PROGRESS IN INTERCALATION RESEARCH

Transcription

1 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

2 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 Insulator Host Lattices Host Lattices with Electronic Conductivity 6 3. Materials Insulator Host Lattices Framework Systems Layered Systems Layered Double Hydroxides Redox Type Systems: Oxides Oxide Host Lattices Layered Oxides Oxyhalides of Transition Metals Oxocuprate Superconductors Redox Type Systems: Chalcogenides and Halides Framework Chalcogenides Chalcogen Spineis Frameworks with Isolated Parallel Lattice Channels Layered Chalcogenide Phases Layered Halides One-Dimensional Systems Molecular Hosts Amorphous and Strongly Defect Phases Chalcogenides Oxides GuestSpecies Synthesis and Intracrystalline Reactions Characterization Application Models Structural Transitions Host Matrix Layered Systems Staging Transitions Guest Sublattice Irreversible Processes 47 v

3 VI TABLE OF CONTENTS 4.3. Electron Transfer and Reaction Mechanisms: Cation Mixed Valence Molybdenum Cluster Chalcogenides Electronic Transport Thresholds Solvolysis Mechanisms Neutral Molecular Guest Species p-band Holes and Anion Mixed Valence Electron/Anion Transfer Electron/Proton Transfer Electron Transfer: A Basic Model Conclusions 71 References 71 R. SCHLÖGL / Graphite - A Unique Host Lattice Introduction Prologue Intercalation The Host Materials Guest Species Preparation of Graphite Intercalation Compounds Thermal Methods Intercalation from the Liquid State Electrochemical Intercalation Chemical Oxidation Processes Photochemical Intercalation Structural Organization Staging The Mechanisms of Intercalation Stage Transformations In-Plane Structures Chemical Bonding Non-Spectroscopic Concepts Low Energy Spectroscopic Experiments High Energy Spectroscopy Chemical Reactivity Reactions with GIC AirStability Epilogue 170 Acknowledgements 171 References 171 R. BREC, P. DENIARD and J. ROUXEL / Electronic Properties and Reactivity 177

4 TABLE OF CONTENTS V11 1. Introduction About the Electronic Structures of Transition Metal Chalcogenides Electronic Transfer and Reactivity Electronic Transfer and Phase Transitions Order and Disorder versus Electronic Structure Conclusion 218 References 218 A. CLEARFIELD / Intercalation Chemistry of Selected Layered Oxides and Phosphates Introduction Layered Ternary Oxides Titanates Titanoniobates Layered Perovskites Calcium Niobates Lanthanum Niobates Lanthanum Titanates Isopolyniobates Silicic Acids Group 4 and 14 Metal Phosphates General Information Intercalation Reactions of a-zirconium Phosphate Intercalation of Aromatic Amines Intercalation of Cyclodextrin a-zirconium Phosphate as Host for a Chiral Molecular Recognition Reaction NMR Studies of a-zrp Intercalation Compounds Intercalation by Staged Zirconium Phosphates Intercalation Reactions of 7 Phases Tin(IV) Phosphate Pillaring of Layered Compounds Organically Pillared Group 4 Phosphates Pillaring with Inorganic Polymers Layered Metal Phosphonates Zirconium Phosphonates Vanadium Phosphonates Zirconium Alkyl Phosphates Divalent and Trivalent Metal Phosphonates Miscellany of Topics V Gels Vanadyl Phosphates 264

5 Vlll TABLE OF CONTENTS 8.3. Layered Double Hydroxides Buckminsterfullerene Conclusion 265 Acknowledgements 266 References 266 D. BILLAUD / Intercalation Processes in Redox Conducting Polymers Introduction Synthesis, Morphology and Structure of Undoped Polymers Polyacetylene Polyparaphenylene (PPP) Polyparaphenylenevinylene (PPV) Polypyrrole (PPy), Polythiophene (PTh) and Derivatives Polyaniline (PANI) Intercalation Methods Introduction Oxidative Intercalation Chemical Techniques Electrochemical Techniques Cationic Intercalation ('n-doping') Chemical Methods Electrochemical Techniques Intercalation Mechanisms - Nature of the Intercalated Species Polyacetylene, Polyparaphenylene and Derivatives Reaction with Alkali Metals Reaction with Oxidant Species Polypyrrole, Polythiophene and Derivatives Polyaniline (PANI) Structural Evolution of Conducting Polymers upon Intercalation Alkali Metal Intercalation into Polyacetylene (PA), Polyparaphenylene Vinylene (PPV) and Polyparaphenylene (PPP) Anionic Intercalation in Conducting Polymers Polymers with Ion Exchange Properties Conclusion 327 Acknowledgements 328 References 329 W. MULLER-WARMUTH / Structure, Bonding, Dynamics: NMR Studies Introduction General Aspects of NMR Spectroscopy and Its Application to Intercalation Compounds 340

6 TABLE OF CONTENTS IX 2.1. Basic Principles Interactions in Solids NMR Spectra of Single Crystals and Crystal Powders Experimental Methods Magnetic Field-Induced Orientation in Powders of Layered Compounds Hydrated Layered Chalcogenides Structure of the Guest Phase Anisotropie Mobility and Proton Exchange of Water Nb and 2 H NMR Studies of the Intercalation ! H NMR Studies of the Electronic Properties of the Host Lattice Layered Chalcogenides with Intercalated Ammonia, Metal-Ammonia and Amines H NMR of Metal-Ammonia Intercalation Compounds Intercalation of Ammonia and Ammonium Compounds with Intercalated Methylamines Intercalation of Further Atomic and Molecular Species in Layered Materials Lithiated Compounds and Related Systems Dichalcogenides Intercalated with Copper Intercalated Molecules Ruthenium Trichloride and Layered Oxides Graphite Intercalation Compounds NMR of Inserted Alkali Species C NMR Studies ofthe Host Lattice 'H NMR Spectra ofternary Systems Compounds Containing Fluorine Hydrogen Bronzes Transition Metal Disulphide Host Lattices Layered Molybdenum Oxide Bronzes H x MoÜ Bronzes of Oxides in the ReÜ3 and I1-WO3 Systems Intercalation Compounds of Host Lattices with Framework Structure Channel Oxides and Chalcogenides Molybdenum Cluster Chalcogenides The Compounds LiiMo 6 X Molybdenum Cluster Chalcogenides Li x Mo 6 X 8 with x > NMR Investigations of Further Chevrel Phases 446 Acknowledgements 450 References 450

7 X TABLE OF CONTENTS J. O. BESENHARD / Applications: From Battery Materials to Sensor Systems Scope Introduction Intercalation Electrodes in Electrochemical Power Sources General Considerations Insertion of Hydrogen into Oxide Electrodes Insertion of Hydrogen into Metals Intercalation Compounds in Alkali Metal Batteries Intercalation Cathodes in Lithium Batteries Intercalation Anodes in Lithium Batteries Commercially Available Rechargeable Lithium Batteries Polymer Electrolyte and Thin Film Lithium Batteries Intercalation Compounds in Electrochromic Devices Inorganic Chromogenic Materials Electrolytes, Electrodes and Reservoirs for Electrochromic Devices Electrochromic Devices Intercalation Chemistry and Chemical Sensors Operating Principles of Semiconductor Sensors Construction of Metal Oxide Conductivity Gas Sensors Graphite Intercalation Compounds in Electrochemical Sensors Miscellaneous Applications of Intercalation Compounds Highly Conductive Materials Catalysis by Intercalation Compounds Nanocomposites Intercalation Compounds as Solid Lubricants 496 References 497 Index 509