Non-stoichiometry, grain boundary transport and chemical stability of proton conducting perovskites

The interrelationship between defect chemistry, non-stoichiometry, grain bo undary transport and chemical stability of proton conducting perovskites (d oped alkaline earth cerates and zirconates) has been investigated. Non-stoi chiometry, defined as the deviation of the A : M molar ratio in AMO(3) from 1 : 1, dramatically impacts conductivity, sinterability and chemical stabi lity with respect to reaction with CO2. In particular, alkaline earth defic iency encourages dopant incorporation onto the A-atom site, rather than the intended M-atom site, reducing the concentration of oxygen vacancies. Tran sport along grain boundaries is, in general, less favorable than transport through the bulk, and thus only in fine-grained materials does microstructu re impact the overall electrical properties. The chemical stability of high conductivity cerates is enhanced by the introduction of Zr. The conductivi ty of BaCe0.9-xZrxM0.1O3 perovskites monotonically decreases with increasin g x (increasing Zr content), with the impact of Zr substitution increasing in the order M = Yb --> Gd --> Nd. Furthermore, the magnitude of the conduc tivity follows the same sequence for a given zirconium content. This result is interpreted in terms of dopant ion incorporation onto the divalent ion site. (C) 2001 Kluwer Academic Publishers.