Electronic Redistribution in Heterogeneous Composite Toward Advanced Rechargeable Zinc–Air Batteries with Exceptional Power Density and Ultralong Cyclability

Abstract Developing efficient and stable bifunctional oxygen catalysts is essential for addressing the trade‐off between reduction and oxidation reactions in rechargeable zinc–air batteries (ZABs). In this work, a novel composite regulation‐enhanced strategy is proposed to prepare a heterogeneous composite catalyst, FeCoNiCuMn@NC/NiFeCe LDH, exhibiting exceptional bifunctional activity. The catalyst achieves a half‐wave potential of 0.905 V for the oxygen reduction reaction and a 266 mV overpotential at 10 mA cm −2 for oxygen evolution reactions. Experimental and theoretical analyses reveal that the heterogeneous interface between FeCoNiCuMn@NC and NiFeCe LDH effectively optimizes the electronic structure of materials by shifting the d‐band center closer to the Fermi level. This optimization not only enhances the continuous distribution of electronic density but also improves the adsorption and desorption processes of intermediates, thereby effectively overcoming the trade‐off between catalyst activity and stability. When applied in rechargeable ZABs, the catalyst demonstrates remarkable cycling stability over 750 h and a peak power density of 268.5 mW·cm −2 . This study lead to a breakthrough in bifunctional oxygen catalyst design, significantly advancing rechargeable ZABs and inspiring new strategies for diverse energy storage and conversion systems.