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. Electrochemical Engineering 1 Contents 6 Preface 10 List of Symbols 12 About the Companion Website 16 Chapter 1: Introduction and Basic Principles 20 1.1 Electrochemical Cells 20 1.2 Characteristics of Electrochemical Reactions 21 1.3 Importance of Electrochemical Systems 23 1.4 Scientific Units, Constants, Conventions 24 1.5 Faraday’s Law 25 1.6 Faradaic Efficiency 27 1.7 Current Density 28 1.8 Potential and Ohm’s Law 28 1.9 Electrochemical Systems: Example 29 Closure 32 Further Reading 32 Problems 32 Chapter 2: Cell Potential and Thermodynamics 34 2.1 Electrochemical Reactions 34 2.2 Cell Potential 34 2.3 Expression for Cell Potential 36 2.4 Standard Potentials 37 2.5 Effect of Temperature on Standard Potential 40 2.6 Simplified Activity Correction 41 2.7 Use of the Cell Potential 43 2.8 Equilibrium Constants 44 2.9 Pourbaix Diagrams 44 2.10 Cells with a Liquid Junction 46 2.11 Reference Electrodes 46 2.12 Equilibrium at Electrode Interface 49 2.13 Potential in Solution Due to Charge: Debye–Hückel Theory 50 2.14 Activities and Activity Coefficients 52 2.15 Estimation of Activity Coefficients 54 Closure 55 Further Reading 55 Problems 55 Chapter 3: Electrochemical Kinetics 60 3.1 Double Layer 60 3.2 Impact of Potential on Reaction Rate 61 3.3 Use of the Butler–Volmer Kinetic Expression 65 3.4 Reaction Fundamentals 68 3.5 Simplified Forms of the Butler–Volmer Equation 69 3.6 Direct Fitting of the Butler–Volmer Equation 71 3.7 The Influence of Mass Transfer on the Reaction Rate 73 3.8 Use of Kinetic Expressions in Full Cells 74 3.9 Current Efficiency 77 Closure 77 Further Reading 78 Problems 78 Chapter 4: Transport 82 4.1 Fick’s Law 82 4.2 Nernst–Planck Equation 82 4.3 Conservation of Material 84 4.4 Transference Numbers, Mobilities, and Migration 90 4.5 Convective Mass Transfer 94 4.6 Concentration Overpotential 98 4.7 Current Distribution 101 4.8 Membrane Transport 105 Closure 107 Further Reading 107 Problems 107 Chapter 5: Electrode Structures and Configurations 112 5.1 Mathematical Description of Porous Electrodes 113 5.2 Characterization of Porous Electrodes 115 5.3 Impact of Porous Electrode on Transport 116 5.4 Current Distributions in Porous Electrodes 117 5.5 The Gas–Liquid Interface in Porous Electrodes 121 5.6 Three-Phase Electrodes 122 5.7 Electrodes with Flow 124 Closure 127 Further Reading 127 Problems 127 Chapter 6: Electroanalytical Techniques and Analysis of Electrochemical Systems 132 6.1 Electrochemical Cells, Instrumentation, and Some Practical Issues 132 6.2 Overview 134 6.3 Step Change in Potential or Current for a Semi-Infinite Planar Electrode in a Stagnant Electrolyte 135 6.4 Electrode Kinetics and Double-Layer Charging 137 6.5 Cyclic Voltammetry 141 6.6 Stripping Analyses 146 6.7 Electrochemical Impedance 148 6.8 Rotating Disk Electrodes 155 6.9 iR Compensation 158 6.10 Microelectrodes 160 Closure 164 Further Reading 164 Problems 164 Chapter 7: Battery Fundamentals 170 7.1 Components of a Cell 170 7.2 Classification of Batteries and Cell Chemistries 171 7.3 Theoretical Capacity and State of Charge 175 7.4 Cell Characteristics and Electrochemical Performance 177 7.5 Ragone Plots 182 7.6 Heat Generation 183 7.7 Efficiency of Secondary Cells 185 7.8 Charge Retention and Self-Discharge 186 7.9 Capacity Fade in Secondary Cells 187 Closure 188 Further Reading 188 Problems 188 Chapter 8: Battery Applications: Cell and Battery Pack Design 194 8.1 Introduction to Battery Design 194 8.2 Battery Layout Using a Specific Cell Design 195 8.3 Scaling of Cells to Adjust Capacity 197 8.4 Electrode and Cell Design to Achieve Rate Capability 200 8.5 Cell Construction 202 8.6 Charging of Batteries 203 8.7 Use of Resistance to Characterize Battery Peformance 204 8.8 Battery Management 205 8.9 Thermal Management Systems 207 8.10 Mechanical Considerations 209 Closure 210 Further Reading 210 Problems 210 Chapter 9: Fuel-Cell Fundamentals 214 9.1 Introduction 214 9.2 Types of Fuel Cells 216 9.3 Current–Voltage Characteristics and Polarizations 217 9.4 Effect of Operating Conditions and Maximum Power 221 9.5 Electrode Structure 224 9.6 Proton-Exchange Membrane (PEM) Fuel Cells 225 9.7 Solid Oxide Fuel Cells 230 Closure 234 Further Reading 234 Problems 235 Chapter 10: Fuel-Cell Stack and System Design 242 10.1 Introduction and Overview of Systems Analysis 242 10.2 Basic Stack Design Concepts 245 10.3 Cell Stack Configurations 247 10.4 Basic Construction and Components 248 10.5 Utilization of Oxidant and Fuel 250 10.6 Flow-Field Design 254 10.7 Water and Thermal Management 257 10.8 Structural–Mechanical Considerations 260 10.9 Case Study 264 Closure 266 Further Reading 266 Problems 266 Chapter 11: Electrochemical Double-Layer Capacitors 270 11.1 Capacitor Introduction 270 11.2 Electrical Double-Layer Capacitance 272 11.3 Current–Voltage Relationship for Capacitors 278 11.4 Porous EDLC Electrodes 280 11.5 Impedance Analysis of EDLCs 282 11.6 Full Cell EDLC Analysis 285 11.7 Power and Energy Capabilities 286 11.8 Cell Design, Practical Operation, and Electrochemical Capacitor Performance 288 11.9 Pseudo-Capacitance 290 Closure 292 Further Reading 292 Problems 292 Chapter 12: Energy Storage and Conversion for Hybrid and Electrical Vehicles 296 12.1 Why Electric and Hybrid-Electric Systems? 296 12.2 Driving Schedules and Power Demand in Vehicles 298 12.3 Regenerative Braking 300 12.4 Battery Electrical Vehicle 301 12.5 Hybrid Vehicle Architectures 303 12.6 Start–Stop Hybrid 304 12.7 Batteries for Full-Hybrid Electric Vehicles 306 12.8 Fuel-Cell Hybrid Systems for Vehicles 310 Closure 312 Further Reading 313 Problems 313 Appendix: Primer on Vehicle Dynamics 314 Chapter 13: Electrodeposition 318 13.1 Overview 318 13.2 Faraday’s Law and Deposit Thickness 319 13.3 Electrodeposition Fundamentals 319 13.4 Formation of Stable Nuclei 322 13.5 Nucleation Rates 324 13.6 Growth of Nuclei 327 13.7 Deposit Morphology 329 13.8 Additives 330 13.9 Impact of Current Distribution 331 13.10 Impact of Side Reactions 333 13.11 Resistive Substrates 335 Closure 338 Further Reading 338 Problems 338 Chapter 14: Industrial Electrolysis, Electrochemical Reactors, and Redox-Flow Batteries 342 14.1 Overview of Industrial Electrolysis 342 14.2 Performance Measures 343 14.3 Voltage Losses and the Polarization Curve 347 14.4 Design of Electrochemical Reactors for Industrial Applications 350 14.5 Examples of Industrial Electrolytic Processes 356 14.6 Thermal Management and Cell Operation 360 14.7 Electrolytic Processes for a Sustainable Future 362 14.8 Redox-Flow Batteries 367 Closure 369 Further Reading 369 Problems 369 Chapter 15: Semiconductor Electrodes and Photoelectrochemical Cells 374 15.1 Semiconductor Basics 374 15.2 Energy Scales 377 15.3 Semiconductor–Electrolyte Interface 379 15.4 Current Flow in the Dark 382 15.5 Light Absorption 385 15.6 Photoelectrochemical Effects 387 15.7 Open-Circuit Voltage for Illuminated Electrodes 388 15.8 Photo-Electrochemical Cells 389 Closure 394 Further Reading 394 Problems 394 Chapter 16: Corrosion 398 16.1 Corrosion Fundamentals 398 16.2 Thermodynamics of Corrosion Systems 399 16.3 Corrosion Rate for Uniform Corrosion 402 16.4 Localized Corrosion 409 16.5 Corrosion Protection 413 Closure 418 Further Reading 418 Problems 418 Appendix A: Electrochemical Reactions and Standard Potentials 422 Appendix B: Fundamental Constants 423 Appendix C: Thermodynamic Data 424 Appendix D: Mechanics of Materials 427 Index 432 End User License Agreement -1 "This book covers both fundamental principles and applications of electrochemical engineering. The goal is to create a text for classroom instruction or independent study at the senior undergraduate and beginning graduate student level. It provides numerous worked out illustrations as well as a large number of end-of chapter problems. A supplementary solution manual has been developed"-- Provided by publisher "This book covers both fundamental principles and applications of electrochemical engineering. The goal is to create a text for classroom instruction or independent study at the senior undergraduate and beginning graduate student level. It provides numerous worked out illustrations as well as a large number of end-of chapter problems. A supplementary solution manual has been developed"-- Résumé de l'éditeur