Electrochemical Engineering

A Comprehensive Reference for Electrochemical Engineering Theory and Application

From chemical and electronics manufacturing, to hybrid vehicles, energy storage, and beyond, electrochemical engineering touches many industries—any many lives—every day. As energy conservation becomes of central importance, so too does the science that helps us reduce consumption, reduce waste, and lessen our impact on the planet. Electrochemical Engineering provides a reference for scientists and engineers working with electrochemical processes, and a rigorous, thorough text for graduate students and upper-division undergraduates.

Merging theoretical concepts with widespread application, this book is designed to provide critical knowledge in a real-world context. Beginning with the fundamental principles underpinning the field, the discussion moves into industrial and manufacturing processes that blend central ideas to provide an advanced understanding while explaining observable results. Fully-worked illustrations simplify complex processes, and end-of chapter questions help reinforce essential knowledge.

With in-depth coverage of both the practical and theoretical, this book is both a thorough introduction to and a useful reference for the field. Rigorous in depth, yet grounded in relevance, Electrochemical Engineering: 

• Introduces basic principles from the standpoint of practical application
• Explores the kinetics of electrochemical reactions with discussion on thermodynamics, reaction fundamentals, and transport
• Covers battery and fuel cell characteristics, mechanisms, and system design
• Delves into the design and mechanics of hybrid and electric vehicles, including regenerative braking, start-stop hybrids, and fuel cell systems
• Examines electrodeposition, redox-flow batteries, electrolysis, regenerative fuel cells, semiconductors, and other applications of electrochemical engineering principles

Overlapping chemical engineering, chemistry, material science, mechanical engineering, and electrical engineering, electrochemical engineering covers a diverse array of phenomena explained by some of the important scientific discoveries of our time. Electrochemical Engineering provides the critical understanding required to work effectively with these processes as they become increasingly central to global sustainability.

THOMAS F. FULLER is Professor of Chemical & Biomolecular Engineering at Georgia Institute of Technology and a Technical Editor for the Journal of the Electrochemical Society, responsible for fuel cells, electrolyzers, and energy conversion.

JOHN N. HARB is Professor of Chemical Engineering in the Ira A. Fulton College of Engineering and Technology at Brigham Young University.

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–Hückel 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 Heyrovský

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

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