Fuel Cells E-Book

Vladimir S. Bagotsky

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Serie: Electrochemical Society Series
• Sprache: Englisch

Seitenzahl: 742

Veröffentlichungsjahr: 2012

Beschreibung

The comprehensive, accessible introduction to fuel cells, their applications, and the challenges they pose

Fuel cells—electrochemical energy devices that produce electricity and heat—present a significant opportunity for cleaner, easier, and more practical energy. However, the excitement over fuel cells within the research community has led to such rapid innovation and development that it can be difficult for those not intimately familiar with the science involved to figure out exactly how this new technology can be used. Fuel Cells: Problems and Solutions, Second Edition addresses this issue head on, presenting the most important information about these remarkable power sources in an easy-to-understand way.

Comprising four important sections, the book explores:

• The fundamentals of fuel cells, how they work, their history, and much more

• The major types of fuel cells, including proton exchange membrane fuel cells (PEMFC), direct liquid fuel cells (DLFC), and many others

• The scientific and engineering problems related to fuel cell technology

• The commercialization of fuel cells, including a look at their uses around the world

Now in its second edition, this book features fully revised coverage of the modeling of fuel cells and small fuel cells for portable devices, and all-new chapters on the structural and wetting properties of fuel cell components, experimental methods for fuel cell stacks, and nonconventional design principles for fuel cells, bringing the content fully up to date.

Designed for advanced undergraduate and graduate students in engineering and chemistry programs, as well as professionals working in related fields, Fuel Cells is a compact and accessible introduction to the exciting world of fuel cells and why they matter.

Leseprobe

Table of Contents

Series Page

Title Page

Copyright

Preface

Preface to the first edition

Symbols

Abbreviations and Acronyms

Part I: Introduction

Chapter 1: The Working Principles of a Fuel Cell

1.1 Thermodynamic Aspects

1.2 Schematic Layout of Fuel Cell Units

1.3 Types of Fuel Cells

1.4 Layout of a Real Fuel Cell: the Hydrogen–Oxygen Fuel Cell with Liquid Electrolyte

1.5 Basic Parameters of Fuel Cells

Reference

Chapter 2: The Long History of Fuel Cells

2.1 The Period Prior to 1894

2.2 The Period from 1894 to 1960

2.3 The Period from 1960 to the 1990s

2.4 The Period after the 1990s

References

Part 2: Major Types of Fuel Cells

Chapter 3: Proton-Exchange Membrane Fuel Cells

3.1 History of the PEMFC

3.2 Standard PEMFC Version from the 1990s

3.3 Special Features of PEMFC Operation

3.4 Platinum Catalyst Poisoning by Traces of CO in the Hydrogen

3.5 Commercial Activities in Relation to PEMFCs

3.6 Future Development of PEMFCs

3.7 Elevated-Temperature PEMFCs

References

Chapter 4: Direct Liquid Fuel Cells

4.1 Part A: Direct Methanol Fuel Cells

4.2 Methanol as a Fuel for Fuel Cells

4.3 Current-Producing Reactions and Thermodynamic Parameters

4.4 Anodic Oxidation of Methanol

4.5 Milestones in DMFC Development

4.6 Membrane Penetration by Methanol (Methanol Crossover)

4.7 Varieties of DMFCs

4.8 Special Operating Features of DMFCs

4.9 Practical Models of DMFCs and their Features

4.10 Problems to be Solved in Future DMFCs

4.11 Part B: Direct Liquid Fuel Cells

4.12 The Problem of Replacing Methanol

4.13 Fuel Cells using Organic Liquids as Fuels

4.14 Fuel Cells Using Inorganic Liquids as Fuels

References

Chapter 5: Phosphoric Acid Fuel Cells

5.1 Early Work on Phosphoric Acid Fuel Cells

5.2 Special Features of Aqueous Phosphoric Acid Solutions

5.3 Construction of PAFCs

5.4 Commercial Production of PAFCs

5.5 Development of Large Stationary Power Plants

5.6 The Future of PAFCs

5.7 Importance of PAFCs for Fuel Cell Development

References

Chapter 6: Alkaline Fuel Cells

6.1 Hydrogen–Oxygen AFCs

6.2 Alkaline Hydrazine Fuel Cells

6.3 Anion-Exchange (Hydroxyl Ion–Conducting) Membranes

6.4 Methanol Fuel Cells with Anion-Exchange Membranes

6.5 Methanol Fuel Cell with an Invariant Alkaline Electrolyte

6.6 Direct ammonia fuel cell with an anion-exchange membrane

References

Chapter 7: Molten Carbonate Fuel Cells

7.1 Special Features of High-Temperature Fuel Cells

7.2 Structure of Hydrogen–Oxygen MCFCs

7.3 MCFCs with Internal Fuel Reforming

7.4 Development of MCFC Work

7.5 The Lifetime of MCFCs

References

Chapter 8: Solid-Oxide Fuel Cells

8.1 Schematic Design of Conventional SOFCs

8.2 Tubular SOFCs

8.3 Planar SOFCs

8.4 Monolithic SOFCs

8.5 Varieties of SOFCs

8.6 Utilization of Natural Fuels in SOFCs

8.7 Interim-Temperature SOFCs

8.8 Low-Temperature SOFCs

8.9 Factors Influencing the Lifetime of SOFCs

References

Chapter 9: Other Types of Fuel Cells

9.1 Redox Flow Cells

9.2 Biological Fuel Cells

9.3 Semi-Fuel Cells

9.4 Direct Carbon Fuel Cells

References

Chapter 10: Fuel Cells and Electrolysis Processes

10.1 Water Electrolysis

10.2 Chlor-Alkali Electrolysis

10.3 Electrochemical Synthesis Reactions

References

Part III: Inherent Scientific and Engineering Problems

Chapter 11: Fuel Management

11.1 Reforming of Natural Fuels

11.2 Production of Hydrogen for Autonomous Power Plants

11.3 Purification of Technical Hydrogen

11.4 Hydrogen Transport and Storage

References

Chapter 12: Electrocatalysis

12.1 Fundamentals of Electrocatalysis

12.2 Putting Platinum Catalysts on the Electrodes

12.3 Supports for Platinum Catalysts

12.4 Platinum Alloys and Composites as Catalysts for Anodes

12.5 Nonplatinum Catalysts for Fuel Cell Anodes

12.6 Electrocatalysis of the Oxygen Reduction Reaction

12.7 Stability of Electrocatalysts

References

Chapter 13: Membranes

13.1 Fuel Cell–Related Membrane Problems

13.2 Work to Overcome Degradation of Nafion Membranes

13.3 Modification of Nafion Membranes

13.4 Membranes Made From Polymers Without Fluorine

13.5 Membranes Made From Other Materials

13.6 Matrix-Type Membranes

13.7 Membranes with Hydroxyl Ion Conduction

References

Chapter 14: Structural and wetting properties of fuel cell components*

14.1 Methods for investigating porous materials

14.2 A new method: the method of standard contact porosimetry

14.3 Catalysts used in fuel cells

14.4 The catalytic layer

14.5 The gas-diffusion layer

14.6 Membranes

14.7 Influence of structural and wetting properties on fuel cell performance

References

Chapter 15: Mathematical modeling of fuel cells

15.1 Zero-dimensional models

15.2 One-dimensional models

15.3 Two-dimensional models

15.4 Three-dimensional models

15.5 Time domain

15.6 Concluding remarks

References

Chapter 16: Experimental methods for investigating fuel cell stacks

16.1 Methods developed before 2007

16.2 Optical, X-ray, and EM methods

16.3 Neutron beam–based methods

16.4 Electrochemical methods

16.5 Miscellaneous methods

References

Chapter 17: Small Fuel Cells for Portable Devices

17.1 Special operating features of mini-fuel cells

17.2 Flat mini-fuel batteries

17.3 Silicon-based mini-fuel cells

17.4 PCB-based mini-fuel cells

17.5 Mini-solid-oxide fuel cells

17.6 The problem of air-breathing cathodes

17.7 Prototypes of power units with mini-fuel cells

17.8 Concluding remarks

References

Chapter 18: Nonconventional design principles for fuel cells

18.1 Conventional design principles and their drawbacks

18.2 The principle of mixed-reactant supply: Mixed-reactant fuel cells

18.3 Coplanar fuel cell design: Strip cells

18.4 The flow-through electrode principle

18.5 Single-Chamber SOFCs

18.6 Microfluidic Fuel Cells

References

Part IV: Commercialization of Fuel Cells

Chapter 19: Applications

19.1 Large Stationary Power Plants

19.2 Small Stationary Power Units

19.3 Fuel Cells for Transport Applications

19.4 Portables

19.5 Military Applications

19.6 Handicaps preventing a broader commercialization of fuel cells

References

Chapter 20: Fuel Cell Work in Various Countries

20.1 Driving Forces for Fuel Cell Work

20.2 Fuel Cells and the Hydrogen Economy

20.3 Activities in North America

20.4 Activities in Europe

20.5 Activities in other Countries

20.6 The Volume of Published Fuel Cell Work

20.7 Legislation and Standardization in the Field of Fuel Cells

References

Chapter 21: Outlook

21.1 Periods of Alternating Hope and Disappointment

21.2 Some Misconceptions*

21.3 Ideal Fuel Cells

21.4 Projected Future of Fuel Cells

References

General Bibliography

Historical Books

Contemporary Books

Periodicals

Reviews on General Topics

Author Index

Subject Index

Wiley Series

For further information visit: the book web page http://www.openmodelica.org, the Modelica Association web page http://www.modelica.org, the authors research page http://www.ida.liu.se/labs/pelab/modelica, or home page http://www.ida.liu.se/~petfr/, or email the author at [email protected]. Certain material from the Modelica Tutorial and the Modelica Language Specification available at http://www.modelica.org has been reproduced in this book with permission from the Modelica Association under the Modelica License 2 Copyright © 1998–2011, Modelica Association, see the license conditions (including the disclaimer of warranty) at http://www.modelica.org/modelica-legal-documents/ModelicaLicense2.html. Licensed by Modelica Association under the Modelica License 2.

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Copyright © 2011 by the Institute of Electrical and Electronics Engineers, Inc.

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Library of Congress Cataloging-in-Publication Data:

Bagotsky, V. S. (Vladimir Sergeevich)

Fuel cells : problems and solutions / Vladimir S. Bagotsky.–2nd ed.

p. cm.

Includes bibliographical references and index.

ISBN 978-1-118-08756-5 (hardback)

1. Fuel cells. I. Title.

TK2931.B35 2012

621.31'2429–dc23

2011051083

Preface

The first edition of this book was published in December 2008. This second edition is updated with information published after this date up to October 2011. Two chapters of the first edition were rewritten: Chapter 1 (modeling of fuel cells) and Chapter 14—now Chapter 17 (small fuel cells for portable devices). In this edition three new chapters of high current interest are also included: Chapter 14 (structural and wetting properties of fuel cell components), Chapter 16 (experimental methods for fuel cell stacks), and Chapter 18 (nonconventional design principles for fuel cells).

My thanks go to Ms. Catherine Lysova for her help in editing some chapters of the book.

Vladimir Sergeevich Bagotsky

Moscow, Russia and Boulder, Colorado

October 2011

E-mail: [email protected]

Preface to the first edition

When fuel cells were first suggested and discussed back in the nineteenth century, it was firmly hoped that distinctly higher efficiencies could be attained with them when converting the chemical energy of natural fuels to electric power. Now that the world supply of fossil fuels is seen to be finite, this hope turns into a need, into a question of maintaining advanced standards of life. Apart from conversion efficiency, fuel cells have other aspects which make them attractive: Their conversion process is clean, they may cogenerate useful heat, and can be used in many different fields. One worker in the field put it this way: “Fuel cells have the potential to supply electricity to power a wristwatch or a large city, replacing a tiny battery or an entire power generating station.”

With some important achievements made in the past, fuel cells today are a subject of vigorous R&D, engineering, and testing conducted on a broad international scale in universities, research centers, and private companies in different sectors of the economy. Between engineers, technicians, and scientists, several 10,000 workers contribute their efforts and skills to advance the field.

Progress in the field is fast. Hundreds of publications monthly report new results and discoveries. Important synergies exist with work done to advance the concepts of a hydrogen economy.

The book is intended for people who have heard about fuel cells but ignore the detailed potential and applications of fuel cells, and wish to obtain the information they need (as engineers in civil, industrial, and military jobs, R&D people of diverse profile, investors, decision makers in government, industry, trade, and all levels of administration, journalists, school and university teachers, students, and hobby scientists). It is also intended for people in industry and research who in their professional work are concerned with different special aspects of the development and applications of fuel cells and want to gain an overview of fuel cell problems and their economic and scientific significance.

This book is thus focused on providing readers across the trades and life styles with a compact, readable introduction and explanation of what fuel cells do, how they do it, where they are important, where the problems are, how fuel cells will continue in the field, and how they can perform against air pollution and for portable devices. All this is done with a critical attitude based on a sufficiently detailed and advanced presentation. Problems and achievements are discussed at the level attained by the end of 2007.

Contradictions and a lack of consensus have existed in the field, along with ups and downs. In a field where the subject may range in size from milliwatt to megawatt output and many technical systems compete, this will not come as a surprise. To guide the reader through the maze, a sampling of literature references is provided. This sampling is intended to illustrate but had to be compiled while omitting a lot of work just as important as the work cited. Selection was also made difficult because of the strongly interdisciplinary character of fuel cell work.

The presentation is made against the historical background, and looks at future prospects, including those of synergy with a potential future hydrogen economy. Where views diverge, they are presented as such. Some of the ideas offered may well be open to further discussion.

My gratitude goes to my colleagues Dr. Nina Osetrova and Dr. Alexander Skundin, Moscow, for their help in selecting relevant literature, and to Timophei Pastushkin for preparing graphical representations. My thanks also go to Dr. Klaus Mueller, formerly at the Battelle Institute of Geneva, who transformed chapters written in Russian into English reading material, and contributed by making a number of very valuable suggestions.

I sincerely hope that what has inspired me during a long lifetime, of more than 50 years of research and teaching at the Moscow Quant Power Sources Institute and at the A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, will continue to inspire current and future specialists and people in general who work to improve our lives and solve our problems.

Vladimir Sergeevich Bagotsky

Moscow, Russia and Mountain View, California

May 2008

E-mail: [email protected]

Abbreviations and Acronyms

acalternating currentAFCalkaline fuel cellAPUauxiliary power unitATRautothermal reformingBETBrunaer Emmett TellerCDcurrent densityCHPcombined heat and powerCNTcarbon nanotubeCTcomputed tomographyCTEcoefficient of thermal expansionDBHFCduirect borohydride fuel celldcdirect currentDCFCdirect carbon fuel cellDEFCdirect ethanol fuel cellDFAFCdirect formic acid fuel cellDHFCdirect hydrazine fuel cellDLFCdirect liquid fuel cellDMFCdirect methanol fuel cellDSAdimensionally stable anodeDVBdivinylbenzeneEMelectron microscopyEMFelectromotive forceEPSelectrochemical power sourceET-PEMFCelevated-temperature PEMFCFCVfuel cell vehicleGDLgas-diffusion layerGDMgas-diffussion mediumGLDLgas–liquid diffusion layerICEinternal combustion engineICVinternal combustion vehicleIRFCinternal reforming fuel cellIT-SOFCinterim-temperature SOFCLHVlower heat valueLPGliquefied petroleum gasLT-SOFClow-temperature SOFCMCFCmolten arbonate fuel cellMEAmembrane–electrode assemblyMMPmethod of mercury porosimetryMPLmicroporous layerMSCPmethod of standard contact porosimetryOCPopen-circuit potentialOCVopen-circuit voltageORRoxygen reduction reactionOx,oxoxidized formPAFCphosphoric acid fuel cellPBIpolybenzimidazolePCBprinted circuit boardPDpotential differencePEEKpoly(ether ether ketone)PEMFCproton-exchange membrane fuel cell (also polymer electrolyte membrane fuel cell)PFSAperfluorinated sulfonic acidPOXpartial oxidation (reforming by)PSDFpore size distribution functionPTFEpolytetrafluoroethylenePVDphysical vapor depositionRed, redreduced formSC-SOFCsingle-chamber solid-oxide fuel cellSHEstandard hydrogen electrodeSOFCsolid-oxide fuel cellSRsteam reformingSSAspecific surface areaSWCNTsingle-walled carbon nanotubeURFCunitized regenerative fuel cellUTCUnited Technologies CorporationWGSRwater-gas shift reaction

1These abbreviations and acronyms are used in most chapters. Abbreviations for oxide maerials used as electrolytes and electrodes in solid-oxide fuel cells are given in Chapter 8.

Part I

INTRODUCTION