1. Introduction ................................................. 1
1.1. Motivation: The Hydrogen Economy ........................... 1
1.2. Brief, Synchronic History of Development of Hydrides
and Nanomaterials .......................................... 7
1.2.1. Early Investigations of Metal-Hydrogen Systems
and Hydrides ........................................ 7
1.2.2. Early Routes to Nanomaterials ...................... 10
1.2.3. Historical Development of Classical Hydrogen
Storage AB5 Alloys ................................. 13
1.2.4. Historical Development of Interstitial Hydrides
in Other Intermetallic Systems ..................... 15
1.2.5. Historical Development of Nanophase AB2
Intermetallic Hydrides ............................. 16
1.2.6. New Routes to Nanomaterials: Mechanical Alloying
and Mechanochemical Activation ..................... 17
1.2.7. Historical Development of Lightweight Metal
Hydrides and Hydride Complexes ..................... 18
1.2.8. Early Studies of Noninterstitial Transition
Metal Ternary Hydrides ............................. 20
1.2.9. Toward Chemical/Complex Hydrides ................... 21
1.2.10.Historical Development of Nanocarbons
and Carbon Nanotubes ............................... 23
1.2.11. New Materials and Techniques ...................... 25
1.3. Nanoprocessing in Solid State in High-Energy Ball
Mills ..................................................... 27
1.3.1. Processes for the Synthesis of Nanostructured
Materials ................................................. 27
1.3.2. Milling Processes and Equipment .................... 28
1.3.3. Nanoprocessing Methods and Mechanisms .............. 37
1.3.3.1. Mechanical Milling ........................ 38
1.3.3.2. Mechanical Alloying ....................... 39
1.3.3.3. Mechanochemical Activation ................ 40
1.3.3.4. Mechanochemical Synthesis
(Mechanosynthesis) of Nanohydrides ........ 52
1.3.3.5. Mechanical Amorphization .................. 55
1.4. Important Hydride Properties and Experimental
Techniques ................................................ 56
1.4.1. Thermodynamics ..................................... 56
1.4.1.1. Pressure-Composition-Temperature
(PCT) Properties .......................... 56
1.4.1.2. Calculation of Activation Energy .......... 60
1.4.2. PCT and Kinetic Curves Determination by
Volumetric Method in a Sieverts-Type Apparatus ..... 65
1.4.3. Microstructural Characterization of В all-
Milled Hydrides .................................... 71
1.4.4. Weight Percent of a Hydride Phase and Hydrogen
by DSC Method ...................................... 73
References ................................................ 74
2. Simple Metal and Intermetallic Hydrides ..................... 83
2.1. Mg/MgH2 ................................................... 83
2.1.1. Crystallographic and Material Characteristics ...... 83
2.1.2. Hydrogen Storage Characteristics of Commercial
Mg and MgH2 ........................................ 87
2.1.2.1. Absorption ................................ 87
2.1.2.2. Desorption ................................ 93
2.1.3. Hydrogen Storage Characteristics of Mechanically
(Ball) Milled MgH2 ................................ 102
2.1.3.1. Microstructural Evolution During
Milling and Subsequent Cycling of
Commercial MgH2 Powders .................. 103
2.1.3.2. Hydrogen Absorption of Ball-milled
Commercial MgH2 Powders .................. 112
2.1.3.3. Hydrogen Desorption of Ball-milled
Commercial MgH2 Powders .................. 115
2.1.4. Hydrogen Storage Characteristics of MgH2
Synthesized by Reactive Mechanical (Ball)
Milling of Mg ..................................... 129
2.1.5. Aging Effects in Stored MgR, Powders .............. 146
2.1.6. Other Methods of Synthesis of Nanostructured
MgH2 than Ball Milling ............................ 147
2.2. MgH2 with Catalytic Additives ............................ 151
2.2.1. Mg/MgH2-Metals and Intermetallics ................. 152
2.2.1.1. Desorption in Vacuum ..................... 152
2.2.1.2. Desorption at Atmospheric Pressure of
Hydrogen ................................. 153
2.2.2. Mg/MgH2-Metal Oxides .............................. 165
2.2.3. Mg/MgH2-Carbon/Graphite and Carbon Nanotubes ...... 169
2.3. Other Metal Hydrides Containing Mg ....................... 170
2.4. A1H3 ..................................................... 174
2.5. Other Metal and Intermetallic-based Hydrides:
New Developments ......................................... 177
2.5.1. Metal Hydrides .................................... 179
2.5.2. Rare-Earth AB5 Compounds .......................... 181
2.5.3. Titanium-Iron AB Compounds ........................ 182
2.5.4. Titanium and Zirconium AB2 Compounds .............. 183
2.5.5. Other Novel Intermetallic Hydrides ................ 183
References ............................................... 183
3. Complex Hydrides ........................................... 195
3.1. Ternary Transition Metal Complex Hydrides ................ 196
3.1.1. Mg2NiH4 ........................................... 196
3.1.2. Mg2FeH6 ........................................... 198
3.1.3. Mg2CoH5 ........................................... 204
3.2. Alanates ................................................. 206
3.2.1. NaAlH4 ............................................ 206
3.2.2. LiAlH4 ............................................ 213
3.2.3. Mg(AlH4)2 and Ca(AlH4)2 ........................... 223
3.3. Amides ................................................... 231
3.4. Metal Borohydrides ....................................... 240
3.5. Destabilization of High Desorption Temperature
Hydrides by (Nano)Compositing ............................ 253
3.5.1. MgH2-LiAlH4 Composite System ...................... 255
3.5.2. MgH2-NaAlH4 Composite System ...................... 265
3.5.3. MgH2-NaBH4 Composite System ....................... 270
References ............................................... 281
4. Carbons and Nanocarbons .................................... 291
4.1. Diamond and Nanodiamonds ................................. 291
4.2. Graphene, Ordered Graphite, and Nanographites ............ 294
4.2.1. Graphene .......................................... 294
4.2.1.1. In-Plane a and Out-of-Plane к Bonding .... 295
4.2.1.2. Van der Walls Interplanar and
Intermolecular Interactions .............. 296
4.2.1.3. Physisorption of Hydrogen on Carbons ..... 297
4.2.1.4. Chemisorption of Hydrogen on Carbons ..... 298
4.2.2. Graphitic Nanofibers, Whiskers, and Polyhedral
Crystals .......................................... 299
4.2.3. Graphite .......................................... 299
4.3. Disordered and Active Carbons ............................ 301
4.3.1. Disordered Graphites and Mechanically-Activated
Carbons ........................................... 301
4.3.2. Active Carbons and Chemically Activated Carbons ... 303
4.3.3. Amorphous Carbon .................................. 304
4.4. Highly Ordered Fullerenes, Carbon Nanotubes, and
Carbon Nanohorns ......................................... 305
4.4.1. Fullerenes and Hydrofullerenes .................... 305
4.4.2. Carbon Nanotubes .................................. 308
4.4.3. Carbon Nanohorns .................................. 312
4.4.4. Nanostructured Carbon Shells and Carbon Onions .... 314
References ............................................... 317
5. Summary .................................................... 321
5.1. Metal/Intermetallic Hydrides ............................. 322
5.2. Complex Hydrides ......................................... 323
5.3. Nanocarbons and Others ................................... 324
Index ......................................................... 327
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