Cobalt‐Induced d‐p Orbital Hybridization in Covalent Organic Frameworks Enables Synergistic Adsorption‐Catalysis for Ultralong‐Life Zinc‐Iodine Battery

Abstract Zinc‐iodine batteries (ZIBs) based on conversion chemistry are promising candidates for portable electronics owing to their high theoretical capacity, low cost, and environmental friendliness. However, practical implementation is hindered by critical challenges, including sluggish redox kinetics and the detrimental polyiodide shuttle effect. To address these limitations, a cobalt‐coordinated metalated covalent organic framework (MCOF) is designed as an advanced iodine host. Theoretical analyses reveal that effective orbital hybridization between the d‐orbital of metal centers and the p‐orbital of the covalent organic framework (COF) skeleton tailors the HOMO‐LUMO alignment, significantly narrowing the bandgap to facilitate efficient electron transport and enhance electrical conductivity. The cobalt coordination modifies the electronic structure of the Co‐TAPT‐Tp‐COF framework, creating a more positive electronic potential surface that greatly enhances iodine species adsorption. Multimodal spectroscopic analyses confirm that the metalated MCOF accelerates iodine redox kinetics by reducing the reaction energy barriers and simultaneously suppresses the shuttle effect, thereby collectively improving reaction reversibility and cycling stability. The ZIB featuring an I 2 @Co‐TAPT‐Tp‐COF cathode retains 82% of its capacity after 130 000 cycles at 15 A g −1 , surpassing most other previously reported ZIBs. This work establishes a novel paradigm for rational host materials development in conversion‐based batteries.