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Preface xiii Part I: Chemical and Electrochemical Hydrogen Storage 1 1 Metal Hydride Hydrogen Compression Systems - Materials, Applications and Numerical Analysis 3 Evangelos I. Gkanas and Martin Khzouz 1.1 Introduction 3 1.2 Adoption of a Hydrogen-Based Economy 4 1.2.1 Climate Change and Pollution 4 1.2.2 Toward a Hydrogen-Based Future 4 1.2.3 Hydrogen Storage 5 1.2.3.1 Compressed Hydrogen Storage 5 1.2.3.2 Hydrogen Storage in Liquid Form 5 1.2.3.3 Solid-State Hydrogen Storage 6 1.3 Hydrogen Compression Technologies 6 1.3.1 Reciprocating Piston Compressor 7 1.3.2 Ionic Liquid Piston Compressor 8 1.3.3 Piston-Metal Diaphragm Compressor 9 1.3.4 Electrochemical Hydrogen Compressor 9 1.4 Metal Hydride Hydrogen Compressors (MHHC) 11 1.4.1 Operation of a Two-Stage MHHC 11 1.4.2 Metal Hydrides 14 1.4.3 Thermodynamic Analysis of the Metal Hydride Formation 14 1.4.3.1 Pressure-Composition-Temperature (P-c-T) Properties 14 1.4.3.2 Slope and Hysteresis 16 1.4.4 Material Challenges for MHHCs 17 1.4.4.1 AB5 Intermetallics 18 1.4.4.2 AB2 Intermetallics 19 1.4.4.3 TiFe-Based AB-Type Intermetallics 19 1.4.4.4 Vanadium-Based BCC Solid Solution Alloys 19 1.5 Numerical Analysis of a Multistage MHHC System 20 1.5.1 Assumptions 20 1.5.2 Physical Model and Geometries 21 1.5.3 Heat Equation 22 1.5.4 Hydrogen Mass Balance 22 1.5.5 Momentum Equation 23 1.5.6 Kinetic Expressions for the Hydrogenation and Dehydrogenation 23 1.5.7 Equilibrium Pressure 24 1.5.8 Coupled Mass and Energy Balance 24 1.5.9 Validation of the Numerical Model 25 1.5.10 Material Selection for a Three-Stage MHHC 26 1.5.11 Temperature Evolution of the Complete Three-Stage Compression Cycle 27 1.5.12 Pressure and Storage Capacity Evolution During the Complete Three-Stage Compression Cycle 29 1.5.13 Importance of the Number of Stages and Proper Selection 31 1.6 Conclusions 32 Acknowledgments 32 Nomenclature 32 References 33 2 Nitrogen-Based Hydrogen Storage Systems: A Detailed Overview 39 Ankur Jain, Takayuki Ichikawa and Shivani Agarwal 2.1 Introduction 40 2.2 Amide/Imide Systems 41 2.2.1 Single-Cation Amide/Imide Systems 41 2.2.1.1 Lithium Amide/Imide 41 2.2.1.2 Sodium Amide/Imide 44 2.2.1.3 Magnesium Amide/Imide 47 2.2.1.4 Calcium Amide/Imide 49 2.2.2 Double-Cation Amide/Imide Systems 51 2.2.2.1 Li-Na-N-H 52 2.2.2.2 Li-Mg-N-H 54 2.2.2.3 Other Double-Cation Amides/Imides 58 2.3 Ammonia (NH3) as Hydrogen Storage Media 62 2.3.1 NH3 Synthesis 63 2.3.1.1 Catalytic NH3 Synthesis Using Haber-Bosch Process 63 2.3.1.2 Alternative Routes for NH3 Synthesis 68 2.3.2 NH3 Solid-State Storage 69 2.3.2.1 Metal Ammine Salts 69 2.3.2.2 Ammine Metal Borohydride 70 2.3.3 NH3 Decomposition 71 2.3.4 Application of NH3 to Fuel Cell 73 2.4 Future Prospects 74 References 75 3 Nanostructured Mg-Based Hydrogen Storage Materials: Synthesis and Properties 89 Huaiyu Shao, Xiubo Xie, Jianding Li, Bo Li, Tong Liu and Xingguo Li 3.1 Introduction 90 3.2 Experimental Details 92 3.2.1 Synthesis of Metal Nanoparticles 92 3.2.2 Formation of the Nanostructured Hydrides and Alloys 93 3.2.3 Characterization and Measurements 93 3.3 Synthesis Results of the Nanostructured Samples 94 3.4 Hydrogen Absorption Kinetics 98 3.5 Hydrogen Storage Thermodynamics 99 3.6 Novel Mg-TM (TM=V, Zn, Al) Nanocomposites 103 3.6.1 Introduction 103 3.6.2 Structure and Morphology of Mg-TM Nanocomposites 105 3.6.3 Hydrogen Absorption Kinetics 107 3.6.4 Phase Evolution During Hydrogenation/Dehydrogenation 108 3.6.5 Summary 109 3.7 Summary and Prospects 110 Acknowledgments 111 References 111 4 Hydrogen Storage in Ti/Zr-Based Amorphous and Quasicrystal Alloys 117 Akito Takasaki, ?ukasz Gondek, Joanna Czub, Alicja Klimkowicz, Antoni ?ywczak and Konrad ?wierczek 4.1 Introduction 118 4.2 Production of Ti/Zr-Based Amorphous and Quasicrystals Alloys 119 4.3 Hydrogen Storage in T-Zr-Based Amorphous Alloys 124 4.3.1 Gaseous Hydrogenation 124 4.3.2 Electrochemical Hydrogenation 129 4.4 Hydrogen Storage in the Ti/Zr-Based Quasicrystal Alloys 130 4.4.1 Gaseous Hydrogenation 131 4.4.2 Electrochemical Hydrogenation 133 4.5 Comparison of Amorphous and Quasicrystal Phases on the Hydrogen Properties 140 4.6 Conclusions 141 References 142 5 Electrochemical Method of Hydrogenation/Dehydrogenation of Metal Hydrides 147 N.E. Galushkin, N.N. Yazvinskaya and D.N. Galushkin 5.1 Introduction 148 5.2 Electrochemical Method of Hydrogenation of Metal Hydrides 151 5.2.1 Hydrogen Accumulation in Electrodes of Cadmium-Nickel Batteries Based on Electrochemical Method 151 5.2.2 Hydrogen Accumulation in Sintered Nickel Matrix of Oxide-Nickel Electrode 155 5.2.2.1 Active Substance of Oxide-Nickel Electrodes 155 5.2.2.2 Sintered Nickel Matrices of Oxide-Nickel Electrodes 157 5.3 Electrochemical Method of Dehydrogenation of Metal Hydrides 161 5.3.1 Introduction 161 5.3.2 Thermal Runaway as the New Method of Hydrogen Desorption from Hydrides 164 5.3.2.1 Thermo-Chemical Method of Hydrogen Desorption 164 5.3.2.2 Thermal Runaway: A New Method of Hydrogen Desorption from Metal Hydrides 164 5.4 Discussion 166 5.5 Conclusions 172 References 173 Part II: Carbon-Based Materials for Hydrogen Storage 177 6 Activated Carbon for Hydrogen Storage Obtained from Agro-Industrial Waste 179 Yesid Murillo-Acevedo, Paola Rodriguez-Estupinan, Liliana Giraldo Gutierrez and Juan Carlos Moreno-Pirajan 6.1 Introduction 180 6.2 Experimental 182 6.3 Results and Discussion 183 6.4 Conclusions 192 Acknowledgments 193 References 193 7 Carbonaceous Materials in Hydrogen Storage 197 R. Pedicini, I. Gatto, M. F. Gatto and E. Passalacqua 7.1 Introduction 198 7.2 Materials Consisting of Only Carbon Atoms 199 7.2.1 Graphite 199 7.2.2 Carbon Nanofibers 200 7.2.3 Carbon Nanostructures 202 7.2.4 Graphene 203 7.2.5 Carbon Nanotubes (CNTs) and Carbon Multi-Walled Nanotubes (MWCNTs) 203 7.3 Materials Containing Carbon and Other Light Elements 205 7.3.1 Polyaniline (PANI), Polypyrrole (PPy) and Polythiophene (PTh) 206 7.3.2 Hyperbranched Polyurea (P-Urea) and Poly(Amide-Amine) (PAMAM) 207 7.3.3 Microporous Polymers (PIMs) 207 7.3.4 Conjugated Microporous Polymers (CMPs) 208 7.3.5 Hyper-Cross-Linked Polymers (HCPs) 209 7.3.6 Porous Aromatic Frameworks (PAFs) 209 7.4 Composite Materials Made by Polymeric Matrix 210 7.4.1 Composite Poly(Amide-Amine) (PAMAM) 211 7.4.2 Polymer-Dispersed Metal Hydrides (PDMHs) 211 7.4.3 Mn Oxide Anchored to a Polymeric Matrix 212 7.5 Waste and Natural Materials 217 7.6 Conclusions 220 References 223 8 Beneficial Effects of Graphene on Hydrogen Uptake and Release from Light Hydrogen Storage Materials 229 Rohit R Shahi 8.1 Introduction 230 8.2 General Aspects of Graphene 232 8.2.1 Synthesis of Graphene 233 8.2.1.1 Mechanical Cleavage of Highly Oriented Pyrolytic Graphite 233 8.2.1.2 Chemical Vapor Deposition 233 8.2.1.3 Chemical and Thermal Exfoliation of Graphite Oxide 234 8.2.1.4 Arc Discharge Method 234 8.2.2 Graphene as a Beneficial Additive for HS Materials 234 8.3 Beneficial Effect of Graphene: Key Results with Light Metal Hydrides (e.g., LiBH4, NaAlH4, MgH2) 236 8.3.1 Borohydrides (Tetrahydroborate) as HS Material 236 8.3.1.1 Effect of Graphene on Desorption Properties of LiBH4 237 8.4 Alanates as HS Materials 239 8.4.1 Effect of Graphene on Sorption Behavior of NaAlH4 240 8.4.2 Carbon Nanomaterial-Assisted Morphological Tuning of NaAlH4 to Improve Thermodynamics and Kinetics 242 8.5 Magnesium Hydride as HS Material 243 8.5.1 Catalytic Effect of Graphene on Sorption Behavior of Mg/MgH2 244 8.5.2 Nanoparticles Templated Graphene as an Additive for MgH2 246 8.6 Summary and Future Prospects 253 Acknowledgment 254 References 254 9 Hydrogen Adsorption on Nanotextured Carbon Materials 263 G. Sdanghi, G. Maranzana, A. Celzard and V. Fierro 9.1 Introduction 264 9.1.1 Essential Features of Hydrogen Adsorption on Porous Carbon Materials 264 9.1.2 Measurement of the Hydrogen Storage Capacity 267 9.1.3 Excess, Absolute and Total Hydrogen Adsorption 268 9.2 Hydrogen Storage in Carbon Materials 270 9.2.1 Activated Carbons 270 9.2.2 Carbon Nanomaterials 273 9.2.2.1 Graphene 273 9.2.2.2 Fullerenes 276 9.2.2.3 Carbon Nanotubes 276 9.2.2.4 Carbon Nanofibers 279 9.2.3 Templated Carbons 282 9.2.3.1 Zeolite- and Silica-Derived Carbons 282 9.2.3.2 MOFs-Derived Carbons 284 9.2.4 Other Carbon Materials 289 9.2.4.1 Carbide-Derived Carbons 289 9.2.4.2 Hybrid Carbon-MOF Materials 289 9.2.4.3 Hyper-Cross-Linked Polymers-Derived Carbons 291 9.2.4.4 Carbon Nanorods, Nanohorns and Nanospheres 291 9.2.4.5 Carbon Nitrides 293 9.2.4.6 Carbon Aerogels 293 9.2.4.7 Other Exotic Carbon Materials 294 9.3 Conclusion 295 Acknowledgments 297 References 297 Appendix 310 Index 321

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