Solid State Proton Conductors: Properties and Applications in Fuel Cells -- Contents -- Preface -- About the Editors -- Contributing Authors -- 1 Introduction and Overview: Protons, the Nonconformist Ions -- 1.1 Brief History of the Field -- 1.2 Structure of This Book -- References -- 2 Morphology and Structure of Solid Acids -- 2.1 Introduction -- 2.1.1 Preparation Technique of Solid Acids -- 2.1.2 Imaging Technique with the Scanning Electron Microscope -- 2.2 Crystal Morphology and Structure of Solid Acids -- 2.2.1 Hydrohalic Acids -- 2.2.2 Main Group Element Oxoacids -- 2.2.3 Transition Metal Oxoacids -- 2.2.4 Carboxylic Acids -- References -- 3 Diffusion in Solid Proton Conductors: Theoretical Aspects and Nuclear Magnetic Resonance Analysis -- 3.1 Fundamentals of Diffusion -- 3.1.1 Phenomenology of Diffusion -- 3.1.2 Solutions of the Diffusion Equation -- 3.1.3 Diffusion Coefficients and Proton Conduction -- 3.1.4 Measurement of the Diffusion Coefficient -- 3.2 Basic Principles of NMR -- 3.2.1 Description of the Main NMR Techniques Used in Measuring Diffusion Coefficients -- 3.3 Application of NMR Techniques -- 3.3.1 Polymeric Proton Conductors -- 3.3.2 Inorganic Proton Conductors -- 3.4 Liquid Water Visualization in Proton-Conducting Membranes by Nuclear Magnetic Resonance Imaging -- 3.5 Conclusions -- References -- 4 Structure and Diffusivity in Proton-Conducting Membranes Studied by Quasielastic Neutron Scattering -- 4.1 Survey -- 4.2 Diffusion in Solids and Liquids -- 4.3 Quasielastic Neutron Scattering: A Brief Introduction -- 4.4 Proton Diffusion in Membranes -- 4.4.1 Microstructure by Means of SAXS and SANS -- 4.4.2 Proton Conductivity and Water Diffusion -- 4.4.3 QENS Studies -- 4.5 Solid State Proton Conductors -- 4.5.1 Aliovalently Doped Perovskites -- 4.5.2 Hydrogen-Bonded Systems -- 4.6 Concluding Remarks -- References.

5 Broadband Dielectric Spectroscopy: A Powerful Tool for the Determination of Charge Transfer Mechanisms in Ion Conductors -- 5.1 Basic Principles -- 5.1.1 The Interaction of Matter with Electromagnetic Fields: The Maxwell Equations -- 5.1.2 Electric Response in Terms of ε*m(ω), σ*m(ω), and Z*m(ω) -- 5.2 Phenomenological Background of Electric Properties in a Time-Dependent Field -- 5.2.1 Polarization Events -- 5.3 Theory of Dielectric Relaxation -- 5.3.1 Dielectric Relaxation Modes of Macromolecular Systems -- 5.3.2 A General Equation for the Analysis in the Frequency Domain of σ*(ω) and ε*(ω) -- 5.4 Analysis of Electric Spectra -- 5.5 Broadband Dielectric Spectroscopy Measurement Techniques -- 5.5.1 Measurement Systems -- 5.5.2 Contacts -- 5.5.3 Calibration -- 5.5.4 Calibration in Parallel Plate Methods -- 5.5.5 Measurement Accuracy -- 5.6 Concluding Remarks -- References -- 6 Mechanical and Dynamic Mechanical Analysis of Proton-Conducting Polymers -- 6.1 Introduction -- 6.1.1 Molecular Configurations: The Morphology and Microstructure of Polymers -- 6.1.2 Molecular Motions -- 6.1.3 Glass Transition and Other Molecular Relaxations -- 6.2 Methodology of Uniaxial Tensile Tests -- 6.2.1 Elasticity and Young's Modulus E -- 6.2.2 Elasticity and Shear Modulus G -- 6.2.3 Elasticity and Cohesion Energy -- 6.3 Relaxation and Creep of Polymers -- 6.3.1 Stress Relaxation of Polymers -- 6.3.2 Creep of Polymers -- 6.4 Engineering Stress-Strain Curves of Polymers -- 6.4.1 True Stress-Strain Curve for Plastic Flow and Toughness of Polymers -- 6.4.2 Behavior of Composite Membranes -- 6.4.3 Behavior in the Glassy Regime -- 6.4.4 Influence of the Rate of Deformation -- 6.4.5 Effect of Temperature on Mechanical Properties -- 6.4.6 Thermal Strain -- 6.5 Stress-Strain Tensile Tests of Proton-Conducting Ionomers -- 6.5.1 Influence of Heat Treatment and Cross-Linking.

6.5.2 Behavior of Composites -- 6.5.3 Conclusions -- 6.6 Dynamic Mechanical Analysis (DMA) of Polymers -- 6.6.1 Principle of Measurement -- 6.6.2 Molecular Motions and Dynamic Mechanical Properties -- 6.6.3 Experimental Considerations: How Does the Instrument Work? -- 6.6.4 Parameters of Dynamic Mechanical Analysis -- 6.7 The DMA of Proton-Conducting Ionomers -- 6.7.1 Perfluorosulfonic Acid Ionomer Membranes -- 6.7.2 Nonfluorinated Membranes -- 6.7.3 Organic-Inorganic Composite (or Hybrid) Membranes -- Glossary -- References -- 7 Ab Initio Modeling of Transport and Structure of Solid State Proton Conductors -- 7.1 Introduction -- 7.2 Theoretical Methods -- 7.2.1 Ab Initio Electronic Structure -- 7.2.2 Ab Initio Molecular Dynamics (AIMD) -- 7.2.3 Empirical Valence Bond (EVB) Models -- 7.3 Polymer Electrolyte Membranes -- 7.3.1 Local Microstructure -- 7.3.2 Proton Dissociation, Transfer, and Separation -- 7.4 Crystalline Proton Conductors and Oxides -- 7.4.1 Crystalline Proton Conductors -- 7.4.2 Oxides -- 7.5 Concluding Remarks -- References -- 8 Perfluorinated Sulfonic Acids as Proton Conductor Membranes -- 8.1 Introduction on Polymer Electrolyte Membranes for Fuel Cells -- 8.2 General Properties of Polymer Electrolyte Membranes -- 8.2.1 Ion Exchange of Polymers Electrolytes in H+ Form -- 8.3 Perfluorinated Membranes Containing Superacid -SO3H Groups -- 8.3.1 Nafion Preparation -- 8.3.2 Nafion Morphology -- 8.3.3 Nafion Water Uptake in Liquid Water at Different Temperatures -- 8.3.4 Water-Vapor Sorption Isotherms of Nafion -- 8.3.5 Curves T/nc for Nafion 117 Membranes in H+ Form -- 8.3.6 Water Uptake and Tensile Modulus of Nafion -- 8.3.7 Colligative Properties of Inner Proton Solutions in Nafion -- 8.3.8 Thermal Annealing of Nafion -- 8.3.9 MCPI Method -- 8.3.10 Proton Conductivity of Nafion.

8.4 Some Information on Dow and on Recent Aquivion® Ionomers -- 8.5 Instability of Proton Conductivity of Highly Hydrated PFSA Membranes -- 8.6 Composite Nafion Membranes -- 8.6.1 Silica-Filled Ionomer Membranes -- 8.6.2 Metal Oxide-Filled Nafion Membranes -- 8.6.3 Layered Zirconium Phosphate- and Zirconium Phosphonate-Filled Ionomer Membranes -- 8.6.4 Heteropolyacid-Filled Membranes -- 8.7 Some Final Remarks and Conclusions -- References -- 9 Proton Conductivity of Aromatic Polymers -- 9.1 Introduction -- 9.2 Synthetic Strategies of the Various Acid-Functionalized Aromatic Polymers with Proton Transport Ability -- 9.2.1 Sulfonated Poly(arylene ether)s -- 9.2.2 Sulfonated Polyimides -- 9.2.3 Other Aromatic Polymers as PEMs -- 9.3 Approaches to Enhance Proton Conductivity -- 9.3.1 Nanophase-Separated Microstructures Containing Proton-Conducting Channels -- 9.3.2 Replacement of -Ph-SO3H by -CF2 -SO3H -- 9.3.3 Synthesis of High-IEC PEMs -- 9.3.4 Composite Membranes -- 9.4 Balancing Proton Conductivity, Dimensional Stability, and Other Properties -- 9.5 Electrochemical Performance of Aromatic Polymers -- 9.5.1 PEMFC Performance -- 9.5.2 DMFC Performance -- 9.6 Summary -- References -- 10 Inorganic Solid Proton Conductors -- 10.1 Fundamentals of Ionic Conduction in Inorganic Solids -- 10.1.1 Defect Concentrations -- 10.1.2 Defect Mobilities -- 10.1.3 Kr€oger-Vink Nomenclature -- 10.1.4 Ionic Conduction in the Bulk: Hopping Model -- 10.2 General Considerations on Inorganic Solid Proton Conductors -- 10.2.1 Classification of Solid Proton Conductors -- 10.3 Low-Dimensional Solid Proton Conductors: Layered and Porous Structures -- 10.3.1 β- and β"-Alumina-Type -- 10.3.2 Layered Metal Hydrogen Phosphates -- 10.3.3 Micro- and Mesoporous Structures -- 10.4 Three-Dimensional Solid Proton Conductors: "Quasi-Liquid" Structures -- 10.4.1 Solid Acids.

10.4.2 Acid Salts -- 10.4.3 Amorphous and Gelled Oxides and Hydroxides -- 10.5 Three-Dimensional Solid Proton Conductors: Defect Mechanisms in Oxides -- 10.5.1 Perovskite-Type Oxides -- 10.5.2 Other Structure Types -- 10.6 Conclusion -- References -- Index.