PROGRESS IN INTERCALATION RESEARCH Edited by W. MÜLLER-WARMUTH Institute ofphysical Chemistry Westphalian Wilhelms University Münster, Germany and R. SCHÖLLHORN Institute of Inorganic and Analytical Chemistry Technical University Berlin, Germany KLUWER ACADEMIC PUBLISHERS DORDRECHT / BOSTON / LONDON
TABLE OF CONTENTS List of contributors Preface xi xiii R. SCHÖLLHORN / Materials and Models: Faces of Intercalation Chemistry 1 1. Introduction 1 2. Concepts and Categories 3 2.1. Insulator Host Lattices 4 2.2. Host Lattices with Electronic Conductivity 6 3. Materials 7 3.1 Insulator Host Lattices 8 3.1.1. Framework Systems 8 3.1.2. Layered Systems 11 3.1.3. Layered Double Hydroxides 14 3.2. Redox Type Systems: Oxides 17 3.2.1. Oxide Host Lattices 17 3.2.2. Layered Oxides 19 3.2.3. Oxyhalides of Transition Metals 20 3.2.4. Oxocuprate Superconductors 21 3.3. Redox Type Systems: Chalcogenides and Halides 23 3.3.1. Framework Chalcogenides 24 3.3.2. Chalcogen Spineis 25 3.3.3. Frameworks with Isolated Parallel Lattice Channels 26 3.3.4. Layered Chalcogenide Phases 27 3.3.5. Layered Halides 29 3.4. One-Dimensional Systems 29 3.5. Molecular Hosts 30 3.6. Amorphous and Strongly Defect Phases 30 3.6.1. Chalcogenides 32 3.6.2. Oxides 33 3.7. GuestSpecies 34 3.8. Synthesis and Intracrystalline Reactions 35 3.9. Characterization 39 3.10 Application 40 4. Models 41 4.1. Structural Transitions 41 4.1.1. Host Matrix 41 4.1.2. Layered Systems 42 4.1.3. Staging Transitions 43 4.1.4. Guest Sublattice 46 4.2. Irreversible Processes 47 v
VI TABLE OF CONTENTS 4.3. Electron Transfer and Reaction Mechanisms: Cation Mixed Valence 49 4.3.1. Molybdenum Cluster Chalcogenides 53 4.3.2. Electronic Transport Thresholds 54 4.4. Solvolysis Mechanisms 55 4.5. Neutral Molecular Guest Species 56 4.6. p-band Holes and Anion Mixed Valence 57 4.7. Electron/Anion Transfer 62 4.8. Electron/Proton Transfer 66 4.9. Electron Transfer: A Basic Model 70 5. Conclusions 71 References 71 R. SCHLÖGL / Graphite - A Unique Host Lattice 83 1. Introduction 83 1.1. Prologue 83 1.2. Intercalation 83 1.3. The Host Materials 85 1.4. Guest Species 101 2. Preparation of Graphite Intercalation Compounds 113 2.1. Thermal Methods 113 2.2. Intercalation from the Liquid State 115 2.2.1. Electrochemical Intercalation 116 2.2.2. Chemical Oxidation Processes 117 2.2.3. Photochemical Intercalation 118 3. Structural Organization 122 3.1. Staging 123 3.2. The Mechanisms of Intercalation 134 3.3. Stage Transformations 138 3.4. In-Plane Structures 141 4. Chemical Bonding 149 4.1. Non-Spectroscopic Concepts 149 4.2. Low Energy Spectroscopic Experiments 157 4.3. High Energy Spectroscopy 160 5. Chemical Reactivity 164 5.1. Reactions with GIC 165 5.2. AirStability 167 6. Epilogue 170 Acknowledgements 171 References 171 R. BREC, P. DENIARD and J. ROUXEL / Electronic Properties and Reactivity 177
TABLE OF CONTENTS V11 1. Introduction 177 2. About the Electronic Structures of Transition Metal Chalcogenides 178 3. Electronic Transfer and Reactivity 192 4. Electronic Transfer and Phase Transitions 196 5. Order and Disorder versus Electronic Structure 208 6. Conclusion 218 References 218 A. CLEARFIELD / Intercalation Chemistry of Selected Layered Oxides and Phosphates 223 1. Introduction 223 2. Layered Ternary Oxides 227 2.1. Titanates 227 2.2. Titanoniobates 227 3. Layered Perovskites 232 3.1. Calcium Niobates 232 3.2. Lanthanum Niobates 235 3.3. Lanthanum Titanates 235 3.4. Isopolyniobates 236 4. Silicic Acids 239 5. Group 4 and 14 Metal Phosphates 240 5.1. General Information 240 5.2. Intercalation Reactions of a-zirconium Phosphate 241 5.3. Intercalation of Aromatic Amines 244 5.4. Intercalation of Cyclodextrin 244 5.5. a-zirconium Phosphate as Host for a Chiral Molecular Recognition Reaction 246 5.6. NMR Studies of a-zrp Intercalation Compounds 247 5.7. Intercalation by Staged Zirconium Phosphates 250 5.8. Intercalation Reactions of 7 Phases 252 5.9. Tin(IV) Phosphate 254 6. Pillaring of Layered Compounds 256 6.1. Organically Pillared Group 4 Phosphates 256 6.2. Pillaring with Inorganic Polymers 257 7. Layered Metal Phosphonates 259 7.1. Zirconium Phosphonates 259 7.2. Vanadium Phosphonates 261 7.3. Zirconium Alkyl Phosphates 261 7.4. Divalent and Trivalent Metal Phosphonates 262 8. Miscellany of Topics 263 8.1. V 2 0 5 Gels 263 8.2. Vanadyl Phosphates 264
Vlll TABLE OF CONTENTS 8.3. Layered Double Hydroxides 264 8.4. Buckminsterfullerene 265 9. Conclusion 265 Acknowledgements 266 References 266 D. BILLAUD / Intercalation Processes in Redox Conducting Polymers 273 1. Introduction 273 2. Synthesis, Morphology and Structure of Undoped Polymers 274 2.1. Polyacetylene 274 2.2. Polyparaphenylene (PPP) 278 2.3. Polyparaphenylenevinylene (PPV) 281 2.4. Polypyrrole (PPy), Polythiophene (PTh) and Derivatives 281 2.5. Polyaniline (PANI) 282 3. Intercalation Methods 284 3.1. Introduction 284 3.2. Oxidative Intercalation 285 3.2.1. Chemical Techniques 285 3.2.2. Electrochemical Techniques 287 3.3. Cationic Intercalation ('n-doping') 288 3.3.1. Chemical Methods 288 3.3.2. Electrochemical Techniques 290 4. Intercalation Mechanisms - Nature of the Intercalated Species 291 4.1. Polyacetylene, Polyparaphenylene and Derivatives 291 4.1.1. Reaction with Alkali Metals 292 4.1.2. Reaction with Oxidant Species 292 4.2. Polypyrrole, Polythiophene and Derivatives 293 4.3. Polyaniline (PANI) 295 5. Structural Evolution of Conducting Polymers upon Intercalation 297 5.1. Alkali Metal Intercalation into Polyacetylene (PA), Polyparaphenylene Vinylene (PPV) and Polyparaphenylene (PPP) 297 5.2. Anionic Intercalation in Conducting Polymers 316 6. Polymers with Ion Exchange Properties 326 7. Conclusion 327 Acknowledgements 328 References 329 W. MULLER-WARMUTH / Structure, Bonding, Dynamics: NMR Studies 339 1. Introduction 339 2. General Aspects of NMR Spectroscopy and Its Application to Intercalation Compounds 340
TABLE OF CONTENTS IX 2.1. Basic Principles 341 2.2. Interactions in Solids 342 2.3. NMR Spectra of Single Crystals and Crystal Powders 346 2.4. Experimental Methods 349 2.5. Magnetic Field-Induced Orientation in Powders of Layered Compounds 353 3. Hydrated Layered Chalcogenides 355 3.1. Structure of the Guest Phase 355 3.2. Anisotropie Mobility and Proton Exchange of Water 358 3.3. 93 Nb and 2 H NMR Studies of the Intercalation 362 3.4.! H NMR Studies of the Electronic Properties of the Host Lattice 366 4. Layered Chalcogenides with Intercalated Ammonia, Metal-Ammonia and Amines 369 4.1. 1 H NMR of Metal-Ammonia Intercalation Compounds 370 4.2. Intercalation of Ammonia and Ammonium 373 4.3. Compounds with Intercalated Methylamines 379 5. Intercalation of Further Atomic and Molecular Species in Layered Materials 382 5.1. Lithiated Compounds and Related Systems 384 5.2. Dichalcogenides Intercalated with Copper 388 5.3. Intercalated Molecules 391 5.4. Ruthenium Trichloride and Layered Oxides 397 6. Graphite Intercalation Compounds 399 6.1. NMR of Inserted Alkali Species 399 6.2. 13 C NMR Studies ofthe Host Lattice 403 6.3. 'H NMR Spectra ofternary Systems 409 6.4. Compounds Containing Fluorine 411 7. Hydrogen Bronzes 414 7.1. Transition Metal Disulphide Host Lattices 415 7.2. Layered Molybdenum Oxide Bronzes H x MoÜ3 418 7.3. Bronzes of Oxides in the ReÜ3 and I1-WO3 Systems 424 8. Intercalation Compounds of Host Lattices with Framework Structure 429 8.1. Channel Oxides and Chalcogenides 430 8.2. Molybdenum Cluster Chalcogenides 434 8.3. The Compounds LiiMo 6 X 8 435 8.4. Molybdenum Cluster Chalcogenides Li x Mo 6 X 8 with x > 1 440 8.5. NMR Investigations of Further Chevrel Phases 446 Acknowledgements 450 References 450
X TABLE OF CONTENTS J. O. BESENHARD / Applications: From Battery Materials to Sensor Systems 457 1. Scope 457 2. Introduction 458 3. Intercalation Electrodes in Electrochemical Power Sources 458 3.1. General Considerations 458 3.2. Insertion of Hydrogen into Oxide Electrodes 461 3.3. Insertion of Hydrogen into Metals 464 3.4. Intercalation Compounds in Alkali Metal Batteries 465 3.4.1. Intercalation Cathodes in Lithium Batteries 468 3.4.2. Intercalation Anodes in Lithium Batteries 473 3.4.3. Commercially Available Rechargeable Lithium Batteries 478 3.4.4. Polymer Electrolyte and Thin Film Lithium Batteries 481 4. Intercalation Compounds in Electrochromic Devices 483 4.1. Inorganic Chromogenic Materials 483 4.2. Electrolytes, Electrodes and Reservoirs for Electrochromic Devices 484 4.3. Electrochromic Devices 486 5. Intercalation Chemistry and Chemical Sensors 489 5.1. Operating Principles of Semiconductor Sensors 489 5.2. Construction of Metal Oxide Conductivity Gas Sensors 494 5.3. Graphite Intercalation Compounds in Electrochemical Sensors 494 6. Miscellaneous Applications of Intercalation Compounds 495 6.1. Highly Conductive Materials 495 6.2. Catalysis by Intercalation Compounds 495 6.3. Nanocomposites 496 6.4. Intercalation Compounds as Solid Lubricants 496 References 497 Index 509