基于3D碳纳米材料的全固态超级电容器的制备及性能研究

Due to their high electrical conductivity and large specific surface area, three-dimensional (3D) carbon nanomaterials have been widely used as electrode materials for high-performance liquid electrolyte-based supercapacitors. However, until now, only a few literatures focused on the all-solid-state supercapacitor using 3D carbon nanomaterials as the electrode, the performance of which was much lower than liquid electrolyte-based system. In all-solid-state supercapacitors based on 3D carbon nanomaterials, it is difficult for the gel electrolyte solution to infiltrate all the holes of 3D materials, which caused ineffective contact between the electrode materials and electrolyte, resulted relative lower performance than expected. Therefore, how to resolve the above problem is the key to develop 3D carbon nanomaterials-based all-solid-state supercapacitors with high performance. Based on the previous research experience, this project will focus on fabricating 3D carbon nanomaterials with different structures and components, the effects of different synthetic methods and processes on the structures, morphologies and properties of obtained 3D carbon nanomaterials will be systematically studied. To achieve effective contact between electrode and electrolyte, new method will be developed using pressure difference to force gel electrolyte solution infiltrate into the holes in 3D materials. At the same time, some materials with pseudocapacitive effect, such as conductive polymers and metal oxide, will be introduced into the developed 3D carbon nanomaterials by in-situ electrochemical deposition method. Based on the 3D carbon nanomaterials and their composites, a series of all-solid-state supercapacitor with high performance will be developed.

三维（3D）碳纳米材料不仅具有良好的导电性还具有较大的比表面积，被广泛应用于基于液体电解质体系的超级电容器的研究，并且能够获得较高的性能；但是，在全固态超级电容器中却很少涉及，主要面临的问题是凝胶电解质很难充分地填充到3D材料的孔洞中，使电解质与电极材料的接触不好，导致器件的性能远低于预期。如何解决电解质与电极材料接触较差的问题，是开发基于3D碳纳米材料的高性能全固态超级电容器的关键。基于前期的工作积累，本项目将通过多种方式制备具有不同结构、不同组分的3D碳纳米材料，着重研究不同合成方法、工艺对所得3D材料的结构、形貌及性能的影响；提出利用压力差驱动凝胶电解质充分渗透到3D材料的孔洞中，使电解质与电极材料具有良好的接触；同时，结合具有赝电容效应的导电高分子和金属氧化物，制备3D结构的碳纳米复合材料，在此基础上，发展出一大类具有较高性能的全固态超级电容器器件。

柔性、便携式、可穿戴电子产品的兴起与发展，亟需与之匹配的柔性能量储存器件，比如柔性超级电容器。目前，制约柔性超级电容器发展的技术瓶颈主要在于电极材料，因为常用的纳米碳电极材料极易发生聚集，导致器件的性能达不到预期。为解决上述问题，本项目首先设计并合成了三维（3D）结构的纳米碳宏观体，能有效避免纳米碳之间的聚集，基于此，在以下三个方面取得了重要进展。1）提出了电极材料致密化、有序化的设计理念，一方面能有效促进电荷的传输或收集，另一方面能够有效提升相关能量储存器件的柔性及可拉伸性能；2）通过对电极材料和器件结构的协同化设计，发展了工作电压高达1.8 V的基于水系凝胶电解质的非对称超级电容器，器件兼具超高的能量密度和柔性；3）通过简单的自由基聚合反应，合成了具有高的离子导电性和柔韧性的高分子水凝胶电解质，进一步发展了具有超高柔性、可剪裁的全固态超级电容器。该项目所发展的柔性、可拉伸超级电容器，在柔性、可穿戴电子设备领域具有极大的应用价值和潜力。项目执行期间，项目负责人作为通讯作者发表SCI论文7篇（包括Angew. Chem. Int. Ed.、Adv. Mater.、Adv. Sci.等国际知名期刊）、中文核心论文1篇；申请中国发明专利4项；共同主编英文专著一部，由Elsevier出版社出版；项目负责人获得“上海市高校特聘教授（东方学者）”、“上海市青年拔尖人才”和“上海市青年科技启明星计划”等荣誉称号；培养出站博士后一名，已留同济大学任教，目前在读博士4人、硕士研究生3人。