In this review the phenomenon of proton conductivity in materials and the elements of proton conduction mechanismsproton transfer, structural reorganization and diffusional motion of extended moietiesare discussed with special emphasis on proton chemistry. This is characterized by a strong proton localization within the valence electron density of electronegative species (e.g., oxygen, nitrogen) and self-localization effects due to solvent interactions which allows for significant proton diffusivities only when assisted by the dynamics of the proton environment in Grotthuss and vehicle type mechanisms. In systems with high proton density, proton/proton interactions lead to proton ordering below first-order phase transition rather than to coherent proton transfers along extended hydrogen-bond chains as is frequently suggested in textbooks of physical chemistry. There is no indication for significant proton tunneling in fast proton conduction phenomena for which almost barrierless proton transfer is suggest...

Proton Conductivity: Materials and Applications

▪ Abstract The structural and chemical parameters determining the formation and mobility of protonic defects in oxides are discussed, and the paramount role of high-molar volume, coordination numbers, and symmetry are emphasized. Symmetry also relates to the structural and chemical matching of the acceptor dopant. Y-doped BaZrO3-based oxides are demonstrated to combine high stability with high proton conductivity that exceeds the conductivity of the best oxide ion conductors at temperatures below about 700°C. The unfavorably high grain boundary impedances and brittleness of ceramics have been reduced by forming solid solutions with small amounts of BaCeO3, and an initial fuel cell test has demonstrated that proton-conducting electrolytes based on Y-doped BaZrO3 provide alternatives for separator materials in solid oxide fuel cells (SOFCs). These materials have the potential to operate at lower temperatures compared with those of conventional SOFCs, and the appearance of chemical water diffusion across the...

Proton-conducting oxides

1. Introduction 46372. Theoretical Methodologies and Simulation Tools 46402.1. Ab Initio Quantum Chemistry 46412.2. Molecular Dynamics 46422.2.1. Classical Molecular Dynamics and MonteCarlo Simulations46432.2.2. Empirical Valence Bond Models 46442.2.3. Ab Initio Molecular Dynamics (AIMD) 46452.3. Poisson−Boltzmann Theory 46452.4. Nonequilibrium Statistical Mechanical IonTransport Modeling46462.5. Dielectric Saturation 46473. Transport Mechanisms 46483.1. Proton Conduction Mechanisms 46483.1.1. Homogeneous Media 46483.1.2. Heterogeneous Systems (ConfinementEffects)46553.2. Mechanisms of Parasitic Transport 46613.2.1. Solvated Acidic Polymers 46613.2.2. Oxides 46654. Phenomenology of Transport inProton-Conducting Materials for Fuel-CellApplications46664.1. Hydrated Acidic Polymers 46664.2. PBI−H

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Transport in proton conductors for fuel-cell applications: simulations, elementary reactions, and phenomenology.

Appraisal of Ce1−yGdyO2−y/2 electrolytes for IT-SOFC operation at 500°C

Physical, chemical and electrochemical properties of pure and doped ceria

Oxygen-ion conductivity and defect interactions in yttria-doped ceria

High-temperature protonic conductors with perovskite-related structures

The “grain-boundary effect,” which leads to a greatly reduced dc ionic conductivity due to the presence of a blocking layer in the vicinity of the grain boundaries, is studied in detail for ceria ceramics doped with various trivalent dopants (particularly Y3+, Gd3+, and La3+). The effects of porosity, of sintering time, and of dopant size and dopant concentration are investigated. Finally, it is shown that the grain-boundary effect virtually disappears when nearly silicon-free starting materials are used.

A.S. Nowick

Papers

Oxygen-ion conductivity and defect interactions in yttria-doped ceria

High-temperature protonic conductors with perovskite-related structures

Grain‐Boundary Effect in Ceria Doped with Trivalent Cations: I, Electrical Measurements

Ionic conductivity of CeO2 with trivalent dopants of different ionic radii

Isotope effect and proton hopping in high-temperature protonic conductors