CN112592464B - 一种二维共轭2-氯苯基芴类共聚物光伏材料、制备方法和应用 - Google Patents
一种二维共轭2-氯苯基芴类共聚物光伏材料、制备方法和应用 Download PDFInfo
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- CN112592464B CN112592464B CN202011167424.9A CN202011167424A CN112592464B CN 112592464 B CN112592464 B CN 112592464B CN 202011167424 A CN202011167424 A CN 202011167424A CN 112592464 B CN112592464 B CN 112592464B
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- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
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Abstract
本发明属于聚合物光伏材料技术领域,具体是涉及到一种二维共轭2‑氯苯基芴类共聚物光伏材料、制备方法和应用,结构式如下:,其中,X和Y分别为H或F,n为10‑30,二维共轭2‑氯苯基芴类共聚物光伏材料具有与非富勒烯受体材料互补的光学吸收和匹配的HOMO以及LUMO能级,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7.0%,具有良好的光电转换效率。
Description
技术领域
本发明属于聚合物光伏材料技术领域,具体是涉及到一种二维共轭2-氯苯基芴类共聚物光伏材料、制备方法和应用。
背景技术
为了人类生活和社会经济的可持续健康发展,高效合理的利用可再生清洁能源成为摆在世界各国科学界面前的重大科学问题。太阳能作为一种可再生清洁能源越来越得到全球科学界和产业界的重视,开发一类将太阳能转换为电能的装置—太阳电池具有重大的战略意义。利用光伏效应的工作原理,太阳电池吸收具有一定能量的光子后产生激子,激子分离成空穴和电子,在正负极材料功函差产生的内建电场作用下,电子和空穴分别向负极和正极移动形成光电流。
近十年,非富勒烯聚合物太阳能电池取得了快速的发展,获得了超过15%的能量转换效率[Jun Yuan, Yunqiang Zhang, Liuyang Zhou, Guichuan Zhang, Hin-Lap Yip,Tsz-Ki Lau, Xinhui Lu,Can Zhu,Hongjian Peng, Paul A.Johnson,Mario Leclerc,Yong Cao,Jacek Ulanski, Yongfang Li,Yingping Zou.Joule,3,1140-1151.],但是聚合物给体材料和非富勒烯受体材料之间需要对各个性能进行优化,如:(1)通过调控聚合物材料的能级和带隙来获得较高的开路电压和短路电流;(2)提高聚合物材料的平面性来增加其电荷迁移率,但是在该过程中,要确保材料的溶解性和稳定性。这些因素相互关联,理想状态下,应该对这些因素同时优化,但是实际上这是十分困难的。因此,找到一个平衡点使电池取得最大光电转化效率,是材料化学家设计聚合物给体材料的关键。在设计有机太阳能电池聚合物材料的过程中,要遵循以下几个原则:(1)聚合物应具有较窄的能带间隙;(2)较高的摩尔消光系数;(3)良好的平面性;(4)高的电荷迁移率;(5)较好的光稳定性。同时,较高的分子量、较高的电荷迁移率、最优化的形貌、填充因子等等都可以影响材料的性能。
发明内容
本发明要解决的技术问题是提供一种二维共轭2-氯苯基芴类共聚物光伏材料、制备方法和应用,其具有良好的光电转换效率。
本发明的内容包括一种二维共轭2-氯苯基芴类共聚物光伏材料,结构式如下:
,
其中,X和Y分别为H或F,n为10-30。
一种二维共轭2-氯苯基芴类共聚物光伏材料的制备方法,包括如下步骤:
1)2-氯-4-羟基苯甲醛与碱性试剂混合在有机溶剂(有机溶剂优选为二甲基甲酰胺)中,搅拌,滴加溴代-2-辛基十二烷,升温至60-80℃(优选为70℃)下反应,反应时间优选为10-14h(更优选为12h),冷却,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-氯-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(t-BuOK),搅拌,升温至50-65℃(优选为60℃),反应时间优选为6-10h(更优选为8h),加入2-氯-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,过滤,得到9-(2-氯-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4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑类化合物与9-(2-氯-4-(2-辛基十二烷氧基)苯基亚甲基)-2,7-二溴芴混合,加入到无水甲苯中,再加入四(三苯基膦)钯,100-115℃(优选为110℃)下反应,反应时间优选为20-30h(更优选为24h),冷却,沉析,过滤,提取(优选为索氏提取),得到二维共轭2-氯苯基芴类共聚物光伏材料;
所述4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑类化合物为4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑、5-氟-4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑或5,6-二氟-4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑。
所述步骤2)和步骤3)优选为在保护气氛下进行。
在本发明中,优选的,步骤1)中所述2-氯-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。
优选的,步骤2)中所述2,7-二溴芴与2-氯-4-(2-辛基十二烷氧基)苯甲醛的摩尔比为1:1.0~1.5。
优选的,所述步骤3)中所述4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑类化合物与9-(2-氯-4-(2-辛基十二烷氧基)苯基亚甲基)-2,7-二溴芴的摩尔比为1:1。
在本发明中,当X=H,Y=H时,合成的目标聚合物为9-(4-(2-辛基十二烷氧基)-2-氯-苯基亚甲基)-2,7-芴-4’,7’-二(噻吩基)-苯并噁二唑(PDTBXF-B-2Cl);
当X=H,Y=F时,合成的目标聚合物为9-(4-(2-辛基十二烷氧基)-2-氯-苯基亚甲基)-2,7-芴-5’-氟-4’,7’-二(噻吩基)-苯并噁二唑(PfDTBXF-B-2Cl);
当X=F,Y=F时,合成的目标聚合物为9-(4-(2-辛基十二烷氧基)-2-氯-苯基亚甲基)-2,7-芴-5’,6’-二氟-4’,7’-二(噻吩基)-苯并噁二唑(PffDTBXF-B-2Cl)。
本发明提供的一系列二维共轭2-氯苯基芴类共聚物光伏材料的制备方法是采用Stille偶联的方法,将2-氯苯基芴电子给体单元与二噻吩苯并噁二唑电子受体单元直接偶联而成。
其中,2-氯-4-(2-辛基十二烷氧基)苯甲醛的结构式如下式(1)所示:
9-(2-氯-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:
4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑的结构式如下式(3)所示:
5-氟-4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑的结构式如下式(4)所示:
5,6-二氟-4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑的结构式如下式(5)所示:
本发明目标聚合物(Ⅰ)的合成路线如下:
本发明合成了一种新型2-氯苯基芴电子给体单元,通过Stille偶联的方法,将2-氯苯基芴单元通过碳-碳单键与另一个电子受体单元二噻吩苯并噁二唑相连接,得到二维共轭2-氯苯基芴类共聚物光伏材料。它们在常见的有机溶剂(如三氯甲烷、甲苯、氯苯、四氢呋喃等)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,这些聚合物给体光伏材料具有与非富勒烯受体材料互补的光学吸收和匹配的HOMO以及LUMO能级。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7.0%,具有良好的光电转换效率。
本发明还提供一种二维共轭2-氯苯基芴类共聚物光伏材料在太阳能电池中的应用,具体的,所述二维共轭2-氯苯基芴类共聚物光伏材料用作太阳能电池电子给体材料。
本发明用上述二维共轭2-氯苯基芴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:
将本发明的二维共轭2-氯苯基芴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。
本发明提供的二维共轭2-氯苯基芴类共聚物光伏材料具有与非富勒烯受体材料互补的光学吸收和匹配的HOMO以及LUMO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二维共轭2-氯苯基芴类共聚物光伏材料的光学性能。用循环伏安法研究了二维共轭2-氯苯基芴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。
本发明的有益效果是,
(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)本发明的二维共轭2-氯苯基芴类聚合物光伏材料具有与非富勒烯受体材料互补的光学吸收,能够保障吸收足够多的太阳光子,获得高的光电流。
(3)本发明的二维共轭2-氯苯基芴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)本发明用二维共轭2-氯苯基芴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=7.0%),具有良好的应用前景。
附图说明
图1为本发明二维共轭2-氯苯基芴类共聚物光伏材料的吸收光谱图;
图2为本发明二维共轭2-氯苯基芴类共聚物光伏材料的电化学分析图;
图3为本发明二维共轭2-氯苯基芴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。
本发明二维共轭2-氯苯基芴类共聚物光伏材料的合成路线如下所示:
实施例19-(4-(2-辛基十二烷氧基)-2-氯-苯基亚甲基)-2,7-芴-4’,7’-二(噻吩基)-苯并噁二唑(PDTBXF-B-2Cl)的制备
①化合物1的合成
将2-氯-4-羟基苯甲醛(15.7 g,100 mmol),氢氧化钠 (6.0 g,150 mmol) 和DMF(150 mL) 置于250 mL的三口烧瓶中,溴代-2-辛基十二烷基(43.3 g,120 mmol)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80℃下搅拌反应12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 (36.3 g,产率:83%)。
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), 7.81 (d, 1H), 6.98 (d, 2H), 3.92(d, 2H), 1.75 (m, 1H), 1.49-1.31 (m, 32H), 0.92 (t, 6H).
GC-MS: m/z =437.
②化合物2的合成
氮气保护下,将2,7-二溴芴(1.3 g,4.0 mmol)与无水乙醇(60 mL)加入150 mL三口圆底烧瓶中,搅拌,再加入t-BuOK(0.9 g,8.0 mmol),升温至60 ℃继续搅拌一小时后,然后加入化合物1(2.6 g,6.0 mmol),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(2.0 g,产率:69%)。
化合物2的核磁共振谱、质谱如下所示:
1H NMR (δ/ppm, CDCl3): 7.81(s, 2H), 7.51-7.49(d, 3H), 7.45-7.39(m,2H), 7.29-7.27(t, 2H), 7.03(t, 1H), 3.97(d, 2H), 1.86(t, 1H), 1.52-1.24(m,32H), 0.88(t, 6H).
GC-MS: m/z =743.
③聚合物PDTBXF-B-2Cl的合成
氮气保护下,将等摩尔量的化合物2和4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑(0.1 mmol,购买于苏州纳凯科技有限公司)加入到12 mL无水甲苯中,再加入Pd(PPh3)4(10 mg),110 ℃下搅拌反应24小时后,冷却至室温,倒入100 mL甲醇中沉析,过滤,粗产物经过甲醇、正己烷、三氯甲烷分别抽提,得到聚合物PDTBXF-B-2Cl(82 mg,产率95%)。
聚合物PDTBXF-B-2Cl的凝胶渗透色谱分析如下所示:
Mn=15,000, Mw=33,500, PDI =2.2。
实施例29-(4-(2-辛基十二烷氧基)-2-氯-苯基亚甲基)-2,7-芴-5’-氟-4’,7’-二(噻吩基)-苯并噁二唑(PfDTBXF-B-2Cl)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,电子受体单元采用5-氟-4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑,具体步骤如下:
①化合物1的合成
将2-氯-4-羟基苯甲醛(15.7 g,100 mmol),氢氧化钠 (6.0 g,150 mmol) 和DMF(150 mL) 置于250 mL的三口烧瓶中,溴代-2-辛基十二烷基(43.3 g,120 mmol)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80℃下搅拌反应12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 (36.3 g,产率:83%)。
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), 7.81 (d, 1H), 6.98 (d, 2H), 3.92(d, 2H), 1.75 (m, 1H), 1.49-1.31 (m, 32H), 0.92 (t, 6H).
GC-MS: m/z =437.
②化合物2的合成
氮气保护下,将2,7-二溴芴(1.3 g,4.0 mmol)与无水乙醇(60 mL)加入150 mL三口圆底烧瓶中,搅拌,再加入t-BuOK(0.9 g,8.0 mmol),升温至60 ℃继续搅拌一小时后,然后加入化合物1(2.6 g,6.0 mmol),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(2.0 g,产率:69%)。
化合物2的核磁共振谱、质谱如下所示:
1H NMR (δ/ppm, CDCl3): 7.81(s, 2H), 7.51-7.49(d, 3H), 7.45-7.39(m,2H), 7.29-7.27(t, 2H), 7.03(t, 1H), 3.97(d, 2H), 1.86(t, 1H), 1.52-1.24(m,32H), 0.88(t, 6H).
GC-MS: m/z =743.
③聚合物PfDTBXF-B-2Cl的合成
氮气保护下,将等摩尔量的化合物2和5-氟-4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑(0.1 mmol,购买于苏州纳凯科技有限公司)加入到12 mL无水甲苯中,再加入Pd(PPh3)4(10 mg),110 ℃下搅拌反应24小时后,冷却至室温,倒入100 mL甲醇中沉析,过滤,粗产物经过甲醇、正己烷、三氯甲烷分别抽提,得到聚合物PfDTBXF-B-2Cl(81 mg,产率92%)。
聚合物PfDTBXF-B-2Cl的凝胶渗透色谱分析如下所示:
Mn=24,900, Mw=47,200, PDI =1.9。
实施例39-(4-(2-辛基十二烷氧基)-2-氯-苯基亚甲基)-2,7-芴-5’,6’-二氟-4’,7’-二(噻吩基)-苯并噁二唑(PffDTBXF-B-2Cl)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,电子受体单元采用5,6-二氟-4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑,具体步骤如下:
①化合物1的合成
将2-氯-4-羟基苯甲醛(15.7 g,100 mmol),氢氧化钠 (6.0 g,150 mmol) 和DMF(150 mL) 置于250 mL的三口烧瓶中,溴代-2-辛基十二烷基(43.3 g,120 mmol)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80℃下搅拌反应12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 (36.3 g,产率:83%)。
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), 7.81 (d, 1H), 6.98 (d, 2H), 3.92(d, 2H), 1.75 (m, 1H), 1.49-1.31 (m, 32H), 0.92 (t, 6H).
GC-MS: m/z =437.
②化合物2的合成
氮气保护下,将2,7-二溴芴(1.3 g,4.0 mmol)与无水乙醇(60 mL)加入150 mL三口圆底烧瓶中,搅拌,再加入t-BuOK(0.9 g,8.0 mmol),升温至60 ℃继续搅拌一小时后,然后加入化合物1(2.6 g,6.0 mmol),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(2.0 g,产率:69%)。
化合物2的核磁共振谱、质谱如下所示:
1H NMR (δ/ppm, CDCl3): 7.81(s, 2H), 7.51-7.49(d, 3H), 7.45-7.39(m,2H), 7.29-7.27(t, 2H), 7.03(t, 1H), 3.97(d, 2H), 1.86(t, 1H), 1.52-1.24(m,32H), 0.88(t, 6H).
GC-MS: m/z =743.
③聚合物PffDTBXF-B-2Cl的合成
氮气保护下,将等摩尔量的化合物2和4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑(0.1 mmol,购买于苏州纳凯科技有限公司)加入到12 mL无水甲苯中,再加入Pd(PPh3)4(10 mg),110℃下搅拌反应24小时后,冷却至室温,倒入100 mL甲醇中沉析,过滤,粗产物经过甲醇、正己烷、三氯甲烷分别抽提,得到聚合物PffDTBXF-B-2Cl(79 mg,产率87%)。
聚合物PffDTBXF-B-2Cl的凝胶渗透色谱分析如下所示:
Mn=26,100, Mw=55,700, PDI =2.1。
实施例4聚合物太阳能电池的制备
本发明以二维共轭2-氯苯基芴类共聚物作为工作介质,制备太阳能电池的方法是:将上述二维共轭2-氯苯基芴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:3.0 mg的PffDTBXF-B-2Cl与3.0 mg的ITIC混合,加入0.3 mL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100 nm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=10.9 mA/cm2;开路电压=0.87 V;填充因子=47%;
模拟太阳光(A.M.1.5,100 mW/cm2)下的能量转换效率=4.5%。
实施例5聚合物太阳能电池的制备
2.0 mg的PffDTBXF-B-2Cl与4.0 mg的ITIC混合,加入0.3 mL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100 nm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=12.5 mA/cm2;开路电压=0.90 V;填充因子=62.0%;
模拟太阳光(A.M.1.5,100 mW/cm2)下的能量转换效率=7.0%。
实施例6聚合物太阳能电池的制备
2.0 mg的PffDTBXF-B-2Cl与6.0 mg的ITIC混合,加入0.4 mL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100 nm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=11.8 mA/cm2;开路电压=0.89 V;填充因子=56%;
模拟太阳光(A.M.1.5,100 mW/cm2)下的能量转换效率=6.1%。
实施例7聚合物PffDTBXF-B-2Cl的光谱分析
聚合物PffDTBXF-B-2Cl在三氯甲烷溶液下的吸收光谱如图1所示,在实施例7所制备的溶液状态下,聚合物PffDTBXF-B-2Cl在300-700 nm范围内对光有明显吸收,与电子受体ITIC的吸收光谱形成很好的互补,因而光伏活性层可以吸收更多的太阳光,获得高的短路电流。说明二维共轭2-氯苯基芴类聚合物光伏材料在太阳能电池中有着广阔的应用前景。
实施例8聚合物PffDTBXF-B-2Cl的电化学性能分析
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PffDTBXF-B-2Cl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1.10 V和-0.55 V,根据公式HOMO=-e(+4.8) (eV),LUMO= -e(/>+4.8) (eV) 计算得到对应的HOMO和LUMO能级分别是-5.90 eV和-4.25 eV,电化学能隙为1.65 eV。低的HOMO能级表明PffDTBXF-B-2Cl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。
实施例9聚合物PffDTBXF-B-2Cl的光伏性能分析
聚合物PffDTBXF-B-2Cl的光伏性能如图3所示,结果表明聚合物PffDTBXF-B-2Cl与ITIC共混比例为1:1时,具有最好的光伏性能,对应的短路电流=11.83 mA/cm2;开路电压=0.97 V;填充因子=61.2%;模拟太阳光(AM.1.5,100 mW/cm2)下的能量转换效率=7.02%,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PffDTBXF-B-2Cl的光伏性能结果
Active layer | Voc (V) | Jsc (mAcm-2) | FF (%) | PCE (%) |
PffDTBXF-B-2Cl:ITIC=1:1 | 0.87 | 10.9 | 47.0 | 4.5 |
PffDTBXF-B-2Cl:ITIC=1:2 | 0.90 | 12.5 | 62.0 | 7.0 |
PffDTBXF-B-2Cl:ITIC=1:3 | 0.89 | 11.8 | 56.0 | 6.1 |
由实施例1-9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;本发明的二维共轭2-氯苯基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;本发明的二维共轭2-氯苯基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;本发明用二维共轭2-氯苯基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=7.0%),具有良好的应用前景。
综上所述,本发明合成了一种2-氯苯基芴有机电子给体单元,通过Stille偶联的方法,将2-氯苯基芴给体单元通过碳-碳单键与另一个电子受体单元二噻吩苯并噻二唑相连接,得到二维共轭2-氯苯基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7.0%,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)
1.一种二维共轭2-氯苯基芴类共聚物光伏材料,其特征是,结构式如下:
,
其中,X和Y分别为H或F,n为10-30。
2.一种如权利要求1所述的二维共轭2-氯苯基芴类共聚物光伏材料的制备方法,其特征是,包括如下步骤:
1)2-氯-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,升温至60-80℃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-氯-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,搅拌,升温至50-65℃,加入2-氯-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,过滤,得到9-(2-氯-4-(2-辛基十二烷氧基)苯基亚甲基)-2,7-二溴芴;
3)将4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑类化合物与9-(2-氯-4-(2-辛基十二烷氧基)苯基亚甲基)-2,7-二溴芴混合,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,提取,得到二维共轭2-氯苯基芴类共聚物光伏材料;
所述4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑类化合物为4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑、5-氟-4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑或5,6-二氟-4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑。
3.如权利要求2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。
4.如权利要求2或3所述的制备方法,其特征是,所述步骤1)中所述2-氯-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。
5.如权利要求2或3所述的制备方法,其特征是,所述步骤1)中反应的温度为70℃,时间为10-14h。
6.如权利要求2或3所述的制备方法,其特征是,所述步骤2)中反应的温度为60℃,时间为6-10h。
7.如权利要求2或3所述的制备方法,其特征是,所述步骤2)中所述2,7-二溴芴与2-氯-4-(2-辛基十二烷氧基)苯甲醛的摩尔比为1:1.0~1.5。
8.如权利要求2或3所述的制备方法,其特征是,所述步骤3)中反应的温度为110℃,时间为20-30h。
9.如权利要求2或3所述的制备方法,其特征是,所述步骤3)中所述4,7-二(5-三甲基锡基-噻吩基)-苯并噁二唑类化合物与9-(2-氯-4-(2-辛基十二烷氧基)苯基亚甲基)-2,7-二溴芴的摩尔比为1:1。
10.一种如权利要求1所述的二维共轭2-氯苯基芴类共聚物光伏材料在太阳能电池中的应用。
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