CN111040134B - 一种基于并芴稠环与氟代异靛蓝共聚的共轭聚合物 - Google Patents

一种基于并芴稠环与氟代异靛蓝共聚的共轭聚合物 Download PDF

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CN111040134B
CN111040134B CN201911247737.2A CN201911247737A CN111040134B CN 111040134 B CN111040134 B CN 111040134B CN 201911247737 A CN201911247737 A CN 201911247737A CN 111040134 B CN111040134 B CN 111040134B
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methanol
fluoroisoindigo
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郭旺军
刘英哲
伍致生
康莹
李建国
刘亚东
牛毅
张�杰
刘建群
宋新潮
王户生
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Xian Modern Chemistry Research Institute
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Abstract

本发明属于有机光电材料技术领域，具体涉及一种基于并芴稠环与氟代异靛蓝共聚的共轭聚合物，其结构式为

Description

一种基于并芴稠环与氟代异靛蓝共聚的共轭聚合物
技术领域
本发明属于功能高分子和有机光电技术领域，具体涉及一种基于并芴稠环与氟代异靛蓝 共聚的共轭聚合物。
背景技术
进入21世纪以后，随着世界经济的飞速发展，能源问题逐渐成为各国可持续发展的主要 瓶颈，对可再生能源的有效利用成为亟待解决的问题。太阳能是一种取之不尽、用之不竭的 能源。目前占主导地位的光伏技术主要基于无机材料，其高昂的材料制备成本以及高能耗的 加工工艺限制了它的广泛应用。有机太阳能电池则是一种主要基于有机半导体碳基材料的光 伏器件，相对于无机太阳能电池，有机太阳能电池制造成本低廉、材料质量轻、加工性能好， 可以利用先进的卷对卷以及喷涂打印技术进行大规模生产，并具有柔性，可以加工成为半透 明器件，易于携带，生产过程中能耗低，环境污染少等优点。有机聚合物材料以其原料易得、 廉价、制备简单、稳定性高、良好的光伏效应等优点，日益被人们所重视，科研工作者对不 同类型的聚合物材料进行了广泛研究，并取得了很大进展。为了获得良好的聚合物材料，将 富电子单元D和缺电子单元A交替引入聚合物共轭主链形成的D-A型聚合物材料成为目前作 为电子给体材料的聚合物研究重点。
氟原子由于原子半径小、电负性强，其与氯原子因缺电性能常被引入缺电子单元中，降 低给体材料的HOMO能级。Yu等合成的聚合物PTB5的HOMO能级为-5.01eV，引入氟原子后 聚合物材料HOMO能级降低到-5.12eV，在器件中表现出开路电压提升了0.08V(J.Am.Chem. Soc.,2009,131,7792–7799)。近期，Deng等设计与合成了一种基于异靛蓝受体单元的聚合物 材料P(IID-DTC)，具有良好的光电材料性能，并通过氟原子取代降低了基于异靛蓝给体材料 的HOMO能级，当引入一个氟原子材料HOMO能级降低了0.08eV，引入双氟原子HOMO能级 降低到-5.36eV，较未氟代的给体材料0.14eV，表现在器件上开路电压提升了0.09V(Adv. Mater.2014,26,471–476)。此外，多并稠环增加给电单元的共轭骨架具有稳定好、迁移率高 等优势，常应用于聚合物材料中，如Lee等设计合成了基于二噻吩并咔唑的聚合物材料，迁移 率最高达到1.36×10-2cm2 V-1s-1(Macromolecules 2013,46,7687-7695)。鉴于以上所述氟原 子、氯原子以及稠环骨架对材料性能的影响，在异靛蓝缺电子单元上引入氟原子或氯原子， 通过改变原子的取代基位置和个数制备新型的异靛蓝聚合物材料，有望进一步提升材料的光 电性能。此外，迄今还未见有关此类材料的制备及其应用于聚合物光伏电池中的报道。
发明内容
针对现有技术存在的缺陷或不足，本发明一个目的是提供基于给电子单元并芴稠环与取 代异靛蓝共聚的共轭聚合物，以满足聚合物光伏电池活化层电子给体材料的需要。本发明通 过改变材料给体单元的取代基种类以及缺电子单元异靛蓝中取代基个数和原子种类，有望进 一步拉低材料的HOMO能级和降低材料的能隙，提高器件的开路电压和短路电流，进而提升 光伏电池光电性能。
发明构思：通过改变给体单元的取代基种类以及异靛蓝中取代基个数和种类，进一步拉 低材料的HOMO能级和降低材料的能隙，进而提升聚合物光伏电池的开路电压和短路电流。
为了实现上述任务，本发明采取如下的技术解决方案：
一种基于并芴稠环与氟代异靛蓝共聚的共轭聚合物，其特征在于其结构通式为：
Figure BDA0002308159790000021
其中，Z为O或S；X，Y独立地为H，F或Cl；R为烷基，R’独立地为烷基、烷基苯基、 烷氧基苯基或烷基噻吩基，R”独立地为烷基、烷基苯基、烷氧基苯基或烷基噻吩基；其中， 烷指的为C6～C20的直链或支链。
一种基于并芴稠环与氟代异靛蓝共聚的共轭聚合物，其应用于有机聚合物太阳能电池给 体材料。
上述一种基于并芴稠环与氟代异靛蓝共聚的共轭聚合物，其聚合反应如下所示反应方程 式进行。
Figure BDA0002308159790000022
具体的合成步骤如下：
氮气保护下，将受体单元取代异靛蓝二溴化合物的摩尔量作为配比标准，和等摩尔量的 供电子单元双锡化合物加入到干燥的两口烧瓶中，加入甲苯，控制材料的摩尔浓度在0.01～0.1 M之间，抽真空充氮气三次。随后，在氮气保护下加入0.02倍摩尔量的催化剂三(二苯亚甲 基丙酮)二钯和0.08倍摩尔量的三邻甲基苯基磷配体，抽真空充氮气三次后开始加热，回流 反应24～48小时。停止反应，冷却至室温，旋除部分溶剂，在甲醇中沉降，过滤，收集的聚 合物在真空烘箱50℃烘干12小时，依次经甲醇、正己烷、氯仿进行索氏提取，浓缩氯仿液， 用甲醇再次沉降，固体再经柱色谱分离后，于甲醇中沉降，抽滤，真空烘干得上述所示的基 于氟代异靛蓝共轭聚合物。
本发明的有益效果
本发明通过在异靛蓝单元中引入氟原子和改变取代个数来调控材料的HOMO能级，通过 引入多并稠环作为供电单元，能够提升光伏电池的开路电压和短路电流，在与PCBM共混体 系中，开路电压在0.8～1.45V，短路电流在10.8～19.3mA/cm2，光电转换效率在7.6％～13.1％。
具体实施方式
下面通过具体实施例对本发明做进一步的解释说明。
聚合物P1合成路线如下：
Figure RE-GDA0002386041030000031
在50mL两口圆底烧瓶中加入化合物1(154.5mg)和化合物2(101.3mg)溶于20mL甲苯 中，抽真空通氮气三次，氮气保护下加入Pd2(dba)3(5.5mg)和配体三邻甲苯基磷(9.8mg)，加 热回流反应48h。冷却至室温，在甲醇中沉降，过滤，收集的聚合物在真空烘箱50℃烘干12 小时，依次经甲醇、正己烷、氯仿进行索氏提取，浓缩氯仿液，用甲醇再次沉降，固体再经 柱色谱分离后，于甲醇中沉降，抽滤，真空烘干得聚合物P1，收率80％，数均分子量38210， 分布系数2.45。
光伏性能测试：采用玻璃/PEDOT：PSS/P1：PC71BM/LiF/Al电池结构，光伏器件的有效 面积为0.16cm2。用配有AM 1.5滤光片Newport 500W氙灯作为模拟太阳光源，在100mW/cm2光强下对器件进行光伏性能测试，光强通过标准单晶硅太阳能电池校准；I-V曲线使用Keithley 2400进行测量，通过Labview软件由计算机进行控制，测得开路电压为0.86V，短路电流为 15.3mA/cm2，光电转换效率在8.3％。
聚合物P2合成路线如下：、
Figure RE-GDA0002386041030000032
在50mL两口圆底烧瓶中加入化合物3(151.3mg)和化合物2(101.3mg)溶于20mL甲苯 中，抽真空通氮气三次，氮气保护下加入Pd2(dba)3(5.5mg)和配体三邻甲苯基磷(9.8mg)，加 热回流反应48h。冷却至室温，在甲醇中沉降，过滤，收集的聚合物在真空烘箱50℃烘干12 小时，依次经甲醇、正己烷、氯仿进行索氏提取，浓缩氯仿液，用甲醇再次沉降，固体再经 柱色谱分离后，于甲醇中沉降，抽滤，真空烘干得聚合物P2，收率70％，数均分子量29630， 分布系数2.85。
光伏性能测试：采用玻璃/PEDOT：PSS/P2：PC71BM/LiF/Al电池结构，光伏器件的有效 面积为0.16cm2。用配有AM 1.5滤光片Newport 500W氙灯作为模拟太阳光源，在100mW/cm2光强下对器件进行光伏性能测试，光强通过标准单晶硅太阳能电池校准；I-V曲线使用Keithley 2400进行测量，通过Labview软件由计算机进行控制，测得开路电压为0.85V，短路电流为 14.3mA/cm2，光电转换效率在7.6％。
聚合物P3合成路线如下：
Figure RE-GDA0002386041030000041
在50mL两口圆底烧瓶中加入化合物1(154.5mg)和化合物4(103.1mg)溶于20mL甲苯 中，抽真空通氮气三次，氮气保护下加入Pd2(dba)3(5.5mg)和配体三邻甲苯基磷(9.8mg)，加 热回流反应48h。冷却至室温，在甲醇中沉降，过滤，收集的聚合物在真空烘箱50℃烘干12 小时，依次经甲醇、正己烷、氯仿进行索氏提取，浓缩氯仿液，用甲醇再次沉降，固体再经 柱色谱分离后，于甲醇中沉降，抽滤，真空烘干得聚合物P3，收率83％，数均分子量36210， 分布系数2.03。
光伏性能测试：采用玻璃/PEDOT：PSS/P3：PC71BM/LiF/Al电池结构，光伏器件的有效 面积为0.16cm2。用配有AM 1.5滤光片Newport 500W氙灯作为模拟太阳光源，在100mW/cm2光强下对器件进行光伏性能测试，光强通过标准单晶硅太阳能电池校准；I-V曲线使用Keithley 2400进行测量，通过Labview软件由计算机进行控制，测得开路电压为0.95V，短路电流为 17.3mA/cm2，光电转换效率在10.3％。
聚合物P4合成路线如下：
Figure RE-GDA0002386041030000051
在50mL两口圆底烧瓶中加入化合物1(154.5mg)和化合物5(104.9mg)溶于20mL甲苯 中，抽真空通氮气三次，氮气保护下加入Pd2(dba)3(5.5mg)和配体三邻甲苯基磷(9.8mg)，加 热回流反应48h。冷却至室温，在甲醇中沉降，过滤，收集的聚合物在真空烘箱50℃烘干12 小时，依次经甲醇、正己烷、氯仿进行索氏提取，浓缩氯仿液，用甲醇再次沉降，固体再经 柱色谱分离后，于甲醇中沉降，抽滤，真空烘干得聚合物P4，收率71％，数均分子量35235， 分布系数2.76。
光伏性能测试：采用玻璃/PEDOT：PSS/P4：PC71BM/LiF/Al电池结构，光伏器件的有效 面积为0.16cm2。用配有AM 1.5滤光片Newport 500W氙灯作为模拟太阳光源，在100mW/cm2光强下对器件进行光伏性能测试，光强通过标准单晶硅太阳能电池校准；I-V曲线使用Keithley 2400进行测量，通过Labview软件由计算机进行控制，测得开路电压为1.45V，短路电流为 18.7mA/cm2，光电转换效率在12.6％。
聚合物P5合成路线如下：、
Figure RE-GDA0002386041030000052
在50mL两口圆底烧瓶中加入化合物1(154.5mg)和化合物6(106.5mg)溶于20mL甲苯 中，抽真空通氮气三次，氮气保护下加入Pd2(dba)3(5.5mg)和配体三邻甲苯基磷(9.8mg)，加 热回流反应48h。冷却至室温，在甲醇中沉降，过滤，收集的聚合物在真空烘箱50℃烘干12 小时，依次经甲醇、正己烷、氯仿进行索氏提取，浓缩氯仿液，用甲醇再次沉降，固体再经 柱色谱分离后，于甲醇中沉降，抽滤，真空烘干得聚合物P5，收率78％，数均分子量31420， 分布系数2.62。
光伏性能测试：采用玻璃/PEDOT：PSS/P5：PC71BM/LiF/Al电池结构，光伏器件的有效 面积为0.16cm2。用配有AM 1.5滤光片Newport 500W氙灯作为模拟太阳光源，在100mW/cm2光强下对器件进行光伏性能测试，光强通过标准单晶硅太阳能电池校准；I-V曲线使用Keithley 2400进行测量，通过Labview软件由计算机进行控制，测得开路电压为1.25V，短路电流为19.1mA/cm2，光电转换效率在13.1％。
聚合物P6合成路线如下：、
Figure RE-GDA0002386041030000061
在50mL两口圆底烧瓶中加入化合物1(154.5mg)和化合物7(104.7mg)溶于20mL甲苯 中，抽真空通氮气三次，氮气保护下加入Pd2(dba)3(5.5mg)和配体三邻甲苯基磷(9.8mg)，加 热回流反应48h。冷却至室温，在甲醇中沉降，过滤，收集的聚合物在真空烘箱50℃烘干12 小时，依次经甲醇、正己烷、氯仿进行索氏提取，浓缩氯仿液，用甲醇再次沉降，固体再经 柱色谱分离后，于甲醇中沉降，抽滤，真空烘干得聚合物P6，收率78％，数均分子量31420， 分布系数2.62。
光伏性能测试：采用玻璃/PEDOT：PSS/P6：PC71BM/LiF/Al电池结构，光伏器件的有效 面积为0.16cm2。用配有AM 1.5滤光片Newport 500W氙灯作为模拟太阳光源，在100mW/cm2光强下对器件进行光伏性能测试，光强通过标准单晶硅太阳能电池校准；I-V曲线使用Keithley 2400进行测量，通过Labview软件由计算机进行控制，测得开路电压为0.82V，短路电流为 17.6mA/cm2，光电转换效率在9.6％。
聚合物P7合成路线如下：、
Figure RE-GDA0002386041030000062
在50mL两口圆底烧瓶中加入化合物1(154.5mg)和化合物8(108.1mg)溶于20mL甲苯 中，抽真空通氮气三次，氮气保护下加入Pd2(dba)3(5.5mg)和配体三邻甲苯基磷(9.8mg)，加 热回流反应48h。冷却至室温，在甲醇中沉降，过滤，收集的聚合物在真空烘箱50℃烘干12 小时，依次经甲醇、正己烷、氯仿进行索氏提取，浓缩氯仿液，用甲醇再次沉降，固体再经 柱色谱分离后，于甲醇中沉降，抽滤，真空烘干得聚合物P7，收率75％，数均分子量30320， 分布系数2.41。
光伏性能测试：采用玻璃/PEDOT：PSS/P7：PC71BM/LiF/Al电池结构，光伏器件的有效 面积为0.16cm2。用配有AM 1.5滤光片Newport 500W氙灯作为模拟太阳光源，在100mW/cm2光强下对器件进行光伏性能测试，光强通过标准单晶硅太阳能电池校准；I-V曲线使用Keithley 2400进行测量，通过Labview软件由计算机进行控制，测得开路电压为0.93V，短路电流为 18.5mA/cm2，光电转换效率在11.3％。
聚合物P8合成路线如下：、
Figure RE-GDA0002386041030000071
在50mL两口圆底烧瓶中加入化合物9(155.8mg)和化合物2(101.3mg)溶于20mL甲苯 中，抽真空通氮气三次，氮气保护下加入Pd2(dba)3(5.5mg)和配体三邻甲苯基磷(9.8mg)，加 热回流反应48h。冷却至室温，在甲醇中沉降，过滤，收集的聚合物在真空烘箱50℃烘干12 小时，依次经甲醇、正己烷、氯仿进行索氏提取，浓缩氯仿液，用甲醇再次沉降，固体再经 柱色谱分离后，于甲醇中沉降，抽滤，真空烘干得聚合物P8，收率77％，数均分子量31580， 分布系数2.93。
光伏性能测试：采用玻璃/PEDOT：PSS/P8：PC71BM/LiF/Al电池结构，光伏器件的有效 面积为0.16cm2。用配有AM 1.5滤光片Newport 500W氙灯作为模拟太阳光源，在100mW/cm2光强下对器件进行光伏性能测试，光强通过标准单晶硅太阳能电池校准；I-V曲线使用Keithley 2400进行测量，通过Labview软件由计算机进行控制，测得开路电压为0.80V，短路电流为 19.3mA/cm2，光电转换效率在10.5％。
聚合物P9合成路线如下：
Figure RE-GDA0002386041030000072
在50mL两口圆底烧瓶中加入化合物1(154.5mg)和化合物10(103.1mg)溶于20mL甲苯中，抽真空通氮气三次，氮气保护下加入Pd2(dba)3(5.5mg)和配体三邻甲苯基磷(9.8mg)，加热回流反应48h。冷却至室温，在甲醇中沉降，过滤，收集的聚合物在真空烘箱50℃烘干12小时，依次经甲醇、正己烷、氯仿进行索氏提取，浓缩氯仿液，用甲醇再次沉降，固体再 经柱色谱分离后，于甲醇中沉降，抽滤，真空烘干得聚合物P9，收率72％，数均分子量38410，分布系数2.98。
光伏性能测试：采用玻璃/PEDOT：PSS/P9：PC71BM/LiF/Al电池结构，光伏器件的有效 面积为0.16cm2。用配有AM 1.5滤光片Newport 500W氙灯作为模拟太阳光源，在100mW/cm2光强下对器件进行光伏性能测试，光强通过标准单晶硅太阳能电池校准；I-V曲线使用Keithley 2400进行测量，通过Labview软件由计算机进行控制，测得开路电压为0.97V，短路电流为 17.8mA/cm2，光电转换效率在10.9％。

Claims (2)

1.一种基于并芴稠环与氟代异靛蓝共聚的共轭聚合物，其特征在于，其结构通式为：
Figure FDA0002308159780000011
Z为O或S；
X，Y独立地为H，F或Cl；
R为烷基；
R’独立地为烷基、烷基苯基、烷氧基苯基或烷基噻吩基；
R”独立地为烷基、烷基苯基、烷氧基苯基或烷基噻吩基；
其中，烷指的为C6～C20的直链或支链。
2.根据权利要求1所述的基于并芴稠环与氟代异靛蓝共聚的共轭聚合物，其特征在于，将其应用于有机聚合物太阳能电池给体材料。
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