CN108034042B - 一种主链给体-侧链受体型共轭聚合物及其制备和应用 - Google Patents

一种主链给体-侧链受体型共轭聚合物及其制备和应用 Download PDF

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CN108034042B
CN108034042B CN201711304290.9A CN201711304290A CN108034042B CN 108034042 B CN108034042 B CN 108034042B CN 201711304290 A CN201711304290 A CN 201711304290A CN 108034042 B CN108034042 B CN 108034042B
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黄飞
胡志诚
应磊
曹镛
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Dongguan volt ampere Photoelectric Technology Co., Ltd
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Abstract

本发明属于高分子光电材料领域，公开了一种主链给体‑侧链受体型共轭聚合物及其制备方法和在单组分有机太阳电池中的应用。本发明共轭聚合物结构如下：其中，n为小于等于100万的正整数，a为3～40的正整数，R为甲基、甲氧基、腈基或氟原子，R1、R2、R3、R4相同或不同的分别为烷基链，A为缺电子共轭单元结构，为苯并噻二唑及其衍生物、苯并三唑酰亚胺及其衍生物、萘二并噻二唑及其衍生物、萘二并三唑及其衍生物中的至少一种。本发明共轭聚合物主链为P型共轭结构，侧链引入窄带隙吸光型n型小分子，将其应用于单组分有机太阳电池，不需要给受体；通过调节侧链烷基链的长度，可有效增强电池器件活性层的纳米相分离，提高器件效率。

Description

一种主链给体-侧链受体型共轭聚合物及其制备和应用
技术领域
本发明属于高分子光电材料领域，特别涉及一种主链给体-侧链受体型共轭聚合物及其制备方法和在单组分有机太阳电池中的应用。
背景技术
随着全球对于能源需求的逐年增加，石油、煤炭等传统能源的日益枯竭，以及对保护地球生态环境的需要，全世界越来越多的科学家将研究集中在氢气、太阳能等取之不尽用之不竭的可再生清洁能源。已经成熟的无机硅、砷化镓、磷化铟等基于无机材料的光伏器件已经在市场上占有主导地位，然而由于其对于材料纯度的要求高，加工过程中会产生高能耗及污染等问题，且其价格非常昂贵，因此在追求低成本和绿色环保的今天，其大规模应用受到了限制。
有机光伏器件作为一种新型薄膜光伏电池技术，具有全固态、光伏材料性质可调范围宽、可实现半透明、柔性电池、具有大面积低成本制备潜力等突出优点。有机材料的光伏性能可调范围宽，可利用化学手段对材料的能级、载流子迁移率以及吸收等性能进行有效的调控。有机/聚合物光伏器件可采用打印、印刷等方法进行加工，可借鉴传统塑料的加工工艺，通过卷对卷滚动加工流程制造大面积、柔性的薄膜光伏器件，该生产工艺能够有效降低光伏电池的制造成本。有机光伏器件几乎不受环境和场地限制，在许多场合可将光能转换为电能，同时与无机半导体光伏器件有非常强的互补性，无疑具有巨大的商业开发价值和市场竞争力。因此有机光伏器件的研究引起了广泛关注，以有机光伏器件为核心的科学研究已经成为世界范围内竞争激烈的材料科学前沿研究领域。
有机太阳电池活性层经历了从单组分到双组分以及多组分共混体系的发展。目前，代表性的结构为由一个给体和一个受体共同组成的本体异质结结构，展现出了优良的光电转化效率。与此同时，单组分太阳电池也一直受到人们的广泛关注，受本体异质结启发，人们设计一个分子中同时含有给受体的嵌段共轭聚合物用于光活性层，但是器件效率远低于预想值。主要原因是在嵌段共聚物中给受体很难形成合适的纳米相分离，使得在电池器件中电荷很容易复合。
对此，本发明通过对共轭聚合物分子结构的调节，设计合成了一系列主链给体-侧链受体型共轭聚合物并将其用于有机太阳电池。所述主链给体-侧链受体型共轭聚合物可单独作为有机太阳电池活性层，而不需要给受体。所述共轭聚合物主链为P型共轭结构，侧链引入窄带隙吸光型n型小分子，使得新型的共轭聚合物在可见光-近红外区有良好的吸收；而且通过调节侧链烷基链的长度，可以有效增强电池器件中活性层的纳米相分离，进而提高器件效率。
发明内容
为了克服上述现有技术的缺点与不足，本发明的首要目的在于提供一种主链给体-侧链受体型共轭聚合物。
本发明另一目的在于提供上述主链给体-侧链受体型共轭聚合物的制备方法。
本发明再一目的在于提供上述主链给体-侧链受体型共轭聚合物在单组分有机太阳电池中的应用。
本发明的目的通过下述方案实现：
一种主链给体-侧链受体型共轭聚合物，结构如下：
其中，n为小于等于100万的正整数，a为3～40的正整数，R为甲基、甲氧基、腈基或氟原子，R1、R2、R3、R4相同或不同的分别为烷基链，A为缺电子共轭单元结构，可为苯并噻二唑及其衍生物、苯并三唑酰亚胺及其衍生物、萘二并噻二唑及其衍生物、萘二并三唑及其衍生物中的至少一种。
进一步地，所述的R1、R2、R3、R4相同或不同的分别为具有1～40个碳原子的直链、支链或者环状烷基链；所述直链、支链或者环状烷基链中的一个或一个以上碳原子可被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基、甲基、乙基、甲氧基、硝基取代；所述直链、支链或者环状烷基链中的一个或一个以上氢原子可被氟原子、氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基、甲基、乙基、甲氧基、硝基取代。
进一步地，所述的A为缺电子共轭单元结构，具有如下结构的一种或一种以上：
本发明的主链给体-侧链受体型共轭聚合物可通过Stille聚合反应得到。
本发明的主链给体-侧链受体型共轭聚合物可用于单组分有机太阳电池中，作为单组分有机太阳电池的活性层。本发明的主链给体-侧链受体型共轭聚合物，主链为P型共轭结构，侧链引入窄带隙吸光型n型小分子，使得新型的共轭聚合物在可见光-近红外区有良好的吸收；将其应用于单组分有机太阳电池中作为活性层，而不需要给受体；而且通过调节侧链烷基链的长度，可以有效增强电池器件中活性层的纳米相分离，提高器件效率。
基于本发明主链给体-侧链受体型共轭聚合物的有机光伏器件结构如图1所示，由衬底、阳极、阳极界面层、光吸收层、阴极界面层、阴极依次层叠构成。所述光吸收层含有本发明的主链给体-侧链受体型共轭聚合物。
上述有机光伏器件中，所述阳极的材料优选为铝、银、金、钙/铝合金或钙/银合金。
所述的阳极界面层优选为有机共轭聚合物(如聚3,4-乙撑二氧噻吩/聚苯乙烯磺酸盐)或无机半导体。
所述的阴极优选为金属、金属氧化物(如氧化铟锡导电膜(ITO)，掺杂二氧化锡(FTO)，氧化锌(ZnO)，铟镓锌氧化物(IGZO))和石墨烯及其衍生物中的至少一种。
所述的衬底优选为玻璃、柔性材料(如聚酰亚胺、聚对苯二甲酸乙二醇酯、乙烯对苯二甲酸酯、聚萘二甲酸乙二醇酯或其他聚酯材料)、金属、合金和不锈钢薄膜中的至少一种。
本发明相对于现有技术，具有如下的优点及有益效果：
(1)本发明设计了主链给体-侧链受体型共轭聚合物，所述共轭聚合物可单独作为有机太阳电池活性层，而不需要给受体。
(2)所述共轭聚合物主链为P型共轭结构，侧链引入窄带隙吸光型n型小分子，使得新型的共轭聚合物在可见光-近红外区有良好的吸收；
(3)通过调节所述共轭聚合物侧链烷基链的长度，可以有效增强电池器件中活性层的纳米相分离，提高器件效率。
附图说明
图1为本发明有机光伏器件结构示意图。
图2为本发明主链给体-侧链受体型共轭聚合物(P1、P2、P3)的紫外-可见光-近红外吸收谱图。
图3为本发明主链给体-侧链受体型共轭聚合物(P4、P5、P6)的紫外-可见光-近红外吸收谱图。
图4为电池结构为ITO阳极/阳极界面层/活性层/阴机界面层/阴极(正装结构)时，本发明共轭聚合物(P1、P2、P3)作为活性层材料时电池器件的电流-电压曲线图。
图5为电池结构为ITO阳极/阳极界面层/活性层/阴机界面层/阴极(正装结构)时，本发明共轭聚合物(P4、P5、P6)作为活性层材料时电池器件的电流-电压曲线图。
图6～图7为本发明聚合物代表性合成路线图。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
下列实施例中涉及的物料均可从商业渠道获得。
实施例1
本发明聚合物代表性合成路线见图6～图7。
(1)单体M1，M2参考按照文献[Journal of Materials Chemistry A,2014,2(23):8773-8781.]公开的方法合成。
(2)单体M3按照文献[Chemistry of Materials,2014,26(11):3495-3501.]公开的方法合成。
(3)单体M4按照文献[Energy&Environmental Science,2017,10(5):1243-1251.]公开的方法合成。
(4)单体M5按照文献[Advanced Materials,2016,28(44):9811-9818.]公开的方法合成。
(5)聚合物P1、P2、P3的合成：
P1：将单体M1(0.5mmol)和单体M3(0.5mmol)加入到25mL两口烧瓶中，通入氮气保护，加入8mL甲苯。抽换气两次后加入5mg Pd(PPh3)4，95℃反应12h后用甲醇将聚合物沉淀出来，洗涤三次。得深色聚合物P1，产率81.7％。1H NMR(CDCl3 500MHz):δ:7.53-7.84(m,18H),6.20-6.48(m,12H),2.00-1.85(m,24H),1.05-1.30(br,104H),0.87(t,24H).GPC:Mn＝32.4KDa,Mw＝114.37KDa,PDI＝3.53.Elem.Anal.:C,72.53；H5.57；F,1.40；N,5.16；O,2.36；S,12.99.
P2：将单体M1(0.5mmol)和单体M4(0.5mmol)加入到25mL两口烧瓶中，通入氮气保护，加入12mL甲苯。抽换气两次后加入7mg Pd(PPh3)4，95℃反应12h后用甲醇将聚合物沉淀出来，洗涤三次。得深色聚合物P2，产率80.9％。1H NMR(CDCl3 500MHz):δ:7.63-7.82(m,16H),6.22-6.41(m,12H),4.12-3.50(m,4H),2.00-1.85(m,28H),1.05-1.30(br,124H),0.87(t,30H).GPC:Mn＝35.8KDa,Mw＝126.73KDa,PDI＝3.54.Elem.Anal.:C,73.06；H,6.13；F,1.27；N,5.62；O,3.21；S,10.71.
P3：将单体M1(0.5mmol)和单体M5(0.5mmol)加入到25mL两口烧瓶中，通入氮气保护，加入11mL甲苯。抽换气两次后加入4mg Pd(PPh3)4，95℃反应12h后用甲醇将聚合物沉淀出来，洗涤三次。得深色聚合物P3，产率81.0％。1H NMR(CDCl3 500MHz):δ:7.66-7.86(m,18H),6.24-6.45(m,12H),2.04-1.87(m,24H),1.15-1.40(br,104H),0.90(t,24H).GPC:Mn＝38.8KDa,Mw＝140.07KDa,PDI＝3.61.Elem.Anal.:C,71.46；H,5.35；F,1.35；N,5.95；O,2.27；S,13.62.
(6)聚合物P4、P5、P6的合成
P4：将单体M2(0.5mmol)和单体M3(0.5mmol)加入到25mL两口烧瓶中，通入氮气保护，加入11mL甲苯。抽换气两次后加入3mg Pd(PPh3)4，95℃反应12h后用甲醇将聚合物沉淀出来，洗涤三次。得深色聚合物P4，产率80.1％。1H NMR(CDCl3 500MHz):δ:7.64-7.82(m,16H),6.34-6.55(m,12H),2.08-1.88(m,24H),1.16-1.48(br,80H),0.85(t,24H).GPC:Mn＝34.8KDa,Mw＝118.32KDa,PDI＝3.40.Elem.Anal.:C,72.53；H,5.57；F,1.40；N,5.16；O,2.36；S,12.99.
P5：将单体M2(0.5mmol)和单体M4(0.5mmol)加入到25mL两口烧瓶中，通入氮气保护，加入11mL甲苯。抽换气两次后加入4mg Pd(PPh3)4，95℃反应12h后用甲醇将聚合物沉淀出来，洗涤三次。得深色聚合物P5，产率81.2％。1H NMR(CDCl3 500MHz):δ:7.54-7.72(m,16H),6.35-6.56(m,12H),4.25-3.66(m,4H),2.18-1.98(m,28H),1.26-1.58(br,100H),0.91(t,30H).GPC:Mn＝35.8KDa,Mw＝126.37KDa,PDI＝3.53.Elem.Anal.:C,73.06；H,6.13；F,1.27；N,5.62；O,3.21；S,10.71.
P6：将单体M2(0.5mmol)和单体M5(0.5mmol)加入到25mL两口烧瓶中，通入氮气保护，加入12mL甲苯。抽换气两次后加入5mg Pd(PPh3)4，95℃反应12h后用甲醇将聚合物沉淀出来，洗涤三次。得深色聚合物P6，产率80.2％。1H NMR(CDCl3 500MHz):δ:7.58-7.76(m,18H),6.39-6.59(m,12H),2.22-1.98(m,24H),1.27-1.56(br,80H),0.89(t,24H).GPC:Mn＝36.8KDa,Mw＝133.58KDa,PDI＝3.63.Elem.Anal.:C,71.46；H,5.35；F,1.35；N,5.95；O,2.27；S,13.62.
将所得的聚合物进行溶液的吸收光谱的测定，结果如图2和图3所示。从溶液的浓度(0.02mg/mL)和所测得的吸收值可以计算出聚合物P1、P2、P3、P4、P5、P6的吸收系数。P1、P2、P3、P4、P5、P6在最高峰的吸收系数分别为2.37×106cm-1，2.21×106cm-1，2.23×106cm-1，2.45×106cm-1，2.19×106cm-1和2.23×106cm-1。
实施例2
以实施例1所合成的共轭聚合物P1、P2、P3作为活性层在有机光伏器件(ITO阳极/阳极界面层/活性层/阴机界面层/阴极)中应用
将ITO导电玻璃，方块电阻～20欧/平方厘米，预切成15毫米×15毫米方片。依次用丙酮、微米级半导体专用洗涤剂、去离子水、异丙醇超声清洗，氮气吹哨后置于恒温烘箱备用。在ITO上旋凃一层20nm厚的PEDOT:PSS，然后分别旋涂活性层材料P1，P2，P3，厚度均为100纳米。然后旋涂一层5nm厚的PFN-Br，最后蒸镀Al电极。所有制备过程均在提供氮气氛围的手套箱内进行。所制备的正装电池器件的电流-电压曲线如图4所示，相关的数据在表1中列出。
实施例3
以实施例1所合成的共轭聚合物P4、P5、P6作为活性层在有机光伏器件(ITO阳极/阳极界面层/活性层/阴机界面层/阴极)中应用
将ITO导电玻璃，方块电阻～20欧/平方厘米，预切成15毫米×15毫米方片。依次用丙酮、微米级半导体专用洗涤剂、去离子水、异丙醇超声清洗，氮气吹哨后置于恒温烘箱备用。在ITO上旋凃一层20nm厚的PEDOT:PSS，然后分别旋涂活性层材料P4、P5、P6，厚度均为100纳米。然后旋涂一层5nm厚的PFN-Br，最后蒸镀Al电极。所有制备过程均在提供氮气氛围的手套箱内进行。所制备的正装电池器件的电流-电压曲线如图5所示，相关的数据在表1中列出。
表1含本发明共轭聚合物的有机光伏器件的性能参数
效率(％) 短路电流(mA/cm<sup>2</sup>) 开路电压(V) 填充因子
P1 7.72 16.5 0.78 0.60
P2 7.93 16.4 0.78 0.62
P3 7.62 16.5 0.77 0.60
P4 6.92 15.5 0.77 0.58
P5 6.88 15.2 0.78 0.58
P6 6.79 15.2 0.77 0.58
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (6)

1.一种主链给体-侧链受体型共轭聚合物，其特征在于结构如下：
其中，n为小于等于100万的正整数，a为3～40的正整数，R为甲基、甲氧基、腈基或氟原子，R1、R2、R3、R4相同或不同的分别为烷基链，A为缺电子共轭单元结构，为苯并噻二唑及其衍生物、苯并三唑酰亚胺及其衍生物、萘二并噻二唑及其衍生物、萘二并三唑及其衍生物中的至少一种。
2.根据权利要求1所述的主链给体-侧链受体型共轭聚合物，其特征在于：所述的R1、R2、R3、R4相同或不同的分别为具有1～40个碳原子的直链、支链或者环状烷基链。
3.根据权利要求2所述的主链给体-侧链受体型共轭聚合物，其特征在于：所述直链、支链或者环状烷基链中的一个或一个以上氢原子被氟原子、氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基、甲基、乙基、甲氧基或硝基取代。
4.根据权利要求1所述的主链给体-侧链受体型共轭聚合物，其特征在于：所述的A为缺电子共轭单元结构，具有如下结构的一种或一种以上：
5.一种权利要求1～4任一项所述的主链给体-侧链受体型共轭聚合物的制备方法，其特征在于通过Stille聚合反应得到。
6.权利要求1～4任一项所述的主链给体-侧链受体型共轭聚合物在单组分有机太阳电池中的应用。
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