有序纳米阵列的调控制备及其超级电容特性研究

The redox reactions of metal oxides as electrode materials for supercapacitor are reversible in the chemistry and structure, and always exhibit wonderful specific capacitance and charge/discharge performance. This project intends to systematically investigate the supercapacitive properties of ordered metal oxides nanoarrays. Firstly, NiO/MnO2/Co3O4-TiO2 heterojunction nanoarrays will be achieved through anodic oxidation and then electrochemical depositon process. Relationships between the nanopaticle size, morphology and distribution manner with the electrochemical performance will be tested. Secondly, nanostructure CuxO arrays on the surface of highly pure copper foils will be prepared and then electrochemically modified for the flexible supercapacitor device. We will characterize the electrochemical performance and the cycling stability of the device. Finally, nanostructured MxOy (M = Zr, Mn, Fe,Co, Ni, Cr, W, V, Nb) arrays will be synthesized by electrochemical anodization and then modified with NiO/MnO2/Co3O4 quantum dots using electrophoretic deposition technology. At the same time, nanostructured MxOy arrays will be promoted by hydrothermal treatment for the mesoporous structures on the surface of the nanoarrays in order to enlarge the specific surface area and also for the improvement of the electrochemically active surface for applications as electrode materials for supercapacitor. This project aims to expand the scope of ordered nanostructured metal oxide arrays as electrode materials and to develop a nanopore - quantum dots / mesoporous morphology multi-level structured electrode materials for supercapacitor. The achievement of this project will provide the theoretical basis for the future development of electrode materials for supercapacitor.

金属氧化物作为超级电容器电极材料时发生的氧化还原反应在化学和结构上是可逆的，且比电容大，充放电性能好。本项目拟以金属氧化物有序纳米阵列材料为主体，首先通过阳极氧化、电化学沉积工艺制备NiO/MnO2/Co3O4-TiO2异质结有序纳米复合材料，阐明NiO/MnO2/Co3O4纳米颗粒形貌、分布状态对电化学性能的影响规律；其次在高纯铜箔表面构筑有序CuxO纳米阵列并进行电化学修饰改性，封装为新型柔性超级电容器原理型器件后研究其超级电容特性及循环稳定性；最后拟通过阳极氧化并结合电化学沉积、电泳沉积、水热处理等工艺，合成MxOy有序纳米材料并对其修饰改性，M为金属元素，包括Zr, Mn, Fe, Co, Ni, Cr, W, V, Nb等基体材料，拓展超级电容器用金属氧化物有序纳米阵列电极材料的范围，发展一种超级电容器用纳米孔-量子点/介孔多层次结构电极材料，为超级电容器的发展提供基础理论依据。

纳米尺度的金属氧化物作为超级电容器电极材料是具有较高的能量密度和功率密度，对于构造高性能超级电容器有着重要意义。本项目在电化学阳极氧化工艺制备有序排列TiO2纳米管阵列薄膜的基础上，首先设计和构筑了MnO2/TiO2纳米管复合材料，并组装了对称型全固态超级电容器，获得了良好的循环稳定性，5000次充放电测试后电容保持率为91.5%。通过氩气保护和氢气气氛保护退火处理工艺，实现了对TiO2纳米管阵列基体的氧空位掺杂、碳层修饰及氢化，并进一步制备了Cu2O/TiO2, NiO/TiO2, Co3O4/TiO2纳米管复合阵列，系统研究了所构筑复合阵列的超电容性能，结果表明通过对基体的改性处理，可以有效优化导电率和载流子密度，复合纳米阵列的比电容量得到提升，循环稳定性也明显提高。创新地发展了一种恒电流阳极氧化工艺，在柔性高纯铜箔表面构筑了有序排列的CuO/Cu2O纳米棒/片阵列，并进一步通过水热沉积处理工艺实现了CoO@CuO/Cu2O核壳结构，NiOOH@CuO/Cu2O复合纳米片阵列的制备，电化学性能测试表明：基于柔性铜箔表面纳米棒/片阵列的电极材料，其比电容量可达1206 mF cm-2, 且经过3000次循环稳定性测试后其电容保持率为84.6%；NiCo2O4-C@CuO/Cu2O||Activated Carbon 非对称超级电容器件组装及性能测试结果表明：最大功率密度能达到15 mW cm-2，最大能量密度有36.9 μWh cm-2，经过4000次充放电循环测试后，电容保持率为91%。基于高纯铜箔表面纳米结构的超级电容器充分利用了铜箔的柔韧特性和优异的导电特性，为发展新型柔性超级电容器电极材料提供了新的思路。