PEM electrolysis for hydrogen production : principles and applications

392 Pages·2016·42.739 MB·English

by  Bessarabov, Dmitri Georgievich, Li, Hui, Wang, Haijiang, Zhao, Nana

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
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Version Date: 20150814
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© 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