Surface and Bulk Defect Equilibria in Strontium-Doped Lanthanum Cobalt Iron Oxide

Strontium-doped lanthanum cobalt iron oxide is used in solid oxide fuel cells, oxygen separation membranes, and fuel reforming applications because of its mixed ionic and electronic conductivity. With changes in temperature and oxygen partial pressure , the defect concentration changes and there is a corresponding change in strain (chemical expansion) and performance. In this paper, the oxygen nonstoichiometry of 0.5% A-site cation deficient is studied in the temperature range of and modeled using a metallic model and three semiconductor models assuming itinerant electrons and holes or electrons localized on B-site, cations, with holes localized on either B-site cations or oxygen anions. The model consisting of holes localized on B-site cations fits the data best. The surface oxygen nonstoichiometry was determined by measuring oxygen loss of samples with different surface areas, and the surface is much more defective than the bulk. A long-term mass change measurement was also performed at in air, and a mass loss was observed that may be due to cation segregation to the surface.