Ionic Liquids II (eBook)

Dedication 6
Contents 7
Foreword 9
Ionic Liquids in Lithium-Ion Batteries 12
Abstract 12
Lithium-Ion Batteries 12
Electrolyte in Lithium-Ion Batteries: Requirements and State-of-the-Art 13
Ionic Liquids 16
Aprotic Ionic Liquids As Electrolytes for LIB 16
Protic Ionic Liquids As Electrolytes for LIBs 22
Mixtures of Ionic Liquids and Organic Solvents As Electrolytes for Lithium-Ion Batteries 26
Ionic Liquids-Based Electrolytes and Inactive Components: the Case of Anodic Dissolution of Aluminum 31
Conclusions 33
Acknowledgements 34
References 34
Ionic Liquids for Supercapacitor Applications 39
Abstract 39
Introduction 39
Bulk Properties 42
Thermal Stability 42
Operating Voltage 43
Ionic Conductivity 44
Interfacial Properties 45
The Double-Layer in ILs 45
Planar Interfaces 45
Confinement Effects 49
Performances of ILs in Supercapacitors 52
Methodological Aspects 52
Interfacial Capacitances 55
Redox-Active ILs 57
Conclusions and Perspectives 58
References 59
Electrochemical Synthesis of Battery Electrode Materials from Ionic Liquids 64
Abstract 64
1 Introduction 64
2 Electrode Materials for Li-Ion Batteries 66
3 Electrode Materials for Na-Ion Batteries 72
4 Li–Air and Zn–Air Batteries with Ionic Liquid Electrolyte 75
4.1 Li–Air Batteries 75
4.2 Zn–Air Batteries 79
5 Al–Air, Al–Ion and Al–S Batteries 84
5.1 Al-Ion Battery 84
5.2 Al–Air Battery 86
5.3 Al–S Battery 86
6 Conclusions 86
References 87
Ionic Liquid--Liquid Chromatography: A New General Purpose Separation Methodology 93
Abstract 93
Introduction 94
Introduction to Countercurrent Chromatography 95
Ionic Liquids in Chromatography 97
Introduction to Ionic Liquids 97
The Use of Ionic Liquids in Chromatography 98
The Use of Ionic Liquids in Countercurrent Chromatography 99
Phase Behaviour of Ionic Liquids 102
Ionic Liquid-Organic Solvent 103
Ionic Liquid--Water Systems 105
Ionic Liquid--Ionic Liquid 107
Solvent Engineering and Ionic Liquid--Liquid Chromatography 108
Ionic Liquid Solvent Systems and Instrumentation in Countercurrent Chromatography 109
Introduction 109
Instrument Design 109
Solvent Selection 111
Stationary Phase Retention Curves with Ionic Liquids 114
Ionic Liquid--Liquid Separations 118
Separation of Organic Compounds 118
Separation of Saccharides 118
Aromatic/Alkane Separations 119
Separation of Vetiver Oil 121
Separation of Transition Metal Salts 122
Transition Metal Behaviour in the Water/[P6 6 6 14]Cl/Ethyl Ethanoate Solvent System 123
Transition Metal Separation 125
Conclusions 127
Acknowledgements 128
References 128
Proteins in Ionic Liquids: Current Status of Experiments and Simulations 134
Abstract 134
Introduction 134
From the Ionic Liquids Point of View 135
Polarity and Hydrophobicity 135
Anionic Hydrogen Bonding and Cationic Surfactant Effects 137
Hofmeister Series 138
Kosmotropic and Chaotropic Ions 139
Law of Matching Water Affinities 140
Determination of Kosmotropic/Chaotropic Character 141
Impact of Ion Concentration 142
Through the Eyes of the Protein 143
Protein Solubility 143
At the Protein Surface 144
Following the Hofmeister Series 145
Protein Crystallization 145
Separation of Proteins 146
Two-Phase Systems 147
Protein Detection 148
Protein Stability 148
Gibbs Free Energy of Unfolding 148
Computer Simulations 150
The Impact of the Ionic Liquid Ions 152
Thermodynamics of the Hofmeister Series 153
Acknowledgement 156
References 156
Metal Nanoparticles in Ionic Liquids 160
Abstract 160
Introduction 161
Ionic Liquids 163
Metal Nanoparticles in Ionic Liquids 164
Stabilization of Metal Nanoparticles 166
Derjaguin-Landau-Verwey-Overbeek theory (DLVO theory)--- Electrostatic Stabilization and Van Der Waals Interactions 166
Steric Stabilization 168
Combination of Both Electrostatic and Steric Stabilization 169
Stabilization of Metal Nanoparticles in Ionic Liquids 169
Electrostatic and Steric = Electrosteric Stabilization 169
Hydrogen Bonding Interactions 174
Influence of Polar and Non-Polar Domains in ILs 176
Cation and Anion Effects 176
Alkyl Chain Effects 179
Viscosity 181
Influence of Functional ILs to Metal Nanoparticles 182
N-Heterocyclic Carbene Formation During Metal Nanoparticle Synthesis in Imidazolium ILs 184
Conclusion 185
References 186
Lewis Acidic Ionic Liquids 192
Abstract 192
Introduction 192
Chlorometallate Ionic Liquids 193
Historical Context 193
Speciation 195
Chloroaluminate(III) Ionic Liquids 195
Chlorogallate(III) Ionic Liquids 199
Chloroindate(III) Ionic Liquids 199
Chloroferrate(III) Ionic Liquids 200
Chlorozincate(III) Ionic Liquids 200
Chlorostannate(II) Ionic Liquids 201
Acidity Measurements 202
Gutmann Acceptor Number: NMR Spectroscopic Method 202
Adapted Solid-State Methods: FT-IR Spectroscopy 205
Activity in Catalytic Process 207
Selected Applications 207
Refinery Alkylation with Chloroaluminate(III) Ionic Liquids 207
SILP and SCILL 209
Inorganic Synthesis 211
Liquid Coordination Complexes (LCCs) 213
Historical Context 213
Speciation 213
Acidity Measurements 217
Ionic Liquids with Lewis Acidic Cations 218
Solvate Ionic Liquids 218
Historical Context 218
Speciation 219
Acidity Measurements 220
Applications 222
Borenium ILs (Group 13 Lewis Acids) 223
Historical Context 223
Speciation 224
Acidity Measurements 224
Applications 225
Conclusions 226
Open Access 226
References 226
Quantum Chemical Modeling of Hydrogen Bonding in Ionic Liquids 232
Abstract 232
Introduction 233
H-bonds and ILs 234
Quantum Chemical Computational Modeling of H-bonds Within ILs 237
Quantum Chemical Methods 238
Comparison with Other Computational Methods 241
Procedures for Carrying Out Calculations 244
Properties and Bonding Analysis 245
Generalised Solvation 246
Conclusions 250
Open Access 250
References 250
Mesoscopic organization in ionic liquids 254
Abstract 254
Introduction 255
Effect of cation symmetry 255
Effect of pressure 257
Effect of ether chains 258
Effect of fluorination 261
Binary mixtures of ethylammonium nitrate and alcohols: amphiphile meets amphiphile 263
Conclusions 267
Acknowledgements 267
References 267
Hydrogen Sulfide and Ionic Liquids: Absorption, Separation, and Oxidation 271
Abstract 271
Introduction 271
Capture and Separation by Physical and/or Chemical Absorption 274
Absorption and Oxidation 285
Computational Studies 288
Ab Initio Calculations 288
Dynamic Simulation 290
Predictive Models 291
Conclusions 292
References 293