蒽类光敏染料的合成及在太阳能电池中的应用与研究
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摘要
光敏染料是染料敏化太阳能电池(DSSC)中的一个关键组成部分,在太阳光的照射下将被激发的电子注入Ti02导带中,与此同时,还原态的电解质(13-/I-)将氧化态的染料分子还原成基态。由于纯有机敏化太阳能电池较低的制作成本,与传统的金属化合物敏化电池相比,纯有机染料敏化太阳能电池有了广泛的研究和长足的发展。
本文共设计并合成了9个芳胺类纯有机敏化染料,包括7个蒽类染料和两个三苯胺类染料。并利用1HNMR和13CNMR谱对这些化合物进行了结构表征。同时,对这9个光敏染料进行了光物理性质,电化学性质,密度泛函理论计算和光伏性能的各项测试和研究。
敏化染料的光物理性质和其结构有着紧密的联系。实验表明,染料分子的共轭性会显著的影响其光物理性质,空间位阻越大,体系的共轭性就越差,阻碍了电子在染料分子中的传递,使染料的吸收光谱蓝移,吸收太阳光的能力下降。在作为桥键的噻吩环上引入取代基可以调节染料的吸收光谱,吸电子基的引入能使染料的吸收光谱发生红移。实验设计和合成的所有敏化染料的HOMO轨道能级都能保证染料的重生,LUMO轨道能级都能使电子有效的注入半导体导带。染料HOMO和LUMO能级值受到染料分子结构变化的影响。并三噻吩做为桥键时,敏化染料的HOMO能级值有所升高,使其与电解液中I3-/I-电对之间的电位差变小,最终导致了染料还原再生的驱动力的降低。
敏化染料的结构变化对电池的光伏性质也会产生重要的影响。通过对不同电子给体蒽类和三苯胺类染料的研究表明,电子给体是非平面结构的光敏染料在不含分子聚集抑制剂的情况下,能够有效阻止其在二氧化钛表面的H聚集,并获得较高的光电转换效率。
Photosensitizer is the key component for the dye sensitized solar cells (DSSCs), which leading excited state electrons injection into the conduction band of the TiO2under the irradiation of sunlight. At the same time, the dye is quickly regenerated by the electrolyte(l3-/I-). In order to reduce the cost of the dye sensitized solar cells, the organic sensitizers have developed rapidly in recent years compared with the noble metal complex sensitizers.
In this thesis, nine aromatic organic dyes have been designed and synthesized as the sensitizers for the dye sensitized solar cells, which containing seven heteroan thracene sensitizers and two triphenylamine sensitizers. The structures of the dyes have been characterized by1HNMR and13CNMR technology. At the same time, we study the electrochemical and photophysical properties of the DSSCs.
The photophysical properties of sensitizers is closely linked to its structure. The experiments show that the photophysical properties of sensitizers is significantly affected by its conjugacy. The more steric hindrance, the worse its conjugacy, which impedes transfer of electrons in the dye molecule and lead to the decrease of the ability to absorbing sunlight. For the dyes, the introduction of electron-withdrawing units to π-conjugation spacer can achieve red-shifted of absorption spectra. LUMO and HOMO levels of sensitizers match well with the I3-/I-and the TiO2conduction band respectively. The structure of sensitizers have a crucial effect on the HOMO and LUMO level of the dyes. Introduction of DTT unit as π-conjugation spacer moieties will increased value of the HOMO level, so that the electrolyte I3-/I-electrical potential difference between a pair of smaller, which resulting in reduction the driving force regeneration of the dyes.
The structure of sensitizers have a important effect on the photovoltaic properties of the dyes. The study of various electron donor on triphenyl amine and anthracene show that The electron donor is non-planar configuration of the photosensitive dye can effectively prevent the surface of the titanium dioxide H-aggregation and obtain a higher photoelectric conversion efficiency in the absence of the molecule aggregation inhibitor.
本文共设计并合成了9个芳胺类纯有机敏化染料,包括7个蒽类染料和两个三苯胺类染料。并利用1HNMR和13CNMR谱对这些化合物进行了结构表征。同时,对这9个光敏染料进行了光物理性质,电化学性质,密度泛函理论计算和光伏性能的各项测试和研究。
敏化染料的光物理性质和其结构有着紧密的联系。实验表明,染料分子的共轭性会显著的影响其光物理性质,空间位阻越大,体系的共轭性就越差,阻碍了电子在染料分子中的传递,使染料的吸收光谱蓝移,吸收太阳光的能力下降。在作为桥键的噻吩环上引入取代基可以调节染料的吸收光谱,吸电子基的引入能使染料的吸收光谱发生红移。实验设计和合成的所有敏化染料的HOMO轨道能级都能保证染料的重生,LUMO轨道能级都能使电子有效的注入半导体导带。染料HOMO和LUMO能级值受到染料分子结构变化的影响。并三噻吩做为桥键时,敏化染料的HOMO能级值有所升高,使其与电解液中I3-/I-电对之间的电位差变小,最终导致了染料还原再生的驱动力的降低。
敏化染料的结构变化对电池的光伏性质也会产生重要的影响。通过对不同电子给体蒽类和三苯胺类染料的研究表明,电子给体是非平面结构的光敏染料在不含分子聚集抑制剂的情况下,能够有效阻止其在二氧化钛表面的H聚集,并获得较高的光电转换效率。
Photosensitizer is the key component for the dye sensitized solar cells (DSSCs), which leading excited state electrons injection into the conduction band of the TiO2under the irradiation of sunlight. At the same time, the dye is quickly regenerated by the electrolyte(l3-/I-). In order to reduce the cost of the dye sensitized solar cells, the organic sensitizers have developed rapidly in recent years compared with the noble metal complex sensitizers.
In this thesis, nine aromatic organic dyes have been designed and synthesized as the sensitizers for the dye sensitized solar cells, which containing seven heteroan thracene sensitizers and two triphenylamine sensitizers. The structures of the dyes have been characterized by1HNMR and13CNMR technology. At the same time, we study the electrochemical and photophysical properties of the DSSCs.
The photophysical properties of sensitizers is closely linked to its structure. The experiments show that the photophysical properties of sensitizers is significantly affected by its conjugacy. The more steric hindrance, the worse its conjugacy, which impedes transfer of electrons in the dye molecule and lead to the decrease of the ability to absorbing sunlight. For the dyes, the introduction of electron-withdrawing units to π-conjugation spacer can achieve red-shifted of absorption spectra. LUMO and HOMO levels of sensitizers match well with the I3-/I-and the TiO2conduction band respectively. The structure of sensitizers have a crucial effect on the HOMO and LUMO level of the dyes. Introduction of DTT unit as π-conjugation spacer moieties will increased value of the HOMO level, so that the electrolyte I3-/I-electrical potential difference between a pair of smaller, which resulting in reduction the driving force regeneration of the dyes.
The structure of sensitizers have a important effect on the photovoltaic properties of the dyes. The study of various electron donor on triphenyl amine and anthracene show that The electron donor is non-planar configuration of the photosensitive dye can effectively prevent the surface of the titanium dioxide H-aggregation and obtain a higher photoelectric conversion efficiency in the absence of the molecule aggregation inhibitor.
引文
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