石墨烯、石墨烯无机复合物三维构架的构筑及其在超级电容器中的应用

Low dimensional Carbon nanomaterials such as 1D-CNTs and 2D-graphene are individually considered the most conductive materials with high surface area, and therefore at the forefront of electrochemical energy storage (EES)research. However, the performance of these materials in practice is somehow below the expectations. In order to go beyond the performance of these low dimensional carbon electrode material, we will join force to develop simple, reliable and reproducible techniques for achieving custom designed 3D-templates, based on wet-chemistry synthesis of 3D-FeWO4/ZnO oxides and additive layer manufacturing of 3D-Ni and ZnO foams, suitable for subsequent creation of the customised graphene-like 3D architecture carbon electrodes by chemical vapour deposition. Different preparation methods can effectively control the 3D structure graphene flexibility,porosity, active area, electron transfer rate and mass transfer performance. These different 3D-electrodes of the 3D-architectured graphene were study in electrochemical applications. In addition, the composite 3D-graphene electrodes were formed when redox-active materials was incorporated on remaining the 3D-graphene after template removal and applied to the super capacitor.When 3D-architectured graphene is constructed by 2D-graphene, 3D-architectured graphene functional devices with excellent performance is of great significance to the expansion of the application of graphene.

低维碳纳米材料，如一维（1D）碳纳米管和2D石墨烯有高比表面和高导电性，因此它们处在电化学储能材料研究的最前沿。但在实际研究中发现这些材料的性能与期望值相差甚远。为了超越这些低维炭材料电极的性能，本项目用溶剂热法，或者用增材制造法合成3D-ZnO和3D-泡沫Ni模板，再用CVD法通过特定的设计获得桁长、梁直径合适的构架结构不同的3D构架石墨烯无机复合物和3D构架共价石墨烯。不同的制备方法，可以有效调控3D构架石墨烯柔韧性、多孔性、活性面积、电子传递速度及传质等性能。研究这些不同3D构架石墨烯无机复合物制备的超级3D电极在超级电容器的应用；还研究用移除模板后的3D构架石墨烯或者在3D构架石墨烯上涂一薄层氧化还原活性物形成复合层后制成的超级互联3D电极在超级电容器上的应用。这种整合2D石墨烯片构筑具有特殊3D构架结构的石墨烯宏观组装体，进而制备性能优异的功能器件对于拓展石墨烯的应用具有重要意义

项目围绕石墨烯、石墨烯无机复合物三维构架等纳米材料的制备、形貌调控、表征和超级电容性能以及传感应用开展了研究，用溶剂热法合成了一系列无机氧化物石墨烯复合物。研究了超声剥离时间、溶剂热反应温度、溶剂种类以及反应时间对合成石墨烯、石墨烯无机复合物纳米材料和石墨烯无机复合物纳米材料对其电化学性能的影响规律；发现基于象薄纱一样的超薄3D石墨烯无机复合物纳米材料能显著增加超级电容器的电容和基于石墨烯无机复合物纳米材料能明显提高电化学传感器的灵敏度、选择性，并建立了对天然中草药有效成分、环境污染物的高灵敏检测的新方法，用于实际样品分析，结果准确，结果与LC-MS一致。在《Ionics》、《Journal of Electronic Materials》等SCI和北京大学核心期刊上发表第一作者和通讯作者论文8篇；圆满完成了各项研究任务。主要成果如下： CoOOＨ／MnO2／石墨烯复合材料的合成及其超级电容性能成果发表在《化工新型材料》(2015，3: 96–99); Fe2O3/石墨烯复合材料的合成及对芦丁的电化学催化和测定成果发表在《Ionics》(2015，21: 1427–1434，引用11次)；复合材料石墨烯基氧化铁的制备及对厚朴酚与和厚朴酚的电分析成果发表在《Journal of Electroceramics》 (2018，40 : 1-10，引用2次)；MoO3-石墨烯复合材料的合成及对黄芩苷的电化学测定成果发表在《Journal of Electronic Materials》（2018，47：1151-1157）；FeWO4纳米花修饰碳糊电极检测厚朴酚成果发表在Journal of Wuhan University of Technology-Mater. Sci. Ed.(2016，31: 722-726)；基于纳米Nb205/石墨烯复合材料的增强效应电化学测定绿原酸成果发表在分析测试学报, (2017，36：319－324，引用2次）；黄芩苷在Nb2O5-石墨烯纳米复合材料修饰电极上的电化学行为及测定成果发表在分析科学学报(2018，34: 90-94, 引用1次。