Steric Hindrance Modulation of Hexaazatribenzanthraquinone Isomers for High-capacity and Wide-temperature-range Aqueous Proton Battery

Organic materials with rich active sites are good candidates of high-capacity anodes in aqueous batteries, but commonly low utilization of active sites limits their capacity. Herein, two isomers, symmetric and asymmetric hexaazatribenzanthraquinone (s-HATBAQ and a-HATBAQ), with rich active sites have been synthesized in a controllable manner. It has been revealed for the first time that a sulfuric acid catalyst can facilitate the stereoselective formation of s-HATBAQ. Attributed to the reduced steric hindrance in favor of proton insertion as well as the amorphous structure conducive to electrochemical dynamics, s-HATBAQ exhibits 1.5 times larger specific capacity than a-HATBAQ. Consequently, the electrode of s-HATBAQ with 50% reduced graphene oxide (s-HATBAQ-50%rGO) delivers a record high specific capacity of 405 mAh g in HSO electrolyte. Moreover, the assembled MnO//s-HATBAQ-50%rGO aqueous proton full batteries show an exceptional cycling stability at 25°C and can maintain ∼92% capacity after 1000 cycles at 0.5 A g at -80°C. This work demonstrates the controllable synthesis of isomers, showcases a wide-temperature-range prototype proton battery and highlights the significance of precise molecular structure modulation in organic energy storage.