Solid State Proton Conductors

Name: Solid State Proton Conductors | Properties and Applications in Fuel Cells
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Properties and Applications in Fuel Cells

Philippe Knauth Maria Luisa Di Vona(Autor*in)

Wiley (Verlag)

Erschienen am 11. Januar 2012

432 Seiten

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Inhalt

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 e*m(?), s*m(?), and Z*m(?)
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 s*(?) and e*(?)
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 ß- and ß"-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

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