B‐Site Co Ion Doping Activates the Bifunctional Catalytic Activity of Perovskite Oxides for the Zinc–Air Battery Cathode

ABSTRACT The practical deployment of zinc–air batteries remains constrained by the inherently sluggish kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at bifunctional air cathodes. This work synthesized B‐site Co‐doped Pr 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ and systematically investigated its enhanced catalytic performance and related structural modifications. Electrochemical tests demonstrate that the presence of Co ions facilitates the ORR on perovskite oxides, shifting the process from a two‐electron pathway to a more efficient four‐electron pathway. Theoretical calculations confirm that cobalt ion doping causes a positive shift in the d‐band center of the B‐site metal elements, thereby optimizing the adsorption energy of intermediates in OER/ORR. Compared to that undoped Pr 0.6 Sr 0.4 FeO 3−δ , Pr 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ as a cathode material for zinc–air batteries increases peak power density by 1.3 times and significantly improves charge–discharge cycle efficiency.