随着社会经济的迅猛发展，人们对能源的清洁高效利用也提出了更高要求。超级电容器作为一种清洁、高效、安全的储能器件已经成为研究的热点之一。用于超级电容器的氧化物类电极材料，因具有理论比容量高、环境友好等特点，逐渐受到广泛关注。然而多数氧化物材料存在电子传输阻力大、循环稳定性差的问题难以实际应用，而氧化钌材料则因成本高等问题限制了其大规模商业化应用。对过渡金属氧化物进行纳米结构的设计，将氧化物团簇化、空心化及与廉价过渡金属异质复合是解决上述问题的重要思路。本论文的具体研究内容和结果如下：（1）采用氧化还原法，以RuCl3和NaBH4为原料，通过控制反应体系的pH值、碳材料吸附和热处理过程，获得比表面积为158 m2·g-1的团簇RuO2/rGO复合材料。系统考察了反应体系pH值和不同碳基体对合成RuO2团簇颗粒及电化学性能的影响规律。结果表明，当pH值为4.9时，制得2.0 nm左右的RuO2团簇颗粒，且可均匀地分散于碳基体材料的表面，不同碳基体负载RuO2团簇材料均具有比商业RuO2/C更高的比容量和更低的电阻值，其中RuO2·xH2O/rGO纳米复合材料具有优异的电化学性能，比容量达1099 F·g-1。（2）采用油胺还原法、碳材料吸附、热处理过程和多晶银核自扩散机制，分别制得核壳结构Ag/RuO2/C和空心结构RuO2/C复合电极材料。对比分析了核壳结构Ag/RuO2/C空心结构和RuO2/C复合电极材料对氧化物材料电化学性能的影响规律。结果表明，空心结构RuO2/C为电化学反应提供了更多的电化学活性位点，有利于缩短离子扩散距离，降低电极阻抗，因而空心结构RuO2/C比核壳结构Ag/RuO2/C复合材料具有更高的比容量，其比容量达到805.8 F·g-1。（3）为减少RuO2的用量，降低材料的成本，以Cu金属核作为模板，利用种子生长法、油胺还原法和热处理过程合成出了空心结构的CuO/RuO2复合颗粒。深入分析了空心结构CuO/RuO2材料形成机理。结果表明，由于Cu晶相在Cl-和O2的诱导下向颗粒外部扩散，Ru原子向内部扩散，Cu原子的扩散速度大于Ru原子，从而形成空心结构复合材料。进一步将该工艺拓展到其他过渡金属核体系，制备出了Co，Ni，CuNi等空心复合氧化物，考察了不同复合氧化物材料电化学性能，其中含19.6 wt% RuO2的NiO/RuO2/C材料的比容量可达907.3 F·g-1，优于商业RuO2/C等其它几种复合氧化物材料。（4）采用种子生长法和热处理过程制备了核壳十二面体框架结构CuO/Pt复合电极材料，深入分析了空心十二面体结构CuO/Pt形成的机理。结果表明，由于Cu核和Pt框架间的相互扩散，Cu原子的扩散速度大于Pt原子，以及O2对Cu核的刻蚀作用，从而形成空心结构CuO/Pt复合电极材料。同时对比分析了核壳结构和空心结构对CuO/Pt复合材料的比表面积和电化学性能的影响规律，其中空心结构CuO/Pt电极材料具有更高的比表面积、更低的电阻、更高的比容量和更好的倍率性能，这可能是由于空心结构CuO/Pt电极存在明显的微孔电极扩散效应，有利于提高材料比容量。;With the development of society and the improvement of living standards, the requirements for clean and efficient energy are constantly increasing. As a kind of clean, efficient and safe energy storage device, supercapacitors have attracted a lot of researches and attention. The key factor influencing the performance of supercapacitors is electrode materials. Oxide electrode materials have attracted more and more attention due to their high theoretical specific capacity and friendly environment. However, most of the oxide materials have the problems of large electron transport resistance and low specific surface area, and the high cost of the yttrium oxide material with excellent performance needs to be solved. The design of nanostructures for transition metal oxides, such as clustering of oxides, hollowing out and recombining heterogeneously, is important idea for solving the above problems. The specific research content and results of this paper are as follows:(1) Using redox method and RuCl3 and NaBH4 as raw materials, RuO2/rGO composites with specific surface area of 158 m2·g-1 can be obtained by controlling the pH of the reaction system, carbon material adsorption and heat treatment. The effect of the pH value of the reaction system on the cluster particles is investigated. The size of the cluster particles rapidly increases with the increase of the pH value. When the pH value is 4.9, the Ru cluster particles with an average size of 1.7 nm prepared, which can be stably dispersed in the aqueous phase. At the same time, the influence of different carbon matrix on the electrochemical performance of RuO2 cluster particles is investigated. The result shows that RuO2 cluster materials loaded on different carbon substrates have higher specific capacities and lower resistance values than commercial RuO2/C. Besides, It is observed that RuO2?xH2O/rGO nanocomposites have the best electrochemical performance and the specific capacity reaches 1099 F·g-1.(2) The core-shell Ag/Ru nanoparticles are prepared by the oleylamine reduction method using silver core as the template, and the hollow structure RuO2/C composite materials with the wall thickness of about 2 nm prepared by using the self-diffusion mechanism of polycrystalline silver and the heat treatment process. The influences of hollow structure and core-shell composites on the electrochemical properties of oxide materials are compared and analyzed. The result shows that the hollow structure provides more electrochemical active sites for electrochemical reactions, shortens the ion diffusion distance, and reduces the electrodes impedance, so hollow structure RuO2/C composite material has higher specific capacity than core-shell structure Ag/RuO2/C composite and its specific capacity reaches 805.8 F·g-1.(3) A transition metal core used as a template instead of a silver core, CuO/RuO2 composites nanoparticles with a hollow structure are synthesized using a seed growth method, an oleylamine reduction method and a heat treatment process in order to reduce the amount of RuO2 and the cost of materials. The formation mechanism of the hollow structural material is investigated. The result shows that the hollow structure is formed by the bimetallic diffusion process. Other transition metal core systems are also explored and found that the preparation method can be extended to cobalt, nickel, copper nickel and other hollow composite oxides. In addition, the effect of different composite oxides on the electrochemical performance of the material is examined. The result shows that the specific capacity of NiO/RuO2/C material with an RuO2 content of 19.6 wt% is 907.3 F·g-1, which is better than commercial RuO2/C composites.(4) A CuO/Pt nanocomposite with a hollow dodecahedron frame structure is designed by using the method of bimetallic diffusion and oxygen etching. The mechanism of formation of hollow dodecahedron structure is investigated. The effects of different structures on the specific surface area and conductivity of nanomaterials are compared and analyzed. The result shows that compared with the core-shell materials, the hollow structure increases the specific surface area of CuO/Pt nanomaterials to 122.5 m2·g-1. The influence of different structures on the electrochemical properties of nanomaterials is investigated. It is found that the hollow structure CuO/Pt has higher capacity, lower resistance and better rate performance. Moreover, AC impedance analysis result shows that the microporous electrode diffusion effect is beneficial to the improvement of the specific capacity of the material.