咔唑类染料敏化剂的合成及在太阳能电池中的应用研究
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摘要
染料敏化剂在染料敏化太阳能电池(DSSC)中主要起光电转化的作用,是染料敏化太阳能电池的核心部件之一。纯有机染料敏化剂由于其自身特点的原因,已经逐渐成为染料敏化太阳能电池敏化剂的首选。寻找转化效率高且合成方法简单、成本低廉的纯有机染料敏化剂成为人们研究工作的重点。
通过阅读大量的参考文献,结合前人的研究成果和合成方法,本论文设计合成了七个咔唑类染料敏化剂。以N-乙基咔唑作为供电子基团,氰基乙酸为拉电子基团,通过变换不同的Π桥键来合成。所有染料均通过核磁共振氢谱,质谱和红外吸收光谱对其结构进行表征。对所有光敏染料进行了光物理和电化学性质测试,并将其制作成染料敏化太阳能电池器件,系统的研究了染料的光伏性能。另外,还对所有染料分子进行了密度泛函理论方面的理论计算研究。
染料分子的光物理和电化学性质与其结构密切相关。通过变换不同的Π桥键,可以改变染料的吸收光谱范围。实验数据表明,染料分子的共轭性和共平面性会影响其光物理性质和分子内电子传输能力。染料分子的空间位阻越大,其分子的共平面性就越差,导致使染料分子吸收光谱发生蓝移,使电池器件的光电转化效率下降。通过密度泛函理论计算出所有染料分子的HOMO和LUMO能级同时满足了染料激发态电子向TiO2导带注入和染料再生的能级要求。
对这七种染料敏化剂进行电化学性质和光伏特性的测试,从电化学和光伏特性的测试结果分析得出这一系列染料的光电转化效率和结构变化的关系；结合其紫外吸收光谱数据,分析得出了染料分子结构和紫外吸收波长的关系。在电池器件制作条件未经过优化的情况下进行测试的,其中染料Ⅴ、Ⅵ和Ⅶ的光电转化效率依次为2.03%、4.18%和2.74%.若将其制备条件加以优化,其光电转化效率有可能提高至5%-6%左右。
Dye sensitizer plays a mainly important role in the terms of photoelectric conversion,and which is one of the core member in dye sensitized solar cells. Pure organic dye sensitizers has gradually become the first choice of the dye-sensitized solar cell sensitizer due to its own characteristics. Looking for a high conversion efficiency and simple synthetic method, low-cost organic dye sensitizer become the focus of people's work around the world.
By reading a lot of references, combined with the results of previous studies and the synthesis method, designed seven carbazoles dye sensitizer. We use N-ethyl carbazole as the electron donating group, and the cyanoacetate as the electron-withdrawing group, connecting the two parts together by converting different II bridge bonds. The structures of these dyes are confirmed by1HNMR, mass spectrometry and infrared absorption spectrum.The photophysical and electrochemical properties of these photosensitive dye was studied. These dyes were made into dye-sensitized solar cell devices and studied relationship between the structures of dyes and the cell performances. In addition, the theory of the density functional theory calculations of all dye molecules have been studied.
Photophysical and electrochemical properties of the dye molecules is closely related to its structure. The absorption spectral range of the dye can be changed by varying the type of Ⅱ bridge. Experimental data show that the conjugated and coplanar of the dye molecules affect their photophysical properties and intramolecular electron transfer. Steric hindrance of Dye molecules are larger,the plane of the Dye molecules are the worse，which are resulting blue-shifted absorption spectrum of the the dye molecules and the photoelectric conversion efficiency of the battery device down.. Through the density functional theory calculations of dye molecules HOMO and LUMO levels while they are all meeting the dye excited electrons injected into the conduction band of TiO2and dye renewable energy level requirements.
We have also tested electrochemical and photovoltaic properties of these dye sensitizers. Analyzed the results,we may get the relationship of these Dye sensitizers which are between the photoelectric conversion efficiency and the structural; Combined with the UV absorption spectrum data of the dye molecules, we can analyzes the relationship between the structure of the photosensitions and absorption spectrum. At the condition of the battery device fabrication unoptimized test case, in which the photoelectric conversion efficiency of the dye Ⅴ、 Ⅵ and Ⅶ are followed by2.03%,4.18%and2.74%.Replace their preparation conditions to be optimized, the photoelectric conversion efficiency may be increased to about5%-6%.
通过阅读大量的参考文献,结合前人的研究成果和合成方法,本论文设计合成了七个咔唑类染料敏化剂。以N-乙基咔唑作为供电子基团,氰基乙酸为拉电子基团,通过变换不同的Π桥键来合成。所有染料均通过核磁共振氢谱,质谱和红外吸收光谱对其结构进行表征。对所有光敏染料进行了光物理和电化学性质测试,并将其制作成染料敏化太阳能电池器件,系统的研究了染料的光伏性能。另外,还对所有染料分子进行了密度泛函理论方面的理论计算研究。
染料分子的光物理和电化学性质与其结构密切相关。通过变换不同的Π桥键,可以改变染料的吸收光谱范围。实验数据表明,染料分子的共轭性和共平面性会影响其光物理性质和分子内电子传输能力。染料分子的空间位阻越大,其分子的共平面性就越差,导致使染料分子吸收光谱发生蓝移,使电池器件的光电转化效率下降。通过密度泛函理论计算出所有染料分子的HOMO和LUMO能级同时满足了染料激发态电子向TiO2导带注入和染料再生的能级要求。
对这七种染料敏化剂进行电化学性质和光伏特性的测试,从电化学和光伏特性的测试结果分析得出这一系列染料的光电转化效率和结构变化的关系；结合其紫外吸收光谱数据,分析得出了染料分子结构和紫外吸收波长的关系。在电池器件制作条件未经过优化的情况下进行测试的,其中染料Ⅴ、Ⅵ和Ⅶ的光电转化效率依次为2.03%、4.18%和2.74%.若将其制备条件加以优化,其光电转化效率有可能提高至5%-6%左右。
Dye sensitizer plays a mainly important role in the terms of photoelectric conversion,and which is one of the core member in dye sensitized solar cells. Pure organic dye sensitizers has gradually become the first choice of the dye-sensitized solar cell sensitizer due to its own characteristics. Looking for a high conversion efficiency and simple synthetic method, low-cost organic dye sensitizer become the focus of people's work around the world.
By reading a lot of references, combined with the results of previous studies and the synthesis method, designed seven carbazoles dye sensitizer. We use N-ethyl carbazole as the electron donating group, and the cyanoacetate as the electron-withdrawing group, connecting the two parts together by converting different II bridge bonds. The structures of these dyes are confirmed by1HNMR, mass spectrometry and infrared absorption spectrum.The photophysical and electrochemical properties of these photosensitive dye was studied. These dyes were made into dye-sensitized solar cell devices and studied relationship between the structures of dyes and the cell performances. In addition, the theory of the density functional theory calculations of all dye molecules have been studied.
Photophysical and electrochemical properties of the dye molecules is closely related to its structure. The absorption spectral range of the dye can be changed by varying the type of Ⅱ bridge. Experimental data show that the conjugated and coplanar of the dye molecules affect their photophysical properties and intramolecular electron transfer. Steric hindrance of Dye molecules are larger,the plane of the Dye molecules are the worse，which are resulting blue-shifted absorption spectrum of the the dye molecules and the photoelectric conversion efficiency of the battery device down.. Through the density functional theory calculations of dye molecules HOMO and LUMO levels while they are all meeting the dye excited electrons injected into the conduction band of TiO2and dye renewable energy level requirements.
We have also tested electrochemical and photovoltaic properties of these dye sensitizers. Analyzed the results,we may get the relationship of these Dye sensitizers which are between the photoelectric conversion efficiency and the structural; Combined with the UV absorption spectrum data of the dye molecules, we can analyzes the relationship between the structure of the photosensitions and absorption spectrum. At the condition of the battery device fabrication unoptimized test case, in which the photoelectric conversion efficiency of the dye Ⅴ、 Ⅵ and Ⅶ are followed by2.03%,4.18%and2.74%.Replace their preparation conditions to be optimized, the photoelectric conversion efficiency may be increased to about5%-6%.
引文
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