基于导电聚合物-碳复合材料水凝胶电极的新型柔性超级电容器研究

Recently, an increasing amount of flexible consumer electronics come into our sights, however, the development of the relevant flexible energy storage unit is dissatisfied. Supercapacitors have received widely attentions because of their high power, wide temperature operation range and safety. This research focuses on synthesis of new electrode materials and preparation of flexible devices. To address the current issues of conducing polymers (CPs) electrode research, such as poor charge-discharge cyclic stability, we propose a new strategy which combines crosslinking of polymer chain with forming carbon composite to prepare CPs – carbon composite hydrogel electrode. The new electrode materials are expected to obtain high capacitance, good rate capability and long cycle life. Besides, the mechanical properties of the composite hydrogel will be enhanced due to the carbon nanomaterials. The electrochemical performance and mechanical properties of the composite hydrogel electrode could be tuned by changing the components and their concentration. Hydrogel supercapacitor with both high electrochemical performance and flexibility will be prepared based on this new hydrogel material as electrodes. Furthermore, the new prototype (fiber-like or on-chip device) of flexible supercapacitor will be designed and prepared by taking the advantage of the excellent process ability of hydrogel materials, which will bring new route of developing high performance flexible energy storage device.

近年来，越来越多的柔性消费电子品进入人们视野，但是相应的柔性能量存储器件的开发却远远落后。超级电容器因具有高功率、宽温度使用范围和高安全性等特点受到了研究者的广泛关注。本研究立足于新型电极材料的合成及柔性器件的制备，针对导电聚合物循环稳定性差等目前研究中存在的问题，提出综合采用分子链交联和与碳材料复合这两种策略，制备导电聚合物-碳复合材料水凝胶电极。这种新型电极材料，有望获得高的电容容量、良好倍率性能和长循环寿命。此外，碳纳米材料的加入可提高聚合物水凝胶的力学性能。通过调控复合材料的成分、相对含量等，可调控其电化学和力学性能。基于制备的凝胶电极，可实现制备既有优良电化学性能、又耐弯折的凝胶柔性超级电容器。进一步，充分利用水凝胶电极的加工性强特点，设计制备具有新型器件结构的柔性超级电容器，比如纤维状电容器、芯片上的微型电容器等原型器件，为开发高性能柔性储能器件提供新的思路。

为了开发可穿戴设备用高性能柔性固态超级电容器，针对导电聚合物循环稳定性差等目前研究中存在的问题，本研究综合采用分子链交联和与碳材料复合这两种策略，合成导电聚合物-碳复合材料水凝胶电极，制备具有高电容容量、良好倍率性能和长循环寿命的柔性储能器件。开展的系列研究包括：（1）通过离子交联制备出导电聚苯胺水凝胶电极，进一步组装了基于导电聚合物水凝胶电极的柔性固态超级电容器。（2）引入化学交联，制备了导电聚合物复合水凝胶薄膜，并研制出具有集成式一体化结构的柔性固态超级电容器。该器件表现出优异的容量、倍率和循环寿命。（3）将导电聚合物与三维石墨烯水凝胶复合，获得导电聚合物-石墨烯复合水凝胶电极。该电极展现出优异的比电容和超快的充放电倍率性能。（4）以导电聚合物-氧化石墨烯多级次复合纳米结构材料为前驱体，研制了纳米复合电极，组装制备了基于离子液体凝胶电解质的有机体系柔性固态超级电容器。（5）以聚合物-氧化石墨为前驱体，通过碳化-活化工艺研制了含有多层次孔结构的石墨烯复合电极，并且研究了其储硫电化学性能。通过上述材料合成与器件制备研究，充分理解了复合材料水凝胶制备过程的动力学和热力学影响因素，建立了调控其电化学性能和力学性能的方法。掌握了制备新型柔性超级电容器的关键工艺，获得了性能优异的柔性超级电容器，并对器件结构进行了深入研究和创新，开发出了新概念原型器件。通过本项目的研究，项目负责人作为第一作者和通讯作者已在Adv. Mater., Adv. Funct. Mater., Chem. Marter.等国际期刊发表SCI论文5篇，申报国家发明专利3项，并参加国内外学术会议5次。通过本项目，培养博士研究生1名，硕士研究生2名，博士后1名。