[内容简介]
Supercapacitors are a relatively new energy storage system that provides higher energy density than dielectric capacitors and higher power density than batteries. They are particularly suited to applications that require energy pulses during short periods of time, e.g., seconds or tens of seconds. They are recommended for automobiles, tramways, buses, cranes, fork-lifts, wind turbines, electricity load leveling in stationary and transportation systems, etc. Despite the technological maturity of supercapacitors, there is a lack of comprehensive literature on the topic. Many high performance materials have been developed and new scientific concepts have been introduced. Taking into account the commercial interest in these systems and the new scientific and technological developments now is the ideal time to publish this book, capturing all this new knowledge. The book starts by giving an introduction to the general principles of electrochemistry, the properties of electrochemical capacitors, and electrochemical characterization techniques. Electrical double layer capacitors and pseudocapacitors are then discussed, followed by the various electrolyte systems. Modelling, manufacture of industrial capacitors, constraints, testing, and reliability as well as applications are also covered. 'Supercapacitors - Materials, Systems, and Applications' is part of the series on Materials for
Sustainable Energy and Development edited by Prof. G.Q. Max Lu. The series covers advances in materials science and innovation for renewable energy, clean use of fossil energy, and greenhouse gas mitigation and associated environmental technologies.
[目录]
Series Editor Preface XVII
Preface XIX
About the Series Editor XXI
About the Volume Editors XXIII
List of Contributors XXV
1 General Principles of Electrochemistry 1
Scott W. Donne
1.1 Equilibrium Electrochemistry 1
1.1.1 Spontaneous Chemical Reactions 1
1.1.2 The Gibbs Energy Minimum 1
1.1.3 Bridging the Gap between Chemical Equilibrium and Electrochemical Potential 3
1.1.4 The Relation between E and Gr 3
1.1.5 The Nernst Equation 4
1.1.6 Cells at Equilibrium 5
1.1.7 Standard Potentials 5
1.1.8 Using the Nernst Equation – Eh–pH Diagrams 6
1.2 Ionics 6
1.2.1 Ions in Solution 6
1.2.1.1 Ion–Solvent Interactions 7
1.2.1.2 Thermodynamics 8
1.2.2 The Born or Simple Continuum Model 8
1.2.2.1 Testing the Born Equation 9
1.2.3 The Structure of Water 9
1.2.3.1 Water Structure near an Ion 11
1.2.3.2 The Ion–Dipole Model 11
1.2.3.3 Cavity Formation 12
1.2.3.4 Breaking up the Cluster 12
1.2.3.5 Ion–Dipole Interaction 12
1.2.3.6 The Born Energy 13
1.2.3.7 Orienting the Solvated Ion in the Cavity 13
1.2.3.8 The Leftover Water Molecules 14
1.2.3.9 Comparison with Experiment 14
1.2.3.10 The Ion–Quadrupole Model 14
1.2.3.11 The Induced Dipole Interaction 14
1.2.3.12 The Results 15
1.2.3.13 Enthalpy of Hydration of the Proton 15
1.2.4 The Solvation Number 16
1.2.4.1 Coordination Number 16
1.2.4.2 The Primary Solvation Number 16
1.2.5 Activity and Activity Coefficients 16
1.2.5.1 Fugacity (f ) 16
1.2.5.2 Dilute Solutions of Nonelectrolytes 16
1.2.5.3 Activity (a) 17
1.2.5.4 Standard States 17
1.2.5.5 Infinite Dilution 18
1.2.5.6 Measurement of Solvent Activity 18
1.2.5.7 Measurement of Solute Activity 18
1.2.5.8 Electrolyte Activity 18
1.2.5.9 Mean Ion Quantities 19
1.2.5.10 Relation between f, γ, andy 19
1.2.6 Ion–Ion Interactions 20
1.2.6.1 Introduction 20
1.2.6.2 Debye–Huckel Model for Calculating ψ2 21
1.2.6.3 Poisson–Boltzmann Equation 22
1.2.6.4 Charge Density 22
1.2.6.5 Solving the Poisson–Boltzmann Equation 23
1.2.6.6 Calculation of μi−I 24
1.2.6.7 Debye Length, K−1 or LD 24
1.2.6.8 The Activity Coefficient 24
1.2.6.9 Comparison with Experiment 26
1.2.6.10 Approximations of the Debye–Huckel Limiting Law 26
1.2.6.11 The Distance of Closest Approach 27
1.2.6.12 Physical Interpretation of the Activity Coefficient 27
1.2.7 Concentrated Electrolyte Solutions 27
1.2.7.1 The Stokes–Robinson Treatment 27
1.2.7.2 The Ion-Hydration Correction 28
1.2.7.3 The Concentration Correction 28
1.2.7.4 The Stokes–Robinson Equation 29
1.2.7.5 Evaluation of the Stokes–Robinson Equation 29
1.2.8 Ion Pair Formation 29
1.2.8.1 Ion Pairs 29
1.2.8.2 The Fuoss Treatment 30
1.2.9 Ion Dynamics 32
1.2.9.1 Ionic Mobility and Transport Numbers 32
1.2.9.2 Diffusion 33
1.2.9.3 Fick’s Second Law 33
1.2.9.4 Diffusion Statistics 35
1.3 Dynamic Electrochemistry 36
1.3.1 Review of Fundamentals 36
1.3.1.1 Potential 36
1.3.1.2 Potential inside a Good Conductor 37
1.3.1.3 Charge on a Good Conductor 37
1.3.1.4 Force between Charges 37
1.3.1.5 Potential due to an Assembly of Charges 37
1.3.1.6 Potential Difference between Two Phases in Contact (φ) 38
1.3.1.7 The Electrochemical Potential (μ) 39
1.3.2 The Electrically Charged Interface or Double Layer 39
1.3.2.1 The Interface 39
1.3.2.2 Ideally Polarized Electrode 40
1.3.2.3 The Helmholtz Model 40
1.3.2.4 Gouy–Chapman or Diffuse Model 42
1.3.2.5 The Stern Model 43
1.3.2.6 The Bockris, Devanathan, and Muller Model 45
1.3.2.7 Calculation of the Capacitance 48
1.3.3 Charge Transfer at the Interface 49
1.3.3.1 Transition State Theory 49
1.3.3.2 Redox Charge-Transfer Reactions 50
1.3.3.3 The Act of Charge Transfer 53
1.3.3.4 The Butler–Volmer Equation 55
1.3.3.5 I in Terms of the Standard Rate Constant (k0) 56
1.3.3.6 Relation between k0 and I0 56
1.3.4 Multistep Processes 57
1.3.4.1 The Multistep Butler–Volmer Equation 57
1.3.4.2 Rules for Mechanisms 58
1.3.4.3 Concentration Dependence of I0 59
1.3.4.4 Charge-Transfer Resistance (Rct) 60
1.3.4.5 Whole Cell Voltages 60
1.3.5 Mass Transport Control 61
1.3.5.1 Diffusion and Migration 61
1.3.5.2 The Limiting Current Density (IL) 62
1.3.5.3 Rotating Disk Electrode 64
Further Reading 64
2 General Properties of Electrochemical Capacitors 69
Tony Pandolfo, Vanessa Ruiz, Seepalakottai Sivakkumar, and Jawahr Nerkar
2.1 Introduction 69
2.2 Capacitor Principles 70
2.3 Electrochemical Capacitors 71
2.3.1 Electric Double-Layer Capacitors 75
2.3.1.1 Double-Layer and Porous Materials Models 75
2.3.1.2 EDLC Construction 77
2.3.2 Pseudocapacitive Electrochemical Capacitors 86
2.3.2.1 Electronically Conducting Polymers 87
2.3.2.2 Transition Metal Oxides 93
2.3.2.3 Lithium-Ion Capacitors 98
2.4 Summary 100
Acknowledgments 101
References 101
3 Electrochemical Techniques 111
Pierre-Louis Taberna and Patrice Simon
3.1 Electrochemical Apparatus 111
3.2 Electrochemical Cell 111
3.3 Electrochemical Interface: Supercapacitors 114
3.4 Most Used Electrochemical Techniques 115
3.4.1 Transient Techniques 115
3.4.1.1 Cyclic Voltammetry 115
3.4.1.2 Galvanostatic Cycling 117
3.4.2 Stationary Technique 119
3.4.2.1 Electrochemical Impedance Spectroscopy 119
3.4.2.2 Supercapacitor Impedance 124
References 129
4 Electrical Double-Layer Capacitors and Carbons for EDLCs 131
Patrice Simon, Pierre-Louis Taberna, and Fran¸cois B´eguin
4.1 Introduction 131
4.2 The Electrical Double Layer 132
4.3 Types of Carbons Used for EDLCs 135
4.3.1 Activated Carbon Powders 135
4.3.2 Activated Carbon Fabrics 137
4.3.3 Carbon Nanotubes 138
4.3.4 Carbon Aerogels 138
4.4 Capacitance versus Pore Size 138
4.5 Evidence of Desolvation of Ions 141
4.6 Performance Limitation: Pore Accessibility or Saturation of Porosity 148
4.6.1 Limitation by Pore Accessibility 148
4.6.2 Limitation of Capacitor Performance by Porosity Saturation 150
4.7 Beyond the Double-Layer Capacitance in Microporous Carbons 153
4.7.1 Microporous Carbons in Neat Ionic Liquid Electrolyte 153
4.7.2 Extra Capacitance with Ionic Liquids in Solution 157
4.7.3 Ions Trapping in Pores 159
4.7.4 Intercalation/Insertion of Ions 161
4.8 Conclusions 162
References 163
5 Modern Theories of Carbon-Based Electrochemical Capacitors 167
Jingsong Huang, Rui Qiao, Guang Feng, Bobby G. Sumpter, and Vincent Meunier
5.1 Introduction 167
5.1.1 Carbon-Based Electrochemial Capacitors 167
5.1.2 Elements of EDLCs 169
5.2 Classical Theories 172
5.2.1 Compact Layer at the Interface 172
5.2.2 Diffuse Layer in the Electrolyte 173
5.2.3 Space Charge Layer in the Electrodes 175
5.3 Recent Developments 176
5.3.1 Post-Helmholtz Models with Surface Curvature Effects 176
5.3.1.1 Models for Endohedral Capacitors 176
5.3.1.2 Models for Hierarchically Porous Carbon Materials 185
5.3.1.3 Models for Exohedral Capacitors 187
5.3.2 EDL Theories Beyond the GCS Model 189
5.3.3 Quantum Capacitance of Graphitic Carbons 191
5.3.4 Molecular Dynamics Simulations 192
5.3.4.1 EDLs in Aqueous Electrolytes 193
5.3.4.2 EDLs in Organic Electrolytes 196
5.3.4.3 EDLs in Room-Temperature ILs 197
5.4 Concluding Remarks 201
Acknowledgments 202
References 203
6 Electrode Materials with Pseudocapacitive Properties 207
El??zbieta Fra??ckowiak
6.1 Introduction 207
6.2 Conducting Polymers in Supercapacitor Application 208
6.3 Metal Oxide/Carbon Composites 212
6.4 Pseudocapacitive Effect of Heteroatoms Present in the Carbon Network 214
6.4.1 Oxygen-Enriched Carbons 215
6.4.2 Nitrogen-Enriched Carbons 216
6.5 Nanoporous Carbons with Electrosorbed Hydrogen 222
6.6 Electrolytic Solutions – a Source of Faradaic Reactions 226
6.7 Conclusions – Profits and Disadvantages of Pseudocapacitive Effects 231
References 233
7 Li-Ion-Based Hybrid Supercapacitors in Organic Medium 239
Katsuhiko Naoi and Yuki Nagano
7.1 Introduction 239
7.2 Voltage Limitation of Conventional EDLCs 239
7.3 Hybrid Capacitor Systems 242
7.3.1 Lithium-Ion Capacitor (LIC) 243
7.3.2 Nanohybrid Capacitor (NHC) 247
7.4 Material Design for NHC 248
7.5 Conclusion 254
Abbreviations 255
References 255
8 Asymmetric and Hybrid Devices in Aqueous Electrolytes 257
Thierry Brousse, Daniel B´elanger, and Daniel Guay
8.1 Introduction 257
8.2 Aqueous Hybrid (Asymmetric) Devices 259
8.2.1 Principles, Requirements, and Limitations 259
8.2.2 Activated Carbon/PbO2 Devices 262
8.2.3 Activated Carbon/Ni(OH)2 Hybrid Devices 267
8.2.4 Aqueous-Based Hybrid Devices Based on Activated Carbon and Conducting Polymers 269
8.3 Aqueous Asymmetric Electrochemical Capacitors 272
8.3.1 Principles, Requirements, and Limitations 272
8.3.2 Activated Carbon/MnO2 Devices 274
8.3.3 Other MnO2-Based Asymmetric or Hybrid Devices 278
8.3.4 Carbon/Carbon Aqueous Asymmetric Devices 279
8.3.5 Carbon/RuO2 Devices 280
8.4 Tantalum Oxide–Ruthenium Oxide Hybrid Capacitors 282
8.5 Perspectives 282
References 283
9 EDLCs Based on Solvent-Free Ionic Liquids 289
Mariachiara Lazzari, Catia Arbizzani, Francesca Soavi, and Marina Mastragostino
9.1 Introduction 289
9.2 Carbon Electrode/Ionic Liquid Interface 291
9.3 Ionic Liquids 292
9.4 Carbon Electrodes 297
9.5 Supercapacitors 298
9.6 Concluding Remarks 302
Ionic Liquid Codes 303
Glossary 304
References 305
10 Manufacturing of Industrial Supercapacitors 307
Philippe Aza¨??s
10.1 Introduction 307
10.2 Cell Components 309
10.2.1 Electrode Design and Its Components 309
10.2.1.1 Current Collector 309
10.2.1.2 Activated Carbons for Supercapacitors 312
10.2.1.3 Industrial Activated Carbons for Industrial Supercapacitors 317
10.2.1.4 Particle Size Distribution of Activated Carbons and Its Optimization 320
10.2.1.5 Binders 322
10.2.1.6 Conductive Additives 325
10.2.2 Electrolyte 326
10.2.2.1 Electrolyte Impact on Performance 327
10.2.2.2 Liquid-State Electrolyte and Remaining Problems 340
10.2.2.3 Ionic Liquid Electrolyte 341
10.2.2.4 Solid-State Electrolyte 343
10.2.3 Separator 343
10.2.3.1 Separator Requirements 343
10.2.3.2 Cellulosic Separators and Polymeric Separators 343
10.3 Cell Design 345
10.3.1 Small-Size Components 347
10.3.2 Large Cells 347
10.3.2.1 High-Power Cells 348
10.3.2.2 Energy Cells 350
10.3.2.3 Pouch Cell design 351
10.3.2.4 Debate on Cell Design: Prismatic versus Cylindrical Cells 351
10.3.2.5 Aqueous Medium Cells 351
10.4 Module Design 352
10.4.1 Large Modules Based on Hard-Type Cells 353
10.4.1.1 Metallic Connections Between Cells 354
10.4.1.2 Electric Terminal for Module 354
10.4.1.3 Insulator for Module 354
10.4.1.4 Cell Balancing and Other Information Detection 356
10.4.1.5 Module Enclosure 357
10.4.2 Large Modules Based on Pouch-Type Cells 357
10.4.3 Large Modules Working in Aqueous Electrolytes 359
10.4.4 Other Modules Based on Asymmetric Technologies 360
10.5 Conclusions and Perspectives 362
References 363
11 Supercapacitor Module Sizing and Heat Management under Electric, Thermal, and Aging Constraints 373
Hamid Gualous and Roland Gallay
11.1 Introduction 373
11.2 Electrical Characterization 374
11.2.1 C and ESR Measurement 374
11.2.1.1 Capacitance and Series Resistance Characterization in the Time Domain 374
11.2.1.2 Capacitance and Series Resistance Characterization in the Frequency Domain 375
11.2.2 Supercapacitor Properties, Performances, and Characterization 376
11.2.2.1 Capacitance and ESR as a Function of the Voltage 376
11.2.2.2 Capacitance and ESR as a Function of the Temperature 378
11.2.2.3 Self-Discharge and Leakage Current 378
11.2.3 ‘‘Ragone Plot’’ Theory 381
11.2.3.1 Match Impedance 383
11.2.3.2 Power Available for the Load, Ragone Equation 384
11.2.4 Energetic Performance and Discharging at Constant Current 387
11.2.5 Energetic Performance and Discharging at Constant Power 389
11.2.6 Energetic Performance and Discharging at Constant Load 394
11.2.7 Efficiency 394
11.3 Thermal Modeling 395
11.3.1 Thermal Modeling of Supercapacitors 397
11.3.2 Conduction Heat Transfer 397
11.3.3 Thermal Boundary Conditions 399
11.3.4 Convection Heat Transfer Coefficient 401
11.3.5 Solution Procedure 402
11.3.6 BCAP0350 Experimental Results 404
11.4 Supercapacitor Lifetime 410
11.4.1 Failure Modes 411
11.4.2 Temperature and Voltage as an Aging Acceleration Factor 411
11.4.3 Physical Origin of Aging 413
11.4.4 Testing 415
11.4.5 DC Voltage Test 415
11.4.6 Voltage Cycling Test 417
11.5 Supercapacitor Module Sizing Methods 418
11.6 Applications 420
11.6.1 Power Management of Fuel Cell Vehicles 421
11.6.1.1 Problem Statement 421
11.6.1.2 Fuel Cell Modeling 421
11.6.1.3 Supercapacitors Modeling 422
11.6.2 The Power Management of a Fuel Cell Vehicle by Optimal Control 422
11.6.2.1 Optimal Control without Constraint 423
11.6.2.2 The Hamilton–Jacobi–Bellman Equation 423
11.6.3 Optimal Control with Inequality Constraints on the Fuel Cell Power and on the Fuel Cell Power Rate 427
11.6.3.1 Constraints on the Fuel Cell Power 427
11.6.3.2 Constraints on the Fuel Cell Power Rate 427
11.6.4 Power Management of Fuel Cell Vehicle by Optimal Control Associated to Sliding Mode Control 429
11.6.5 Conclusion 433
References 434
12 Testing of Electrochemical Capacitors 437
Andrew Burke
12.1 Introduction 437
12.2 Summaries of DC Test Procedures 437
12.2.1 USABC Test Procedures 439
12.2.2 IEC Test Procedures 440
12.2.3 UC Davis Test Procedures 441
12.3 Application of the Test Procedures to Carbon/Carbon Devices 443
12.3.1 Capacitance 443
12.3.2 Resistance 443
12.3.3 Energy Density 448
12.3.4 Power Capability 449
12.3.5 Pulse Cycle Testing 453
12.4 Testing of Hybrid, Pseudocapacitive Devices 456
12.4.1 Capacitance 456
12.4.2 Resistance 456
12.4.3 Energy Density 459
12.4.4 Power Capability and Pulse Cycle Tests 460
12.5 Relationships between AC Impedance and DC Testing 460
12.6 Uncertainties in Ultracapacitor Data Interpretation 465
12.6.1 Charging Algorithm 466
12.6.2 Capacitance 466
12.6.3 Resistance 466
12.6.4 Energy Density 467
12.6.5 Power Capability 467
12.6.6 Round-Trip Efficiency 469
12.7 Summary 469
References 469
13 Reliability of Electrochemical Capacitors 473
John R. Miller
13.1 Introduction 473
13.2 Reliability Basics 473
13.3 Cell Reliability 474
13.4 System Reliability 478
13.5 Assessment of Cell Reliability 481
13.5.1 Experimental Approach Example 484
13.6 Reliability of Practical Systems 491
13.6.1 Cell Voltage Nonuniformity 492
13.6.2 Cell Temperature Nonuniformity 494
13.7 Increasing System Reliability 499
13.7.1 Reduce Cell Stress 499
13.7.2 Burn-in of Cells 501
13.7.3 Use Fewer Cells in Series 501
13.7.4 Use ‘‘Long-Life’’ Cells 501
13.7.5 Implement Maintenance 502
13.7.6 Add Redundancy 502
13.8 System Design Example 503
13.8.1 Problem Statement 503
13.8.2 System Analysis 504
13.8.3 Cell Reliability 506
References 507
14 Market and Applications of Electrochemical Capacitors 509
John R. Miller
14.1 Introduction: Principles and History 509
14.2 Commercial Designs: DC Power Applications 510
14.2.1 Bipolar Designs 510
14.2.2 Cell Designs 512
14.2.3 Asymmetric Designs 513
14.3 Energy Conservation and Energy Harvesting Applications 516
14.3.1 Motion and Energy 516
14.3.2 Hybridization: Energy Capture and Reuse 518
14.3.3 Energy Conservation and Efficiency 521
14.3.4 Engine Cranking 521
14.4 Technology Combination Applications 523
14.4.1 Battery/Capacitor Combination Applications 523
14.5 Electricity Grid Applications 523
14.5.1 Storage and the Utility Grid 523
14.6 Conclusions 524
References 525
Index 527
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