四氢喹啉类光敏染料用于染料敏化太阳能电池的研究
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摘要
在染料敏化太阳能电池体系中，最核心的部分是吸附了单层光敏染料的纳米多孔半导体电极。光敏染料起到吸收太阳光并将激发态电子转移到纳米半导体导带的作用，同时产生的染料氧化态又能快速的从电解质(I_3~-／I~-)中得到电子而被还原至基态。光敏染料是染料敏化太阳能电池获得高光电转换效率和长寿命的决定因素之一。
本论文设计合成了13个以取代四氢喹啉为供电子基、氰基丙烯酸基或氰乙烯基磷酸基为吸电子基并通过不同π-桥基相连的电子推拉型光敏染料，并利用质谱、核磁共振氢谱对这些化合物进行结构表征，研究了光敏染料的光物理、电化学等性质，并将其应用于染料敏化太阳能电池，系统地考察了光敏染料结构与电池性能之间的关系。同时，本论文还对2个模型化合物的分子内电荷转移性质进行了实验和理论方面的研究，并将其结果用于解释光敏染料结构与性能之间的关系。
光敏染料的结构与其光物理、电化学性质具有密切关系。通过在π-桥基中引入更多的噻吩基或乙烯基结构单元，增大了染料的共轭体系，使其吸收光谱发生红移和拓宽，增强了染料对光的吸收能力，而苯基桥基的引入对染料吸收光谱的影响较小。同时发现，光敏染料中多个噻吩基或者乙烯基结构单元的引入使得染料在TiO-2表面的聚集趋势增大，导致染料在TiO_2表面吸收光谱的蓝移。光敏染料的基态和激发态氧化还原电位同时满足了染料激发态电子向TiO_2导带注入和染料还原的电位要求。噻吩基和乙烯基结构单元会导致染料基态氧化还原电位的升高，降低其与电解质中I_3~-／I~-电对的电位差，从而降低染料被还原的驱动力。与氰基丙烯酸基相比，氰乙烯基磷酸基作为吸电子基更能升高染料的激发态氧化还原电位，从而使得激发态染料分子具有更高的电子注入驱动力。
四氢喹啉衍生物作为染料敏化太阳能电池光敏染料，展现出良好的电池性能。研究发现，进行TiO_2膜的染料敏化时所用的溶剂和添加剂的用量会对最终的电池性能产生较大的影响。由于光物理和电化学性质的改变，光敏染料的结构变化对电池的性能也会产生重要影响。对本论文所合成的大部分染料来说，乙烯基作为π-桥基的组成部分对电池的开路电压、短路电流密度和光电转换效率都会产生不利的影响。π-桥基中较多噻吩基结构单元的存在也会导致电池开路电压的降低，但由于噻吩基拓宽了染料的光谱响应范围，进而提高短路电流密度，因此光敏染料中含有适当数目的噻吩基有助于获得更好的光电转换效率。经过优化和对比测试，C2-2染料敏化的太阳能电池在获得了最好电池性能，在模拟太阳光(AM 1.5，100 mW／cm~2)下，总的光电转换效率可达4.53％，短路电流密度为12.00 mA／cm~2，开路电压为597 mV，填充因子0.63，在同样条件下，以N3染料作为光敏染料的太阳能电池的光电转换效率为6.16％。
实验和理论研究结果显示，某些含噻吩基和乙烯基C=C双键的模型化合物的激发念具有明显的分子内电荷转移性质，而且它们的激发态构型为扭转的分子内电荷转移念。构型的扭转导致这类化合物的激发态通过振动驰豫去活化的可能性增大，减少了类似结构染料的激发态电子向TiO_2导带注入的概率，从而可能会对这些含乙烯基桥基的染料在染料敏化太阳能电池中的应用性能产生不利的影响。
At the heart of the dye-sensitized solar cell (DSSC) system is a mesoporous oxide layer composed of nanometer-sized particles anchored by a monolayer of the charge transfer dye. Sunlight is harvested by a dye sensitizer, photo-excitation of the dye results in the injection of electrons into the conduction band of the oxide. The dye is regenerated by the electrolyte, such as an ionic liquid containing most frequently the iodide/triiodide couple as a redox system. Dye is one of the most important parts for DSSCs getting higher efficiency and longer lifetime.
In this thesis, thirteen novel donor acceptorπ-conjugated (D-π-A) metal-free organic dyes have been engineered and synthesized as sensitizers for the application in DSSCs. The electron-donating moieties are substituted tetrahydroquinoline and the electron-withdrawing parts are cyanoacrylic acid group or cyanovinylphosphonic acid group. Differentπ-conjugation moieties (thienyl, thienylvinyl, dithieno[3, 2-b; 2′, 3′-d] thienyl and phenyl, etc) are introduced to the molecules and serve as electron spacers. The structures of the dyes have been characterized by mass spectra (MS) and proton nuclear magnetic resonance (~1H NMR) technology. The photophysical and electrochemical properties of the dyes were studied. DSSCs were constructed based on these dyes and detailed relationship between dye structures and solar cell performances has been investigated. At the same time, two model compounds were synthesized for the intromolecular charge transfer (ICT) study. The findings are used to interpret the relationship between dye structures and solar cell performances.
The change of dye structures has important effect on the photophysical and electrochemical properties of the sensitizers. The absorption band of a dye can be red-shifted and broadened by the introduction of a largeπ-conjugation spacer, such as more thienyl or vinyl moieties. This will enhance the light absorption ability of a dye, while the phenyl moiety has lower effect on the absorption character. The thienyl or vinyl in theπ-conjugation spacer will enhance aggregation of a dye on TiO_2 surface and results in the blue-shift of the absorption band. Redox potentials of ground and excited states of the dyes match well with that of I_3~-/I~- and TiO_2 conduction band, respectively. Introduction of more thienyl or vinyl moieties will shift the ground state redox potential of a dye negatively, and results in a reduced gap between that and redox potential of I_3~-/I~-. This might reduce the efficiency of regeneration of the oxidized dye by I~-. A dye with cyanovinylphosphonic acid as anchoring group has more negative excited state redox potential than a cyanoacrylic acid group containing one, and thus has more efficient electron injection from the excited dye to the conduction band of TiO_2.
The tetrahydroquinoline derivates show well performance in DSSC applications. Dye bath solvents and coadsorbent for TiO_2 sensitization influence the solar cell performances. As the result of changing of photophysical and elecrtrochemical properties, structural change of the dyes has important effect on the performances of DSSCs based on these dyes. For most cases, a dye containing the vinyl moiety inπ-conjugation spacer gives worse solar cell performance, such as lower short-circuit current density (Jsc), open-circuit voltage (Voc) and the overall solar-to-electrical energy conversion efficiency (η). The thienyl moiety in a dye molecule also leads to lower Voc value of the DSSC, but a higherηvalue could be obtained as the result of broadened spectral response and higher J_(SC). A maximumηvalue of 4.53% was achieved under simulated AM 1.5 irradiation (100 mW/cm~2) with a DSSC based on C2-2 dye (Voc= 597 mV, Jsc=12.00 mA/cm~2, FF=0.63). Under the same conditions, theηvalue of a DSSC based on N3 dye is 6.16%.
From the experimental and theoretical investigations, it is found that the excited states of model compounds containing thienyl and vinyl moieties have obvious ICT character. The optimized lowest energy geometry is a twisted intramolecular charge transfer (TICT) structure because of the coexistence of thienyl and vinyl moieties. Geometrical twist in the excited state will increase the probability of de-excitation through vibration relaxation pathway, and thus reduce the probability of electron injection to the TiO_2 conduction band and lower the solar cell performance.
本论文设计合成了13个以取代四氢喹啉为供电子基、氰基丙烯酸基或氰乙烯基磷酸基为吸电子基并通过不同π-桥基相连的电子推拉型光敏染料，并利用质谱、核磁共振氢谱对这些化合物进行结构表征，研究了光敏染料的光物理、电化学等性质，并将其应用于染料敏化太阳能电池，系统地考察了光敏染料结构与电池性能之间的关系。同时，本论文还对2个模型化合物的分子内电荷转移性质进行了实验和理论方面的研究，并将其结果用于解释光敏染料结构与性能之间的关系。
光敏染料的结构与其光物理、电化学性质具有密切关系。通过在π-桥基中引入更多的噻吩基或乙烯基结构单元，增大了染料的共轭体系，使其吸收光谱发生红移和拓宽，增强了染料对光的吸收能力，而苯基桥基的引入对染料吸收光谱的影响较小。同时发现，光敏染料中多个噻吩基或者乙烯基结构单元的引入使得染料在TiO-2表面的聚集趋势增大，导致染料在TiO_2表面吸收光谱的蓝移。光敏染料的基态和激发态氧化还原电位同时满足了染料激发态电子向TiO_2导带注入和染料还原的电位要求。噻吩基和乙烯基结构单元会导致染料基态氧化还原电位的升高，降低其与电解质中I_3~-／I~-电对的电位差，从而降低染料被还原的驱动力。与氰基丙烯酸基相比，氰乙烯基磷酸基作为吸电子基更能升高染料的激发态氧化还原电位，从而使得激发态染料分子具有更高的电子注入驱动力。
四氢喹啉衍生物作为染料敏化太阳能电池光敏染料，展现出良好的电池性能。研究发现，进行TiO_2膜的染料敏化时所用的溶剂和添加剂的用量会对最终的电池性能产生较大的影响。由于光物理和电化学性质的改变，光敏染料的结构变化对电池的性能也会产生重要影响。对本论文所合成的大部分染料来说，乙烯基作为π-桥基的组成部分对电池的开路电压、短路电流密度和光电转换效率都会产生不利的影响。π-桥基中较多噻吩基结构单元的存在也会导致电池开路电压的降低，但由于噻吩基拓宽了染料的光谱响应范围，进而提高短路电流密度，因此光敏染料中含有适当数目的噻吩基有助于获得更好的光电转换效率。经过优化和对比测试，C2-2染料敏化的太阳能电池在获得了最好电池性能，在模拟太阳光(AM 1.5，100 mW／cm~2)下，总的光电转换效率可达4.53％，短路电流密度为12.00 mA／cm~2，开路电压为597 mV，填充因子0.63，在同样条件下，以N3染料作为光敏染料的太阳能电池的光电转换效率为6.16％。
实验和理论研究结果显示，某些含噻吩基和乙烯基C=C双键的模型化合物的激发念具有明显的分子内电荷转移性质，而且它们的激发态构型为扭转的分子内电荷转移念。构型的扭转导致这类化合物的激发态通过振动驰豫去活化的可能性增大，减少了类似结构染料的激发态电子向TiO_2导带注入的概率，从而可能会对这些含乙烯基桥基的染料在染料敏化太阳能电池中的应用性能产生不利的影响。
At the heart of the dye-sensitized solar cell (DSSC) system is a mesoporous oxide layer composed of nanometer-sized particles anchored by a monolayer of the charge transfer dye. Sunlight is harvested by a dye sensitizer, photo-excitation of the dye results in the injection of electrons into the conduction band of the oxide. The dye is regenerated by the electrolyte, such as an ionic liquid containing most frequently the iodide/triiodide couple as a redox system. Dye is one of the most important parts for DSSCs getting higher efficiency and longer lifetime.
In this thesis, thirteen novel donor acceptorπ-conjugated (D-π-A) metal-free organic dyes have been engineered and synthesized as sensitizers for the application in DSSCs. The electron-donating moieties are substituted tetrahydroquinoline and the electron-withdrawing parts are cyanoacrylic acid group or cyanovinylphosphonic acid group. Differentπ-conjugation moieties (thienyl, thienylvinyl, dithieno[3, 2-b; 2′, 3′-d] thienyl and phenyl, etc) are introduced to the molecules and serve as electron spacers. The structures of the dyes have been characterized by mass spectra (MS) and proton nuclear magnetic resonance (~1H NMR) technology. The photophysical and electrochemical properties of the dyes were studied. DSSCs were constructed based on these dyes and detailed relationship between dye structures and solar cell performances has been investigated. At the same time, two model compounds were synthesized for the intromolecular charge transfer (ICT) study. The findings are used to interpret the relationship between dye structures and solar cell performances.
The change of dye structures has important effect on the photophysical and electrochemical properties of the sensitizers. The absorption band of a dye can be red-shifted and broadened by the introduction of a largeπ-conjugation spacer, such as more thienyl or vinyl moieties. This will enhance the light absorption ability of a dye, while the phenyl moiety has lower effect on the absorption character. The thienyl or vinyl in theπ-conjugation spacer will enhance aggregation of a dye on TiO_2 surface and results in the blue-shift of the absorption band. Redox potentials of ground and excited states of the dyes match well with that of I_3~-/I~- and TiO_2 conduction band, respectively. Introduction of more thienyl or vinyl moieties will shift the ground state redox potential of a dye negatively, and results in a reduced gap between that and redox potential of I_3~-/I~-. This might reduce the efficiency of regeneration of the oxidized dye by I~-. A dye with cyanovinylphosphonic acid as anchoring group has more negative excited state redox potential than a cyanoacrylic acid group containing one, and thus has more efficient electron injection from the excited dye to the conduction band of TiO_2.
The tetrahydroquinoline derivates show well performance in DSSC applications. Dye bath solvents and coadsorbent for TiO_2 sensitization influence the solar cell performances. As the result of changing of photophysical and elecrtrochemical properties, structural change of the dyes has important effect on the performances of DSSCs based on these dyes. For most cases, a dye containing the vinyl moiety inπ-conjugation spacer gives worse solar cell performance, such as lower short-circuit current density (Jsc), open-circuit voltage (Voc) and the overall solar-to-electrical energy conversion efficiency (η). The thienyl moiety in a dye molecule also leads to lower Voc value of the DSSC, but a higherηvalue could be obtained as the result of broadened spectral response and higher J_(SC). A maximumηvalue of 4.53% was achieved under simulated AM 1.5 irradiation (100 mW/cm~2) with a DSSC based on C2-2 dye (Voc= 597 mV, Jsc=12.00 mA/cm~2, FF=0.63). Under the same conditions, theηvalue of a DSSC based on N3 dye is 6.16%.
From the experimental and theoretical investigations, it is found that the excited states of model compounds containing thienyl and vinyl moieties have obvious ICT character. The optimized lowest energy geometry is a twisted intramolecular charge transfer (TICT) structure because of the coexistence of thienyl and vinyl moieties. Geometrical twist in the excited state will increase the probability of de-excitation through vibration relaxation pathway, and thus reduce the probability of electron injection to the TiO_2 conduction band and lower the solar cell performance.
引文
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