Boosting H+ Storage in Aqueous Zinc Ion Batteries via Integrating Redox‐Active Sites into Hydrogen‐Bonded Organic Frameworks with Strong π‐π Stacking

Abstract In the emerging aqueous zinc ion batteries (AZIBs), proton (H + ) with the smallest molar mass and fast (de)coordination kinetics is considered as the most ideal charge carrier compared with Zn 2+ counterpart, however, searching for new hosting materials for H + storage is still at its infancy. Herein, redox‐active hydrogen‐bonded organic frameworks (HOFs) assembled from diaminotriazine moiety decorated hexaazatrinnphthalene (HOF‐HATN) are for the first time developed as the stable cathode hosting material for boosting H + storage in AZIBs. The unique integration of hydrogen‐bonding networks and strong π‐π stacking endow it rapid Grotthuss proton conduction, stable supramolecular structure and inclined H + storage. As a consequence, HOF‐HATN displays a high capacity (320 mAh g −1 at 0.05 A g −1 ) and robust cyclability of (>10000 cycles at 5 A g −1 ) based on three‐step cation coordination storage. These findings get insight into the proton transport and storage behavior in HOFs and provide the molecular engineering strategy for constructing well‐defined cathode hosting materials for rechargeable aqueous batteries.