柔性导电高分子/石墨烯基三维组装体的储能性质研究

The flexible lightweight conductive materials with three-dimensional continuous network structure exhibit an important application value in the capacitor technology. The self supporting, supporting graphene based three-dimensional continuous assembly will be prepared through self assembly method by using graphene oxide, carbon nanotubes and commercial porous material as the source material in this project. Conductive polymer and its composites will be deposited on the assembly through electrochemical deposition, electroless deposition and gas phase polymerization. In the composite, the electrically active material and carbon material will be assembled well in the three-dimensional space and the multi scale. The graphene with large specific surface area can be favorable to improve the mass of the loaded electrically active material, the supporting structure provided by the carbon nanotubes and graphene will improve the dispersion of conductive polymer, which will overcome the adverse factors caused by the volume changes of conductive polymer during the charge and discharge process, while the electrically active materials dispersed on the assembly can improve the mechanical strength of the composites. The utilization rate and the performance of fast charging and discharging of the electric active material will be improved through the conductive stability of carbon material in the process of charge and discharge. The regulation of the macro, micro structure of the assembly, the action mode of the electrical active materials and assembly and the morphological structure will be researched detailedly in this project. Furthermore, high performance flexible composite electrode material will be developed, and the application of the composite material, the relationship between the structure and performance will be elucidated when the project is finished.

具有三维连续网络结构的柔性轻质导电材料在电容技术中有着重要的应用价值。本项目将利用氧化石墨烯、碳纳米管和商用多孔材料为基础材料，通过组装法制备自支撑、支撑石墨烯基三维连续组装体，通过电化学沉积、化学沉积和单体气相聚合法在组装体上负载导电聚合物及其复合物，实现电活性物质和炭材料在三维空间的多尺度复合。利用石墨烯的大比表面积提高电活性物质的负载量，利用炭纳米管、石墨烯提供的支撑体结构改善导电聚合物的分散性，克服充放电过程中导电高分子体积变化导致的不利因素，同时电活性物质在组装体上的复合又有利于提高复合材料的机械强度。通过碳材料在充放电过程中的导电稳定性来克服还原态导电高分子导电性能低的缺点，提高电活性物质的利用率，改善材料快速充放电的性能。研究组装体的宏、微观结构的调控规律，研究电活性物质与组装体的作用方式、结构形态、研制出高性能的柔性复合电极材料，阐明复合材料的应用方式，结构与性能间的关系。

用电化学共沉积法在导电玻璃表面沉积了聚吡咯/氧化石墨烯（PPy/GO）、聚3,4-乙烯二氧噻吩/氧化石墨烯(PEDOT/SDS-GO)和PEDOT包裹于多壁纳米管表面(MWCNT@PEDOT/PSS)的复合膜。在10mV/s的扫描速率下，PPy/GO复合膜的面电容高达152mF/cm2，但是随着膜的厚度增加，离子的扩散电阻明显增加并且随着扫描速率的增大，膜的比电容也快速减小；PEDOT/SDS-GO复合膜具有花瓣形状，最佳的复合膜在10mV/s的扫描速率下有79.6mF/cm2的面电容；而MWCNTs@PEDOT/PSS复合膜具有三维的网络结构，聚合物包裹于MWCNT表面，其面电容在5mV/s的扫描速率下为98.1mF/cm2，并且具有非常好的循环稳定性。采用浸渍法制备了MWCNT和石墨烯修饰的海绵和无纺布，然后通过吡咯蒸汽与吸附的氧化剂反应生成负载有聚吡咯的柔性复合物，研究发现在复合材料表面再包裹一层MWCNT会大大增强材料的电容性能。以氧化石墨烯为原料，发展了“羟胺扩散诱导组装法”，制备了大面积N掺杂石墨烯膜以及大面积多壁炭纳米管与石墨烯的复合膜、沉积于基底表面的大面积透明N石墨烯膜及其复合膜以及N掺杂石墨烯纤维毡。研究发现大面积石墨烯膜具有极好的力学性能、极高的导热性能和较大的导电率，并详细研究材料其用于超快速电容电极材料的性能；研究了透明N掺杂石墨烯膜厚度与其透光率和导电性能的关系；研究了处理温度对N掺杂石墨烯纤维毡的表面积、孔结构以及用于电化学电容电极材料的影响。通过氢氧化钾活化法制备了多孔石墨烯，利用多孔石墨烯构建了负载酶的高效农药电化学传感器。在磷酸缓冲液中，以高锰酸钾为原料电沉积法制备了沉积于炭纸基底的二氧化锰及二氧化锰与石墨烯的复合物，研究了复合材料的电容性能，发现在磷酸缓冲液中电沉积，能大大提高二氧化锰的比电容并且掺入石墨烯后，材料的比电容进一步提高。用两步循环伏安法在导电玻璃FTO表面沉积了具有枝形聚苯胺（PANI）纳米线，用作染料敏化太阳能电池（DSSC）的对电极，DSSC的光电转换效率可达铂对电极光电转换效率的97%。以沉积于FTO表面的PANI同时作为光敏剂和空穴传输材料，采用注入生成金属有机钙钛矿法制备了全固态钙钛矿电池，其光电转换效率可达到7.34%。采用原位生成法制备金属有机钙钛矿构建了光电转换效率达10.03%的全固态光伏电池。