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PEM Electrolysis for Hydrogen Production Principles and Applications © 2016 by Taylor & Francis Group, LLC © 2016 by Taylor & Francis Group, LLC PEM Electrolysis for Hydrogen Production Principles and Applications Edited by Dmitri Bessarabov Haijiang Wang Hui Li Nana Zhao Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Group, an informa business © 2016 by Taylor & Francis Group, LLC CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2016 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Version Date: 20150814 International Standard Book Number-13: 978-1-4822-5232-3 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources. 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Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com © 2016 by Taylor & Francis Group, LLC Contents Preface .......................................................................................................................................................................................vii Editors .........................................................................................................................................................................................ix Contributors ...............................................................................................................................................................................xi 1. Overview of PEM Electrolysis for Hydrogen Production .........................................................................................1 Nicola Briguglio and Vincenzo Antonucci 2. Fundamentals of PEM Water Electrolysis ..................................................................................................................11 Tom Smolinka, Emile Tabu Ojong, and Thomas Lickert 3. Electrocatalysts for Oxygen Evolution Reaction (OER) ...........................................................................................35 Magnus Thomassen and Svein Sunde 4. Electrocatalysts for the Hydrogen Evolution Reaction ............................................................................................65 Marcelo Carmo, Wiebke Lüke, and Detlef Stolten 5. 3M NSTF for PEM Water Electrolysis .........................................................................................................................87 Krzysztof Lewinski 6. Membranes.......................................................................................................................................................................119 Hiroshi Ito 7. Bipolar Plates and Plate Materials .............................................................................................................................135 Conghua “CH” Wang 8. Current Collectors (GDLs) and Materials ................................................................................................................147 Hiroshi Ito 9. Proton Exchange Membrane Electrolyzer Stack and System Design .................................................................157 Julie Renner, Kathy Ayers, and Everett Anderson 10. Characterization Tools for Polymer Electrolyte Membrane (PEM) Water Electrolyzers ................................179 Pierre Millet 11. Degradation Processes and Failure Mechanisms in PEM Water Electrolyzers ................................................219 Pierre Millet 12. Modeling of PEM Water Electrolyzer ........................................................................................................................243 Ravindra Datta, Drew J. Martino, Yan Dong, and Pyoungho Choi 13. Fundamentals of Electrochemical Hydrogen Compression .................................................................................269 Peter Bouwman v © 2016 by Taylor & Francis Group, LLC vi Contents 14. Large-Scale Water Electrolysis for Power-to-Gas ...................................................................................................303 Rob Harvey, Rami Abouatallah, and Joseph Cargnelli 15. Depolarized Proton Exchange Membrane Water Electrolysis: Coupled Anodic Reactions ..........................315 Sergey Grigoriev, Irina Pushkareva, and Artem Pushkarev 16. Generation of Ozone and Hydrogen in a PEM Electrolyzer.................................................................................339 Dmitri Bessarabov 17. Isotope Separation Using PEM Electrochemical Systems ....................................................................................361 Mikhail Rozenkevich and Irina Pushkareva Index ........................................................................................................................................................................................383 © 2016 by Taylor & Francis Group, LLC Preface Currently, there are two distinct commercial water elec- power sources, such as renewable or nuclear power, are trolysis technologies that operate at low temperatures— used in combination with large-scale PEM water elec- alkaline and PEM (proton-exchange membranes) trolysis, the resulting system will become suitable for electrolyzers. Alkaline electrolyzers, a commercially large-scale clean and economically attractive hydrogen more mature technology among the two, contain two production and energy storage applications. Water elec- electrodes immersed in a liquid alkaline electrolyte trolysis provides a sustainable solution for hydrogen consisting of a concentrated KOH solution. In contrast, production and is very well suited to be coupled with PEM electrolyzers use a solid proton-conducting poly- renewable energy sources. Thus, yet another vector of mer as the electrolyte and deionized water. As a result, hydrogen applications for energy storage, called power- PEM electrolyzers have many advantages over alkaline to-gas, is emerging and large utility companies are electrolyzers, such as a relatively simple system design becoming involved. and being able to operate safely at higher current densi- To address technology gaps for large-scale PEM water ties. A third technology, currently at the precommercial electrolysis systems, the following areas require addi- stage, alkaline exchange membrane (AEM) systems, has tional development: improved stack performance, scale the potential to place water electrolysis on a new cost up to megawatt size, grid integration, high pressure reduction trajectory. operation, high current density operation, degrada- PEM water electrolysis has been known for many tion of components associated with transient operation, years; however, due to expensive components, such as and a variety of market issues. All of these gaps relate membranes and bipolar plate materials and limited directly to increased participation of PEM water elec- lifetime, PEM electrolyzers became established only in trolysis systems in hydrogen markets for various appli- relatively small-scale niche applications, such as labo- cations, not limited to fuel cells only. Megawatt scale-up, ratory hydrogen and oxygen generators, life support needed for such applications as power-to-gas and on-site systems, fuel supply for small fuel cell systems, etc. In refueling stations, includes requirements to reduce capi- general, PEM water electrolysis systems can provide a tal costs by 50% on a per kilowatt basis and availabil- relatively simple, scalable, and easily deployable source ity of low-cost testing facilities; for example, electricity of high-purity hydrogen for smaller retail and commer- costs for PEM electrolysis megawatt testing can alone be cial applications near the point of consumption. a great challenge. Another challenge that the PEM water In recent years, hydrogen PEM fuel cells made signifi- electrolysis industry has hardly discussed before is the cant progress toward commercialization, resulting in large-scale manufacturing of cathode c atalyst-coated growing interest in technologies for hydrogen on-site membranes and stack components, availability of irid- production, such as PEM water electrolysis. Thus, the ium, etc. use of PEM water electrolysis for hydrogen fuel produc- It is expected that demand for hydrogen as a fuel for tion became a vector of interest for fuel cell deployment fuel cells in both transport and stationary applications opportunities in such sectors as sustainable mobility, will continue to grow, alongside hydrogen for energy material handling, and back-up power. storage (the power-to-gas vector), thus generating more The rapid development of relatively small-scale PEM and more demands for PEM water electrolysis systems fuel cell technology also contributed to a “leapfrog” of large capacities. effect in the fundamental understanding of the require- It is well recognized that PEM water electrolysis sys- ments and functionalities of certain components and tems are robust and dynamic. These systems can offer attributes of the PEM electrolysis technology that are a fast response to volatile renewable energy sources. both common for PEM fuel cells and electrolyzers, such Due to the use of a dense proton-exchange membrane, as manufacturing aspects, components (membranes, PEM water electrolysis systems are capable of produc- plates, catalyst), flow-field design, etc. However, new ing hydrogen at relatively high and practical discharge trends in PEM water electrolysis systems development pressure, suitable, for example, for the injection of opened up new technology gaps and requirements that hydrogen into the grid of natural gas pipes. PEM water have not been discussed before with respect to PEM electrolyzers can also be scaled up to address various water electrolysis. For example, hydrogen is considered demands for energy storage. as one of the best solutions for large-scale energy stor- Addressing climate change and the associated need age that comes from renewable and intermittent power for increasing renewable energy supply makes energy sources such as wind and solar electricity. If zero-carbon storage a critical technological component of the future vii © 2016 by Taylor & Francis Group, LLC viii Preface energy landscape. PEM water electrolysis when coupled fundamental aspects as well as examples of applica- with renewable energy sources and when electrolytic tions, provide a review of the state-of-the-art technolo- hydrogen is used to capture CO to produce synthetic gies and challenges related to each of the components of 2 methane via the Sabatier reaction can also be attractive the PEM electrolysis, identify various failure modes and as an additional power-to-gas application reducing CO failure mechanisms, and discuss component degrada- 2 emissions. tion testing methods and protocols. Due to the ever-increasing desire for green energy, the This book provides researchers and technology engi- last decade has seen regained research interest in PEM neers with the most comprehensive and updated knowl- electrolysis. However, significant challenges still remain edge on PEM electrolysis technology, thus helping them for PEM electrolysis to be a commercially feasible large- identify technology gaps and develop new materials scale hydrogen production solution. These challenges and novel designs that lead to commercially viable include the insufficient durability of the catalysts and PEM electrolysis systems. We believe that students and membrane, high cost associated with the use of platinum professionals in disciplines such as electrochemical group metal-based catalysts, corrosion of the current col- engineering, electrochemistry, material science in elec- lectors and separator plates, and the development of a trocatalyst development, material science in polymer stack concept for the megawatt power range. development, and chemical and mechanical engineers The intention of this book is to provide a compre- working on energy storage and clean technologies will hensive research source for PEM electrolysis, discuss find this book useful. © 2016 by Taylor & Francis Group, LLC Editors Dr. Dmitri Bessarabov joined the DST HySA Dr. Haijiang Wang is a senior research officer and Infrastructure Center of Competence at North-West project manager in the National Research Council of University (NWU) and Council for Scientific and Canada (NRC). He has been with NRC for 10 years. His Industrial Research (CSIR) in 2010. He is an internation- research covers PEM fuel cell, electrolyzer, metal-air ally recognized scientist with academic and industrial battery, microbial fuel cell, and lithium-sulfur battery. decision-making experience in the area of hydrogen and Dr. Wang earned his PhD in electrochemistry from electrocatalytic membrane systems for energy appli- the University of Copenhagen, Denmark, in 1993. He cations and fuel cells. Dr. Bessarabov has more than then joined Dr. Vernon Parker’s research group at Utah 15 years of progressively increasing responsibility in State University as a postdoctoral researcher to study academic and industrial R&D environment and leader- electrochemically generated anion and cation radicals. ship roles in the hydrogen energy sector in Canada and In 1997, he began working with Natural Resources South Africa. His current responsibilities include lead- Canada as a research scientist to carry out research on ership in the National Hydrogen and Fuel Cell Program fuel cell technology. In 1999, he joined Ballard Power (HySA). He is currently also leading PEM electrolyzer Systems as a senior research scientist to continue his development projects at the HySA Infrastructure, which investigations. After spending five years with Ballard includes the establishment of technology platforms for Power Systems, he joined NRC in 2004. He is currently electrolyzer development, related characterization tools, adjunct professor at five universities, including the electrochemical hydrogen compression, and hydrogen University of British Columbia and the University of production using renewables. Waterloo. Dr. Wang has 30 years’ professional research Dr. Bessarabov received his fundamental training experience in electrochemistry and fuel cell technol- in chemistry at the renowned Lomonosov Moscow ogy. To date, he has published more than 160 journal State University in Russia (MSc, 1991). He contin- papers, three books, 10 book chapters, 40 industrial ued further education at the Russian Academy of reports, and 30 conference papers or presentations and Sciences in membrane gas separations at the Topchiev has been issued five patents. Institute of Petrochemical Synthesis of the Russian Academy of Sciences. In 1993, he joined the PhD pro- Dr. Hui Li is a research officer and a master project gram at the Institute for Polymer Science, University lead under the energy storage program at the National of Stellenbosch in South Africa. He earned his PhD Research Council of Canada—Energy, Mining and in 1996, specializing in membrane technology for gas Environment Portfolio (NRC-EME, which used to be separation. His postdoctoral research at the University the Institute for Fuel Cell Innovation). Dr. Li earned of Stellenbosch was in the area of electrocatalytic her BS and MSc in chemical engineering from Tsinghu membrane systems and electrochemical ozone gen- University in 1987 and 1990, respectively. After complet- eration (1997–1998), for which NRF granted him a ing her MSc, she joined Kunming Metallurgical Institute “Y” rating. In 1999, Dr. Bessarabov was appointed as a research engineer for four years and then took a senior lecturer at the University of Stellenbosch’s position as an associate professor at Sunwen University Chemistry Department. In 2001, he joined Aker for eight years. In 2002, she started her PhD program in Kvaerner Chemetics in Vancouver, Canada, to work in electrochemical engineering at the University of British the area of membrane technology for the chloralkali Columbia (Canada). After earning her PhD in 2006, she industry. In 2006, he joined Ballard Power Systems carried out one term of postdoctoral research at the in Canada (and afterwards AFCC, Automotive Fuel Clean Energy Research Centre (CERC) at the University Cell Cooperation Corp.), where he was leading an of British Columbia with Professors Colin Oloman and R&D group on MEA integration and evaluation. His David Wilkinson. Since joining NRC in 2007, Dr. Li has main areas of professional interest include fuel cells, been working on PEM fuel cell contamination and dura- PEM electrolysis, hydrogen energy, hydrogen storage, bility, PEM electrolysis, and zinc-air batteries. Dr. Li has hydrogen infrastructure, membranes, separations, many years of research and development experience in applied electrochemistry, applied polymer science, theoretical and applied electrochemistry and in electro- environmental technologies, and water treatment. To chemical engineering. Her research is based on PEM date, he has published more than 100 journal papers fuel cell contamination and durability testing, prepara- and 14 conference papers, and has been issued three tion and development of electrochemical catalysts with patents. long-term stability, catalyst layer/cathode structure, and ix © 2016 by Taylor & Francis Group, LLC x Editors catalyst layer characterization and electrochemical eval- synthesis and application. Dr. Zhao received her BS in uation, failure diagnosis and mitigation for PEM fuel polymer chemistry and physics from Beijing Normal cells and electrolyzers, and air-cathodes for zinc-air bat- University in 2000. After that, she joined Changchun tery. Dr. Li has coauthored more than 30 research papers University of Science and Technology as a teaching published in refereed journals and coedited three books assistant for two years and then started her PhD pro- related to PEM fuel cells. Dr. Li has two granted pat- gram on polymer chemistry and physics at Changchun ents and one technology licensed to the Mantra Energy Institute of Applied Chemistry, Chinese Academic Group. Sciences, in 2002. After earning her PhD in 2008, she joined Professor Ting Xu’s group as a postdoctoral Dr. Nana Zhao is a research scientist at Vancouver fellow in material science and engineering at the International Clean-Tech Research Institute Inc. University of California, Berkeley. At the same time, (VICTRII), Burnaby, British Columbia, Canada. Her she also worked at Professor Frantisek Svec’s team in research interests include synthesis, evaluation and Molecular Foundry at the Lawrence Berkeley National characterization of PFSA and hydrocarbon ionomer and Laboratory. After one term of postdoctoral research, she membranes; MEA design and fabrication; characteriza- took a position as a research associate at the National tion and electrochemical evaluation of catalyst layer; Research Council of Canada—Energy, Mining and membrane and catalyst layer durability testing and Environment Portfolio (NRC-EME, which used to be diagnosis; synthesis and characterization of CO sepa- the Institute for Fuel Cell Innovation) for two years. In 2 ration membranes; preparation and characterization of 2013, she began working at VICTRII as a research sci- subnanometer porous membrane for proton transpor- entist. Currently, she is taking a lead role in several col- tation and gas transport; and inorganic nanocrystals laborative PEM fuel cell projects. © 2016 by Taylor & Francis Group, LLC