Preface ix
List of Symbols xi
About the Companion Website xv
1. Introduction and Basic Principles 1
Charles W. Tobias
1.1 Electrochemical Cells 1
1.2 Characteristics of Electrochemical Reactions 2
1.3 Importance of Electrochemical Systems 4
1.4 Scientific Units, Constants, Conventions 5
1.5 Faraday's Law 6
1.6 Faradaic Efficiency 8
1.7 Current Density 9
1.8 Potential and Ohm's Law 9
1.9 Electrochemical Systems: Example 10
Closure 13
Further Reading 13
Problems 13
2. Cell Potential and Thermodynamics 15
Wendell Mitchell Latimer
2.1 Electrochemical Reactions 15
2.2 Cell Potential 15
2.3 Expression for Cell Potential 17
2.4 Standard Potentials 18
2.5 Effect of Temperature on Standard Potential 21
2.6 Simplified Activity Correction 22
2.7 Use of the Cell Potential 24
2.8 Equilibrium Constants 25
2.9 Pourbaix Diagrams 25
2.10 Cells with a Liquid Junction 27
2.11 Reference Electrodes 27
2.12 Equilibrium at Electrode Interface 30
2.13 Potential in Solution Due to Charge: Debye-Huckel Theory 31
2.14 Activities and Activity Coefficients 33
2.15 Estimation of Activity Coefficients 35
Closure 36
Further Reading 36
Problems 36
3. Electrochemical Kinetics 41
Alexander Naumovich Frumkin
3.1 Double Layer 41
3.2 Impact of Potential on Reaction Rate 42
3.3 Use of the Butler-Volmer Kinetic Expression 46
3.4 Reaction Fundamentals 49
3.5 Simplified Forms of the Butler-Volmer Equation 50
3.6 Direct Fitting of the Butler-Volmer Equation 52
3.7 The Influence of Mass Transfer on the Reaction Rate 54
3.8 Use of Kinetic Expressions in Full Cells 55
3.9 Current Efficiency 58
Closure 58
Further Reading 59
Problems 59
4. Transport 63
Carl Wagner
4.1 Fick's Law 63
4.2 Nernst-Planck Equation 63
4.3 Conservation of Material 65
4.4 Transference Numbers, Mobilities, and Migration 71
4.5 Convective Mass Transfer 75
4.6 Concentration Overpotential 79
4.7 Current Distribution 81
4.8 Membrane Transport 86
Closure 87
Further Reading 88
Problems 88
5. Electrode Structures and Configurations 93
John Newman
5.1 Mathematical Description of Porous Electrodes 94
5.2 Characterization of Porous Electrodes 96
5.3 Impact of Porous Electrode on Transport 97
5.4 Current Distributions in Porous Electrodes 98
5.5 The Gas-Liquid Interface in Porous Electrodes 102
5.6 Three-Phase Electrodes 103
5.7 Electrodes with Flow 105
Closure 108
Further Reading 108
Problems 108
6. Electroanalytical Techniques and Analysis of Electrochemical Systems 113
Jaroslav Heyrovsky
6.1 Electrochemical Cells, Instrumentation, and Some Practical Issues 113
6.2 Overview 115
6.3 Step Change in Potential or Current for a Semi-Infinite Planar Electrode in a Stagnant Electrolyte 116
6.4 Electrode Kinetics and Double-Layer Charging 118
6.5 Cyclic Voltammetry 122
6.6 Stripping Analyses 127
6.7 Electrochemical Impedance 129
6.8 Rotating Disk Electrodes 136
6.9 iR Compensation 139
6.10 Microelectrodes 141
Closure 145
Further Reading 145
Problems 145
7. Battery Fundamentals 151
John B. Goodenough
7.1 Components of a Cell 151
7.2 Classification of Batteries and Cell Chemistries 152
7.3 Theoretical Capacity and State of Charge 156
7.4 Cell Characteristics and Electrochemical Performance 158
7.5 Ragone Plots 163
7.6 Heat Generation 164
7.7 Efficiency of Secondary Cells 166
7.8 Charge Retention and Self-Discharge 167
7.9 Capacity Fade in Secondary Cells 168
Closure 169
Further Reading 169
Problems 169
8. Battery Applications: Cell and Battery Pack Design 175
Esther Sans Takeuchi
8.1 Introduction to Battery Design 175
8.2 Battery Layout Using a Specific Cell Design 176
8.3 Scaling of Cells to Adjust Capacity 178
8.4 Electrode and Cell Design to Achieve Rate Capability 181
8.5 Cell Construction 183
8.6 Charging of Batteries 184
8.7 Use of Resistance to Characterize Battery Peformance 185
8.8 Battery Management 186
8.9 Thermal Management Systems 188
8.10 Mechanical Considerations 190
Closure 191
Further Reading 191
Problems 191
9. Fuel-Cell Fundamentals 195
Supramaniam Srinivasan
9.1 Introduction 195
9.2 Types of Fuel Cells 197
9.3 Current-Voltage Characteristics and Polarizations 198
9.4 Effect of Operating Conditions and Maximum Power 202
9.5 Electrode Structure 205
9.6 Proton-Exchange Membrane (PEM) Fuel Cells 206
9.7 Solid Oxide Fuel Cells 211
Closure 215
Further Reading 215
Problems 216
10. Fuel-Cell Stack and System Design 223
Francis Thomas Bacon
10.1 Introduction and Overview of Systems Analysis 223
10.2 Basic Stack Design Concepts 226
10.3 Cell Stack Configurations 228
10.4 Basic Construction and Components 229
10.5 Utilization of Oxidant and Fuel 231
10.6 Flow-Field Design 235
10.7 Water and Thermal Management 238
10.8 Structural-Mechanical Considerations 241
10.9 Case Study 245
Closure 247
Further Reading 247
Problems 247
11. Electrochemical Double-Layer Capacitors 251
Brian Evans Conway
11.1 Capacitor Introduction 251
11.2 Electrical Double-Layer Capacitance 253
11.3 Current-Voltage Relationship for Capacitors 259
11.4 Porous EDLC Electrodes 261
11.5 Impedance Analysis of EDLCs 263
11.6 Full Cell EDLC Analysis 266
11.7 Power and Energy Capabilities 267
11.8 Cell Design, Practical Operation, and Electrochemical Capacitor Performance 269
11.9 Pseudo-Capacitance 271
Closure 273
Further Reading 273
Problems 273
12. Energy Storage and Conversion for Hybrid and Electrical Vehicles 277
Ferdinand Porsche
12.1 Why Electric and Hybrid-Electric Systems? 277
12.2 Driving Schedules and Power Demand in Vehicles 279
12.3 Regenerative Braking 281
12.4 Battery Electrical Vehicle 282
12.5 Hybrid Vehicle Architectures 284
12.6 Start-Stop Hybrid 285
12.7 Batteries for Full-Hybrid Electric Vehicles 287
12.8 Fuel-Cell Hybrid Systems for Vehicles 291
Closure 293
Further Reading 294
Problems 294
Appendix: Primer on Vehicle Dynamics 295
13. Electrodeposition 299
Richard C. Alkire
13.1 Overview 299
13.2 Faraday's Law and Deposit Thickness 300
13.3 Electrodeposition Fundamentals 300
13.4 Formation of Stable Nuclei 303
13.5 Nucleation Rates 305
13.6 Growth of Nuclei 308
13.7 Deposit Morphology 310
13.8 Additives 311
13.9 Impact of Current Distribution 312
13.10 Impact of Side Reactions 314
13.11 Resistive Substrates 316
Closure 319
Further Reading 319
Problems 319
14. Industrial Electrolysis, Electrochemical Reactors, and Redox-Flow Batteries 323
Fumio Hine
14.1 Overview of Industrial Electrolysis 323
14.2 Performance Measures 324
14.3 Voltage Losses and the Polarization Curve 328
14.4 Design of Electrochemical Reactors for Industrial Applications 331
14.5 Examples of Industrial Electrolytic Processes 337
14.6 Thermal Management and Cell Operation 341
14.7 Electrolytic Processes for a Sustainable Future 343
14.8 Redox-Flow Batteries 348
Closure 350
Further Reading 350
Problems 350
15. Semiconductor Electrodes and Photoelectrochemical Cells 355
Heinz Gerischer
15.1 Semiconductor Basics 355
15.2 Energy Scales 358
15.3 Semiconductor-Electrolyte Interface 360
15.4 Current Flow in the Dark 363
15.5 Light Absorption 366
15.6 Photoelectrochemical Effects 368
15.7 Open-Circuit Voltage for Illuminated Electrodes 369
15.8 Photo-Electrochemical Cells 370
Closure 375
Further Reading 375
Problems 375
16. Corrosion 379
Ulick Richardson Evans
16.1 Corrosion Fundamentals 379
16.2 Thermodynamics of Corrosion Systems 380
16.3 Corrosion Rate for Uniform Corrosion 383
16.4 Localized Corrosion 390
16.5 Corrosion Protection 394
Closure 399
Further Reading 399
Problems 399
Appendix A: Electrochemical Reactions and Standard Potentials 403
Appendix B: Fundamental Constants 404
Appendix C: Thermodynamic Data 405
Appendix D: Mechanics of Materials 408
Index 413
