Selenide-driven electron delocalization in Co single-atom@metal-cluster sites on periodic macroporous carbon framework for synergistic oxygen/iodine electrocatalysis in zinc-air/iodine hybrid batteries

Abstract

Zinc-air batteries are crucial for next-generation energy storage; however, challenges related to energy efficiency persist owing to the kinetically sluggish oxygen evolution reaction in conventional cathodes. Groundbreaking zinc-air/iodine hybrid batteries (ZAIHBs) incorporate reversible iodine redox reactions; however, the design of bifunctional catalysts capable of synergistically mediating oxygen and iodine redox reactions remains challenging. In this study, we achieve efficient and reversible oxygen/iodine catalysis using a pioneering hierarchical heterointerface-engineered catalyst comprising single Co atoms coupled with Co/CoSe₂ nanoclusters within a three-dimensionally ordered macroporous carbon framework (3DOM Co(Se)/NC). Spectroscopic analysis and density functional theory calculations reveal that CoSe₂ incorporation induces partial electron delocalization at the Co single-atom@Co-cluster interface, while preserving a locally enriched electron density. This electronic configuration balances the adsorption/desorption energetics of the oxygen and iodine intermediates, while the 3DOM architecture facilitates rapid mass transport and exposes abundant active sites. Consequently, ZAIHBs equipped with 3DOM Co(Se)/NC deliver a remarkably low voltage gap (ΔE = 0.40 V) and outstanding cycling stability over 400 h at 10 mA cm^-2. This study provides a novel approach to multi-redox cathode design and facilitates the development of highly efficient hybrid batteries.

Keywords

3DOM structure / Co/CoSe₂ heterojunction / iodide/iodate redox / oxygen electrocatalyst / zinc-air/iodide hybrid batteries

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