Tailoring Se‐Mediated Co‐Co Dual‐Atom Sites for Oxygen and Iodide Electrocatalysis Toward High‐Efficiency and Ultradurable Zinc‐Air/Iodide Hybrid Batteries

ABSTRACT Rechargeable zinc‐air batteries are severely limited by the sluggish oxygen evolution reaction (OER), which induces large overpotentials and poor cycle life. Here, we report a high‐performance zinc‐air/iodide hybrid battery (ZAIHB) that circumvents the OER bottleneck by introducing an efficient iodide/iodate (I − /IO 3 − ) redox couple, integrated with a rationally designed hollow‐structured multi‐asymmetric Co dual‐atom catalyst mediated by selenium (H‐CoSe‐NC). The atomic‐level Co‐Se d‐p orbital hybridization enables dynamic charge redistribution, forming adaptive adsorption sites that significantly enhance oxygen reduction (0.90 V half‐wave potential) and iodide oxidation (1.265 V at 10 mA cm −2 ), yielding a record‐low potential gap of 0.365 V. The resulting ZAIHB delivers exceptional cycling stability exceeding 1150 h with an energy efficiency of 77% at 10 mA cm −2 , and superior durability over state‐of‐the‐art hybrid systems. Operando spectroscopy and density functional theory calculations uncover that Se‐induced distortion of Co‐Co dual sites and electronic reconfiguration modulate the reaction pathways from OOH* to OH*–OH* intermediates and stabilize I*–I* adsorption, effectively lowering activation barriers. This study pioneers a versatile atomic‐scale electronic modulation strategy, offering a new paradigm for designing multi‐redox battery systems with minimized polarization losses and extended durability.