Fuel Cells: Problems and Solutions Book

Preface xi

Symbols xiii

Acronyms And Abbreviations xv

I Introduction 1

Introduction 3

1 The Working Principles Of A Fuel Cell 7

1.1 Thermodynamic Aspects 7

1.2 Schematic Layout of Fuel Cell Units 11

1.3 Types of Fuel Cells 15

1.4 Layout of a Real Fuel Cell: The Hydrogen-Oxygen Fuel Cell wth Liquid Electrolyte 15

1.5 Basic Parameters of Fuel Cells 20

Reference 26

2 The Long History Of Fuel Cells 27

2.1 The Period Prior to 1894 27

2.2 The Period from 1894 to 1960 30

2.3 The Period from 1960 to the 1990s 33

2.4 The Period After the 1990s 39

References 40

II Major Types Of Fuel Cells 43

3 Proton-Exchange Membrane Fuel Cells 45

3.1 History of the PEMFC 46

3.2 Standard PEMFC Version from the 1990s 49

3.3 Special Features of PEMFC Operation 54

3.4 Platinum Catalyst Poisoning by Traces of CO in the Hydrogen 57

3.5 Commercial Activities in Relation to PEMFCs 59

3.6 Future Development of PEMFCs 60

3.7 Elevated-Temperature PEMFCs 67

References 70

4 Direct Liquid Fuel Cells 73

Part A Direct Methanol Fuel Cells 73

4.1 Methanol as a Fuel for Fuel Cells 73

4.2 Current-Producing Reactions and thermodynamic Parameters 74

4.3 Anodic Oxidation of Methanol 74

4.4 Milestones in DMFC Development 76

4.5 Membrane Penetration by Methanol (Methanol Crossover) 77

4.6 Varieties of DMFCs 79

4.7 Special Operating Features of DMFCs 81

4.8 Practical Models of DMFCs and Their Features 83

4.9 Problems To Be Solved in Future DMFCs 85

Part B Direct Liquid Fuel Cells 87

4.10 The Problem of Replacing Methanol 87

4.11 Fuel Cells Using Organic Liquids as Fuels 88

4.12 Fuel Cells Using Inorganic Liquids as Fuels 94

References 97

5Phosphoric Acid Fuel Cells 101

5.1 Early Work on Phosphoric Acid Fuel Cells 101

5.2 Special Features of Aqueous Phosphoric Acid Solutions 102

5.3 Construction of PAFCs 103

5.4 Commercial Production of PAFCs 104

5.5 Development of Large Stationary Power Plants 105

5.6 The Future of PAFCs 105

5.7 Importance of PAFCs for Fuel Cell Development 107

References 107

6 Alkaline Fuel Cells 109

6.1 Hydrogen-Oxygen AFCs 110

6.2 Alkaline Hydrazine Fuel Cells 117

6.3 Anion-Exchange (Hydroxyl Ion-Conducting) Membranes 121

6.4 Methanol Fuel Cells with Anion-Exchange Membranes 122

6.5 Methanol Fuel Cell with an Invariant Alkaline Electrolyte 123

References 123

7 Molten Carbonate Fuel Cells 125

7.1 Special Features of High-Temperature Fuel Cells 125

7.2 Structure of Hydrogen-Oxygen MCFCs 126

7.3 MCFCs with Internal Fuel Reforming 128

7.4 Development of MCFC Work 130

7.5 The Lifetime of MCFCs 131

References 133

8 Solid-Oxide Fuel Cells 135

8.1 Schematic Design of Conventional SOFCs 136

8.2 Tubular SOFCs 138

8.3 Planar SOFCs 143

8.4 Monolithic SOFCs 146

8.5 Varieties of SOFCs 147

8.6 Utilization of Natural Fuels in SOFCs 149

8.7 Interim-Temperature SOFCs 151

8.8 Low-Temperature SOFCs 155

8.9 Factors Influencing the Lifetime of SOFCs 157

References 158

9 Other Types Of Fuel Cells 161

9.1 Redox Flow Cells 161

9.2 Biological Fuel Cells 164

9.3 Semi-Fuel Cells 167

9.4 Direct Carbon Fuel Cells 170

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

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 Plantinum 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 219

12.6 Electrocatalysis of the Oxygen Reduction Reaction 221

12.7 The Stability of Electrocatalysts 227

References 228

13 Membranes 231

13.1 Fuel Cell-Related Membrane Problems 232

13.2 Work to Overcome Degradation of Nafion Membranes 233

13.3 Modification of Nafion Membranes 233

13.4 Membranes Made from Polymers Without Fluorine 235

13.5 Membranes Made from Other Materials 237

13.6 Matrix-Type Membranes 237

13.7 Membranes with Hydroxyl Ion Conduction 238

References 239

14 Small Fuel Cells For Portable Devices 241

14.1 Special Operating Features of Mini-Fuel Cells 242

14.2 Flat Miniature Fuel Batteries 243

14.3 Silicon-Based Mini-Fuel Cells 245

14.4 PCB-Based Mini-Fuel Cells 247

14.5 Mini-Solid Oxide Fuel Cells 248

14.6 The Problem of Air-Breathing Cathodes 249

14.7 Prototypes of Power Units with Mini-Fuel Cells 250

14.8 Concluding Remarks 253

References 253

15 Mathematical Modeling Of Fuel Cells Felix N. Buchi 255

15.1 Zero-Dimensional Models 257

15.2 One-Dimensional Models 257

15.3 Two-Dimensional Models 258

15.4 Three-Dimensional Models 259

15.5 Concluding Remarks 260

References 260

IV Commercialization Of Fuel Cells 263

16 Applications 265

16.1 Large Stationary Power Plants 265

16.2 Small Stationary Power Units 269

16.3 Fuel Cells for Transport Applications 272

16.4 Portables 277

16.5 Military Applications 281

References 283

17 Fuel Cell Work In Various Countries 285

17.1 Driving Forces for Fuel Cell Work 285

17.2 Fuel Cells and the Hydrogen Economy 287

17.3 Activities in North America 289

17.4 Activities in Europe 290

17.5 Activities in Other Countries 291

17.6 The Volume of Published Fuel Cell Work 294

17.7 Legislation and Standardization in the Field of Fuel Cells 295

References 296

18 Outlook 297

18.1 Periods of Alternating Hope and Disappointment 297

18.2 Some Misconceptions Klaus Muller 299

18.3 Ideal Fuel Cells 300

18.4 Projected Future of Fuel Cells 302

References 304

General Bibliography 305

Author Index 309

Subject Index 315