Physical Chemistry of Ionic Materials

Joachim Maier, PhD, is Director of the Max Planck Institute for Solid State Research, Stuttgart, Germany, a position he has held since 1991. He has lectured at elite universities in both Europe and the United States, and his work in pioneering the field of nanoionics has earned him numerous international awards and distinctions.

• Preface to the Second Edition ixPreface to the First Edition xi1 Introduction 11.1 Motivation 11.2 The Defect Concept: Point Defects as the Main Actors 3References 112 Bonding Aspects: From Atoms to Solid State 132.1 Chemical Bonding in Simple Molecules 132.1.1 Ideal Covalent Bonding 132.1.2 Polar Covalent Bonding 172.1.3 The Ionic Bonding 192.1.4 Metallic Bonding 202.1.5 Further Intermediate Forms of Chemical Bonding 212.1.6 Two-Body Potential Functions 212.2 Many Atoms in Contact: The Solid State as a Giant Molecule 232.2.1 The Band Model 232.2.2 Ionic Crystals 362.2.3 Molecular Crystals 412.2.4 Covalent Crystals 432.2.5 Metallic Crystals 442.2.6 Mixed Forms of Bonding in Solids 462.2.7 Crystal Structure and Solid State Structure 472.2.8 Atomistic Modelling 49References 513 Phonons 553.1 Einstein and Debye models 553.2 Deviations From Ideality 58References 614 Equilibrium Thermodynamics of the Perfect Solid 634.1 Preliminary Remarks 634.2 The Formalism of Equilibrium Thermodynamics 634.3 Examples of Equilibrium Thermodynamics 764.3.1 Solid–Solid Phase Transition 764.3.2 Melting and Evaporation 774.3.3 Solid–Solid Reaction 784.3.4 Solid–Gas Reaction 784.3.5 Phase Equilibria and Mixing Reactions 794.3.6 Spatial Equilibria in Inhomogeneous Systems 884.3.7 Thermodynamics of Elastically Deformed Solids 904.3.8 The Thermodynamic Functions of State of the Perfect Solid 91References 935 Equilibrium Thermodynamics of the Real Solid 955.1 Preliminary Remarks 955.2 Equilibrium Thermodynamics of Point Defect Formation 965.3 Equilibrium Thermodynamics of Electronic Defects 1105.4 Higher-Dimensional Defects 1195.4.1 Equilibrium Concentration 1195.4.2 Dislocations: Structure and Energetics 1205.4.3 Interfaces: Structure and Energetics 1245.4.4 Interfacial Thermodynamics and Local Mechanical Equilibria 1305.5 Point Defect Reactions 1395.5.1 Simple Internal Defect Equilibria 1395.5.2 External Defect Equilibria 1435.6 Doping and Freezing Effects 1585.7 Interactions Between Defects 1795.7.1 Associates 1795.7.2 Activity Coefficients 1875.8 Boundary Layers 1945.8.1 General 1945.8.2 Concentration Profiles in the Space Charge Zones 2005.8.3 Conductivity Effects 2045.8.4 Defect Thermodynamics of Interface: The Core-Space Charge Picture 2095.8.5 Examples and Supplementary Comments 216References 2346 Kinetics and Irreversible Thermodynamics 2436.1 Transport and Reaction 2436.1.1 Transport and Reaction in the Light of Irreversible Thermodynamics 2446.1.2 Transport and Reaction in the Light of Chemical Kinetics 2496.2 Electrical Mobility 2566.2.1 Ion Mobility 2566.2.2 Electron Mobility 2656.3 Phenomenological Diffusion Coefficients 2676.3.1 Ion Conduction and Self-Diffusion 2686.3.2 Tracer Diffusion 2696.3.3 Chemical Diffusion 2726.3.4 A Comparison of the Phenomenological Diffusion Coefficients 2766.4 Concentration Profiles 2786.5 Diffusion Kinetics of Stoichiometry Change 2826.6 Complications of Matter Transport 2896.6.1 Internal Interactions 2896.6.2 Diffusion in Multicomponent Systems 3006.6.3 Chemical Diffusion and Electrochemical Storage 3016.6.4 Boundary Layers and Grain Boundaries 3016.7 Surface Reactions 3086.7.1 Elementary Processes 3086.7.2 Coupled Reactions 3106.7.3 Phenomenological Rate Constants 3156.7.4 Reactivity, Chemical Resistance and Chemical Capacitance 3286.8 Catalysis 3296.9 Solid State Reactions 3336.9.1 Fundamental Principles 3336.9.2 Morphological and Mechanistic Complications 3436.10 Processes Under Illumination 3466.11 Nonlinear Phenomena 3526.11.1 Irreversible Thermodynamics and Chemical Kinetics far From Equilibrium, and the Special Role of Autocatalysis 3526.11.2 Nonequilibrium Structures in Time and Space 3576.11.3 The Concept of Fractal Geometry 363References 3687 Solid State Electrochemistry I: Measurement Techniques 3797.1 Preliminary Remarks 3797.1.1 Current and Voltage in the Light of Defect Chemistry 3797.1.2 Electrochemical Measurement Cells 3837.2 Open Circuit Cells 3847.2.1 Equilibrium Cells: Thermodynamic Measurements 3847.2.2 Permeation Cells and Chemical Polarization: Measurement of Transport Parameters 3907.3 Polarization Cells 3957.3.1 Dielectric and Interfacial Polarization 3977.3.2 Stoichiometry Polarization 4147.3.3 Impedance Spectroscopy 4277.3.4 Cyclic Voltammetry 4377.3.5 Inhomogeneities and Heterogeneities: Many-Point Measurements and Point Electrodes 4407.4 Coulometric Titration Cells 448References 4518 Solid State Electrochemistry II: Applications and Devices 4578.1 Sensors, Actuators and Related Devices 4578.1.1 Electrochemical Sensors 4588.1.2 Electrochemical Actuators 4648.2 Electrochemical Devices for Energy Conversion and Storage 4678.2.1 Cells Generating Current: General 4678.2.2 Fuel Cells 4708.2.3 Batteries 4778.2.4 Supercapacitors 4958.2.5 Photoelectrochemical Devices 4968.3 Bioelectrochemical Elements 4988.4 Outlook 500References 5019 Nanoionics 5079.1 Thermodynamic Aspects of Nanoparticles 5089.2 Charge Carrier Thermodynamics in Nanosystems 5169.3 Ion and Mass Transport Involving Interfaces 5179.3.1 Ion Transport: Semi-Infinite 5179.3.2 Ion Transport: Mesoscopic 5209.3.3 Ion Transport: Mesoscopic Phase Transition 5249.3.4 Fluoride Heterolayers 5269.3.5 Nanocrystalline Oxides 5319.3.6 Chemical Diffusion in Nano-Systems 5359.4 Storage in Nanoparticles and Nanocomposites 5369.4.1 Thermodynamics and Kinetics of Storage in Nanoparticles 5369.4.2 Thermodynamics and Kinetics of Storage at Interfaces 5399.4.3 Storage and Nano-Morphology 5459.5 Nanoionics: Beyond Solid State Ionics Applications 5469.6 Pushing Nanoionics to the Limits 547References 549Index 555