功能化COFs电极材料的设计与电容性能研究

Novel structures of electrode materials and new strategies for controllable preparation are the effective way to improve the energy density of supercapacitors. This project aims to design new electrode materials with high density energy storage active sites and reasonable microcrystalline structure for supercapacitor application. By introducing superconducting charge transfer complex into 2D covalent organic frameworks (COFs), effective electron transport paths between COFs conjugated planes can be constructed so that the intrinsic conductivity of COFs materials get improved. At the same time, the pillar molecules (Aminoanthraquinone) covalently grafted on the surface of the graphene hydrogel as the nucleation sites of COFs will induce the in situ oriented and controlled growth of the functionalized COFs on the surface of the graphene. The reasonable COF micro-crystal interface structure ultimately maximizes the energy storage performance of high density active sites in the covalent organic frameworks. In the project, optimal synthetic conditions of the functionalized COFs will be studied systematically, and the mechanism of the induced COFs crystal growth by molecular pillars is expected to illustrated. Besides, we will objectively describe the electrochemical kinetics of such novel conjugated systems, and recognize the key factors affecting their energy storage capacity and power performance, laying the theoretical and experimental foundation for related research.

电极材料新结构及可控制备新策略是提高超级电容器能量密度的有效途径。本项目以构筑具有高密度储能活性位点和合理微观晶体结构的新型超级电容器电极材料为目标，通过在具有高密度储能活性位点的二维共价有机骨架（COFs）中引入超导电荷转移复合盐，来构建COFs共轭平面间的有效电子传输路径，实现COFs材料本征电导率的有效提高。在此基础上，借助共价接枝在石墨烯水凝胶表面的分子支柱（氨基蒽醌）作为COFs成核位点，诱导该类功能化COFs材料在石墨烯表面原位定向、可控生长，以此构筑合理的COFs微观晶体界面结构，最终实现COFs骨架中高密度活性位点储能性能的最大化发挥。本项目将系统研究功能化COFs材料的最优合成条件，重点阐明分子支柱对于诱导COFs晶体生长的作用机制，客观表述这类新型共轭系统中的电化学动力学特征，掌握影响其储能容量和功率性能的关键因素，为相关研究奠定理论和实验基础。

电极材料新结构及可控制备新策略是提高超级电容器能量密度的有效途径。本项目以构筑具有高密度储能活性位点和合理微观晶体结构的共价有机框架（COFs）基新型超级电容器电极材料为目标。通过在具有高密度储能活性位点的二维共价有机骨架中引入高导电性基底或对共轭结构进行功能化改性，来构建COFs共轭平面间的有效电子传输路径，实现电极材料电化学储能性能的提高及电极形式多元化构筑。具体工作如下：1、基于对亚氨基COFs 动态共价可逆聚合反应的深入理解，通过精确调节其生长过程中的热力学/动力学参数，进而获得具有不同结晶度和微观形貌的COFs电极材料并对其聚合机理进行归纳总结；2、利用阳离子驱动静电自组装策略，分别制备出COFs/石墨烯复合气凝胶电极以及COF/MXene柔性薄膜电极，不仅克服了粉末状 COFs 难以加工的难题，同时实现了电极材料快速传质和活性位点的高效利用；3、通过共价桥联方式实现COFs晶体在柔性碳布导电基底表面的原位定向、可控生长，以此构筑合理的COFs微观晶体界面结构；4、通过在具有高密度储能活性位点的二维共价有机骨架中引入超导电荷转移复合盐，来构建COFs共轭平面间的有效电子传输路径，实现COFs材料本征电导率的提高；5、以非晶态聚氨基蒽醌材料为研究对象，进行了一系列形貌控制及储能、催化方面的研究。