CN108795089B - 基于二(噻吩并吡咯)并苯并噻二唑π桥的纯有机染料及其在染料敏化太阳能电池中的应用 - Google Patents
基于二(噻吩并吡咯)并苯并噻二唑π桥的纯有机染料及其在染料敏化太阳能电池中的应用 Download PDFInfo
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Abstract
本发明公开了基于二(噻吩并吡咯)并苯并噻二唑π桥的纯有机染料及其在染料敏化太阳能电池中的应用,属于精细化工中的光电转化材料应用领域。本发明以烷氧基苯基为电子供体,二(噻吩并吡咯)并苯并噻二唑为共轭π桥,苯并噻二唑‑苯‑羧基为电子受体和锚固基团,合成了一系列新型的D‑π‑A结构纯有机染料。二(噻吩并吡咯)并苯并噻二唑单元是一个大共轭平面结构,它的引入能够有效地拓宽染料的吸光范围和提高摩尔消光系数,另一方面,其独特的D‑A‑D结构也有利于π电子离域,促进分子内电荷转移,进而提高了染料敏化太阳电池的光电转换效率。综合这两方面的作用,使得其在染料敏化太阳电池中有很好的应用前景。
Description
技术领域
本发明涉及光敏纯有机染料及染料敏化太阳能电池技术领域,具体涉及了基于二(噻吩并吡咯)并苯并噻二唑π桥的纯有机染料及其在染料敏化太阳能电池中的应用。
背景技术
染料敏化太阳电池(DSSCs)是一种新型的光电转换装置。与传统的硅基太阳电池相比,染料敏化太阳电池具有制作工艺简单、原料成本低廉、染料结构易于调控、可制作大面积柔性器件等方面的优点,是一类非常具有广泛应用前景的光电转换装置。光敏染料作为DSSCs中的重要组成部分,在整个电池中扮演着至关重要的作用,它起到吸收太阳光和注入电子的作用。可以说光敏染料的好坏直接决定了电池的光电转换效率。因此,合理的染料结构设计对于获得高光电转换效率的染料敏化太阳电池显得尤为重要。
目前,光敏染料主要有两类,一类是金属配合物染料,主要指的是钌多吡啶配合物和锌-卟啉配合物染料,另一类为纯有机染料。然而,在金属配合物染料中,金属钌属于稀有贵金属,储量很少而且价格昂贵,锌-卟啉配合物染料的合成步骤繁琐、分离提纯困难、产率低等特点也限制了这一类染料的产业化发展。为此,开发不含金属的纯有机光敏染料对发展DSSCs显得非常重要,也成为该领域的重要研究方向。
与钌多吡啶配合物染料和锌-卟啉配合物染料相比,纯有机光敏染料具有结构调控简单、制备提纯相对容易、摩尔消光系数高、成本低廉等诸多优点,近年来纯有机光敏染料也取得了飞快的发展,品种多样的纯有机染料得到开发和应用。
大共轭平面结构引入到染料中能够有效地提高染料的捕光能力,该策略被成功地应用用于染料敏化太阳电池研究中。目前还没有以具有电子给体-受体- 电子给体(D-A-D)结构的二(噻吩并吡咯)并苯并噻二唑为π桥,4-取代苯基为电子供体,以苯并噻二唑-苯甲酸为为电子受体和锚固基团的D-π-A结构纯有机染料的报道。
因此,为了开发高性能染料敏化太阳电池,本发明人设计并合成一类基于二(噻吩并吡咯)并苯并噻二唑π桥的纯有机染料的方案。
发明内容
本发明的目的是为了克服现有技术存在的缺点和不足,而提供一种基于二 (噻吩并吡咯)并苯并噻二唑π桥的纯有机染料及其在染料敏化太阳能电池中的应用,该染料具有吸光范围宽,稳定性好,光电转化性能良好等优点。
作为本发明的第一个方案,本发明提供一种基于二(噻吩并吡咯)并苯并噻二唑π桥的纯有机染料,其技术方案是基于二(噻吩并吡咯)并苯并噻二唑π桥的纯有机染料,其结构通式为:
其中:X为O或S,R为C1~C20的直链烷基、C1~C20的支链烷基、C1~C20的酰胺基,R1为C1~C20的直链烷基、C1~C20的支链烷基、C1~C20的烷氧基或卤素。
本发明的基于二(噻吩并吡咯)并苯并噻二唑π桥的纯有机染料的合成方法简单,原料价廉易得,其合成按如下反应式进行:
当R=iC8H17,R1=O-iC8H17,X=S时的反应式参见图1所示:
图1中,化合物2的合成方法:
以o-DCB为溶剂,将1份化合物1、6份三苯基膦溶解在o-DCB中,在Ar 保护下于70℃下搅拌反应16h。冷却至室温后,减压蒸馏除去反应溶剂,通过柱层析分离提纯环化产物,将环化中间产物直接投入下一步反应,以DMSO为溶剂,将1份环化中间产物,6份溴代异辛烷,6份KOH和少量KI加入到反应瓶中,在Ar保护下,于70℃下搅拌反应12h。待反应冷却至常温后,加水并用乙酸乙酯萃取,合并的有机相用水洗多次,干燥,旋蒸浓缩,粗产物通过柱层析分离提纯。
化合物3的合成方法:
冰水浴条件下,以THF为溶剂,加入1份化合物2和1份NBS,在0℃下搅拌反应1.5h,反应结束后加入水,再加入二氯甲烷萃取,合并有机相用水洗,干燥,旋蒸浓缩,粗产物柱层析分离提纯。
化合物5的合成方法:
在Ar保护下,以THF为溶剂,加入1份化合物3,1.5份化合物4,3份 K2CO3和5%的催化剂Pd(PPh3)4,在70℃下搅拌反应16h。冷却至室温后,将反应液倒入水中,用二氯甲烷萃取,合并有机相用水洗多次,干燥,旋蒸浓缩,粗产物通过柱层析分离提纯。
化合物6的合成方法:
冰水浴条件下,以THF为溶剂,加入1份化合物5和1份NBS,在0℃下搅拌反应1.5h,反应结束后加入水,再加入二氯甲烷萃取,合并有机相用水洗,干燥,旋蒸浓缩,粗产物柱层析分离提纯。
化合物7的合成方法:
在Ar保护下,以THF为溶剂,加入1份化合物7,3份三异丙基硅基乙炔, 10%的催化剂Pd(PPh3)2Cl2,30%的CuI和5mL的三乙胺,该混合液在氩气保护环境下,升温回流6h,冷却至室温后,旋蒸除去溶剂,粗产物通过柱层析分离提纯。
化合物9的合成方法:
在Ar保护下,将1份化合物7溶解在干燥的THF中,然后加入5份的TBAF (1M inTHF),反应液在25℃下搅拌反应30min,反应结束后加入水,然后用二氯甲烷萃取,合并的有机相用无水硫酸镁干燥,干燥后旋蒸浓缩得到粘稠状化合物直接投入下一步反应。将上述所得粘稠状物质溶解在THF和三乙胺的混合液中,再加入10%的催化剂Pd2(dba)3,2份三苯基砷,反应混合液在Ar保护下,于70℃下搅拌反应4h。冷却至室温后,旋蒸除去有机溶剂,粗产物通过柱层析分离提纯。
化合物H1的合成方法:
在Ar保护下,将1份化合物9溶解在干燥的THF中,再加入20mL的MeOH 和8mL的20%的NaOH水溶液,将反应液加热至40℃搅拌反应2h。反应结束后,反应混合液用乙醚萃取,并用蒸馏水和1M的HCl各洗涤两次,粗产物通过柱层析分离提纯并重结晶后即可得到目标染料分子。
本发明还提供一种所述的纯有机染料在光敏染料的应用,将该纯有机染料作为光敏染料,应用于将太阳能转变成电能。
本发明还提供一种基于权利要求1所述的纯有机染料在染料敏化太阳能电池中的应用,其特征在于:该染料敏化太阳能电池包括有吸附了光敏染料的光阳极、对电极、导电玻璃和电解质;
所述的导电玻璃为FTO导电玻璃,FTO导电玻璃导电一侧中间铺上纳米晶多孔TiO2薄膜,该纳米晶多孔TiO2薄膜吸附所述基于二(噻吩并吡咯)并苯并噻二唑π桥的纯有机染料,构成光阳极,该纯有机染料作为光敏染料,将太阳能转变成电能;对电极为导电玻璃导电一侧中间铺上的Pt催化剂层;光阳极和对电极相对间隔设置,所述纳米晶多孔TiO2薄膜周边用密封材料密封形成密闭的腔体,腔体内填充有电解质。
本发明还提供一种染料敏化太阳能电池的制备方法,包括有以下步骤:
a.FTO导电玻璃的预处理:对FTO导电玻璃进行表面清洗并干燥备用;
b.TiO2纳晶颗粒的制备:室温下,将20mL EtOH和15mL Ti(OBu)4的混合,在搅拌条件下,于上述溶液中加入35mL乙酸和20mL蒸馏水并继续搅拌1h,然后将此混合液移入高压反应釜中并置于230℃下处理 12h,冷却至室温后,将所得悬浊液过滤,分别用无水乙醇和蒸馏水洗涤多次,所得固体置于烘箱中升温至50℃烘6h,得到粒径为20nm±2 的TiO2纳米晶颗粒;
c.称取TiO2纳米晶颗粒1.0g于一小烧杯中,分别加入乙基纤维素0.5g、松油醇3.0g、无水乙醇10.0mL、冰乙酸0.2mL,将此混合物用玻璃棒搅拌并充分研磨30min,然后泥浆物在超声仪中作用20min后即得到所需的白色粘性的TiO2纳米晶浆料;
d.纳米晶TiO2膜的制备:将步骤a预处理后的导电玻璃导电面朝上,将丝网板放置于玻璃上方,控制网距为1cm,再将TiO2纳米晶浆料置于丝网上进行印刷,每次印刷的TiO2膜需放入100℃的烘箱中烘烤5min使有机溶剂充分挥发;一次印刷的TiO2薄膜厚度约为4μm,再重复3次上述操作即可得到约16μm厚度的TiO2薄膜;将制备好的TiO2膜置于马弗炉中依次在如下不同的温度下处理:升温至325℃烘焙5min,再升温至375℃烘焙5min,再升温至450℃烘焙15min,最后升温至 500℃烘焙15min,冷却至室温后将烘好的TiO2薄膜浸于0.04M的TiCl4水溶液,在放入70℃的真空干燥箱中处理30min;将处理结束的TiO2膜取出并用蒸馏水反复冲洗干净后,置于马弗炉中升温至500℃再次烘焙30min,冷至室温后保存在棕色干燥器中备用;
e.光敏染浴溶液的配置:将权利要求1所述的纯有机染料溶于二氯甲烷溶剂中,配制成3×10-4M的光敏染浴溶液;
f.电解质溶液的配制:用乙睛和戊腈配制的含有0.1M硫氰酸胍,0.6M 1-甲基-3-丙基碘化咪唑嗡,0.03M I2和0.5M对叔丁基吡啶的溶液;
g.光阳极的敏化:在黑暗条件下,步骤d制备的作为光阳极的纳米晶TiO2膜浸入步骤e配制的染浴溶液中浸泡16h;
h.对电极的制备:将H2PtCl6·6H2O溶于异丙醇溶液中,配制成浓度为5 ×10-3M的溶液,然后用注射器吸取溶液滴在清洗干净的所述FTO导电玻璃表面上,并用玻璃棒在表面滚动使之均匀涂覆,自然晾干后放入马弗炉中升温至400℃下烧结20min,此时H2PtCl6因为热分解生成Pt而沉积在导电玻璃表面,降温后将其取出,切割成设定的尺寸置于棕色干燥器中备用;
i.电池的组装:在TiO2电极上盖一个铂电极,两边用夹子固定即形成了待测的开放性敏化染料太阳电池;将步骤d制备的电解液从对电极的小孔中注入;待两个电极之间没有气泡后,将其密封,制得染料敏化太阳能电池。
本发明所制备的染料敏化太阳能电池性能测试:从电池的光阳极和光阴极分别引出导线,接到电池性能测试装置上,电池的工作面积为0.16cm2,用太阳光模拟器模拟太阳光,将光强度调节至100mW/cm2测得的光电转化效率为 6~9%。
本发明以烷氧基苯基为电子供体,二(噻吩并吡咯)并苯并噻二唑为共轭π桥,苯并噻二唑-苯-羧基为电子受体和锚固基团,合成了一系列新型的D-π-A 结构纯有机染料。二(噻吩并吡咯)并苯并噻二唑单元是一个大共轭平面结构,它的引入能够有效地拓宽染料的吸光范围和提高摩尔消光系数,另一方面,其独特的D-A-D结构也有利于π电子离域,促进分子内电荷转移,进而提高了染料敏化太阳电池的光电转换效率。综合这两方面的作用,使得其在染料敏化太阳电池中有很好的应用前景。
与现有技术相比,本发明具有如下优点和技术效果:通过在π桥中引入二 (噻吩并吡咯)并苯并噻二唑大共轭平面可以起到使吸收光谱红移和提高染料摩尔消光系数的效果,提高了敏化太阳电池的光电转换效率。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,根据这些附图获得其他的附图仍属于本发明的范畴;
图1本发明的纯有机染料的合成路线图;
图2为实施例1中所合成的染料在二氯甲烷溶剂中(浓度2×10-5M)紫外/ 可见吸收光谱图;
图3为实施例1中所合成的染料在二氯甲烷溶剂中配成3×10-4M的染浴所测得的J-V曲线图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将结合附图对本发明作进一步地详细描述。
实施例1
基于二(噻吩并吡咯)并苯并噻二唑π桥的纯有机染料H1的合成
(1)化合物2的合成
在氩气的保护下,在一个100mL的二口圆底烧瓶中,以20mL o-DCB为溶剂,往其中加入1.25g(3.20mmol)化合物1,将反应体系升温至180℃反应16 h。冷却至室温后,减压蒸馏除去反应溶剂,残余物用硅胶柱层析分离提纯。石油醚:乙酸乙酯(2:1)为流动相,得到黄色固体产物直接投入下一步反应。取一个100mL的二口圆底烧瓶,依次加入前面制得的黄色固体,3.71g(19.20mmol) 溴代异辛烷,2.43g(32mmol)KOH,100mg(0.62mmol)KI和30mLDMSO 溶剂。反应在氩气保护下,于85℃条件下搅拌反应12h。待反应液冷却至室温后,往反应液中加入30mL去离子水,并用乙酸乙酯萃取多次。萃取合并得到的有机相用无水硫酸镁干燥后旋蒸除去有机溶剂,粗产物用硅胶柱层析进行分离提纯,以石油醚:乙酸乙酯(10:1)为流动相,得到(0.93g)黄色油状产物 2,两步反应的产率为53%。核磁:1H NMR(400MHz,CDCl3)δ7.42(d,J=4.9Hz, 2H),7.17(d,J=5.0Hz,2H),4.56–4.46(m,4H),1.98–1.95(m,2H),1.05–0.99(m, 4H),0.87–0.80(m,12H),0.65–0.63(m,12H).高分辨质谱:HRMS(ESI,m/z):[M+ H]+calcd for C30H39N4S3:551.2331,found:551.2326.
(2)化合物3的合成
在50mL的圆底烧瓶中,将0.21g(0.38mmol)化合物2加入到15mL的四氢呋喃中。用冰水浴将反应降温至0℃,然后将67mg(0.38mmol)NBS一次性加入,加完后在该温度下再搅拌反应2h。反应结束后,往反应液中倒入30mL 蒸馏水,用30mL二氯甲烷萃取,有机层用水洗两次。干燥,浓缩,粗产物用硅胶柱层析分离提纯。丙酮:石油醚(1:30)作为流动相,得到0.22g黄色粘稠状液体。收率为92%。核磁:1H NMR(400MHz,CDCl3)δ7.43(d,J=5.2Hz,1H),7.20(s,1H),7.16(d,J=5.2Hz,1H),4.52–4.39(m,4H),1.95–1.88(m,2H), 1.04–0.97(m,6H),0.93–0.82(m,10H),0.66–0.60(m,12H).高分辨质谱:HRMS (ESI,m/z):[M+H]+calcdfor C30H38 79BrN4S3:629.1436,found:629.1425;calcd for C30H38 81BrN4S3:631.1418,found:631.1406.
(3)化合物5的合成
氩气保护下,在50mL的二口圆底烧瓶中,依次加入150mg(0.24mmol) 化合物3,120mg(0.36mmol)化合物4,0.36mL K2CO3(2M)水溶液,28mg Pd(PPh3)4和20mL THF。将反应液升温至70℃反应16h。反应结束后,待反应液降至常温后,往二口瓶中加入30mL水,用60mL二氯甲烷萃取。合并的有机相用水洗涤两次,干燥,浓缩,粗产物用硅胶柱层析分离提纯,以丙酮:石油醚(1:30)作为流动相,得到141mg淡黄色粘稠状液体5。产率:78%。核磁:1H NMR(400MHz,CDCl3)δ7.66(d,J=8.6Hz,2H),7.42(d,J=5.2Hz,1H),7.28 (s,1H),7.17(d,J=5.2Hz,1H),6.98(d,J=8.6Hz,2H),4.56–4.46(m,4H), 3.93–3.86(m,2H),2.03–1.95(m,2H),1.80–1.73(m,1H),1.56–1.42(m,4H), 1.36–1.34(m,4H),1.06–1.03(m,6H),0.97–0.82(m,16H),0.67–0.62(m,12H).高分辨质谱:HRMS(ESI,m/z):[M+H]+calcd forC55H59N4OS3:755.3846,found: 755.3840.
(4)化合物6的合成
在50mL的圆底烧瓶中,将0.20g(0.27mmol)化合物5加入到15mL的四氢呋喃中。用冰水浴将反应降温至0℃,然后将48mg(0.27mmol)NBS一次性加入,加完后在该温度下再搅拌2h。反应结束后,往反应液中倒入30mL蒸馏水,用30mL二氯甲烷萃取,有机层用水洗两次。合并的有机相用无水硫酸镁干燥,旋蒸除去有机溶剂,粗产物用硅胶柱层析分离提纯。丙酮:石油醚(1:25) 作为流动相,得到0.22g黄色粘稠状液体6。收率为92%。核磁:1H NMR(400MHz, CDCl3)δ7.65(d,J=7.6Hz,2H),7.27(s,1H),7.21(s,1H),6.98(d,J=8.7Hz,2H), 4.53–4.40(m,4H),3.90(d,J=5.4Hz,2H),2.03–1.92(m,2H),1.79–1.73(m,1H),1.57–1.40(m,4H),1.36–1.32(m,4H),1.10–1.01(m,6H),0.95–0.84(m,16H), 0.68–0.62(m,12H).高分辨质谱:HRMS(ESI,m/z):[M+H]+calcd for C44H58 79BrN4OS3:833.2951,found:833.2936;calcd for C44H58 81BrN4OS3:835.2937, found:835.2917.
(5)化合物7的合成
氩气保护下,在50mL的二口圆底烧瓶中,依次加入350mg(0.42mmol) 化合物6,306.4mg(1.68mmol)三异丙基硅基乙炔,7.69mg(0.042mmol)碘化亚铜,5.0mL三乙胺,29.5mg(0.042mmol)Pd(PPh3)4和15mL干燥THF。油浴升温至60℃反应24h。反应结束并冷却至常温后,旋蒸除去有机溶剂,残余物用硅胶柱层析分离提纯,以丙酮:石油醚=1:35为洗脱剂。真空干燥后得到369mg红色粘稠状液体7,产率为94%。核磁:1H NMR(500MHz,CDCl3)δ7.67–7.66(m,2H),7.32–7.29(m,2H),6.99–6.98(m,2H),4.57–4.47(m,4H),3.91 (m,2H),2.02(m,2H),1.77–1.76(m,1H),1.50–1.45(m,2H),1.36(m,4H),1.20(s, 21H),1.07(m,6H),0.96–0.88(m,18H),0.66(m,12H).高分辨质谱:HRMS(ESI, m/z):[M+H]+calcd forC55H79N4OS3Si:935.5180,found:935.5176.
(6)化合物9的合成
在50mL的二口圆底烧瓶中加入375mg(0.40mmol)化合物7和20mL THF,抽真空氩气保护,然后再用注射器注入2.0mL TBAF(1M in THF)。将反应置于常温下搅拌反应0.5h,往反应液中加入20mL去离子水淬灭反应,然后用20mL二氯甲烷萃取。合并的有机相用无水硫酸镁干燥,旋蒸除去有机溶剂,得到的红色残余物直接投入到下一步反应。取一个100mL二口圆底烧瓶,氩气保护下,往二口瓶中依次加入上述所得的红色产物,552mg(1.60mmol) 化合物8,10mL三乙胺,200mg(0.65mmol)三苯基砷,30mL THF和100mg 催化剂Pd(dba)3。将混合液升温至70℃搅拌反应5h,反应结束待反应液温度降至常温后,用旋蒸仪旋蒸除去反应溶剂,粗产物用硅胶柱层析进行分离提纯,以石油醚:乙酸乙酯:二氯甲烷=20:1:4为洗脱剂。真空干燥后得到217mg紫色固体9,两步反应的产率为52%。核磁:1H NMR(400MHz,CDCl3)δ8.22(d,J =8.3Hz,2H),8.08(d,J=8.3Hz,2H),7.95(d,J=7.4Hz,1H),7.80(d,J=7.4Hz, 1H),7.66(d,J=8.6Hz,2H),7.55(s,1H),7.28(s,1H),6.99(d,J=8.6Hz,2H),4.56–4.46(m,4H),3.98(s,3H),3.94–3.88(m,2H),2.06–1.98(m,2H),1.78–1.74 (m,1H),1.57–1.41(m,6H),1.37–1.31(m,4H),1.10–1.02(m,6H),0.96–0.91(m, 14H),0.69–0.65(m,12H).高分辨质谱:HRMS(ESI,m/z):[M+H]+calcd for C60H67N6O3S4:1047.4152,found:1047.4144.
(7)染料H1的合成
在50mL的圆底烧瓶中依次加入80mg(0.076mmol)化合物9,16mL 20%的氢氧化钠水溶液,25mL THF和15mL甲醇。添加完毕后将反应液升温至40℃搅拌反应2h,反应结束后往反应混合液中加入30mL去离子水并用乙醚萃取,再用20mL的HCl溶液洗涤两次。有机相用无水硫酸镁干燥,用旋蒸仪旋蒸除去有机溶剂,粗产物用硅胶柱层析进行分离提纯,以二氯甲烷:甲醇=30:1为洗脱剂。真空干燥后得到73mg目标染料H1,反应产率为:93%。核磁:1HNMR (500MHz,CDCl3)δ8.29(d,J=7.0Hz,2H),8.12(d,J=6.9Hz,2H),7.95(d,J=7.0 Hz,1H),7.82(d,J=7.0Hz,1H),7.67–7.65(m,2H),7.55(s,1H),7.28(s,1H),6.99(d, J=7.9Hz,2H),4.56–4.48(m,4H),3.92–3.91(m,2H),2.03–2.02(m,2H), 1.78–1.75(m,1H),1.59–1.54(m,4H),1.35–1.34(m,4H),1.11–1.08(m,6H), 0.96–0.91(m,16H),0.69–0.67(m,12H).高分辨质谱:HRMS(ESI,m/z):[M+H]+ calcd for C59H65N6O3S4:1033.3996,found:1033.3985.
实施例2
对实施例1的紫外-可见吸收光谱测试,紫外-可见吸收光谱如图2所示。
溶剂:二氯甲烷
浓度:2×10-5M
温度:室温
仪器:Shimadzu UV-2450紫外可见分光光度计
将所得的数据汇总于表1中
表1实施例1染料的紫外可见光谱数据
实施例3
本发明中染料敏化太阳电池的制作如下:
a.导电玻璃(FTO)的预处理:将导电玻璃依次在去油剂、无水乙醇和去离子水中用超声波充分清洗,然后烘干备用;
b.TiO2纳晶颗粒及其浆料的制备:室温下,10mL Ti(OBu)4和20mL EtOH 的混合液搅拌10分钟后,剧烈搅拌下于上述溶液中加入18mL乙酸和50mL去离子水并维持搅拌1h,然后将此混合液移入高压釜于230℃下处理12h,自然冷却至室温,将所得悬浊液过滤,分别用去离子水和乙醇洗涤多次,50℃下于烘箱中烘6h至干,得到粒径约为20nm的TiO2纳晶颗粒;
c.取TiO2纳晶颗粒1.0g,分别加入乙醇8.0mL、乙酸0.2mL、松油醇3.0g、乙基纤维素0.5g,将此混合物充分研磨40min,然后泥浆物经超声作用15min 后得到所需的白色粘性TiO2纳晶浆料;
d.纳米晶TiO2膜的制备:将处理好的导电玻璃导电面朝上,将丝网板放置于玻璃上方,控制1cm的网距,再将TiO2纳晶浆料置于丝网上进行印刷。每次印刷的TiO2膜需放入125℃的烘箱内烘烤5分钟,以便有机溶剂挥发。单次印刷的TiO2膜厚度约为4μm,重复数次得到厚度约16μm的TiO2膜。将制备好的TiO2膜放于马弗炉中依次在不同的温度下处理(325℃烘焙5min,375℃烘焙5min,375℃烘焙5min,450℃烘焙15min,500℃烘焙15min),而后将烘焙好的TiO2浸于70℃0.04M的TiCl4水溶液中处理30min。将处理结束的TiO2膜取出并用去离子水反复冲洗干净后,置于马弗炉中升温520℃再次烘焙30min,冷至室温后置于密封袋并存于干燥器中备用;
e.染料溶液的配制:将权利要求1所述的共轭三苯胺染料溶于四氢呋喃和二氯甲烷(体积比1:1)中,配制成3×10-4mol·L-1染浴溶液;
f.电解质溶液的配制:用乙睛和戊腈(体积比85:15)配制的含有0.6M 1- 甲基-3-丙基碘化咪唑嗡,0.1M硫氰酸胍,0.03M I2和0.5M对叔丁基吡啶的溶液;
g.光阳极的敏化:通过步骤d制备的光阳极纳米多孔TiO2薄膜层浸染在权利要求1所述的按步骤e配制的染料中;
h.对电极的制备:将H2PtCl6·6H2O溶于异丙醇溶液中,配制成浓度为5×10-3 M的溶液,然后将配好的液体小心的滴在干净的导电玻璃表面上,并用玻棒轻轻滚动使之均匀涂覆在表面,将其自然晾干后置于马弗炉中400℃下烧结15 min,此时H2PtCl6由于热分解生成Pt而沉积在导电玻璃表面,降温后将其取出,切割成所需尺寸并浸泡于无水乙醇中备用;
i.在TiO2电极上盖一个铂电极,两边用夹子固定即形成了待测的开放性敏化染料太阳电池。将步骤d制备的电解液从对电极的小孔中注入;待两个电极之间没有气泡后,将其密封,制得染料敏化太阳电池。
实施例4
染料敏化太阳电池性能测试:
按照实施例3中的电池制备步骤,分别以实施例1合成的染料组装成电池,分别从光阳极和光阴极引出导线,接到电池性能测试装置上,电池的工作面积为0.16cm2时,用太阳光模拟器模拟太阳光,将光强度调节至100mW/cm2分别测其光电转化效率。
将所测得的J-V曲线图如图3所示,数据汇总于表2。
表2实施例1染料用于染料敏化太阳电池性能数据
以上所揭露的仅为本发明较佳实施例而已,当然不能以此来限定本发明之权利范围,因此依本发明权利要求所作的等同变化,仍属本发明所涵盖的范围。
Claims (5)
2.根据权利要求1所述的纯有机染料,其特征在于:R=iC8H17,R1=O-iC8H17,X=S。
3.一种基于权利要求1所述的纯有机染料在光敏染料的应用,其特征在于:将该纯有机染料作为光敏染料,应用于将太阳能转变成电能。
4.一种基于权利要求1所述的纯有机染料在染料敏化太阳能电池中的应用,其特征在于:该染料敏化太阳能电池包括有光阳极、对电极、导电玻璃和电解质;
所述的导电玻璃为FTO导电玻璃,FTO导电玻璃导电一侧中间铺上纳米晶多孔TiO2薄膜,该纳米晶多孔TiO2薄膜吸附权利要求1所述基于二(噻吩并吡咯)并苯并噻二唑π桥的纯有机染料,构成光阳极,该纯有机染料作为光敏染料,将太阳能转变成电能;对电极为导电玻璃导电一侧中间铺上的Pt催化剂层;光阳极和对电极相对间隔设置,所述纳米晶多孔TiO2薄膜周边用密封材料密封形成密闭的腔体,腔体内填充有电解质。
5.一种染料敏化太阳能电池的制备方法,其特征在于包括有以下步骤:
a.FTO导电玻璃的预处理:对FTO导电玻璃进行表面清洗并干燥备用;
b.TiO2纳米晶颗粒的制备:室温下,将20mL EtOH和15mL Ti(OBu)4混合,在搅拌条件下,于上述溶液中加入35mL乙酸和20mL蒸馏水并继续搅拌1h,然后将此混合液移入高压反应釜中并置于230℃下处理12h,冷却至室温后,将所得悬浊液过滤,分别用无水乙醇和蒸馏水洗涤多次,所得固体置于烘箱中升温至50℃烘6h,得到粒径为20nm±2的TiO2纳米晶颗粒;
c.称取TiO2纳米晶颗粒1.0g于一小烧杯中,分别加入乙基纤维素0.5g、松油醇3.0g、无水乙醇10.0mL、冰乙酸0.2mL,将此混合物用玻璃棒搅拌并充分研磨30min,然后泥浆物在超声仪中作用20min后即得到所需的白色粘性的TiO2纳米晶浆料;
d.纳米晶TiO2膜的制备:将步骤a预处理后的导电玻璃导电面朝上,将丝网板放置于玻璃上方,控制网距为1cm,再将TiO2纳米晶浆料置于丝网上进行印刷,每次印刷的TiO2膜需放入100℃的烘箱中烘烤5min使有机溶剂充分挥发;一次印刷的TiO2薄膜厚度约为4μm,再重复3次上述操作即可得到约16μm厚度的TiO2薄膜;将制备好的TiO2膜置于马弗炉中依次在如下不同的温度下处理:升温至325℃烘焙5min,再升温至375℃烘焙5min,再升温至450℃烘焙15min,最后升温至500℃烘焙15min,冷却至室温后将烘好的TiO2薄膜浸于0.04M的TiCl4水溶液,在放入70℃的真空干燥箱中处理30min;将处理结束的TiO2膜取出并用蒸馏水反复冲洗干净后,置于马弗炉中升温至500℃再次烘焙30min,冷至室温后保存在棕色干燥器中备用;
e.光敏染浴溶液的配置:将权利要求1所述的纯有机染料溶于二氯甲烷溶剂中,配制成3×10-4M的光敏染浴溶液;
f.电解质溶液的配制:用乙睛和戊腈配制的含有0.1M硫氰酸胍,0.6M1-甲基-3-丙基碘化咪唑嗡,0.03MI2和0.5M对叔丁基吡啶的溶液;
g.光阳极的敏化:在黑暗条件下,步骤d制备的作为光阳极的纳米晶TiO2膜浸入步骤e配制的染浴溶液中浸泡16h;
h.对电极的制备:将H2PtCl6·6H2O溶于异丙醇溶液中,配制成浓度为5×10-3M的溶液,然后用注射器吸取溶液滴在清洗干净的所述FTO导电玻璃表面上,并用玻璃棒在表面滚动使之均匀涂覆,自然晾干后放入马弗炉中升温至400℃下烧结20min,此时H2PtCl6因为热分解生成Pt而沉积在导电玻璃表面,降温后将其取出,切割成设定的尺寸置于棕色干燥器中备用;
i.电池的组装:在TiO2电极上盖一个铂电极,两边用夹子固定即形成了待测的开放性敏化染料太阳电池;将步骤f制备的电解质溶液从对电极的小孔中注入;待两个电极之间没有气泡后,将其密封,制得染料敏化太阳能电池。
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