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The performance of a solid oxide fuel cell (SOFC) is strongly associated with the activity and durability of the cathode, where the oxygen reduction reaction occurs. In this study, we report our findings in the development of an Nb-doped PrBa0.8Ca0.2Co2O6−δ (PrBa0.8Ca0.2Co2−xNbxO6−δ, x = 0, 0.025, 0.05, and 0.1, denoted as PBCCNx) perovskite composite as the SOFC cathode. Analyses of X-ray diffraction (XRD) patterns and energy-dispersive transmission electron microscopy (TEM-EDS) images suggest that after being treated at 950 °C in air, PBCCN0.05 mainly contains phases of Ca- and Nb-doped PrBaCo2O6−δ double perovskite, PrCoO3 perovskite with Ca and Nb doping, and Ba3Ca1.18Nb1.82O9−δ. When evaluated as an SOFC cathode, the PBCCN0.05 mixture has shown a low polarization resistance of 0.0074 Ω∙cm2 at 800 °C in La0.8Sr0.2Ga0.8Mg0.2O3 electrolyte symmetrical cells. Accordingly, anode-supported single cells with a configuration of Ni–Zr0.84Y0.16O2−δ (YSZ)/YSZ/Gd0.1Ce0.9O2−δ/PBCCN0.05 display high electrochemical performance, with a peak power density of 1.81 W∙cm−2 and a reasonable durability of 100 h at 800 °C. PBCCN0.05 possesses a higher concentration of oxygen vacancies, a faster oxygen surface adsorption‒dissociation rate, and an increased mass ratio of PrCoO3 perovskite with Ca and Nb doping compared to PrBa0.8Ca0.2Co2O6−δ without Nb doping.
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