Boosting the Activity of BaCo_0.4Fe_0.4Zr_0.1Y_0.1O_3−δ Perovskite for Oxygen Reduction Reactions at Low-to-Intermediate Temperatures through Tuning B-Site Cation Deficiency

Doped perovskite oxides with the general formula of A_xA′_1−xB_yB′_1−yO₃ have been extensively exploited as the cathode materials of solid oxide fuel cells (SOFCs), but the performance at low-to-medium temperatures still needs improvement. BaCo_0.4Fe_0.4Zr_0.1Y_0.1O_3−δ (BCFZY) has been recently reported to show promising oxygen reduction reaction (ORR) activity under SOFCs' operating conditions. Here, it is reported that the activity of BCFZY can be further boosted via introducing a slight B-site cation deficiency into the oxide lattice, and such an improvement is assigned to an increase in oxygen mobility that brings enhancement in both surface exchange and bulk diffusion kinetics. Specifically, materials with the nominal composition of Ba(Co_0.4Fe_0.4Zr_0.1Y_0.1)_0.975O_3−δ and Ba(Co_0.4Fe_0.4Zr_0.1Y_0.1)_0.95O_3−δ show significantly improved activity for ORR at reduced temperatures with the area specific resistances of 0.011 and 0.024 Ω cm² at 600 °C, as a comparison of 0.042 Ω cm² for the cation stoichiometric BCFZY. Excessive B-site deficiencies, however, lead to the formation of impurity phases, which cause a block for charge transfer and, consequently, a reduction in electrode performance. Introducing a B-site cation deficiency is a promising way to optimize the activity of perovskite oxides for ORR at reduced temperatures, but the degree of deficiency shall be carefully tuned.