CN112574396A - 一种2-氟苯基芴与吡咯并吡咯二酮共聚物光伏材料、制备方法和应用 - Google Patents
一种2-氟苯基芴与吡咯并吡咯二酮共聚物光伏材料、制备方法和应用 Download PDFInfo
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- -1 2-fluoro-4- (2-octyldodecyloxy) benzaldehyde Chemical compound 0.000 claims description 44
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 25
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Abstract
Description
技术领域
本发明属于聚合物光伏材料技术领域,具体是涉及到一种2-氟苯基芴与吡咯并吡咯二酮共聚物光伏材料、制备方法和应用。
背景技术
在过去的二十年中,聚合物太阳能电池(PSCs)受到人们的广泛关注,主要是由于聚合物太阳能电池具有制备工艺简单、质量轻、成本低廉、容易制备大面积柔性器件等优点[Huifeng Yao,Long Ye,Hao Zhang,Sunsun Li,Shaoqing Zhang,and JianhuiHou.Chem.Rev.2016,116,7397-7457.]。设计和合成新的共轭聚合物在PSCs的发展过程中扮演着一个重要的角色。共轭聚合物由给体(D)和受体(A)单元组成,通过改变不同的给受单元很容易调节聚合物的性能,因此被广泛运用到PSCs上。选择合适的给体(D)和受体(A)单元是制备高能量转换效率D-A共聚物的关键。
发明内容
本发明要解决的技术问题是提供一种2-氟苯基芴与吡咯并吡咯二酮共聚物光伏材料、制备方法和应用,其具有良好的光电转换效率。
基于上述目的,本发明提供的一种2-氟苯基芴与吡咯并吡咯二酮共聚物光伏材料,该聚合物光伏材料的结构如式(Ⅰ)所示:
其中,R为烷基,n为10-30。
式(Ⅰ)所示的化合物为9-(4-(2-辛基十二烷氧基)-2-氟-苯基亚甲基)-2,7-芴-3’,6’-二(呋喃基)-2’,5’-二(烷基)-吡咯并吡咯二酮。
在本发明中,优选的,R为8~20个碳原子的直链或支链烷烃。
在本发明中,进一步优选的,所述R选自以下基团中的一种:
本发明提供的一种2-氟苯基芴与吡咯并吡咯二酮共聚物光伏材料具有良好的可加工性,并且经过初步尝试证明具有较好的光电转换特性,作为聚合物太阳能电池的工作介质有着广阔的应用前景。
进一步的,本发明还提供了一种所述的2-氟苯基芴与吡咯并吡咯二酮共聚物光伏材料的制备方法,包括以下步骤:
1)2-氟-4-羟基苯甲醛与碱性试剂(优选为氢氧化钠)混合在有机溶剂(优选为DMF)中,搅拌,滴加溴代-2-辛基十二烷,在60-80℃(优选为70℃)条件下反应,反应10-14h(优选为12小时),冷却至室温,将混合物倒入水中,萃取,干燥,旋干溶剂,过滤(优选为过硅胶柱),得到2-氟-4-(2-辛基十二烷氧基)苯甲醛;
2)优选氮气保护下,将2,7-二溴芴加入到无水乙醇中,搅拌,然后加入叔丁醇钾,继续搅拌,升温至50-65℃(优选为60℃),加入2-氟-4-(2-辛基十二烷氧基)苯甲醛,反应,反应6-10h(优选为8小时),将混合物倒入水中,萃取,干燥,旋干溶剂,过硅胶柱,得到9-(2-氟-4-(2-辛基十二烷氧基)苯基亚甲基)-2,7-二溴芴;
3)优选氮气保护下,将2,5-二烷基-3,6-二(5-(三甲基锡基)呋喃)-2-吡咯并吡咯二酮与9-(2-氟-4-(2-辛基十二烷氧基)苯基亚甲基)-2,7-二溴芴加入到无水甲苯中,再加入(四(三苯基膦)钯),100-115℃(优选115℃)下反应40-50h(优选48h),冷却至室温,沉析,过滤,索氏提取,得到2-氟苯基芴与吡咯并吡咯二酮共聚物光伏材料;
上述2,5-二烷基-3,6-二(5-(三甲基锡基)呋喃)-2-吡咯并吡咯二酮包括2,5-二(异辛基)-3,6-二(5-(三甲基锡基)呋喃)-2-吡咯并吡咯二酮、2,5-二(正辛基)-3,6-二(5-(三甲基锡基)呋喃)-2-吡咯并吡咯二酮或2,5-二(2-辛基十二烷基)-3,6-二(5-(三甲基锡基)呋喃)-2-吡咯并吡咯二酮。
其中,2-氟-4-(2-辛基十二烷氧基)苯甲醛的结构式如下式(1)所示:
9-(2-氟-4-(2-辛基十二烷氧基)苯基亚甲基)-2,7-二溴芴的结构式如下式(2)所示:
2,5-二(异辛基)-3,6-二(5-(三甲基锡基)呋喃)-2-吡咯并吡咯二酮的结构式如下式(3)所示:
2,5-二(正辛基)-3,6-二(5-(三甲基锡基)呋喃)-2-吡咯并吡咯二酮的结构式如下式(4)所示:
2,5-二(2-辛基十二烷基)-3,6-二(5-(三甲基锡基)呋喃)-2-吡咯并吡咯二酮的结构式如下式(5)所示:
本发明目标化合物(Ⅰ)的合成路线如下:
在本发明中,优选的,步骤1)中所述2-氟-4-羟基苯甲醛与溴代-2-辛基十二烷的摩尔比为1:1.0~1.3。
在本发明中,优选的,步骤2)中所述2,7-二溴芴与2-氟-4-(2-辛基十二烷氧基)苯甲醛的摩尔比为1:1.0~1.5,反应温度为50~65℃。
在本发明中,优选的,步骤3)中所述9-(2-氟-4-(2-辛基十二烷氧基)苯基亚甲基)-2,7-二溴芴与2,5-二(异辛基)-3,6-二(5-(三甲基锡基)呋喃)-2-吡咯并吡咯二酮的摩尔比为1:1,反应温度为100~115℃,反应时间为48小时。
在本发明中,优选的,步骤3)中所述9-(2-氟-4-(2-辛基十二烷氧基)苯基亚甲基)-2,7-二溴芴与2,5-二(正辛基)-3,6-二(5-(三甲基锡基)呋喃)-2-吡咯并吡咯二酮的摩尔比为1:1,反应温度为100~115℃,反应时间为48小时。
在本发明中,优选的,步骤3)中所述9-(2-氟-4-(2-辛基十二烷氧基)苯基亚甲基)-2,7-二溴芴与2,5-二(2-辛基十二烷基)-3,6-二(5-(三甲基锡基)呋喃)-2-吡咯并吡咯二酮的摩尔比为1:1,反应温度为100~115℃,反应时间为48小时。
本发明提供的一系列2-氟苯基芴与吡咯并吡咯二酮类共聚物光伏材料的制备方法是采用Stille偶联的方法,将DPP电子受体单元与2-氟苯基芴电子给体单元直接偶联而成。
本发明合成了一种含有二维共轭侧链的芴电子给体单元,通过Stille偶联的方法,将芴单元通过碳-碳单键与另一个电子受体体单元DPP相连接,得到2-氟苯基芴与吡咯并吡咯二酮类共聚物光伏材料。它们在常见的有机溶剂(如甲苯、氯苯、二氯苯等)中有良好的溶解性,可以用溶液旋涂的方法制备高质量的聚合物薄膜。同时,这些聚合物光伏材料具有宽的可见光-近红外区吸收,合适的HOMO以及LUMO能级和相对较窄的带隙。以此类聚合物为电子给体、有机小分子为电子受体制备了聚合物太阳能电池,其最高能量转换效率可达到5.65%,具有良好的光电转换效率。
因此,更进一步的,本发明还提供了所述的2-氟苯基芴与吡咯并吡咯二酮类共聚物光伏材料在太阳能电池中的应用。
在本发明中,优选的,所述2-氟苯基芴与吡咯并吡咯二酮类共聚物光伏材料用作太阳能电池电子给体材料。
本发明用上述2-氟苯基芴与吡咯并吡咯二酮类共聚物光伏材料为电子给体材料,应用于聚合物太阳能电池,其制备方法如下:
将本发明的2-氟苯基芴与吡咯并吡咯二酮类共聚物电子给体材料与电子受体(有机小分子)物质共混,加入氯苯,使混合物充分溶解,旋涂在导电玻璃ITO上制备出导电薄膜,然后在薄膜上蒸镀金属铝电极。
本发明提供的2-氟苯基芴与吡咯并吡咯二酮类共聚物光伏材料具有宽的吸收光谱和合适的电化学能级,并用核磁共振谱、质谱和元素分析的方法表征了各步合成产物的分子结构。用紫外-可见吸收光谱研究了2-氟苯基芴与吡咯并吡咯二酮类共聚物光伏材料的光学性能。用循环伏安法研究了2-氟苯基芴与吡咯并吡咯二酮类共聚物光伏材料的电化学性能。并以其作为电子给体做成了太阳能电池器件,获得了良好的光电转换效率。
与现有技术相比,本发明具有以下有益效果:
(1)本发明合成的路线简单,成本低,且合成方法具有普适性,可以较好的推广应用到其他的芴类光伏材料的合成。
(2)本发明的2-氟苯基芴与吡咯并吡咯二酮类聚合物光伏材料在可见-近红外光区具有较宽的光学吸收,能够保障吸收足够多的太阳光子,获得高的光电流。
(3)本发明的2-氟苯基芴与吡咯并吡咯二酮类聚合物光伏材料具有较为平面的共轭结构,有利于载流子的分离与传输,从而获得较高的填充因子。
(4)本发明用2-氟苯基芴与吡咯并吡咯二酮类共聚物光伏材料为电子给体材料,应用于聚合物太阳能电池获得了较高的能量转换效率(PCE=5.65%),具有良好的应用前景。
在本发明中,我们通过优化给体或受体单元的结构可以很好地改变吸收范围、电化学能级和活性层形貌,从而大大提高能量转换效率。与侧链为柔性链的芴类聚合物相比,二维共轭的芴类聚合物具有更好的平面结构和共轭长度,可以显著的改善和提高聚合物的吸收光谱和载流子迁移率,因此,采用共轭结构的苯环作为侧链,来取代烷基侧链是一个非常好的途径。
本发明合成了2-氟苯基芴电子给体单元,并与含有不同柔性侧链的DPP电子受体单体,采用Stille偶联的方法制备了一类二维共轭2-氟苯基芴类共聚物太阳能电池材料,对它们进行了光学和电化学等表征,并对其在太阳能电池上的应用进行了研究。
附图说明
图1为本发明2-氟苯基芴与吡咯并吡咯二酮类共聚物光伏材料的吸收光谱图;
图2为本发明2-氟苯基芴与吡咯并吡咯二酮类共聚物光伏材料的电化学分析图;
图3为本发明2-氟苯基芴与吡咯并吡咯二酮类共聚物光伏材料的光电转换效率图;
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明白,以下结合具体实施例,并参照附图,对本发明进一步详细说明。
本发明2-氟苯基芴与吡咯并吡咯二酮类共聚物光伏材料的合成路线如下所示:
实施例1 9-(4-(2-辛基十二烷氧基)-2-氟-苯基亚甲基)-2,7-芴-2’,5’-二(异辛基)-3’,6’-二(呋喃基)-2’-吡咯并吡咯二酮(P1)的制备
具体步骤如下:
①化合物1的合成
将2-氟-4-羟基苯甲醛(14.0g,100mmol),氢氧化钠(6.0g,150mmol)和DMF(150mL)置于250mL的三口烧瓶中,溴代-2-辛基十二烷基(43.3g,120mmol)在60分钟内逐滴加入上面的反应液中,完毕后,反应混合溶液在100℃下搅拌反应24小时后,冷却至室温,反应物倾入水中,用二氯甲烷萃取,无水硫酸镁干燥有机相,过滤,旋干溶剂,用石油醚/二氯甲烷=10/1作为淋洗液经硅胶层析柱分离得到无色液体化合物1(37.9g,产率:90%)。
化合物1的核磁共振谱、质谱如下所示:
1H NMR(δ/ppm,CDCl3):9.87(s,1H),7.83(d,1H),6.90(d,2H),3.82(d,2H),1.77(m,1H),1.46-1.25(m,32H),0.90(t,6H).
GC-MS:m/z=421.
②化合物2的合成
氮气保护下,将2,7-二溴芴(1.3g,4.0mmol)与无水乙醇(60mL)加入150mL三口圆底烧瓶中,搅拌,再加入t-BuOK(0.9g,8.0mmol),升温至60℃继续搅拌一小时后,然后加入化合物1(2.5g,6.0mmol),反应12小时,停止反应,冷却至室温,反应物倾入水中,用二氯甲烷萃取,无水硫酸镁干燥有机相,过滤,旋干溶剂,粗产物用石油醚/二氯甲烷=10/1作为淋洗液经硅胶层析柱分离得到目标产物化合物2(2.1g,产率:74%)。
化合物2的核磁共振谱、质谱如下所示:
1H NMR(δ/ppm,CDCl3):8.04(s,1H),7.81(s,1H),7.56(s,1H),7.49-7.34(m,8H),7.21(d,2H),7.11(t,1H),6.92(d,2H),3.68(d,2H),1.87(s,1H),1.42-1.21(m,32H),0.88(t,6H).
GC-MS:m/z=727.
③聚合物P1的合成
氮气保护下,将等摩尔量的化合物2和2,5-二(异辛基)-3,6-二(5-(三甲基锡基)呋喃)-2-吡咯并吡咯二酮(0.15mmol,购买于无锡赛乐光电材料科技有限公司)加入到15mL无水甲苯中,再加入Pd(PPh3)4(15mg),115℃下搅拌反应48小时后,冷却至室温,倒入200ml甲醇中沉析,过滤,粗产物经过甲醇、正己烷和三氯甲烷一次抽提,得到绿色固体P1(64mg,产率40%);其中聚合物P1中R基团如下所示:
聚合物P1的凝胶渗透色谱分析如下所示:
Mn=13,700,Mw=30,900,PDI=2.26.
实施例2 9-(4-(2-辛基十二烷氧基)-2-氟-苯基亚甲基)-2,7-芴-2’,5’-二(正辛基)-3’,6’-二(呋喃基)-2’-吡咯并吡咯二酮(P2)的制备
化合物2的合成方法与实施例1中化合物2的合成方法相同,溴代烷烃采用溴代正辛烷,具体步骤如下:
①化合物1的合成
将2-氟-4-羟基苯甲醛(14.0g,100mmol),氢氧化钠(6.0g,150mmol)和DMF(150mL)置于250mL的三口烧瓶中,溴代-2-辛基十二烷基(43.3g,120mmol)在60分钟内逐滴加入上面的反应液中,完毕后,反应混合溶液在100℃下搅拌反应24小时后,冷却至室温,反应物倾入水中,用二氯甲烷萃取,无水硫酸镁干燥有机相,过滤,旋干溶剂,用石油醚/二氯甲烷=10/1作为淋洗液经硅胶层析柱分离得到无色液体化合物1(37.9g,产率:90%)。
化合物1的核磁共振谱、质谱如下所示:
1H NMR(δ/ppm,CDCl3):9.87(s,1H),7.83(d,1H),6.90(d,2H),3.82(d,2H),1.77(m,1H),1.46-1.25(m,32H),0.90(t,6H).
GC-MS:m/z=421.
②化合物2的合成
氮气保护下,将2,7-二溴芴(1.3g,4.0mmol)与无水乙醇(60mL)加入150mL三口圆底烧瓶中,搅拌,再加入t-BuOK(0.9g,8.0mmol),升温至60℃继续搅拌一小时后,然后加入化合物1(2.5g,6.0mmol),反应12小时,停止反应,冷却至室温,反应物倾入水中,用二氯甲烷萃取,无水硫酸镁干燥有机相,过滤,旋干溶剂,粗产物用石油醚/二氯甲烷=10/1作为淋洗液经硅胶层析柱分离得到目标产物化合物2(2.1g,产率:74%)。
化合物2的核磁共振谱、质谱如下所示:
1H NMR(δ/ppm,CDCl3):8.04(s,1H),7.81(s,1H),7.56(s,1H),7.49-7.34(m,8H),7.21(d,2H),7.11(t,1H),6.92(d,2H),3.68(d,2H),1.87(s,1H),1.42-1.21(m,32H),0.88(t,6H).
GC-MS:m/z=727.
③聚合物P2的合成
氮气保护下,将等摩尔量的化合物2和2,5-二(正辛基)-3,6-二(5-(三甲基锡基)呋喃)-2-吡咯并吡咯二酮(0.15mmol,购买于无锡赛乐光电材料科技有限公司)加入到15mL无水甲苯中,再加入Pd(PPh3)4(15mg),115℃下搅拌反应48小时后,冷却至室温,倒入200ml甲醇中沉析,过滤,粗产物经过甲醇、正己烷和三氯甲烷一次抽提,得到绿色固体P2(57mg,产率36%);其中聚合物P2中R基团如下所示:
聚合物P2的凝胶渗透色谱分析如下所示:
Mn=8,900,Mw=23,600,PDI=2.65.
实施例3 9-(4-(2-辛基十二烷氧基)-2-氟-苯基亚甲基)-2,7-芴-2’,5’-二(2-辛基十二烷基)-3’,6’-二(呋喃基)-2’-吡咯并吡咯二酮(P3)的制备
化合物2的合成方法与实施例1中化合物2的合成方法相同,溴代烷烃采用溴代2-辛基-十二烷,具体步骤如下:
①化合物1的合成
将2-氟-4-羟基苯甲醛(14.0g,100mmol),氢氧化钠(6.0g,150mmol)和DMF(150mL)置于250mL的三口烧瓶中,溴代-2-辛基十二烷基(43.3g,120mmol)在60分钟内逐滴加入上面的反应液中,完毕后,反应混合溶液在100℃下搅拌反应24小时后,冷却至室温,反应物倾入水中,用二氯甲烷萃取,无水硫酸镁干燥有机相,过滤,旋干溶剂,用石油醚/二氯甲烷=10/1作为淋洗液经硅胶层析柱分离得到无色液体化合物1(37.9g,产率:90%)。
化合物1的核磁共振谱、质谱如下所示:
1H NMR(δ/ppm,CDCl3):9.87(s,1H),7.83(d,1H),6.90(d,2H),3.82(d,2H),1.77(m,1H),1.46-1.25(m,32H),0.90(t,6H).
GC-MS:m/z=421.
②化合物2的合成
氮气保护下,将2,7-二溴芴(1.3g,4.0mmol)与无水乙醇(60mL)加入150mL三口圆底烧瓶中,搅拌,再加入t-BuOK(0.9g,8.0mmol),升温至60℃继续搅拌一小时后,然后加入化合物1(2.5g,6.0mmol),反应12小时,停止反应,冷却至室温,反应物倾入水中,用二氯甲烷萃取,无水硫酸镁干燥有机相,过滤,旋干溶剂,粗产物用石油醚/二氯甲烷=10/1作为淋洗液经硅胶层析柱分离得到目标产物化合物2(2.1g,产率:74%)。
化合物2的核磁共振谱、质谱如下所示:
1H NMR(δ/ppm,CDCl3):8.04(s,1H),7.81(s,1H),7.56(s,1H),7.49-7.34(m,8H),7.21(d,2H),7.11(t,1H),6.92(d,2H),3.68(d,2H),1.87(s,1H),1.42-1.21(m,32H),0.88(t,6H).
GC-MS:m/z=727.
③聚合物P3的合成
氮气保护下,将等摩尔量的化合物2和2,5-二(2-辛基十二烷基)-3,6-二(5-(三甲基锡基)呋喃)-2-吡咯并吡咯二酮(0.15mmol,购买于无锡赛乐光电材料科技有限公司)加入到15mL无水甲苯中,再加入Pd(PPh3)4(15mg),115℃下搅拌反应48小时后,冷却至室温,倒入200ml甲醇中沉析,过滤,粗产物经过甲醇、正己烷和三氯甲烷一次抽提,得到绿色固体P3(111mg,产率53%);其中聚合物P3中R基团如下所示:
聚合物P3的凝胶渗透色谱分析如下所示:
Mn=17,200,Mw=45,100,PDI=2.62.
实施例4聚合物太阳能电池的制备
本发明以2-氟苯基芴与吡咯并吡咯二酮类共聚物作为工作介质,制备太阳能电池的方法是:将上述2-氟苯基芴与吡咯并吡咯二酮类共聚物材料与适量的有机小分子电子受体混合,加入适量的溶剂溶解,通过常规的旋涂在ITO(氧化铟锡)导电玻璃上制备出一层半透明的薄膜,然后通过真空蒸镀的方式在光伏活性层上制备金属电极。
具体步骤为:2.0mg的聚合物P1与3.0mg的SFBRCN混合,加入0.2mL二氯苯溶解,通过旋涂方式在经PEDOT:PSS修饰过的导电玻璃上制备出一层约110nm厚的薄膜,然后通过真空蒸镀的方式用铝/氟化锂在光伏活性层上制备金属电极。其聚合物太阳能电池器件性能表现为:
短路电流=14.76mA/cm2;开路电压=0.89V;填充因子=0.43;
模拟太阳光(A.M.1.5,100mW/cm2)下的能量转换效率=5.65%。
实施例5聚合物太阳能电池的制备
2.0mg的聚合物P2与3.0mg的SFBRCN混合,加入0.2mL二氯苯溶解,通过旋涂方式在经PEDOT:PSS修饰过的导电玻璃上制备出一层约110nm厚的薄膜,然后通过真空蒸镀的方式用铝/氟化锂在光伏活性层上制备金属电极。其聚合物太阳能电池器件性能表现为:
短路电流=13.72mA/cm2;开路电压=0.87V;填充因子=0.45;
模拟太阳光(A.M.1.5,100mW/cm2)下的能量转换效率=5.37%。
实施例6聚合物太阳能电池的制备
2.0mg的聚合物P3与3.0mg的SFBRCN混合,加入0.2mL二氯苯溶解,通过旋涂方式在经PEDOT:PSS修饰过的导电玻璃上制备出一层约110nm厚的薄膜,然后通过真空蒸镀的方式用铝/氟化锂在光伏活性层上制备金属电极。其聚合物太阳能电池器件性能表现为:
短路电流=13.53mA/cm2;开路电压=0.86V;填充因子=0.44;
模拟太阳光(A.M.1.5,100mW/cm2)下的能量转换效率=5.12%。
实施例7
以聚合物P1为例,对其进行吸收光谱分析、电化学性能分析、光伏性能分析。
①聚合物P1的光谱分析
聚合物P1在溶液状态下的吸收光谱如图1所示,在实施例7所制备的溶液状态下,聚合物P1在300~770nm范围内对光有明显吸收,光学帯隙为1.61eV,说明聚合物P1是窄帯隙光伏材料,可以吸收更多的太阳光,获得高的短路电流。较窄的能隙主要归因于2-氟苯基芴电子给体单元引入到A-D型聚合物中,形成了分子内电荷转移态,从而降低带隙,达到更宽的吸光范围。这类二维共轭的DPP类聚合物光伏材料在太阳能电池的制备中有着广阔的应用前景。
②聚合物P1的电化学性能
在电化学中,循环伏安法通常被用来测定物质的起始氧化和还原电位,进而计算得到相应的HOMO和LUMO能级。图2是P1在0.1mol/L的Bu4NPF6/CH3CN溶液中测得的循环伏安曲线,从图中可以测得对应的氧化和还原电位分别是0.79V和-0.59V,根据公式 计算得到对应的HOMO和LUMO能级分别是-5.59eV和-4.21eV,电化学能隙为1.39eV。低的HOMO能级表明P1有良好的空气稳定性,非常适合制备长使用寿命的太阳能电池器件。
③聚合物P1的光伏性能分析
聚合物P1的光伏性能如图3所示,结果表明聚合物P1与SFBRCN共混比例为1:1.5时,具有最好的光伏性能,对应的短路电流=14.76mA/cm2;开路电压=0.89V;填充因子=0.43;模拟太阳光(AM.1.5,100mW/cm2)下的能量转换效率=5.65%,参见表1。我们相信太阳能电池的转换效率可以通过器件条件的优化得到进一步提升。
表1聚合物P1的光伏性能结果
由实施例1-7可知,本发明合成的路线简单,成本低,且合成方法具有普适性,可以较好的推广应用到其他的芴类材料的合成;本发明的芴类聚合物光伏材料具有强给电子作用而产生共振能量传递,有望获得更宽的紫外-可见吸收光谱;本发明的芴类聚合物光伏材料具有较低的HOMO能级,对氧的稳定性高,有利于制备性能更加稳定的太阳能电池器件;本发明用芴类聚合物光伏材料为电子给体材料,应用于聚合物太阳能电池获得了较高的能量转换效率(PCE=5.65%),具有良好的应用前景。
综上所述,本发明合成了一种二维共轭芴有机电子给体单元,通过Stille偶联的方法,将芴给体单元通过碳-碳单键与另一个电子受体单元DPP相连接,得到芴类聚合物光伏材料。它们在常见的有机溶剂(如氯苯、二氯苯、甲苯等)中有良好的溶解性,可以用溶液方法制备高质量的薄膜。同时,这些聚合物光伏材料具有宽的可见光区吸收,合适的HOMO以及LUMO能级和相对较窄的带隙。以此类聚合物为电子给体、有机小分子为电子受体制备了有机太阳能电池,其最高能量转换效率可达到5.65%,具有良好的光电转换效率。
所属领域的普通技术人员应当理解:以上任何实施例的讨论仅为示例性的,并非旨在暗示本公开的范围(包括权利要求)被限于这些例子;在本发明的思路下,以上实施例或者不同实施例中的技术特征之间也可以进行组合,并存在如上所述的本发明的不同方面的许多其它变化,为了简明它们没有在细节中提供。因此,凡在本发明的精神和原则之内,所做的任何省略、修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
2.如权利要求1所述的2-氟苯基芴与吡咯并吡咯二酮共聚物光伏材料,其特征是,R为8~20个碳原子的直链或支链烷烃。
4.一种如权利要求1-3任一项所述的2-氟苯基芴与吡咯并吡咯二酮共聚物光伏材料的制备方法,其特征是,包括如下步骤:
1)2-氟-4-羟基苯甲醛与碱性试剂混合在有机溶剂中,搅拌,滴加溴代-2-辛基十二烷,在60-80℃条件下反应,冷却,将混合物倒入水中,萃取,干燥,旋干溶剂,过滤,得到2-氟-4-(2-辛基十二烷氧基)苯甲醛;
2)将2,7-二溴芴加入到无水乙醇中,搅拌,然后加入叔丁醇钾,继续搅拌,升温至50-65℃,加入2-氟-4-(2-辛基十二烷氧基)苯甲醛,反应,将混合物倒入水中,萃取,干燥,旋干溶剂,过硅胶柱,得到9-(2-氟-4-(2-辛基十二烷氧基)苯基亚甲基)-2,7-二溴芴;
3)将2,5-二烷基-3,6-二(5-(三甲基锡基)呋喃)-2-吡咯并吡咯二酮与9-(2-氟-4-(2-辛基十二烷氧基)苯基亚甲基)-2,7-二溴芴加入到无水甲苯中,再加入(四(三苯基膦)钯),100-115℃下反应,冷却,沉析,过滤,索氏提取,得到2-氟苯基芴与吡咯并吡咯二酮共聚物光伏材料。
5.如权利要求4所述的制备方法,其特征是,所述步骤1)中的有机溶剂为二甲基甲酰胺。
6.如权利要求4或5所述的制备方法,其特征是,步骤1)中所述2-氟-4-羟基苯甲醛与溴代-2-辛基十二烷的摩尔比为1:1.0~1.3。
7.如权利要求4或5所述的制备方法,其特征是,步骤1)中反应的温度为70℃,时间为10-14h。
8.如权利要求4或5所述的制备方法,其特征是,步骤2)中所述2,7-二溴芴与2-氟-4-(2-辛基十二烷氧基)苯甲醛的摩尔比为1:1.0~1.5。
9.如权利要求4或5所述的制备方法,其特征是,步骤3)中所述9-(2-氟-4-(2-辛基十二烷氧基)苯基亚甲基)-2,7-二溴芴与2,5-二烷基-3,6-二(5-(三甲基锡基)呋喃)-2-吡咯并吡咯二酮的摩尔比为1:1。
10.一种如权利要求1-3任一项所述的2-氟苯基芴与吡咯并吡咯二酮共聚物光伏材料在太阳能电池中的应用。
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