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Supercapacitors: Materials, Systems and Applications

Max Lu (Series Editor), Francois Beguin (Editor), Elzbieta Frackowiak (Editor)
ISBN: 978-3-527-32883-3
568 pages
April 2013
Supercapacitors: Materials, Systems and Applications (3527328831) cover image
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.
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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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François Béguin is Professor of Materials Chemistry at Orléans University, France. His research activities are devoted to chemical and electrochemical applications of carbon materials, with special attention to the development of nano-carbons with controlled porosity and surface functionality for applications in energy conversion/storage and environment protection. He has published over 230 papers, owns several patents, and his works have been cited over 3000 times. Beguin is the Director of two national programmes in the French Agency for Research (ANR), one on Energy Storage (Stock-E), the other on Hydrogen and Fuel Cells (H-PAC).

Elzbieta Frackowiak is a full professor at Poznan University of Technology, Poland. She is an electrochemist, with research interests focused on energy storage/conversion. Frackowiak has more than 150 publications and 2800 citations to her name, and is Chair Elect of Division 3 (Electrochemical Energy Conversion and Storage) of the International Society of Electrochemistry.
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