Redox‐active organics based on a multi‐electron mechanism are of great interest in battery electrode materials as they are capable of delivering high capacity per molecular weight. However, most of such organics shows huge voltage gap that is inherited from their stepwise redox reactions occurring in the same conjugated redox moiety. This study focuses on the voltage tailoring of polymeric dihydrophenazine derivative which shows high specific capacity as a cathode electrode material and decent cycling stability, but suffers huge voltage gap of ca. 0.8 V. We demonstrate a strategy to modify the voltage gap of dihydrophenazine derivatives through the incorporation of functional groups with different electron affinity near the redox moiety. The as‐designed dihydrophenazine derivatives are further copolymerized to yield a polymeric material with significantly smoothened charge‐discharge profiles and good capacity retention. We further demonstrate through theoretical calculation based on density‐functional theory that the substitute site and types of functional groups are of great importance in voltage tailoring as well as structural stability of the dihydrophenazine derivatives.

中文翻译：

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基于多电子氧化还原化学方法定制有机电池材料的电压差

基于多电子机理的氧化还原活性有机物在电池电极材料中备受关注，因为它们能够提供较高的单位分子量容量。然而，大多数此类有机物显示出巨大的电压间隙，这是由它们在同一共轭氧化还原部分中发生的逐步氧化还原反应所继承的。这项研究的重点是聚合的二氢吩嗪衍生物的电压调整，该衍生物显示出高的比容量作为阴极材料，并具有良好的循环稳定性，但其电压缺口约为。0.8V。我们展示了通过在氧化还原部分附近引入具有不同电子亲和力的官能团来修饰二氢吩嗪衍生物的电压间隙的策略。将设计好的二氢吩嗪衍生物进一步共聚，得到具有明显平滑的充放电曲线和良好的容量保持率的聚合物材料。通过基于密度泛函理论的理论计算，我们进一步证明了取代基和官能团的类型在二氢吩嗪衍生物的电压调整以及结构稳定性方面具有重要意义。