有机染料敏化剂的结构调控及其光伏性能的研究
发布时间：2018-07-20 14:38
【摘要】：能源危机的日益加重促使人类加快对新能源的研究与开发,目前染料敏化太阳能电池(DSSC)由于其价格低廉,光电转化效率高,轻便,易做成柔性器件以及建筑一体化易于实现而成为最有前途的光伏技术。自1991年Gratzel小组报道了突破性进展之后,DSSC的研究开始受到了广泛的关注,全球众多的课题都在努力提高DSSC的光电转化效率(PCE)以及稳定性。目前基于钌吡啶以及卟啉类染料的最大光电转化效率分别为11.9%和13%,而基于有机染料的光电转化效率已经达到14%,因此有机染料为进一步提高DSSC的效率提供了新途径。有机染料由于其轻便,多样性,易合成,来源广泛以及易建筑一体化而受到了广泛的关注,但是其结构与性能间的构效关系仍不是十分的明确,而一般较为有效的敏化剂均采用了 D-π-A构型,因此本文设计了一系列新的该类型染料,分别优化组成染料的供体,π桥以及受体三个部分,考察结构调整对染料性能的影响,进而寻找结构影响性能的一般规律。具体分以下三个部分:(1)采用三苯胺为供体通过调节π桥合成了 ZHG1、ZHG2、ZHG3和ZHG4四种新的染料。对比敏化剂ZHG1和ZHG2的PCE,在引入乙炔基之后ZHG2的PCE被提高到了6.1%,但是在敏化剂ZHG3中继续引入生色团4,8-二正辛基-苯并[l,2-b:4,5-b']二噻吩进一步提高连接体的共轭程度发现体系的PCE反而下降至4.6%。在敏化剂ZHG4希望通过噻吩替换与固定基团相连的苯环提高共轭性从而提高电池性能,但是发现ZHG4的PCE却进一步下降到了 4.3%。理论计算表明敏化剂ZHG3和ZHG4电子云主要分布在远离固定基闭的苯并噻二唑上。循环伏安测试表明敏化剂ZHG3和ZHG4的LUMOs能级要比ZHG1和ZHG2要低。这些结果均会影响敏化剂ZHG3和ZHG4激发态电子注入到TiO2导带的效率。X-射线光电子能谱(XPS)测试表明染料ZHG1、ZHG2、ZHG3和ZHG4在光阳极表面负载的厚度分别为16 A、18 A、27 A和24 A。因此染料在TiO2表面吸附倾斜角大小顺序为ZHG1ZHG2ZHG4ZHG3,倾斜角越小则染料越垂直于光阳极,相应的分子间的π-π聚集效应更加严重,因此π桥过长的敏化剂ZHG3和ZHG4相对与敏化剂ZHG1和ZHG2具有更加严重的π-π聚集效应。由此注入效率较低以及π-π聚集效应加重这两方面是造成敏化剂ZHG3和ZHG4光电性能下降的主要原因。因此这部分工作证实在电子注入效率,分子间π-π聚集效应以及拓宽光谱吸收范围之间寻找到平衡是提高DSSC性能的关键。(2)通过逐步增加辅助供体的空间位阻而合成ZHG5、ZHG6和ZHG7三种包含吩噻嗪的敏化剂。基于这三种敏化剂的DSSC光电转化效率分别为5.64%、5.32%和2.74%。紫外吸收光谱测试证实摩尔吸光系数随着辅助供体位阻增加而减小。XPS测试证实ZHG5和ZHG6在光阳极表面的吸附倾斜角基本相似,而拥有最大辅助供体的ZHG7吸附倾斜角最小且基本上是垂直于光阳极表面。染料解吸附测试以及XPS测试均表明ZHG6由于空间位阻更大而吸附量小于ZHG5,但是ZHG7由于其几乎以垂直的方式负载在光阳极薄膜上,因此染料ZHG7拥有最大的染料负载量。ZHG6相对于ZHG5(Voc= 730 mV,Jsc =12.63 mA cm-2)由于其更大的辅助供体而具有更大的开路电压(Voc= 734 mV),但是同时相对更小的短路电流(Jsc=12.06mAcm-2)。然而染料ZHG7由于其密集的负载方式导致其更加严重的π-π堆积效应,因此高的π-π堆积效应以及低的摩尔消光系数是染料ZHG7效率最低的原因。因此以上结果也说明过大的辅助供体将减小染料负载角度,提高染料的负载量,但同时会增加π-π堆积效应。(3)固定基团作为染料分子的电子受体,在DSSC效率以及稳定性上都将会起到非常重要的作用。因此开发新的固定基团来提高DSSC的效率以及稳定性不失为一种有效的方法。因此我们通过合成两种含新固定基团的染料(ZHG8、ZHG9)与氰基内烯酸固定基团染料(ZHG7)来予以比较。在敏化剂ZHG8以及ZHG9当中氰基丙烯酸中的氰基分别被替换为乙酰胺基以及吡啶基团。染料解吸附和光电性能测试证实ZHG8(2.33%)在光电转化效率相对于ZHG7(2.74%)只有少量下降的情况下,染料吸附稳定性有很大程度的提高,而ZHG9虽然表现出最强的染料吸附稳定性,但是光电性能却最低(0.37%)。FTIR分析表明ZHG8中的乙酰胺采用了双齿配位模式而ZHG9中的吡啶则与光阳极薄膜上的路易酸位点形成了配位键,因此ZHG8和ZHG9的染料吸附稳定都得到了提高。我们认为这样的结果将会有利于今后设计更加高效和稳定的固定基团。
[Abstract]:The increasing energy crisis has accelerated the research and development of new energy. At present, dye-sensitized solar cell (DSSC) has become the most promising photovoltaic technology because of its low price, high photoelectric conversion efficiency, lightweight, easy to make flexible devices and easy realization of building integration. Since 1991, the Gratzel team reported the breakthrough. After the progress, the research of DSSC has attracted wide attention. Many global topics are trying to improve the photoelectric conversion efficiency (PCE) and stability of DSSC. The maximum photoelectric conversion efficiency based on ruthenium pyridine and porphyrin dyes is 11.9% and 13% respectively, and the photoelectric conversion efficiency based on the organic dyes has reached 14%. Organic dyes provide a new way to further improve the efficiency of DSSC. Organic dyes have been widely concerned because of their light, diversity, easy synthesis, extensive sources and easy building integration, but the structure and performance relationship between them is still not very clear, and a more effective sensitizer uses the D- PI -A configuration. Therefore, a series of new dyes are designed to optimize the dye donor, the PI bridge and the three parts of the receptor, to investigate the influence of the structure adjustment on the performance of the dye, and to find the general rules of the structure affecting the performance. The following three parts are divided into the following parts: (1) using three aniline as the donor by adjusting the PI bridge to synthesize ZHG1, ZHG2, ZH G3 and ZHG4 four new dyes. Compared to the PCE of sensitizer ZHG1 and ZHG2, the PCE of ZHG2 was increased to 6.1% after the introduction of acetylene group, but the chromophore 4,8- two n octyl benzo benzo [l was introduced in the sensitizer ZHG3, and 2-b:4,5-b'] two thiophene further increased the conjugation degree of the conjugated system and decreased to the sensitizer. 4 it is hoped that the thiophene can improve the conjugation by replacing the benzene ring connected with the fixed group to improve the battery performance, but it is found that the PCE of ZHG4 is further reduced to the 4.3%. theoretical calculation indicating that the sensitizer ZHG3 and ZHG4 electron clouds are mainly distributed on the benzothiazoles, which are far away from the fixed base of benzothiazoles. The cyclic voltammetry test forms the LUM of the sensitizer ZHG3 and the LUM of ZHG4. The Os energy level is lower than that of ZHG1 and ZHG2. These results all affect the efficiency of the sensitizer ZHG3 and ZHG4 excited states into the TiO2 conduction band, the efficiency of.X- ray photoelectron spectroscopy (XPS) test shows that the thickness of the dye ZHG1, ZHG2, ZHG3 and ZHG4 at the photoanode surface is 16, 18, 27 and 24 The smaller the tilting angle is ZHG1ZHG2ZHG4ZHG3, the more the dyestuff is perpendicular to the photo anode, and the corresponding pion - pi aggregation effect is more serious. Therefore, the long pion sensitizer ZHG3 and ZHG4 have a more serious pion pion aggregation effect with the sensitizer ZHG1 and ZHG2. The two aspects are the low injection efficiency and the aggravation of the Pi Pi aggregation effect. The main reasons for the decrease of photosensitizer ZHG3 and ZHG4 photoelectric properties. Therefore, this work confirms that the key to improving the performance of DSSC is the efficiency of electron injection, the intermolecular Pi Pi aggregation effect and the widening of the spectral absorption range. (2) the synthesis of ZHG5, ZHG6 and ZHG7 by gradually increasing the space hindrance of the auxiliary donor. The photosensitizer containing phenothiazine. The DSSC photoelectric conversion efficiency based on these three sensitizers was 5.64%, 5.32% and 2.74%. UV absorption spectra confirmed that the molar absorbance coefficient decreased with the increase of the auxiliary donor steric resistance and the.XPS test confirmed that the adsorption inclination angle of ZHG5 and ZHG6 on the surface of the photoanode was basically similar, and the ZHG with the largest auxiliary donor. 7 the dip angle is the smallest and basically perpendicular to the surface of the photo anode. The dye desorption test and XPS test all show that the adsorption capacity of ZHG6 is larger than ZHG5, but ZHG7 is loaded on the photo anode film almost vertically, so the dye ZHG7 has the largest dye load.ZHG6 relative to ZHG5 (Voc=). 730 mV, Jsc =12.63 mA cm-2) has larger open circuit voltage (Voc= 734 mV) due to its larger auxiliary donor, but relatively smaller short-circuit current (Jsc=12.06mAcm-2). However, dye ZHG7 due to its dense load mode leads to its more serious Pi Pi accumulation effect, thus high pion piling effect and low Moore extinction The coefficient is the lowest cause of the dye ZHG7 efficiency. So the above results also show that the large auxiliary donor will reduce the dye load angle and increase the load of the dye, but it will increase the pion pion accumulation effect at the same time. (3) the fixed group, as the electron acceptor of the dye molecules, will play a very important role in the efficiency and stability of the DSSC. It is an effective method to develop a new fixed group to improve the efficiency and stability of DSSC. Therefore, we compare the dye (ZHG8, ZHG9) with the cyanic enoic acid fixed group dye (ZHG7) by synthesizing two new fixed groups. Cyanic acid in cyanoacrylic acid is replaced in the sensitizer ZHG8 and ZHG9 respectively. Acetaminophen and pyridine groups. Dyestuff desorption and photoelectrical properties test confirmed that the dye adsorption stability of ZHG8 (2.33%) was greatly improved when the photoelectric conversion efficiency was only a small decrease relative to ZHG7 (2.74%), while ZHG9 showed the strongest dye absorption stability, but the photoelectrical performance was the lowest (0.37%).FTIR fraction. It is shown that the acetamide in ZHG8 uses the double tooth coordination mode and the pyridine in ZHG9 forms a coordination bond with the Louis acid site on the photo anode film, so the dye adsorption stability of ZHG8 and ZHG9 is improved. We think that this result will be beneficial to the design of more efficient and stable fixed groups in the future.
【学位授予单位】：南京大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TQ610.1;TM914.4
[Abstract]:The increasing energy crisis has accelerated the research and development of new energy. At present, dye-sensitized solar cell (DSSC) has become the most promising photovoltaic technology because of its low price, high photoelectric conversion efficiency, lightweight, easy to make flexible devices and easy realization of building integration. Since 1991, the Gratzel team reported the breakthrough. After the progress, the research of DSSC has attracted wide attention. Many global topics are trying to improve the photoelectric conversion efficiency (PCE) and stability of DSSC. The maximum photoelectric conversion efficiency based on ruthenium pyridine and porphyrin dyes is 11.9% and 13% respectively, and the photoelectric conversion efficiency based on the organic dyes has reached 14%. Organic dyes provide a new way to further improve the efficiency of DSSC. Organic dyes have been widely concerned because of their light, diversity, easy synthesis, extensive sources and easy building integration, but the structure and performance relationship between them is still not very clear, and a more effective sensitizer uses the D- PI -A configuration. Therefore, a series of new dyes are designed to optimize the dye donor, the PI bridge and the three parts of the receptor, to investigate the influence of the structure adjustment on the performance of the dye, and to find the general rules of the structure affecting the performance. The following three parts are divided into the following parts: (1) using three aniline as the donor by adjusting the PI bridge to synthesize ZHG1, ZHG2, ZH G3 and ZHG4 four new dyes. Compared to the PCE of sensitizer ZHG1 and ZHG2, the PCE of ZHG2 was increased to 6.1% after the introduction of acetylene group, but the chromophore 4,8- two n octyl benzo benzo [l was introduced in the sensitizer ZHG3, and 2-b:4,5-b'] two thiophene further increased the conjugation degree of the conjugated system and decreased to the sensitizer. 4 it is hoped that the thiophene can improve the conjugation by replacing the benzene ring connected with the fixed group to improve the battery performance, but it is found that the PCE of ZHG4 is further reduced to the 4.3%. theoretical calculation indicating that the sensitizer ZHG3 and ZHG4 electron clouds are mainly distributed on the benzothiazoles, which are far away from the fixed base of benzothiazoles. The cyclic voltammetry test forms the LUM of the sensitizer ZHG3 and the LUM of ZHG4. The Os energy level is lower than that of ZHG1 and ZHG2. These results all affect the efficiency of the sensitizer ZHG3 and ZHG4 excited states into the TiO2 conduction band, the efficiency of.X- ray photoelectron spectroscopy (XPS) test shows that the thickness of the dye ZHG1, ZHG2, ZHG3 and ZHG4 at the photoanode surface is 16, 18, 27 and 24 The smaller the tilting angle is ZHG1ZHG2ZHG4ZHG3, the more the dyestuff is perpendicular to the photo anode, and the corresponding pion - pi aggregation effect is more serious. Therefore, the long pion sensitizer ZHG3 and ZHG4 have a more serious pion pion aggregation effect with the sensitizer ZHG1 and ZHG2. The two aspects are the low injection efficiency and the aggravation of the Pi Pi aggregation effect. The main reasons for the decrease of photosensitizer ZHG3 and ZHG4 photoelectric properties. Therefore, this work confirms that the key to improving the performance of DSSC is the efficiency of electron injection, the intermolecular Pi Pi aggregation effect and the widening of the spectral absorption range. (2) the synthesis of ZHG5, ZHG6 and ZHG7 by gradually increasing the space hindrance of the auxiliary donor. The photosensitizer containing phenothiazine. The DSSC photoelectric conversion efficiency based on these three sensitizers was 5.64%, 5.32% and 2.74%. UV absorption spectra confirmed that the molar absorbance coefficient decreased with the increase of the auxiliary donor steric resistance and the.XPS test confirmed that the adsorption inclination angle of ZHG5 and ZHG6 on the surface of the photoanode was basically similar, and the ZHG with the largest auxiliary donor. 7 the dip angle is the smallest and basically perpendicular to the surface of the photo anode. The dye desorption test and XPS test all show that the adsorption capacity of ZHG6 is larger than ZHG5, but ZHG7 is loaded on the photo anode film almost vertically, so the dye ZHG7 has the largest dye load.ZHG6 relative to ZHG5 (Voc=). 730 mV, Jsc =12.63 mA cm-2) has larger open circuit voltage (Voc= 734 mV) due to its larger auxiliary donor, but relatively smaller short-circuit current (Jsc=12.06mAcm-2). However, dye ZHG7 due to its dense load mode leads to its more serious Pi Pi accumulation effect, thus high pion piling effect and low Moore extinction The coefficient is the lowest cause of the dye ZHG7 efficiency. So the above results also show that the large auxiliary donor will reduce the dye load angle and increase the load of the dye, but it will increase the pion pion accumulation effect at the same time. (3) the fixed group, as the electron acceptor of the dye molecules, will play a very important role in the efficiency and stability of the DSSC. It is an effective method to develop a new fixed group to improve the efficiency and stability of DSSC. Therefore, we compare the dye (ZHG8, ZHG9) with the cyanic enoic acid fixed group dye (ZHG7) by synthesizing two new fixed groups. Cyanic acid in cyanoacrylic acid is replaced in the sensitizer ZHG8 and ZHG9 respectively. Acetaminophen and pyridine groups. Dyestuff desorption and photoelectrical properties test confirmed that the dye adsorption stability of ZHG8 (2.33%) was greatly improved when the photoelectric conversion efficiency was only a small decrease relative to ZHG7 (2.74%), while ZHG9 showed the strongest dye absorption stability, but the photoelectrical performance was the lowest (0.37%).FTIR fraction. It is shown that the acetamide in ZHG8 uses the double tooth coordination mode and the pyridine in ZHG9 forms a coordination bond with the Louis acid site on the photo anode film, so the dye adsorption stability of ZHG8 and ZHG9 is improved. We think that this result will be beneficial to the design of more efficient and stable fixed groups in the future.
【学位授予单位】：南京大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TQ610.1;TM914.4
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