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.

Autorentext

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.

Inhalt
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: DebyeHückel 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 ButlerVolmer Kinetic Expression 46

3.4 Reaction Fundamentals 49

3.5 Simplified Forms of the ButlerVolmer Equation 50

3.6 Direct Fitting of the ButlerVolmer 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 NernstPlanck 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 GasLiquid 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 <p...