Comprehensive understanding of charge and mass transport in BaZr0.1Ce0.7Y0.1Yb0.1O3−δ

Abstract

This work reports transport properties of BaZr0.1Ce0.7Y0.1Yb0.1O3−δ (BZCYYb1711), studied during oxidation/reduction and hydration/dehydration using electrical conductivity relaxation (ECR) measurements. The oxidation/reduction displayed typical monotonic conductivity relaxation behavior, attributed to the ambipolar diffusion of oxygen vacancies (Vo∙∙) and electron-holes (h∙), and oxygen surface exchange coefficient (k) were >1 order of magnitude higher than bulk diffusivities (D˜), indicating a diffusion-controlled process. Whereas, hydration/dehydration displayed a temperature-dependent gradual transition from monotonic to non-monotonic relaxation profile. At lower temperatures, transient defect concentration profile indicated that overall hydration/dehydration involved an acid-base-type reaction, comprising the diffusion of oxygen vacancy (Vo∙∙) and proton (Hi∙) couples. However, at higher temperatures and high [h∙], it involved a combination of a hydrogenation reaction (comprising component H via diffusion of h∙ and Hi∙ couple) and an oxidation reaction (involving component O via diffusion of h∙ and Vo∙∙ couple), thus giving rise to a two-fold non-monotonic relaxation profile. The k and D˜ values for oxygen vacancies (kVO∙∙; DVO∙∙) were lower than those for protons (kHi∙;DHi∙) with the respective Ea being 57.51 ± 3.14 and 60.72 ± 1.48 kJ∙mol−1 for oxygen-vacancies and 68.78 ± 12.65 and 71.05 ± 13.87 kJ∙mol−1 for protons.