In situ, fast constructing interface/doping-engineered NiCo bimetal-based composites boosting electrocatalytic oxygen reduction for zinc-air battery

Investigating cost-effective, high-performance, stable and durable oxygen reduction reaction (ORR) catalysts is imperative, yet it's still a formidable obstacle in the advancement of metal-air batteries. In this research, NiCo-bimetallic oxides in situ combined with NiCo-bimetal alloy upon the surface of carbon-based matrix (reduced graphene oxide) (NiCo/Co-NiO/rGO) were synthesized by microwave hydrothermal treatment coupled with an ultrafast Joule heating shock process. The interfacial charge transfer between the bimetal alloy and metal oxide in NiCo/Co-NiO/rGO resulted in electron redistribution at the heterointerface, where *O species migrated to the NiCo alloy surface through Mn+-O-M0 (M=Ni, Co and n=2, 3) bonds, facilitating continuous electron transport between the two phases and unveiling added active sites. Introducing abundant oxygen vacancies by Ni3+ and Co3+ facilitated charge transfer between different valence states and led to forming more active sites, thus significantly enhancing ORR performance. More importantly, solid solution strengthening within the NiCo-bimetallic alloy mitigated the oxidation and corrosion of the catalyst. Therefore, the as-synthesized NiCo/Co-NiO/rGO(5 % Co) exhibited excellent ORR performance under an alkaline medium. It achieved a half-wave potential(E1/2) of 0.85 V(vs. RHE) and maintained 89.10 % of its current density after a 12-h long-term reaction. The assembled zinc-air battery (ZAB) employing this catalyst proved remarkable specific capacity (807.04 mAh·gZn−1), power density (95.54 mW cm−2) and cycling stability (over 240 h), outperforming that of commercial Pt/C+RuO2-based ZAB device. This study presents a viable approach for fabricating low-cost dual transition metal-based catalysts, thereby boosting their electrocatalytic performance and enhancing the efficiency and longevity of metal-air batteries.