Suppression of Cation Segregation in (La,Sr)CoO_3-δ by Elastic Energy Minimization

Strontium segregation at perovskite surfaces deteriorates the oxygen reduction reaction kinetics of cathodes and therefore the long-term stability of solid oxide fuel cells (SOFCs). For the systematic and quantitative assessment of the elastic energy in perovskite oxides, which is known to be one of the main origins for dopant segregation, we report the fractional free volume as a new descriptor for the elastic energy in the perovskite oxide system. To verify the fractional free volume model, three samples were prepared with different A-site dopants: La_0.6Sr_0.4CoO_3-δ, La_0.6Sr_0.2Ca_0.2CoO_3-δ, and La_0.6Ca_0.4CoO_3-δ. A combination of the theoretical calculations of the segregation energy and oxide formation energy and experimental measurements of the structural, chemical, and electrochemical degradation substantiated the validity of using the fractional free volume to predict the dopant segregation. Furthermore, the dopant segregation could be significantly suppressed by increasing the fractional free volume in the perovskite oxides with dopant substitution. Our results provide insight into dopant segregation from the elastic energy perspective and offer a design guideline for SOFC cathodes with enhanced stability at elevated temperatures.