Materials for High-Temperature Fuel Cells E-Book
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- Herausgeber: Wiley-VCH
- Kategorie: Wissenschaft und neue Technologien
- Serie: Materials for Sustainable Energy and Development
- Sprache: Englisch
The world's ever-growing demand for power has created an urgent need for new efficient and sustainable sources of energy and electricity. Today's consumers of portable electronics also demand devices that not only deliver more power but are also environmentally friendly. Fuel cells are an important alternative energy source, with promise in military, commercial and industrial applications, for example power vehicles and portable devices.
A fuel cell is an electrochemical device that directly converts the chemical energy of a fuel into electrical energy. Fuel cells represent the most efficient energy conversion technologies to-date and are an integral part in the new and renewable energy chain (e.g., solar, wind and hydropower). Fuel cells can be classified as either high-temperature or lowtemperature, depending on their operating temperature, and have different materials requirements. This book is dedicated to the study of high temperature fuel cells. In hightemperature fuel cells, the electrolyte materials are ceramic or molten carbonate, while the electrode materials are ceramic or metal (but not precious metal). High operation temperature fuel cells allow internal reforming, promote rapid kinetics with non-precious materials and offer high flexibilities in fuel choice, and are potential and viable candidate to moderate the fast increase in power requirements and to minimize the impact of the
increased power consumption on the environment.
'Materials for High Temperature Fuel Cells' is part of the series on Materials for Sustainable Energy and Development edited by Prof. Max Q. Lu. The series covers advances in materials science and innovation for renewable energy, clean use of fossil energy, and greenhouse gas mitigation and associated environmental technologies.
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Seitenzahl: 812
Veröffentlichungsjahr: 2013
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Table of Contents
Related Titles
Title Page
Copyright
Editorial Board
Series Editor Preface
Preface
About the Series Editor
About the Volume Editor
List of Contributors
Chapter 1: Advanced Anodes for Solid Oxide Fuel Cells
1.1 Introduction
1.2 Ni–YSZ Anode Overview
1.3 Insights from Real Ni–YSZ Microstructures
1.4 Mechanistic Understanding of Fuel Oxidation in Ni-Based Anodes
1.5 Poisoning of Ni-Based Anodes
1.6 Alternative Anode Materials for Direct Hydrocarbon Utilization
1.7 Infiltration as an Alternative Fabrication Method
1.8 Summary and Outlook
References
Chapter 2: Advanced Cathodes for Solid Oxide Fuel Cells
2.1 Introduction
2.2 Cathodes on Oxygen-Ion-Conducting Electrolytes
2.3 Cathodes on Proton-Conducting Electrolytes
2.4 Advanced Techniques in Cathode Fabrication
2.5 Summary
References
Chapter 3: Oxide Ion-Conducting Materials for Electrolytes
3.1 Introduction
3.2 Oxide Ion Conductivity in Metal Oxide
3.6 Concluding Remarks
References
Chapter 4: Proton-Conducting Materials as Electrolytes for Solid Oxide Fuel Cells
4.1 Introduction
4.2 The Principle of Proton-Conducting Oxides
4.3 Proton-Conducting Materials for Solid Oxide Fuel Cells
4.4 Solid Oxide Fuel Cells Based on Proton-Conducting Electrolytes
4.5 Electrode Materials and Anode Reactions for SOFCs Based on Proton-Conducting Electrolytes
4.6 Conclusion
References
Chapter 5: Metallic Interconnect Materials of Solid Oxide Fuel Cells
5.1 Introduction
5.2 Oxidation Behaviors of Candidate Alloys
5.3 Electrical Properties of Oxide Scale
5.4 Surface Modifications and Coatings
5.5 New Alloy Development
5.6 Summary
References
Chapter 6: Sealants for Planar Solid Oxide Fuel Cells
6.1 Introduction
6.2 Glass and Glass–Ceramic Sealants
6.3 Mica
6.4 Metal Braze
6.5 Composite Sealants
6.6 Conclusion
Acknowledgment
References
Chapter 7: Degradation and Durability of Electrodes of Solid Oxide Fuel Cells
7.1 Introduction
7.2 Anodes
7.3 Cathodes
7.4 Degradation of Solid Oxide Electrolysis Cells
7.5 Summary and Conclusions
References
Chapter 8: Materials and Processing for Metal-Supported Solid Oxide Fuel Cells
8.1 Introduction
8.2 Cell Architectures
8.3 Substrate Materials and Challenges
8.4 Cell Fabrication and Challenges
8.5 Summary
References
Chapter 9: Molten Carbonate Fuel Cells
9.1 Introduction
9.2 Operating Principle
9.3 State-of-the-Art Components
9.4 General Needs
9.5 Status of MCFC Systems Implementation
References
Index
Related Titles
Stolten, D., Emonts, B. (eds.)
Fuel Cell Science and Engineering
Materials, Processes, Systems and Technology
2012
ISBN: 978-3-527-33012-6
Stolten, D. (ed.)
Hydrogen and Fuel Cells
Fundamentals, Technologies and Applications
2010
ISBN: 978-3-527-32711-9
Wieckowski, A., Norskov, J. (eds.)
Fuel Cell Science
Theory, Fundamentals, and Biocatalysis
ISBN: 978-0-470-41029-5
Vielstich, W., Gasteiger, H.A., Yokokawa,~H. (eds.)
Handbook of Fuel Cells
Advances in Electrocatalysis, Materials, Diagnostics and Durability, Volumes 5 & 6
2 Volumes
ISBN: 978-0-470-72311-1
Bagotsky, V. S.
Fuel Cells
Problems and Solutions
ISBN: 978-0-470-23289-7
Sundmacher, K., Kienle, A., Pesch, H.J., Berndt, J.F., Huppmann, G. (eds.)
Molten Carbonate Fuel Cells
Modeling, Analysis, Simulation, and Control
2007
ISBN: 978-3-527-31474-4
The Editors
Prof. San Ping Jiang
Curtin University
Fuels and Energy Technology Institute & Department of Chemical Engineering
1, Turner Avenue
Perth, WA 6845
Australia
Prof. Yushan Yan
Dept. Chem. Engineering
University of Delaware
150 Academy Street
Newark, DE 19716
USA
All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.
Library of Congress Card No.: applied for
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library.
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The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at <http://dnb.d-nb.de>.
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany
All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form — by photoprinting, microfilm, or any other means — nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.
Print ISBN: 978-3-527-33041-6
ePDF ISBN: 978-3-527-64428-5
ePub ISBN: 978-3-527-64427-8
mobi ISBN: 978-3-527-64429-2
oBook ISBN: 978-3-527-64426-1
Editorial Board
Members of the Advisory Board of the “Materials for Sustainable Energy and Development” Series
Professor Huiming Cheng
Professor Calum Drummond
Professor Morinobu Endo
Professor Michael Grätzel
Professor Kevin Kendall
Professor Katsumi Kaneko
Professor Can Li
Professor Arthur Nozik
Professor Detlev Stöver
Professor Ferdi Schüth
Professor Ralph Yang
Series Editor Preface
The Wiley Series on New Materials for Sustainable Energy and Development
Sustainable energy and development are attracting increasing attention from scientific research communities and industries alike, with an international race to develop technologies for clean fossil energy, hydrogen, and renewable energy, as well as water reuse and recycling. According to the REN21 (Renewables Global Status Report 2012, p. 17), total investment in renewable energy reached $257 billion in 2011, up from $211 billion in 2010. The top countries for investment in 2011 were China, Germany, the United States, Italy, and Brazil. In addressing the challenging issues of energy security, oil price rise, and climate change, innovative materials are essential enablers.
In this context, there is a need for an authoritative source of information, presented in a systematic manner, on the latest scientific breakthroughs and knowledge advancement in materials science and engineering, as they pertain to energy and the environment. The aim of the Wiley Series on New Materials for Sustainable Energy and Development is to serve the community in this respect. This has been an ambitious publication project on materials science for energy applications. Each volume of the series will include high-quality contributions from top international researchers and is expected to become the standard reference for many years to come.
This book series covers advances in materials science and innovation for renewable energy, clean use of fossil energy, and greenhouse gas mitigation and associated environmental technologies. Current volumes in the series are
In presenting this volume on Materials for High-Temperature Fuel Cells, I would like to thank the authors and editors of this important book, for their tremendous effort and hard work in completing their manuscripts in a timely manner. The quality of the chapters reflects well the caliber of the contributing authors to this book, and will no doubt be recognized and valued by readers.
Finally, I would like to thank the editorial board members. I am grateful to them for their excellent advice and help in terms of examining coverage of topics and suggesting authors, and evaluating book proposals.
I would also like to thank the editors from the publisher Wiley-VCH with whom I have worked since 2008, Dr. Esther Levy, Dr. Gudrun Walter, and Dr. Bente Flier for their professional assistance and strong support during this project.
I hope you will find this book interesting, informative, and valuable as a reference in your work. We will endeavor to bring to you further volumes in this series or update you on the future book plans in this growing field.
Brisbane, Australia
G.Q. Max Lu
31 July 2012
Preface
Electricity is the most convenient form of energy today. For the past 100 years, electricity is primarily produced by combustion of fossil fuels, which have an intrinsically low conversion efficiency and emit carbon dioxide and other air pollutants. Carbon dioxide contributes to climate changes. With increasing energy demand, depleting fossil fuel reserves, and growing concern about the climate and environment, there is an urgent need to increase electricity generation efficiency and to develop renewable energy sources. Fuel cell is an energy conversion device to electrochemically convert directly the chemical energy of fuels such as hydrogen, methanol, ethanol, natural gas, and hydrocarbons to electricity, and hence, fuel cells inherently have a significantly higher efficiency than conventional energy conversion technologies such as internal combustion engine (ICE). Among the various types of fuel cells, high-temperature solid oxide fuel cells (SOFCs) and molten carbonate fuel cells (MCFCs) are considered to be the most efficient, as they allow internal reforming, promote rapid kinetics with nonprecious materials, and offer high flexibilities in fuel choice.
During the past 20 years, SOFCs and MCFCs have received enormous attention worldwide as alternative electrical energy conversion systems. The book starts with Chapters 1–3 on the materials, ionic transport process, conductivity, electrocatalytic characteristics, and synthesis of key SOFC components of anode, cathode, and oxide ion electrolyte. Chapter 4 presents an overview of proton-conducting electrolytes, a separate class of ion-conducting material. The use of proton-conducting electrolyte materials can have some advantages such as water generation at the cathode side, prevention of fuel dilution at the anode, and the formation of NOx or SOx can be avoided when ammonia or H2S is used as the fuel. This is followed by Chapters 5 and 6 on the materials, processing, and thermal and electrical properties of metallic interconnect and sealants, the most important stack material for an SOFC. Chapter 7 is dedicated to degradation and durability of SOFC electrodes, one of the most challenging problems associated with an SOFC system over a 5 year lifetime. Chapter 8 presents the materials, processing, and status of metal-supported SOFCs or MS-SOFCs, an alternative cell configuration developed to address the critical issues of SOFC systems on cost, durability, and thermal cyclability. Last but not the least, Chapter 9 covers the brief history, operating principles, and status of the state-of-the-art materials and components of MCFCs, one of the most mature and technologically advanced fuel cell technologies.
All chapters were written by leading international experts. It was the intension of the editors and authors that the book be designed to help those involved in the research and development of high-temperature fuel cells and, at the same time, to serve as a reference book for students, materials engineer, and researchers interested in fuel cells technology in general.
Perth, Australia
San Ping Jiang
Newark, USA
Yushan Yan
About the Series Editor
Professor Max Lu
Editor, New Materials for Sustainable Energy and Development Series
Professor Lu's research expertise is in the areas of materials chemistry and nanotechnology. He is known for his work on nanoparticles and nanoporous materials for clean energy and environmental technologies. With over 500 journal publications in high-impact journals, including Nature, Journal of the American Chemical Society, Angewandte Chemie, and Advanced Materials, he is also coinventor of 20 international patents. Professor Lu is an Institute for Scientific Information (ISI) Highly Cited Author in Materials Science with over 17 500 citations (h-index of 63). He has received numerous prestigious awards nationally and internationally, including the Chinese Academy of Sciences International Cooperation Award (2011), the Orica Award, the RK Murphy Medal, the Le Fevre Prize, the ExxonMobil Award, the Chemeca Medal, the Top 100 Most Influential Engineers in Australia (2004, 2010, and 2012), and the Top 50 Most Influential Chinese in the World (2006). He won the Australian Research Council Federation Fellowship twice (2003 and 2008). He is an elected Fellow of the Australian Academy of Technological Sciences and Engineering (ATSE) and Fellow of Institution of Chemical Engineers (IChemE). He is editor and editorial board member of 12 major international journals including Journal of Colloid and Interface Science and Carbon.
Max Lu has been Deputy Vice-Chancellor and Vice-President (Research) since 2009. He previously held positions of acting Senior Deputy Vice-Chancellor (2012), acting Deputy Vice-Chancellor (Research), and Pro-Vice-Chancellor (Research Linkages) from October 2008 to June 2009. He was also the Foundation Director of the ARC Centre of Excellence for Functional Nanomaterials from 2003 to 2009.
Professor Lu had formerly served on many government committees and advisory groups including the Prime Minister's Science, Engineering and Innovation Council (2004, 2005, and 2009) and the ARC College of Experts (2002–2004). He is the past Chairman of the IChemE Australia Board and former Director of the Board of ATSE. His other previous board memberships include Uniseed Pty Ltd., ARC Nanotechnology Network, and Queensland China Council. He is currently Board member of the Australian Synchrotron, National eResearch Collaboration Tools and Resources, and Research Data Storage Infrastructure. He also holds a ministerial appointment as member of the National Emerging Technologies Forum.
About the Volume Editors
Dr. San Ping Jiang is a professor at the Department of Chemical Engineering, the Deputy Director of Fuels and Energy Technology Institute, Curtin University, Australia, and an Adjunct Professor of the University of the Sunshine Coast, Australia. He also holds Visiting/Guest Professorships at the Harbin Institute of Technology, Guangzhou University, Huazhong University of Science and Technology, Wuhan University of Technology, University of Science and Technology of China, Sichuan University, and Shandong University. After receiving his BEng from the South China University of Technology and Ph. D. from the City University, London, Dr. Jiang worked at the CSIRO Manufacturing Science and Technology Division, Ceramic Fuel Cells Ltd (CFCL) in Australia and the Nanyang Technological University in Singapore. His research interests encompass solid oxide fuel cells, proton exchange and direct methanol fuel cells, direct alcohol fuel cells, and electrolysis. With an h-index of 44, he has published over 240 journal papers, which have accrued ∼6500 citations.
Yushan Yan has been a Distinguished Engineering Professor at the University of Delaware since 2011. He received his B. S. from the University of Science and Technology of China and Ph. D. from the California Institute of Technology. He worked for AlliedSignal Inc. as Senior Staff Engineer before joining the faculty at the University of California at Riverside (Assistant Professor 1998, Associate Professor 2002, Professor 2005, University Scholar 2006, Department Chair 2008, Presidential Chair 2010). He is a Fellow of the American Association for the Advancement of Science. He was recognized with the Donald Breck Award by the International Zeolite Association. He was one of the 37 awardees in ARPA-E OPEN 2009 for his fuel cell technology and one of the 66 awardees in ARPA-E OPEN 2012 for his redox flow battery concept by the US Department of Energy. His patents were licensed to form startup companies, for example, NanoH2O, Full Cycle Energy, Zeolite Solution Materials, and OH-Energy. He has published more than 140 journal articles (h-index = 46, total number of citations = more than 6700).
List of Contributors
1
Advanced Anodes for Solid Oxide Fuel Cells
Steven McIntosh
1.1 Introduction
The solid oxide fuel cell (SOFC) anode must perform four basic functions: (i) transport oxygen anions from the 2D electrolyte–electrode interface out into the higher surface area 3D electrode structure, (ii) transport gas-phase fuel to the reaction site and products from the reaction site, (iii) catalyze the electrochemical oxidation of the fuel, and (iv) transport the product electrons from the reaction site to the current collector at the electrode surface. These requirements are in addition to considerations of material stability, manufacturability, redox tolerance, and resistance to possible poisons in the fuel.
The most developed and widely utilized SOFC anode is a porous ceramic–metallic (cermet) composite of Ni with the oxide electrolyte, most commonly 8 mol% yttria-stabilized zirconia (YSZ). Ni provides electronic conductivity and electrocatalytic activity, while YSZ provides oxygen anion conductivity. The reaction in the Ni–yttria-stabilized zirconia (Ni–YSZ) anode can thus only occur at the triple phase boundary (TPB) involving the Ni, YSZ, and gas phases – these are the regions of the anode where all the electrode requirements are met. When the relative fractions of these materials and the cermet porosity are optimized, the Ni–YSZ cermet electrode can provide performance sufficient for commercialization [1]. The required performance metric for the anode is a function of cost and the relative performance of the other cell components. A rough rule of thumb performance target for an SOFC anode is a polarization resistance of less than 0.15 Ω cm [2]. In addition, Ni and YSZ can be cosintered at the sintering temperatures required to create a dense YSZ electrolyte, 1400–1550 °C, thus simplifying cell fabrication [3]. This combination of performance and manufacturability makes Ni–YSZ cermets the anode of choice for current commercial SOFC technologies.
Ni-based cermet electrodes are not without disadvantages. Perhaps the most significant of them is that the use of Ni places significant restrictions on the fuel choice for SOFCs. Unlike other fuel cells, the SOFC operating principle is based on the transport of the oxidant to the fuel; as such, SOFCs can theoretically operate on any oxidizable fuel [4]. This makes SOFCs an attractive option for efficient power generation from current fossil and future renewable hydrocarbon fuels. However, Ni catalyzes the formation of graphitic carbon in dry hydrocarbon atmospheres [5–7], limiting the fuel choice to H2 and CO. This problem can be partially surmounted by steam reforming of the hydrocarbon fuel to form H2 and CO either before feeding to the cell (external steam reforming) or on the Ni-based anode itself (internal steam reforming). The first solution increases cost by requiring an additional reactor in the system. The second places large thermal stresses on the cells and stack by combining the highly endothermic reforming reaction with the exothermic fuel oxidation reaction. Another potential disadvantage of Ni anodes is their potential instability toward reduction and oxidation cycling. Accidental oxidation of Ni to form NiO is accompanied by a large lattice expansion, potentially leading to mechanical failure of the cell [8]. There are also concerns regarding the tolerance of Ni toward impurities in the feed, including sulfur and heavy metals, although many of these impurities can be removed by fuel pretreatment. These disadvantages and the potential advantages of direct hydrocarbon utilization have led to significant research efforts to develop new anode compositions. The majority of these are mixed metal oxides with the perovskite or a related structure. However, the development of these oxide materials that can provide the cell performance levels required for economic implementation is a significant challenge.
SOFC anode understanding and optimization are the topics of a large number of studies around the world: a citation search for the concept “SOFC anode” yields more than 900 results for 2011 alone. It is not possible to cover all this material in a single chapter, requiring focus. In this chapter, we first provide a background overview of Ni–YSZ anodes before discussing the most recent advances in our understanding of their function, from techniques that enable study of real microstructures to recent insights into the anode reaction mechanism. We then focus on the challenge of developing novel anode materials to facilitate SOFCs operating with hydrocarbon fuels. The reader is directed to the large number of excellent review articles available in the literature for further discussion of these and related topics [3, 4, 9–19].
1.2 Ni–YSZ Anode Overview
On the basis of the overall reaction mechanism, there are some basic requirements of the Ni–YSZ microstructure () [20]. First, there must be sufficient porosity for gas transport. Second, there must be continuous connectivity within the YSZ phases and Ni phases to facilitate ion and electron transport, respectively. Third, the microstructure should be optimized to achieve a high density of TPB regions to facilitate reaction. The anode must also provide sufficient mechanical strength, as most SOFC designs utilize a relatively thick anode cermet as the physical support structure for a thin electrolyte film.
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