Lithium Batteries (eBook)

Dr. Christian M. Julien received his engineer degree in Physics from Conservatoire des Arts et Métiers, Paris and obtained his PhD in materials science from Université Pierre et Marie Curie, Paris. He has 35 years of research experience in the field of solid state ionics and materials for energy storage and conversion, and, has developed lithium microbatteries. He is especially well known for his contributions on vibrational spectroscopy of lithium intercalation compounds. He was director of NATO Advanced Study Institutes on intercalation compounds and materials for batteries. Presently, he joints the laboratory PHENIX at Université Pierre et Marie Curie where he is investigating cathode and anode materials for lithium-ion batteries. Dr. Julien is an active member of The Electrochemical Society and international editorial boards and editor of Journal of Materials.Dr. Alain Mauger attended the University of Paris where he graduated in solid state physics, obtained the PhD degree in 1974, and Doctorat d'État in 1980. His work focussed on the theory of impurities in semi-metals, electronic structure of solids, and magnetic semiconductors. He left Paris to spend a year at the University of California, Irvine where he continued his work on magnetic semiconductors and optical properties of liquid crystals in collaboration with Professor D.L. Mills, and shared his time between the University of Paris and the University of California up to 1985. He went on to do research at the University of Paris 07 on spin glasses and statistical physics. Since 1992, he has been in university Paris 06, leading different groups on solid state and complex matter physics, before joining IMPMC in 2007 to work on the materials science for Li-ion batteries.Dr. Ashok Vijh is Maître-de-recherche at the Institut de Recherche d’Hydro-Québec and, concurrently, invited Professor at the INRS of Université du Québec. Elected to The Royal Society of Canada in 1985, he was President of its Academy of Science (2005-2007). He is an electrochemist and materials scientist who has published over 360 refereed papers and six books on various problems of charge transfers across electrified interfaces. His work has been awarded over 60 distinctions: prizes, medals, decorations, fellowships, honorary doctorates, named lectureships and professorships, academy memberships and international editorial boards. Dr. Karim Zaghib received his Ph.D. from the Institut National Polytechnique de Grenoble in 1990 and undertook post-doctoral studies under a Saft-DGA contract (1990-1992). From 1992 to 1995, he was a guest researcher at the Japanese Ministry of International Trade and Industry (MITI) and at the Osaka National Research Institute (ONRI). In 1995, he joined Hydro-Québec, where he currently serves as Administrator of the energy storage and conversion unit. Dr. Zaghib is especially well known for his contributions to the development and understanding of lithium-ion battery materials, particularly through his collaborations on graphite anodes, and on olivine cathodes. In 1996, he was the first to propose the use of nano-scale LTO for lithium-ion batteries and hybrid supercapacitors.

Chapter 1. Basic elements for energy storage and conversion 1.1 Energy storage ability 1.2 The sustained energy 1.3 Energy storage for nano-electronics 1.4 Energy storage 1.5 Brief history of electrochemical cells 1.5.1 Milestones 1.5.2 Battery designs 1.6 Key parameters of batteries 1.6.1 Basic parameters 1.6.2 Cycle life and calendar life 1.6.3 Energy, capacity and power 1.6.3.1 Modified Peukert plot 1.6.3.2 Ragone figure 1.7 Electrochemical Systems 1.7.1 Batteries 1.7.2 Electrochromics and smart windows 1.7.3 Supercapacitors 1.8 Concluding remarks References Chapter 2. Lithium batteries 2.1 Introduction 2.2 Historical overview 2.3 Primary lithium batteries 2.3.1 High temperature lithium cells 2.3.1.1 Lithium iron disulfide battery 2.3.1.2 Lithium chloride battery 2.3.2 Solid-State electrolyte lithium batteries 2.3.2.1 Lithium-iodine cells 2.3.2.2 Li/LiI-Al2O3/PbI2 cells 2.3.2.3 Carbon tetramethyl-ammonium penta-iodide batteries 2.3.2.4 Lithium bromine trifluoride battery 2.3.3 Liquid cathode lithium batteries 2.3.3.1 Lithium thionyl-chloride batteries 2.3.3.2 Lithium-sulfur dioxide batteries 2.3.4 Solid Cathode lithium Batteries 2.3.4.1 Lithium polycarbon fluoride cells 2.3.4.2 Lithium manganese oxide batteries 2.3.4.3 Low temperature lithium iron batteries 2.3.4.4 Silver vanadium oxide cells 2.3.4.5 Other primary lithium batteries 2.4 Secondary lithium batteries 2.4.1 Lithium-metal batteries 2.4.2 Lithium-ion batteries 2.4.2.1 Principle 2.4.2.2 Energy diagram 2.4.2.3 Design and manufacturing 2.4.3 Lithium polymer batteries 2.4.4 Lithium sulfur batteries 2.5 Economy of lithium batteries 2.6 Battery modeling References Chapter 3. Principle of intercalation 3.1 Introduction 3.2 Intercalation mechanism 3.3 The Gibbs’ phase rule 3.4 Classification of intercalation reactions 3.4.1 The perfectly non-stoichiometric compounds. Type-I electrode 3.4.2 The pseudo two-phase system. Type-II electrode 3.4.3. The two-phase system. Type-III electrode 3.4.4 The adjacent domain. Type-IV electrode 3.5 Intercalation in layered compounds 3.5.1 Synthesis of ICs 3.5.2 Alkali intercalation into layered compounds 3.6 Electronic energy in ICs 3.7 Origin of the high voltage in ICs 3.8 Lithium battery cathodes 3.9 Conversion reaction 3.10 Alloying reaction References Chapitre 4. Reliability of the rigid-band model in lithium intercalation compounds 4.1 Introduction 4.2 Evolution of the Fermi level 4.3 Electronic structure of TMDs 4.4 Lithium intercalation in TiS2 4.5 Lithium intercalation in TaS2 4.6 Lithium intercalation in 2H-MoS2 4.7 Lithium intercalation in WS2 4.8 Lithium intercalation in InSe 4.10 Electrochemical properties of TMCs 4.11 Concluding remarks References Chapter 5. Cathode materials with 2-dimensional structure 5.1 Introduction 5.2 Binary layered oxides 5.2.1 MoO3 5.2.2 V2O5 5.2.3 LiV3O8 5.3 Ternary layered oxides 5.3.1 LiCoO2 (LCO) 5.3.2 LiNiO2 (LNO) 5.3.3 LiNi1-yCoyO2 (NCO) 5.3.4 Doped LiCoO2 (d-LCO) 5.3.5 LiNi1-y-zCoyAlzO2 (NCA) 5.3.6 LiNi0.5Mn0.5O2 (NMO) 5.3.7 LiNi1-y-zMnyCozO2 (NMC) 5.3.8 Li2MnO3 5.3.9 Li-rich layered compounds (LNMC) 5.3.10 Other layered compounds 5.3.10.1 Mn-based oxides 5.3.10.2 Chromium oxides 5.3.10.3 Iron-based oxides 5.4 Concluding remarks References Chapter 6. Cathode materials with monoatomic ions in a 3-D framework 6.1 Introduction 6.2 Manganese dioxides 6.2.1 MnO2 6.2.2 MnO2-based composites 6.2.3 MnO2 nanorods 6.2.4 Birnessite 6.3 Lithiated manganese dioxides 6.3.1 Li0.33MnO2 6.3.2 Li0.44MnO2 6.3.3 LiMnO2 6.3.4 LixNa0.5-xMnO2 6.4 Lithium manganese spinels 6.4.1 LiMn2O4 (LMO) 6.4.2 Surface modified LMO 6.4.3 Defect spinels 6.4.4 Li doped spinels 6.5 Five-volt Spinels 6.6. Vanadium oxides 6.6.1 V6O13 6.6.2 LiVO2 6.6.3 VO2(B) 6.7 Concluding remarks References Chapter 7. PO4-based compounds as cathode materials 7.1 Introduction 7.2 Synthesis routes 7.2.1 Solid-state reaction 7.2.2 Sol-gel method 7.2.3 Hydrothermal method 7.2.4 Coprecipitation method 7.2.5 Microwave synthesis 7.2.6 Polyol and solvothermal process 7.2.7 Micro-emulsion 7.2.8 Spray technique 7.2.9 Template method 7.2.10 Mechanical activation 7.3 Crystal chemistry 7.3.1 Structure of olivine phosphate 7.3.2. The inductive effect 7.4 Structure and morphology of optimized LiFePO4 particles 7.4.1 XRD patterns of LFP 7.4.2 Morphology of optimized LFP 7.4.3 Local structure, lattice dynamics 7.5 Magnetic and electronic features 7.5.1 Intrinsic magnetic properties 7.5.2 Effect of the -Fe2O3 impurity 7.5.3 Effect of the Fe2P impurity 7.5.4 Magnetic polaron effects 7.6 Carbon coating 7.6.1 Characterization of the carbon layer 7.6.2 Quality of the carbon layer 7.7. Effects of deviation from stoichiometry 7.8 Aging of LFP Particles exposed to water 7.8.1 Water-immersed LFP particles 7.8.2 Long-term water-exposed LFP particles 7.9 Electrochemical performance of LFP 7.9.1 Cycling behaviour 7.9.1 Electrochemical features vs. temperature 7.10 LiMnPO4 as a 4-V cathode 7.11 Polyanionic high-voltage cathodes 7.11.1 Synthesis of olivine materials 7.11.2 LiNiPO4 as 5-V cathode 7.11.3 LiCoPO4 as 5-V cathode 7.12. NASICON-like compounds 7.13. Silicates Li2MSiO4 (M=Fe, Mn, Co) 7.14 Summary and outlook References Chapter 8. Fluoro-polyanionic compounds 8.1 Introduction 8.2. Properties of polyanionic compounds 8.3. Fluorophosphates 8.3.1. Fluorine-doped LiFePO4 8.3.2. LiVPO4F 8.3.3. LiMPO4F (M=Fe, Ti) 8.3.4. Li2FePO4F (M=Fe, Co, Ni) 8.3.5. Li2MPO4F (M=Co, Ni) 8.3.6. Na3V2(PO4)2F3 hybrid-ion cathode 8.3.7. Other fluorophosphates 8.4. Fluorosulfates 8.4.1. LiFeSO4F 8.4.2. LiMSO4F (M = Co, Ni, Mn) 8.5. Concluding remarks References Chapter 9. Disordered compounds 9.1 Introduction 9.2 Disordered MoS2 9.3 Hydrated MoO3 9.4 MoO3 thin films 9.5 Disordered vanadium oxides 9.6 LiCoO2 thin films 9.7 Disordered LiMn2O4 9.8 Disordered LiNiVO4 References Chapter 10. Negative electrodes for Li-ion batteries 10.1 Introduction 10.2 Carbon-based anodes 10.2.1 Hard carbon 10.2.2 Soft carbon 10.2.3 Carbon nanotubes 10.2.4 Graphene 10.2.5 Surface-modified carbons 10.3 Silicon anodes 10.3.1 Si thin films 10.3.2 Si nanowires (Si Nw) 10.3.3 Porous silicon 10.3.4 Porous nanotubes and nanowires versus nanoparticles 10.3.5 Coated Si nanostructures and stabilization of the SEI 10.4 Germanium 10.5 Tin and lead 10.6 Oxides with intercalation-deintercalation reaction 10.6.1 TiO2 10.6.1.1 Anatase 10.6.1.2 Rutile TiO2 10.6.1.3 TiO2-B 10.6.2 Li4Ti5O12 10.6.3 Ti-Nb oxide 10.7. Oxides based on alloying/de-alloying reaction 10.7.1 Si oxides 10.7.2 GeO2 and germanates 10.7.3 Sn oxides 10.8 Anodes based on conversion reaction 10.8. 1 CoO 10.8.2 NiO 10.8.3 CuO 10.8.4 MnO 10.8.5 Oxides with spinel structure 10.8.5.1 Co3O4 10.8.5.2 Fe3O4 10.8.5.3 Mn3O4 10.8.6 Oxides with the corundum structure: M2O3 (M=Fe, Cr, Mn) -Fe2O3 10.8.6.2 Cr2O3 10.8.6.3 Mn2O3 10.8.7 Dioxides 10.9 Ternary metal oxides with spinel structure 10.9.1 Molybenum compounds 10.9.2 Oxide bronzes 10.9.3 Mn2Mo3O8 10.10 Anodes based on both alloying and conversion reaction 10.10.1 ZnCo2O4 10.10.2 ZnFe2O4 10.11 Concluding remarks References Chapter 11. Electrolytes for lithium batteries 11.1 Introduction 11.2 Characteristics of an ideal electrolyte 11.2.1 Electrolyte components 11.2.2 Solvents 11.2.3 Solutes 11.2.4 Electrolytes with ionic liquids 11.2.4.1 Lithium metal rechargeable batteries in ionic liquids 11.2.4.2 Lithium intercalation rechargeable batteries involving ionic liquids 11.3. Passivation Phenomena at electrode-electrolyte interfaces in Li batteries 11.4 Some Problems with the current commercial electrolyte systems 11.4.1 Irreversible capacity loss 11.4.2 Temperature range 11.4.3 Thermal runaway: safety and hazards 11.4.4 Enhanced ion transport 11.5 Electrolyte designs 11.5.1 Control of the SEI 11.5.2 Safety concerns with Li salts 11.5.3 Protection against overcharge 11.5.4 Fire retardants 11.6 Summary and conclusions References Chapter 12. Nanotechnology 12.1 Introduction 12.2 Synthesis methods of nanomaterials 12.2.1 Wet-Chemical methods 12.2.1.1 Sol-gel method 12.2.1.2 Pechini technique 12.2.1.3 Precipitation method 12.2.1.4 Polyol process 12.2.1.5 Combustion method 12.2.1.6 Pyrolysis method 12.2.2. Template synthesis 12.2.3 Spray-pyrolysis method 12.2.4 Hydrothermal method 12.2.5 Jet milling 12.3 The disordered surface layer 12.3.1 General considerations 12.3.2 DSL of LiFePO4 nanoparticles 12.3.3 DSL of LiMO2 layered compounds 12.4 Electrochemical properties of nanoparticles 12.5 Nanoscale functional materials 12.5.1 WO3 nanocomposites 12.5.2 WO3 nanorods 12.5.3 WO3 nanopowders and nanofilms 12.5.4 Li2MnO3 rock-salt nano-structure 12.5.5 Aluminium doping effect in NCA materials 12.5.6 MnO2 nanorods 12.5.7 MnO3 nanofibers 12.6 Concluding remarks References Chapter 13 Electrochemical measurements in solids 13.1 Introduction 13.2 Theory 13.3 Measurements of insertion kinetics 13.3.1 Electrochemical-potential spectroscopy (EPS) 13.3.2 Galvanostatic intermittent titration technique (GITT) 13.3.2.1 Short relaxation time (tL2/ ) 13.3.3 Electrochemical impedance spectroscopy 13.4 Application: kinetics in MoO3 electrode 13.4.1 MoO3 crystal 13.4.2 MoO3 films 13.5 Incremental capacity analysis (ICA) 13.5.1 Introduction 13.5.2 Incremental capacity analysis of half cell 13.5.2.1 V6O13 13.5.2.2 LiNiO2 13.5.2.3 LiNi0.5Mn0.5O2 13.5.2.4 Li3V2(PO4)3 13.5.2.5 Silicon nanowires 13.5.3 ICA and DVA of full cell 13.6 Transport measurements in solids 13.6.1 Resistivity measurements 13.6.2 Hall effect 13.6.3 Van der Pauw method 13.6.4 Optical properties 13.6.4.1. Limit >1 for the free electron gas (no mixing with phonons) 13.6.4.2 Reflectivity near the plasma edge in a solid 13.6.5 Ionic conductivity: complex impedance technique 13.7 Magnetism as a tool in the solid-state chemistry of cathode materials 13.7.1 LiNiO2 13.7.2 LiNi1-yCoyO2 13.7.3 Boron-doped LiCoO2 13.7.4 LiNi1/3Mn1/3Co1/3O2 References Chapter 14. Safety aspects of Li-ion batteries 14.1 Introduction 14.2 Experiments and methods 14.2.1 Coin cell fabrication 14.2.2 Differential scanning calorimetry 14.2.3 Experiments on commercial 18650 cells 14.2.3.1 Hybrid pulse power characterization 14.2.3.2 Isothermal microcalorimetry 14.2.3.3 Accelerating rate calorimeter 14.2.3.4 Safety tests 14.3 Safety of LiFePO4-graphite cells 14.4 Li-ion batteries involving ionic liquids 14.4.1 Graphite anode against different electrolytes 14.4.2 LiFePO4 cathode against different electrolytes 14.5 Surface modification 14.5.1 Energy diagram 14.5.2 Surface coating of layered electrodes 14.5.2.1 LiCoO2 14.5.2.2 LiNi0.7Co0.3O2 14.5.3 Surface modifications of spinel electrodes 14.5.3.1 LiMn2O4 14.5.3.2 LiNi0.5Mn1.5O4 14.6 Concluding remarks References Chapter 15. Technology of the Li-ion batteries 15.1 The capacity 15.2 Negative/positive capacity ratio 15.3 Electrode loading 15.4 Degradations 15.4.1 Damage of the crystalline structure 15.4.2 Dissolution of the SEI 15.4.3 Migration of cathode species 15.4.4 Corrosion 15.5 Manufacturing and packaging 15.5.1 Step 1: preparation of the active particles of the electrodes 15.5.2 Step 2: preparation of the electrode laminates 15.5.2.1 The binder 15.5.2.2 Deposition on the current collector 15.5.2.3 Roll pressing process 15.5.3 Assembly process 15.5.4 Formation process 15.5.5 The charger References