In‐Situ Interfacial Reconstruction in Activated Porous Carbon for Dual‐Mechanism Polyiodide Anchoring and Catalytic Conversion in Long‐Life Zinc‐Iodine Batteries

ABSTRACT Zinc‐iodine (Zn‐I 2 ) batteries hold great promise for safe and cost‐effective energy storage, but suffer from sluggish iodine conversion kinetics and the severe polyiodide shuttle effect. Herein, we rationally design a KOH‐activated, ZnCoNi‐MOFs‐derived hierarchical porous carbon (KMPC2) as a highly efficient iodine host, which shows unique “crystalline‐amorphous” carbon heterostructures, enabling efficient electron transport and physical confinement channels. The Co/Ni nanoparticles (NPs) optimize the electronic structure to trigger strong d‐p orbital hybridization with iodine. Co sites dominate the catalytic conversion, while Ni provides auxiliary hybridization and synergizes with the carbon matrix to enhance conductivity. Additionally, during initial charging, internal CoNPs undergo in‐situ reconstruction to form a Co(OH) 2 interface, enabling a synergistic “dual‐anchoring” mechanism via Metal‐I coordination and O‐H···I hydrogen bonds. Consequently, the assembled Zn//KMPC2@I 2 battery delivers exceptional rate capability and an ultralong lifespan, retaining 90.6% capacity after 20,000 cycles at a high rate of 20 C. Furthermore, the flexible pouch cell with a high iodine loading of 10.4 mg cm −2 delivers a high areal capacity of 1.8 mAh cm −2 over 120 stable cycles. This work provides fundamental insights into in‐situ interfacial reconstruction and atomic‐scale dual‐anchoring mechanisms, establishing a robust foundation for next‐generation Zn‐I 2 batteries with superior performance.