Fuel Cells: Problems and Solutions, Second Edition

Vladimir S. Bagotsky is an acclaimed scientist in the field of electrochemical phenomena. A former department head at the Moscow Power Sources Institute, where he supervised the development of fuel cells for various national and international projects, including the Sputnik satellites, Dr. Bagotsky also spent twenty years as a department head and principal scientist at the A. N. Frumkin Institute of Physical Chemistry and Electrochemistry. He has published more than 400 papers in scientific journals and in 2010 was acknowledged by the ECS for his sixty-five years spent working in theoretical electrochemistry, electrocatalysis, and applied electrochemistry.

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 Muller 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