半导体激光直写碳基微型超级电容器及其碳化机理研究

High-performance micro-supercapacitors have been recognized as promising power supply units in miniaturized portable and wearable electric devices, and the preparation of micro-supercapacitors by semiconductor laser direct writing has many advantages, such as simple and direct process, low cost, environment-friendliness, and integrated compatibility. Recently, we have demonstrated high-performance carbon micro-supercapacitors by using 405nm semiconductor continuous wave laser direct writing on polyimide (PI) in air, but the laser carbonization mechanism is unclear and the conductivity and pore size distribution of obtained carbon materials need further improvement. This project focuses on resolving the problems in the preparation of high-performance micro-supercapacitors by semiconductor continuous wave laser direct writing on polymer films, clarifying laser carbonization mechanism, and studying the influence of experimental parameters on the pore structures and conductivity of resulted carbon materials. Further, on the basis of the above results, we will try to tune the pore size distribution, conductivity and heteroatom doping by mixing structure modifiers or doping additives into polyimide films, and study the formation mechanism of pore structures as well as the heteroatom doping mechanism, in order to obtain high-performance carbon micro-supercapacitors. This study will provide theory basis for the research on semiconductor laser carbonization from polymer films, as well as beneficial reference for the design, fabrication, application and commercialization of high-performance carbon micro-supercapacitors.

高性能微型超级电容器是微型便携电子器件及可穿戴电子器件潜在能量供应单元，半导体激光直写法制备碳基微型超级电容器具有简捷、廉价、环境友好和易于集成等优点。项目组前期首次利用405nm波长半导体连续波激光在聚酰亚胺薄膜上直写碳化得到了高性能碳基微型超级电容器，但碳化机理尚不明了，且碳材料的导电性及孔径分布也需要进一步优化。本项目着眼于解决半导体连续波激光在聚合物表面直写制备高性能微型超级电容器中存在的问题，研究半导体连续波激光直写碳化机理以及不同外界条件对孔结构、导电性的影响。在此基础上，通过向聚酰亚胺薄膜中加入结构调控剂或掺杂调控剂，调控激光碳化材料的孔径分布、导电性及杂原子掺杂，研究孔结构形成机制及杂原子掺杂机理，以获得高性能的微型超级电容器。本研究将为半导体连续波激光碳化研究提供理论基础，并为高性能碳基微型超级电容器的设计、制备、应用及工业化生产提供有益参考。

高性能微型超级电容器是微型便携电子器件及可穿戴电子器件潜在能量供应单元，半导体激光直写法制备碳基微型超级电容器具有简捷、廉价、环境友好和易于集成等优点。本项目围绕激光直写聚合物碳化制备高性能碳基微型超级电容器及碳化机理这一主线展开研究工作，系统研究了激光波长、激光功率、聚合物膜光吸收等因素对激光碳化过程的影响及碳化机制，激光直写高性能杂原子掺杂碳基微型超级电容器及碳化掺杂机制以及基于激光直写碳化技术在碳基柔性电子器件上的应用。主要取得了如下研究进展：1）系统研究了多种聚合物薄膜在不同波长和强度激光照射下的碳化行为及碳基微型超级电容器性能，理解了实现连续波激光直写碳化所需条件及碳化机制；2）激光直写实现了多种杂原子掺杂多孔碳的制备，实现了孔径分布的调控，并揭示了激光碳化掺杂机制，激光直写的杂原子掺杂碳基微型超级电容器性能得到极大提高；3）以特殊高分子氧化石墨烯薄膜作为前体物，激光直写还原制备了全碳基无电解质微型超级电容器，并用于快速响应高性能湿度传感器；4）激光直写碳化固定催化剂粒子结合无电沉积方法制备了碳/镍复合结构，导电性得到极大提高，并与激光直写的高性能碳基微型超级电容器集成，得到了无线充电和能量存储器件，与微型芯片集成，得到了近场无线通讯器件，证明了激光直写技术在柔性电子器件上的应用价值；5）激光直写结合电泳沉积技术制备碳/TiO2可光充电微型超级电容器，实现了集能储能一体化；此外，化学刻蚀碳纳米管结合激光刻画技术，获得了高性能多孔碳纳米管微型超级电容器；低共熔溶剂法结合激光刻画技术，制备了高性能的杂原子掺杂多孔碳基微型超级电容器。本项目的研究结果将为半导体连续波激光碳化研究提供借鉴，并为高性能碳基微型超级电容器及柔性电子器件的激光直写制备、应用及工业化生产提供有益参考。