聚合金属配合物论文：D-π-A型聚合金属配合物光敏染料的合成及光伏性能.doc

聚合金属配合物论文：D-A型聚合金属配合物光敏染料的合成及光伏性能【中文摘要】太阳能作为一种清洁无污染且取之不尽、用之不竭的可再生能源日益受到人们的广泛关注,染料敏化太阳能电池具有高效率、低成本、易组装等技术优势,因而成为近年来太阳能光电转换领域的研究热点。目前普遍使用的光敏染料为金属钌吡啶配合物,然而贵金属钌的引入使得成本增高,并且严重污染环境。聚合金属配合物染料不仅具有有机高分子材料所具有的特性,同时因为结构中无机金属的存在,从而可以通过配位键和d-反馈键调控能隙宽度。因此,聚合金属配合物染料与配合物染料相比,具有的良好的光、热稳定性和吸收光谱范围宽的优点,在光学、电学等方面都表现出独特的性能。本课题设计合成了含有D-A结构的聚合金属配合物染料,由于D-A体系能够加强电子推拉能力,不仅可以有效地拓宽染料分子的光谱响应范围,而且还可以实现染料激发态时的电荷有效分离。我们通过一系列测试手段(例如红外光谱、核磁共振和元素分析)对材料的结构进行了表征,并分别探讨了中心金属离子是Co(), Ni(), Cd()时对材料性质的影响；同时通过热重分析和玻璃化转变温度测试了其热稳定性；利用紫外光谱、荧光光谱、循环伏安法研究了光物理性质和电化学性质,并测试了它们的光伏性能。主要研究结果如下：1、通过在含有噻吩和苯乙撑或芴乙烯的主链中引入8-羟基喹啉的Cd()配合物,设计合成了给体-连接桥-受体(D-A)结构的主链型聚合金属配合物染料B8QMEHP-Cd(), B8QF-Cd()和B8QP-Cd(),并将其应用于染料敏化太阳能电池。研究发现长烷基链的引入改善了聚合金属配合物的溶解性,B8QMEHP-Cd()支链中甲氧基的加入能够提高电池短路光电流,其光电转换效率为1.77%高于B8QF-Cd()(1.48%)和B8QP-Cd()(1.57%)。2、设计合成以噻吩和苯乙烯撑或芴乙烯作为给体(D),金属配合物作为受体(A),碳碳双键为连接桥的支链型共轭聚合金属配合物PCo-F、PCo-B、PNi-F和PNi-B,并将其应用于染料敏化太阳能电池,其能量转换效率分别为0.96%,1.01%,1.00%和1.21%。研究发现所合成的支链型含有Co()金属配合物和Ni()金属配合物的聚合物比我们之前在实验室中通过Yamamoto偶合得到的支链型含有Eu()金属配合物的聚合物具有更好的溶解度,并有相近的能量转化效率,这为用过渡金属代替贵金属的研究提供了一个可能性。【英文摘要】Over the last years, as a novel renewable energy conversion system, the use of solar cells is gradually moving into high gear. Currently, dye-sensitized solar cells (DSSCs) as the most promising alternatives for the photovoltaic conversion of solar energy have attracted much interesting attention due to their high efficiency, potential low-cost and so forth.Ru complexes as dyes are widely used in DSSCs, due to the advantages of broad absorption spectrum and good electrochemical stability. However, the rarity and high cost of the ruthenium metal may limit their development for large-scale applications. Polymeric metal complex have good thermal stability, and their energy gap and transmission of electron also can be controled by coordination bond and d-bond. Comprise with complexes, polymeric metal complexes display unique electrical, optical, magnetic propertie, generating a new and versatile class of functional materials. In this study, a series of donor-acceptor (D-A) type polymeric metal complexes containing Cd(), Co(II) or Ni() complexes were synthesized and characterized by GPC, FT-IR,1H NMR, TGA, TMA, UV-vis, PL, CV and the application in dye-sensitized solar cells (DSSCs) as dye sensitizers are also determined and studied. The main work summarized as follows:1. Three novel D-A type main chain polymeric metal complexes based on Polystyrene or Polyfluorenevinyl containing complexes of thienyl-(8-hydroxyquinoline) with Cd() have been synthesized by Heck coupling and utilized as dyes for dye-sensitized solar cells (DSSCs). It was found that the longer alkyl chains may improve the solubility of polymeric metal complex. In addition, the solar irradiation conversion efficiency of B8QMEHP-Cd() were higher than B8QF-Cd()(1.48%) and B8QP-Cd(II)(1.57%), mainly resulting from the methoxy group may improve the short-circuit photocurrent.2. A series donor-acceptor type polymeric metal complexes PCo-F, PCo-B, PNi-F and PNi-B consist of the Co () or Ni () complexes as an acceptor (A), C=C as a-conjugation linkage, and thiophene-fluorene or phenylene as a donor group (D). The DSSCs fabricated by branched chain polymeric metal complexes with power conversion efficiency up to 0.96%, 1.01%,1.00% and 1.21%, respectively, under simulated AM 1.5G solar irradiation (100 mW/cm2). The result showed that polymeric metal complexes with Co(II), Ni() complexes in the side chain exhibited good solubility and have similar energy conversion efficiency, indicating a possibility to use common metal instead of rare earth metals.【关键词】聚合金属配合物 芴乙烯 苯乙烯 染料敏化电池 D-A有机光敏染料【英文关键词】Polymeric metal complexes Phenylenevinylene Fluorenevinylene DSSCs D-A organic dye【目录】D-A型聚合金属配合物光敏染料的合成及光伏性能摘要4-5Abstract5第1章 绪论8-261.1 引言8-91.2 太阳能电池的定义和发展9-101.3 有机太阳能电池10-161.3.1 有机太阳能电池的定义10-111.3.2 异质结聚合物太阳能电池11-121.3.3 电子给体材料12-151.3.4 电子受体材料15-161.4 染料敏化纳米晶太阳能电池16-211.4.1 染料敏化纳米晶太阳能电池发展进展161.4.2 染料敏化纳米晶太阳能电池的基本结构16-171.4.3 染料敏化纳米晶太阳能电池的工作原理17-181.4.4 染料敏化纳米晶太阳能电池的性能参数18-211.5 光敏染料21-231.5.1 有机光敏染料211.5.2 金属配合物光敏染料21-231.6 聚合金属配合物的研究进展与应用23-241.6.1 主链型聚合金属配合物23-241.6.2 支链型聚合金属配合物241.7 论文的设计思想与研究内容24-26第2章 实验方法及测试原理26-312.1 主要实验试剂及实验仪器26-282.1.1 主要试剂26-272.1.2 主要仪器及测试条件27-282.2 材料的结构分析与表征28-292.2.1 核磁共振测试(1H-NMR)282.2.2 红外光谱测试(IR)28-292.2.3 紫外-可见光谱测试(UV-vis)292.2.4 循环伏安测试(CV)292.3 聚合金属配合物/TiO_2染料敏化太阳能电池体系的制作29-31第3章 主链型D-A结构含苯乙烯和芴乙烯的聚合金属配合物光敏染料的合成与应用31-533.1 引言31-323.2 实验部分32-453.2.1 主链型聚合金属配合物的的合成32-453.3 结果与讨论45-523.3.1 配体和主链型聚合金属配合物的表征45-473.3.2 主链型聚合金属配合物的热性能47-483.3.3 主链型聚合金属配合物的紫外-可见吸收及荧光性能48-503.3.4 主链型聚合金属配合物的电化学测试及分析50-513.3.5 主链型聚合金属配合物的光伏性能51-523.4 本章小节52-53第4章 支链型含8-羟基喹啉的D-A型聚合金属配合物光敏染料的合成与应用53-664.1 引言53-544.2 实验部分54-584.2