硒吩-EDOT类共聚物热电新材料的制备及性能

Development of novel conducting polymer thermoelectric materials is very significant from both theoretical and practical aspects, and most recently it has aroused widespread concern in the international range. Polyselenophene and its derivatives have numerous advantages compared with other conducting polymers, such as lower band gap, higher carrier mobility, lower oxidation potentials, etc., and hold promise for applications in thermoelectric field. Despite these advantages, very little research about the thermoelectric performances of polyselenophenes has been reported. Therefore, the design and synthesis of novel polyselenophenes with improved properties suffice for applications are very necessary and significant, and apparently also a considerable challenge. In this project, in order to improve the properties of polyselenophenes, novel selenophenes-EDOT copolymers will be prepared by electrochemical polymerization of a series of polymerizable precursors, which are firstly designed and synthesized from some selenophenes containing electron-donating groups (alkyl and alkoxy, etc.) and 3,4-ethylenedioxythiophene (EDOT). Then the properties of the resulting copolymer materials, such as structural information, spectroscopic properties, thermoelectric properties, electrical conductivity, will be investigated in detail. Further, those selenophenes-EDOT copolymers with better properties will be chosen to fabricate thermoelectric devices, whose performances will be improved by optimizing preparing technology and working conditions. Finally, the structure-property relationship of these selenophenes-EDOT copolymer materials will be summarized and explored to provide theory instruction and technique basis for future research.

开发导电聚合物热电新材料具有重要的理论和现实意义，近年来引起了国际范围内的广泛关注。聚硒吩类导电高分子具有带宽低、迁移率高等诸多优点，在热电领域展现出良好的应用前景，且其各项性能仍有较大的提升空间，然而当前未能引起重视。本项目在申请人前期成功合成部分硒吩衍生物的基础上，设计制备硒吩及其衍生物与3,4-二氧乙撑噻吩（EDOT）的共聚物新材料，以期实现聚硒吩类材料与明星高分子聚(3,4-二氧乙撑噻吩)（PEDOT）两者之间热电性能的优势互补；对所获共聚物进行系统的结构表征和性能测试；基于热电转换技术应用，筛选性能较好的硒吩-EDOT类共聚物材料，开展热电器件制作、工艺优化及性能评估；同时总结实验研究，探讨硒吩-EDOT类共聚物结构组成及序列排布与材料性能之间的关系，为后续研究提供一定的理论指导与技术基础。

开发导电聚合物热电新材料具有重要的理论和现实意义，近年来引起了国际范围内的广泛关注。聚硒吩类导电高分子具有带宽低、迁移率高等诸多优点，在热电领域展现出良好的应用前景，且其各项性能仍有较大的提升空间，然而当前未能引起重视。本项目先后合成了3-甲基硒吩、α连硒吩、3,4-二甲基硒吩、3,4-二甲氧基硒吩、EDOS及其衍生物/类似物等50余种单体化合物，并设计合成了系列硒吩、3-甲基硒吩、α连硒吩等与3,4-二氧乙撑噻吩（EDOT）等结构的共聚前驱体10余种，建立了硒吩类、EDOTs类化合物及硒吩-EDOT类前驱体的合成方法；研究了所有化合物的电化学聚合行为，优化了聚合物制备条件，获得了电合成聚硒吩、PEDOTs及共聚物材料的优化条件及工艺。系统表征了聚合物的结构及各项性能，探讨总结了取代基、共聚物结构、组成及序列排布等因素对材料电子性质、氧化还原过程及活性、稳定性及热电等各项性能的影响规律。筛选出了性能较稳定的共聚物材料，初步探讨并研制了基于此类材料的热电转换器件，并开展了器件的制备工艺优化。与此同时，系统研究了所获聚合物材料的部分新性能，如电致变色、电容性能、传感性能等，获得了一些有趣的结果，并进行了相关报道。共计发表在Polym Chem、ACS Appl Mater & Interfaces、Langmuir、PhysChemChemPhys、Electrochim Acta、J Polym Sci Polym Chem/Phys、New J Chem、RSC Adv等学术期刊上发表SCI论文40余篇（影响因子3.0以上25篇，封面论文8篇），申请发明专利3项，培养研究生8名，参加国际学术会议4次、国内学术会议3次。研究成果获江西省自然科学三等奖1项。