有機(jī)染料敏化劑的結(jié)構(gòu)調(diào)控及其光伏性能的研究
發(fā)布時間：2018-07-20 14:38
【摘要】：能源危機(jī)的日益加重促使人類加快對新能源的研究與開發(fā),目前染料敏化太陽能電池(DSSC)由于其價格低廉,光電轉(zhuǎn)化效率高,輕便,易做成柔性器件以及建筑一體化易于實(shí)現(xiàn)而成為最有前途的光伏技術(shù)。自1991年Gratzel小組報道了突破性進(jìn)展之后,DSSC的研究開始受到了廣泛的關(guān)注,全球眾多的課題都在努力提高DSSC的光電轉(zhuǎn)化效率(PCE)以及穩(wěn)定性。目前基于釕吡啶以及卟啉類染料的最大光電轉(zhuǎn)化效率分別為11.9%和13%,而基于有機(jī)染料的光電轉(zhuǎn)化效率已經(jīng)達(dá)到14%,因此有機(jī)染料為進(jìn)一步提高DSSC的效率提供了新途徑。有機(jī)染料由于其輕便,多樣性,易合成,來源廣泛以及易建筑一體化而受到了廣泛的關(guān)注,但是其結(jié)構(gòu)與性能間的構(gòu)效關(guān)系仍不是十分的明確,而一般較為有效的敏化劑均采用了 D-π-A構(gòu)型,因此本文設(shè)計(jì)了一系列新的該類型染料,分別優(yōu)化組成染料的供體,π橋以及受體三個部分,考察結(jié)構(gòu)調(diào)整對染料性能的影響,進(jìn)而尋找結(jié)構(gòu)影響性能的一般規(guī)律。具體分以下三個部分:(1)采用三苯胺為供體通過調(diào)節(jié)π橋合成了 ZHG1、ZHG2、ZHG3和ZHG4四種新的染料。對比敏化劑ZHG1和ZHG2的PCE,在引入乙炔基之后ZHG2的PCE被提高到了6.1%,但是在敏化劑ZHG3中繼續(xù)引入生色團(tuán)4,8-二正辛基-苯并[l,2-b:4,5-b']二噻吩進(jìn)一步提高連接體的共軛程度發(fā)現(xiàn)體系的PCE反而下降至4.6%。在敏化劑ZHG4希望通過噻吩替換與固定基團(tuán)相連的苯環(huán)提高共軛性從而提高電池性能,但是發(fā)現(xiàn)ZHG4的PCE卻進(jìn)一步下降到了 4.3%。理論計(jì)算表明敏化劑ZHG3和ZHG4電子云主要分布在遠(yuǎn)離固定基閉的苯并噻二唑上。循環(huán)伏安測試表明敏化劑ZHG3和ZHG4的LUMOs能級要比ZHG1和ZHG2要低。這些結(jié)果均會影響敏化劑ZHG3和ZHG4激發(fā)態(tài)電子注入到TiO2導(dǎo)帶的效率。X-射線光電子能譜(XPS)測試表明染料ZHG1、ZHG2、ZHG3和ZHG4在光陽極表面負(fù)載的厚度分別為16 A、18 A、27 A和24 A。因此染料在TiO2表面吸附傾斜角大小順序?yàn)閆HG1ZHG2ZHG4ZHG3,傾斜角越小則染料越垂直于光陽極,相應(yīng)的分子間的π-π聚集效應(yīng)更加嚴(yán)重,因此π橋過長的敏化劑ZHG3和ZHG4相對與敏化劑ZHG1和ZHG2具有更加嚴(yán)重的π-π聚集效應(yīng)。由此注入效率較低以及π-π聚集效應(yīng)加重這兩方面是造成敏化劑ZHG3和ZHG4光電性能下降的主要原因。因此這部分工作證實(shí)在電子注入效率,分子間π-π聚集效應(yīng)以及拓寬光譜吸收范圍之間尋找到平衡是提高DSSC性能的關(guān)鍵。(2)通過逐步增加輔助供體的空間位阻而合成ZHG5、ZHG6和ZHG7三種包含吩噻嗪的敏化劑�；谶@三種敏化劑的DSSC光電轉(zhuǎn)化效率分別為5.64%、5.32%和2.74%。紫外吸收光譜測試證實(shí)摩爾吸光系數(shù)隨著輔助供體位阻增加而減小。XPS測試證實(shí)ZHG5和ZHG6在光陽極表面的吸附傾斜角基本相似,而擁有最大輔助供體的ZHG7吸附傾斜角最小且基本上是垂直于光陽極表面。染料解吸附測試以及XPS測試均表明ZHG6由于空間位阻更大而吸附量小于ZHG5,但是ZHG7由于其幾乎以垂直的方式負(fù)載在光陽極薄膜上,因此染料ZHG7擁有最大的染料負(fù)載量。ZHG6相對于ZHG5(Voc= 730 mV,Jsc =12.63 mA cm-2)由于其更大的輔助供體而具有更大的開路電壓(Voc= 734 mV),但是同時相對更小的短路電流(Jsc=12.06mAcm-2)。然而染料ZHG7由于其密集的負(fù)載方式導(dǎo)致其更加嚴(yán)重的π-π堆積效應(yīng),因此高的π-π堆積效應(yīng)以及低的摩爾消光系數(shù)是染料ZHG7效率最低的原因。因此以上結(jié)果也說明過大的輔助供體將減小染料負(fù)載角度,提高染料的負(fù)載量,但同時會增加π-π堆積效應(yīng)。(3)固定基團(tuán)作為染料分子的電子受體,在DSSC效率以及穩(wěn)定性上都將會起到非常重要的作用。因此開發(fā)新的固定基團(tuán)來提高DSSC的效率以及穩(wěn)定性不失為一種有效的方法。因此我們通過合成兩種含新固定基團(tuán)的染料(ZHG8、ZHG9)與氰基內(nèi)烯酸固定基團(tuán)染料(ZHG7)來予以比較。在敏化劑ZHG8以及ZHG9當(dāng)中氰基丙烯酸中的氰基分別被替換為乙酰胺基以及吡啶基團(tuán)。染料解吸附和光電性能測試證實(shí)ZHG8(2.33%)在光電轉(zhuǎn)化效率相對于ZHG7(2.74%)只有少量下降的情況下,染料吸附穩(wěn)定性有很大程度的提高,而ZHG9雖然表現(xiàn)出最強(qiáng)的染料吸附穩(wěn)定性,但是光電性能卻最低(0.37%)。FTIR分析表明ZHG8中的乙酰胺采用了雙齒配位模式而ZHG9中的吡啶則與光陽極薄膜上的路易酸位點(diǎn)形成了配位鍵,因此ZHG8和ZHG9的染料吸附穩(wěn)定都得到了提高。我們認(rèn)為這樣的結(jié)果將會有利于今后設(shè)計(jì)更加高效和穩(wěn)定的固定基團(tuán)。
[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.
【學(xué)位授予單位】：南京大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：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.
【學(xué)位授予單位】：南京大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TQ610.1;TM914.4
【相似文獻(xiàn)】
相關(guān)期刊論文 前10條
1 吳振奕,楊森根,林永生,程大典,詹夢熊;碳60·雙二苯基膦乙烷合鈀的合成和光電轉(zhuǎn)化性能[J];無機(jī)材料學(xué)報;2005年06期
2 孫瓊;孫先淼;李陽;董立峰;;氮摻雜二氧化鈦納米棒陣列的制備和光電轉(zhuǎn)化性能表征[J];中國科技論文;2013年09期
3 梁曉琴;安忠維;陳新兵;陳沛;;取代聯(lián)噻吩染料敏化劑的合成與光伏性能[J];精細(xì)化工;2013年09期
4 劉，
本文編號：2133858
本文鏈接：http://sikaile.net/shoufeilunwen/gckjbs/2133858.html
最近更新
教材專著
