等性sp2-N（B、P）交叉共轭型稠杂环有机电池活性材料的设计及其机理研究

利用有机材料进行电化学储能的策略是缓解当前电池中无机材料种类有限、部分元素资源匮乏且空间分布不均的重要方案之一，相关研究已成为电化学储能领域的重要前沿。合理设计分子结构实现高效电能存储是有机电池活性材料领域的核心科学问题。本申请针对充放电过程中因化学键重排和活泼中间体自由基的生成严重降低有机电池活性材料稳定性的瓶颈问题，提出以等性sp2-N（B、P）交叉共轭稠杂环化合物作为电极材料的研究思路。利用第一性原理计算，以等性sp2轨道杂化原子为活性中心，参与反应的为π轨道孤对电子，避免化学键重排；通过共轭基团和稠杂环之间的共轭增强电子离域，稳定充放电过程中生成的中间体自由基，突破因电荷离域不足导致稳定性差的限制。此外，在共轭结构中引入O、S重构分子骨架及官能团修饰优化放电电压，揭示分子结构与电化学性质之间的构-效关系，扩大材料筛选和适用范围。研究结果将为发展新型高效有机电池活性材料提供理论依据。

The strategy of using organic materials for electrochemical energy storage is one of the important solutions to alleviate the limited types, the lack of some element resources and the uneven spatial distribution of inorganic materials, related research has become an important frontier in the field of electrochemical energy storage. Reasonable design of molecular structure to achieve efficient energy storage is the core scientific problem in the field of organic battery active materials. In order to solve the bottleneck problem that the rearrangement of chemical bonds and the generation of active intermediates free radicals in the process of charge and discharge seriously reduced stability of organic battery active materials, this application proposes a research idea of using isotropic sp2-N (B, P) cross-conjugated thick heterocyclic compounds as electrode materials. Using first principles calculation, the atoms with isotropic sp2 orbital hybridization as the active center, the π orbital lone pair electrons participate in the reaction, avoiding chemical bond rearrangement；the electron delocalization can be enhanced through the conjugate effect between conjugate groups and thick heterocyclic conjugated, which can stabilize the intermediates free radicals generated during the process of charge and discharge, and break through the limitation of poor stability caused by insufficient delocalization of charge. In addition, O and S were introduced into the conjugated structure to reconstruct the molecular skeleton combined with the functional group to optimize the discharge voltage, revealing the structure-activity relationship between the molecular structure and electrochemical properties, and expanding the scope of material screening and application. The research results will provide a theoretical basis for the development of new high efficiency organic battery active materials.