Redox-active organic compounds with accessible redox states and structural diversity are essentially important as promising electrode materials for rechargeable batteries. Herein, we propose a new bipolar redox chemistry that involves anion delocalization and cation localization in a ladder-like polymer ((C₆S₂O₂)_n)-based aqueous Zn-battery. Notably, a unique irreversible electrolyte anion-doping followed by a reversible cation insertion is revealed in (C₆S₂O₂)_n during the operation of the battery, which works excellent regardless of either charge or discharge is applied first. Due to the in-situ formation of the S⋅⋅⋅S intermolecular interaction, the stabilized battery delivers a fast-charge ability (in 30.6 s) and an ultra-stable cycle-life (>6000 cycles). The combination results of CV, ex-situ FTIR, EDS elemental mapping and DFT calculations are discussed to confirm the proposed mechanism. This novel redox chemistry provides an effective strategy to design highly stable and long-cycle-life aqueous batteries.

具有可及的氧化还原态和结构多样性的氧化还原活性有机化合物作为可再充电电池的有前景电极材料至关重要。在这里，我们提出了一种新的双极氧化还原化学方法，该方法涉及基于梯形聚合物（（C ₆ S ₂ O ₂）_n）的水性Zn电池中的阴离子离域和阳离子局部化。值得注意的是，在电池工作期间，在（C ₆ S ₂ O ₂）_n中揭示了独特的不可逆电解质阴离子掺杂和可逆阳离子插入，无论首先施加充电还是放电，其效果都很好。由于原位通过形成S⋅⋅⋅S分子间相互作用，稳定的电池可提供快速充电能力（30.6 s）和超稳定的循环寿命（> 6000次循环）。讨论了CV，非原位FTIR，EDS元素映射和DFT计算的组合结果，以确认所提出的机制。这种新颖的氧化还原化学方法提供了设计高稳定性和长寿命水基电池的有效策略。