AbstractElectrochemical proton storage plays an essential role in designing next‐generation high‐rate energy storage devices, e.g., aqueous batteries. Two‐dimensional conjugated covalent organic frameworks (2D c‐COFs) are promising electrode materials, but their competitive proton and metal‐ion insertion mechanisms remain elusive, and proton storage in COFs is rarely explored. Here, we report a perinone‐based poly(benzimidazobenzophenanthroline) (BBL)‐ladder‐type 2D c‐COF for fast proton storage in both a mild aqueous Zn‐ion electrolyte and strong acid. We unveil that the discharged C−O− groups exhibit largely reduced basicity due to the considerable π‐delocalization in perinone, thus affording the 2D c‐COF a unique affinity for protons with fast kinetics. As a consequence, the 2D c‐COF electrode presents an outstanding rate capability of up to 200 A g−1 (over 2500 C), surpassing the state‐of‐the‐art conjugated polymers, COFs, and metal–organic frameworks. Our work reports the first example of pure proton storage among COFs and highlights the great potential of BBL‐ladder‐type 2D conjugated polymers in future energy devices.
摘要电化学质子存储在设计下一代高速率储能装置(如水电池)中发挥着至关重要的作用。二维共价有机框架(2D c-COFs)是一种很有前景的电极材料,但其质子和金属离子的竞争性插入机制仍然难以捉摸,质子在 COFs 中的存储也很少被探索。在这里,我们报告了一种基于perinone的聚(苯并咪唑-苯并菲罗啉)(BBL)-梯形二维c-COF,可在温和的Zn离子水溶液电解质和强酸中快速储存质子。我们发现,由于哌啶酮中存在大量的π位移,排出的 C-O- 基团在很大程度上降低了碱性,从而使二维 c-COF 对质子具有独特的亲和力和快速动力学特性。因此,二维 c-COF 电极具有高达 200 A g-1 (超过 2500 C)的出色速率能力,超越了最先进的共轭聚合物、COF 和金属有机框架。我们的工作报告了 COFs 中纯质子存储的第一个实例,并强调了 BBL 梯形二维共轭聚合物在未来能源设备中的巨大潜力。