含均三嗪结构聚三苯胺微介孔有机锂电池正极材料的制备与电化学性能研究

The free radical based cathodic material is one of the hot-topics in the field of the organic lithium battery technologies, presently. For the aromatic-based free radical polymer-polytriphenyamine, to overcome its low energy density and the low utilization coefficition during the charge/discharge process, the series of novel functional polymers with high energy density, in this project, are molecular-designed and synthesized by introducing the 1,3,5-triazine as both the electron-withdrawing and electrochemical active group into triphenylamine unit. Also, the microporous conjugated polymers based on the polytriphenylamine derivatives will be prepared by controlling the polymerization reaction process. According to the above studies, the composite cathode material with the graphene as the conducting fillers is finally in-situ prepared, aiming to improve the utilization coefficition of the material during the charge/discharge process. Furthermore, the relationship among the molecular structure of the novel polytriphenylamine free radical polymers, the micro-morphology of material, the preparation technology of the composite electrode and the charge-discharge performances of the prepared mateirals is studed in detail. Also, it will further be illuminated about that effects of the introduction of triazine on the electronic structure, the electrochemical characteristic, the charge-stored property of the polytriphenylamine derivatives. And the charge-discharge process mechanism for the novle triazine-contained polytriphenylamine, as well the nature relationship of the micromorphology structure-electron/ion conducting balance-cell charge/dicharge process, will also be revealed. All work will provide the helpful theoretical and experimental basis for the novel molecular design of free racial material, the morphology control of the material, and the composite electrode propertion in the future research.

自由基正极材料是目前有机锂电池技术发展的热点之一。针对芳胺型自由基聚合物-聚三苯胺正极材料比容量偏低和材料聚集所导致的在充放电过程中活性材料利用率不高等问题，本项目拟通过分子结构设计，将具有吸电子效应和电化学活性的1,3,5-均三嗪引入三苯胺并合成高能量密度的聚三苯胺衍生物；通过控制聚合条件制备微孔有机聚三苯胺新材料，并在此基础上将该聚合物与石墨烯原位复合制备开放结构复合锂电池正极，以提高活性材料在充放电过程中利用率。研究该新型自由基聚合物材料的分子结构、微相结构，以及电极复合工艺与正极材料的充放电性能关系；阐明氮杂苯-均三嗪引入对聚三苯胺的电子结构、电化学特性、电荷存储性能和微形貌等的影响；揭示新型聚合物的充放电机制及聚合物电极的微相结构-电子/离子传输平衡-电池充放电性能间的规律等。上述工作开展将为新型自由基聚合物锂电池正极材料的分子设计、形貌控制及其复合电极的制备提供理论与实验依据。

自由基正极材料是目前有机锂电池技术发展的热点之一。针对芳胺型自由基聚合物-聚三苯胺正极材料比容量偏低和材料聚集所导致的在充放电过程中活性材料利用率不高等问题，本项目通过分子结构设计，合成系列三苯胺功能单体（N, N, N, N-四苯基-1, 4-苯二胺 (DDP) 、4,4′,4"-三(N,N-二苯基氨基)三苯基胺（TDATA）、2,4,6-三（三苯胺）-1,3,5-均三嗪单体(TDAPTz)、4,4',6,6'-（4-三苯基）-2,2'-二三嗪（TPADTz））以及具有不同电子集团的聚三苯胺功能单体。采用上述制备的不同分子结构的三苯胺衍生物为单体，通过氧化偶联聚合法制备聚三苯胺衍生物功能材料。研究合成路线、反应条件、提纯方法等对制备聚合物材料的影响。通过控制分子结构和聚合反应条件，得到高比表面积的微孔有机共轭聚合物材料系类（PTDATA材料具有783.63 m2/g的高比表面积和微介孔形貌、PTDAPTz材料具有931.06 m2.g-1的比表面积和微介孔形貌、PTPADTz具有~657 m2. g-1的BET比表面积和微介孔形貌）。并在此基础上，采用制备各类聚三苯胺聚合物为电极活性材料，通过优化电池组装制备工艺，并组装锂金属电池。研究复合材料的制备工艺、聚合物活性材料的分子结构、制备复合材料的物相显微结构、以及电池的组装工艺等对制备复合正极材料的电化性能和电池性能的影响。揭示新型聚合物的充放电机制及聚合物电极的微相结构-电子/离子传输平衡-电池充放电性能间的规律等。在此基础上，探索了新型聚三苯胺自由基电活性材料的充放电过程和储能机制。上述工作开展将为新型自由基聚合物锂电池正极材料的分子设计、形貌控制及其复合电极的制备提供理论与实验依据。