D-π-A型二硫富瓦烯敏化剂的合成及其在染料敏化太阳能电池中的应用

发布时间：2018-04-22 04:37

本文选题：二硫富瓦烯敏化剂 + D-π-A　；参考：《太原理工大学》2016年硕士论文

【摘要】：在染料敏化太阳能电池(DSSCs)中,敏化剂起着捕获太阳光转换为电子的作用,而有机敏化剂在染料敏化太阳能电池研究中具有很大的应用价值。其中,二硫富瓦烯作为电子给体(D),可以和电子受体(A)通过共轭桥(π)构建具有D-π-A型结构的二硫富瓦烯敏化剂,该敏化剂体系分子合成简单且分子空间位阻较小。以氰乙酸作为拉电子基团和吸附基团制备的二硫富瓦烯基染料敏化太阳能电池,取得了大于800 mV的开路电压及8.29%的电池效率,展示了D-π-A型二硫富瓦烯敏化剂用于制备高效DSSCs的潜在价值。在发展高效D-π-A型二硫富瓦烯敏化剂的同时,对二硫富瓦烯敏化剂在二氧化钛表面的吸附模式进行研究,探索具有新受体结构的二硫富瓦烯敏化剂在DSSCs中的应用,成为该体系在DSSCs研究领域中的重要课题。本论文中,我们以含正己基取代的二硫富瓦烯作为电子给体,设计合成了一系列D-π-A型二硫富瓦烯敏化剂。随后系统研究了这类敏化剂的光光电化学性能,以及在DSSCs中的应用。主要开展了以下几方面的研究工作:1.合成了二硫富瓦烯为电子给体、氰乙酸为电子受体和吸附基团、“苯环-3,4-乙烯二氧噻吩(EDOT)-苯环”单元为π-共轭桥结构的二硫富瓦烯敏化剂分子DTF-C4。研究了染料在二氧化钛表面吸附过程中形成不同聚集态对电池性能的影响。实验结果表明通过不良溶剂淋洗吸附了染料的二氧化钛光阳极,可以有效形成DTF-C4的J-聚集体。与通过共吸附脱氧鹅胆酸破坏J-聚集体相比,这种J-聚集体为主的吸附模式可使电池开路电压提高至850 mV,光电转换效率提高至7.48%。2.合成了一系列二硫富瓦烯为电子给体、吡啶环为电子受体和吸附基团、π共轭桥不同的D-π-A型二硫富瓦烯敏化剂h-DTF-Py1,h-DTF-Py2,h-DTF-Py3和h-DTF-Py4。研究结果表明,延长共轭结构,调整共轭桥中噻吩和苯单元的结构顺序,可有效提高敏化剂的光捕获能力和电池性能。其中,h-DTF-Py4的光捕获性能最好,吸附在TiO2表面时吸收波长红移至600nm。基于h-DTF-Py4的DSSCs电池器件,开路电压为636 m V、短路电流为8.02 mA cm-2,填充因子FF为0.54,光电转换效率为2.68%。
[Abstract]:In Dye-sensitized Solar cells (DSSCs), sensitizers play an important role in capturing solar light to convert into electrons, while organic sensitizers have great application value in the research of dyestuff sensitized solar cells. As an electron donor, dithiafulvalene and electron receptor A can be used as conjugate bridge (蟺) to construct a D- 蟺 -A type dithiafulvalene sensitizer. The system is simple in molecular synthesis and has small steric hindrance in molecular space. Using cyanuric acid as the electron-pulling group and adsorption group, the dithiofuvalene-based dye sensitized solar cell was prepared. The open circuit voltage of more than 800mV and the efficiency of 8.29% were obtained. The potential value of D- 蟺 -A type dithiafurane sensitizer for the preparation of high efficiency DSSCs was demonstrated. While developing the highly efficient D- 蟺 -A type dithiofovene sensitizer, the adsorption mode of the dithiofovene sensitizer on the surface of titanium dioxide was studied, and the application of the new receptor structure dithiafurane sensitizer in DSSCs was explored. It has become an important subject in the field of DSSCs research. In this thesis, a series of D- 蟺 -A type dithiafurane sensitizers were designed and synthesized by using dithiofurane containing n-hexyl substituted dithiofurane as electron donor. Then the photoelectrochemical properties of the sensitizers and their applications in DSSCs are systematically studied. Mainly carried out the following aspects of research work: 1. Dithiafulvalene was synthesized as electron donor, cyanuric acid as electron acceptor and adsorption group. The "benzene ring-3o 4-ethylene dioxothiophene EDOT- benzene ring" unit is a 蟺-conjugated dithiofovene sensitizer molecule DTF-C4. The effect of different aggregation states on the performance of the cell was studied during the adsorption of dyes on the surface of titanium dioxide. The experimental results show that the DTF-C4 J-aggregates can be effectively formed by eluting the TIO _ 2 photoanode which is adsorbed by dyestuffs. Compared with the destruction of J-aggregates by co-adsorption of chenodeoxycholic acid, the main adsorption mode of J-aggregates can increase the open circuit voltage of the battery to 850 MV, and the photoelectric conversion efficiency to 7.48 MV. 2. A series of dithiafurane as electron donor, pyridine ring as electron acceptor and adsorption group were synthesized. The sensitizers h-DTF-Py1, h-DTF-Py2h-DTF-Py3 and h-DTF-Py4 with different 蟺 conjugated bridges were synthesized. The results show that prolonging the conjugate structure and adjusting the structure sequence of thiophene and benzene units in the conjugate bridge can effectively improve the photocapture ability of sensitizer and the performance of the cell. The optical trapping performance of hDTF-Py4 is the best, and the absorption wavelength shifts to 600 nm when adsorbed on the surface of TiO2. The DSSCs battery device based on h-DTF-Py4 has an open circuit voltage of 636mV, a short circuit current of 8.02 Ma cm-2, a filling factor FF of 0.54, and an optoelectronic conversion efficiency of 2.68m.
【学位授予单位】：太原理工大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：TM914.4

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