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: LaSrCoO, LaSrCaCoO, and LaCaCoO. 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.

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This work reports the precise diameter control of electrospun yttria‐stabilized zirconia (YSZ) nanofibers from 200 to 900 nm after calcination. Fabricated YSZ nanofibers showed porous nanocrystalline structures with high aspect ratios of more than 500:1 and high surface‐to‐volume ratios with a specific surface area of 43.32 m2/g. The diameter of the YSZ nanofibers increased with the viscosity of the precursor solution, which was controlled by the concentrations of either polymers (polyacrylonitrile) or ceramic precursors (YSZ). We present a modified correlation between the diameter of a nanofiber and the synthetic conditions, as the observed behavior for calcined ceramic nanofibers deviated from the expected behavior. Our results demonstrate a modified but simple approach to fabricate ceramic nanofibers with desired diameters, providing a new design guideline for many electrochemical applications.

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