Graphite Intercalation Compounds I : Structure and Dynamics

In this book emphasis is laid on the basic physics and chemistry of graphite intercalation compounds arising from their quasi-two-dimensional structure. The various chapters are designed to guide graduate students and other newcomers into the new and exciting field of two-dimensional physics, and at the same time to pro- vide a comprehensive review of the current status of the field.

1. Introduction.- References.- 2. Structural Properties and Phase Transitions.- 2.1 Effects of Intercalation on the Graphite Host.- 2.1.1 Pure Graphite.- 2.1.2 Intercalation Effects.- 2.2 Intercalate Structures: General Features.- 2.2.1 Stage Disorder.- 2.2.2 Interlayer Intercalant Correlations in the Liquid State.- 2.2.3 Two-Dimensional Melting.- 2.3 The Two-Dimensional Liquid State.- 2.3.1 Alkali Liquids ― Experimental Results.- 2.3.2 Modulated 2d Liquids ― Theory and Application to Alkalis.- 2.3.3 Molecular Dynamics Simulations.- 2.3.4 Acceptor Liquids.- 2.4 Phase Transitions and Ordered States.- 2.4.1 Overview.- 2.4.2 Donors.- 2.4.3 Acceptors ― General Remarks.- 2.5 Conclusions.- References.- 3. Staging and Kinetics.- 3.1 The Energetics of Staging.- 3.1.1 Charge Transfer.- 3.1.2 Host Layer Cohesion and Homogeneous Elastic Strains.- 3.1.3 Elasticity, Intercalate Islands and Domains.- 3.1.4 Intralayer and Guest-Host Interactions.- 3.2 Classical Staging Models and Their Implications.- 3.2.1 Safran’s Model of Staging.- 3.2.2 The Need for Modifications.- 3.2.3 Models That Describe Simple Stages.- 3.2.4 Towards an Explanation of the Anomalous Fractional Stages.- 3.3 Experimental Staging Phase Diagrams.- 3.3.1 Typical Graphite Intercalation Compounds.- 3.3.2 Systems Exhibiting a Reentrant Dilute Stage 1 Phase at High Temperatures.- 3.3.3 Staging Under Pressure.- 3.4 Stage Disorder.- 3.4.1 Thermal Theory of Stage Disorder in Daumas-H6rold Domains.- 3.4.2 Experiments: General Trends.- 3.4.3 Experiments: Stage Disorder and Stage Transformations.- 3.5 Staging and the Kinetics of the Intercalation Process.- 3.5.1 Experiments.- 3.5.2 Computer Simulations.- 3.6 The Kinetics of Stage Transformations.- 3.6.1 Kinetic Models and Experiments.- 3.6.2 Computer Simulations and More Experiments.- References.- 4. Lattice Dynamics I: Neutron Studies.- 4.1 Lattice Dynamics and Inelastic Neutron Scattering.- 4.1.1 Lattice Dynamical Models.- 4.1.2 Inelastic Neutron Scattering.- 4.2 [00q]L Phonon Dispersion.- 4.2.1 Lattice Dynamical Models for [00q]L Modes.- 4.2.2 Experimental Results.- 4.2.3 Interlayer Force Constants.- 4.3 [q00]T? Phonon Dispersion.- 4.3.1 Introductory Remarks.- 4.3.2 Experimental Results.- 4.4 Phonon Density of States of Intercalate Modes.- 4.4.1 Introductory Remarks.- 4.4.2 Experimental Results.- 4.4.3 Anisotropy of Intercalate Interaction.- 4.5 Thermal Properties.- 4.5.1 Specific Heat.- 4.5.2 Debye-Waller Factor.- 4.5.3 Thermal Expansion.- 4.6 Conclusion.- References.- 5. Lattice Dynamics II: Optical Studies.- 5.1 Theoretical Considerations.- 5.1.1 First-Order Raman Scattering.- 5.1.2 Second-Order Raman Scattering.- 5.2 Experimental Techniques.- 5.2.1 Traditional Methods.- 5.2.2 Novel Techniques.- 5.3 Pristine Graphite.- 5.3.1 Structure and Symmetry.- 5.3.2 First-Order Optical Spectra.- 5.3.3 Second-Order Raman Scattering.- 5.3.4 Finite-Size Effects.- 5.4 Binary Graphite Intercalation Compounds.- 5.4.1 Lattice Dynamics and First-Order Optical Spectra.- 5.4.2 Lattice Dynamics and Second-Order Raman Scattering.- 5.4.3 Charge Transfer and Phonon Frequencies.- 5.5 Ternary Graphite Intercalation Compounds.- 5.5.1 Homogeneous TGICs.- 5.5.2 Heterogeneous TGICs.- 5.5.3 Trilayer TGICs.- 5.5.4 Localized TGICs.- 5.6 Applications of Optical Phonon Spectroscopy.- 5.7 Concluding Remarks.- References.- 6. Intercalate Diffusion.- 6.1 Quasi-Elastic Neutron Scattering.- 6.1.1 Scattering Cross Sections.- 6.1.2 Scattering Laws and Correlation Functions.- 6.2 Alkali-GICs.- 6.2.1 Stage-1 Compounds.- 6.2.2 Stage-2 Compounds.- 6.3 Molecular Intercalates and Ternary Compounds.- 6.3.1 Stage-2 HN03 GIC (C10HNO3).- 6.3.2 Stage-1 H2SO4 GICs.- 6.3.3 Ternary Cs(THF)x Compounds.- 6.3.4 Stage-1 K(NH3)4.3C24.- 6.4 Conclusions.- References.- 7. Microscopic Properties of Graphite Intercalation Compounds.- 7.1 Layer Structure and Staging.- 7.1.1 High-Resolution Transmission Electron Microscopy Studies.- 7.1.2 High-Resolution Scanning Ion Probe Studies.- 7.2 In-Plane Structure.- 7.2.1 Acceptor GICs.- 7.2.2 Donor GICs.- 7.3 Summary and Concluding Remarks.- References.- 8. New Graphite-Donor Compounds and Synthesis.- 8.1 Preliminary Remarks Concerning the Donor-Graphite Intercalation Compounds.- 8.2 New Binary Phases Obtained at High Pressure and/or High Temperature.- 8.2.1 The Graphite-Lithium System.- 8.2.2 The Graphite-Potassium System.- 8.3 The New Ternary Compounds with Multiple Single Layers.- 8.3.1 Synthesis of Heterostructures with Two Heavy Alkali Metals.- 8.3.2 Structures and Reaction Mechanisms.- 8.4 The New Ternary Compounds with Multiple-Layer Intercalated Sheets.- 8.4.1 Hydrogen Derivatives.- 8.4.2 Compounds of Mercury, Thallium and Bismuth.- 8.5 Conclusion and Vistas.- References.- 9. Ternary Systems.- 9.1 Ternary Compounds Containing Only Alkali Metals or Halogens.- 9.1.1 Solid Solution Ternaries Involving Two Alkali Metals.- 9.1.2 Solid Solution Ternaries Involving Two Halogens Other than Fluorine.- 9.2 Ternary Compounds of Metals with a Nitrogen-Containing Base.- 9.2.1 Ternary Metal-Ammonia-Graphite Intercalation Compounds.- 9.2.2 Other Ternary Compounds of Metals with a Nitrogen Base.- 9.2.3 Physical Properties of the Ternary Metal-Base Compounds.- 9.3 The Metal-Organic-Molecule-Graphite Intercalation Compounds.- 9.3.1 Ternary Donor Compounds Containing Aromatic Hydrocarbons.- 9.3.2 Ternary Metal Compounds of Oxygen Derivatives.- 9.3.3 Synergetic Intercalation.- 9.3.4 Problems Associated with the Stoichiometry of the Ternary Compounds.- 9.4 Ternary Acceptor Intercalation Compounds.- 9.4.1 Ternary Metal-Halide-Ammonia-Graphite Intercalation Compounds.- 9.4.2 Ternary Intercalation Compounds Containing a Solid Solution of Two Metal Halides.- 9.4.3 Ternary Systems Involving the Fluorides of Transition Metals.- 9.4.4 Intercalation of Metal Halides from Solutions.- 9.4.5 Intercalation Compounds Containing Solvated Complex Anions.- 9.4.6 Physical Properties.- 9.5 Multi-Intercalation Compounds.- 9.5.1 Donor Bi-Intercalation Compounds.- 9.5.2 Acceptor Bi-Intercalation Compounds.- 9.5.3 Mixed Bi-Intercalation Compounds.- 9.5.4 Physical Properties.- 9.6 Ternary Systems Involving Fluorinated Graphite.- 9.6.1 Compounds of Fluorinated Graphite with Metal Fluorides.- 9.6.2 Compounds of Fluorinated Graphite with Nonmetal Fluorides.- References.