Supramolecular Engineering of Cathode Materials for Aqueous Zinc‐ion Energy Storage Devices: Novel Benzothiadiazole Functionalized Two‐Dimensional Olefin‐Linked COFs

Two-dimensional covalent organic frameworks (COFs) have emerged as promising materials for energy storage applications exhibiting enhanced electrochemical performance. While most of the reported organic cathode materials for zinc-ion batteries use carbonyl groups as electrochemically-active sites, their high hydrophilicity in aqueous electrolytes represents a critical drawback. Herein, we report a novel and structurally robust olefin-linked COF-TMT-BT synthesized via the aldol condensation between 2,4,6-trimethyl-1,3,5-triazine (TMT) and 4,4'-(benzothiadiazole-4,7-diyl)dibenzaldehyde (BT), where benzothiadiazole units are explored as novel electrochemically-active groups. Our COF-TMT-BT exhibits an outstanding Zn²⁺ storage capability, delivering a state-of-the-art capacity of 283.5 mAh g^-1 at 0.1 A g^-1 . Computational and experimental analyses reveal that the charge-storage mechanism in COF-TMT-BT electrodes is based on the supramolecularly engineered and reversible Zn²⁺ coordination by the benzothiadiazole units.