Surface and Bulk Oxygen Kinetics of BaCo_0.4Fe_0.4Zr_0.2-XY_XO_3-δ Triple Conducting Electrode Materials

Triple ionic-electronic conductors have received much attention as electrode materials. In this work, the bulk characteristics of oxygen diffusion and surface exchange were determined for the triple-conducting BaCo_0.4Fe_0.4Zr_0.2-XY_XO_3-δ suite of samples. Y substitution increased the overall size of the lattice due to dopant ionic radius and the concomitant formation of oxygen vacancies. Oxygen permeation measurements exhibited a three-fold decrease in oxygen permeation flux with increasing Y substitution. The DC total conductivity exhibited a similar decrease with increasing Y substitution. These relatively small changes are coupled with an order of magnitude increase in surface exchange rates from Zr-doped to Y-doped samples as observed by conductivity relaxation experiments. The results indicate that Y-doping inhibits bulk O^2- conduction while improving the oxygen reduction surface reaction, suggesting better electrode performance for proton-conducting systems with greater Y substitution.