Bipolar Conjugated Cathodes Reinforced by a Hydrogen-Bonding Network for Durable Aqueous Zinc-Ion Batteries

The cycling stability of organic cathodes remains a critical bottleneck for aqueous zinc-ion batteries. Here, we report a bipolar organic cathode, Azo-T, in which TEMPO radicals are covalently grafted onto an azobenzene backbone via amide linkages. This design establishes an extensive intermolecular hydrogen-bonding network that suppresses active material dissolution and facilitates ion transport. The Zn||Azo-T battery delivers a high specific capacity of 177 mAh g –1 at 0.1 A g –1 and exceptional durability with 95% capacity retention after 10,000 cycles at 10 A g –1 . Operando and ex situ spectroscopic analyses reveal a reversible six-electron transfer and multi-ion cooperative storage mechanism, wherein p-type and n-type redox centers alternately participate. Notably, the hydrogen-bonding network remains intact throughout cycling, anchoring redox sites and preserving electrode structural integrity. This work establishes a hydrogen-bonding interaction reinforced molecular engineering strategy for durable, high-performance organic cathodes in aqueous zinc-ion batteries.