Proton‐Conductive Supramolecular Hydrogen‐Bonded Organic Superstructures for High‐Performance Zinc‐Organic Batteries

Abstract With fast (de)coordination kinetics, the smallest and the lightest proton stands out as the most ideal charge carrier for aqueous Zn‐organic batteries (ZOBs). Hydrogen‐bonding networks with rapid Grotthuss proton conduction is particularly suitable for organic cathodes, yet not reported. We report the supramolecular self‐assembly of cyanuric acid and 1,3,5‐triazine‐2,4,6‐triamine into organic superstructures through in‐plane H‐bonds and out‐of‐plane π‐π interaction. The supramolecular superstructures exhibit highly stable lock‐and‐key H‐bonding networks with an ultralow activation energy for protonation (0.09 eV vs. 0.25 eV of zincification). Then, high‐kinetics H + coordination is prior to Zn 2+ into protophilic C=O sites via a two‐step nine‐electron reaction. The assembled ZOBs show high‐rate capability (135 mAh g −1 at 150 A g −1 ), high energy density (267 Wh kg −1 cathode ) and ultra‐long life (50 000 cycles at 10 A g −1 ), becoming the state‐of‐the‐art ZOBs in comprehensive performances.