协同分散石墨烯为模板原位聚合湿法加工制备透明电极及其柔性光伏器件

With absence of poly(styrenesulfonate) (PSS), highly conductive and transparent, large-scare, solution-processed, flexible electrode can be fabricated by in-situ polymerization of 3,4-ethylenedioxythiophene with synergistic dispersible graphene/carbon nanotubes as template. The introduction of carbon nanomaterials and conjugated molecules with sulfonic acid groups leads to the conformational change of PEDOT chains from benzenoid to quinoid structure and the realization of doping effect, which allows the formation of more conductive PEDOT channels. Moreover, the construction of three-dimensional interpenetrating conductive network contributes to improving the conductivity of composite transparent electrode. The preparation methods for in-situ polymerization of PEDOT and the mechanism of synergistic dispersion, as well as the effect of carbon nanomaterials based templates on the degree of polymerization and conductivity for PEDOT needs to been studied. The effect of the relative amount of carbon materials/PEDOT on the transmittance, conductivity, mechanical property, thermal and chemical stabilities of the transparent electrode, and the further effect on the power conversion efficiency of polymer solar cells also needs to been investigated. In order to further resolve the key scientific problem of solution processing large-scare and flexible organic photoelectric devices, the roll-to-roll printing technology of fabricating composite transparent electrodes and ITO-free polymer solar cells needs to be explored deeply.

本项目研究无绝缘性的聚苯磺酸（PSS）存在下，以高浓度协同分散的石墨烯/碳纳米管为模板，原位聚合3,4-乙烯二氧噻吩（EDOT），制备得到高电导率和透光性、可大面积溶液加工的柔性复合透明电极。带磺酸基团的碳纳米材料及共轭分子的引入使得PEDOT高分子链发生由苯式到醌式构象转变并实现掺杂效应，有利于PEDOT获得更多的岛状导电通道。此外，构建三维互穿导电网络，使得复合透明电极的电导率得到显著提升。研究EDOT原位聚合方法和碳纳米材料的协同分散作用机理，以及不同碳纳米材料为模板对EDOT聚合反应程度和导电性能的影响。探讨碳纳米材料/PEDOT的相对含量对透明电极的透光率和电导率、机械性能和稳定性的影响，以及对柔性聚合物太阳能电池器件的能量转换效率等性能的影响。探索复合透明电极和ITO-free太阳能电池器件的卷对卷印刷工艺，解决柔性有机光电器件大面积溶液加工的关键科学技术问题。

项目已在Adv. Mater. (2篇), Adv. Energy Mater. (1篇), Adv. Funct. Mater. (3篇), Adv. Sci. (1篇), J. Mater. Chem. A (2篇), ACS Appl. Mater. Interfaces (5篇) 等期刊发表SCI论文29篇，其中封面论文4篇，影响因子10.0以上9篇。编著《钙钛矿太阳电池》专著1部。研究成果受到先进材料官网等广泛报道，获2020年度江西省自然科学二等奖（排名第一，已公示）、2019年度教育部自然科学成果二等奖（排名第三）。获授权发明专利7项，实现成果转化2项。提出原位聚合PEDOT和纳米复合导电增强策略，通过碳基纳米材料剪切剥离分散PEDOT，实现柔性透明电极湿法加工印刷，解决太阳电池透明电极大角度弯折问题。以π磺酸分散多壁碳纳米管和Ag纳米线为模板原位聚合PEDOT，获得较低的方块电阻，降低了吸湿性 (EA 2017, JMCC 2018)。通过卷对卷印刷制备大面积、低成本PEDOT:PSS/银网格复合透明电极 (AMT 2017, ACS AMI 2018)，同时发展一套多功能柔性电子涂布机。针对有机太阳电池活性层在实验室旋涂工艺和大面积制备印刷工艺中形貌演变的差异，提出了柔性有机太阳电池活性层形貌演化的转换因子和大面积制备工艺 (AM 2019)。针对钙钛矿太阳电池离子迁移、水氧侵蚀和机械弯折导致稳定性问题，提出了含氟半导体以及AIE分子填补钙钛矿太阳电池晶界缺陷，抑制离子迁移和实现晶界链接，大幅提高器件稳定性 (AEM 2019, AFM 2019a)。提出了原位构筑自主纵向支架和弹性体修复钙钛矿晶界缺陷，赋予活性层耐弯折性 (AM 2020, AFM 2017)。提出了自密性高分子EVA封装钙钛矿界面层，有效改善钛矿太阳能电池的长期稳定性、阻水性以及弯曲耐久性，从而制备出25 cm2刚性和柔性太阳电池模组 (AFM 2019b)。针对有机/钙钛矿太阳电池的无机界面层固有的脆性导致耐弯折问题，通过贻贝仿生交联氧化物纳米晶，既保证界面层电荷传输作用，又赋予太阳电池界面和活性层耐弯折性 (AS 2019, CC 2019)。