大孔聚合物诱导组装有序多孔碳基复合材料及其集流体性能研究

Due to the urgent demands of current collectors with excellent conductive networks and high deformation tolerant performances for flexible and deformation-tolerant energy storage devices, based on our previous studies on the hybridization and controllable assembly of carbon nanoelements, in this project, the optimizations for the surface and interfacial properties of the carbon nanoelements such as carbon nanotubes and graphene, the building of new technologies for the functionalization and composition of carbon nanoelements, as well as the regulations based on the construction of high-quality three-dimensional ordered carbon architectures through the layer-by-layer self-assembly of carbon nanoelements onto the skeleton of macroporous polymers are simultaneously achieved. Discussions on the general rules on the macro-scale assembly of carbon nanoelements on three-dimensional templates are proposed, and a series of three-dimensional ordered carbon architectures are finally obtained by the removal of macroporous polymer templates. The relationship of fabrication, structure and physical properties of the three-dimensional ordered carbon architectures will be thoroughly explored. In addition, the effects of the hybridization compositions, the micro/nano-structures as well as the surface/interface interactions of the three-dimensional ordered carbon architectures on the final device performances are intensely explored. The implementation of this project will provide useful references for the construction of high-performance three-dimensional ordered carbon architectures, as well as the design and development of a new type of deformation-tolerant current collectors for wearable energy storage devices.

高强度导电网络骨架和高抗形变特性是柔性耐形变储能器件用集流体的关键特性，针对当前柔性集流体存在抗形变（如拉伸、压缩、扭转等）性能差等问题，申请人在前期碳纳米杂化材料可控构筑及组装的工作基础上，提出对碳纳米管和石墨烯等碳纳米基元材料进行功能化修饰以改善其表界面和组装性能，利用层层自组装方法在大孔聚合物三维骨架表面构筑出高质量的三维有序宏观尺度碳纳米组装体，精确调控三维有序碳纳米组装体的组成、厚度、孔隙结构等特性，探讨不同维度、不同尺寸碳纳米基元材料在三维宏观尺度组装过程中的规律，经除去聚合物模板后获得一系列有序多孔碳基复合材料。揭示该有序多孔碳基复合材料组成、微/纳结构、界面性质等对其宏观性质(柔性、导电、传质等)的影响规律，利用其高导电、柔性、抗形变等特性拓展其作为柔性集流体方面的应用。本项目的实施将为优化构筑高性能有序多孔碳基复合材料和设计研发可穿戴设备用柔性集流体等提供有益借鉴。

高性能柔性导电集流体是发展下一代柔性耐形变能源器件的关键。针对目前柔性导电集流体材料面临的耐复杂形变性能差、可逆形变范围窄等瓶颈问题，本项目围绕利用大孔聚合物材料诱导组装制备柔性导电复合材料开展了系统研究，实现了有序多孔碳基复合材料的设计构筑和可控制备，拓展了高导电性、高孔隙率和高稳定性的柔性导电复合材料在柔性储能和可穿戴传感领域中的应用。本项目取得的主要研究结果如下：（1）提出了自模板碳化策略，可控构筑了三维结构碳气凝胶复合材料等有序多孔碳基复合材料，拓展了所制备的有序多孔碳基复合材料在柔性电化学储能领域中的应用，建立了有序多孔碳基复合材料的微观结构与其电化学功能特性之间的关系，为实现有序碳纳米组装体与大孔聚合物材料的可控组装和功能化应用提供了实验基础；（2）发展了界面组装策略实现了碳纳米材料在大孔聚合物三维骨架表面的可控组装，利用自容器冷冻铸造、表面约束水蒸气雾化和界面聚合等制备方法，获得了可拉伸/可压缩回弹、耐环境稳定性的柔性导电复合材料，探讨了有序多孔柔性导电复合材料的组成、结构对其力学、导电和传质性能的影响规律，实现了有序多孔柔性导电复合材料在柔性电化学储能和可穿戴力学传感器件中的应用。通过本项目的实施，发展了大孔聚合物诱导组装构筑有序多孔碳基复合材料的新方法，获得了耐复杂形变、宽可逆形变范围的新型有序多孔柔性导电复合材料，为发展高性能柔性集流体材料及其在柔性储能和可穿戴力学传感等领域中的应用奠定了良好的基础。