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Batteries. Present and Future Energy Storage Challenges. Edition No. 1. Encyclopedia of Electrochemistry

  • ID: 5185548
  • Book
  • September 2020
  • 960 Pages
  • John Wiley and Sons Ltd
Part of the Encyclopedia of Electrochemistry, this comprehensive, two-volume handbook offers an up-to-date and in-depth review of the battery technologies in use today. It also includes information on the most likely candidates that hold the potential for further enhanced energy and power densities. It contains contributions from a renowned panel of international experts in the field.
Batteries are extremely commonplace in modern day life. They provide electrochemically stored energy in the form of electricity to automobiles, aircrafts, electronic devices and to smart power grids. Comprehensive in scope, 'Batteries' covers information on well-established battery technologies such as charge-carrier-based lead acid and lithium ion batteries. The contributors also explore current developments on new technologies such as lithium-sulfur and -oxygen, sodium ion, and full organic batteries.
Written for electrochemists, physical chemists, and materials scientists, 'Batteries' is an accessible compendium that offers a thorough review of the most relevant current battery technologies and explores the technology in the years to come.
Note: Product cover images may vary from those shown

About the Editors xxiii

List of Contributors xxvii

Preface xxxiii

Section I Introduction 1

1 The Role of Batteries for the Successful Transition to

Renewable Energy Sources 3

Dominic Bresser, Arianna Moretti, Alberto Varzi, and Stefano Passerini

1 The Need for Transitioning to Renewable Energy Sources 3

2 Energy Storage as Key Enabler 5

2.1 Stationary Energy Storage 5

2.2 Energy Storage Technologies for Transportation 7

2.3 Storage Technologies for Portable Electronic Devices 8

3 The Variety of Battery Chemistries and Technologies 9

References 10

2 Fundamental Principles of Battery Electrochemistry 13

Francesco Nobili and Roberto Marassi

1 Introduction 13

2 Main Battery Components 16

2.1 Electrodes 16

2.2 Electrolyte 17

3 Voltage, Capacity, and Energy 19

3.1 Theoretical Cell Voltage 19

3.2 Theoretical Capacity 23

3.3 Energy Storage and Delivery 26

4 Current and Power 29

4.1 Kinetics and Overvoltage 29

4.2 Ohmic Polarization 31

4.3 Kinetic Polarization 31

4.4 Mass Transfer Polarization 32

5 Practical Operating Parameters 35

5.1 Coulombic Efficiency and Energy Efficiency (Round-Trip

Efficiency) 35

5.2 Capacity Retention and Cycle Life 36

5.3 Rate Capability 37

6 Main Classes of Batteries and Alternative Electrochemical Power

Sources 37

6.1 Primary Batteries 38

6.1.1 Volta’s Pile 39

6.1.2 Daniell Cell 39

6.1.3 Leclanché Cell 39

6.1.4 Alkaline Batteries 40

6.1.5 Li Primary Batteries 40

6.2 Secondary Batteries (Accumulators) 41

6.2.1 Lead-Acid Batteries 42

6.2.2 Nickel-Cadmium Batteries 42

6.2.3 Ni-Metal-Hydride Batteries 42

6.2.4 Lithium-Ion Batteries 43

6.2.5 Redox Flow Batteries 44

6.3 Fuel Cells 44

6.3.1 Alkaline Fuel Cells (AFCs) 45

6.3.2 Polymer Electrolyte Membrane Fuel Cells (PEMFCs) 45

6.3.3 Direct Methanol Fuel Cells (DMFCs) 45

6.3.4 Phosphoric Acid Fuel Cells (PAFCs) 46

6.3.5 Molten Carbonate Fuel Cells (MCFCs) 46

6.3.6 Solid Oxide Fuel Cells (SOFCs) 46

References 47

Section II Presently Employed Battery Technologies 49

3 Lead-Acid – Still the Battery Technology with the Largest

Sales 51

Johannes Buengeler and Bernhard Riegel

1 Introduction and History 51

2 Fundamentals of the Lead-Acid Accumulator 52

2.1 Operating Principle 52

2.2 Electrode Potentials in Equilibrium 54

2.2.1 Thermodynamic Fundamentals 54

2.2.2 Equilibrium Potential of the Main Reaction 55

2.2.3 Single-Electrode Potentials 57

2.2.4 Important Reference Electrodes 58

2.3 Side Reactions 59

2.3.1 Negative Electrode 60

2.3.1.1 Hydrogen Evolution 60

2.3.1.2 Oxygen Reduction 60

2.3.2 Positive Electrode 61

2.3.2.1 Oxygen Evolution 61

2.3.2.2 Grid Corrosion 61

2.3.3 Oxidation of Organic Substances 62

3 Behavior of the Lead-Acid Accumulator During Current Flow 62

3.1 Overpotentials in Lead-Acid Accumulators 63

3.2 Mathematic Concept to Describe the Electron Transfer Reaction 63

3.3 Inhibition of the Electron Transfer Reaction During Charge 64

3.4 Current/Voltage Characteristics During Overcharge 65

4 AgingMechanisms 67

4.1 Sulfation of Negative Active Mass 69

5 Acid Stratification 73

6 BatteryDesign 76

6.1 Types of Electrodes 77

6.2 Valve-Regulated Lead-Acid Batteries 78

7 Discharge Characteristic 80

8 Charging Algorithms 82

8.1 IUIa Charging Algorithms 83

9 TemperatureEffects 86

9.1 Theoretical Description of the Heat Sources and Sinks 86

10 New Development Trends for Advanced Lead-Acid Batteries 89

10.1 Thin Plate Pure Lead Technology 89

10.2 Enhanced Lead-Carbon Batteries 90

10.3 Bipolar Lead-Acid Batteries 91

References 91

4 Ni/Cd and Ni-MH – The Transition to “Charge Carrier”-Based

Batteries 95

HuiWang andMin Zhu

1 Introduction to Ni/Cd and Ni-MH Batteries 95

2 Basic Structure of Ni-MH Battery 97

3 Electrochemistry of Ni-MH Battery 98

4 Positive Electrode Materials of Ni-MH Batteries 100

4.1 Crystal Structure 102

4.2 Electrochemical Characteristics 103

5 Negative Electrode Materials of Ni-MH Batteries 104

5.1 Electrochemical Reaction Thermodynamics of Hydrogen Storage

Electrode Alloys 105

5.2 Electrochemical Reaction Kinetics of Hydrogen Storage Alloys 106

5.3 Requirements for Hydrogen Storage Electrode Alloys 108

5.4 Classification of Hydrogen Storage Electrode Alloys 110

5.4.1 AB5-Type Alloys 110

5.4.2 AB2-Type Laves Alloys 113

5.4.3 A2B7-Type and AB3-Type Superlattice Alloys 114

6 State-of-the-Art of Ni-MH Battery 116

6.1 High Power Ni-MH Battery 117

6.2 High-Capacity Ni-MH Battery 118

6.3 High-/Low-Temperature Ni-MH Battery 123

6.4 Low Self-Discharge Ni-MH Battery 124

7 Summary 125

References 126

5 Brief Survey on the Historical Development of LIBs 131

Kazunori Ozawa

1 Introduction 131

2 Aqueous Electrolyte System 131

3 Nonaqueous Electrolyte System 132

4 Insertion/Extraction of Lithium Ion 135

5 Success of Sony 135

5.1 Patent Issue 136

5.2 Cathode Material 136

5.3 Anode Material 136

5.4 Electrolyte 138

5.5 Separator 141

5.6 Cathode Collector and Conductive Material 141

5.7 Anode Collector 142

5.8 Anode Can 142

5.9 Mixing and Coating Technology 142

5.10 Assembly of Lithium-Ion Cells 143

5.11 Pack 144

6 Conclusion 147

References 147

6 Present LIB Chemistries 149

1 General Introduction 149

Zempachi Ogumi

2 Positive Electrodes 150

Hajime Arai

2.1 Basic Principles 150

2.2 LiCoO2 Family 153

2.3 LiNiO2 Family 155

2.4 LiMn2O4 Family 156

2.5 LiFePO4 Family 158

3 Negative Electrodes 159

Takeshi Abe

3.1 Commercialized Carbons in LIBs 159

3.2 Graphitized Carbons 161

3.3 Nongraphitic Carbons 162

3.4 Hard Carbons (Nongraphitizable Carbons) 164

3.5 High-Potential Negative Electrode 164

3.6 Silicon-Based Materials 165

4 Electrolytes 167

Masayuki Morita

4.1 Introduction – General Concept of Electrolyte Designing in Practical

LIBs 167

4.2 Classification of LIB Electrolytes 168

4.3 Organic Solvent Electrolytes 170

4.4 Polymeric Solid and Gel Electrolytes 173

4.5 Inorganic Solid Electrolytes 174

4.6 Ionic Liquid-Based Electrolytes 176

4.7 New Trends 177

References 179

7 Anticipated Progress in the Near- to Mid-Term Future of

LIBs 185

Seung-TaekMyung, Jongsoon Kim, and Yang-Kook Sun

1 Cathode 185

1.1 Summary 185

1.2 Layered Structure 186

1.3 Spinel Structure 188

1.4 Olivine Structure 188

1.5 Performance Improvements 189

2 Anode 192

2.1 Summary 192

2.2 Lithium Metal 192

2.3 Intercalation-Based Anode 193

2.3.1 Graphite-Based Materials 193

2.3.2 Spinel Li4Ti5O12 194

2.3.3 TiO2 195

2.4 Alloying-Based Anode 196

2.4.1 Silicon 196

2.4.2 Other Metal Elements: Tin, Lead, Antimony, and Bismuth 197

2.5 Conversion-Based Anode 198

2.5.1 Metal Oxide 198

2.5.2 Metal Sulfides 199

3 Electrolyte 199

3.1 Summary 199

3.2 Organic Liquid Electrolyte 200

3.2.1 Organic Solvent 201

3.2.2 Lithium Salt 202

3.2.3 Additives 202

3.2.4 Ionic Liquids 202

3.3 Gel Polymer Electrolyte 203

4 Separator 204

4.1 Summary 204

4.2 Detailed Requirements of Separator 204

4.3 Polyolefin Separators 205

4.4 PVdF Separators 206

4.5 Inorganic Composite Separators 206

5 Outlook 206

References 207

8 Safety Considerations with Lithium-Ion Batteries 217

Jürgen Garche and Klaus Brandt

1 Introduction 217

2 Material Influence on Risks 218

2.1 Cathode Materials 218

2.2 Anode Materials 222

2.3 Electrolytes 223

3 RiskClasses 224

3.1 Chemical Risks 224

3.2 Thermal Risks 224

3.3 Kinetical Risks 227

3.4 Electrical Risks 227

4 Triggering of Risks 228

4.1 Triggers External to the Cell 228

4.2 Internal Cell Triggers 230

4.3 Propagation of Cell Failures 231

4.4 Safety Testing 232

5 Handling of Risk Events 234

5.1 General Considerations 234

5.2 Fire Extinction 236

5.3 Fire-Extinguishing Agents 237

6 Summary and Outlook 238

References 239

9 Recycling of Lithium-Ion Batteries 243

Marit Mohr, MarcelWeil, Jens Peters, and ZhangqiWang

1 Introduction 243

2 Recycling Technologies/Processes 246

2.1 Thermal Pretreatment 247

2.2 Mechanical Treatment 247

2.2.1 Crushing 247

2.2.2 Separation 248

2.3 Pyrometallurgical Treatment 248

2.4 Hydrometallurgical Treatment 249

2.5 Direct Recycling 249

2.6 Current Recycling Activities in Europe 250

2.6.1 Accurec 250

2.6.2 Duesenfeld 252

2.6.3 Umicore 252

2.6.4 ERLOS: SeparateWashing of Anode and Cathode Foils 254

2.6.5 Laboratory- and Pilot-Scale Processes 256

2.6.5.1 Supercritical CO2 for Electrolyte Extraction 256

2.6.5.2 Froth Flotation for Separating Active Material 256

2.6.6 Electrohydraulic Fragmentation 257

3 Assessment of Battery Recycling Processes 259

3.1 Techno-Economic Performance of the Different Recycling

Processes 259

3.2 Environmental Performance of the Different Recycling

Processes 263

4 Challenges and Potentials 265

4.1 Technological Challenges 265

4.1.1 Safety and Design for Recycling 265

4.1.2 Electrolyte 266

4.1.3 Variety of Materials and Mixed BatteryWaste Streams 266

4.1.4 Battery Collection 267

4.2 Economic Viability 267

4.2.1 Value of Recycling Products 267

4.2.2 Temporal Mismatch of Recycling Products 268

4.2.3 Increasing Raw Material Prices 269

4.3 Environmental Considerations 269

4.3.1 Recycling Depth 269

4.3.2 Legislation and Enforcement 269

4.3.3 Limits 270

4.4 Further Aspects 270

5 Conclusion 270

References 272

10 Vanadium Redox Flow Batteries 277

Ruiyong Chen, Zhifeng Huang, Rolf Hempelmann, Dirk Henkensmeier, and

Sangwon Kim

1 Introduction 277

2 Vanadium Electrolytes 278

2.1 Synthesis of Vanadium Electrolytes 278

2.2 Concentration and Chemical Stability of Vanadium Electrolytes 280

2.3 Ionic Conductivity and Viscosity of Electrolyte 283

2.4 Mixed-Acid Vanadium Electrolytes 283

2.5 Additives for Vanadium Electrolytes 285

2.6 State-of-Charge (SOC) 287

3 Membranes and Transport of Species 288

3.1 Function of the Membranes 288

3.2 CharacterizationMethods of Membranes 289

3.2.1 Swelling Behavior and Acid Absorption 289

3.2.2 Permeability and Crossover 290

3.2.3 Conductivity and Resistance 291

3.2.4 Chemical Stability of Membranes 292

3.3 Membrane Types 293

4 Electrode Materials 296

4.1 Electrode Reactions 296

4.2 Carbon Paper Electrodes and “Zero-Gap” Concept of Cell

Configuration 297

4.3 Degradation Study of Carbon Electrodes 300

5 Conclusions 301

References 301

11 Redox Flow – Zn–Br 311

Hee-Tak Kim, Ju-Hyuk Lee, Dae Sik Kim, and Jung Hoon Yang

1 Overview of Zn–Br Batteries 311

2 Battery Components 315

2.1 Membrane 315

2.2 Electrolyte 317

2.2.1 Formation of ZnBr2−n

n Complexes 317

2.2.2 Complexation Reactions of Polybromide Anions 320

2.2.3 Bromine Sequestration Agents 320

2.2.4 Electrolyte Additive for the Negative Electrolyte 323

2.3 Positive Electrode 324

2.3.1 Electrochemistry of Br−∕Br2 Redox Reaction in Positive

Electrode 324

2.3.2 Charge Transfer Reaction 324

2.3.3 Electrode Developments 325

2.4 Negative Electrode 328

2.4.1 Electrochemistry of Zn0/Zn2+ Redox Reaction 328

2.4.2 Kinetics of Zn Electrodeposition 328

2.4.3 Structures of Zn Deposit 330

2.4.4 Electrode Development 332

3 BatteryDesign 334

3.1 Stack Design 334

3.2 Module and System Design 336

4 BatteryManagement 338

4.1 Operation Mode 338

4.2 Heat and pH Management 339

5 Summary 340

References 340

12 The Sodium/Nickel Chloride Battery 349

Marco Ottaviani, Alberto Turconi, and Diego Basso

1 General Characteristics 349

2 Description of the Electrochemical Systems 350

2.1 Main Electrochemical Reactions 350

2.2 Overcharge 352

2.3 Overdischarge 352

3 Cell Design and Performance Characteristics 353

3.1 Solid Electrolyte Description 354

3.2 Performance Characteristics 355

3.3 Discharge at Different Rates 358

3.4 Open Circuit Voltage 358

3.5 Peak Pulse Power Test 358

4 Battery Design and Performance Characteristics 360

4.1 TL Series 361

4.2 Safety 361

5 Series Production Technology 364

6 Market Overview and Application 365

7 Transport of Cells and Batteries 366

7.1 Packaging 367

7.2 Training 367

7.3 Marking 367

7.4 Labeling 367

7.4.1 Transport Document 369

References 369

13 High-Temperature Battery Technologies: Na-S 371

Verónica Palomares, Karina B. Hueso,Michel Armand, and Teófilo Rojo

1 Introduction 371

2 High-Temperature Sodium–Sulfur Systems 373

2.1 Basics of Sodium–Sulfur Batteries 373

2.2 Advantages of Sodium–Sulfur Batteries 376

2.3 Challenges to Overcome 377

2.4 Solid Electrolytes: Alternatives 378

3 Intermediate-Temperature Sodium–Sulfur Systems 386

4 Low-Temperature Sodium–Sulfur Systems 387

5 Sodium–Sulfur Technology Implementation in Industry 393

6 Conclusions 396

Acknowledgments 396

References 396

14 Solid-State Batteries with Polymer Electrolytes 407

Cristina Iojoiu and Elie Paillard

1 Introduction 407

2 Lithium-Ion Batteries and “Soft” Gel Electrolytes 410

3 Lithium Metal Batteries and SPEs 412

3.1 State of the art 412

3.2 The Lithium Metal Anode 414

3.3 Approaches Developed 417

3.3.1 Plasticized SPEs 418

3.3.2 Modification of PEO by Physical Interactions 419

3.3.3 Chemical Modification of PEO 422

4 Perspectives 424

4.1 Polycarbonate Solid Polymer Electrolytes 426

4.2 Hybrid Solid-State Polymer Electrolytes 427

4.2.1 “Polymer-In-Ceramics” and Layered Electrolytes 427

4.2.2 Ionogels 428

4.3 Block Copolymers 428

4.4 Liquid Crystal Electrolytes 430

4.5 Oligomeric Anions, Polyanions, and Single-Ion Conductors 432

5 Conclusions 436

References 436

Section III Potential Candidates for the Future Energy

Storage 457

15 Solid-State Batteries with Inorganic Electrolytes 459

Naoki Suzuki, TakuWatanabe, Satoshi Fujiki, and Yuichi Aihara

1 Introduction 459

1.1 Research Background 459

1.2 Energy Density and Safety Issue of Li Batteries 461

1.3 Differences between Solid and Liquid Electrolyte Batteries 462

1.4 Theoretical Models 463

1.5 Li Metal and Li Ion Secondary Batteries 466

1.6 Solid Electrolytes:Their Stability, Issues, and Approaches 466

1.7 Hybrid Solid-State Batteries 469

2 All-Solid-State Li Primary Batteries 470

3 All-Solid-State Secondary Battery 472

3.1 Oxide-Based ASSB 472

3.1.1 Micro-Batteries Based on Oxide 475

3.1.2 Thin-Film Batteries Based on LiPON Family 475

3.2 Sulfide-Based ASSB 478

3.2.1 Hidden Grain-Boundary Resistance 480

3.2.2 Thio-Phosphate (LPS) Family 480

3.2.3 Li10GeP2S12 (LGPS) 483

3.2.4 Argyrodite 486

3.2.5 Transition Metal Oxide for Cathode in Sulfide-Based ASSB 486

3.2.6 Sulfur Cathode for Sulfide-Based ASSB 490

3.2.7 Anode Materials 494

3.2.8 Pelletized Test Cells 496

3.2.9 Process of Large-Size Cells 497

3.2.9.1 Electrodes 497

3.2.9.2 SE Layer 500

3.2.9.3 Pressing 501

3.2.10 Demonstration Cells 502

3.3 Other SE Types 503

3.3.1 Borohydride and Others 504

3.3.2 Antiperovskite 505

3.3.3 Search for New SEs Using Material Informatics 505

4 Outlook 508

4.1 Future Applications of ASSBs and Their Markets 508

4.2 Challenge of ASSBs to xEV Battery Application 509

4.2.1 Safety Issues on Sulfide-Based Cells 509

4.2.2 Gap Between the Image and Present Status in Sulfide-Based

Batteries 510

4.2.3 Approaches to Fill the Gap in Sulfide-Based Batteries 510

4.3 Prospect of Solid-State Batteries 510

References 511

16 Li/S 521

Sheng-Heng Chung and Arumugam Manthiram

1 Introduction 521

1.1 Principles of Lithium–Sulfur Batteries 522

1.2 Historical Development 525

2 IntrinsicMaterials Issues 528

2.1 Insulating Nature 528

2.2 Polysulfides 530

2.3 Volume Changes 532

2.4 Lithium-Metal Anode 533

2.5 Electrolyte 533

2.6 Electrode Instability 535

2.7 Summary of the Intrinsic Materials Issues 535

3 Extrinsic Technical Issues 536

3.1 Effective Capacity and Energy Density 537

3.2 Amount of Sulfur 538

3.3 Electrolyte/Sulfur Ratios 541

3.4 Lithium Anode 542

3.5 Cell-Testing Conditions 543

3.6 Summary of the Extrinsic Technical Challenges 545

4 Conclusion 546

Acknowledgment 547

References 547

17 Lithium–Oxygen Batteries 557

Yann K. Petit, Eléonore Mourad, and Stefan A. Freunberger

1 Introduction 557

2 Attainable PerformanceMetrics ofMetal–O2 Cells 558

3 Reaction Mechanism of the Li–O2 Cathode 561

3.1 Li2O2 Formation on Discharge 561

3.2 Oxidation Mechanism 563

3.3 Li2O2 Conductivity 566

3.4 Alternative Storage Media 567

4 Parasitic Chemistry in Metal–O2 Cathodes 568

4.1 Metrics Indicating Reversible Cell Operation 568

4.2 Reactivity of Molecular and Reduced Oxygen 570

4.3 Singlet Oxygen in Metal–O2 Cells 571

4.3.1 Evidence for Singlet Oxygen as the Main Culprit for Parasitic

Chemistry 571

4.3.2 Pathways Toward Singlet Oxygen 573

4.3.3 Quenching Singlet Oxygen 576

5 TheElectrodes 578

5.1 The Cathode 578

5.2 Cathode Catalysts 579

5.3 The Anode 580

6 Moving the Li–O2 Cathode Chemistry into Solution 581

6.1 The Concept 581

6.2 Reduction Mediators 581

6.3 Oxidation Mediators 582

7 Electrolytes and Their Stability 585

8 Conclusions 586

References 588

18 Nonlithium Aprotic Metal/Oxygen Batteries Using Na, K, Mg, or

Ca as Metal Anode 599

Daniel Schröder, Jürgen Janek, and Philipp Adelhelm

1 Introduction 599

2 Basic Principles and Performance Metrics 600

3 Redox Reactions in the Various Metal/Oxygen Batteries 605

3.1 Na/O2 Batteries 605

3.1.1 Thermodynamics and Kinetics 605

3.1.2 History of Development, State-of-the-Art, and Current Trends 608

3.1.2.1 Impact of the Carbon Material on the Cathode Reactions 609

3.1.2.2 Impact of the Solvent on Cathode Reactions and Product

Stability 610

3.1.2.3 Impact ofWater on the Cathode Reactions 610

3.1.2.4 Electrolyte Degradation 610

3.1.2.5 Current Trends on Cathode Materials and Electrolyte Additives 611

3.1.2.6 Increasing the Oxygen Availability 611

3.1.3 Unsolved Challenges 612

3.2 K/O2 Batteries – Analogy from Na to K 614

3.2.1 Major Discharge Product and Main Advantages 615

3.2.2 State-of-the-Art and Challenges 615

3.2.3 Use of Liquid Alloy Anodes 616

3.3 Ca/O2 and Mg/O2 –The Challenging Transport of Multivalent

Ions 616

3.3.1 Working Principles 617

3.3.2 Research Progress, State-of-the-Art, and Challenges 617

3.3.2.1 Progress on Cathode Reactions for Ca 617

3.3.2.2 Progress on Anode Reactions for Ca 618

3.3.2.3 Progress on Cathode Reactions for Mg 618

3.3.2.4 Progress on Anode Reactions for Mg 619

3.3.2.5 Final Evaluation and Current Trends 619

4 Summary and Prospects 619

Acknowledgments 620

References 621

Further Reading 627

19 Na-Ion Batteries 629

Kei Kubota and Shinichi Komaba

1 Introduction 629

2 Active Materials, Electrolyte, and Binders for a Negative

Electrode 632

2.1 Research Progress of Negative Electrode Materials 632

2.2 Electrolyte Salts, Solvents, Additives, and Binders 636

2.3 Hard Carbon Materials 645

2.4 Titanium Phosphates and Oxides 647

2.5 Alloy-Based Materials 648

3 Positive Electrode Materials 651

3.1 Research Progress of Positive Electrode 651

3.2 Layered 3d Transition Metal Oxides 653

3.3 O3-Type NaMeO2 (Me = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) 656

3.3.1 O3-NaScO2, O3-NaTiO2, and O3-NaVO2 656

3.3.2 O3-NaCrO2 658

3.3.3 O3-NaFeO2 659

3.3.4 O3-NaCoO2 660

3.3.5 O’3-NaNiO2 660

3.4 P2-Type Na2∕3MeO2 (Me = V, Mn, and Co) 664

3.5 Potential Jump and Na/Vacancy Ordering in Layered Oxides 666

3.6 Polyanionic Materials 668

4 Summary and Perspective 671

Acknowledgments 674

References 674

20 Multivalent Charge Carriers 693

Jan Bitenc, Alexandre Ponrouch, Robert Dominko, Patrik Johansson,

and M. Rosa Palacin

1 Introduction 693

2 Magnesium-Based Batteries 698

2.1 Anodes and Electrolytes 699

2.2 Cathodes 701

3 Calcium-Based Batteries 706

3.1 Cathodes 707

3.2 Anodes 708

3.3 Electrolyte 710

4 Aluminum-Based Batteries 710

4.1 Anode 712

4.2 Electrolytes 713

4.3 Cathodes 714

5 Technological Prospects 715

6 Conclusion 718

Acknowledgments 718

References 719

21 Aqueous Zinc Batteries 729

Simon Clark, Niklas Borchers, Zenonas Jusys, R. Jürgen Behm,

and Birger Horstmann

1 Introduction 729

2 History 730

3 Zinc as an Electrode Material 733

3.1 Benefits and Challenges 735

3.2 Electrode Structure 736

4 Alkaline Zn–MnO2 Batteries 737

4.1 Operating Principle 738

4.2 Manganese Dioxide Cathodes 738

4.3 Anode 739

4.4 Rechargeable Zinc Alkaline Manganese Dioxide Batteries 739

5 Zinc-IonBatteries 740

5.1 Operating Principle 741

5.2 Cathode Materials 741

5.2.1 Manganese Oxides 742

5.2.2 Vanadium Compounds 743

5.2.3 Prussian Blue Analogs 745

5.2.4 Alternative Cathode Materials 745

5.3 Metal Anodes for Zinc-Ion Batteries 745

5.4 Electrolytes 747

6 Zinc-AirBatteries 748

6.1 Operating Principle 748

6.2 Cell Designs 751

6.3 Zinc Metal Electrodes 753

6.4 Air Electrode 754

6.4.1 Gas-Diffusion Electrode 755

6.4.2 Catalysts 756

6.5 Electrolytes 761

7 Conclusion 765

Acknowledgement 766

References 767

22 Full-Organic Batteries 783

Lionel Picard and Thibaut Gutel

1 Why Full-Organic Batteries? 783

2 Advantages and Challenges Around Organic Materials 784

2.1 Advantages of the Organic Materials 784

2.2 Challenges 788

3 The Different Configurations of Full-Organic Batteries 789

4 The Main Electroactive Functions andTheir Mechanisms 790

4.1 Conjugated Polymers 790

4.2 Organic Stable Radicals 794

4.3 The Sulfur-Based Materials 797

4.3.1 Organodisulfides (Molecule or Polymer) with S - S Bond in the Main

Chain 798

4.3.2 Organodisulfides (Molecule or Polymer) with S - S Bond in Side

Chains 798

4.4 Carbonyl Function 799

4.5 Miscellaneous Approaches 803

4.5.1 Aromatic Amines 803

4.5.2 Conjugated Nitrogen 804

4.5.3 Cyanide Group 805

4.5.4 Azo Group 806

4.5.5 Schiff Bases 806

4.6 Conclusions 806

5 Strategies Against Solubilization of the Active Organic Materials 807

5.1 Electroactive Polymers and Electroactive Pendant Groups on

Polymers 807

5.1.1 Organic Radical Polymers 807

5.1.2 The Sulfur-Based Polymers 808

5.1.2.1 Polymeric Organodisulfides with S - S Bonds in the Main Chain 808

5.1.2.2 Polymeric Organodisulfides with S - S Bonds in Side Chains 812

5.1.3 The Carbonyl-Based Polymers 812

5.2 Polyanionic Salt Formation 826

5.3 Solid-State Electrolyte Approach 830

6 Strategies for Improving Electronic Conductivity 834

6.1 Carbon Additives 834

6.2 Functionalization of Conducting Polymers 835

6.2.1 Conducting Polymers Functionalized by TEMPO Group 836

6.2.2 Conducting Polymers Functionalized by Disulfide Bonds 836

6.2.3 Conducting Polymers Functionalized by Quinone Derivatives 837

6.2.4 Conducting Polymers Functionalized by Ferrocene Groups 837

7 Full-Organic Batteries 837

7.1 n-Type Organic Materials in Full-Organic Cells 838

7.2 n- and p-Type Organics in Full-Organic Dual-Ion Cells 838

7.3 p-Type Organic Materials in Full-Organic Cells 841

8 Concluding Remarks 845

References 846

Index 857

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Stefano Passerini
Dominic Bresser
Arianna Moretti
Alberto Varzi
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