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本文简要回顾了本人在中科院化学所30年的研究历程,重点介绍了在共轭高分子(包括导电聚吡咯电化学、聚合物发光电化学池(LEC)和共轭聚合物给体光伏材料)方面的研究成果。在导电聚吡咯电化学方面,对导电聚吡咯的电化学制备和电化学性质进行了深入研究,阐明了各种电化学聚合条件对制备的导电聚吡咯电导和力学强度等的影响,发现电解液溶剂给电子性(Donor number)对吡咯电化学聚合制备的导电聚吡咯电导的影响:溶剂Donor number越小制备的导电聚吡咯电导越高;使用非离子表面活性剂添加剂在水溶液中制备出表面非常光滑和高力学强度的导电聚吡咯薄膜;对于吡咯电化学聚合提出了电解液阴离子参与的阳离子自由基聚合机理,并推到出吡咯电化学聚合反应的动力学方程;发现在NaNO3水溶液中电化学聚合制备的导电聚吡咯除存在主链氧化、对阴离子掺杂结构外,还存在质子酸掺杂结构;阐明了导电聚吡咯在水溶液中电化学还原和再氧化的机理及其电化学过程的可逆性和稳定性,以及导电聚吡咯在有机电解液中特殊的第一次还原和再氧化的机理。在LEC方面,通过交流阻抗法确认了LEC的电化学掺杂机理和p-i-n结构,合成了多种适用于LEC的主链带离子导电单元的兼具离子导电性的发光嵌段共聚物,避免了LEC活性层中存在的发光聚合物和离子导电聚合物的分相问题;使用离子液体作为电解质制备了室温准冷冻p-i-n结LEC,改善了LEC的电致发光性能。在共轭聚合物给体光伏材料方面,我们提出了通过共轭侧链来拓宽聚合物吸收和提高空穴迁移率的分子设计思想,设计和合成了一系列带共轭侧链的二维共轭聚噻吩衍生物以及基于二噻吩取代苯并二噻吩的窄带隙高效二维共轭聚合物给体光伏材料。我们使用烷硫基取代进一步降低了这类二维共轭聚合物的HOMO能级从而进一步提高了其光伏性能。最后介绍了本组二维共轭聚合物给体光伏材料在非富勒烯聚合物太阳能电池方面的最新研究进展。
This review briefly reviews my 30 years’ history of research at the Chinese Academy of Sciences and highlights the advances in the field of conjugated polymers (including conductive polypyrrole chemistries, LECs and conjugated polymer donor PV materials) The research results. In conducting polypyrrole electrochemistry, electrochemical preparation and electrochemical properties of conductive polypyrrole were studied in depth, and the influence of various electrochemical polymerization conditions on the conductivity and mechanical strength of the prepared polypyrrole was elucidated. It was found that the electrolyte Effect of Donor number on conductive polypyrrole conductance prepared by electrochemical pyrrole polymerization: the smaller the Donor number, the higher the conductance of conductive polypyrrole prepared; the non-ionic surfactant additive is used to prepare the surface of poly Smooth and high mechanical strength of the conductive polypyrrole film; for the pyrrole electrochemical polymerization electrolyte anion involved in the cationic free radical polymerization mechanism, and pushed to the pyrrole electrochemical polymerization kinetics equation; found in aqueous NaNO3 electrochemical Conductive polypyrrole prepared by polymerization has the main chain oxidation and anion doping structure, and there is proton acid doping structure. The mechanism of electrochemical reduction and reoxidation of conductive polypyrrole in aqueous solution and its reversible electrochemical process Sexual and stability, as well as conductive polypyrrole in the organic electrolyte special first reduction and reoxygenation Mechanisms. In the aspect of LEC, the electrochemical doping mechanism and the pin structure of LEC were confirmed by the AC impedance method, and a number of ion-conductive luminescent block copolymers suitable for the main chain with ion conducting units of LEC were synthesized, avoiding Phase separation of the light-emitting polymer and the ion-conducting polymer present in the LEC active layer. A quasi-frozen pin junction LEC at room temperature was prepared using the ionic liquid as the electrolyte, thereby improving the electroluminescent properties of the LEC. In the conjugated polymer donor photovoltaic materials, we propose a molecular design idea to broaden the polymer absorption and improve the hole mobility through the conjugation of side chains. We designed and synthesized a series of two-dimensional Conjugated polythiophene derivatives and narrow-band-gap efficient two-dimensional conjugated polymer donor photovoltaic materials based on dithiophene-substituted benzodithiophene. Our use of alkylthio substitution further reduces the HOMO energy levels of these two-dimensional conjugated polymers to further improve their photovoltaic performance. Finally, the latest research progress of this group of two-dimensional conjugated polymer donor photovoltaic materials in non-fullerene polymer solar cells is introduced.