The major types of fuel cells, including proton exchange membrane fuel cells (PEMFC), direct liquid
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Table of Contents
PREFACE xi
PREFACE TO THE FIRST EDITION xiii
SYMBOLS xv
ABBREVIATIONS AND ACRONYMS xvii
PART I INTRODUCTION 1
Introduction 3
What Is a Fuel Cell? Definition of the Term, 3
Significance of Fuel Cells for the Economy, 3
1 The Working Principles of a Fuel Cell 5
1.1 Thermodynamic Aspects, 5
1.2 Schematic Layout of Fuel Cell Units, 9
1.3 Types of Fuel Cells, 13
1.4 Layout of a Real Fuel Cell: The Hydrogen–Oxygen Fuel Cell with Liquid Electrolyte, 13
1.5 Basic Parameters of Fuel Cells, 18
Reference, 24
2 The Long History of Fuel Cells 25
2.1 The Period Prior to 1894, 25
2.2 The Period from 1894 to 1960, 28
2.3 The Period from 1960 to the 1990s, 31
2.4 The Period After the 1990s, 37
References, 38
PART II MAJOR TYPES OF FUEL CELLS 41
3 Proton-Exchange Membrane Fuel Cells 43
3.1 History of the PEMFC, 44
3.2 Standard PEMFC Version from the 1990s, 47
3.3 Special Features of PEMFC Operation, 51
3.4 Platinum Catalyst Poisoning by Traces of CO in the Hydrogen, 54
3.5 Commercial Activities in Relation to PEMFCs, 56
3.6 Future Development of PEMFCs, 57
3.7 Elevated-Temperature PEMFCs, 64
References, 67
4 Direct Liquid Fuel Cells 71
Part A: Direct Methanol Fuel Cells, 71
4.1 Methanol as a Fuel for Fuel Cells, 71
4.2 Current-Producing Reactions and Thermodynamic Parameters, 72
4.3 Anodic Oxidation of Methanol, 72
4.4 Milestones in DMFC Development, 74
4.5 Membrane Penetration by Methanol (Methanol Crossover), 74
4.6 Varieties of DMFCs, 77
4.7 Special Operating Features of DMFCs, 79
4.8 Practical Models of DMFCs and Their Features, 81
4.9 Problems to Be Solved in Future DMFCs, 83
Part B: Direct Liquid Fuel Cells, 85
4.10 The Problem of Replacing Methanol, 85
4.11 Fuel Cells Using Organic Liquids as Fuels, 86
4.12 Fuel Cells Using Inorganic Liquids as Fuels, 91
References, 94
5 Phosphoric Acid Fuel Cells 99
5.1 Early Work on Phosphoric Acid Fuel Cells, 99
5.2 Special Features of Aqueous Phosphoric Acid Solutions, 100
5.3 Construction of PAFCs, 101
5.4 Commercial Production of PAFCs, 102
5.5 Development of Large Stationary Power Plants, 103
5.6 The Future of PAFCs, 103
5.7 Importance of PAFCs for Fuel Cell Development, 104
References, 105
6 Alkaline Fuel Cells 107
6.1 Hydrogen–Oxygen AFCs, 108
6.2 Alkaline Hydrazine Fuel Cells, 115
6.3 Anion-Exchange (Hydroxyl Ion–Conducting) Membranes, 118
6.4 Methanol Fuel Cells with Anion-Exchange Membranes, 119
6.5 Methanol Fuel Cell with an Invariant Alkaline Electrolyte, 120
6.6 Direct Ammonia Fuel Cell with an Anion-Exchange
Membrane, 121
References, 121
7 Molten Carbonate Fuel Cells 123
7.1 Special Features of High-Temperature Fuel Cells, 123
7.2 Structure of Hydrogen–Oxygen MCFCs, 124
7.3 MCFCs with Internal Fuel Reforming, 126
7.4 Development of MCFC Work, 128
7.5 The Lifetime of MCFCs, 129
References, 131
8 Solid-Oxide Fuel Cells 133
8.1 Schematic Design of Conventional SOFCs, 134
8.2 Tubular SOFCs, 136
8.3 Planar SOFCs, 140
8.4 Monolithic SOFCs, 143
8.5 Varieties of SOFCs, 144
8.6 Utilization of Natural Fuels in SOFCs, 146
8.7 Interim-Temperature SOFCs, 148
8.8 Low-Temperature SOFCs, 152
8.9 Factors Influencing the Lifetime of SOFCs, 154
References, 156
9 Other Types of Fuel Cells 159
9.1 Redox Flow Cells, 159
9.2 Biological Fuel Cells, 162
9.3 Semi-Fuel Cells, 167
9.4 Direct Carbon Fuel Cells, 169
References, 174
10 Fuel Cells and Electrolysis Processes 177
10.1 Water Electrolysis, 177
10.2 Chlor-Alkali Electrolysis, 182
10.3 Electrochemical Synthesis Reactions, 185
References, 187
PART III INHERENT SCIENTIFIC AND ENGINEERING PROBLEMS 189
11 Fuel Management 191
11.1 Reforming of Natural Fuels, 192
11.2 Production of Hydrogen for Autonomous Power Plants, 196
11.3 Purification of Technical Hydrogen, 199
11.4 Hydrogen Transport and Storage, 202
References, 205
12 Electrocatalysis 207
12.1 Fundamentals of Electrocatalysis, 207
12.2 Putting Platinum Catalysts on the Electrodes, 211
12.3 Supports for Platinum Catalysts, 214
12.4 Platinum Alloys and Composites as Catalysts for Anodes, 217
12.5 Nonplatinum Catalysts for Fuel Cell Anodes, 220
12.6 Electrocatalysis of the Oxygen Reduction Reaction, 221
12.7 Stability of Electrocatalysts, 227
References, 228
13 Membranes 233
13.1 Fuel Cell–Related Membrane Problems, 234
13.2 Work to Overcome Degradation of Nafion Membranes, 235
13.3 Modification of Nafion Membranes, 235
13.4 Membranes Made from Polymers Without Fluorine, 237
13.5 Membranes Made from Other Materials, 239
13.6 Matrix-Type Membranes, 239
13.7 Membranes with Hydroxyl Ion Conduction, 240
References, 241
14 Structural and Wetting Properties of Fuel Cell Components 243
Coauthor: Yurij M. Volfkovich
14.1 Methods for Investigating Porous Materials, 244
14.2 A New Method: The Method of Standard Contact Porosimetry, 245
14.3 Catalysts Used in Fuel Cells, 248
14.4 The Catalytic Layer, 252
14.5 The Gas-Diffusion Layer, 254
14.6 Membranes, 257
14.7 Influence of Structural and Wetting Properties on Fuel Cell Performance, 262
References, 264
15 Mathematical Modeling of Fuel Cells 267
Felix N. B¨uchi
15.1 Zero-Dimensional Models, 270
15.2 One-Dimensional Models, 270
15.3 Two-Dimensional Models, 271
15.4 Three-Dimensional Models, 272
15.5 Time Domain, 273
15.6 Concluding Remarks, 273
References, 274
16 Experimental Methods for Investigating Fuel Cell Stacks 275
16.1 Methods Developed Before 2007, 277
16.2 Optical, X-Ray, and EM Methods, 278
16.3 Neutron Beam–Based Methods, 281
16.4 Electrochemical Methods, 283
16.5 Miscellaneous Methods, 286
References, 288
17 Small Fuel Cells for Portable Devices 291
17.1 Special Operating Features of Mini-Fuel Cells, 292
17.2 Flat Mini-Fuel Batteries, 293
17.3 Silicon-Based Mini-Fuel Cells, 296
17.4 PCB-Based Mini-Fuel Cells, 298
17.5 Mini-Solid-Oxide Fuel Cells, 299
17.6 The Problem of Air-Breathing Cathodes, 300
17.7 Prototypes of Power Units with Mini-Fuel Cells, 301
17.8 Concluding Remarks, 304
References, 305
18 Nonconventional Design Principles for Fuel Cells 307
18.1 Conventional Design Principles and Their Drawbacks, 307
18.2 The Principle of Mixed-Reactant Supply: Mixed-Reactant Fuel Cells, 308
18.3 Coplanar Fuel Cell Design: Strip Cells, 310
18.4 The Flow-Through Electrode Principle, 312
18.5 Single-Chamber SOFCs, 313
18.6 Microfluidic Fuel Cells, 319
References, 321
PART IV COMMERCIALIZATION OF FUEL CELLS 325
19 Applications 327
19.1 Large Stationary Power Plants, 327
19.2 Small Stationary Power Units, 332
19.3 Fuel Cells for Transport Applications, 335
19.4 Portables, 341
19.5 Military Applications, 345
19.6 Handicaps Preventing a Broader Commercialization of Fuel Cells, 347
References, 348
20 Fuel Cell Work in Various Countries 351
20.1 Driving Forces for Fuel Cell Work, 351
20.2 Fuel Cells and the Hydrogen Economy, 353
20.3 Activities in North America, 355
20.4 Activities in Europe, 356
20.5 Activities in other Countries, 357
20.6 The Volume of Published Fuel Cell Work, 359
20.7 Legislation and Standardization in the Field of Fuel Cells, 361
References, 362
21 Outlook 363
21.1 Periods of Alternating Hope and Disappointment, 363
21.2 Some Misconceptions, 364
Klaus Müller
21.3 Ideal Fuel Cells, 366
21.4 Projected Future of Fuel Cells, 368
References, 369
GENERAL BIBLIOGRAPHY 371
AUTHOR INDEX 373
SUBJECT INDEX 379
