Enhanced oxygen exchange of perovskite oxide surfaces through strain-driven chemical stabilization

Surface cation segregation and phase separation, of strontium in particular, have been suggested to be the key reason behind the chemical instability of perovskite oxide surfaces and the corresponding performance degradation of solid oxide electrochemical cell electrodes. However, there is no well-established solution for effectively suppressing Sr-related surface instabilities. Here, we control the degree of Sr-excess at the surface of SrTi_0.5Fe_0.5O_3-δ thin films, a model mixed conducting perovskite O₂-electrode, through lattice strain, which significantly improves the electrode surface reactivity. Combined theoretical and experimental analyses reveal that Sr cations are intrinsically under a compressive state in the SrTi_0.5Fe_0.5O_3-δ lattice and that the Sr-O bonds are weakened by the local pressure around the Sr cation, which is the key origin of surface Sr enrichment. Based on these findings, we successfully demonstrate that when a large-sized isovalent dopant is added, Sr-excess can be remarkably alleviated, improving the chemical stability of the resulting perovskite O₂-electrodes.