Unleashing Multi‐Electron Storage in Synergistic Dual‐Active‐Center Bridged Covalent Organic Polymer Cathode for High‐Capacity and Long‐Life Aqueous Zinc‐Ion Batteries

The development of aqueous zinc‐ion batteries is hindered by the scarcity of advanced cathode materials. Covalent organic polymers (COPs) have garnered substantial interest due to their tunable structures. However, simultaneously achieving high capacity and structural stability remains a formidable challenge. Herein, we propose an active dual‐unit bridging strategy to construct an extended conjugated framework, enabling high specific capacity and structural stability. This bridging design integrates six‐electron‐storage hexaazatrinaphthalene (HAT) and redox‐active 2,5‐dihydroxy‐1,4‐benzoquinone (DHBQ) units, departing from the disadvantage that conventional strategies only rely on inactive linkers. Theoretical calculations and spectroscopic analyses elucidate a cascaded Zn 2+ storage pathway characterized by the preferential reaction of HAT sites, followed by subsequent participation of the benzoquinone moieties. Electrochemical evaluations of the HAT‐DHBQ cathode reveal a high initial capacity of 316.2 mAh g −1 at 0.1 A g −1 , along with impressive cycling stability, as evidenced by maintaining discharge capacities of 190.3 mAh g −1 and 147.0 mAh g −1 after 10 000 cycles at 1.0 A g −1 and 5.0 A g −1 , corresponding to low‐capacity attenuation rates of 0.0029% and 0.0030% per cycle, respectively. By synergistically integrating multi‐electron‐storage units through an active‐bridging strategy, this work establishes a promising molecular design paradigm for high‐performance organic active materials in aqueous multivalent‐ion secondary batteries.