CN110105548B - 一种掺杂二维苯并二噻吩基团的三元无规聚合物受体材料及其制备方法与应用 - Google Patents
一种掺杂二维苯并二噻吩基团的三元无规聚合物受体材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明涉及一种掺杂含噻吩烷基侧链的二维苯并二噻吩基团的三元无规聚合物受体材料的合成及其在全聚合物太阳能电池中的应用。该材料通过掺杂不同摩尔比的苯并二噻吩基团，来调节聚合物材料本身的聚集性质，改善全聚合物活性层的结晶行为，提高全聚合物太阳能电池器件的短路电流和填充因子，进而提升能量转换效率。本发明通过三种单体经过Stille反应得到三元无规共聚物，合成工艺简单，原料易得，产物易于纯化。使用三种不同性质的聚合物作为电子给体和该系列聚合物受体制备全聚合物太阳能电池，均得到相比于原二元受体更高的能量转换效率，证明该方法能够客观有效的提升全聚合物太阳能电池的能量转换效率。
Description
技术领域
本发明涉及有机光伏材料领域，具体涉及一种掺杂二维苯并二噻吩(BDT)基团的三元无规聚合物电子受体材料及其在有机光伏中的应用，更具体的是在全聚合物太阳能电池中的应用。
背景技术
有机光伏，或称有机太阳能电池，是一种利用光生伏打效应发电的清洁能源技术。相比于无机太阳能电池，有机太阳能电池具有材料化学结构易修饰，质量轻，价格低，可柔性制备，可溶剂加工等优势。经过有机电子给、受体活性层吸收光子，光子生成激子，激子解离成空穴和电子，载流子转移等步骤，有机光伏器件可以将太阳能转化成电能。
根据活性层中电子受体材料的类型，有机太阳能电池可分为小分子受体类，富勒烯受体类及全聚合物类。其中，全聚合物太阳能电池，即电子给、受体均由聚合物材料构成的有机光伏器件，具有更优秀的光、热、环境稳定性，更适用于卷对卷印刷等大面积制备技术，具有广阔的未来应用前景。然而，受限于聚合物受体材料的种类匮乏，全聚合物太阳能电池的能量转换效率仍不理想。因此，开发新型的聚合物受体材料成为全聚合物太阳能电池研究领域的重点。
萘二酰亚胺(NDI)基团，具有良好的分子平面性及电子传输能力，广泛应用于聚合物电子受体的设计合成中。其中，萘二酰亚胺基团和联二噻吩基团共聚得到的二元聚合物PNDIT2(商品名N2200)是目前应用最为广泛的聚合物受体材料。但是由于其分子平面性过强，通常会在活性层中形成过强的受体堆积，以至于影响给、受体之间接触，形成过大尺度的给、受体相分离，进而影响电荷转移，抑制器件的能量转换效率。
发明内容
本发明的目的在于提供一种三元无规聚合物受体，并采用这类聚合物受体材料制备全聚合物太阳能电池。该类材料是在原二元聚合物受体PNDIT2基础上，通过三元无规共聚的方式，引入不同摩尔比的带噻吩烷基侧链的苯并二噻吩基团。该苯并二噻吩基团带有噻吩烷基侧链，具有空间二维结构，能有效地改善PNDIT2过强的平面聚集。该类材料能广泛应用于全聚合物太阳能电池中，并可获得相比于PNDIT2更高的能量转换效率。
为解决上述技术问题，本发明提供如下技术方案：
通过芳香环之间的偶联反应(施蒂勒偶联反应)，将不同摩尔比的含噻吩烷基侧链的苯并二噻吩基团，化学掺杂到二元聚合物受体PNDIT2中，合成一系列含不同摩尔比的苯并二噻吩三元无规聚合物受体，其化学反应式如图6所示。
掺杂二维苯并二噻吩基团的三元无规聚合物命名为PNDI-BDTx(x的数值为苯并二噻吩基团的投料摩尔比百分数，x＝5,10,20)，其结构如式(Ⅰ)所示：
其中，x表示二维苯并二噻吩基团的投料比，x＝0.05,0.10,0.20，及代表其投料比为5mol％、10mol％、20mol％。
上述掺杂二维苯并二噻吩基团的三元无规聚合物的制备方法，包括如下步骤：
(1)反应物A：4,5,9,10-四溴-2,7-双(2-辛基十二烷基)苯并[3,8]菲咯啉-1,3,6,8-四酮、反应物B：5,5'-双(三甲基锡)-2,2'-二噻吩、反应物C：2,6-二(三甲基锡)-4,8-二(5-(2-乙基己基)噻吩基-2-)苯并二噻吩按照投料比例投入反应容器中，同时加入4.5mol％(相比于联二噻吩基团的摩尔比)的四三苯基膦钯作为催化剂；
投料比(指原料摩尔比)及产物对应关系为：
PNDI-BDT5：反应物A:反应物B:反应物C的摩尔比为1:0.95:0.05
PNDI-BDT10：反应物A:反应物B:反应物C的摩尔比为1:0.90:0.10
PNDI-BDT20：反应物A:反应物B:反应物C的摩尔比为1:0.80:0.20
(2)加入超干甲苯及超干N,N’-二甲基甲酰胺作为溶剂，两种溶液的体积比为4:1；
(3)在氮气氛围下加热回流12～14h，温度为110～120℃；
(4)反应结束后将产物逐滴滴入甲醇进行重沉淀；
(5)沉淀物使用索氏提取器进行抽提，淋洗剂按顺序分别为：甲醇、正己烷、氯仿；
(6)氯仿相浓缩后在甲醇中重沉淀，抽滤干燥后得到产物。
上述掺杂二维苯并二噻吩基团的三元无规聚合物作为聚合物受体材料在全聚合物太阳能电池器件中应用在本发明的保护范围之内。
相比于目前广泛使用的二元聚合物受体PNDIT2，掺杂二维苯并二噻吩基团的三元聚合物受体，能有效改善聚合物分子本身的平面性，优化活性层中受体的堆积行为，可有助于形成良好的给、受体相分离，进而优化活性层中的电荷转移，提高全聚合物太阳能电池的能量转换效率。
反应得到的产物化学结构如图1所示。反应产率较高，原料易得，反应条件温和。
有益效果：
本发明中合成的掺杂二维苯并二噻吩的三元无规聚合物受体材料制备的全聚合物太阳能电池器件相比于原二元聚合物受体材料PNDIT2构筑的器件具有较高的短路电流密度和填充因子，进而有着更加优秀的能量转换效率。并且该材料经过试验验证，使用三种不同给体PBDB-T，PTB7-Th及PDCBT均可实现效率提升，即证明这种掺杂二维苯并二噻吩三元无规共聚的设计思路具有针对多种给体的普适性，能够有效地提升多种全聚合物太阳能电池器件体系的能量转换效率。
附图说明
图1为掺杂二维苯并二噻吩的三元无规聚合物受体PNDI-BDTx的化学结构。
图2为本发明中使用的聚合物给体PBDB-T，PTB7-Th及PDCBT的化学结构。
图3为以PBDB-T作为电子给体，PNDI-BDTx作为受体的全聚合物太阳能电池的短路电流密度-电压曲线。
图4为以PTB7-Th作为电子给体，PNDI-BDTx作为受体的全聚合物太阳能电池的短路电流密度-电压曲线。
图5为以PDCBT作为电子给体，PNDI-BDTx作为受体的全聚合物太阳能电池的短路电流密度-电压曲线。
图6为本发明涉及的聚合物受体材料的合成线路图。
具体实施方式
为了更好的理解本发明，下面通过具体的实施例来说明本发明的技术方案。以PNDI-BDTx作为聚合物受体构筑全聚合物太阳能电池。实施例中通过使用三种不同的聚合物给体材料来说明：通过掺杂一定量的二维苯并二噻吩基团可以有效的提升原二元聚合物PNDIT2的能量转换效率。
本发明中使用的聚合物电子受体材料的合成方法如下：
(1)将反应物A：4,5,9,10-四溴-2,7-双(2-辛基十二烷基)苯并[3,8]菲咯啉-1,3,6,8-四酮，反应物B：5,5'-双(三甲基锡)-2,2'-二噻吩，反应物C：2,6-二(三甲基锡)-4,8-二(5-(2-乙基己基)噻吩基-2-)苯并二噻吩按照投料比例投入反应容器中，同时加入4.5mol％(相比于联二噻吩基团的摩尔比)的四三苯基膦钯作为催化剂；
投料比(指原料摩尔比)及产物对应关系为：
PNDI-BDT5：反应物A:反应物B:反应物C的摩尔比为1:0.95:0.05
PNDI-BDT10：反应物A:反应物B:反应物C的摩尔比为1:0.90:0.10
PNDI-BDT20：反应物A:反应物B:反应物C的摩尔比为1:0.80:0.20
(2)加入超干甲苯及超干N,N’-二甲基甲酰胺作为溶剂，两种溶液的体积比为4:1；
(3)在氮气氛围下加热回流12-14h，温度为110-120℃；
(4)反应结束后将产物逐滴滴入甲醇进行重沉淀；
(5)沉淀物使用索氏提取器进行抽提，淋洗剂按顺序分别为：甲醇、正己烷、氯仿；
(6)氯仿相浓缩后在甲醇中重沉淀，抽滤干燥后得到产物。
制备全聚合物太阳能电池器件包括一下材料：透明ITO玻璃基板，空穴传输层材料，电子给体材料，已合成的聚合物受体材料，电子传输层材料及其他金属电极材料。
本实施方案中，全聚合物太阳能电池采用正向器件结构，器件结构为：ITO(正极)/PEDOT:PSS(空穴传输层，40nm)/聚合物给、受体活性层/PDINO(电子传输层，15nm)/Al(负极，100nm)。对于一系列不同的聚合物受体，采用相同的器件结构及器件制备条件以保证实验结果公正，平行比较客观有效。
实施例(1)：以PBDB-T作为聚合物给体材料，PNDI-BDTx作为聚合物电子受体材料制备正向结构全聚合物太阳能电池器件。器件短路电流密度-电压曲线如图1所示，表1列出实施例(1)的太阳能电池器件性能，平均能量转换效率取自至少15个独立器件。
表1实施例(1)中器件性能参数
实施例(2)：以PTB7-Th作为聚合物给体材料，PNDI-BDTx作为聚合物电子受体材料制备正向结构全聚合物太阳能电池器件。器件短路电流密度-电压曲线如图2所示，表2列出实施例(2)的太阳能电池器件性能，平均能量转换效率取自至少15个独立器件。
表2实施例(2)中器件性能参数
实施例(3)：以PDCBT作为聚合物给体材料，PNDI-BDTx作为聚合物电子受体材料制备正向结构全聚合物太阳能电池器件。器件短路电流密度-电压曲线如图3所示，表3列出实施例(3)的太阳能电池器件性能，平均能量转换效率取自至少15个独立器件。
表3实施例(3)中器件性能参数
三个具体实施例中，以掺杂10mol％二维苯并二噻吩基团的聚合物受体PNDI-BDT10的器件能量转换效率最佳，证明该方法能有效的提升以PNDIT2为聚合物受体的全聚合物太阳能电池的器件效率。
Claims (7)
1.掺杂二维苯并二噻吩基团的三元无规聚合物PNDI-BDTx，其结构如式(Ⅰ)所示：
式(Ⅰ)中，x＝0.10，n为大于0的自然数。
2.权利要求1所述掺杂二维苯并二噻吩基团的三元无规聚合物的制备方法，其特征在于，包括如下步骤：
(1)将反应物A：4,5,9,10-四溴-2,7-双(2-辛基十二烷基)苯并[3,8]菲咯啉-1,3,6,8-四酮、反应物B：5,5'-双(三甲基锡)-2,2'-二噻吩、反应物C：2,6-二(三甲基锡)-4,8-二(5-(2-乙基己基)噻吩基-2-)苯并二噻吩按照比例投入反应容器中，同时加入催化剂；
(2)加入超干甲苯及超干N,N’-二甲基甲酰胺作为溶剂，两种溶液的体积比为4:1；
(3)在氮气氛围下加热回流12～14h，温度为110～120℃；
(4)反应结束后将产物逐滴滴入甲醇进行重沉淀；
(5)沉淀物使用索氏提取器进行抽提，淋洗剂按顺序分别为：甲醇、正己烷、氯仿；
(6)氯仿相浓缩后在甲醇中重沉淀，抽滤干燥后得到产物。
3.根据权利要求2所述掺杂二维苯并二噻吩基团的三元无规聚合物的制备方法，其特征在于，步骤(1)中，所述催化剂为四三苯基膦钯。
4.根据权利要求3所述掺杂二维苯并二噻吩基团的三元无规聚合物的制备方法，其特征在于，步骤(1)中，所述四三苯基膦钯相比于联二噻吩基团的摩尔比为4.5mol％。
5.根据权利要求2所述掺杂二维苯并二噻吩基团的三元无规聚合物的制备方法，其特征在于，步骤(1)中，反应物A、反应物B、反应物C的的摩尔比为：1:0.90:0.10。
6.权利要求2～5任一所述掺杂二维苯并二噻吩基团的三元无规聚合物的制备方法制备得到的掺杂二维苯并二噻吩基团的三元无规聚合物。
7.权利要求1或6所述掺杂二维苯并二噻吩基团的三元无规聚合物作为聚合物受体材料在全聚合物太阳能电池器件中应用。
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