基于纳米结构聚苯胺的多层次多尺度表面微纳结构的可控构筑与应用研究

Polyaniline (PANI) is the conductive polymer with the most potential for industry application. Currently, how to realize the micro/nanostructured surface and its devices with high performance and stretchability is a big challenge. In this project, nanostructured PANI film is deposited on an elastic substrate. The combination of uniaxial stretching and doping/de-doping is used to induce the formation and the well-defined control of multiscale wrinkled micro/nanostructures. The regional flash-induced heating welding and laser interference patterning are further utilized to realize the selective de-wrinkle and the multilevel and multiscale assembled micro/nanostructures from the well-defined organization of the wrinkles and the non-wrinkled patterns. In this project, the as-formed micro/nanostructures are explored to smartly tailor surface wettability. They are also used as the stretchable sensors for the super-sensitive and high-speed detect of the goal materials, and as the high-performance flexible supercapacitors for application in the fields such as the new energy resources storage. In this project, a new method for surface wrinkling and a new avenue to realize the surface wrinkling with large scale and repeatability will be developed; a simple versatile strategy for realization of the complicated micro/nanostructured surface will also be provided, which can be further utilized to fabricate devices with high performance and good flexibility. The internal relation between the hierarchical assembled structures and the surface wettability as well as the flexible device performance will be revealed, which will direct the materials design and device fabrication in theory, and will also lay the foundation for the industry application.

作为最具工业化应用前景的导电聚合物，聚苯胺材料的表面微纳结构化与器件高性能柔性化是当前一大挑战性课题。本项目拟以弹性基底沉积生长的纳米结构聚苯胺膜为研究对象，借助单轴拉伸与新颖的掺杂/脱掺杂的组合来诱导多尺度皱纹微纳结构的形成与精细调控，结合区域化闪光加热消融和激光干涉图案法进一步实现选区消皱，以及皱纹与非皱纹图案有机复合的多层次多尺度高级组装微纳结构。探索所得微纳结构在表面润湿性智能调控，以及作为柔性传感器应用于目标物质的超高灵敏快速检测，作为高性能柔性超级电容器在新能源存储等领域的应用。通过本项目研究，拓展一种新的表面起皱的方法以及一种大面积可重复实现表面起皱的新思路；发展一种简单普适性的实现表面高级组装微纳结构化的策略，并利用来实现器件高性能化柔性化；深入揭示高级微纳结构与表面润湿性和柔性器件性能的内在关系，为其性能优化的材料设计与器件构造等提供理论指导，并为其工业应用打下坚实基础。

作为一种常见的应力失稳驱动的表现形式，表面起皱在材料物性表征、非刻蚀法微纳制造和柔性器件构筑等方面具有独特的应用优势。如何实现材料表面的可控起皱并寻求其潜在应用仍是亟待急需解决的难题。在本项目中: 1)结合聚苯胺（PANI）自身特点，开发了一种原位自起皱新技术，一锅法实现了平面和曲面PANI膜上多种高级微结构化形貌的大面积非刻蚀法构筑，揭示了其中的物理机制。2)提出了机械/化学偶联新方法，一锅法构筑了两种周期复合的稳定高级皱纹形貌，进而实现了皱纹化膜的自支撑性，结合膜转移技术获得了转移至目标基底表面的功能器件，深入阐明了表面起皱与原位加固效应的全新协同机制。3)充分利用PANI独特的酸掺杂和碱去掺杂引起的体积可逆变化,驱动了表面起皱/无皱态间可逆转换；利用其不同氧化还原环境不同的溶胀/去溶胀能力，实现了氧化/还原反应操控的表面起皱/无皱态的可逆调制，由此开启了一类新型的基于表面起皱的响应性智能系统。4)以PANI为氧化剂和沉积模板，诱导其他材料在其膜内聚合生长，由此获得了二者形成的互穿网络结构，构建了无裂纹的稳定皱纹微结构复合图案。5）采用超声处理辅助法对表面起皱PANI膜进行微观尺度再加工，得到了多种高级阵列式微结构图案。6)以基底失稳形成的creasing结构为可逆结构化模板，结合表面起皱技术指导了高级微结构化导电膜的可控构筑。7)开发了基于膜尺寸调控的表面防皱新策略，建立了不同维度体系中膜尺寸与临界起皱应变间简单定量关系，提出了普适性的临界起皱应变公式。利用原位表面起皱与去润湿二者间协同作用，可控构筑了二维高度有序、可预制自组装微结构的功能微球阵列。所得结果已成功应用于表面润湿性调控、传感器、智能窗口、柔性电极等领域，并在解决表面防皱和表面皱纹不稳定性等方面提供了新的策略和理论基础。现以通讯作者身份发表SCI学术论文22篇（如ACS NANO, Macromolecules, ACS Appl. Mater. Interfaces），申请发明专利14项，含8项授权。