基于纳米结构的钴（镍）氧化物/碳纤维纸复合薄膜电极的可控制备及电容性能研究

Cobalt and nickel oxides are considered as potential electrode materials for supercapacitors because of their high theoretical specific capacitance, excellent chemical stability and low cost. However, their low utilization rate and poor electronic conductivity limit their practical applications. In this project, based on the design and construction of high-performance electrode materials, we propose a novel strategy for the synthesis of nanostructure cobalt and nickel oxide/carbon fiber paper (CFP) film electrodes using M3(HCOO)6 (M=Co, Ni) films grown on the CFP substrate as the precursor. The morphology, structure and active material loading of oxide/CFP film electrodes will be modulated by changing the morphology and structure of M3(HCOO)6 films to obtain high-performance film electrodes. The physical and chemical experimental measurements will be applied to investigate the relationship between the structure, morphology and electrochemical performance of the film electrode. The mechanism of the nanosise effect and synergistic effect on improving the electrochemical performance will be proposed. The principle of the structure design and optimization of high-performance film electrodes will be established. This project will provide a theoretical basis and experimental guidance for the development and application of the high-performance electrode materials.

钴、镍氧化物作为超级电容器电极材料，具有理论容量高、化学性质稳定和价格低廉等优点，但其较低的材料利用率和较差的电子电导率限制了其应用。本项目基于高性能电极材料的结构设计，提出以碳纤维纸基体上生长的M3(HCOO)6（M=Co，Ni）金属有机框架膜为前驱体构筑具有纳米结构的钴（镍）氧化物/碳纤维纸复合薄膜电极的新思路。通过对M3(HCOO)6膜形态的控制实现复合薄膜电极形貌、结构及活性物质负载量的调控，以获得高性能超级电容器薄膜电极。综合相关结构表征及电化学性能测试建立薄膜电极的构效关系，阐明纳米尺寸效应、组分间协同效应改善材料性能的机理，建立高性能复合薄膜电极的设计和优化原则，为高性能电极材料的研发及应用提供理论基础和技术依据。

本项目采用低温液相反应制备了钴（镍）有机金属框架（MOF）粉体材料，并以其为前驱体，热处理得到具有纳米结构的金属氧化物，研究表明，该类材料由于具有三维多孔结构以及组成颗粒的纳米尺寸效应，从而显示了良好的电化学性能；在此基础上，本项目改用碳布为基底，通过电化学沉积方法，成功实现了MOF晶体材料在碳布碳纤维表面的可控生长，得到高负载量的MOF/碳布薄膜，并研究了其作为锂离子电池电极材料的电化学性能；以所得MOF/碳布薄膜为前驱体，经热处理制备金属氧化物/碳布薄膜，通过对MOF膜形态的控制实现复合薄膜电极形貌、结构及活性物质负载量的调控，以获得高性能薄膜电极材料。本项目成功验证了以MOF 膜为前驱体制备具有纳米结构金属氧化物/碳布复合薄膜电极的技术路线的可行性，从而为构建高性能薄膜电极及MOF材料在储能领域的应用提供重要的参考依据。