Metallophthalocyanine‐Based Covalent Organic Frameworks Modified Separator for High‐Performance Aqueous Zinc‐Iodine Batteries

ABSTRACT Aqueous zinc‐iodine (Zn─I ₂ ) batteries are promising candidates for large‐scale energy storage owing to their inherent safety, low cost, and high theoretical capacity. However, their practical application is hindered by the polyiodide shuttle effect, sluggish iodine redox kinetics, and uncontrolled zinc dendrite growth. Herein, we design a functional separator modified with metallophthalocyanine‐based covalent organic frameworks (MPc‐COFs, M═Co, Ni, Cu) to simultaneously regulate iodine electrochemistry and zinc deposition behavior. The optimized Gr@CoPc‐COF@GF separator leverages a synergistic mechanism: atomically dispersed Co active sites strongly adsorb polyiodides to suppress shuttling while accelerating iodine redox kinetics, and the well‐ordered CoPc‐COF nanochannels facilitate uniform Zn ²⁺ flux. As a result, the corresponding Zn─I ₂ battery delivers a high specific capacity of 208.6 mAh g ⁻¹ at 571 mA g ⁻¹ and achieves excellent capacity retention with 96.97% Coulombic efficiency after 48 h of open‐circuit rest. This work presents a rational separator design strategy for high‐performance Zn─I ₂ batteries, highlighting the importance of molecular‐level engineering in advanced energy storage systems.