First Principles Calculations of Oxygen Vacancy Formation and Migration in Ba_1−xSr_xCo_1−yFe_yO_3−δPerovskites

Based on first principles DFT calculations, we analyze oxygen vacancy formation and migration energies as a function of chemical composition in complex multicomponent (Ba,Sr)(Co,Fe)O 3−δ perovskites which are candidate materials for SOFC cathodes and permeation membranes. The atomic relaxation, electronic charge redistribution and energies of the transition states of oxygen migration are compared for several perovskites to elucidate the atomistic reason for the exceptionally low migration barrier in Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3−δ that was previously determined experimentally. The critical comparison of Ba 1−x Sr x Co 1−y Fe y O 3−δ perovskites with different cation compositions and arrangements shows that in addition to the geometric constraints the electronic structure plays a considerable role for the height of the oxygen migration barrier in these materials. These findings help understand advantages and limitations of the fast oxygen permeation and exchange properties of Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3−δ .