Abstract: | A series of iron‐based perovskite oxides BaFe1−xCuxO3−δ (x = 0.10, 0.15, 0.20 and 0.25, abbreviated as BFC‐10, BFC‐15, BFC‐20 and BFC‐25, respectively) as cathode materials have been prepared via a combined EDTA‐citrate complexing sol‐gel method. The effects of Cu contents on the crystal structure, chemical stability, electrical conductivity, thermal expansion coefficient (TEC) and electrochemical properties of BFC‐x materials have been studied. All the BFC‐x samples exhibit the cubic phase with a space group Pm3m (221). The electrical conductivity decreases with increasing Cu content. The maximum electrical conductivity is 60.9 ± 0.9 S cm−1 for BFC‐20 at 600 °C. Substitution of Fe by Cu increases the thermal expansion coefficient. The average TEC increases from 20.6 × 10−6 K−1 for BFC‐10 to 23.7 × 10−6 K−1 for BFC‐25 at the temperature range of 30–850 °C. Among the samples, BFC‐20 shows the best electrochemical performance. The area specific resistance (ASR) of BFC‐20 on SDC electrolyte is 0.014 Ω cm2 at 800 °C. The single fuel cell with the configguration of BFC‐20/SDC/NiO‐SDC delivers the highest power density of 0.57 W cm−2 at 800 °C. The favorable electrochemical activities can be attributed to the cubic lattice structure and the high oxygen vacancy concentration caused by Cu doping. |