Li-ion Batteries
Development and Perspectives
Didier Bloch, Sébastien Martinet, Thierry Priem and Christian Ngô
EDP sciences
PrefaceIII
Chapter 1
Introduction1
1.1 Brief History of Primary and Secondary Batteries6
1.2 General Information on Li-ion Batteries9
Bibliography11
Chapter 2
Positive Electrode Materials for « Lithium-ion » Accumulators13
2.1 Positive Electrode Materials of « Spinel » Structure14
2.2 Positive Electrode Materials with Lithiated Layered Oxide Structure20
2.3 Positive Electrode Materials with Olivine Structure32
References37
Chapter 3
Negative Electrode Materials45
3.1 Negative Electrode Materials : Several Solutions45
3.1.1 Insertion-Intercalation46
3.1.2 Conversion47
3.1.3 Alloying47
3.2 Carbon48
3.2.1 Historical Background48
3.2.2 Interest49
3.2.3 Relationship between Structural Characteristics and Performance50
3.3 Silicon53
3.3.1 (De)lithiation Mechanisms53
3.3.2 Degradation Mechanisms54
3.3.3 Material Improvement Approaches56
3.4 Lithium Metal57
Bibliography59
Chapter 4
Organic Electrode Materials63
4.1 Different Types of Organic Electrode Materials65
4.1.1 ?-Extended System (Conducting Polymers)65
4.1.2 Stable Radical66
4.1.3 Organosulfides & Thioethers67
4.1.4 Carbonyl Functions67
4.1.5 Aromatic Amines68
4.2 Implementation Strategies68
4.2.1 Grafting on Inorganic or Organic Support69
4.2.2 Polyanionic Salt Formation71
References74
Chapter 5
Electrolytes and Separators79
5.1 Liquid Electrolytes80
5.1.1 Lithium Salts and Organic Solvents80
5.1.2 Lithium Salts and Ionic Liquids84
5.2 Separators85
5.2.1 Properties of Separators85
5.2.2 The Separator Market86
5.2.3 Cost and Security87
Bibliography88
Chapter 6
Na-ion Batteries : Should/Can Lithium be Replaced ?89
6.1 General Aspects89
6.1.1 Should Lithium be Replaced ?89
6.1.2 Can Lithium be Replaced ? Towards a 100% Abundant Element-Based Battery92
6.2 The Na-ion Technology93
6.2.1 Brief History93
6.2.2 Operating Principle93
6.3 State of the Art95
6.3.1 Negative Electrode Materials95
6.3.2 Non-Carbon Materials96
6.3.3 Positive Electrode Materials98
6.3.4 Electrolytes and Interfaces101
6.4 Full System Performance102
6.5 Outlook102
6.5.1 Low Cost Approach102
6.5.2 High Power Approach103
References103
Chapter 7
Metal-Sulfur Batteries107
7.1 The Metal-Sulfur Cell107
7.1.1 Advantages and Comparison with Other Technologies107
7.1.2 Working Mechanism of the Metal-Sulfur Cell108
7.1.3 The (Li,Na)-ion Sulfur Cell110
7.2 Technology State of the Art and Performances110
7.2.1 Main Actors110
7.2.2 Understanding the Complex Mechanism110
7.2.3 Development Strategies112
7.2.4 All-Solid-State Metal-Sulfur Batteries119
7.2.5 Industrial Actors119
7.3 Perspectives and Applications121
Bibliography122
Chapter 8
All Solid-State Batteries125
8.1 Introduction and Overview125
8.2 Main Families of Solid Ionic Conductors127
8.2.1 Polymeric Solid Electrolytes127
8.2.2 Inorganic Solid Electrolytes130
8.2.3 Hybrid Solid Electrolytes133
8.3 Electrochemical Stability of Solid Electrolytes135
8.4 All-Solid-State Cells137
8.5 Academic & Industrial Players138
Bibliography139
Chapter 9
Supercapacitors : From Material to Cell145
9.1 Operating Principle147
9.2 Carbon/Carbon Based Technology152
9.2.1 Electrode Design and Components152
9.2.2 Electrolyte166
9.2.3 Separators176
9.3 Hybrid Systems179
9.3.1 Activated Carbon/Mn02 System181
9.3.2 Lead Oxide/Activated Carbon System182
9.3.3 NiOOH/Activated Carbon System182
9.3.4 Graphite/Activated Carbon System182
Bibliography186
Chapter 10
Supercapacitors : Cells and Modules199
10.1 Cell Design199
10.1.1 Small Cells200
10.1.2 High-Capacity Cells200
10.2 Design of Modules and Systems207
10.2.1 Modules Based on Hard Casing Cells208
10.2.2 High Capacity Modules Based on Soft Packaging Cells (Pouch Cells)213
10.2.3 High Capacity Modules Working in Aqueous Medium216
Bibliography218
Chapter 11
Characterization of the Electrical Performance of Li-ion Cells221
11.1 Characterization of the Electrical Performance of Individual Cells221
11.1.1 Acceptance Tests221
11.1.2 Beginning of Life Performance Tests223
11.1.3 Ageing Performance Tests227
11.2 Resistance Measurements of Individual Cells229
11.2.1 Introduction229
11.2.2 How to Define an Internal Resistance ?229
11.2.3 Different Methods of Measuring Internal Resistance231
11.2.4 Conclusion243
Bibliography244
Chapter 12
Microstructural and Physical and Chemical Characterizations of Battery Materials245
12.1 Introduction : Characterization Methodology to Understand the Electrochemical Response of a Battery245
12.2 Analysis of Mechanisms Associated with Exchangeable Lithium Loss249
12.2.1 SEI Formation and Li Metal Precipitation on Negative Electrode249
12.2.2 Loss of Lithium Content of Positive Electrode252
12.3 Analysis of Phase Transformations that Limit Lithium Mobility254
12.3.1 Microstructural Modification of a Positive Electrode254
12.4 Mechanical Blocking, Obstruction, Disconnection and Loss of Electrical Contact255
12.4.1 Loss of Graphite Electrode Capacity in Cycling at Low Temperatures255
12.4.2 Exogenous Deposits257
12.5 Electrolyte Degradation258
12.6 Perspectives259
Bibliography259
Chapter 13
Cells and Electrodes Manufacturing Process263
13.1 General Principles263
13.2 Cell Design264
13.3 Electrode Manufacturing Process268
13.3.1 Electrode Formulation268
13.3.2 Slurry Preparation269
13.4 Electrodes270
13.4.1 Calendering272
13.5 Cell Fabrication Process272
13.5.1 Slitting272
13.5.2 Cell Assembly273
13.5.3 Electrolyte Filling275
13.5.4 Electrical Formation275
13.6 Cells Bill of Materials and Cost Aspects275
13.7 New Processes/Perspectives276
13.8 Conclusion277
Bibliography277
Chapter 14
Battery System and Battery Management System (BMS)279
14.1 Battery System Architecture279
14.2 Battery System in Its Electrical Environment281
14.3 Power Component Associated to Battery Pack284
14.4 Multiples Functions of BMS287
14.5 Design and Manufacture of Battery Packs293
14.6 Examples of Innovation on Battery Systems296
References301
Chapter 15
Definition of the State Estimation Algorithms of a Battery System and Associated Calculation Methods303
15.1 Battery State Indicator Definition303
15.1.1 State of Charge303
15.1.2 State of Energy304
15.1.3 State of Health304
15.1.4 State of Function305
15.1.5 State of Safety305
15.2 Battery Diagnosis Methods306
15.2.1 State of Charge Estimation307
15.2.2 Kalman Filter Exploitation for State of Charge Estimation312
15.2.3 Battery Total Capacity Estimation312
15.2.4 Alternative Battery State Diagnosis Method315
Bibliography316
Chapter 16
Standards and Safety317
16.1 Phenomena Involved in Abusive Conditions318
16.1.1 Phenomena at Cell Level319
16.1.2 Phenomena at Module and Pack Level323
16.2 Regulation325
16.3 Standards327
16.4 Tests and Additional Analysis333
16.5 Solutions to Improve Safety at Different Levels334
16.5.1 Improvement of the Components within the Cell335
16.5.2 Safety Devices at Cell Level340
16.5.3 Safety Devices at the Module and Battery System Level342
16.6 Conclusions and Prospects346
Bibliography347
Chapter 17
Li-ion Battery Recycling351
17.1 Contextual Elements351
17.2 Process Head353
17.3 Process Core (Separation - Valorization)354
17.3.1 Pyrometallurgy354
17.3.2 Hydrometallurgy355
17.4 Conclusion363
References364
Chapter 18
Li-ion Batteries Environmental Impacts and Life Cycle Assessment (LCA)369
18.1 Why a Focus on Battery Environmental Impacts ?369
18.2 How to Quantify Batteries Environmental Impacts ?370
18.3 What are the Main Impacts of Lithium-ion Batteries ?372
18.4 What are the Impact Sources ?379
18.5 Guidelines for Ecodesign381
Bibliography383
Chapter 19
Applications and Markets - User Cost385
19.1 General Elements of Market Analysis - Focus on the Electrified Vehicle Market385
19.2 Issue of User Cost388
References389
Conclusion391
Glossary395
The Authors407