摘要
染料敏化太阳能电池是可能替代化石能源而最具发展潜力的可再生与清洁能源之一，而染料敏化剂（简称染料）是影响染料敏化太阳能电池光伏性能的最关键活性组成部分，承担着吸收太阳光以产生电子并传输电子的最重要功能，因此研究合成高光伏性能、低成本、高稳定性、强形体适应性的染料敏化剂具有重大的理论和实际应用意义。本论文课题研究合成不同于现有研究的钌等金属配合物染料、金属卟啉和酞氰染料以及有机染料等三大类染料，而研究与设计合成新型的将无机、有机和高分子组分融合为一体的聚合金属配合物用作染料。研究合成了两个系列新型的吸光性能较优良、载流子传输性能好、高稳定性与低成本的聚合金属配合物染料，并研究了其组成与结构对其光伏性能的影响规律，探索了合成新型优良染料的制备方法与应用，内容如下：
（1）设计合成了系列以邻菲咯啉类锌（II）或铜（II）金属配合物为受体（A）、对苯二撑、咔唑或芴等衍生物为给体（D）、噻吩乙烯基为π桥的D-A与D-π-A型12个聚合金属配合物N1-N12染料敏化剂、分析表征并测试分析了它们作为染料的光伏性能。结果表明：a，D-π-A型结构的聚合金属配合物N7-N12的光电转化效率（PCE)比相应D-A型结构的N1-N6要高（PCE高1.2-2.5%）；b，聚合铜（II）配合物比聚合锌（II）配合物的光电效率高（PCE高0.2-0.8%）；c，以咔唑衍生物为给体的聚合金属配合物染料的光电转化效率比相应对苯二撑和芴的高（PCE高0.2-0.6%）；d，其中光电转化效率最高的为D-π-A型聚合铜配合物N10，达3.18%。
（2）设计合成了系列以8-羟基喹啉类锌（II）或铜（II）金属配合物为受体（A）、对苯二撑或咔唑或芴衍生物或芴与对苯二撑和咔唑混连的衍生物为给体（D）、乙烯基或噻吩乙烯基为π桥的D-π-A型10个聚合金属配合物Q1-Q10染料敏化剂，分析表征并测试分析了它们用作染料的光伏性能，结果表明：a，具有给电性较好的混连给体（D）的聚合金属配合物染料Q7-Q10比只有单一苯乙撑或咔唑或芴给体的聚合金属配合物Q1-Q6的光电转换效率高（PCE高1.0-2.6%）；b，聚合铜（II）金属配合物比聚合锌（II）配合物的光电转换效率高（PCE高0.2-0.6%）；c，其中光电转化效率（PCE）最高的为聚合铜（II）配合物Q10，达3.78%。
结果表明，两个系列聚合金属配合物染料都有较优良的光伏性能和高的热稳定性，是染料敏化剂发展的一个重要的新方向。
Dye-sensitized solar cells (DSSCs) have become one of the most promising renewableand clean energy sources with the potential to be an alternative of fossil energy. Thedye-sensitizer (dye) which bears the most important function of absorbing sunlight to generateand transfer electrons is the most crucial component in affecting the photovoltaic performanceof dye-sensitized solar cells. It has great theoretical and practical significance to synthesize anew dye with high photovoltaic performance, low-cost and high stability. The subject of thisthesis is different from the existed ruthenium metal complex dyes, metal porphyrin and phthalocyaninedyes as well as the organic dyes, we are aim to design and synthesize new polymeric metal complexesdyes that integrate inorganic, organic and macromolecule components into a whole. We have synthesizeda series of new polymeric metal complexes dyes with excellent light absorption performance, high carriertransfer properties, high stability and low cost, the influences of their composition and structure on thephotovoltaic performances were investigated, and the preparation methods and applications of these newexcellent synthesized dyes were explored,.The details are as follows:
(1) A series of D-A and D-π-A type polymeric metal complexes dyes N1-N12have been designedand synthesized by used zinc (II) or copper (II) phenanthroline metal complexes as the acceptor (A),p-phenylenevinylene, carbazole or fluorene derivatives as the donor (D), thienyl vinyl as π bridge, and theirphotovoltaic performances were characterized and analyzed. The results show that: a, D-π-A typepolymeric metal complexes N7-N12exhibit higher photo-electron power conversion efficiency(PCE) thancorresponding D-A type N1-N6(PCE above1.0-2.5%); b, copper (II) polymeric complexes exhibit higherphoto-electron power conversion efficiency than zinc (II) polymeric complexes (PCE above0.2-0.5%); c,polymeric metal complexes with fluorene derivatives as donor exhibit higher photo-electron powerconversion efficiency than corresponding polymeric metal complexes with p-phenylenevinylene andcarbazole derivatives as donor (PCE above0.2-0.6%); d, In N1-N12, D-π-A type copper (II) polymericcomplexes N10exhibit the highest photo-electron power conversion efficiency,up to3.18%.
(2) A series of D-π-A type polymeric metal complexes dyes Q1-Q10have been designed andsynthesized by used zinc (II) or copper (II)8-hydroxyquinoline metal complexes as the acceptor (A),p-phenylenevinylene, carbazole or fluorene derivatives, or a mixed derivative connected by them as thedonor (D), a vinyl group or thienyl vinyl as π bridge, and their photovoltaic performances werecharacterized and analyzed, the result show that: a, polymeric metal complexes dyes Q7-Q10with mixedconnection derivatives as donor (D) which show excellent electron-donating ability exhibit higherphoto-electron power conversion efficiency than the polymeric metal complexes dyes Q1~Q6with onlyp-phenylenevinylene, carbazole or fluorene derivatives as donor (PCE above1.0-2.5%); b, copper (II) polymeric metal complexes exhibit higher photo-electron power conversion efficiency than zinc (II)polymeric metal complexes (PCE above0.2-0.6%); c, copper (II) polymeric complexes Q10exhibit thehighest photo-electron power conversion efficiency,up to3.78%.
The results showed that the two series of polymeric metal complexes dyes have excellentphotovoltaic performance and high thermal stability; these give us a new important direction of dyesensitizers’development.
引文
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