Defect‐Engineered ZIF‐Derived Carbon Hosts for Long‐Life Aqueous Zinc‐Iodine Batteries

Abstract Aqueous zinc‐iodine batteries have garnered significant attention in substitution energy storage devices owing to their inherent environmental sustainability and exceptional theoretical capacity. Nevertheless, critical challenges such as the dissolution and shuttle effect of soluble polyiodides, coupled with inefficient reversible redox conversion, severely compromise long‐term cyclability and commercial viability. Herein, this work innovatively modified the conventional zeolitic–imidazolate framework (ZIF)‐derived carbons through precursor pre‐activation, integrating Ni/Zn bimetallic anchoring with nitrogen self‐doping to construct a concave polyhedron‐structure and defect‐rich NZ‐aNC carbon host. The abundant heteroatoms doping and tailored unsaturated coordination environment establish multiple strong chemisorption sites that synergistically suppress polyiodide migration while accelerating redox reaction kinetics. Moreover, the increased graphitic degree and enlarged micro‐/meso‐pore size can facilitate the electron transfer and iodine species immobilization efficiency. Therefore, the Zn//I 2 battery demonstrates a high specific capacity of 219 mAh g −1 at 5 A g −1 , ultralong cycling stability with 95% capacity retention over 20 000 cycles, and superior energy efficiency. This work not only establishes a simple and easy‐scalable precursor‐guided protocol for advanced iodine host fabrication but also elucidates mechanistic correlations between coordination defects and electrochemical dynamics in ZIF‐derived carbon systems.