This review paper focuses on the phenomenon of thermochemical expansion of two specific categories of conducting ceramics: Proton Conducting Ceramics (PCC) and Mixed Ionic-Electronic Conductors (MIEC). The theory of thermal expansion of ceramics is underlined from microscopic to macroscopic points of view while the chemical expansion is explained based on crystallography and defect chemistry. Modelling methods are used to predict the thermochemical expansion of PCCs and MIECs with two examples: hydration of barium zirconate (BaZr1−xYxO3−δ) and oxidation/reduction of La1−xSrxCo0.2Fe0.8O3−δ. While it is unusual for a review paper, we conducted experiments to evaluate the influence of the heating rate in determining expansion coefficients experimentally. This was motivated by the discrepancy of some values in literature. The conclusions are that the heating rate has little to no effect on the obtained values. Models for the expansion coefficients of a composite material are presented and include the effect of porosity. A set of data comprising thermal and chemical expansion coefficients has been gathered from the literature and presented here divided into two groups: protonic electrolytes and mixed ionic-electronic conductors. Finally, the methods of mitigation of the thermal mismatch problem are discussed.

Here, for the first time, we present data on proton conductivity of high-entropy, single-phase perovskites. The BaZr0.2Sn0.2­Ti0.2Hf0.2Ce0.2O3−δ, BaZr0.2Sn0.2­Ti0.2Hf0.2­Y0.2O3−δ, BaZr1/7Sn1/7­Ti1/7Hf1/7­Ce1/7Nb1/7Y1/7O3−δ, and BaZr0.15Sn0.15­Ti0.15Hf0.15­Ce0.15Nb0.15­Y0.10O3−δ single-phase perovskites were synthesized. Before electrical measurements, materials were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). The following experimental results demonstrated that studied high-entropy perovskites are proton conductors: (1) The observed mass increase upon the switch from dry to wet atmosphere confirmed the water incorporation into materials structure. (2) The electrochemical impedance spectroscopy (EIS) revealed that the total conductivity increased while its activation energy decreased in the presence of water vapor in the atmosphere. (3) The conductivity in atmosphere humidified with H2O and D2O differed one from another, showing typical of proton conductors isotope effect in high-entropy oxides.

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The results of ionic transport measurements for the lanthanum orthoniobate substituted with 10 and 30 mol% of antimony (LaNb0.9Sb0.1O4 and LaNb0.7Sb0.3O4) are presented and discussed. The influence of calcium co-doping on these properties has also been analysed. It has been shown that for the investigated material protonic conductivity predominates at temperatures up to 800 °C in oxidizing atmospheres, in wet conditions. Maximum observed protonic conductivity reaches ~10-4 S/cm at 800 °C (in humidified air); in the dry conditions the increasing influence of oxygen vacancies and holes is detected. Oxygen self-diffusivity has also been analysed by isotopic exchange to investigate the possible diffusion paths.