新型分级孔结构Ni-MOF复合材料的构筑及其柔性全固态超级电容器性能研究

To explore newly flexible solid-state supercapacitors, a new kind of flexible composite is planning to be designed with novel hierarchically structure based on the electrode material of Ni-MOF which is focused on constructing reasonable structure of the aperture, as well as the conductivity, flexibility, reaction activity and so on. Firstly, a newly micro-meso-macro hierarchically structure of Ni-MOF/CNT/GF composite material will be synthesized. The construction mechanism and morphology forming process will be studied on the newly hierarchically structure of this composite, and a controllable synthesis system will be established on the micro-meso-macro hierarchically structure. Secondly, a flexible solid-state supercapacitor will be constructed based on the synthesized composite materials. It will be studied about the structure-activity relationship between the electrochemical performance and the intrinsic properties such as phase, composition, morphology, structure and so on. Moreover, the ion/electron transport mechanism will be revealed at the electrode/electrolyte interface between different composition and aperture structure, and a theoretical model may be established with the content that this kind of newly hierarchical structure promotes the high capacitive performance of the device. All the study mentioned above will provide a theoretical foundation for the development of newly flexible solid-state supercapacitor in future.

围绕着研制新型高性能柔性超级电容器，拟以新型电极材料Ni-MOF为基础，以构筑合理的孔径结构为出发点，同时兼顾材料的导电性、柔性、电化学活性等因素，设计构筑具有新型分级孔结构的Ni-MOF柔性复合材料。通过合成具有微孔-介孔-大孔分级孔结构的Ni-MOF/CNT/GF柔性复合材料，探索复合材料分级孔结构的构筑机理与形貌调控规律，建立微孔-介孔-大孔分级孔结构复合材料的可控合成体系，并构建基于Ni-MOF/CNT/GF复合材料的柔性全固态超级电容器，研究电极材料的物相、组成、形貌、结构、孔径分布、比表面积等结构特性与其电化学性质之间的构效关系，揭示电极/电解质界面处各组分之间、不同孔结构之间的离子/电子传输机制，建立新型分级孔结构电极材料促使器件高电容性能的理论模型，为研制高性能的柔性全固态超级电容器提供理论依据。

近年来，金属有机框架（MOF）电极材料在超级电容器领域快速发展，但还存在大倍率性能低、长循环稳定性差等问题，因而限制了它在超级电容器领域的实际应用。本项目围绕研制高性能超级电容器的目标，设计构筑了具有合理孔径结构的高导电Ni-MOF柔性复合材料，构建了基于多孔基底的可控合成方法，完成了系列多孔复合电极材料的成功制备，掌握了新型多孔结构复合材料的相关制备技术。同时研究了它们的电化学性能，探明了复合材料的结构特点与其储能性能之间的构效关系，阐释了电极与电解液界面处的微观传输机制，为研制新型高性能全固态超级电容器提供了相应的理论依据。主要研究结果包括：（1）通过原位制备技术制备得到了基于Ni-MOF的新型多孔复合结构，并研制了基于该电极材料的高性能柔性全固态电容器。该电容器表现出了大的比容量、高的倍率性、稳定的循环能力、良好的机械柔性，尤其是具有较高的能量密度。这些良好的电化学性能可能与CNT的高电子传输能力、石墨烯层的电子传输作用、复合电极结构的多孔特征、复合材料物相结构中含氧基团的变化等因素有关。（2）成功合成了一系列多孔复合电极材料，研究并构建了基于多孔基底的可控合成技术，包括Ni-MOF@CNT/GN、NF/graphene/Mn3O4、ＭnOOH-石墨烯-泡沫镍、Ce-UIO-66/TNF四种复合电极制备方法，同时申请了相关的制备技术专利并最终得到授权。（3）通过相关的表征及测试，探明了各种复合电极的分级孔结构特征、电极活性材料的纳米化特征、高比面积特征、自支撑结构特征等与其高电容性能之间的构效关系，阐释了电极与电解液界面处的电子传递路径、离子传输通道、赝电容反应机理等微观理论。