cells. He may be reached at dong.ding@inl.gov. https://orcid.org/0000-0002-6921-4504
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69. U. P. Muecke, S. Graf, U. Rhyner, and L. J. Gauckler, Acta Mater., 56, 677 (2008) https://linkinghub.elsevier.com/retrieve/ pii/S1359645407006398. 70. H.-S. Noh et al., J. Electrochem. Soc., 156, B1484 (2009) https:// iopscience.iop.org/article/10.1149/1.3243859. 71. H.-S. Noh et al., J. Power Sources, 247, 105 (2014) https:// linkinghub.elsevier.com/retrieve/pii/S0378775313014225. 72. P. M. Martin, Ed., in Handbook of Deposition Technologies for Films and Coatings (Third Edition),, p. 1–31, William Andrew Publishing, Boston (2010) http://www.sciencedirect.com/ science/article/pii/B9780815520313000016. 73. G. Meng, H. Song, C. Xia, X. Liu, and D. Peng, Fuel Cells, 4, 48 (2004) http://doi.wiley.com/10.1002/fuce.200400006. 74. D. Y. Jang et al., J. Electrochem. Soc., 164, F484 (2017) https:// iopscience.iop.org/article/10.1149/2.0181706jes. 75. S. C. Snyder et al., Phys. Rev. E, 50, 519 (1994) https://link.aps. org/doi/10.1103/PhysRevE.50.519. 76. D. Soysal, J. Arnold, P. Szabo, R. Henne, and S. A. Ansar, J. Therm. Spray Tech., 22, 588 (2013) https://doi.org/10.1007/ s11666-013-9929-4. 77. Q. Zhang, D. Sando, and V. Nagarajan, J. Mater. Chem. C, 4, 4092 (2016) http://xlink.rsc.org/?DOI=C6TC00243A. 78. G. Faraji, H. S. Kim, and H. T. Kashi, in Severe Plastic Deformation, p. 1–17, Elsevier (2018) https://linkinghub. elsevier.com/retrieve/pii/B9780128135181000205. 79. M. Wang, in Biomedical Composites,, p. 127–177, Elsevier (2010) https://linkinghub.elsevier.com/retrieve/pii/B9781845694364500068.
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Aerosol Jet Deposition for Structured Materials by Lok-Kun Tsui, John Plumley, and Fernando H. Garzon History of Aerosol Jet Printing (AJP)
T
he roots of Aerosol Jet Printing (AJP) materials trace back to the development of digital inkjet printing. Pressure driven, continuous flow methods for inkjet printing were first developed at Stanford University by R. Sweet in the 1960s1 and led to a number of continuous flow printing technologies by the 1970s. Electrostatic control was used to guide the trajectory of continuously flowing ink drops. The drops were either directed to the print media or deflected into a gutter. These systems required the recirculation of the unused ink, adding considerable system complexity. In the 1970s, Ichiro Endo, working for Canon, noticed that when a syringe needle filled with ink was heated by the tip of a soldering iron, small bubbles of ink were expelled from the tip.2 The printing technology developed using this approach was appropriately named bubble jet printing. John Vaugh at Hewlett-Packard independently developed a similar approach named thermal inkjet printing. This method of controlled ink delivery dominated the early consumer market for inkjet printers. Drop-on-demand (DOD) inkjet printing technology using piezoelectric transducers was first developed by Zoltan3 and Kyser and Sears.4 The piezoelectric nozzle created a pressure wave that could be used to propel single droplets and modulated at high rates. This acoustic process greatly simplified the design of pressure-driven printing processes. The technology was also adapted to solid wax inks that were melted in heated ultrasonic print heads and solidified in contact with the print medium. The later development in the 1980s and 90s of acoustic focusing methods at Xerox Corporation5 enabled smaller feature sizes over larger printhead to sheet distances. Homogeneous phase inks were mostly used in the early processes. Inks comprised of colloidal suspensions also were developed; however, problems with colloid instability, rheology, and nozzle clogging posed challenges. Still, this early work on inkjet printing laid the groundwork for materials deposition by aerosol jet methods. The development of aerosol printing was started in the early 2000s, and Marquez et al. reported on the aerosol jetting of protein and colloidal cell suspensions.6 In the last decade, AJP has emerged as a complementary technique to inkjet printing and has found promising applications in printed electronics, sensors, and electrochemical power systems. In this article, we will review the working principles of AJP and its applications to topics of interest to The Electrochemical Society.
of the pneumatic configuration is the support for higher viscosity inks (1- 1,000 cp), while the ultrasonic atomizers are limited to inks with viscosity <10 cp.7 Although pneumatic atomization can support higher viscosities, additional processing downstream with a virtual impactor is needed to obtain a sufficiently narrow distribution of droplet sizes, which is not required in ultrasonic atomization.7 Upon reaching the outlet (Fig. 1, locations 4-5), the ink stream is focused on the action of aerodynamic focusing nozzles and an additional sheath gas stream to a linewidth on the order of 10-100 micron wide.8,9 Figure 2 shows one such “Nanojet” aerosol printer procured from Integrated Deposition Solutions (Albuquerque, NM, USA) as it deposits Pt nanoparticle ink onto the surface of an alumina substrate. The main tuning parameters for AJP are the atomization strength, either the ultrasonic power or the flow rate of the pneumatic atomizer gas stream, the aerosol gas flow rate, and the sheath gas flow rate. Increasing the atomization strength and the aerosol gas flow rate both increase the rate of deposition, and the sheath gas flow can be tuned to decrease the printed line width.8 Judicious selection of deposition conditions is needed to minimize overspray, the deposition of diffuse ink droplets adjacent to the printed line.9 For nanoparticle inks, an optimum must be identified between low flow rates where the focusing is insufficient and high flow rates where the excessive sheath gas flow results in the drying of the ink and the dispersal of weakly bound nanoparticles. The substrate preparation and post-processing of aerosol deposited films is critical for obtaining usable printed structures. Unlike vacuum-based deposition methods, substrates cannot be precleaned by sputtering or ion bombardment, and surface quality maintained by holding in an ultrahigh vacuum environment. The exposure to air and the liquid suspension vehicle or solvent can be detrimental to surface adhesion. Titanium or chromium metal adhesion layers are oftentimes ineffective after air exposure. The ambient atmospheric deposition (continued on next page)
Operational Principle of Aerosol Jet Printing AJP has since become an attractive technique for the deposition of thin films of materials with higher resolution compared to conventional DOD inkjet techniques and the ability to support substantial standoff distances in approximate millimeters. The former offers a resolution about 10s of microns, and the latter enables the printing onto nonplanar substrates.7 Aerosol jet printing relies on the generation of an aerosol through pneumatic or ultrasonic means. In the case of the former, a gas stream generates aerosolized droplets as it passes over the surface of an ink reservoir. In the case of the latter, an ultrasonic transducer transmits an atomizing force through a fluid bath to a separate reservoir containing the ink and generates an aerosol. The advantage
Fig. 1. The operational principle of an aerosol jet printer. (1) ink reservoir, (2) aerosol gas inlet, (3) aerosol gas outlet, (4) sheath gas inlet, (5) nozzle, and (6) substrate.7 Used with permission through Creative Commons CC-BY license.
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conditions thus produce challenges for ink chemistry development that provides suitable adhesion characteristics. Post-processing reaction, pyrolysis, and or sintering may include thermal processing via conventional furnace, rapid thermal annealing, microwave, and or laser heating. The deposition of a wide variety of materials has been demonstrated by aerosol jet deposition, including metals, ceramic materials, and dielectrics. Metal conductors can be printed using commercially available nanoparticle inks, and Ag films typically achieve a conductivity on the order of 10-25% of bulk Ag after thermal sintering.10–12 Reactive nanoparticle-free inks use a chemical reaction activated by a heated substrate to catalyze the formation of metal, and conductivities of 73% of bulk were recently reported by Rosker et al.13 Beyond conductors, Sukeshini et al. have demonstrated the use of AJP for printing ceramics, including NiO, YSZ, and strontiumdoped lanthanum manganate.14 Tsui et al. and Tafoya et al. have both demonstrated the printing of magnetic films using the aerosol jet.15,16 Polymer dielectrics have been printed by Gu et al. for use as ramps connecting uneven surfaces on PCBs and as cores for solenoid inductors.17,18 Finally, with two or more ink sources, composites with tunable compositions can be printed as Wang et al. has demonstrated using polyimide-carbon nanotube composites.19 It is helpful to compare the technology of AJP with inkjet printing. A comparison of the two processes is presented in Table 1.7,20 Siefert et al. performed a side-by-side comparison of AJP and inkjet using the same Ag nanoparticle ink.21 They found that the AJP printed lines were between 33-50 microns, while the inkjet-printed lines were from 56-195 microns. On the other hand, they observed a higher volumetric deposition rate that resulted in thicker lines and better edge definition due to overspray in AJP. Depending on the user’s application, in particular the printing of large features using low viscosity inks on planar substrates, inkjet printing may be the preferred technique.
Recent Developments in Aerosol Jet Printing Transparent Conductors With AJP, finely lined metallic grids can be printed onto substrates to fabricate transparent electrodes. Using AJP, Kopola et al. optimized printing parameters, such as temperature and printing speed, to print a current-collecting silver grid as a suitable substitute for vacuumdeposited transparent ITO thin films in lightweight organic solar cells. (ITO is brittle, high cost, and suffers from resistance loss over large area conductive surfaces.)22 It was also found by Eckstein et al.22 that a higher printing temperature of 140°C for depositing metalorganic inks can help prevent inhomogeneities in the printed grid caused by fast printing speeds that can be detrimental to uniform high conductivity desired in large area electrodes.23 Zhang et al. have demonstrated the fabrication of flexible transparent supercapacitors
(a)
by using AJP to deposit the transparent conductive polymer poly(3,4ethylene dioxythiophene) polystyrene sulfonate (PEDOT: PSS) with added RuO2 nanoparticles, giving it the dual functionality of current collecting and energy storage.24 In addition, Tu et al. have investigated the control of printing parameters of AJP to spray deposit Ag nanowires as transparent flexible electrodes for applications in wearable, stretchable electronics.25
Sensors
The ability to print conformally onto non-planar substrates makes AJP technology attractive for developing sensor components in wearables or widely deployed components of an Internet of Things network. Strain sensors consisting of serpentine Ag conduction paths have been printed on flexible films by Agarwala et al., and changes in resistance were used to track the bending of a human arm.26 A number of groups are taking advantage of the ability to deposit carbon nanostructures by AJP for sensing. Liu et al. showed that Pt-decorated carbon nanotubes were effective as a hydrogen sensor at the level of 20 ppm.27 Cantu et al. have used a combination of printed Ag, CNTs, and Ag/AgCl to form a three-electrode sensing device for the detection of Interleukin-8 protein by anodic stripping voltammetry.28 Aerosol jet printing also has been used to integrate discrete components and build upon existing electronics for sensing. Clifford et al. showed the printing of an interdigitated electrode array on the body of an integrated circuit, followed by a Nafion coating, to create a humidity sensor.29
Printable Electrodes for Batteries, Fuel Cells, and Electrolyzers
Aerosol jet printing offers the possibility of producing 3D-graded electrodes, gas diffusion layers, and current collector structures at micron scales of resolution. This creates opportunities for producing mesoscopic architectures of electrochemical functional materials. Ion, electron, reactant, and product multiphase transport can therefore be optimized. Aerosol jet printing also offers rapid prototyping of candidate battery and fuel cell materials geometries. Challenges include the creation of stable colloidal printing inks, droplet wetting and spreading on porous materials, and precursor consolidation/ sintering compatibility.30 The fields of aerosol printing of batteries, PEMFCs, SOFCs, and electrolysis systems are in relative stages of infancy compared to current manufacturing technologies. It remains to be seen if the deposition rates can be competitive against commercial screen-printing, slot die coating, spray, and doctor blade roll-to-roll methods for mass manufacturing of energy conversion devices. SOFCs have been printed via AJP by Sukeshini et al., consisting of a NiO anode layer, Yttria-stabilized zirconia (YSZ) solid electrolyte, and a pasted strontium doped lanthanum manganite cathode layer.31 Using the system’s dual atomizer configuration, different mixtures of NiO and YSZ materials at varying ratios could be deposited into a graded anode interlayer, which was found to enhance cell performance.31
(b)
Fig. 2. An Integrated Deposition System “Nanojet” aerosol jet printer from afar (a) and a close-up of the print head as Pt nanoparticle ink is printed onto an alumina substrate (b). 56
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References
Table l. Comparison Between Inkjet and Aerosol Jet Printing.7,20
Method
Inkjet Single droplet
Droplet Size
18-635 µm diameter droplets
Resolution
20 to 50 µm resolution
Dispersion
Disperses ink colloids
Viscosity
Limited to low viscosity (< 20 mPa·s)
Price
Cheaper
Standoff Distance
Fixed distance (smooth surfaces) (usually 1 mm)
Aerosol Jet Numerous droplets 0.5 to 3 µm diameter droplets 10 µm resolution Sprays atomized ink (mist) Not as viscosity limited (1-1,000 mPa·s) More expensive Varying distance (rough surfaces) (1-5mm)
Further Reading A detailed review of the working principles and applications of aerosol jet printing is presented by Wilkinson et al. in Reference 7. Secor reviews the aerodynamics and the effects of the operating conditions on the print parameters in References 8 and 9. Deiner et al. provide an in-depth review of the applications of aerosol jet printing in electrochemical energy conversion and storage devices in Reference 30. © The Electrochemical Society. DOI: 10.1149.2/2.F07204IF.
About the Authors Lok-Kun Tsui is a research assistant professor at The University of New Mexico Center for Micro-Engineered Materials. He holds a PhD and MS in materials science and engineering from The University of Virginia, and a BS in physics from James Madison University. His current interests are additive manufacturing of electrochemically active materials, gas sensors, machine learning, and printed electronics. He may be reached at lktsui@unm.edu. https://orcid.org/0000-0001-7381-0686 Fernando Garzon is the director of The University of New Mexico Center for MicroEngineered Materials. He also is a professor of chemical and biological engineering at The University of New Mexico. Garzon obtained his master’s and doctoral degrees in materials science and engineering from the University of Pennsylvania. His research interests include materials for electrochemical energy conversion, ceramic and catalytic materials synthesis, electrosynthesis of fuels, the development of advanced gas sensors, and the additive manufacturing of ceramic materials. He may be reached at garzon@unm.edu. https://orcid.org/0000-0002-4511-9932 John Plumley is a postdoctoral appointee and lab manager at The University of New Mexico Center for Micro-Engineered Materials. He earned his PhD and MS in nanoscience and microsystems, as well as his BS in chemical engineering, at The University of New Mexico. His interests include corrosion, electrodeposition, solid oxide fuel cells, and surface characterization and functionalization. He may be reached at john9@unm.edu. https://orcid.org/0000-0002-6404-2467
1. R. G. Sweet, Rev. Sci. Instrum., 36, 131 (1965). 2. Optical Society of America, “Biographies & Memoirs: Ichiro Endo,” Feb. 2020, (Accessed August 11, 2020) URL: https:// www.osa.org/en-us/history/biographies/bios/ichiro_endo/. 3. U.S. Patent US3683212A 4. U.S. Patent US3946398 5. U.S. Patent US4751530 6. G. J. Marquez, M. J. Renn, W. D. Miller, MRS Proc., 698, Q5.2.1. DOI:10.1557/PROC-698-Q5.2. 7. N. J. Wilkinson, M. A. A. Smith, R. W. Kay, and R. A. Harris, Int. J. Adv. Manuf. Technol., (2019). 8. E. B. Secor, Flex. Print. Electron., 3, 035002 (2018) https:// stacks.iop.org/2058-8585/3/i=3/a=035002?key=crossref. ac3f4d7ed9a2c5a591d157c5c3f6db2f. 9. E. B. Secor, Flex. Print. Electron., 3, 035007 (2018) https:// stacks.iop.org/2058-8585/3/i=3/a=035007?key=crossref. ba5b15eabeb3777b3dcd649e4070fcff. 10. N. Dalal et al., J. Electron. Packag., 142, 1 (2020). 11. A. Efimov et al., Materials., 13, 1 (2020). 12. M. Smith, Y. S. Choi, C. Boughey, and S. Kar-Narayan, Flex. Print. Electron., 2 (2017). 13. E. S. Rosker et al., ACS Appl. Mater. Interfaces, 12, 29684 (2020). 14. A. M. Sukeshini, T. Jenkins, P. Gardner, R. M. Miller, and T. L. Reitz, in ASME 2010 8th International Fuel Cell Science, Engineering and Technology Conference: Volume 1, p. 325–332, ASMEDC (2010). 15. L. Tsui, E. Langlois, S. Kayser, and J. Lavin, Aerosol Jet Print. Inductor Devices Power Electron. (2019) https://www.osti.gov/ servlets/purl/1641573. 16. R. R. Tafoya and E. B. Secor, Flex. Print. Electron., 5 (2020). 17. Y. Gu, D. Park, D. Bowen, S. Das, and D. R. Hines, Adv. Mater. Technol., 4, 1 (2019). 18. Y. Gu, D. R. Hines, V. Yun, M. Antoniak, and S. Das, Adv. Mater. Technol., 2, 1 (2017). 19. K. Wang, Y. H. Chang, C. Zhang, and B. Wang, Carbon N.Y., 98, 397 (2016) https://dx.doi.org/10.1016/j.carbon.2015.11.032. 20. P. Sarobol, A. Cook, P. G. Clem, D. Keicher, D. Hirschfeld, A. C. Hall, and N. S. Bell, Annu. Rev. Mater., 46, 41 (2016). 21. T. Siefert, E. Sowade, F. Roscher, M. Wiemer, T. Gessner, R. R. Baumann, Ind. Eng. Chem. Res., 54, 769 (2015). DOI: doi. org/10.1021/ie503636c. 22. P. Kopola, B. Zimmermann, A. Filipovic, H.-F. Schleiermacher, J. Greulicha, S. Rousu, J. Hast, R. Myllylä, and U. Würfel, Sol. Energy Mater Sol., 107, 252 (2012). 23. R. Eckstein, G. Hernandez-Sosa, U. Lemmer, and N. Mechau, Org. Electron., 15, 2135 (2014). 24. C. Zhang, T. M. Higgins, S.-H. Park, S. E. O’Brien, D. Long, J. N. Coleman, and V. Nicolosi, Nano Energy., 28, 495 (2016). 25. L. Tu et al., J. Appl. Phys., 123, 174905 (2018). 26. S. Agarwala, et al., ACS Sensors, 4, 218 (2019). DOI: 10.1021/ acssensors.8b01293. 27. R. Liu et al., Nanotechnology, 23, 505301 (2012). https://doi. org/10.1088/0957-4484/23/50/505301. 28. E. Cantu et al., Sensors, 18, 3719 (2018). DOI:10.3390/ s18113719. 29. Clifford et al., Sens. Actuators B, 255, 1031 (2018). DOI 10.1016/j.snb.2017.08.086. 30. L. J. Deiner and T. L. Reitz, Adv. Eng. Mater., 19, 1600878 (2019). DOI: 10.1002/adem.201600878. 31. M. Sukeshini et al., J. Power Sources, 224, 295 (2013).
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Cold Sintering for High-Temperature Electrochemical Applications by Zane Grady, Joo-Hwan Seo, Kosuke Tsuji, Arnaud Ndayishimiye, Sarah Lowum, Sinan Dursun, Jon-Paul Maria, and Clive A. Randall
A
Introduction
sintered material.14 The pressure solution creep mechanism has been discussed in the geologic literature15–17 as it pertains to the densification of sedimentary rock formations and may play a similar role under cold sintering conditions.18 Details of all the underlying processes require more investigation, and this clarification will take time; it has taken decades of international research to elucidate some of the fundamental aspects of conventional sintering and other alternative sintering techniques (e.g., microwave, spark plasma, and flash sintering).19–22 Phenomenological studies using model systems such as ZnO with both non-isothermal densification and grain growth kinetics have quantified significantly lower activation energies for cold sintering relative to conventional sintering processes. Figure 1 shows the basic cold sintering process as well as the proposed local behavior at the contacting interfaces between particles. At this time, the cold sintering process has been successfully applied to over 80 different compounds varying in every aspect, from crystal structure to elemental complexity. In complex compounds, there is potential for differential rates of dissolution, known as incongruent dissolution. This effect can alter the stoichiometry at the grain boundary and thus hinder densification, which in the case of solid state electrolytes can lead to higher grain boundary resistivities and thus lower the total conductivity. Incongruent dissolution can be limited by employing a secondary phase containing a significant concentration of the components with the fastest dissolution kinetics, thereby reducing the potential chemical gradient for the preferential leaching of these elements. Additionally, the electroactive properties of the grain boundary can be augmented by cold sintering with polymers, 2-D nanomaterials, and gels, all of which can be processed and integrated into the grain boundaries without decomposition.18,23–25 Several major benefits can come from a sintering process that can occur at such low temperatures and fast processing times, such as:
lthough cold sintering remains an emerging processing technique, it is noteworthy to consider recent progress in materials that are of interest to electrochemical systems with elevated service temperatures. Here we discuss a broad number of materials ranging from alkali electrolytes for solid state batteries, to oxygen ion conductors for gas sensing. We also discuss the opportunity to co-fire mixed ionic conductors into multilayered devices. Given the low-temperature sintering temperatures with the cold sintering process (CSP), we will discuss some insights into operating ceramics at temperatures near or above their processing temperature. Sintering as a densification process involves the reduction of the excess surface energy of particulate ensembles that is accomplished through competing mechanisms of grain coarsening and the development of grain boundary interfaces. Sintering requires mass transport through various forms of diffusion, and this in turn requires thermal energy in the form of high temperatures.1,2 Under conventional sintering processes, this requires relative temperatures typically between 0.5<Ts/Tm<0.95, where Ts is the peak sintering temperature, and Tm is the melting temperature.3 In the case of cold sintering, this ratio is significantly renormalized to Ts/Tm<0.2. Additionally, the low-temperature sintering process is also relatively fast; densification from initial densities of packed powders (~55% in ZnO) can be densified to over 94% in eight minutes after heating to 150oC at a heating rate of 15oC/min.4–7 This remarkable densification process is accomplished through the addition of a secondary, often transient, chemistry phase, which drives low-temperature mass transport, possibly via a dissolution and precipitation process, thereby enabling densification under moderate uniaxial pressures in a semiopen system. For example, a secondary aqueous Zn acetate solution • Lower cost and more sustainable manufacturing26,27 phase facilitates cold sintering of the primary ZnO phase. • Unique composites with an unprecedented range of dissimilar Cold sintering is performed in a semi-open system, and this materials differentiates it from earlier studies in hydrothermal sintering • Multilayer structures with low interfacial resistance and processes when the system is closed (hermetically sealed).8–13 With minimal chemical interactions between layers28,29 cold sintering, the transient changes in chemistry, which usually (continued on next page) includes mass loss from the cell, aids in the supersaturation of the solute, driving the densification process through this non-equilibrium thermodynamic process. The secondary chemistry selections and powder surfaces are very important in this process. These mass transport phases are typically about two to 10 volume percent (thus partially filling porosity between powder particles) and must be able to aid in the required chemical processes, such as the dissolution of the powder surfaces, while avoiding the formation of stable impurity phases, such as carbonates. The secondary phase is not restricted to aqueous solutions but can include any polar solvent or hydrated solid phase (e.g., zinc acetate dihydrate (Zn(CH3CO2)2·2H2O) in the densification of ZnO or barium hydroxide octahydrate, Ba(OH2):8H2O in cold sintering BaTiO3). Results thus far suggest that some amount of hydration is necessary to drive the densification process. It is also worth noting that cold sintered ceramic mechanical Fig. 1. Schematic cartoon of the cold sintering process. A cutaway view of the powder loaded into the die and heating jacket is shown at left. A magnified view of three distinct stages of cold sintering strength approaches that of the conventionally is shown at right. The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
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• Integration through printing and sintering on polymer and metal substrates30 • Scalable as a batch process and potentially as a continuous process31 • Directly addresses thermal instabilities in sintering such as light element volatilization and undesired reactions. In the discussion below, we will point to several opportunities with ceramics that are of interest to the solid state electrochemical community. In recent years, the cold sintering process has been newly applied to ceramics with elevated operating temperatures (i.e., > 200°C), such that the sintering temperature is now comparable to the operating temperature. With respect to this special issue, we focus on these material systems.
Alkali Electrolytes The densification of lithium and sodium solid state electrolytes is extremely important for all solid state battery technologies. The Arrhenius scaling of ionic conductivity with temperature is manifested in the dramatically increased conduction at modestly elevated temperatures. Thus all solid state batteries may be most effective when employed at elevated temperatures. There are numerous issues related to sintering solid state electrolytes by conventional sintering, which notably include light element volatilization and electrodeelectrolyte interfacial impedance. Cold sintering has been employed to ameliorate these barriers. The electrolytes which have been densified by cold sintering include the NASICON structured Na3Zr2Si2PO1232–35, Li1+x+yAlxTi2-xSiyP3-yO12 (LATP)25, and Li1.5Al0.5Ge1.5(PO4)3 (LAGP)25,36, in addition to the garnet Li7La3Zr2O12(LLZO)37. The origin of the excellent ionic conductivity in these materials is related to the complex stoichiometry insofar as the necessity of a rigid anionic framework with a mobile monovalent ion sublattice is concerned. This chemical complexity poses an issue for cold sintering in that the different elements are leached from the structure at different rates, i.e., incongruent dissolution. The incongruent dissolution leads to non-stoichiometric and/or amorphous grain boundaries, which are deleterious to total conductivity. Recent advances in cold sintering have addressed this drawback in two ways, which are highlighted here. In the case of LATP, cold sintering is performed at 120°C where the aqueous solvent contains ~ 5 vol% of a lithium salt (lithium bis(trifluoromethanesulfonyl)imide, denoted LiTFSI). The high
concentration of lithium salt acts to not only reduce the propensity for lithium to preferentially solvate, but also serves to increase the bulk conductivity by providing both series and parallel ionic pathways throughout the microstructure. The resulting composite electrolyte demonstrates comparable conductivity to conventionally sintered LATP, as is shown in Fig. 2A. The second way of addressing incongruent dissolution is by using a more reactive solvent than can be achieved with aqueous chemistries. In the case of Na3Zr2Si2PO12 (and other materials in this article), the aqueous solvent in CSP is replaced with a molten hydroxide. In this way, NaOH is used as the solvent in densifying the Na3Zr2Si2PO12 electrolyte at 375°C in three hours, a large reduction in temperature from the conventional 1,200°C. The ionic conductivity compared with conventionally sintering Na3Zr2Si2PO12 is also shown in Fig. 2A, and the results are placed in further context by comparing the relationship between the room temperature conductivity and processing temperature for a number of alternative sintering techniques (Fig. 2B).
Oxygen Ion Conductors Bi2O3 Bi2O3 transforms into the cubic fluorite structure around 730℃ (α→δ Bi2O3). The highly defective crystal structure of δ-Bi2O3 begets the highest ionic conduction among the reported oxide electrolytes.38 From a practical perspective, the δ-form is unstable at low temperatures, and the volumetric expansion/shrinkage upon cycling associated with the phase transition is undesirable in terms of long-term mechanical reliability. Thus, doping with rare-earth elements has been employed to stabilize the δ-form of Bi2O3 in the desired working temperature range. Yttrium-doped Bi2O3 ceramics were prepared by CSP at 300℃ (2 hours) using acetic acid as a transient solvent. The relative density of the sintered material was 88% of the theoretical density, and the total conductivity of the as-CSP ceramics reached ~2 mS/cm at 500℃. When the ceramics were heated to 650℃ for the electrical measurement, the conductivity improved slightly to 2 mS/cm at 500℃ in the second cycle (Fig. 3a). This change in conductivity can be explained by the presence of nanoprecipitates and/or amorphous phases in the as-CSP state, giving the material an initially higher grain boundary impedance. This phase appears to have recrystallized during the high-temperature measurements, resulting in the reduced grain boundary resistance (Fig. 3b,c). Due to the nature of the lowtemperature treatment, such a low crystalline phase is often observed
Fig. 2. (a) The ionic conductivity of two electrolytes, Li1.5Al0.5Ge1.5(PO4)3-LiTFSI composite (LAGP w/ LiTFSI) and Na3Zr2Si2PO12, densified by either cold sintering process (CSP) or conventional sintering (CS). The conventional sintering temperatures were 800°C and 1,200°C, respectively. The inset depicts a pellet of LATP densified by CSP to the point of translucency. (b) The room temperature conductivity of the Na3Zr2Si2PO12 electrolyte is plotted against the maximum densification temperature. Further discussion of the data and context is given in Reference 32. Reference data from 33, 34, and 35. 60
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Fig. 3. (a) Temperature dependence of the cold sintered yttrium-doped bismuth oxide (BYO) in comparison with the reported work by Jiang et al.40 and Takahashi et al.41 (b) Representative microstructures of the as-CSP (b) and annealed at 650oC (c) cold sintered ceramics.
in ceramics prepared by CSP, and it has been suggested that this phase may hinder ionic/electronic conduction.4,36,39 These results indicate that a post-annealing treatment might be necessary to improve the thermal stability for practical applications. In the future, we will continue to study the one-step sintering process.
CeO2
acceptor doping.44 Alternatively, conduction via protons, known to occur in nanocrystalline ceramics, though typically at low temperatures (~300oC), or conduction along with the intergranular secondary chemical phase, may be present. Further work is needed to elucidate the electrical conduction mechanism.
ZrO2
ZrO2 and its solid solutions, such as Zr1-xYxO2-x/2, are widely employed materials in dental, bearing, thermal barrier coating, fuel cell, and chemical sensing applications47–52. Oxygen vacancies are conducted because of the Y-doping onto the Zr-sites, and the desirable cubic phase can be stabilized with temperature or particle/grain size.
Cerium dioxide (CeO2) is a broadly studied electroceramic oxide, as it is used as an electrolyte in solid oxide fuel cells (SOFC) owing to its high oxygen ion conductivity and catalytic activity when appropriately doped and sintered. Pure CeO2 was cold sintered using a NaOH-KOH eutectic flux under 500 MPa for 6 h at different temperatures by Zaengle et al.42 SEM images in Fig. 4a and 4b show (continued on next page) the microstructure of fracture surfaces of CeO2 samples cold sintered at 350°C and 400°C, respectively. The relative density of both these bulk ceramics is above 90%. At 350°C (Fig. 4a), grains with obvious necking but spherical shapes are observed, while multifaceted grains are observed at 400°C (Fig. 4b). Figure 4c shows the temperature dependence of grain conductivity of a cold sintered and a conventionally sintered pure CeO2 ceramic.43 With both these techniques, the temperature dependence of grain conductivity follows a linear trend and the calculated activation energy, Ea, is 0.49 eV for the cold sintered CeO2 and 0.81 eV for the conventionally sintered CeO2. At 800°C (Fig. 4c), the conductivity of the as cold-sintered sample is nearly two orders of magnitude higher than the conventionally sintered one. It is indeed known that pure ceria densified by conventional sintering has a low concentration of oxygen vacancies and subsequently a low conductivity.43–46 Despite not being intentionally doped, the electrical properties of the cold sintered CeO2 (350°C, grain size = 37±7 nm) are similar in magnitude and activation energy to conventionally sintered yttria doped ceria ceramic (6YDC) obtained by Lupetin Fig. 4. SEM images of CeO2 samples cold sintered under 500 MPa for 6 h at (a) 350°C, (b) 400°C using et al. (sintered at 800°C, grain size ≤ 30 NaOH-KOH eutectic hydroxide mixture. (Scale bar: 500 nm.) Arrhenius plot for (c) grain conductivity of nm, activation energy for grain and grain pure CeO conventionally sintered by Maier et al.43 and cold sintered by Zaengle et al.42. (d) Grain boundary 2 boundary conductivity of 0.50 eV and 1.06 conductivity of pure CeO2 cold sintered by Zaengle et al.42 compared to the extrapolated ionic conductivity eV, respectively), suggesting a possible of conventionally sintered acceptor-doped (Ce0.94Y0.06)O2, where the dopant is purposefully segregated to the oxide ion conductivity via unintentional grain boundaries (Lupetin et al.)44 The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
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Initial studies of cold sintering this material used a transient aqueous solvent, which was insufficient to yield good properties without a post-annealing step.53–55 The use of the more reactive solvents detailed above and/or the use of combinatory sintering approaches may warrant revisiting this material system. With respect to the latter, SPS and cold sintering have recently been combined to densify a zirconia hydroxide56, suggesting that the densification of the oxide is well within reach.
Electroactive Oxides Electrolytes in devices need to also be interfaced with electroactive materials that can provide both ionic exchange as well as redox reactions as either anodic or cathodic electrodes. For this, there is often mixed conduction that is required. This mixed conduction is achieved either intrinsically or with a composite design. Here, many systems must be matched to the operating temperatures and potentials to avoid decomposition. It would be beneficial to apply cold sintering to these materials in isolation and in cases of co-sintering. Below we highlight such examples where conventional sintering is challenging, but cold sintering is achieved.
WO3
WO3 has several interesting optical and electronic properties lending it to unique applications in electrochromic devices, catalysis, gas sensing, solar cells, and field-emission systems.57 However, despite its simple binary chemistry, the material is somewhat complex in that it can take on a variety of different phases and stoichiometries, which can significantly impact the functional material properties. The traditional sintering of WO3 is usually carried out at temperatures between 1,100℃ and 1,300℃.58 Such high temperatures can easily alter properties such as stoichiometry, defect chemistry, bandgap, and morphology, all of which often need to be tailored for specific end-use. Frequently, dopants are added to help control final electrical properties, however, these dopants can promote significant grain growth and cause unwanted morphology changes as well.58 Furthermore, WO3 undergoes several relatively low-temperature phase transitions: triclinic to monoclinic at 17℃, monoclinic to orthorhombic at 320℃, and orthorhombic to tetragonal at 740℃. Although the orthorhombic and tetragonal phases are usually not stable at room temperature, the triclinic and monoclinic phases have been found to co-exist at room temperature, and different sintering temperatures can result in differing amounts of triclinic vs. monoclinic phase present in the final sintered ceramic.59 Many of these complications with WO3 could be alleviated with a lowtemperature processing route such as cold sintering.
Cold sintering of WO3 to 92-94% of theoretical density has been demonstrated at temperatures between 160℃ and 200℃. Cold sintering conditions typically entail 530 MPa of pressure for 30 minutes. Both an aqueous NaOH solution (10-20 vol.%)60 and a eutectic NaOH-KOH hydrated flux (5-10 vol.%)61 can facilitate densification in this materials system, offering two different densification paths that can be utilized to tune properties. Figure 5 presents a representative microstructure of WO3 cold sintered with the NaOH-KOH transport phase at 200℃ (Fig. 5a) and a plot of the in-situ compaction process as a function of time (referred to as a sintegram) (Fig. 5b), which can help reveal densification onsets, rates, and mechanisms.62 These low processing temperatures of 200℃ or below offer opportunities to control the microstructure, grain size, stoichiometry, and defect chemistry of WO3 for a particular application space. Future work should be devoted to relating cold sintering conditions to the final material properties of WO3.
Multilayered Devices
Thus far, we have focused on the isolated demonstrations of cold sintering applied to numerous bulk ceramic systems. While these results are promising, demonstration of practical dimensions and device integration is another inevitable challenge. In this respect, there are ongoing studies of the application of cold sintering to multilayered architectures for electroactive applications. An example of such an architecture is shown in Fig. 6, where layers of a ZnO/polyethylimine (PEI) composite with metallic electrodes are densified in a single step. The low processing temperature resulted in no electrical short-circuiting from interlayer metallic diffusion or oxidation of the electrodes. It is foreseeable that such an approach will be successfully applied to other multilayered electroactive devices for operation at elevated temperatures, such as all solid state batteries, chemical sensors, and solid oxide fuel cells.
Concluding Remarks
Cold sintering offers new opportunities for materials integration with intermediate and high-temperature functionality for electrochemical cells, sensors, and catalysis. Progress has already been made on electrochemical materials that are typically sintered at temperatures way above the operational conditions. With cold sintering, we have possibilities to integrate these materials with new strategies, enabling mixtures of materials that chemically react or have vastly different kinetics with conventional sintering approaches. This integration has already been demonstrated in the early work that has been done on these families of materials for which cold sintering can be applied. However, further work identifying the appropriate secondary phases to facilitate densification and optimized properties need to be completed. In several cases, grain boundary impedance for ionic conductivity can be compromised in cold-sintered materials. However, as can be seen in the many examples presented in this short paper, the properties are quite close to conventional materials, and intermediate annealing conditions can heal some of the metastable phases that limit the conductivity across the grain boundaries. The authors hope that with the diversity of crystal structures and conduction processes that are covered here, more efforts will be used to build prototypes of new electrochemical systems to aid energy storage, gas detection, and chemical reactions and purification processes that can Fig. 5. (a) Microstructure of 92% dense WO3 cold-sintered using 7 vol.% of a 51:49 mol.% mixture of NaOH: benefit a sustainable society. KOH as a transport phase. Sintering conditions were 200ºC and 530 MPa for 30 minutes. (b) Associated sintegram (compaction profile as a function of time) of the cold-sintered WO3 showing the densification process. 62
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Fig. 6. (a) An SEM micrograph is the background, and insert is the top view of the copper electrode multilayer and, (b) the associated chemical mapping of a ZnO/PEI composite cross-section with the copper electrodes co-densified with the PEI-ZnO varistor in a single step, demonstrating the potential for cold sintering to be applied to multilayered devices.63
Acknowledgements
Kosuke Tsuji is a doctoral candidate at The Pennsylvania State University in the Department of Materials Science and Engineering in the College of Earth and Mineral Sciences. He received a BSc from Tohoku University, Japan (2014), and an MS degree from The Pennsylvania State University (2017), both in materials science and engineering. He has been working in Clive Randall’s group since 2014. During his PhD research, he received the Robert E. Newnham Award for Research Excellence in 2020. His current research interests include electrical characterizations and low-temperature processing for ferroelectric and piezoelectric ceramics. He may be reached at tuk152@psu.edu. https://orcid.org/0000-0001-9346-4450
About the Authors
Arnaud Ndayishimiye is a postdoctoral scholar at The Pennsylvania State University. He received his engineer’s degree and master’s degree from the Ecole Nationale Superieure de Ceramique Industrielle (ENSCI Limoges, now ENSIL-ENSCI) in 2014, and PhD in physicschemistry of condensed matter from the University of Bordeaux, France (2017). Arnaud joined Clive Randall’s group in 2018. His work focuses on the development of new composites using cold sintering (CS) and the investigation of CS fundamentals. He may be reached at axn536@psu.edu. https://orcid.org/0000-0003-3853-8239
The authors would like to acknowledge the staff of the Materials Characterization Laboratory, and the Microscopy and Cytometry Facility, Huck Institutes of the Life Sciences, both at The Pennsylvania State University, for aiding in the work described here and for the use of their equipment. The authors would like to also acknowledge financial support from the Air Force Office of Scientific Research (FA9550-19-1-0372). This material also is based upon work supported by the National Science Foundation Graduate Research Fellowships Program under Grant No. DGE1255832. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. © The Electrochemical Society. DOI: 10.1149.2/2.F08204IF.
Zane Grady is a doctoral candidate at The Pennsylvania State University in the Department of Materials Science and Engineering in the College of Earth and Mineral Sciences. Prior to joining Penn State, Zane completed his undergraduate degree in materials science and engineering at the University of Connecticut, during which he spent a year at NASA’s Langley Research Center studying next-generation materials and manufacturing for aerospace. In Randall’s group, Zane studies how cold sintering can be applied to ceramics for energy storage, particularly as it pertains to solid state sodium-ion battery technologies. He may be reached at zmg19@psu.edu. https://orcid.org/0000-0001-7610-8905 Joo-Hwan Seo is now a research scientist at LG Hausys in South Korea. He recently graduated with a PhD in materials science and engineering from The Pennsylvania State University in 2020. His research while at Penn State investigated the cold sintering process applied to lithium-ion battery electrodes and electrolytes in addition to the single-step co-sintering of a lithium solid state battery with the same methods. He may be reached at jks5678@psu.edu.
Sarah Lowum is a doctoral candidate and NSF Fellow at The Pennsylvania State University in the Department of Materials Science and Engineering in the College of Earth and Mineral Sciences. Sarah received her undergraduate degree in materials science and engineering from Clemson University prior to joining Penn State. Since that time, Sarah has been working in J. P Maria’s group on ultra-low-temperature densification of oxide ceramics (coined cold sintering in 2015). Sarah is developing new transport phases that expand the number of cold-sinterable ceramics. She may be reached at sml92@psu.edu. https://orcid.org/0000-0003-0771-2820 (continued on next page)
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Sinan Dursun is a postdoctoral scholar at the Materials Research Institute at The Pennsylvania State University. He received a BSc in physics from Ege University, Turkey, in 2007. He has a PhD in materials science and engineering from Gebze Technical University, Turkey (2017), where he worked as a researcher between 2012 and 2017. His main research interests include oxide electronic materials, multilayer prototyping, solid state devices, ceramic processing, and sintering techniques (e.g., single crystal template growth, textured ceramics by templated grain growth, and cold sintering). He may be reached at sxd448@psu.edu. https://orcid.org/0000-0001-9270-3368 Jon-Paul Maria received his bachelor’s, master’s, and PhD degrees from The Pennsylvania State University in ceramic science and engineering, and materials science and engineering, respectively. After graduation, he joined the group of Prof. Angus I. Kingon as a postdoctoral scholar in the Department of Materials Science and Engineering at North Carolina State University. After his postdoc, JonPaul spent 15 years on the NCSU faculty. In 2018, Jon-Paul joined the Department of Materials Science and Engineering at Penn State. He works with the research group at the Steidle Laboratory, a state-of-the-art facility for physical vapor deposition, electroceramics, electronic materials, plasmonics, and synthesis science. Jon-Paul may be reached at jpm133@psu.edu. Clive A. Randall is a professor of materials science and engineering and director of the Materials Research Institute at The Pennsylvania State University (2015-present). He has a BSc (First Class Honors) in physics from the University of East Anglia (UEA), UK (1983), and a PhD in experimental physics from the University of Essex, UK (1987). He was director for the Center for Dielectric Studies (19972013), and co-director of the Center for Dielectrics and Piezoelectrics (2013-2015), now technical advisor. His interests include materials discovery, processing, material physics, the science of reliability, electrical measurements, and compositional design of functional materials. Among his awards are Fellow of The American Ceramic Society, Academician of the World Academy of Ceramics, IEEE Distinguished Lecturer, and Honorary Fellow of the European Ceramic Society. He may be reached at car4@psu.edu. https://orcid.org/0000-0002-5478-2699
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29. D. Wang, B. Siame, S. Zhang, G. Wang, X. Ju, J. Li, Z. Lu, Y. Vardaxoglou, W. Whittow, D. Cadman, S. Sun, D. Zhou, K. Song, and I. M. Reaney, J. Eur. Ceram. Soc., 40, 4029 (2020). https://doi.org/10.1016/j.jeurceramsoc.2020.04.025. 30. A. Baker, H. Guo, J. Guo, and C. Randall, J. Am. Ceram. Soc., 99, 3202 (2016). https://doi.org/10.1111/jace.14467. 31. S. H. Bang, K. Tsuji, A. Ndayishimiye, S. Dursun, J. Seo, S. Otieno, and C. A. Randall, J. Am. Ceram. Soc., 103, 2322 (2020). https://doi.org/10.1111/jace.16976. 32. Z. M. Grady, K. Tsuji, A. Ndayishimiye, J. Hwan-Seo, and C. A. Randall, ACS Appl. Energy Mater., 3, 4356 (2020). https://doi. org/10.1021/acsaem.0c00047. 33. H. Leng, J. Nie, and J. Luo, J. Mater., 5, 237 (2019). https://doi. org/10.1016/J.JMAT.2019.02.005. 34. H. Leng, J. Huang, J. Nie, and J. Luo, J. Power Sources, 391, 170 (2018). https://doi.org/10.1016/j.jpowsour.2018.04.067. 35. J. G. Pereira da Silva, M. Bram, A. M. Laptev, J. Gonzalez-Julian, Q. Ma, F. Tietz, and O. Guillon, J. Euro. Ceram. Soc., 39, 2697 (2019). https://doi.org/10.1016/J. JEURCERAMSOC.2019.03.023. 36. S. S. Berbano, J. Guo, H. Guo, M. T. Lanagan, and C. A. Randall, J. Am. Ceram. Soc., 100, 2123 (2017). https://doi.org/10.1111/ jace.14727. 37. J.-H. Seo, H. Nakaya, Y. Takeuchi, Z. Fan, H. Hikosaka, R. Rajagopalan, E. D. Gomez, M. Iwasaki, and C. A. Randall, J. Euro. Ceram. Soc., 40, 6241 (2020). https://doi.org/10.1016/j. jeurceramsoc.2020.06.050. 38. B. C. H. Steele, in High Conductivity Solid Ionic Conductors; T. Takahashi, Editor, p. 402, WORLD SCIENTIFIC (1989). https://doi.org/10.1142/0729. 39. Y. Jing, N. Luo, S. Wu, K. Han, X. Wang, L. Miao, and Y. Wei, Ceram. Int., 144, 19077 (2018). https://doi.org/10.1016/J. CERAMINT.2018.07.192. 40. N. Jiang and E. D. Wachsman, J. Am. Ceram. Soc., 82, 3057 (1999). https://doi.org/10.1111/j.1151-2916.1999.tb02202.x. 41. T. Takahashi, K. Kuwabara, and M. Shibata, Solid State Ionics, 1, 163 (1980). 42. T. Zaengle, A. Ndayishimiye, K. Tsuji, Z. Fan, S. H. Bang, J. Perini, S. Misture, and C. A. Randall, J. Am. Ceram. Soc., 103, 2979 (2020). https://doi.org/10.1111/jace.17003. 43. X. Guo, W. Sigle, and J. Maier, J. Am. Ceram. Soc., 86, 77 (2003). https://doi.org/10.1111/j.1151-2916.2003.tb03281.x. 44. P. Lupetin, F. Giannici, G. Gregori, A. Martorana, and J. Maier, J. Electrochem. Soc., 159, B417 (2012). https://doi. org/10.1149/2.064204jes. 45. M. Shirpour, G. Gregori, R. Merkle, and J. Maier, Phys. Chem. Chem. Phys., 13, 937 (2011). https://doi.org/10.1039/ c0cp01702g.
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Advanced Manufacturing of Intermediate-Temperature Protonic Ceramic Electrochemical Cells by Shenglong Mu, Zeyu Zhao, Hua Huang, Jincheng Lei, Fei Peng, Hai Xiao, Kyle S. Brinkman, and Jianhua (Joshua) Tong
P
Introduction
roton conducting oxide (i.e., protonic ceramic) has been thought of as an ideal solid electrolyte for energy conversion and storage applications since Iwahara et al. reported the perovskite-type protonic ceramics represented by doped barium/strontium cerates and zirconates in the 1980s.1,2 Proton, as the charge carrier in protonic ceramics, possesses a much lower transport activation energy than oxide-ion, which has rendered protonic ceramics for extensive intermediate-temperature (IT, 400-700oC) electrochemical devices such as protonic ceramic fuel cells (PCFCs),3-7 reversible protonic ceramic fuel cells,8-10 and protonic ceramic membrane reactors.11 In the past four decades, significant effort has focused on discovering high-performance new protonic ceramic materials simultaneously possessing high proton conductivity and good chemical stability.12-17 On one hand, doped barium cerate perovskite oxides usually showed high proton conductivity at intermediate temperatures. For example, BaCe0.8Gd0.2O3-δ showed a proton conductivity as high as 5×10-2 S/cm at 600oC18. However, low chemical stability under carbon dioxide and water vapor atmospheres ruled out the practical applications of doped barium cerate materials. On the other hand, doped barium zirconates (e.g., BaZr0.8Y0.2O3-δ) showed excellent chemical stability under the same atmospheres, whose proton conductivity, however, usually was much lower than their counterparts of doped barium cerates.19 The recent discovery indicated that the phase-pure solutions formed from doped barium cerates and doped barium zirconates (e.g., BaCe1-x20-22 , BaCe0.7Zr0.1Y0.1Yb0.1O3-δ (BCZYYb7111)4, yZrxYyO3-δ (BCZY) BaCe0.4Zr0.4Y0.1Yb0.1O3-δ (BCZYYb4411))5 successfully combined the high proton conductivity from doped barium cerates and the high chemical stability form doped barium zirconates together. The BCZY and doped BCZY perovskite oxides showed a compromised performance of good conductivity and improved stability and became the state-of-the-art protonic ceramic materials, which have been extensively used for the protonic ceramic electrochemical cells (PCECCs). While pursuing high-performance protonic ceramic materials, the proton conductivities for the same nominal compositions always showed a vast distribution according to the reports from different groups. This proton conductivity discrepancy became worse for the protonic ceramic materials with higher zirconium amounts in the perovskite oxide structure. For example, the summary of the proton conductivity for the typical protonic ceramic material of BaZr0.8Y0.2O3-δ (BZY20)23-32 (Fig. 1) showed that the conductivities broadly distribute in the range of 10-5-1 S/cm, which has almost five orders of magnitude difference. The well-accepted reasons for the conductivity discrepancy are the poor control of the microstructure (e.g., low relative density, small grain size, and impurities precipitated in the grain boundary regions) and the significant barium loss (e.g., barium dissolution to solvent during powder processing and barium evaporation during high-temperature firing) for the fabricated protonic ceramic parts due to the high firing temperatures intrinsically required by the refractory nature of the barium zirconatebased materials. Therefore, in addition to the discovery of highperformance protonic ceramic materials, the manufacturing of the
state-of-the-art protonic ceramic materials into protonic ceramic parts (e.g., thin films) to achieve the desired microstructures for ensuring the stable high proton conductivity has been playing a decisive role for the practical application of protonic ceramics to energy conversion and storage devices. In this work, we will first summarize the conventional sintering methods for the manufacturing of protonic ceramics. After that, we will briefly review the state-of-the-art solid state reactive sintering (SSRS) method, which has found extensive applications for manufacturing the button cells to demonstrate the performance of the versatile PCECCs. Then, we will introduce the newest technique of rapid laser reactive sintering (RLRS) for fast and cost-effective sintering of protonic ceramics, which provides the possibility to manufacture PCECC stacks using additive manufacturing rapidly. Finally, we will briefly introduce the development of integrated additive manufacturing and laser processing (I-AMLP) technique to manufacture protonic ceramics.
Conventional Sintering Methods
Many fabrication efforts have been pursued over decades to achieve protonic ceramic parts (e.g., pellets and thin films) with high relative density and desired microstructures. The conventional ceramic processing method of solid state sintering of shaped parts from solid state reaction derived phase-pure protonic ceramic powders usually need sintering temperatures higher than 1,7001,800oC and sintering time longer than 10h to achieve the required (continued on next page)
Fig. 1. Summary of some proton conductivity data for the typical protonic ceramic BZY20 fabricated by different methods in different research groups. The data for plots of 1-11 came from References 23-32 respectively.
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Mu et al.
(continued from previous page)
relative density, which, however, inevitably resulted in severe barium loss and low proton conductivity.20 The two-step sintering method, typically consisting of a high-temperature sintering step for a short time (few minutes) to achieve critical density and a followed lowtemperature sintering step for a long time to fulfill the desired grain growth, improved the microstructure of proton ceramics and achieved decent proton conductivity. However, the two-step sintering method still could not coherently avoid the high sintering temperatures and extended sintering time.33 The protection by using pure oxygen and complicated powder (mixture of barium carbonate and protonic ceramic powders) bath and using wet-chemistry derived highqualify phase-phase protonic ceramic powder are effective methods to prepare dense protonic ceramic pellets with high relative density and increased grain size, which, however, still required a sintering temperature higher than 1,600oC and sintering time longer than 20h.31 The spark plasma sintering (SPS) technique was a powerful tool to achieve high ceramic relative density while limiting the grain size growth.34 The SPS method usually resulted in high relative densities for protonic ceramic pellets, which showed a comparable proton conductivity to the samples obtained from the conventional sintering method. However, the SPS tool is still confronting equipment complexity, high cost, and limitation of sample geometries, making it challenging to utilize for the manufacturing of protonic ceramic devices practically. The pulsed laser deposition (PLD) technique showed the capability to achieve dense epitaxial thin films and demonstrated the high proton conductivity and promising fuel cell performance.30 However, the PLD technique needs to address similar challenges as the SPS technique before its practical application. Therefore, it is not hard to figure out that most of the sintering methods mentioned above are not so useful for the fabrication of PCECCs comprised of the anode, electrolyte, and cathode layers because of the high temperature, long time, or equipment complexity or limitation, and difficulty to integrate with conventional ceramic shaping techniques such as tape casting, screen printing, and extrusion.
Solid State Reactive Sintering
In 2005, Haile et al. reported adding some specific transition metal oxides (e.g., ZnO, NiO, CuO) to phase-pure BaZr0.85Y0.15O3-δ (BZY15) synthesized by the combustion method achieved relative densities higher than 90% at 1,300oC, which were 300-400oC lower than the conventional densification for barium zirconate-based protonic ceramics.35 After that, doped barium cerates and zirconates perovskite-type protonic ceramics showed improved sinterability while adding ZnO as an extra sintering aid or a component of the perovskite structure.21, 25, 36 Inspired by this pioneering work related to improving sinterability for phase-pure perovskite-type protonic ceramics by ZnO, in 2010, Tong et al. developed the solid state reactive sintering (SSRS) method for sintering protonic ceramics at moderate temperatures (<1,500oC) directly from cost-effective raw materials of carbonates and single metal oxides.37 With the fabrication of BZY20 as an example, Fig. 2 schematically describes the SSRS processes. The SSRS consisted of ball milling of the raw material precursor mixture, dry pressing of green pellets, and
Fig. 2. Schematic description of solid state reactive sintering (SSRS) procedure with the fabrication of BZY20 pellets as an example. 68
Fig. 3. SEM images of the fractured cross-sections of BaCe0.6Zr0.3Y0.1O3-δ (BCZY63) pellets were fabricated by using the SSRS method at 1,450oC for 12h with ZnO and MnO2 as sintering aids. (Adapted from Fig. 3 in Reference 39 with copyright permission.)
moderate-temperature sintering of green pellets to achieve final sintered pellets. With the help of a small amount of sintering aid (e.g., NiO), the SSRS method combined the phase formation, pellet densification, and grain growth into a single moderate-temperature sintering step. The SSRS method then showed success for most of the popular perovskite-type protonic ceramic materials of yttrium doped barium cerate (BaCe0.8Y0.2O3-δ)38, yttrium-doped zirconates (e.g., BaZr0.9Y0.1O3-δ)39, yttrium doped barium cerate and zirconate (e.g., BaCe0.6Zr0.3Y0.1O3-δ39, BaCe0.2Zr0.7Y0.1O3-δ40), and ytterbium and yttrium co-doped barium cerate and zirconate (BaCe0.7Zr0.1Y0.1Yb0.1O3-δ).41 The further mechanism study by Tong et al. indicated that the intermediate phase (e.g., BaY2NiO5) formed between the sintering aid single metal oxide and the proton components introduced a partial liquid sintering became the main reason for lowering the sintering temperature of protonic ceramics. The screening of 15 single metal oxides as sintering aids for BaCe0.6Zr0.3Y0.1O3-δ39 showed that single metal oxides could form a solution with BaZrO3 and introduce a large amount of oxygen vacancy and electronic conductivity, which could work as useful sintering aids (e.g., NiO, ZnO, CuO, and CoO). This screening also proved that the sintering aids of Fe2O3 and MnO2 could partially sinter the protonic ceramics, which could manufacture porous protonic ceramic scaffolds. Therefore, as described in Fig. 3, the SSRS method could not only achieve fully densified and largegrained electrolytes but also could achieve a porous electrode scaffold with the desired porosity and small grain size. Recently, Tong et al. also demonstrated the cost-effective and facile fabrication of PCFCs by the SSRS method.3 As indicated in Fig. 4, the SSRS method could fabricate half cells consisting of anode support and electrolyte thin film, and single cells consisting of anode support, electrolyte thin film, and cathode scaffold thin layer by adjusting different kinds of sintering aids or poreformers. The SSRS significantly simplified the fabrication process for the manufacturing of PCFCs from cost-effective raw materials. The PCFCs fabricated by the SSRS method showed peak power density higher than 450mW/cm2 at 500oC and stable operation longer than 1,100 h. After this successful device performance demonstration, the SSRS method has shown extensive successes for PCECCs, such as PCFCs, PCECs, protonic ceramic membrane reactors, reversible PCFCs, and solid state ammonia synthesis. Table 1 summarizes several representative applications that utilized the SSRS method to fabricate the whole or a part of the devices and the representative performance.3, 7, 42-49
Fig. 4. Schematic description of the fabrication of (a) protonic ceramic half cells BCZYYb+NiO anode | BCZYYb electrolyte and (b) single cells BCZYYb+NiO anode | BCZYYb electrolyte | BCZY63 cathode scaffold by using the SSRS method. (Adapted from Fig. 2b and Fig. 2c in Reference 3 with copyright permission.) The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
Table l. Summary of some representative performance for PCECCs fabricated by SSRS.
Classes
Pure Materials
PCFCs
Hydrogen Permeation Membranes
Sintered Materials
Properties
References
BaCe0.4Zr0.5Y0.1O3-δ
6.08 × 10 S/cm
42
BaZr0.5Ce0.3Y0.2O3-δ
2.50 × 10-2 S/cm
43
BaZr0.5Ce0.3Dy0.2O3-δ
4.30 × 10-2 S/cm
43
BaZr0.84Y0.15Cu0.01O3-δ
~1.78 × 10-2 S/cm
44
BaCe0.7Zr0.1Y0.1Yb0.1O3-δ
~650 mW/cm
3
BaCe0.7Zr0.1Y0.1Sm0.1O3-δ
410 mW/cm
45
BaZr0.8Y0.2O3-δ
660 mW/cm
7
BaCe0.7Zr0.1Y0.1Yb0.1O3-δ
237 mW/cm
BaZr0.80Y0.15Mn0.05O3-δ
0.8 mL/ min cm (1000 C)
BaZr0.8Y0.2O3-δ
4.3 × 10 mol cm s (900 C)
BaCe0.8Y0.2O3-δ - Ce0.8Y0.2O2-δ
0.0744 mL min cm (900 C)
Therefore, we can conclude that SSRS is the state-of-theart sintering method for the manufacturing of PCECCs cost effectively. However, the cofiring of anode and electrolyte can still not independently optimize the electrolyte and electrode microstructures. The long-term furnace sintering still cannot satisfy the rapid consolidation of each layer for additive manufacturing. Furthermore, the sintering aid effect and the sintering mechanism need us to contribute more effort to achieve further progress of SSRS for commercial applications to manufacturing large-scale PCECCs.
Rapid Laser Reactive Sintering Although the SSRS technique has demonstrated great success for the fabrication of PCECCs, the long-term (>10h) cofiring of the electrolyte and electrode (e.g., anode cermet) at a high temperature (>1,400°C) is still an inevitable step, which makes the independent optimization of the component layers (e.g., dense and large-grained electrolyte and nanoporous electrode) impossible. Furthermore, the manufacturing of PCECC stacks has to follow complicated procedures: fabrication of half cells consisting of anode support and electrolyte thin film, cofiring of half cells, deposition of the cathode, firing the cathode, and assembly of self-supported thick single cells, which not only make it impossible to achieve high volumetric power density but also make the manufacturing complicated and expensive. In their most recent work, Tong et al. at Clemson University developed a so-called rapid laser reactive sintering (RLRS) method for fast processing protonic ceramics with the desired crystal structures, microstructures, and geometries.50-53 As schematically described in Fig. 5, the RLRS process consists of the preparation of printable paste from component raw materials (carbonate and single metal oxides) mixed with sintering aid, the deposition of a thin green film of the targeted protonic ceramics, and the reactive sintering by rapid CO2 laser scanning. Like the SSRS, the phase formation, densification, and grain growth for achieving protonic ceramic electrolyte thin films could integrate into a single laser sintering step. However, the RLRS method has several apparent advantages over
(a) Paste/slurry preparation
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the SSRS: short processing time (seconds/minutes versus several hours), selectively sintering of pre-programmed regions allowing independent processing of different component layer, and easy controlling of microstructures (grain boundary-free and epitaxially grown dense electrolyte thin films and nanoporous electrodes or electrode scaffolds) by adjusting laser operation parameters and sintering aids. Tong et al. extensively applied the RLRS technique for processing the state-of-the-art protonic ceramics: dense electrolytes (BCZYYb+1wt%NiO, BCZYYb, BZY20+1wt%NiO, and BZY20), porous electrodes/electrode scaffolds (40wt% BCZYYb+60wt%NiO, BaCo0.4Fe0.4Zr0.1Y0.1O3-δ (BCFZY0.1), BaCe0.6Zr0.3Y0.1O3-δ (BCZY63)), dense interconnect (La0.7Sr0.3CrO3-δ/LSC), and dense mixed protonic and electronic-conduction composite (BaCe0.85Fe0.15O3-δ– BaCe0.15Fe0.85O3-δ/BCF).51 Figure 651 summarizes the XRD patterns for the protonic ceramic thin films prepared by the RLRS. All the protonic ceramics achieved the desired crystal structures. The electrolyte, interconnector, cathode scaffold, and cathode all achieved phase-pure perovskite structures, same as those obtained by the conventional furnace sintering method. The XRD patterns for anode included the perovskite and nickel oxide phase without any other impure phases. Even the complicated dual perovskite hydrogenpermeable membrane consisting of two different perovskite phases (BaCe0.85Fe0.15O3-δ–BaCe0.15Fe0.85O3-δ) was successfully achieved by the RLRS method. Figure 751 summarizes the SEM images of (continued on next page)
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Fig. 5. Schematic description of the rapid laser reactive sintering (RLRS) process. (Adapted from Fig. 1 (Route 2) in Reference 51 (open access).)
Fig. 6. Summary of the XRD patterns of protonic ceramic parts prepared by the RLRS method. (Adapted from Fig. 2 in Reference 51 (open access).)
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Fig. 7. Summary of SEM images of fractured cross-sections of protonic ceramic component films prepared by the RLRS method. (a) BCZYYb+1wt%NiO electrolyte, (b) BZY20+1wt%NiO electrolyte, (c) LSC interconnector film, (d) BCF composite film, (e) 40wt%BCZYYb+60wt%NiO anode, (f) BCZY63 cathode scaffold, and (g) BCFZY0.1 cathode. (Adapted from Fig. 3 and Fig. 4 in Reference 51 (open access).)
the representative protonic ceramics of electrolyte, anode, cathode scaffold, cathode, interconnector, and hydrogen-permeable membrane. The protonic ceramic electrolyte films such as BCZYYb+1wt%, BZY20+1wt%NiO, the LSC interconnector, and the BCF hydrogenpermeable membrane obtained by RLRS were all fully dense. With good control of the laser parameters, the 40wt%BCZYYb+60wt%NiO anode, BCFZY0.1 cathode, and BCZY63 cathode scaffold films demonstrated highly porous microstructures. Furthermore, the RLRS method demonstrated the capability to sinter the top layer of the protonic ceramics parts selectively. Figure 8a indicates that the dense BCZYYb electrolyte could be deposited on a pre-fabricated porous BCZYYb + Ni(O) anode substrate, which allowed the independently optimize the microstructures of the electrolyte and anode.53 Figure 8b indicates that the RLRS could achieve the fully dense BCZYYb electrolyte on a porous BCZYYb layer by a single laser scan of the thick BCZYYb film. The vertical temperature distribution caused by the limited laser beam penetration made this fabrication of graded microstructure possible.50 Figure 8c indicates that one-step RLRS could also fabricate the half cell consisting of BCZYYb+NiO anode and BCZYYb electrolyte due to vertical temperature distribution51. In summary, the RLRS made it possible to process the component layers of the PCECCs with the desired crystal structures, microstructures, and geometries within instant time, which provides the potential to manufacture PCECCs and other ceramic devices using the rapid additive manufacturing technique. The selective sintering
of specific locations not only improve the processability but also significantly lower the processing cost. The capability to control the microstructures by controlling laser operation parameters and protonic ceramic precursor composition makes it possible to fabricate PCECCs.
Integrated Additive Manufacturing and Laser Processing Although recently, the PCECCs have achieved the promising device performance at intermediate-temperature (400-700°C), most of those excellent results were from the limited-scale devices (e.g., button cell ≤1.0 cm2) due to the limitation of manufacturing techniques. The novel additive manufacturing (AM) technology starts from designing 3D models of the objects by computer-aided design (CAD) software and then slices the models to successive cross-sectional layers. After that, the AM machines deposit these slices together to build the parts in a layer-by-layer fashion. Recently, the most successful examples focus on the manufacturing of polymers and metals/metal alloys because of the easiness and rapidness of consolidation or sintering of these materials. Although the AM of ceramics has also caught increasing attention, the successful AM of ceramic devices must solve the difficulty for achieving high accuracy due to the significant shrinkage, the difficulty for fulfilling crack-free rapid sintering due to the intrinsic brittleness, and the difficulty for depositing precise layers due to the heavy involvement of additive materials.
Fig. 8. SEM images of protonic ceramic half cells fabricated by using the RLRS method. (a) Independently RLRS deposition of BCZYYb electrolyte dense layer on the preprepared porous anode pellet, (b) one-step RLRS scanning of a thick BCZYYb film to prepare dense electrolyte layer on porous electrode scaffold, and (c) one-step RLRS scanning of a BCZYYb electrolyte | BCZYYb + NiO anode half cells. (Adapted from Fig. 2e in Reference 50 (open access), Fig. 5a in Reference 51 (open access), and Fig. 5e in Reference 53 with copyright permission.) 70
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Fig. 9. I-AMLP system for the advanced manufacturing of ceramics. (a) Photo of I-AMLP system, (b) 3D printing based on microextrusion, (c) rapid laser drying during 3D printing, (d) rapid laser machining during 3D printing, and (e) rapid laser sintering of green layer. (Adapted from Fig. 1 in Reference 54 (open access).)
The recently developed RLRS technique allowed the possibility to utilize AM technology for the manufacturing PCECCs. Tong et al. developed a new integrated additive manufacturing and laser processing (I-AMLP) technique at Clemson University to process protonic ceramics.54 The house-made I-AMLP station (Fig. 9a) consists of X-Y and Z stages, microextruders, a CO2 laser, a picosecond YAG laser, and a Galvano scanner. The I-AMLP system can perform advanced manufacturing of green or sintered ceramic parts smoothly by combining the 3D printing based on fast microextrusion (Fig. 9b), accurate subtractive manufacturing based on laser processing (Fig. 9d), and in-situ consolidation based on high-energy laser sintering (Fig. 9e) and laser fast drying (Fig. 9c). As summarized in Fig. 10, Tong et al. have shown that the I-AMLP method could work with the green and sintered protonic ceramic parts for intermediate-temperature protonic ceramic devices with various complex geometries and controlled microstructures. As a demonstration, the protonic ceramic pellets, cylinders, cones, rings, straight tubes with either closed bottom or top, and lobed-tube with closed bottom were successfully printed using the printable paste developed by us. NiO-BZY20 and NiO–BCZYYb anode, BZY20, BCZYYb electrolytes, triple conducting BCFZY0.1 oxygen/water permeable membrane materials, and BCF hydrogen-permeable composite membrane materials were involved. The effectiveness of laser drying, laser cutting, laser polishing, and laser sintering was demonstrated. Protonic ceramic parts of the 40wt% BZY20+6wt% NiO | BZY20+1wt% NiO tubular half cells, the BCFZY0.1 microchannel membrane, and the planar 40wt%BCZYYb + 60wt%NiO | BCZYYb + 1wt% half cells were successfully prepared. Therefore, we can conclude that the newly developed I-AMLP provided an effective advanced manufacturing technique for rapidly and cost-effectively manufacturing PCECCs, which has a significant commercial future. The same method can also be utilized for the manufacturing of ceramic devices, especially for those devices with complicated geometry or multilayer and multifunctions.
Fig. 10. Summary of the images or microstructures of green and sintered protonic ceramic parts manufactured by I-AMLP. (a) Green anode cylinders, (b) green anode cones, (c) green anode tubes with closed bottom end, (d) green anode with closed top end, (e) green anode tube with four lobes and closed bottom end, (f) green BCF tube with eight lobes introduced by laser cutting, (h) short green anode co-axial tubes with lobes introduced by laser cutting, (i) and (j) sintered BCFZY0.1 membrane with embedded microchannels, (k) sintered protonic ceramic half cells fabricated by microextrusion-based AM process followed by coating and sintering, (l) half cells fabricated by one-step RLRS method, (m) SEM image of the fractured cross-section of the half cells shown in (l), and the high-magnification SEM image of the electrolyte shown in (m). (Adapted from Fig. 3, Fig. 6a, c, d, Fig. 7a, and Fig. 8a, b in Reference 54 (open access).)
Future Direction
The recent progress of manufacturing techniques for PCECCs such as SSRS, RLRS, and I-AMLP provided the possibility to rapidly and cost-effectively manufacture PCECCs on a large scale. The fundamental understanding of the mechanisms why these methods worked well need to be understood for further improving the method and expanded their applications to other materials systems. The demonstration of the I-AMLP for manufacturing PCECC stacks needs to contribute more effort. The understanding of the laser beam and materials need to be further pursued for providing manufacturing guidance. The new efficient design of PCECC devices can move further since the technique for manufacturing complicated and multifunctional ceramics becomes possible.
Acknowledgements
This material is based upon work supported by the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy (EERE) under the Hydrogen and Fuel Cell Technologies Office Award Number DE-EE0008428.
Disclaimer
“This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.” © The Electrochemical Society. DOI: 10.1149.2/2.F09204IF. (continued on next page)
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About the Authors Shenglong Mu is a PhD student from Dr. Tong’s group in materials science and engineering at Clemson University. Shenglong received his MS in polymer engineering from The University of Akron in May 2016 and his BS in materials science and engineering from the Beijing University of Chemical Technology. His main research interests focus on the study of reactive laser sintering and 3D printing of protonic ceramic energy devices. He also has experience in the polymer drying process and uniaxial stretching investigation of polymer film. At Clemson, Shenglong is the first member of Dr. Tong’s Sustainable Clean Energy Laboratory. He has focused on the development of new manufacturing techniques, additive manufacturing, and lasering processing for protonic ceramic energy devices. Shenglong has six first-authored papers published and 12 published papers in addition to one patent. He may be reached at smu@g.clemson.edu. https://orcid.org/0000-0002-2191-7470 Zeyu Zhao received his BS and MS in materials science and engineering from the Beijing University of Chemical Technology in 2013 and 2016, respectively. He is currently in his fifth year as a PhD student in materials science and engineering with Dr. Tong at Clemson University. His research interests focus on developing dualphase or multi-phase materials for energy devices, especially for protonic ceramic fuel cells, and the investigation of ionic conducting properties inside of these materials. He may be reached at zzhao2@g.clemson.edu. https://orcid.org/0000-0001-8649-925X Hua Huang is a postdoctoral researcher of materials science and engineering at Clemson University. His research interests focus on 3D printing integrated with laser rapid sintering processing for protonic ceramic fuel cells and electrolyzers. He also has rich experience in dualphase oxygen separation membrane reactor and phase-inversion tape casting for ceramic devices fabrication. He received his BS in inorganic nonmetal material engineering from Hefei University of Technology in 2009, and a PhD in materials science and engineering from the University of Science and Technology of China in 2014. Before joining Clemson, he worked at the Technical University of Denmark, Risø National Laboratory, as a research assistant in 2013. From 2014 to 2018, he worked at the Institute of Nuclear Energy Safety Technology, Chinese Academy of Sciences, as an assistant researcher for nuclear hydrogen production. He may be reached at hhuang8@clemson.edu. https://orcid.org/0000-0002-6234-2327 Jincheng Lei is a postdoctoral research associate at Clemson University. He received a PhD degree in electrical engineering from Clemson University in 2019, and a bachelor’s degree in materials science and engineering from the South China University of Technology, Guangzhou, China, in 2013. His research interest mainly focuses on design, development, and implementation of advanced manufacturing technologies to enable novel micro/nano materials, structures, devices, and sensors for photonic and electronic applications. He may be reached at jinchel@g.clemson.edu. https://orcid.org/0000-0003-1272-9555
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Fei Peng is an associate professor of materials science and engineering at Clemson University, and an affiliated faculty member of the Clemson University School of Health Research (CUSHR). He received his PhD from the Georgia Institute of Technology, and MS and BS from Tsinghua University. He has extensive training in ceramic processing, modeling, characterization, and testing. Dr. Peng is leading the advanced ceramic processing laboratory at MSE of Clemson University. His research is focused on overcoming the processing challenges during additive manufacturing ceramics, such as extrusion, inkjet printing, and laser sintering and micromachining. He has made significant contributions to the laser sintering of ceramics and fabricating embedded microchannels within ceramics. Dr. Peng has published over 40 peer-reviewed journal papers. He may be reached at fpeng@clemson.edu. https://orcid.org/0000-0002-3924-9028 Hai Xiao is the Samuel Lewis Bell Distinguished Professor of Electrical and Computer Engineering, and professor of bioengineering, at Clemson University. From 2006 to 2013, he was associate professor, then professor of electrical engineering, at the Missouri University of Science and Technology, where he also served as the founding director of the Photonics Technology Laboratory. From 2003 to 2006, he was an assistant professor of electrical engineering at the New Mexico Institute of Mining and Technology. From 2000 to 2003, he was a member of the technical staff at the Optoelectronic Center of Lucent Technologies/Agere Systems. Dr. Xiao received his PhD in electrical engineering from Virginia Tech in 2000. Dr. Xiao is the recipient of a number of prestigious awards, including the Office of Naval Research Young Investigator Program Award in 2006, and the R&D 100 Award in 2004. Dr. Xiao’s research interests mainly focus on sensors, instrumentation, materials, systems, and advanced manufacturing technologies for applications in energy, intelligent infrastructure, clean environment, biomedical sensing/imaging, and national security. Dr. Xiao has authored and coauthored over 160 journal papers and served as the principal investigator or coinvestigator for over 40 research projects. He may be reached at haix@clemson.edu. ORCID iD: https://orcid.org/0000-0003-1460-6241 Kyle S. Brinkman is the chair of the Department of Materials Science and Engineering at Clemson University. He received a BS in chemical engineering in 1998 and MS in materials science and engineering in 2000, both from Clemson. In 2004, he graduated from the Swiss Federal Institute of Technology in Lausanne, Switzerland, with a PhD in materials science and engineering. From 2005-2007, Brinkman served as a postdoctoral fellow at the National Institute of Advanced Industrial Science and Technology in Japan as part of a program sponsored by the Japan Society for the Promotion of Science. He later worked as a principal engineer in the Science and Technology Directorate of the U.S. Department of Energy’s Savannah River National Labratory from 2007-2014. Brinkman joined Clemson as an associate professor in 2014. He has authored or coauthored more than 100 peer-reviewed technical publications and government reports, three patents, and currently serves as an editor for the Journal of Materials Science. He is codirector of Clemson’s Nuclear Environmental Engineering Sciences and Radioactive Waste Management Center. Brinkman was the recipient of the Minerals, Metals and Materials Society (TMS) Young Leader International Scholar Award (2015), and the TMS Brimacombe Medalist Award (2020). He was elected a Fellow of the American Ceramic Society in 2020, and is the vice-chair of the Energy Materials and Systems Division. In 2015, he was awarded the Karl SchwartzwalderProfessional Achievement in Ceramic Engineering Award. Brinkman’s The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
research is related to the formation, structure, and behavior of ceramic composites in diverse application areas, including solid oxide fuel cells and ionic membrane systems, solid state lithium batteries, and ceramics for nuclear waste immobilization. He may be reached at ksbrink@clemson.edu. https://orcid.org/0000-0002-2219-1253 Jianhua (Joshua) Tong is an associate professor of materials science and engineering at Clemson University. Before joining Clemson in 2016, he was a research assistant/associate professor at the Colorado School of Mines. At Clemson, Dr. Tong manages the Sustainable Clean Energy Laboratory. He has published more than 80 peer-reviewed papers and six book chapters, and filed 15 patents. His publications have been cited over 5,200 times, and his h-index is greater than 33. He received his PhD from the Dalian Institute of Chemical Physics, CAS. In addition, he received extensive researcher/ JSPS fellow/postdoc training on catalytic membrane reactors and solid oxide fuel cells at the Research Institute of Innovative Technology for the Earth, the National Institute of Advanced Industrial Science and Technology, the University of Cincinnati, and the California Institute of Technology. He may be reached at jianhut@clemson.edu. https://orcid.org/0000-0002-0684-1658
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SEC TION NE WS Europe Section The ECS Europe Section will select new officers through an online election in late December 2020. The section’s chair for the last two years, Renata Solarska, University of Warsaw, Poland, will be succeeded by a new chair. The candidate for this position, Philippe Marcus, is the director of research at the Centre National de la Recherche Scientifique (CNRS) and head of the research group of physical chemistry of surfaces of the Institut de Recherche de Chimie Paris, École Nationale Supérieure de Chimie de Paris, Chimie ParisTech, France. Candidates for officers of the ECS Europe Section Executive Board are Roberto Paolesse, University of Rome Tor Vergata, Italy, as vicechair; Jan Macák, Brno University of Technology, Czech Republic, as treasurer; and Robert Lynch, University of Limerick, Ireland, as secretary. Current Vice-Chair Davide Bonifazi, Cardiff University, UK, will serve as member-at-large. The terms of office are for two years, from January 1, 2021, to December 31, 2022. The majority of European countries are members of the ECS Europe Section.
Renata Solarska, present chair of the ECS Europe Section.
Philippe Marcus, candidate for the chair position.
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Japan Section – Masayoshi Watanabe, Chair Korea Section – Won-Sub Yoon, Chair Mexico Section – Carlos E. Frontana-Vazquez, Chair National Capital Section – Eric D. Wachsman, Chair New England Section – Sanjeev Mukerjee, Chair Pittsburgh Section – Clifford W. Walton, Chair San Francisco Section – Gao Liu, Chair Singapore Section – Zhichuan Xu, Chair Taiwan Section – Hsisheng Teng, Chair Texas Section – Jeremy P. Meyers, Chair Twin Cities Section – Victoria Gelling, Chair
Open New Doors—Join ECS Sections Benefits: • Global reach • Access to innovative research • Networking and recognition
For more information, contact customerservice@electrochem.org. 74
The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
AWARDS AWAPROGRAM RDS
Awards, Fellowships, Grants ECS distinguishes outstanding technical achievements in electrochemistry, solid state science and technology, and recognizes exceptional service to the Society through the Honors & Awards Program. Recognition opportunities exist in the following categories: Society Awards, Division Awards, Student Awards, and Section Awards. ECS recognizes that today’s emerging scientists are the next generation of leaders in our field, and offers competitive Fellowships and Grants to allow students and young professionals to make discoveries and shape our science long into the future.
See highlights below and visit www.electrochem.org/awards for more information.
Society Awards The Fellow of the Electrochemical Society was established in 1989 as the Society’s highest honor in recognition of advanced individual technological contributions in the field of electrochemistry and solid state science and technology, and active ECS membership and involvement in the affairs of The Electrochemical Society. The award consists of a framed certificate and lapel pin. Materials due by February 1, 2021. The Henry B. Linford Award for Distinguished Teaching was established in 1981 for excellence in teaching in subject areas of interest to the Society. The award consists of a silver medal, a plaque, a $2,500 prize, complimentary meeting, a dinner held in the recipient’s honor during the designated meeting, and life membership. Materials due by April 15, 2021. The Vittorio de Nora Award was established in 1971 to recognize distinguished contributions to the field of electrochemical engineering and technology. The award consists of a $7,500 prize, a gold medal, and a wall plaque, Society life membership, complimentary meeting registration, and award dinner. Materials are due by April 15, 2021.
Division Awards The Battery Division Early Career Award, sponsored by Neware Technology Limited, was established in 2020 to encourage excellence among postdoctoral researchers in battery and fuel cell research with the primary purpose to recognize and support development of talent and future leaders in battery and fuel cell science and technology. The award consists of a framed scroll, a $2,000 prize, and complimentary meeting registration. Materials due by March 15, 2021.
The Battery Division Postdoctoral Associate Research Award, sponsored by MTI Corporation and the Jiang Family Foundation, was established in 2016 to encourage excellence among postdoctoral researchers in battery and fuel cell research and to recognize and support development of talent and future leaders in battery and fuel cell science and technology among early career professionals. The award consists of a framed scroll, a $2,000 prize, and complimentary meeting registration. Two awards are granted each year. Materials due by March 15, 2021. The Battery Division Research Award was established in 1958 to recognize excellence in battery and fuel cell research and encourage publication in ECS outlets. The award recognizes outstanding contributions to the science of primary and secondary cells, batteries, and fuel cells. The award consists of a framed certificate and a $2,000 prize. Materials due by March 15, 2021. The Battery Division Technology Award was established in 1993 to encourage the development of battery and fuel cell technology, and to recognize significant achievements in this area. The award is given to those individuals who have made outstanding contributions to the technology of primary and secondary cells, batteries, and/or fuel cells. The award consists of a certificate and the sum of $2,000. Materials due by March 15, 2021. The High-Temperature Energy, Materials, & Processes Division J. B. Wagner, Jr. Young Investigator Award was established in 1998 to recognize a young Society member who has demonstrated exceptional promise for a successful career in science and/or technology in the field of hightemperature materials. The award consists of an appropriately worded scroll and the sum of $1,000. The recipient may receive (if required) complimentary registration and up to $1,000 in financial assistance toward travel expenses for attendance of the Society meeting at which the award is to be presented. Materials due by January 1, 2021.
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AWARDS PROGRAM (continued from previous page)
The High-Temperature Energy, Materials, & Processes Division Subhash Singhal Award was established in 2017 to recognize excellence and exceptional research contributions of distinguished researchers to the science and engineering of solid oxide fuel cells (SOFC) and electrolyzers (SOEC), materials, processes, and manufacturing. The award consists of a scroll and a $1,000 prize. Materials due by February 5, 2021. The Nanocarbons Division Richard E. Smalley Award was established in 2006 to encourage excellence in fullerenes, nanotubes, and carbon nanostructures research. The award is intended to recognize, in a broad sense, those persons who have made outstanding contributions to the understanding and applications of fullerenes. The award consists of a framed certificate, $1,000 prize, and up to $1,500 in travel assistance. Materials due by January 31, 2021. The Organic and Biological Electrochemistry Division Manuel M. Baizer Award was established in 1992 and currently recognizes outstanding scientific achievements in the electrochemistry of organics and organometallic compounds, carbon-based polymers and biomass, whether fundamental or applied, and including but not limited to synthesis, mechanistic studies, engineering of processes, electrocatalysis, devices such as sensors, pollution control, and separation/recovery. The award consists of a framed certificate and a $1,000 prize. Materials due by January 15, 2021. The Sensor Division Outstanding Achievement Award was created in 1989 to recognize outstanding achievement in research and/or technical contributions to the field of sensors and to encourage work excellence in the field. The award consists of a framed certificate and a $1,000 prize. Materials due by March 1, 2021.
Student Awards The Battery Division Student Research Award, sponsored by Mercedes-Benz Research & Development, recognizes promising young engineers and scientists in the field of electrochemical power sources. The award encourages recipients to initiate or continue careers in the field. Eligible candidates must be enrolled in a college or university at the nomination deadline. The award consists of a framed certificate and a $1,000 prize. Materials due by March 15, 2021. The Canada Section Student Award was established in 1987 to recognize promising young engineers and scientists in the field of electrochemical power sources. The recognition encourages recipients to initiate or continue careers in the field. The award consists of a framed certificate and a $1,500 USD prize. Materials due by February 28, 2021. The San Francisco Section Daniel Cubicciotti Student Award was established in 1994 to assist a deserving student in Northern California in pursuing a career in the physical sciences or engineering. The award consists of an etched metal plaque and a $2,000 prize. Up to two honorable mentions will be extended, each to receive a framed certificate and a $500 prize. Materials due by February 15, 2021.
Section Awards The Canada Section W. Lash Miller Award was established in 1967 to recognize publications and/ or excellence in the field of electrochemical science and technology and/or solid state science and technology. The recipient will be a Canada resident who has obtained his/her last advanced education degree no more than 15 years before the year of the award. The award consists of a framed certificate and a $1,500 CAD prize. Materials due by December 31, 2020.
BENEFITS OF RENEWING YOUR ECS MEMBERSHIP VISIBILITY
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“I couldn’t imagine my professional life without the Society.” – Marca Doeff Senior Scientist at Lawrence Berkeley National Laboratory
Renew online: www.electrochem.org/renew 76
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AWARDS AWAPROGRAM RDS
Award Winners Join us in celebrating your peers as we extend congratulations to all! The following awards are part of the ECS Honors & Awards Program, which has recognized professional and volunteer achievement within our multi-disciplinary sciences for decades.
Section Awards 2020 ECS Canada Section R. C. Jacobsen Award
2020 ECS Georgia Section Outstanding Student Achievement Award
Dr. Aicheng Chen, Professor of Chemistry, Director of the Electrochemical Technology Centre (ETC) at the University of Guelph, Tier 1 Canada Research Chair in Electrochemistry and Nanoscience. Dr. Chen received his MSc from Xiamen University under the supervision of Prof. S.-G. Sun and his PhD from the University of Guelph in 1998 under the direction of Prof. J. Lipkowski. Subsequent to working in the chemical industry as a research scientist and electrochemical specialist for four years, Chen joined Lakehead University in 2002 as an assistant professor, where he was promoted to associate professor in 2005, Tier 2 Canada Research Chair in 2006, and full professor in 2010. He received a senior Japan Society for the Promotion of Science (JSPS) Fellowship in 2006 and worked with Prof. B. Ohtani at Hokkaido University. During his sabbatical in 2008, he worked with Prof. R. Compton as a visiting scholar at Oxford University. Chen relocated from Lakehead University to the University of Guelph in 2017. Dr. Chen received the ECS Canada Section Student Award in 1997 and has been an active Society member since then. Currently Councilor, he has served many roles with the ECS Canada Section. As a faculty advisor and the ESC director, he facilitated the establishment of the ECS University of Guelph Student Chapter in 2018. He also is active with the International Society of Electrochemistry (ISE). In addition, Prof. Chen has been a guest editor of the Journal of The Electrochemical Society, an associate editor of the Canadian Journal of Chemistry, and an editor of Electrochimica Acta. For his accomplishments, Prof. Chen has received numerous awards, including the ECS Canada Section W. Lash Miller Award, Chemical Institute of Canada Fellow, Royal Society of Chemistry Fellow, and International Society of Electrochemistry Fellow.
Z. Jung Fang is a PhD student in Prof. Tom Fuller’s group at the Georgia Institute of Technology, School of Chemical and Biomolecular Engineering. He received his BS degree magna cum laude in chemical engineering from the Rose-Hulman Institute of Technology in 2015. His current research is on proton-exchange membrane fuel cell electrodes and ceramic solid state batteries, and he has published two first-author papers. He was the elected president of the ECS Georgia Tech Student Chapter from 2017-2019. Fang has received numerous awards, including First Place, Student Poster Contest, ECS Georgia Section Conference (2019); The Shell Outstanding Teaching Assistant Award (2018); and the Rose-Hulman Leadership Advancement Program Fellowship (2015).
2020 ECS Georgia Section Outstanding Student Achievement Award Yamin Zhang is a fifth-year PhD student in Prof. Nian Liu’s group at the Georgia Institute of Technology, School of Chemical and Biomolecular Engineering. She received her BS in chemical engineering and technology in 2016 at Tianjin University, and BS in finance in 2016 at Nankai University. Her current research is on electrochemistry and battery technology. She has published more than 15 papers. Her selected awards include the Ziegler Award for Best Paper (2020), Phillips 66 Graduate Fellowship (2020), STAMI Graduate Student Fellowship (2020), First Place Poster–ChBE Graduate Research Symposium (2020), Most Stunning Award–National Nanotechnology Day Image Contest (2019), Outstanding Poster Award at IEN User Day (2019), and ChBE Exemplary Academic Achievement Award (2017).
ECS FELLOWS 2021 Call for Nominations Deadline: February 1, 2021
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NE W MEMBERS ECS is proud to announce the following new members for July, August, and September 2020. (Members are listed alphabetically by family/last name.) Members
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Cassidy Anderson, Kennewick, WA, USA
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Shyamal Bej, Houston, TX, USA W. Bi, Tianjin, Tianjin, China Necmi Biyikli, Storrs, Mansfield, CT, USA
C
Xia Cao, Richland, WA, USA Jianli Cheng, Berkeley, CA, USA Nadine Collaert, Leuven, Flemish Brabant, Belgium
D
John Dale, Auckland, Auckland, New Zealand Arrelaine Dameron, Thorton, CO, USA Yu Duan, Changchun, Jilin, China
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Bryan Erb, Concord, OH, USA Can Erdonmez, Stony Brook, NY, USA
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Adrian Grant, Atlanta, GA, USA
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Abulaiti Hairisha, Menlo Park, CA, USA Kazuhito Higuchi, Yokohama, Kanagawa, Japan Bram Hoex, Sydney, NSW, Australia Linhua Hu, Skokie, IL, USA
Tsuyoshi Minami, Meguro-ku, Tokyo-to, Japan Hyoung-Seok Moon, Busan, Gyeongsangnam-do, South Korea Kevin Musselman, Waterloo, ON, Canada
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Olayinka Ogunro II, San Antonio, TX, USA David O’Meara, Albany, NY, USA
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Jin-Seong Park, Seoul, Gyeonggi-do, South Korea Shengjie Peng, Nanjing, Jiangsu, China Francesco Pino, Concord, OH, USA
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Arunmozhiselvan Rajaram, Chennai, TN, India Christopher Rasik, Lakewood, OH, USA Abdelkrim Rebiai, El Oued, El Oued Province, Algeria Wendell Rhine, Northborough, MA, USA David Roberts, Santa Clara, CA, USA
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Andreas Schulze, Palo Alto, CA, USA Xiaoping Shi, Beijing, Hebei, China Hans-Georg Steinrück, Paderborn, Bavaria, Germany
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Noriaki Toyoda, Himeji, Hyogo, Japan Thien-Toan Tran, Santa Ana, CA, USA
V
I
Paul van der Heide, Leuven, Flemish Brabant, Belgium
J
Xinwei Wang, Shenzhen, Guangdong, China Virginia Wheeler, Alexandria, VA, USA
Naoya Ishida, Noda, Chiba, Japan Takanobu Ishida, Soka, Saitama, Japan Jakes Jacobs, Randburg, Gauteng, South Africa Vibhor Jain, Williston, VT, USA Paul Jamison, Albany, NY, USA Ian Johnson, Chicago, IL, USA Rajiv Joshi, Yorktown Heights, NY, USA
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Sebastian Koelling, Montreal, QC, Canada Coleman Kronawitter, Davis, CA, USA Jiao Kui, Tianjin, Tianjin, China An-Tsung Kuo, Yokohama, Kanagawa, Japan
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James Lamb, Monticello, FL, USA Chuanbo Li, Beijing, Beijing, China
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Anil Mane, Lemont, IL, USA Benjamin Miller, Rochester, NY, USA
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Hwi Yoon, Seoul, Gyeonggi-do, South Korea
Student Members
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Ivon Acosta Ramirez, Lincoln, NE, USA Saeed Ahmadi Vaselabadi, Golden, CO, USA Mert Akin, South Miami, FL, USA Shingo Akiyama, Suita, Osaka, Japan Fawaz Ali, Ann Arbor, MI, USA Zuraya Angeles Olvera, Pachuca, Hidalgo, Mexico Henry Apsey, Swansea, Swansea, UK Jennifer Arcila Castillo, Lincoln, NE, USA Ryo Asakura, Dübendorf, ZH, Switzerland Yasuhiro Ayauchi, Kitami, Hokkaido, Japan Irfan Aydogdu, Calgary, AB, Canada
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Seol Baek, Mishawaka, IN, USA Rashin Basiri Namin, Fredericton, NB, Canada Assem Basurrah, Little Rock, AR, USA David Beck, Honolulu, HI, USA Maximilian Becker, Dübendorf, ZH, Switzerland Caitryn Bell, Charlottesville, VA, USA Helen Bergstrom, Berkeley, CA, USA Eva Bestelink, Guildford, Surrey, UK Aurélien Boucher, Besançon, BorgogneFranche-Comté, France Teerth Brahmbhatt, Knoxville, TN, USA Cailin Buchanan, Ann Arbor, MI, USA Lena Viviane Buehre, Hannover, Lower Saxony, Germany Ha Quoc Thang Bui, Kearny, NJ, USA Lisa Büker, Ilmenau, Thuringia, Germany
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John Carl Camayang, Detroit, MI, USA Weikai Cao, South Bend, IN, USA Lea Caradant, Montreal, QC, Canada Suzane Carneiro, Chicago, IL, USA Millicent Castillo, London, ON, Canada Jishnudas Chakkamalayath, Palakkad, KL, India Shu-Wei Chang, Taipei City, Taipei City, Taiwan Anshuman Chaupatnaik, Bangalore, KA, India Yixuan Chen, Surrey, BC, Canada Yu Chen Chen, Tainan, Tainan City, Taiwan Yu Chen Chen, Hsinchu, Hsinchu County, Taiwan Yuhan Chen, Taipei, Taipei City, Taiwan Meng Han Chiang, Hsinchu, Hsinchu County, Taiwan Yu-Chuan Chiu, Hsinchu, Hsinchu County, Taiwan Jungsang Cho, New York, NY, USA Rebecca Clark, Chapel Hill, NC, USA Thomas Clarke, Chapel Hill, NC, USA Anthony Consiglio, Berkeley, CA, USA Claude Coppex, Calgary, AB, Canada Linda Cortes, Greenville, SC, USA Matthew Crafton, Berkeley, CA, USA Allison Cutri, Mishawaka, IN, USA
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Wafaa Dabaja, Dearborn, MI, USA Siddharth Deshpande, West Lafayette, IN, USA Manali Dhawan, East Lansing, MI, USA Victoria Dickson, Swansea, West Glam, UK Justus Diercks, Villingen, AG, Switzerland Dong Ding, South Bend, IN, USA Xuewei Ding, Auburn, AL, USA Fangyuan Dong, Salt Lake City, UT, USA Daniel Donnell, Boston, MA, USA
The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
NE W MEMBERS Fengmin Du, Munich, Bavaria, Germany Jeffrey DuBose, Notre Dame, IN, USA Christopher Durkee, Boston, MA, USA Abhijit Dutta, Bern, Bern, Switzerland Debayon Dutta, New York, NY, USA
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Corey Efaw, Boise, ID, USA Korinne Erickson, Lincoln, NE, USA
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Wissam Fawaz, Detroit, MI, USA Wes Fermanich, Ann Arbor, MI, USA Marius Flügel, Ulm, Baden-Württemberg, Germany Lucas Freitas de Lima e Freitas, Detroit, MI, USA Kenta Fujihashi, Nishihara-Cho, Okinawa, Japan
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Roberto Garcia, Monterrey, N L, Mexico Felix Gerbig, Karlsruhe, BadenWürttemberg, Germany Matthew Glasscott, Chapel Hill, NC, USA Sondrica Goines, Chapel Hill, NC, USA Leo Gordon, New York, NY, USA Maximilian Graf, Munich, Bavaria, Germany Mary Louise Gucik, Albuquerque, NM, USA Naman Gupta, Ithaca, NY, USA
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Kathryn Hamann, Pasadena, CA, USA Rowan Hanson, Swansea, Wales, UK Joseph Hart, Tustin, CA, USA Mohammad Hasibul Hasan, Potsdam, NY, USA Brendan Hawkins, Brooklyn, NY, USA Joseph Heglin, Lincoln, NE, USA Daniel Herrera, Monterrey, Nuevo León, Mexico Shirin Hesan, Fayetteville, AR, USA Yu Hong, Taichung, Taichung City, Taiwan Chih-Chieh Hsu, Hsinchu, Hsinchu County, Taiwan Tzu-Yu Hsu, Hsinchu, Hsinchu County, Taiwan Lejun Hu, Lowell, MA, USA JiaLin Huang, Hsinchu, Hsinchu County, Taiwan Tzu-Yang Huang, Albany, CA, USA Chih-Hsuan Hung, Seattle, WA, USA Su Min Hwang, Richardson, TX, USA
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Andrea Illiberi, Leuven, Flemish Brabant, Belgium Mana Iwai, Sapporo, Hokkaido, Japan
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Lorn Jackson, Esher, Surrey, UK Roselyne Jeanne-Brou, Grenoble, AuvergneRhône-Alpes, France Su Jie, Hsinchu, Hsinchu County, Taiwan KyuJung Jun, Berkeley, CA, USA Yong Chan Jung, Richardson, TX, USA
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Mitchell Kaiser, Mountlake Terrace, WA, USA Chintan Kankotiya, Waterloo, ON, Canada Youcef Karar, Saint Martin d’Hères, Auvergne-Rhône-Alpes, France Masaki Katatoka, Kitami, Hokkaido, Japan Shuji Katsuta, Nagoya, Aichi-ken, Japan Philip Kauffmann, Chapel Hill, NC, USA Rezvan Kazemi Khouzani, Chapel Hill, NC, USA Adam Kern, Mishawaka, IN, USA Myoungsub Kim, Seoul, Gyeonggi-do, South Korea Seon Yong Kim, Seoul, Gyeonggi-do, South Korea Kiran Kiran, Bern, Bern, Switzerland Zachary Konz, Berkeley, CA, USA Sarathkumar Krishnan, Indore, MP, India Raina Krivina, Eugene, OR, USA Mario Kurniawan, Ilmenau, Thuringia, Germany Duyoung Kwon, Changwon, Gyeongsangnam-do, South Korea Seung-Ryong Kwon, Mishawaka, IN, USA
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Steven Lam, Knoxville, TN, USA Alyna Lange, Potsdam, Baden-Württemberg, Germany Aidan Larsen, Omaha, NE, USA Hsin-Hua Lee, Hsinchu, Hsinchu County, Taiwan Jungeun Lee, Yongsan-gu, Gyeonggi-do, South Korea Meredith Lee, South Bend, IN, USA Rose Yesl Lee, Albuquerque, NM, USA Sangyoon Lee, Seoul, Seoul, South Korea Michelle Lehmann, Knoxville, TN, USA Pei-Yi Li, Hsinchu, Hsinchu County, Taiwan Xin Li, Columbia, SC, USA Yicheng Li, Wuhan, Hubei, China YouXuan Li, Taoyuan, Taoyuan City, Taiwan Yue Li, Malden, MA, USA Zhen-hao Li, Hsinchu, Hsinchu County, Taiwan Zoushuang Li, Wuhan, Hebei, China Chia Yu Lin, Hsinchu, Hsinchu County, Taiwan Po-An Lin, Hsinchu County, Hsinchu County, Taiwan Jiacheng Liu, Notre Dame, IN, USA Yanna Liu, Calgary, AB, Canada Yi-Cheng Liu, Taipei, Taipei City, Taiwan
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Lucile Magnier, Villeurbanne, AuvergneRhône-Alpes, France Amar Malla, Cardiff, Wales, UK Anton Marusenko, Swansea, Wales, UK Preethi Susan Mathew, Notre Dame, IN, USA Andrew May, New York, NY, USA Alexandra McDougall, Calgary, AB, Canada Colm McKeever, Ardee, Leinster, Ireland Justin McMurray, Bryan, TX, USA Eric McShane, Berkeley, CA, USA
The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
Marvin Messing, Burnaby, BC, Canada Lydia Meyer, Golden, CO, USA Anna Michalak, Swansea, Wales, UK Sanat Vibhas Modak, Ann Arbor, MI, USA Leo Monaco, Toronto, ON, Canada Michael Moore, Lexington, KY, USA Ankita Morankar, West Lafayette, IN, USA Saagar Motupally, Avon, CT, USA Richard Murdock, Cambridge, MA, USA
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Fuya Nagano, Leuven, Flemish Brabant, Belgium Takuma Nakagawa, Sapporo-shi, Hokkaido, Japan Anh Tuan Nguyen, Honolulu, HI, USA Tung Nguyen, Lincoln, NE, USA Yuichiro Nishimura, Omihachiman-shi, Shiga, Japan
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Kwang O’Donnell, London, ON, Canada Christiana Oh, Notre Dame, IN, USA Tsubasa Okamura, Suita-shi, Osaka-fu, Japan Ramin Ordikhani Seyedlar, Iowa City, IA, USA Samuel Orenstein, Chapel Hill, NC, USA Alejandro Ortega, Calgary, AB, Canada Ite Osibanjo, Bristol, England, UK
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Aiswarya Padinjarethil, Soborg, Sjælland, Denmark Kuan-Ting Pan, Hsinchu, Hsinchu County, Taiwan Sejoon Park, Austin, TX, USA Nadiia Pastukhova, Chengdu, Sichuan, China Arghya Patra, Urbana, IL, USA Suporna Paul, Mishawaka, IN, USA David Pe, Los Angeles, CA, USA Shakila Peli Thanthri, Detroit, MI, USA Doran Pennington, Los Angeles, CA, USA Yeremi Perez, Monclova, Coahuila, Mexico Nicola Poli, Monticelli Brusati, Lombardia, Italy Heish Pong, Yunlin, Yunlin County, Taiwan Fanny Poon, Markham, ON, Canada
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Marco Ragone, Chicago, IL, USA Joshua Reyes Morales, Chapel Hill, NC, USA Danielle Richards, Ann Arbor, MI, USA Andressa Yasmim Rodrigues Prado, Naperville, IL, USA Ismael Rodriguez Perez, Corvallis, OR, USA Anirban Roy, Knoxville, TN, USA
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Krishnakanth Sada, Bangalore, KA, India Amissi Sadiki, Jamaica Plain, CA, USA Shirin Saffar Avval, Chicago, IL, USA Kei Sakata, Sapporo, Hokkaido, Japan Yota Sampei, Sendaishi, Miyagi-ke, Japan (continued on next page) 79
NE W MEMBERS (continued from previous page)
Nicolas Santana Tijo, Calgary, AB, Canada Kaustubh Sawant, West Lafayette, IN, USA Robin Schuster, Munich, Bavaria, Germany Thivani Senathiraja, Lincoln, NE, USA Jonathan Sepulveda, Apopka, FL, USA Bhamiti Sharma, Lexington, KY, USA Yi-Ru Shih, Hsinchu, Hsinchu County, Taiwan Motonari Shimizu, Sendai, Miyag, Japan Arthur Sloan, York, ON, Canada Sam Jackson Smith, Jamaica Plain, MA, USA William Smith, Golden, CO, USA Simon Birger Solberg, Trondheim, Trøndelag, Norway Morgan Stacey, Maidstone, Kent, UK Joseph Stiles, Princeton, NJ, USA Jonas Stoll, Surrey, BC, Canada Jing-Yuan Su, Toufen, Miaoli County, Taiwan Alicja Szczepanska, Bristol, England, UK
T Yoshiki Tai, Sapporo City, Sapporo, Japan Brandan Taing, Lakeside, CA, USA Darren Tan, San Diego, CA, USA Chao Tang, South Bend, IN, USA
New Members by Country
Nicole Tarolla, Carrboro, NC, USA Kevin Tenny, Cambridge, MA, USA Elif Tezel, Detroit, MI, USA Ding Tian, Troy, NY, USA Linh To, Notre Dame, IN, USA Carrie Trant, Troy, NY, USA Debashis Tripathy, Bangalore, KA, India Yu-Ting Tsai, Chiayi, Chiayi County, Taiwan Chiang Tsung-Che, Hsinchu, Hsinchu County, Taiwan Pragun Tuladhar, Nashville, TN, USA
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Scott Ueda, La Jolla, CA, USA Kailash Veerappan Uma Kumar, Sivaganga, TN, India
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Kathryn Vannoy, Chapel Hill, NC, USA Ravi Teja Velpula, Newark, NJ, USA Chad Verwold, Calgary, AB, Canada Vidyanand Vijayakumar, Pune, MH, India
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Nicole Walker, Carrboro, NC, USA Huiru Wang, Paris, Île-de-France, France
Zixuan Wang, Ann Arbor, MI, USA Kodai Wani, Yokohama, Kanagawa, Japan Steven Watt, New York, NY, USA
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Chen Xuewen, Nagoya, Aichi, Japan
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Chun-Ren Yang, Taichung, Taichung City, Taiwan Julia Yang, Berkeley, CA, USA Lingyu Yang, Mishawaka, IN, USA Lai Yen-Cheng, Hsinchu, Hsinchu County, Taiwan Yikang Yu, Indianapolis, IN, USA Su Yuan, Hsinchu, Hsinchu County, Taiwan
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Ivan Zelocualtecatl, Bern, Bern, Switzerland Elizabeth Zhang, Hawaiian Gardens, CA, USA Xianhui Zhang, Richland, WA, USA Jiangming Zhao, Lincoln, NE, USA You-Syuan Zhou, Tainan City, Tainan, Taiwan
Look who joined ECS in the Third Quarter of 2020.
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Algeria
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Canada
Norway
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Denmark
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Algeria................... 1 Australia................. 1 Belgium................. 5 Canada................. 20 China................... 10 Denmark................ 1 France.................... 7 Germany.............. 10 India....................... 8 Ireland.................... 1 Italy........................ 1 Japan................... 21 Mexico................... 4 New Zealand.......... 1 Norway................... 1 South Africa........... 1 South Korea........... 8 Spain..................... 1 Switzerland............ 6 Taiwan.................. 29 UK........................ 11 USA................... 160
The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
2020 ECS Summer Fellowship Summary Reports Summer Fellowships Each year ECS gives up to five summer fellowships to assist students in continuing their graduate work during the summer months in a field of interest to the Society. Congratulations to the four summer fellowship recipients for 2020. The Society thanks the ECS Summer Fellowship Committee for reviewing the applications and selecting four excellent recipients.
Apply for the Colin Garfield Fink Summer Fellowship This scholarship supports a postdoctoral scientist or engineer during the summer months. https://www.electrochem.org/fink-fellowship Be the next Summer Fellowship recipient! Apply by January 15, 2021, at: www.electrochem.org/summer-fellowships
2020 Edward G. Weston Summer Research Fellowship â&#x20AC;&#x201C; Summary Report Towards Quantifying Ion Kinetics at Confined Nanointerfaces Using Electrochemical Fluctuation Methods by Andrew D. Pendergast
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on transport within confined nanoscale systems has received extensive interest over the past 20 years, driven by fundamental studies to probe ion behavior at electrified nanointerfaces in the context of high-performance energy materials.1 Previously, conical glass nanopores have been used to demonstrate several unique iontransport characteristics, including voltagedependent ion current rectification and tunable negative differential resistance.2,3 Within these nanopores, ion transport is governed by a combination of electric field effects under an applied potential, electric double layer effects at the charged nanopore walls, and chemical or physical gradients imposed across the nanopore orifice into the bulk solution. The resistance of the nanopore is further controlled by the concentration,
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charge, size, and dissociation equilibrium of the electrolyte ion pair, resulting in a number of physicochemical parameters that can be used to probe fundamental ion-transport phenomena. Within this work, glass nanopores were fabricated with radii approximately ~500 nm to study ion transport in monovalent and divalent electrolyte systems to fundamentally probe ion pairing near electrical doublelayers. A schematic and simulated concentration profile at a glass nanopore orifice is presented in Fig.1, demonstrating the interplay of surface charge, electrolyte concentration, and electric fields that leads to non-ohmic behavior. In brief, electrolyte gradients generated under an applied potential result in asymmetric solution conductivity near the nanopore orifice,
generating curved current-potential traces compared to a predicted linear resistive response.4 From the current-potential traces presented in Fig. 2, it is clear that ion-transport in these confined nanopores is highly dependent on both the electrolyte identity and concentration, shown here for the monovalent KCl (blue) and divalent BeSO4 (red) electrolyte systems. Previous efforts have focused on the effects of double-layer structure on iontransport in nanopores.5 However, the kinetics of ion-transport processes can further influence observed electrical properties at these confined nanointerfaces. At electrolyte concentrations below 1 mM, the total number of ions near the nanopore orifice approach the countable regime, i.e., (continued on next page)
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Fig. 1. A. Representative schematic of glass nanopore measurement with BeSO4 electrolyte under an applied negative potential relative to an external Ag/AgCl reference electrode, illustrating ion pairing, ion adsorption, and a static negative charge on the glass nanopore walls. B. Simulated total ion concentration profile monovalent electrolyte model system with a nanopore radius of 260 nm and asymmetric electrolyte concentrations at an applied potential of -1 V vs. external Ag/AgCl reference electrode. The Electrochemical Society Interface â&#x20AC;˘ Winter 2020 â&#x20AC;˘ www.electrochem.org
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tens to hundreds of ions. In this range, inherent statistical chemical fluctuations, such as those due to stochastic ion pair formation, can significantly impact the electrical properties of the nanopore.6 These fluctuations in the ionic species populations, and thus the nanopore resistance, appear as noise under conventional amperometric or potentiometric measurements. However, as these fluctuations can be fundamentally related to transient chemical states, such as the association/dissociation of an ion pair or the adsorption/desorption of an ion at a charged interface, they can be probed using autocorrelation methods to extract characteristic kinetic parameters directly from noisy amperometric or potentiometric data. Presently, this work is focused on addressing instrumentation for electrochemical fluctuation spectroscopy with sensitivity to measure chemical kinetics for populations of tens to hundreds of ions (vide supra). Additionally, this work will be extended to sub-100 nm nanopores to probe the effects of double-layer structure on ion transport at nanointerfaces with dimensions approaching that of the double-layer. © The Electrochemical Society. DOI: 10.1149.2/2.F10204IF.
Acknowledgments I want to thank The Electrochemical Society for support through the Edward G. Weston Fellowship. I would further like to thank Prof. Henry S. White for project guidance and support, in addition to Prof. Joel M. Harris and Prof. Martin A. Edwards for helpful discussions.
About the Author Andrew D. Pendergast received his BS in chemistry with the highest honors from The University of North Carolina at Chapel Hill in 2020. Over the past three years in the lab of Prof. Jeffrey E. Dick, he has explored fundamental electrochemistry at the nanoscale, primarily using aqueous nanodroplets as sub-femtoliter reactors for nanoparticle synthesis and characterization. He has authored and co-authored several manuscripts, including work selected for ACS Editors’ Choice and Nature
Communications Editors’ Highlights. Previously, Pendergast has been awarded a Barry Goldwater Scholarship, an NSF GRFP Honorable Mention, an ACS undergraduate award in analytical chemistry, and an NSF REU Fellowship. As a visiting scholar, he has worked in the labs of Dr. Christophe Renault at École Polytechnique in Paris, France, studying the dynamics of single nanoparticle collisions, and Prof. Henry S. White at The University of Utah, studying interfacial electrogenerated chemiluminescence. As an ECS Summer Fellowship recipient, Andrew will travel to The University of Utah to begin his graduate studies in the lab of Prof. Henry S. White, probing the electrochemically driven formation of a new phase at nanointerfaces in the context of single metallic nanoparticles, small metal clusters, and gaseous nanobubbles. He can be reached at andrew.pendergast@utah.edu. https://orcid.org/0000-0003-3311-1260
References 1. Lan, W.-J.; Edwards, M. A.; Luo, L.; Perera, R. T.; Wu, X.; Martin, C. R.; White, H. S., Voltage-Rectified Current and Fluid Flow in Conical Nanopores. Accounts of Chemical Research 2016, 49 (11), 2605-2613. 2. Luo, L.; Holden, D. A.; White, H. S., Negative Differential Electrolyte Resistance in a Solid-State Nanopore Resulting from Electroosmotic Flow Bistability. ACS Nano 2014, 8 (3), 3023-3030. 3. Siwy, Z. S.; Powell, M. R.; Kalman, E.; Astumian, R. D.; Eisenberg, R. S., Negative Incremental Resistance Induced by Calcium in Asymmetric Nanopores. Nano Letters 2006, 6 (3), 473-477. 4. White, H. S.; Bund, A., Ion Current Rectification at Nanopores in Glass Membranes. Langmuir 2008, 24 (5), 2212-2218. 5. Perera, R. T.; Johnson, R. P.; Edwards, M. A.; White, H. S., Effect of the Electric Double Layer on the Activation Energy of Ion Transport in Conical Nanopores. The Journal of Physical Chemistry C 2015, 119 (43), 24299-24306. 6. Feher, G.; Weissman, M., Fluctuation Spectroscopy: Determination of Chemical Reaction Kinetics from the Frequency Spectrum of Fluctuations. Proceedings of the National Academy of Sciences 1973, 70 (3), 870.
Fig. 2. Representative normalized current-potential traces for monovalent KCl (A) and divalent BeSO4. (B) ion transport at a 610 nm radius nanopore demonstrating concentration-dependent ioncurrent rectification. All potentials are referenced to an external Ag/AgCl quasi-reference electrode. Current values are normalized to the current at an applied potential of 1 V vs. external Ag/AgCl, as represented by ia. 82
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2020 Joseph W. Richards Summer Research Fellowship – Summary Report Towards Using Macro-homogeneous Models to Study Electrode Wetting in CO2 Electrolyzers by McLain E. Leonard
C
arbon dioxide (CO2) electrolyzers increasingly use gas diffusion electrodes (GDEs) to augment productivity. GDEs separate gaseous and electrolyte phases while facilitating reactants/products/electrons transport to/ from catalytically active sites. A material set that can manage diverse (e.g., electrical conductivity and electrocatalytic activity/ selectivity) and contradictory (e.g., permeability and flooding resistance) functionalities is paramount for ensuring robust performance while targeting high product yields and efficiencies. Electrochemical CO2 reduction (CO2R) models have been developed to validate the notion that GDEs enable greater current densities and improved faradaic efficiencies by increasing gaseous species fluxes as compared to flooded electrodes.1,2 These models assume that gas diffusion layers used to support the catalyst layer remain dry during operation; however, flooding of GDEs in contact with liquid electrolytes has been reported at moderate operating conditions (<200 mA cm‒2).3,4 While spatially-variant liquid saturation in porous materials is necessarily considered in polymer electrolyte fuel cell (PEFC) models, where liquid water is both a product
of the cathodic oxygen reduction reaction and present in humidified gas streams, liquid intrusion scenarios remain unarticulated for CO2R. Thus, there is a need to conceptualize, construct, and experimentally validate porous electrode two-phase flow models that are tailored for the environments inherent to CO2R electrolyzers. Constitutive relations are needed to describe simultaneous two-phase (gas and liquid) transport within the different porous electrode components. We use macrohomogeneous statistical descriptions of porous materials as reported by Weber et al.5,6 because they permit variation of microstructural (i.e., pore size distribution, PSD) and surface properties (i.e., contact angle distribution, CAD). An abbreviated workflow is shown in Fig. 1. Within this model framework, Weber et al. were able to systematically vary carbon fiber substrate and microporous layer properties to deconvolute the role of each in managing water transport. However, the (electro) chemical environment of CO2R challenges the electrode wettability assumptions established during the contemplation of PEFCs. More specifically, two phenomena that emerge as possible contributors to GDE flooding during CO2R are (i) electrowetting,
which reduces the solid-liquid-gas contact angle, θ, when liquid electrolyte contacts polarizable electrode surfaces,7,8 and (ii) lowered gas-liquid surface tension, γ, when organic reduction products (e.g., ethanol) enter aqueous electrolytes.9 Electrode microstructure and surface chemistry can be represented by the pore size distribution (PSD) and the contact angle distribution (CAD), respectively. At each location within a porous material, the “saturated” pore volume fraction is determined by the critical pore radius, rC, which is a function (Eq. 1) of the liquid-gas pressure differential, or capillary pressure (PC = PL ‒ PG), as well as the surface tension, γ, and the intrinsic contact angle, θ.
2 cos( ) PC
(Eq. 1) Saturation, S, mapped to PC on a “filling curve” forms a constitutive relation constructed for each GDE component that is integrated into a macro-homogeneous transport model. S is needed to calculate effective transport coefficients (i.e., diffusivities and Darcy permeabilities) according to empirical relations of the form Dijeff ~ Dij(1 ‒ S)n, where n is a fitting parameter that is valued between 2–3 for typical carbon fiber substrates used in PEFCs, for example.6,10 Within the macrohomogeneous framework, increasing liquid saturation facilitates liquid percolation and diminishes gaseous species diffusion. We simulate electrowetting by shifting the center of the CAD (θ) (Fig. 2a) and simulate organic product solutions by varying both γ and θ (Fig. 2b). The surface potentials, Φ, associated with the θ values reported in Fig. 2a, are determined from a functional combination (Eq. 2) of the Young-Dupre and Lippmann equations.7 A double layer capacitance, Cdl, value of 20 μF cm‒2 is assumed to represent a basal plane carbon surface.11 The contact angle at Φ = 0 V is given by θo.
rC
Cdl 2 (Eq. 2) 2 The γ-θ functional relationship used in Fig. 2b is determined from measurements of alcohol-water mixtures wettability on a flat polytetrafluoroethylene (PTFE) surface.9 Both phenomena shift filling curves towards more negative PC, indicating an increasingly hydrophilic pore character. cos( ) cos(ο )
Fig. 1. Workflow for the integration of porous electrode models into electrolyzer simulations. Statistical descriptions of porous media, which consider both microstructure (pore size distribution, PSD) and surface chemistry (contact angle distribution, CAD), are used to generate filling curves. V(r) and Ψ(θ) represent pore volume and contact angle probability density functions, which are taken to be log-normal and normal distributions, respectively.6 These constitutive relations can be used to determine the local GDE saturation as a function of the liquid-gas pressure differential or capillary pressure, PC = PL ‒ PG, in a one-dimensional CO2 electrolyzer transport model. Local saturation, S(x), scales the transport coefficients for gaseous and liquid species (i.e., binary diffusivity, Dij, and Darcy permeability, kLabs) to yield effective values (Dijeff and kLeff) in the presence of liquid. The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
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Fig. 2. Saturation, S, plotted as a function of capillary pressure, PC. The equilibrium fraction of liquid filled pores, S, varies according to the local liquid-gas pressure difference, PC. Positive PC values indicate that higher liquid pressure (PL) is required to fill a portion of the pores, while negative PC values indicate that some fraction of pores fill even when local gas pressure exceeds liquid pressure. (a) Electrowetting is the phenomenon that describes when electrode polarization decreases interfacial surface energy and the gas-liquid-solid contact angle, θ, according to Eq. 2. We simulate this by shifting the center of the CAD towards lower θ values. (b) Introducing organic CO2R products into the electrolyte is simulated by decreasing the gas-liquid surface tension, γ, together with θ. The functional relationship between γ and θ used here was determined with a selection of water-alcohol mixtures on PTFE.9
Such equilibrium shifts could increase steady-state GDE saturation and, in part, account for diminished cell performance. GDE models enable inquiry into how variable wettability predictors (PC, θ, and γ) might alter overall cell performance. Ultimately, filling curves like those in Fig. 2 need to be validated through experimentation by collecting PC-S data for electrodes under polarization and/or with aqueous-organic mixtures as the filling fluids. Once validated, the model results could be used to calculate effective transport coefficients in the presence of two-phase flow, which would improve understanding of CO2 electrolyzer performance in extreme scenarios and might inspire new operational approaches, such as in-cell separation strategies to enhance product recovery.
Acknowledgments The author would like to thank The Electrochemical Society for awarding this Summer Research Fellowship. The author would also like to thank both his thesis advisor, Prof. Fikile R. Brushett, for encouraging exploration at the interfaces between scientific disciplines, and Prof. Antoni Forner-Cuenca for making himself available for numerous discussions about porous materials. This research was made possible thanks to support from the Alfred P. Sloan Foundation.
About the Author McLain E. Leonard received his BS in chemical engineering with a minor in economics from Montana State University in Bozeman, MT. He also was recognized at MSU as a Goldwater Scholar. McLain is currently a final year PhD candidate in chemical engineering working with Prof. Fikile R. Brushett at the Massachusetts Institute of Technology. His research interests focus on gas diffusion electrodes for electrochemical carbon dioxide (CO2) reduction. He is interested in evaluating and improving the properties of porous electrodes and identifying electrolyzer operating modes that could ultimately support stable, selective, highcurrent CO2 conversion to platform chemicals, solvents, and fuels. With the support of the ECS summer fellowship McLain used computational continuum models of CO2 electrolysis to understand the effects of the high-current operation on electrode interfacial stability and device efficiency. He may be reached at mclainl@ mit.edu. https://orcid.org/0000-0003-4572-5251
References 1.
L.-C. Weng, A. T. Bell, and A. Z. Weber, Phys. Chem. Chem. Phys., 20, 16973–16984 (2018). 2. L.-C. Weng, A. T. Bell, and A. Z. Weber, Energy Environ. Sci., 12, 1950– 1968 (2019). 3. S. Verma et al., ACS Energy Lett., 3, 193–198 (2018). 4. M. E. Leonard, L. E. Clarke, A. Forner‐Cuenca, S. M. Brown, and F. R. Brushett, ChemSusChem, 13, 400–411 (2020). 5. A. Z. Weber, R. M. Darling, and J. Newman, J. Electrochem. Soc., 151, A1715 (2004). 6. A. Z. Weber, Journal of Power Sources, 195, 5292–5304 (2010). 7. F. Mugele and J.-C. Baret, J. Phys.: Condens. Matter, 17, R705–R774 (2005). 8. S. P. Schwaminger et al., Anal. Chem., 90, 14131–14136 (2018). 9. M. E. Leonard et al., J. Electrochem. Soc., 167, 124521 (2020). 10. T. G. Tranter, J. T. Gostick, A. D. Burns, and W. F. Gale, Transp Porous Med, 121, 597–620 (2018). 11. H. Shi, Electrochimica Acta, 41, 1633– 1639 (1996).
© The Electrochemical Society. DOI: 10.1149.2/2.F11204IF.
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2020 F. M. Becket Summer Research Fellowship – Summary Report Fluorophosphate Class of Insertion Materials as Efficient Bifunctional Electrocatalysts by Lalit Sharma
M
etal-air batteries exhibiting high energy densities are key to meeting the growing energy demand.1 They function on two key processes, namely oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), the kinetics of which are too sluggish, and hence an electrocatalyst is required to enhance the rate of reaction. The existing precious-metal-based electrocatalysts are selective and expensive, therefore demanding efforts to develop economic bifunctional electrocatalysts. Motivated by the recent reports on the bifunctionality of phosphate-based polyanionic insertion materials, the ORR/OER properties of 3D transition metal-based fluorophosphates were tested for the first time.2-5 Fluorophosphate class of materials are extensively studied as high-voltage cathodes for secondary batteries.6 In this case, Fe-, Mn-, and Co-based fluorophosphates were tested for their bifunctional electrocatalytic activity.7 They were synthesized by solution combustion route leading to nanoscale, carbon-coated, and porous grain morphology as confirmed by scanning and transmission electron micrographs. (See Fig. 1.) The bifunctional activity was tested in 0.1 M KOH electrolyte on a three-electrode setup. In the case of ORR, Na2CoPO4F was found to be exhibiting an onset potential of 0.903 V (vs. RHE), while Na2FePO4F and Na2MnPO4F were
Fig. 1. Transmission electron micrographs and scanning electron micrographs of (a,b) Na2FePO4F, (c,d) Na2CoPO4F, and (e,f) Na2MnPO4F, respectively, showing nanoscale, carbon-coated, and porous morphology.
exhibiting onset potentials of 0.891 V and 0.909 V (vs. RHE), respectively. (See Fig. 2a.) Nearly four-electron transfer was confirmed by Koutecky-Levich (K-L) equation, while the linear nature of K-L plots confirmed first-order kinetics.
In the case of OER, Na2CoPO4F was found to be exhibiting the lowest overpotential of 1.38 V (vs. RHE) as compared to other fluorophosphates, while Na2MnPO4F was exhibiting the (continued on next page)
Fig. 2. (a) Linear sweep voltammetry (LSV) plots of Na2FePO4F, Na2CoPO4F, and Na2MnPO4F, and 20% Pt/C recorded during ORR measurements. (b) LSV plots of Na2FePO4F, Na2CoPO4F, Na2MnPO4F, and RuO2 recorded during OER measurements. The Electrochemical Society Interface • Winter 2020 • www.electrochem.org
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highest overpotential (0.49 V vs. RHE) among these materials. (See Fig. 2b.) The structural stability of the materials was tested by postmortem transmission electron microscopy (TEM). The samples of all three materials were recovered after 100 cyclic voltammetry cycles of ORR. While in the case of Na2FePO4F amorphization was observed, partial retention in the crystallinity was noticed in Na2MnPO4F. In the case of Na2CoPO4F, crystallinity was retained with no amorphization. It further confirmed Na2CoPO4F exhibits superior bifunctional electrocatalytic activity as compared to other fluorophosphates. The mechanism of ORR/OER in fluorophosphates was examined by density functional theory (DFT) calculations. To summarize, 3D transition metalbased fluorophosphates were studied for their bifunctional activity for ORR/OER processes for the first time. Fe-, Mn-, and Co-based fluorophosphates were analyzed. Na2CoPO4F exhibited superior ORR/OER activity as compared to other materials with an onset potential of 0.903 V (vs. RHE) for ORR and an overpotential of 0.38 V (vs. RHE) for OER processes. Structural stability was confirmed by postmortem TEM and DFT studies. Overall, this study opens a new dimension for fluorophosphate class of materials that can be used as efficient cathodes for metalair batteries in the future.8
Acknowledgments I am grateful to The Electrochemical Society (ECS) for the 2020 F.M. Becket Summer Research Fellowship and my PhD supervisor Prof. Prabeer Barpanda for his support and guidance. I also thank Prof. Swapan Pati (JNCASR) and Prof. N. Ravishankar (IISc) for their help in theoretical studies and electron microscopy. © The Electrochemical Society. DOI: 10.1149.2/2.F12204IF.
About the Author Lalit Sharma obtained his undergraduate degree in chemistry from St. Stephens College, Delhi University, India in 2014, before joining the Indian Institute of Science, Bangalore, India, for an integrated PhD course. He is currently a final year PhD student at the Faraday Materials Laboratory under Prof. Prabeer Barpanda. Sharma’s research focuses on structural and electrochemical investigation of fluoro(hydroxy)phosphatebased polyanionic cathode materials for metal-ion and metal-air batteries. He has coauthored eight journal articles. In 2017, he
Soliciting Student Chapter Stories! Keerthana.Varadhan@electrochem.org
received the European Materials Research Society Young Scientist Award. With the help of the ECS Summer Fellowship, he aspired to complete some in-depth electrochemical analyses of fluorophosphate cathode materials. He may be reached at lalitsharma421@gmail.com. https://orcid.org/0000-0002-6566-0398
References 1. T. E. Mallouk, Nat. Chem., 5, 362 (2013). 2. C. Z. Yuan, Y. F. Jiang, Z. Wang, X. Xie, Z. K. Yang, A. B. Yousaf, and A. W. Xu, J. Mater. Chem. A, 4, 8155 (2016). 3. H. Kim, J. Park, I. Park, K. Jin, S. E. Jerng, S. H. Kim, K. T. Nam, and K. Kang, Nat. Commun., 6, 8253 (2015). 4. Y. Gorlin and T. F. Jaramillo, J. Am. Chem. Soc., 132, 13612 (2010). 5. L. Sharma, S. Baskar, and P. Barpanda, ECS Trans., 85, 1221 (2018). 6. L. Sharma, S. P. Adiga, H. N. Alshareef, and P. Barpanda, Adv. Energy Mater., https://doi.org/10.1002/ aenm.202001449 (2020). 7. L. Sharma, N. Bothra, R. K. Rai, S. Pati, and P. Barpanda, J. Mater. Chem. A, 8, 18651 (2020). 8. L. Sharma, R. Gond, B. Senthilkumar, A. Roy, and P. Barpanda, ACS Catal., 10, 43 (2020).
FOR PUBLICATION IN INTERFACE MAGAZINE See your chapter highlighted in a special article. Send all student chapter news to Keerthana.Varadhan@electrochem.org. DEADLINE IS JANUARY 15, 2021.
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2020 H. H. Uhlig Summer Research Fellowship â&#x20AC;&#x201C; Summary Report In-situ Absorbance Monitoring of NAD+ Reduction Using Platinum-Modified Carbon Paper Electrodes by Kody D. Wolfe, David E. Cliffel, and G. Kane Jennings
T
he nicotinamide cofactors, NAD(H) and NADP(H), are critical reactants in many industrially desirable enzymatic pathways. The cofactors are also costly, subject to degradation, and difficult to regenerate.1 Many efforts have been aimed at various routes toward cofactor regeneration, and one promising option is the direct electrochemical conversion between the reduced and oxidized forms at an electrode.1,2 Direct electrochemical regeneration enables great control over the regeneration process and eliminates the need for additional biological components. In the present study, the reduction of NAD+ to NADH is studied on platinum monolayer decorated carbon paper (CP) electrodes using in-situ UV-Vis absorbance spectroscopy. The mechanism of NAD+ reduction is a surface reaction occurring as a twoelectron and one-proton transfer that result in the conversion of the pyridine ring to a dihydropyridine ring (Equation 1).2 + đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018;&#x17D;đ?&#x2018;&#x17D;đ?&#x2018;&#x17D;đ?&#x2018;&#x17D;đ?&#x2018;&#x17D;đ?&#x2018;&#x17D; + 2đ?&#x2018;&#x2019;đ?&#x2018;&#x2019; â&#x2C6;&#x2019; + đ??ťđ??ť + â&#x2020;&#x2019; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; đ?&#x2018; (Eq. 1)
The limiting step in the reaction is the transfer of the proton and second electron, which has a high associated overpotential and is currently not well understood.2 Metallic catalysts known for their affinity for adsorbing protons, such as platinum
and nickel, can aid in the electrochemical production of enzymatically active NADH.35 Herein, a method for producing high active surface areas of platinum on a CP support was investigated as an electrode for NADH production. First, gold nanostructures are potentiostatically deposited onto the CP, Fig. 1.6 The gold nanostructures deposit as groups of individual particles of approximately 25 nm (Fig. 1A) and grow into â&#x20AC;&#x153;coral-likeâ&#x20AC;? structures with additional deposition time (Fig. 1B). A copper monolayer is then deposited onto the gold via underpotential deposition and is electrolessly exchanged for a platinum monolayer.7 The resulting electrode shows an increase in activity for the oxygen reduction reaction (ORR), validating the presence of monolayer platinum. During the in-situ UV-Vis electrochemical studies, the platinum-coated CP (Pt CP) electrodes showed a significant increase in the rate of production of NADH, evidenced by the increase in absorbance at 340 nm, which is a result of the conversion of pyridine to dihydropyridine. (See Fig. 2.) Additionally, the rate of NADH production was found to be dependent on the concentration of NAD+ (Figs. 2A, 2B). With 2 mM NAD+ present (Fig. 2B), the rate of NADH production at the Pt CP is 1.82 Îźmoles h-1 and the bare CP is 0.80 Îźmoles
h-1, based on a calibration of 170 ÎźM NADH/ a.u. at 340 nm, 1 cm2 of electrode material, and a 10 ml reactor volume. In subsequent studies, the rate of production should be improved by deaeration of the electrolyte, which will reduce the parasitic ORR at the platinum surface. The high surface area catalytic electrodes shown here are promising for electrochemical regeneration of NADH due to their scalability and low mass loading of platinum. Continued work to improve NADH production will include long-term studies, normalization to active catalyst area, optimization of nanostructure loading and morphology, and deaeration to mitigate the ORR.
Acknowledgments The authors would like to acknowledge the ECS H. H. Uhlig Summer Research Fellowship for funding this work, as well as Dr. Yannick J. Bomble and Dr. Michael E. Himmel of the National Renewable Energy Laboratory (NREL) for their technical contributions. This project is also funded by the Subcontract XEJ-9-92257-01 under Prime Contract No. DE-AC36-08GO28308. Š The Electrochemical Society. DOI: 10.1149.2/2.F13204IF.
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Fig. 1. Scanning electron microscopy images of the deposition of gold nanostructures at (A) 10 s of deposition and (B) 1,000 s of deposition. The deposition is performed from a 5 mM HAuCl4, 20 mM NaNO3, and 10 mM cetyltrimethylammonium chloride (CTAC) solution at an applied potential of -1.8 V vs. a graphite rod counter electrode. The gold nanostructures then are modified to produce platinum monolayers on the gold features. The Electrochemical Society Interface â&#x20AC;˘ Winter 2020 â&#x20AC;˘ www.electrochem.org
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About the Author Kody Wolfe completed his bachelor’s degree in chemical engineering at Ohio University in 2017. He then continued his education at Vanderbilt University, pursuing a PhD in materials science
and engineering under the supervision of Drs. G. Kane Jennings and David E. Cliffel. Kody’s research interests involve studying electron transfer pathways within biohybrid technologies. His thesis research includes studies of electron transfer between a photoactive protein complex, Photosystem I, which can be derived from plants and various electrode materials to develop biohybrid photovoltaics. Kody recently began a collaboration with staff scientist Dr.
Yannick Bomble at the National Renewable Energy Laboratory (NREL) on a project focused on electrochemical regeneration of nicotinamide adenine dinucleotide (NADH) as an enzymatic cofactor. Efficient regeneration of NADH from NAD+ would allow NADH dependent enzymatic bioreactors being developed at NREL to be more economically feasible. The aim to develop these bioreactors is to produce commodity chemicals, typically derived from the petroleum refining process, through a renewable process based on biological feedstock. Through the ECS Summer Fellowship, Kody had the opportunity to study alternative electrode materials for NADH regeneration. He focused on an analysis of recovering biologically active NADH, as opposed to commonly produced inactive byproducts, and integrated his research with the work of his collaborators at NREL. Kody may be reached at kody.d.wolfe@vanderbilt.edu. https://orcid.org/0000-0002-6452-0107
References 1. H. K. Chenault, E. S. Simon, and G. M. Whitesides, Biotechnology and Genetic Engineering Reviews, 6, 221 (1988). 2. P. J. Elving, W. T. Bresnahan, J. Moiroux, and Z. Samec, Bioelectroch Bioener, 9, 365 (1982). 3. I. Ali, A. Gill, and S. Omanovic, Chemical Engineering Journal, 188, 173 (2012). 4. I. Ali, T. Khan, and S. Omanovic, Journal of Molecular Catalysis A: Chemical, 387, 86 (2014). 5. I. Ali, N. Ullah, M. A. McArthur, S. Coulombe, and S. Omanovic, The Canadian Journal of Chemical Engineering, 96, 68 (2018). 6. S.-P. Tung, T.-K. Huang, C.-Y. Lee, and H.-T. Chiu, RSC Advances, 2, 1068 (2012). 7. B. J. Berron, C. J. Faulkner, R. E. Fischer, P. A. Payne, and G. K. Jennings, Langmuir, 25, 12721 (2009).
Fig. 2. In situ UV-Vis absorbance spectroscopy of NADH production. Absorbance at 340 nm corresponds to the dihydropyridine ring produced when NAD+ is reduced to NADH. A potential of -1.2 V vs. Ag/AgCl was applied to a (A) 0.5 mM NAD+ or (B) 2 mM NAD+ solution in a 50 mM buffer (pH = 8.5). A flow cell connected to a UV-Vis cuvette was operated at a flow rate of 1 mL/min resulting in a cuvette residence time of 3 min. 88
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ST UDENT NE WS British Columbia Student Chapter The ECS British Columbia (BC) Student Chapter Hydrogen, a clean technology start-up for hydrogen recently hosted its 9th Annual Young Electrochemists’ production and carbon utilization based in Gatineau, Symposium (YES) on Zoom. Talks were given by three Quebec, also made a presentation. academic and industry leaders in electrochemistry and Building on prior years’ successes, YES attendance electrochemical technologies. The event concluded increased with nearly 100 confirmed registrants. This with an adjudicated Three Minute Thesis (3MT) event included representatives from the host institutions, presented by eight students from local and international The University of British Columbia and the Simon universities. Fraser University, as well as participants from across ECS and the ECS Canada Section sponsored the Canada and around the globe—Argentina, Belgium, event. Prof. Steven Holdcroft (Department of Chemistry, Brazil, Chile, Estonia, India, Ireland, Japan, Mexico, Simon Fraser University) discussed his work with ionMorocco, the Netherlands, Norway, South Africa, conductive polymers for use in electrochemical devices United Kingdom, United States, and Vietnam. The for clean energy. Prof. David Harrington (Chemistry, event’s virtual nature allowed for collaboration and University of Victoria) reviewed his research with Promotional poster for the 9th participation to reach beyond local representation, fuel cell electrocatalysts and elucidating governing Annual Young Electrochemists’ giving the ECS BC Student Chapter a greatly expanded mechanisms. Dr. Sadaf Tahmasebi, with Planetary Symposium. audience.
Calgary Student Chapter The ECS Calgary Student Chapter remained active over the summer, with the baton passing to new committee members for the 2020-2021 academic year and pivoting from in-person events to socially distanced online workshops. The chapter’s new executive committee was officially announced in September 2020, including President Maedeh Pahlevaninezhad, Vice President Oliver Calderon, Secretary Jialang Li, and Treasurer Samantha Luong. Members at large are Annie Hoang, Hamideh Eskandari, Amir Alihosseinzadeh, and Irfan Aydogdu. The chapter had several significant accomplishments in 2020. At a virtual meeting in September, chapter members were invited to celebrate and thank the efforts and support of those who were part of these activities. The event was a networking opportunity between current and newly joined Calgary members. From June through August, the chapter hosted its annual Analytical Techniques series over Zoom using one-to-two-hour online workshop formats. On June 12, the chapter hosted the virtual workshop, “Confocal Raman Microscopy: Applications in Science and Engineering.” The speaker was Dr. Damilola Momodu, a postdoctoral fellow in the Department of Chemical and Petroleum Engineering at the University of Calgary. Dr. Momodu presented the fundamentals of Confocal Raman microscopy equipment and examples of different applications of Raman microscopy, highlighting applications of carbon materials used in energy applications. For a change of pace, the chapter reached out to Dr. William Matthews, University of Calgary Department of Geology Professor. On July 28, he presented the workshop, “Laser Ablated Inductively Coupled Plasma (ICP).”
Lastly, on August 31, Canada First Research Excellence Fund (CFREF) Postdoctoral Associate Dr. Haris Masood Ansari presented the fundamentals of transmission electron microscopy of bulk materials, thin films, and nanostructures. Examples from his work on ceramic oxide catalysts for high-temperature CO2 electrolysis in solid oxide electrolysis cells were shared, with an extra emphasis on focused ion beam applications.
The ECS University of Calgary Student Chapter (from the top, left to right): Maedeh Pahlevaninezhad, President; Behzad Fuladpanjeh-Hojaghan, and members at large: Annie Hoang, Hamideh Eskandari, Marwa Atwa, Zohreh Fallah; Jialang Li, Secretary; Samantha Luong, Treasurer; and Oliver Calderon, Vice President.
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ST UDENT NE WS Clarkson University Student Chapter The ECS Clarkson University (CU) Student Chapter has adapted well to the COVID-19 pandemic. We shifted most of our activities and events online to meet CU’s requirements. Prof. Ajit Khosla (Yamagata University, Japan) presented an online talk, “Sustainable Advanced Manufacturing: Sensors, Energy Storage Devices, and Soft Robotics,” on May 15. Faculty and students from the Departments of Chemistry, Chemical Engineering, and Environmental Engineering attended this seminar. The chapter assisted Prof. Taeyoung Kim with CU’s annual Horizons program from July 20-31. The program is designed to expose high school students to STEM fields. This year, due to the COVID-19 quarantine, it was held virtually to allow water-based science exploration at home. The chapter’s contributions included creating several tutorials to help students carry out experiments related to water hardness. These tutorials introduced water hardness concepts at an approachable level for high school students and several at-home experiments involving measuring water hardness and the synthesis and decomposition of limescale.
On August 16, a virtual chapter fair was organized to inform freshmen about The Electrochemical Society and the chapter’s activities. All the chapter activities promoted student engagement and recruiting new members.
A video created for Clarkson University’s Horizons program by the student chapter.
Indiana University Student Chapter The ECS Indiana University Student Chapter hosted Dr. Henry White from The University of Utah as the annual student-selected/ ECS-sponsored invited speaker on October 1, 2020. Dr. White gave the virtual seminar, “Coupled Electron- and Phase-Transfer Reactions.” Before and after the seminar, Dr. White met students for a more casual conversation about science and career paths. The seminar was a huge success with over 45 attendees, consisting of students, faculty, and staff members.
The chapter continues to recruit new members and promote The Electrochemical Society. In August, the student chapter met with incoming chemistry graduate students to present the chapter’s mission, describe past and future chapter activities, and to recruit new members. Later this year, new officers for the student chapter will be elected. The chapter is grateful for the opportunities that ECS provides to meet with accomplished and enthusiastic speakers and is eagerly looking forward to planning future events.
Munich Student Chapter Due to COVID-19, the ECS Munich Student Chapter did not host its fourth scientific symposium. Instead, the chapter took part in a Technical University of Munich (TUM) program, which brings young people closer to science and motivate them to consider a scientific career path. Six young female students between the ages of 15 and 16 years visited us for a day at TUM for orientation to career and university studies. On the project day, the students attended three courses, which gave insights into research topics in electrochemistry. In the first course, they learned how to solder an electrical circuit with
resistance and capacitors and measured the resulting impedance. In the second course, attendees learned about a battery’s functionality and built their own coin cell in a glovebox. In the third course, they conducted water electrolysis and analyzed the resulting gases. The students had the chance to ask general questions about the TUM study program at the end of the day. Bavarian television was present to cover this event. In addition, the chapter is organizing two online webinars in the series Material & Methods Club covering XPS analysis of energy materials and battery modeling.
Students solder, work at the glovebox, and perform experiments with a small electrolyzer during the ECS Munich Student Chapter project day.
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ST UDENT NE WS Münster Student Chapter The ECS Münster Student Chapter was officially founded on May 15, 2020. The University of Münster has a strong relation to battery and electrochemistry research as Münster Electrochemical Energy Technology (MEET) and the Helmholtz-Institut Münster (HI MIS) are located in Münster. Germany’s most popular bicycle city is an important site to get students interested in electrochemistry. The missions of MEET and HI MIS are to fortify the success of electrochemistry research within the different excellent institutes in Münster and to unite students to help build a solid foundation for this field. As their first activity, the chapter participated in the Electrochemistry 2020 online conference organized by the Gesellschaft Deutscher Chemiker (GDCH) and hosted a VIP HUB on September 23, “The Mosaic of Battery Research—en Route for the Big Picture.” Participants listened to pitch-style presentations by four chapter members: Julia Wellmann, Yi-Chen Hsieh, Martin Kolek, and Yves Preibisch. Their research topics ranged from anode-free lithium metal batteries to the degradation behavior of ionic liquid-based electrolytes. Afterward, in an open discussion round, the audience and presenters debated the integration of their topics and results into the overall context of battery research. The tone was extremely positive and the chapter thanks all the speakers and participants for the great discussions. The next online event was scheduled for October 28. The chapter organized an event focusing on research possibilities in electrochemistry at the University of Münster. The purpose was to provide an overview of the excellent work of local research groups. The target audience was students pursuing BA and MA degrees who were looking for challenges and opportunities in electrochemistry
research. Following the introduction of the working groups and their research, students were encouraged to ask questions and discuss with the group leaders. The chapter intends to create a link between students and working groups through this event in order to further widen interest and research in electrochemistry in Münster, as well as the growth of the student chapter. Follow the ECS Münster Student Chapter on Twitter (@ecs_ muenster) and Instagram (ecs_muenster) for up-to-date coverage of upcoming events, as well as news about prizes and awards. The chapter is eager to collaborate with other ECS student chapters around the world and organize joint online events. For more information, contact info.chapter.ecs@uni-muenster.de.
Online meeting of the ECS Münster Student Chapter officers and members. Credit: Yves Preibisch
Purdue University Student Chapter For the calendar year 2020, the ECS Purdue University Student Chapter got off the mark with a general body meeting where the student members converged to outline the event plan for the subsequent summer and fall semesters. On January 17, as part of the chapter’s guest lecture series, Prof. Vijay Ramani, Department of Energy, Environmental & Chemical Engineering at Washington University, delivered an enlightening talk, “Advanced Materials for Electrochemical Energy Conversion and Storage.” With the onset of the COVID-19 pandemic and the resulting constraint on in-person activities, the chapter’s initiatives were momentarily stalled. However, the Fall 2020 Webinar Series was launched, featuring eminent speakers from academia and industry sharing their valuable experience. The first session saw Dr. Siddhartha Das from The University of Maryland Department of Mechanical Engineering talking at length on “Ionics and Liquid Transport at Polyelectrolyte-BrushFunctionalized Interfaces.” This chapter’s journey so far has been upwards, and the outreach of technical knowledge has been the underlying theme of all events.
Prof. Vijay Ramani, Department of Energy, Environmental & Chemical Engineering at Washington University, delivers a talk to the student chapter. From left to right, Shaunak Parimal Deshpande, Fahim T. Vora, Julia Meyer, Dr. Mukul Parmananda, Dr. Ankit Verma, Sobana Rangarajan, Conner Fear, Prof. Vijay Ramani, Prof. Partha P. Mukherjee, Amy Bohinsky, Bairav Sabarish Vishnugopi, Navneet Goswami, Binbin Mao, and Susmita Sarkar.
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ST UDENT NE WS University of Kentucky Student Chapter Namal Wanninayake, PhD candidate at the University of Kentucky Department of Chemistry, presented his exit seminar on October 19, 2020, as the first ECS Kentucky Student Chapter seminar. Due to the COVID-19 pandemic, the seminar was organized via Zoom. The title of Wanninayake's presentation was “Structure, Surface, and Interfacial Modifications of Carbon and Supported-Metal Electrodes for Electrochemical Carbon Dioxide Conversion.” Wanninayake demonstrated how nitrogen-doped CNOs (N-CNOs) can tune the local electronic properties of copper catalysts and enhance the composite catalyst’s interfacial properties to selectively produce ethanol. Faculty and students from the College of Engineering and College of Arts & Sciences at the University of Kentucky attended the event. The chapter also hosted a seminar with Dr. Xin Gao, Senior Research Engineer at the UK Center for Applied Energy Research, in November and a two-hour analytical workshop in December.
ECS Kentucky Student Chapter members. Credit: Udari Kodithuwakku
University of Waterloo Student Chapter In response to the unprecedented situation of the COVID-19 pandemic, the ECS University of Waterloo Student Chapter moved its events and activities to an online platform in the past few months. The chapter organized a successful webinar presented by Dr. Kristen Severson, a postdoc at IBM Research, on the exciting topic of “Applications of Machine Learning in Battery Research.” This event had about 200 attendees from 25 countries around the world. The webinar video was made available for everyone on our YouTube channel. The chapter partnered with the Natural Sciences and Engineering Research Council Collaborative Research and Training Experience Program: Materials for Electrochemical Energy Solutions (NSERC CREATE ME2) to co-organize two successful virtual webinars for
researchers and students at many Canadian universities. The first webinar, “Electrochemical Cell Design for Energy and Environmental Applications,” was presented by Dr. Edward (Ted) Roberts, Professor and Associate Head (Research), Department of Chemical and Petroleum Engineering, Schulich School of Engineering, University of Calgary. The second webinar, “Pore-scale Modeling of Battery and Fuel Cell Performance,” was presented by Dr. Jeff Gostick, Associate Professor, Department of Chemical Engineering, University of Waterloo. Both events had a large turnout and received a lot of positive feedback. Moving forward, the chapter aims to continue organizing virtual events to contribute to our community of researchers and bring everyone together in these trying times.
University of Western Ontario Student Chapter To help members maintain research progress during the COVID-19 pandemic, the ECS University of Western Ontario Student Chapter is focusing on developing scientific webinars. The chapter hosted the Electrochemical Impedance Spectroscopy (EIS) Workshop run by Dr. James Noël, Assistant Professor, Department of Chemistry, Western University, and Affiliate Member, Surface Science Western. Dr. Noël specializes in the corrosion performance of metals and alloys in many environments ranging from ambient conditions to aggressive chemical and radiolytic environments. He serves as ECS Education Committee Chair, and instructed many Fundamentals of Electrochemistry short courses at ECS meetings. At the chapter’s workshop, he lectured on the fundamentals of EIS and analyzed real data sets submitted by chapter members. This event was a massive success, with over 50 members attending, including international attendees from three different universities. Dr. Noël provided insight into a technique that many ECS members use and provided a platform for members to discuss EIS data analysis problems. After the overwhelmingly positive response to the EIS workshop, the chapter is currently organizing more workshops relevant to its members. The November workshop featured Dr. Mark Biesinger, Director of Surface Science Western, on the best XPS fitting practices. Further, the annual student symposium was held virtually in December and provide students with experience communicating research in a virtual environment.
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This school year, the chapter had to be creative with its members’ annual social event. These events are essential to the executive team because they offer an opportunity to attract new ECS members and give members a chance to network. After polling members on what kind of event they prefer, the chapter hosted a virtual movie night on August 27, 2020. We watched Hidden Figures, an inspiring story about three female scientists overcoming adversity.
Dr. James Noël demonstrates a sine wave with his garden hose in a slide shown at his EIS workshop.
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ST UDENT NE WS Yamagata & Montreal Student Chapters On July 31, 2020, the ECS Yamagata Student Chapter and ECS Montreal Student Chapter hosted a joint online symposium. The two chapters had planned a symposium for the 237th ECS Meeting in Montreal. When the meeting was canceled due to the COVID-19 outbreak, they switched to a joint online symposium. The 13-hour time difference was a big issue that was overcome by each side’s enthusiasm. It was the first cohosted activity for both student chapters and consisted of an invited lecture from each chapter and chapter member introductions. In the first invited lecture, Prof. Hiroyuki Matsui from Yamagata University, Japan, presented “Flexible and Printed Organic Transistors and Their Application to Electrochemical Health Monitors.” He discussed organic thin-film transistors (OTFTs) and a wearable printed biosensor concept using organic semiconductors. He reviewed examples for device-level tests with lactate and lactate oxidase. Currently, he focuses on materials informatics for optelectronic organic materials, and a lot of DFT calculation results of organic materials were added to the neural network. Prof. Matsui developed software that can predict HOMO and LUMO levels by drawing chemical formula based on the neural network algorithm. Many audiences have shown interest in the software, and it was passionately discussed.
The second invited speaker, Prof. Mickael Dollé from University of Montreal, Canada, gave the lecture, “When Today’s Li-ion Batteries Surge Can Become Tomorrow’s Solution.” He began his talk by discussing the current market for lithium-ion batteries and recycling technologies of electrode materials. Conventional recycling technology generates high disposal cost byproducts. Prof. Dollé is working on options to reduce chemical waste for positive electrode recycling. The new recycling method he has developed can achieve completely closed positive electrode recycling without any waste byproducts. He has also demonstrated that the recycled lithium-ion battery has shown comparable performance to a commercial cell. His method is testing in a large-scale demonstration plant. Participants were interested in topics on the recycling method, and there were many questions from the audience. This symposium was a good opportunity to meet other electrochemical enthusiasts and engage in discussing similar topics. The chapters demonstrated that even in this tough time, they could communicate and expand the electrochemistry community beyond country borders via online tools.
A group screenshot of the virtual Yamagata University and University of Montreal joint student symposium.
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The 17th International Symposium on Solid Oxide Fuel Cells (SOFC-XVII) Sponsored by High-Temperature Energy, Materials, & Processes Division of The Electrochemical Society, Inc. and The SOFC Society of Japan
STOCKHOLM, SWEDEN July 18-23, 2021
The Brewery Conference Center
INFORMATION The Solid Oxide Fuel Cells XVII (SOFC-XVII) Conference will be held in Stockholm, Sweden from July 18-23, 2021, at The Brewery Conference Center. This international conference will bring together scientists, engineers, and researchers from academia, industry, and government laboratories to share results and discuss issues related to solid oxide fuel cells and electrolyzers. This meeting provides an opportunity and forum to learn and exchange information on the latest scientific and technical developments relating to SOFCs and SOECs. ABSTRACT SUBMISSION To give an oral or poster presentation at SOFC-XVII, you must submit an original meeting abstract for consideration via the SOFC website, no later than February 5, 2021. Faxed, e-mailed, and/or late abstracts will not be accepted. Meeting abstracts should explicitly state objectives, new results, and conclusions or significance of the work. Because the number of time slots for oral presentations is limited, it is likely that not all requests for oral presentations can be accepted, which means that oral contributions might be moved into a poster session. Therefore, research groups that submit more than one abstract should seek a reasonable balance between oral and poster presentations. Once the submission deadline has passed, the symposium organizers will evaluate all abstracts for content and relevance to the symposium topic, and will schedule all acceptable submissions as either oral or poster presentations. In March 2021, Letters of Acceptance will be sent via email to the corresponding author of all accepted abstracts, notifying them of the date, time, and location of their presentation. Please note: No abstracts will be scheduled for presentation without the submission of a corresponding proceedings paper to ECS Transactions (see page 3). PAPER PRESENTATION Oral presentations must be in English; LCD projectors and laptops will be provided for all oral presentations. Presenting authors MUST bring their presentation on a USB flash drive to be used with the dedicated laptop that will be in each technical session room. Speakers requiring additional equipment must make written request to meetings@electrochem.org at least one month prior to the meeting so that appropriate arrangements may be worked out, subject to availability, and at the expense of the author. Poster presentations must be displayed in English, on a board approximately 3 feet 10 inches high by 3 feet 10 inches wide (1.17 meters high by 1.17 meters wide), corresponding to their abstract number and day of presentation in the final program. MEETING PUBLICATIONS ECS Meeting Abstracts—All meeting abstracts will be published in the ECS Digital Library, copyrighted by ECS, and all abstracts become the property of ECS upon presentation. ECS Transactions— The authors of all oral and poster presentations scheduled for SOFC-XVII are obligated to submit a full text paper to the online proceedings publication, ECS Transactions (ECST) (see page 3). Abstracts will not be scheduled for presentation without a corresponding full-text ECST paper. Upon completion of the review process, papers from this issue will be published prior to the start of the meeting. Once published, papers will be available for sale through the ECS Digital Library. Please visit the ECST website (www.electrochem.org/ecst) for additional information, including overall guidelines, deadlines for submissions and reviews, author and editor instructions, a manuscript template, and more. ECSarXiv—All authors are encouraged to submit their full-text manuscripts, posters, slides, or data sets to ECS’s preprint service, ECSarXiv. For more information on this offering, please visit www.electrochem.org/ecsarxiv. Please note that submission to ECSarXiv does not preclude submission to ECST. ECS Journals—Authors presenting papers at ECS meetings, and submitting to ECST or ECSarXiv, are also encouraged to submit to the Society’s technical journals: Journal of The Electrochemical Society and ECS Journal of Solid State Science and Technology. Although there is no hard deadline for the submission of these
papers, it is considered that six months from the date of the symposium is sufficient time to revise a paper to meet the stricter criteria of the journals. Author instructions are available from www.electrochem.org/submit. TECHNICAL EXHIBIT The SOFC-XVII Meeting will include a Technical Exhibit, featuring presentations and displays by manufacturers of instruments, materials, systems, publications, and software of interest to meeting attendees. Coffee breaks are scheduled in the exhibit hall along with evening poster sessions. Interested in exhibiting at the meeting with your company? Exhibitor opportunities include unparalleled benefits and provide an extraordinary chance to present your scientific products and services to key constituents from around the world. Exhibit opportunities can be combined with sponsorship items and are customized to suit your needs. Please contact sponsorship@electrochem.org for further details. MEETING REGISTRATION All participants—including authors and invited speakers— are required to pay the appropriate registration fees. Hotel and meeting registration information will be posted on the SOFC website as it becomes available. The deadline for discounted early registration is June 21, 2021. HOTEL RESERVATIONS The SOFC-XVII Meeting will be held at The Brewery Conference Center, Stockholm, Sweden. Please refer to the meeting website for the most up-to date information on hotel availability and information about the blocks of rooms where special rates have been reserved for participants attending the meeting. The deadline for hotel reservations is May 17, 2021. LETTER OF INVITATION Individuals requiring an official letter of invitation should email meetings@electrochem.org; such letters will not imply any financial responsibility of ECS. SPONSORSHIP OPPORTUNITIES The SOFC meeting offers a wonderful opportunity to market your organization through sponsorship, allowing exposure to key industry decision makers, development of collaborative partnerships, and potential business leads. Support is welcomed in the form of general sponsorship at various levels. Sponsors will be recognized by level in the meeting program, onsite signage, and on the ECS website, with a link to your organization. In addition, custom sponsorship packages are available, such as coffee breaks, meeting keepsakes, and the SOFC banquet. These opportunities include additional recognition, and may be customized to create personalized packages. Advertising opportunities for the meeting program are also available. Please contact sponsorship@electrochem.org for further details. SOFC also offers speaker sponsorship. By sponsoring a speaker, your company can help offset travel expenses, registration fees, and/or complimentary proceedings. Please contact sponsorship@electrochem.org for further details.
CONTACT INFORMATION If you have any questions or require additional information, contact ECS. The Electrochemical Society 65 South Main Street, Bldg. D, Pennington, NJ, 08534-2839, USA tel: 1.609.737.1902, fax: 1.609.737.2743 meetings@electrochem.org www.electrochem.org
CALL FOR PAPERS The 17th International Symposium on Solid Oxide Fuel Cells (SOFC-XVII) Sponsored by High-Temperature Energy, Materials, & Processes Division of The Electrochemical Society, Inc. and The SOFC Society of Japan The Seventeenth International Symposium on Solid Oxide Fuel Cells (SOFC-XVII) will provide an international forum for the presentation and discussion of the latest research and developments on solid oxide fuel cells (SOFCs), solid oxide electrolysis cells (SOECs), and related topics. Papers are solicited on all aspects of solid oxide fuel cells and electrolyzers. Following is a partial list of topics to be addressed: (1) materials for cell components (e.g., electrolyte, electrodes, interconnection, and seals); (2) fabrication methods for cell components, complete cells, and stacks; (3) cell designs, electrochemical performance, and modeling; (4) stack designs and their performance; (5) utilization of different fuels with or without reformation; (6) stationary power generation, transportation, and portable power applications; and (7) prototype SOFC and SOEC systems, field test experience, cost, and commercialization plans.
Any questions and inquiries should be sent to the symposium organizers: Eric D. Wachsman, University of Maryland, e-mail: ewach@umd.edu; or Teruhisa Horita, AIST, e-mail: t.horita@aist.go.jp. All papers presented will be included in an electronic issue (on USB drive) of ECS Transactions which will be available at the meeting. All authors are obligated to submit their full text manuscript no later than April 16, 2021. All manuscripts should be submitted online, and must include an MS Word version to allow editors to make minor formatting/editorial changes.
Abstracts should be submitted electronically by February 5, 2021, to
https://ecs.confex.com/ecs/SOFC2021/cfp.cgi.
Meeting abstract submission opens..........................................................................................................August 2020 Meeting abstract submission deadline............................................................................................... February 5, 2021 ECS Transactions submission site opens............................................................................................. March 15, 2021 Meeting registration opens................................................................................................................... March 15, 2021 Technical Program published online/Notification to Corresponding Authors of abstract acceptance or rejection......................................................................................... March 15, 2021 ECS Transactions submission deadline................................................................................................. April 16, 2021 Meeting Sponsor and Exhibitor deadline (for inclusion in printed materials).......................................... May 7, 2021 Hotel block deadline............................................................................................................................... May 17, 2021 Early meeting registration deadline........................................................................................................ June 21, 2021 Release date for ECS Transactions....................................................................................... on or before July 9, 2021 *A full schedule of dates and deadlines may be found at www.electrochem.org/symposium-organizer-info under “Meeting Deadlines.”
Thank you! Benefactor
2020 ECS Institutional Members
research
Patron Energizer (75)
Lawrence Berkeley National Laboratory (16)
Faraday Technology, Inc. (14)
Scribner Associates, Inc. (24)
GE Global Research Center (61)
Toyota Research Institute of North America (12)
Sponsoring BASi (5)
Nissan Motor Co., Ltd. (13)
Central Electrochemical Research Institute (27)
Pacific Northwest National Laboratory (PNNL) (1)
DLR-Institut fĂźr Vernetzte Energiesysteme e.V. (12)
Panasonic Corporation (25)
EL-CELL GmbH (6)
Permascand AB (17)
Ford Motor Corporation (6)
Teledyne Energy Systems, Inc. (21)
GS Yuasa International Ltd. (40)
The Electrosynthesis Company, Inc. (24)
Honda R&D Co., Ltd. (13)
Center for Solar Energy and Hydrogen Research Baden-WĂźrttemberg (ZSW) (16)
Medtronic Inc. (40)
Sustaining General Motors Holdings LLC (68)
Occidental Chemical Corporation (78)
Giner, Inc./GES (34)
Sandia National Laboratories (44)
Hydrogenics Corporation (2)
SanDisk (6)
Ion Power Inc. (6)
Technic, Inc. (24)
Kanto Chemical Co., Inc. (8)
Westlake (25)
Los Alamos National Laboratory (12)
Yeager Center for Electrochemical Sciences (22)
Microsoft Corporation (3)
Please help us continue the vital work of ECS by joining as an institutional member today. Contact Anna.Olsen@electrochem.org for more information.
27/10/2020