Functional Auxiliary Materials in Batteries: Synthesis, Properties, and Applications

Comprehensive reference exploring innovative auxiliary materials as a variety of battery components to enhance battery performance, safety, and longevity Functional Auxiliary Materials in Batteries: Synthesis, Properties, and Applications overviews the latest research on the applications of organic functional materials and low-dimensional structural materials as functional auxiliary materials in batteries. The book introduces the properties and preparation methods of these materials, summarizes the application mechanisms and conclusions, and puts forward novel insights and prospects towards more sustainable and environmentally friendly battery technologies. The first five chapters of this book expand around the application of organic functional materials in batteries, including separators, binders, electrolytes, and functional additives. The last two chapters of this book expand around the application of low-dimensional structural materials in batteries, including conductive agents and functional additives. Functional Auxiliary Materials in Batteries includes information on: Film forming, flame retardant, high voltage, and overcharge protection additives Adjusting factors in biopolymer materials such as molecular structure, composition, and morphology to precisely regulate and optimize battery performance Ionic liquids and single-ion conductors as a more secure and widely usable alternative to traditional organic electrolytes Self-healing materials, covering their positive effects on energy density, cost reduction, safety, and sustainability and their challenges including complexity and material compatibility Carbon-based materials that mitigate polysulfide shuttle effects and extend cycle life Functional Auxiliary Materials in Batteries is an essential reference for new researchers seeking to quickly understand the progress of research in related fields. The book is also valuable for senior researchers seeking inspiration for innovation.

Table of Contents:
Preface xiii 1 Application of Organic Functional Additives in Batteries 1 1.1 Introduction 1 1.2 Fluorinated Additives 2 1.2.1 Functions of Fluorinated Additives 2 1.2.1.1 Improvement of Safety Performance 2 1.2.1.2 SEI-Forming Additives 2 1.2.1.3 High Oxidation Stability 4 1.2.1.4 Promotion of the Formation of Anion-Rich Solvation Structure 5 1.2.1.5 Reduction of Desolvation Barrier 6 1.2.2 Synergies of Fluoroethylene Carbonate with Other Compounds 6 1.2.2.1 Fluoroethylene Carbonate and Other Fluorinated Electrolytes 6 1.2.2.2 Fluoroethylene Carbonate and Lewis Base 7 1.2.2.3 Fluoroethylene Carbonate and Glyme 7 1.2.3 Drawbacks of Fluoroethylene Carbonate 8 1.2.3.1 Generation of HF Gas 8 1.2.3.2 Increase of Impedance and Loss of Impedance 8 1.2.3.3 Incompatibility with Other Electrodes 8 1.2.3.4 Recycling Issues 9 1.3 Nitro Additive 9 1.3.1 Functions of Nitro (NO − 3) 9 1.3.1.1 Participation in Solvation and Desolvation Structures 9 1.3.1.2 Formation of Inorganic-Rich SEI 10 1.3.1.3 CEI-Forming Additives 12 1.3.1.4 Functions in Lithium–Sulfur Batteries 13 1.3.1.5 Stabilization of Water Molecules 14 1.3.2 Organic Nitro Additive 14 1.3.2.1 Complex Nitrate-Based Additives 14 1.3.2.2 Complex Nitro-Based Additives 15 1.3.3 Drawbacks and Solutions of Nitro Additives 15 1.3.3.1 Low Solubility 15 1.3.3.2 Sacrificial Additives 17 1.3.3.3 High Decomposition Activation Energy of LiNO 3 18 1.4 Nitrile Additives 19 1.4.1 Functions of Nitrile Additives 19 1.4.1.1 Plasticization 19 1.4.1.2 Facilitation of Ion Transport 20 1.4.1.3 Promotion of Lithium Salt Dissolution 22 1.4.1.4 Widening of the Electrochemical Window 22 1.4.1.5 Inhibiting the Decomposition of the Electrolyte 22 1.4.1.6 Low Flammability 22 1.4.1.7 Improvement of Polymer Flexibility 23 1.4.1.8 Modification of the Cathode Interface 23 1.4.1.9 Involvement in the Solvation Structure of Zn 2+ 24 1.4.1.10 Weakening of Ionic Association 24 1.4.1.11 Contribution to the Formation of SEI 24 1.4.2 Compatibility Analysis of Nitrile and Lithium Metal 25 1.4.2.1 Incompatibility of Nitrile and Lithium Metal 25 1.4.2.2 Improvement of the Compatibility of Nitrile and Lithium Metal 25 1.4.3 Other Drawbacks of Nitrile Additives 28 1.4.3.1 Low Mechanical Strength 28 1.4.3.2 Prone to Polymerization 28 1.4.3.3 Crystallinity 28 1.5 Phosphate Ester Additives 29 1.5.1 Functions of Phosphate Ester Additives 29 1.5.1.1 Flame Retardant 29 1.5.1.2 Stabilization of Cathodes and Anodes 30 1.5.1.3 Involvement in Solvation Structure Regulation 31 1.5.2 Drawbacks of Phosphate Ester 32 1.5.2.1 Incompatibility with Anodes 32 1.5.2.2 Improvement of the Compatibility of Phosphate Ester and Lithium Metal 32 1.6 Sulfate Ester Additives 34 1.6.1 Functions of Sulfate Ester Additives 34 1.6.1.1 SEI-Forming Additives 34 1.6.1.2 CEI-Forming Additives 36 1.7 Conclusion and Outlook 39 References 40 2 Application of Biopolymers in Batteries 51 2.1 Introduction 51 2.2 Overview of Biopolymers 53 2.2.1 Carboxymethyl Cellulose (CMC) 53 2.2.2 Chitosan (CS) 54 2.2.3 Sodium Alginate (SA) 56 2.2.4 Lignin 57 2.2.5 Gum Arabic (GA) 57 2.2.6 Guar Gum (GG) 59 2.2.7 Xanthan Gum (XG) 59 2.2.8 Starch 60 2.2.9 Gelatin 61 2.2.10 Tragacanth Gum (TG) 62 2.2.11 Cellulose (CLS) 63 2.2.12 Trehalose (THL) 64 2.2.13 Citrulline (Cit) 64 2.2.14 Pectin 65 2.2.15 Carrageenan 66 2.3 Application of Biopolymers in Binders 66 2.3.1 Carboxymethyl Cellulose 67 2.3.2 Chitosan 68 2.3.3 Sodium Alginate 70 2.3.4 Lignin 72 2.3.5 Gum Arabic 74 2.3.6 Guar Gum and Xanthan Gum 75 2.3.7 Starch 75 2.3.8 Gelatin 76 2.3.9 Tragacanth Gum (TG) 78 2.4 Application of Biopolymers in Electrolytes 79 2.4.1 Cellulose 79 2.4.2 Chitosan 81 2.4.3 Lignin 82 2.4.4 Gelatin 85 2.5 Application of Biopolymers in Electrolyte Additives 87 2.5.1 Cellulose 88 2.5.2 Trehalose 88 2.5.3 Citrulline 89 2.5.4 Pectin 90 2.6 Application of Biopolymers in Separators 90 2.6.1 Cellulose 91 2.6.2 Starch 94 2.6.3 Carrageenan 95 2.7 Application of Biopolymers in Anode Functional Layers 95 2.7.1 Cellulose 96 2.7.2 Chitosan and Sodium Alginate 96 2.8 Conclusion and Outlook 98 References 100 3A Application of Synthetic Polymers in Batteries: Carbon-chain Polymers 107 3A.1 Introduction 107 3A.2 Overview of Synthetic Polymers Materials 107 3A.2.1 Polyvinylidene Difluoride (PVDF) 108 3A.2.2 Polytetrafluoroethylene (PTFE) 109 3A.2.3 Styrene-Butadiene Rubber (SBR) 110 3A.2.4 Polyvinyl Alcohol (PVA) 111 3A.2.5 Polyacrylics (PA) 111 3A.2.6 Polyacrylonitrile (PAN) 112 3A.2.7 Polyvinyl Pyrrolidone (PVP) 113 3A.2.8 Polyolefin (PO) 114 3A.3 Application of Synthetic Polymers in Binders 115 3A.3.1 Polyvinylidene Difluoride 115 3A.3.2 Polytetrafluoroethylene 117 3A.3.3 Styrene-Butadiene Rubber 118 3A.3.4 Polyvinyl Alcohol 119 3A.3.5 Polyacrylics 122 3A.4 Application of Synthetic Polymers in Electrolytes 124 3A.4.1 Polyvinylidene Difluoride 125 3A.4.2 Polyacrylonitrile 129 3A.4.3 Polyacrylics 131 3A.4.4 Polyvinyl Alcohol 133 3A.5 Application of Synthetic Polymers in Battery Separators 135 3A.5.1 Polyolefin 136 3A.5.2 Polyvinylidene Difluoride 138 3A.5.3 Polyacrylonitrile 139 3A.5.4 Polyvinyl Alcohol 140 3A.6 Application of Synthetic Polymers in Anodes 142 3A.6.1 Polyacrylonitrile 142 3A.6.2 Polyacrylics 143 3A.7 Conclusions and Outlook 143 References 145 3B Application of Synthetic Polymers in Batteries: Hetero-chain Polymers 155 3B.1 Introduction 155 3B.2 Overview of Synthetic Polymers Materials 155 3B.2.1 Epoxy Resin (EPR) 156 3B.2.2 Polyethylenimine (PEI) 157 3B.2.3 Polyurethane (PU) 158 3B.2.4 Polyethylene Oxide (PEO) 158 3B.2.5 Polyethylene Terephthalate (PET) 159 3B.2.6 Polyimide (PI) 160 3B.3 Application of Synthetic Polymers in Binders 161 3B.3.1 Epoxy Resin 161 3B.3.2 Polyethylenimine 162 3B.3.3 Polyurethane 164 3B.3.4 Polyimide 166 3B.4 Application of Synthetic Polymers in Electrolytes 167 3B.4.1 Epoxy Resin 167 3B.4.2 Polyurethane 170 3B.4.3 Polyethylene Oxide 173 3B.4.4 Polyimide 176 3B.5 Application of Synthetic Polymers in Battery Separators 178 3B.5.1 Polyethylene Terephthalate 178 3B.5.2 Polyimide 179 3B.6 Conclusions and Outlook 180 References 182 4 Application of Nontraditional Organic Ionic Conductors in Batteries 189 4.1 Ionic Liquids 189 4.1.1 Introduction of Ionic Liquids 189 4.1.2 Development of Ionic Liquids 190 4.1.3 Catalog of Ionic Liquids 191 4.1.4 Advantages of Ionic Liquids for Batteries 193 4.1.5 Synthesis and Characterization Method of Ionic Liquids 193 4.1.6 Application of Ionic Liquids 194 4.2 Application of ILs in Batteries 196 4.2.1 Ionic Liquid Electrolyte 198 4.2.2 Ionic Liquid/Organic Solvent Electrolyte 206 4.2.3 Organic–Inorganic Composite Ionic Liquid Electrolyte 210 4.3 Single-Ion Conductive 215 4.3.1 Introduction of Single-Ion Conductive 215 4.3.2 Catalog of Single-Ion Conductive 216 4.4 Application of Single-Ion Conductive in Batteries 217 4.4.1 Organic Single-Ion Conductor Electrolyte 217 4.4.2 Organic–Inorganic Composite Single-Ion Conductor Electrolyte 225 4.5 Conclusions and Outlook 228 References 230 5 Application of Self-Healing Materials in Batteries 239 5.1 Introduction 239 5.1.1 The Need for Battery Innovation 239 5.1.2 Overview of Self-Healing Materials 239 5.1.3 Benefits of Self-Healing Technologies in Batteries 240 5.1.4 Challenges in Scaling and Commercializing Self-Healing Materials 242 5.2 Types of Self-Healing Materials for Battery Applications 243 5.2.1 Physically Bonded Self-Healing Materials 243 5.2.2 Chemically Bonded Self-Healing Materials 243 5.2.3 Composite Self-Healing Materials with Multiple Repair Mechanisms 244 5.3 Applications of Self-Healing Materials in Batteries 244 5.3.1 Gel Polymer Electrolytes 244 5.3.2 Solid Polymer Electrolytes 256 5.3.3 Composite Electrolytes 272 5.3.4 Electrode Binders 275 5.4 Conclusions and Outlook 281 References 282 6 Application of Low-Dimensional Materials in Batteries 287 6.1 Introduction 287 6.1.1 Lithium-Metal Batteries 287 6.1.2 Low-Dimensional Composite Materials 288 6.2 Low-Dimensional Composite Cathode Materials 289 6.2.1 Composite Methods for Low-Dimensional Cathode Materials 290 6.2.2 One-Dimensional Materials in Cathode 293 6.2.2.1 Carbon Nanotube (CNT) Materials 293 6.2.2.2 Carbon Nanofiber (CNF) Materials 297 6.2.3 Two-Dimensional Materials in Cathode 299 6.2.3.1 Graphene Materials 299 6.2.3.2 MXene Materials 304 6.3 Low-Dimensional Composite Materials in Separators 309 6.3.1 Zero-Dimensional Materials in Separators 310 6.3.2 One-Dimensional Materials in Separators 312 6.3.3 Two-Dimensional Materials in Separators 315 6.4 Low-Dimensional Composite Current Collectors 320 6.4.1 Design of Current Collector 320 6.4.2 Nanocomposite Current Collectors 322 6.5 Low-Dimensional Composite Anode Materials 324 6.5.1 Formation of SEI and Failure Mechanism 324 6.5.2 Nanocomposite Lithium Metal Anodes 325 6.5.3 Low-Dimensional Materials in 3D-Printing Anodes 328 6.6 Conclusion and Outlook 329 References 330 7 Applications of Porous Organic Framework Materials in Batteries 339 7.1 Introduction 339 7.1.1 Overview of Energy Demand and Battery Technologies 339 7.1.2 Limitations of Traditional Battery Material 339 7.1.3 Potential of Porous Organic Framework Materials for Energy Storage 340 7.2 Types of Porous Organic Framework Materials 341 7.2.1 Metal-Organic Frameworks (MOFs) 341 7.2.1.1 Types of MOFs 342 7.2.2 Covalent Organic Frameworks (COFs) 342 7.2.2.1 Types of COFs 343 7.2.3 Hydrogen-Bonded Organic Frameworks (HOFs) 343 7.2.3.1 Types of HOF 343 7.3 Applications of Porous Organic Framework Materials in Batteries 345 7.3.1 Applications in Electrode Materials 345 7.3.1.1 MOF as Electrode Materials 345 7.3.1.2 COF as Electrode Materials 352 7.3.1.3 HOF as Electrode Materials 356 7.3.2 Applications in Electrolytes and Electrolyte Additives 359 7.3.2.1 MOF as Electrolytes and Electrolyte Additives 359 7.3.2.2 COF as Electrolytes and Electrolyte Additives 364 7.3.2.3 HOF as Electrolytes and Electrolyte Additives 367 7.3.3 Applications in Catalysts and Catalyst Supports 368 7.3.3.1 MOF as Catalysts and Catalyst Supports 368 7.3.3.2 COF as Catalysts and Catalyst Supports 371 7.3.3.3 HOF as Catalysts and Catalyst Supports 373 7.3.4 Applications in Battery Separators 374 7.3.4.1 MOF as Battery Separator 374 7.3.4.2 COF as Battery Separator 378 7.3.4.3 HOF as Battery Separator 380 7.4 Conclusion and Outlook 381 7.4.1 Conclusion 381 7.4.2 Outlook 382 References 383 Index 389

About the Author :
Wei Hu, PhD, is Associate Professor and Doctoral Supervisor at the University of Science and Technology Beijing (USTB), China. His research interests include polymer composite solid electrolyte, nanomaterials, and intelligent responsive materials. He is currently on the editorial board of Battery Energy.