Synergistic vacancy engineering of Co/MnO@NC catalyst for superior oxygen reduction reaction in liquid/solid zinc-air batteries

Abstract

The pursuit of efficient and economically viable catalysts for liquid/solid-state zinc-air batteries (ZABs) is of paramount importance yet presents formidable challenge. Herein, we synthesized a vacancy-rich cobalt/manganese oxide catalyst (Co/MnO@NC) stabilized on a nitrogen-doped mesoporous carbon (NC) nanosphere matrix by leveraging hydrothermal and high-temperature pyrolysis strategy. The optimized Co/MnO@NC demonstrates fast reaction kinetics and large limiting current densities comparable to commercial Pt/C in alkaline electrolyte for oxygen reduction reaction (ORR). Moreover, the Co/MnO@NC serves as an incredible cathode material for both liquid and flexible solid-state ZABs, delivering impressive peak power densities of 217.7 and 63.3 mW cm−2 and robust long-term stability (459 h), outperforming the state-of-the-art Pt/C and majority of the currently reported catalysts. Research indicates that the superior performance of the Co/MnO@NC catalyst primarily stems from the synergy between the heightened electrical conductivity of metallic Co and the regulatory capacity of MnO on adsorbed oxygen intermediates. In addition, the abundance of vacancies regulates the electronic configuration, and superhydrophilicity facilitates efficient electrolyte diffusion, thereby effectively ensuring optimal contact between the active site and reactants. Besides, the coexisting NC layer avoids the shedding of active sites, resulting in high stability. This work provides a viable approach for designing and advancing high-performance liquid/solid-state ZABs, highlighting the great potential of energy storage technology.