Investigation of In-doped BaFeO3−δ perovskite-type oxygen permeable membranes

Abstract

Cobalt-free BaFe_1−xIn_xO_3−δ perovskites, with Fe partially substituted by indium at the B-site, were synthesized by a conventional solid state reaction and systematically characterized in terms of their phase composition, crystal structure, thermal reducibility, oxygen permeability, as well as structural stability in order to evaluate their application as oxygen permeation membranes. Introduction of more than 10 at.% of In into BaFe_1−xIn_xO_3−δ causes the formation of a single phase material with a cubic perovskite structure, which exhibits no phase transition during the cooling process. The thermal reducibility and thermal expansion coefficient are effectively reduced by indium doping, owing to the less changes of concentration of the oxygen vacancies in these compounds. However, the In occupying B-site breaks the B–O–B double exchange mechanism, and thus results in a gradual decrease of the electrical conductivity upon doping. Rietveld refinement and first principles calculation were performed to get an insight into the In influence on the lattice structure, oxygen migration energy and electron conduction behaviour of BaFe_1−xIn_xO_3−δ. When using He/Air as sweep/feed gas, the BaFe_0.9In_0.1O_3−δ dense membrane with 1.0 mm thickness features a high oxygen permeation flux of 1.11 mL cm⁻² min⁻¹ at 950 °C. The observed good performance is attributed to the relatively high concentration of oxygen vacancies and low energy barrier for oxygen ion migration. It is also found that for membranes thinner than 0.8 mm, the oxygen flux is no longer limited by the bulk diffusion, while the oxygen surface exchange process becomes the dominant factor.