Engineering of Charged Defects at Perovskite Oxide Surfaces for Exceptionally Stable Solid Oxide Fuel Cell Electrodes.

Cation segregation, particularly Sr segregation, toward a perovskite surface has a significant effect on the performance degradation of a solid oxide cell (solid oxide electrolysis/fuel cell). Among the number of key reasons generating the instability of perovskite oxide, surface-accumulated positively charged defects (oxygen vacancy, Vo··) have been considered as the most crucial drivers in strongly attracting negatively charged defects (SrA - site') toward the surface. Herein, we demonstrate the effects of a heterointerface on the redistribution of both positively and negatively charged defects for a reduction of Vo·· at a perovskite surface. We took Sm0.5Sr0.5CoO3-δ (SSC) as a model perovskite film and coated Gd0.1Ce0.9O2-δ (GDC) additionally onto the SSC film to create a heterointerface (GDC/SSC), resulting in an ∼11-fold reduction in a degradation rate of ∼8% at 650 °C and ∼10-fold higher surface exchange (kq) than a bare SSC film after 150 h at 650 °C. Using X-ray photoelectron spectroscopy and electron energy loss spectroscopy, we revealed a decrease in positively charged defects of Vo·· and transferred electrons in an SSC film at the GDC/SSC heterointerface, resulting in a suppression of negatively charged Sr (SrSm') segregation. Finally, the energetic behavior, including the charge transfer phenomenon, O p-band center, and oxygen vacancy formation energy calculated using the density functional theory, verified the effects of the heterointerface on the redistribution of the charged defects, resulting in a remarkable impact on the stability of perovskite oxide at elevated temperatures.