Multiple Protophilic Redox‐Active Sites in Reticular Organic Skeletons for Superior Proton Storage

Abstract Protons (H + ) with the smallest size and fastest redox kinetics are regarded as competitive charge carriers in the booming Zn‐organic batteries (ZOBs). Developing new H + ‐storage organic cathode materials with multiple ultralow‐energy‐barrier protophilic sites and super electron delocalization routes to propel superior ZOBs is crucial but still challenging. Here we design multiple protophilic redox‐active reticular organic skeletons (ROSs) for activating better proton storage, triggered by intermolecular H‐bonding and π–π stacking interactions between 2,6‐diaminoanthraquinone and 2,4,6‐triformylphloroglucinol nanofibrous polymer. ROSs expose reticular electron delocalization geometries to fully access build‐in protophilic carbonyl sites and promote ultrarapid H + migration with an ultralow activation energy (0.13 vs. 0.29 eV of Zn 2+ ions), thus delivering high capacity (359 mAh g −1 ) and large‐current survivability (100 A g −1 ). Moreover, the extended interconnected reticular structures strengthen the anti‐dissolution of ROSs in aqueous electrolytes, affording long‐lasting proton‐storage activity in ZOBs to a superior level (60,000 cycles at 20 A g −1 ). Systematic studies identify the source of excellent charge storage as high‐kinetics H + ‐coupled five‐electron redox process of carbonyl motifs in superstable ROSs. These findings can be of importance for evoking superior proton activity in multiple redox organics to build advanced Zn‐organic batteries.