Hydrogen ‐Bonding and π–π Stacking Stabilized Two‐Dimensional Organic Supramolecular Cathode for Lean‐Aqueous Zinc‐Organic Batteries

ABSTRACT Rechargeable zinc‐ion batteries (RZIBs) represent a promising solution for large‐scale energy storage due to the abundant availability, low cost, and high theoretical capacity of zinc. However, current RZIBs face significant challenges, including the lack of reliable cathode materials and limited anode cycle life, primarily due to the use of aqueous electrolytes. Existing cathode materials are hindered by issues such as limited capacity, slow kinetics, and poor cycle stability. In this study, we present an organic cathode material, benzo[i]benzo[6,7]quinoxalino[2,3‐a]benzo[6,7]quinoxalino[2,3‐c]phenazine‐5,8,13,16,21,24‐hexaone (TBQPH), and apply it in the cathode of an organic zinc‐organic battery. The twelve‐electron transfer mechanism provides a high reversible capacity, with TBQPH delivering a capacity of 205 mAh g ⁻¹ at a current density of 0.1C. Furthermore, the intermolecular hydrogen bonding network and π–π stacking interactions within TBQPH confer robust structural stability and low solubility, and with the organic electrolyte relieving the zinc anode pressure, TBQPH||Zn system achieves an exceptional cycle life of 7000 cycles. In‐situ and ex‐situ characterizations reveal that Zn ²⁺ serves as the charge carriers, reversibly coordinating and dissociating with the C═N and C═O bonds in TBQPH during cycling. This work provides valuable insights for the design of high‐performance organic cathode materials and the development of long‐life batteries.