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⁻/IO₃⁻) 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.

Keywords

d-p orbital hybridization / dual-atom sites / iodide/iodate redox / oxygen electrocatalysts / zinc-air/iodide hybrid batteries

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