Effect of Ba nonstoichiometry on the phase composition, microstructure, chemical stability and electrical conductivity of BaxCe0.7Zr0.1Y0.1Yb0.1O3−δ (0.9≤x≤1.1) proton conductors

The perovskite proton conductors BaxCe0.7Zr0.1Y0.1Yb0.1O3−δ (x=0.9, 0.94, 0.98, 1.0, 1.03, 1.06, and 1.1) have been successfully prepared by the conventional solid state reaction route. X-ray diffraction (XRD) patterns of the samples indicate that BaxCe0.7Zr0.1Y0.1Yb0.1O3−δ (x≥1.0) samples possess a single phase orthorhombic structure, but a secondary phase (Y,Ce)O2−δ exists in BaxCe0.7Zr0.1Y0.1Yb0.1O3−δ (x<1.0) samples. SEM photographs show that the grain size of BaxCe0.7Zr0.1Y0.1Yb0.1O3−δ increases and the porosity decreases with Ba2+ content varying from x=0.9 to 1.1. Because of ZnO addition as sintering aid, the sintering temperature of the samples reduces from 1550 °C to 1250 °C. The chemical stability of the samples against CO2 decreases with the increase in Ba content from x=0.9 to 1.1. All the samples show a excellent stability against water vapor at 850 °C. The conductivities of the samples increase and the activation energies reduce with the increase in Ba content. The present results suggest that it is very important to control the stoichiometry of cations to obtain desired perovskite type high temperature proton conductors.