Electrochemical Power Sources
Batteries, Fuel Cells, and Supercapacitors
The ECS Series of Texts and Monographs Series

Foreword xv

Acknowledgements xvii

Preface xix

Symbols xxi

Abbrevations xxiii

Introduction xxv

Part I Batteries with Aqueous Electrolytes 1

1 General Aspects 3

1.1 Definition 3

1.2 Current-Producing Chemical Reaction 3

1.3 Classification 5

1.4 Thermodynamic Aspects 6

1.5 Historical Development 8

1.6 Nomenclature 9

Reviews and Monographs 10

2 Main Battery Types 11

2.1 Electrochemical Systems 11

2.2 Leclanché (Zinc–Carbon) Batteries 12

2.3 The Zinc Electrode in Alkaline Solutions 14

2.4 Alkaline Manganese–Zinc Batteries 14

2.5 Lead Acid Batteries 17

2.6 Alkaline Nickel Storage Batteries 20

2.7 Silver–Zinc Batteries 23

References 24

Monographs and Reviews 25

3 Performance 27

3.1 Electrical Characteristics of Batteries 27

3.2 Electrical Characteristics of Storage Batteries 30

3.3 Comparative Characteristics 30

3.4 Operational Characteristics 31

References 32

4 Miscellaneous Batteries 33

4.1 Mercury–Zinc Batteries 33

4.2 Compound Batteries 34

4.3 Batteries with Water as Reactant 37

4.4 Standard Cells 38

4.5 Reserve Batteries 39

Reference 41

Reviews and Monographs 41

5 Design and Technology 43

5.1 Balance in Batteries 43

5.2 Scale Factors 44

5.3 Separators 44

5.4 Sealing 46

5.5 Ohmic Losses 47

5.6 Thermal Processes in Batteries 48

6 Applications of Batteries 51

6.1 Automotive Equipment Starter and Auxiliary Batteries 51

6.2 Traction Batteries 52

6.3 Stationary Batteries 53

6.4 Domestic and Portable Systems 53

6.5 Special Applications 54

7 Operational Problems 55

7.1 Discharge and Maintenance of Primary Batteries 55

7.2 Maintenance of Storage Batteries 56

7.3 General Aspects of Battery Maintenance 60

8 Outlook for Batteries with Aqueous Electrolyte 63

References 64

Part II Batteries with Nonaqueous Electrolytes 65

9 Different Kinds of Electrolytes 67

9.1 Electrolytes Based on Aprotic Nonaqueous Solutions 68

9.2 Ionically Conducting Molten Salts 69

9.3 Ionically Conducting Solid Electrolytes 70

References 72

10 Insertion Compounds 73

Monographs and Reviews 76

11 Primary Lithium Batteries 77

11.1 General Information: Brief History 77

11.2 Current-Producing and Other Processes in Primary Power Sources 79

11.3 Design of Primary Lithium Cells 81

11.4 Fundamentals of the Technology of Manufacturing of Lithium Primary Cells 82

11.5 Electric Characteristics of Lithium Cells 82

11.6 Operational Characteristics of Lithium Cells 83

11.7 Features of Primary Lithium Cells of Different Electrochemical Systems 84

Monographs 89

12 Lithium Ion Batteries 91

12.1 General Information: Brief History 91

12.2 Current-Producing and Other Processes in Lithium Ion Batteries 93

12.3 Design and Technology of Lithium Ion Batteries 96

12.4 Electric Characteristics, Performance, and Other Characteristics of Lithium Ion Batteries 98

12.5 Prospects of Development of Lithium Ion Batteries 99

Monographs 101

13 Lithium Ion Batteries: What Next? 103

13.1 Lithium–Air Batteries 103

13.2 Lithium–Sulfur Batteries 106

13.3 Sodium Ion Batteries 108

Reviews 110

14 Solid-State Batteries 111

14.1 Low-Temperature Miniature Batteries with Solid Electrolytes 111

14.2 Sulfur–Sodium Storage Batteries 112

Monographs and Reviews 115

15 Batteries with Molten Salt Electrolytes 117

15.1 Storage Batteries 117

15.2 Reserve-Type Thermal Batteries 120

References 122

Part III Fuel Cells 123

16 General Aspects 125

16.1 Thermodynamic Aspects 125

16.2 Schematic Layout of Fuel-Cell Units 128

16.3 Types of Fuel Cells 131

16.4 Layout of a Real Fuel Cell: The Hydrogen–Oxygen Fuel Cell with Liquid Electrolyte 132

16.5 Basic Parameters of Fuel Cells 134

Reference 140

Monographs 140

17 The Development of Fuel Cells 141

17.1 The Period prior to 1894 141

17.2 The Period from 1894 to 1960 143

17.3 The Period from 1960 to the 1990s 144

17.4 The Period after the 1990s 148

References 149

Monographs and Reviews 150

18 Proton-Exchange Membrane Fuel Cells (PEMFC) 151

18.1 The History of PEMFC 151

18.2 Standard PEMFC Version of the 1990s 154

18.3 Operating Conditions of PEMFC 156

18.4 Special Features of PEMFC Operation 157

18.5 Platinum Catalyst Poisoning by Traces of Co in the Hydrogen 159

18.6 Commercial Activities in Relation to PEMFC 161

18.7 Future Development of PEMFCs 162

18.8 Elevated-Temperature PEMFCs (ET-PEMFCs) 167

References 170

Reviews 170

19 Direct Liquid Fuel Cells with Gaseous, Liquid, And/Or Solid Reagents 171

19.1 Current-Producing Reactions and Thermodynamic Parameters 172

19.2 Anodic Oxidation of Methanol 172

19.3 Use of Platinum–Ruthenium Catalysts for Methanol Oxidation 173

19.4 Milestones in DMFC Development 173

19.5 Membrane Penetration by Methanol (Methanol Crossover) 174

19.6 Varieties of DMFC 176

19.7 Special Operating Features of DMFC 178

19.8 Practical Prototypes of DMFC and Their Features 180

19.9 The Problems to be Solved in Future DMFC 181

19.10 Direct Liquid Fuel Cells (DLFC) 183

Reference 188

Reviews 188

20 Molten Carbonate Fuel Cells (MCFC) 191

20.1 Special Features of High-Temperature Fuel Cells 191

20.2 The Structure of Hydrogen–Oxygen MCFC 192

20.3 MCFC with Internal Fuel Reforming 194

20.4 The Development of MCFC Work 195

20.5 The Lifetime of MCFCs 196

References 198

Reviews and Monographs 198

21 Solid Oxide Fuel Cells (SOFCs) 199

21.1 Schematic Design of a Conventional SOFC 200

21.2 Tubular SOFCs 201

21.3 Planar SOFCs 202

21.4 Varieties of SOFCs 205

21.5 The Utilization of Natural Fuels in SOFCs 206

21.6 Interim-Temperature SOFCs (ITSOFCs) 208

21.7 Low-Temperature SOFCs (LT-SOFC) 211

21.8 Factors Influencing the Lifetime of SOFCs 211

References 212

Monographs and Reviews 212

22 Other Types of Fuel Cells 213

22.1 Phosphoric Acid Fuel Cells (PAFCs) 213

22.2 Redox Flow Fuel Cells 218

22.3 Biological Fuel Cells 221

22.4 Direct Carbon Fuel Cells (DCFCs) 224

References 227

Monographs 227

23 Alkaline Fuel Cells (AFCs) 229

23.1 Hydrogen–Oxygen AFCs 230

23.2 Problems in the AFC Field 233

23.3 The Present State and Future Prospects of AFC Work 235

23.4 Anion-Exchange (Hydroxyl Ion Conducting) Membranes 236

23.5 Methanol Fuel Cell with an Invariant Alkaline Electrolyte 237

References 237

Monograph 237

24 Applications of Fuel Cells 239

24.1 Large Stationary Power Plants 239

24.2 Small Stationary Power Units 242

24.3 Fuel Cells for Transport Applications 243

24.4 Portables 248

24.5 Military Applications 250

References 250

25 Outlook for Fuel Cells 251

25.1 Alternating Periods of Hope and Disappointment—Forever? 252

25.2 Development of Electrocatalysis 252

25.3 “Ideal Fuel Cells” Do Exist 253

25.4 Expected Future Situation with Fuel Cells 255

Reference 256

Monographs 256

Part IV Supercapacitors 257

26 General Aspects 259

26.1 Electrolytic Capacitors 259

References 261

27 Electrochemical Supercapacitors with Carbon Electrodes 263

27.1 Introduction 263

27.2 Main Properties of Electric Double-Layer Capacitors (EDLC) 264

27.3 EDLC Energy Density and Power Density 267

27.4 Fundamentals of EDLC Macrokinetics 271

27.5 Porous Structure and Hydrophilic–Hydrophobic Properties of Highly Dispersed Carbon Electrodes 272

27.6 Effect of Ratio of Ion and Molecule Sizes and Pore Sizes 275

27.7 Effect of Functional Groups on EDLC Characteristics 277

27.8 Electrolytes Used in EDLC 279

27.9 Impedance of Highly Dispersed Carbon Electrodes 283

27.10 Nanoporous Carbons Obtained Using Various Techniques 286

27.11 High-Frequency Carbon Supercapacitors 303

27.12 Self-Discharge of Carbon Electrodes and Supercapacitors 306

27.13 Processes of EDLC Degradation (AGING) 311

References 313

Monograph and Reviews 313

28 Pseudocapacitor Electrodes and Supercapacitors 315

28.1 Electrodes Based on Inorganic Salts of Transition Metals 315

28.2 Electrodes Based on Electron-Conducting Polymers (ECPs) 322

28.3 Redox Capacitors Based on Organic Monomers 333

28.4 Lithium-Cation-Exchange Capacitors 335

References 337

Monograph and Reviews 337

29 Hybrid (Asymmetric) Supercapacitors (HSCs) 339

29.1 HSCs of MeO_x/C Types 339

29.2 HSCs of ECP/C Type 343

References 344

Review 344

30 Comparison of Characteristics of Supercapacitors and Other Electrochemical Devices. Characteristics of Commercial Supercapacitors 345

Reference 350

Reviews 350

31 Prospects of Electrochemical Supercapacitors 351

32 Electrochemical Aspects of Solar Energy Conversion 355

32.1 Photoelectrochemical Phenomena 355

32.2 Photoelectrochemical Devices 356

32.3 Photoexcitation of Metals (Electron Photoemission into Solutions) 356

32.4 Behavior of Illuminated Semiconductors 357

32.5 Semiconductor Solar Batteries (SC-SB) 358

32.6 Dye-Sensitized Solar Cells (DSSC) 360

References 363

Reviews and Monographs 363

Author Index 365

Subject Index 369

The Late Vladimir S. Bagotsky (2013) was an acclaimed scientist in the field of electrochemical phenomena.  He has worked as the Head of Department at the Moscow Power Sources Institute, supervising development of fuel cells for various national and international projects.  For 20 years, he was the Head of Department and Principal Scientist at the A.N. Frumkin Institute of Electrochemistry.  He has published more than 400 papers in scientific journals such as the Russian Journal of Electrochemistry and The Journal of Power Sources.

Alexander  M. Skundin, PhD is a chief scientist at the A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of sciences. He is one of the main experts on lithium batteries in Russia.

Yurij M. Volfkovich, PhD, is chief scientist at the A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of sciences, and is one of the main experts on supercapacitors in Russia.