CN111269399B - 具有不对称结构的有机聚合物及作为光电材料的用途 - Google Patents

具有不对称结构的有机聚合物及作为光电材料的用途 Download PDF

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CN111269399B
CN111269399B CN202010051644.9A CN202010051644A CN111269399B CN 111269399 B CN111269399 B CN 111269399B CN 202010051644 A CN202010051644 A CN 202010051644A CN 111269399 B CN111269399 B CN 111269399B
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organic polymer
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CN111269399A (zh
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刘冬雪
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China Three Gorges Corp
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Abstract

本发明公开了基于具有不对称结构的有机聚合物，制备方法及光电材料的用途。不对称结构的有机聚合物通过给电子D单元和拉电子A单元，在溶剂和催化剂的存在下，进行Stille偶联反应进行聚合得到所述化合物。本申请的化合物具有优良的热稳定性、吸收能级可控、适用于制备具有高效、稳定性好、柔性、大面积的高性能钙钛矿电池空穴材料及有机太阳能电池给体材料。

Description

具有不对称结构的有机聚合物及作为光电材料的用途
技术领域
本申请涉及材料化学领域。更具体地，本申请涉及光电材料领域。
背景技术
近年来，有机-无机杂化钙钛矿太阳能电池发展迅速，其光电转换效率已由2009年的3.8％提升至目前的25.2％。钙钛矿电池不仅效率高，还兼具低成本，可溶液加工的特点；同时钙钛矿材料具备吸收强，迁移率高，载流子寿命长，带隙可调等优点。在钙钛矿材料和金属电极之间插入适当的空穴传输材料，能促使电子和空穴在功能层界面分离，减少电荷复合，同时有利于空穴传输，提高电池效率，并且可以提高器件的稳定性。目前被广泛应用的空穴传输材料(Spiro-OMeTAD和PTAA(poly(triarylamine)))一般价格昂贵，且需要通过掺杂易吸水添加剂得到较高的效率，但牺牲了器件的稳定性。因此，开发成本低廉性能优越的新型空穴传输材料，提高钙钛矿电池效率及器件稳定性乃至推进钙钛矿电池的商业化应用意义深远。
发明内容
一方面，本申请涉及选自化合物(1)至(5)的不对称聚合物：
Figure GDA0002450359510000021
其中R1分别独立地选自C1-C30烷基、C3-C30环烷基、C1-C30烷氧基；
R2分别独立地选自基团7至基团12：
Figure GDA0002450359510000022
其中R选自C1-C30烷基、C3-C30环烷基、C1-C30烷氧基，n>4。
R3分别独立地选自C6-C30烷基、C3-C30环烷基、C6-C30烷氧基及含氧醚链。
作为优选方案，所述的不对称有机聚合物的结构式为
Figure GDA0002450359510000031
一方面目标分子通过给电子单元和拉电子单元，在溶剂和催化剂的存在下，进行Stille偶联反应进行聚合得到所述聚合物。
所述溶剂为混合溶剂，优选甲苯与N,N-二甲基甲酰胺混合溶剂，溶剂的体积比例为甲苯：N,N-二甲基甲酰胺混合溶剂＝6-10:1。
所述催化剂为Pd2(dba)3或Pd(PPh3)4。
所述制备方法在保护气体下进行，所述保护气体优选氮气或氩气。
再一方面，本申请涉及包含的具有通式(1)至通式(6)的不对称聚合物在制备钙钛矿太阳能电池中的用途。
又一方面本申请涉及包含的具有通式(1)至通式(6)的不对称聚合物在钙钛矿电池中空穴传输层的用途。
另一方面Spiro-OMeTAD作为空穴传输材料需要配备LiTFSI和t-BP作为掺杂剂，而掺杂剂具有较强的吸水性，影响电池的稳定性。因此，研发新型非掺杂空穴传输材料，降低电池制备成本，提高器件稳定性，对推动钙钛矿电池的产业化具有重要意义。
附图说明
图1为本申请实施例化合物10的热重曲线。
图2为本申请实施例化合物10的分子量分布曲线。
图3为本申请实施例化合物10的紫外吸收曲线。
图4为本申请实施例化合物10的循环伏安曲线。
图5为本申请实施例化合物10用于钙钛矿电池空穴传输层的电池结构
图6为本申请实施例化合物10的电流密度-电压曲线。
图7为本申请实施例化合物10的UV-Vis下的吸收光谱图。
图8为本申请实施例化合物10在氩气保护下的循环伏安曲线。
图9为光伏器件结构。
图10为电流密度-电压曲线图。
具体实施方式
在以下的说明中，包括某些具体的细节以对各个公开的实施方案提供全面的理解。然而，相关领域的技术人员会认识到，不采用一个或多个这些具体的细节，而采用其它方法、部件、材料等的情况下可实现实施方案。
除非本申请中另外要求，在整个说明书和其后的权利要求书中，词语“包括”和“包含”应解释为开放式的、含括式的意义，即“包括但不限于”。
在整个本说明书中提到的“一实施方案”或“实施方案”或“在另一实施方案中”或“在某些实施方案中”意指在至少一实施方案中包括与该实施方案所述的相关的具体参考要素、结构或特征。因此，在整个说明书中不同位置出现的短语“在一实施方案中”或“在实施方案中”或“在另一实施方案中”或“在某些实施方案中”不必全部指同一实施方案。此外，具体要素、结构或特征可以任何适当的方式在一个或多个实施方案中结合。
Figure GDA0002450359510000051
在某些实施方案中，制备通式(1)的不对称聚合物的方法如下所示，
Figure GDA0002450359510000061
Figure GDA0002450359510000071
化合物7的合成
氮气保护下，在100毫升三口瓶中加入1-溴-4-己基苯(1.06g,4.49mmol)和30mL无水四氢呋喃，降温至-78℃，缓慢滴入n-BuLi(2.8mL,1.6M正己烷溶液)，-78℃下反应30min后，滴入2-溴-3-噻吩甲酸乙酯(0.5g,1.12mmol)反应4h。反应完全后，加水淬灭，乙酸乙酯萃取(3×50mL)，合并有机相，有机相依次用水、饱和NaCl洗涤，无水硫酸钠干燥。蒸去溶剂，得到黄色液体粗产物中间体。
黄色液体粗产物中间体溶于50mL无水甲苯中，氮气鼓泡15min，加入Amberlyst15，升温至110℃反应2h后，蒸去溶剂，剩余物以石油醚：二氯甲烷(v/v＝16:1)为淋洗剂进行柱色谱纯化，得到淡黄色固体化合物7(0.3g，两步反应得总收率为37％)。1H NMR(400MHz,CDCl3),δ(ppm):7.28(dd,J＝13.9,6.1Hz,4H),7.12–7.03(m,6H),6.99(d,J＝4.9Hz,1H),6.96(d,J＝5.3Hz,1H),3.71(d,J＝8.1Hz,2H),2.58(t,J＝7.8Hz,4H),1.59(dd,J＝8.1,4.3Hz,6H),1.38–1.27(m,15H),1.11–1.03(m,2H),0.91(d,J＝6.7Hz,6H),0.77(t,J＝7.3Hz,3H),0.57(d,J＝4.4Hz,6H).13C NMR(101MHz,CDCl3)δ144.94,144.56,141.69,141.47,141.08,136.89,135.61,135.17,134.21,133.53,133.50,131.84,131.24,131.04,129.10,128.33,128.16,127.89,126.04,122.91,122.87,122.76,122.70,114.70,114.63,114.55,110.89,110.83,110.32,110.04,108.68,77.32,77.00,76.68,51.19,51.11,40.38,40.33,35.68,35.57,32.02,31.81,31.71,31.68,31.32,30.60,29.03,28.64,24.03,23.96,22.96,22.93,22.85,22.74,22.58,22.48,14.08,14.01,13.96,13.93,10.65,10.60.。
化合物8的合成。
在100毫升三口瓶中加入7(0.20g,0.28mmol)和30毫升干燥三氯甲烷，抽换氮气并降温至0℃，加入NBS(79.6mg,0.62mmol)的DMF溶液(2mL)，0℃避光反应30min。减压蒸去有机溶剂，以石油醚为淋洗剂，直接柱色谱分离，得到黄色固体8(0.19g,78.8％)。1H NMR(CDCl3,400MHz),δ(ppm):δ7.29(s,1H),7.12(d,J＝8.3Hz,4H),6.96(d,J＝7.1Hz,4H),6.79(s,1H),3.90(t,J＝7.6Hz,2H),2.58(t,J＝7.8Hz,4H),2.04(t,J＝7.4Hz,3H),1.59(q,J＝7.3Hz,6H),1.33–1.27(m,24H),0.88(dd,J＝8.1,2.3Hz,14H),0.55(ddt,J＝12.3,7.2,4.0Hz,2H).；13C NMR(100MHz,CDCl3),δ(ppm):143.64,142.63,142.03,137.41,136.08,135.89,134.68,133.57,132.59,132.53,129.06,128.48,128.43,128.01,126.03,114.66,114.27,114.22,110.21,109.85,109.62,108.75,77.32,77.00,76.68,53.40,51.24,40.30,35.56,32.05,31.69,31.32,30.55,29.01,28.60,23.93,22.92,22.58,22.41,14.07,13.98,13.90,10.57.
化合物10的合成
25mL三口瓶中，将化合物8(80mg,0.113mmol)和化合物9(137mg,0.113mmol)溶于4.5mL甲苯与0.5mL N,N-二甲基甲酰胺的混合溶剂中，氮气鼓泡15min。加入5.17mg Pd2(dba)3和p-(o-tol)6mg，加热回流4h，待溶液粘稠后立即停止加热，冷却后导入100mL无水甲醇中沉降，抽滤，利用索氏提取器提纯后，再利用柱色谱进行二次提纯，得到蓝黑色固体10 0.1g。
化合物10的热稳定性测试
化合物10的热稳定性用热重分析(TG)在TA instrument SDT-TG Q600热重分析仪上进行，氮气流下加热扫描速率为10℃/min，如图5、6所示。
化合物10的紫外吸收测试
本发明利用UV-Vis对化合物10在溶液和薄膜状态下的吸收光谱进行测试，测试结果如图7所示。
化合物10的能级测试
利用上海华晨CHI 600E电化学分析仪电化学工作站进行电化学性质的测试，电解池为三电极体系(玻碳电极为工作极，铂丝电极为辅助电极，甘汞电极为参比电极)，以二茂铁做内标，0.1M的四丁基六氟磷酸胺(n-Bu4NPF6)为支持电解质，扫描速度为100mV s-1。在氩气保护下，其循环伏安曲线如附图8及表1所示。
表1化合物10的光学和电化学性能数据。
Figure GDA0002450359510000091
以实施例化合物10为空穴传输层的钙钛矿太阳能电池器件的制备
光伏器件的制备
器件结构为ITO/SnO2/Perovskite/HTM/MoO3/Ag，如图9所示。具体步骤如下：
(1)清洗基底。首先将刻蚀好的ITO玻璃基底依次用洗洁精水、去离子水、丙酮和异丙醇各超声清洗15分钟，将清洗干净的ITO玻璃用高纯氮气吹干后，再用紫外臭氧(UV/O3)处理20min，清洗表面的有机污染物并增加表面的浸润性。
(2)制备电子传输层和钙钛矿活性层。首先，在ITO基底上旋涂SnO2传输层，用0.22μm的PES材质水系滤膜过滤后，以3000rpm的转速旋涂30s，再将其转移到加热板上150℃退火30min。接着将ITO/SnO2基底转移到氮气手套箱中，待其冷却后，旋涂1.1M的PbI2的DMF溶液，1500rpm的转速旋涂30s，70℃加热15min，然后再旋涂FAI:MAI:MACl＝51：9:12的盐的异丙醇溶液，2000rpm的转速旋涂30s。转移到手套箱外，100℃退火30min。再将旋涂有钙钛矿的基板转移到氮气手套箱中旋涂化合物10的二氯苯溶液(8mg/ml，CB)，以1500rpm转速旋涂40s。
(3)蒸镀金属电极。在高真空度下(<1×10-4Pa)蒸镀15nm厚的MoO3，再蒸Ag电极。每个电池的有效面积为0.1cm2。电流密度-电压曲线图10所示。
采用上述化合物10的步骤合成化合物11-14，得到的化合物如下：
Figure GDA0002450359510000101
表2：实施例10-14的钙钛矿太阳能电池性能(光强为100mW/cm2AM1.5G照射条件下测量)
Figure GDA0002450359510000102
由此可见，本申请的化合物具有优良的热稳定性、吸收能级可控、适用于制备具有高效、稳定性好、柔性、大面积的高性能钙钛矿电池空穴材料及有机太阳能电池给体材料。
从前述中可以理解，尽管为了示例性说明的目的描述了本申请的具体实施方案，但是在不偏离本申请的精神和范围的条件下，本领域所述技术人员可以作出各种变形或改进。这些变形或修改都应落入本申请所附权利要求的范围。

Claims (9)

1.选自化合物1-1至5-1的含有给电子单元和拉电子单元的不对称有机聚合物，其特征在于，包括如下结构式中的任意一种：
Figure FDA0003605860810000011
Figure FDA0003605860810000012
R1分别独立地选自C1-C30烷基、C3-C30环烷基、C1-C30烷氧基中的任意一种，R2分别独立地选自基团7至基团12中的任意一种：
Figure FDA0003605860810000013
其中R选自C1-C30烷基、C3-C30环烷基、C1-C30烷氧基中的任意一种，n>4，R3分别独立地选自C6-C30烷基、C3-C30环烷基、C6-C30烷氧基及含氧醚链中的任意一种。
2.如权利要求1所述的不对称有机聚合物，其特征在于，不对称有机聚合物的结构式为
Figure FDA0003605860810000021
3.制备权利要求1或2所述的不对称有机聚合物的方法，其特征在于，目标分子通过给电子D单元和拉电子A单元在溶剂和催化剂的存在下，进行Stille偶联反应进行聚合得到所述化合物。
4.如权利要求3所述的不对称有机聚合物的方法，其特征在于，给电子D单元分别独立选自下式基团13至17；拉电子A单元分别独立选自下式基团18和19：
Figure FDA0003605860810000022
其中R1分别独立地选自C1-C30烷基、C3-C30环烷基、C1-C30烷氧基中的任意一种；
R2分别独立地选自基团7至基团12中的任意一种：
Figure FDA0003605860810000031
其中R选自C1-C30烷基、C3-C30环烷基、C1-C30烷氧基中的任意一种，n>4；
R3分别独立地选自C6-C30烷基、C3-C30环烷基、C6-C30烷氧基、或含氧醚链中的任意一种。
5.如权利要求3所述的方法，其特征在于，所述溶剂为甲苯与N,N-二甲基甲酰胺混合溶剂，溶剂的体积比例为甲苯：N,N-二甲基甲酰胺混合溶剂＝6-10:1。
6.如权利要求4所述的方法，其特征在于，所述催化剂为Pd2(dba)3或Pd(PPh3)4。
7.如权利要求5所述的方法，其特征在于，所述制备方法在保护气体下进行，所述保护气体为氮气、或氩气。
8.权利要求1或2所述的不对称有机聚合物在制备钙钛矿太阳能电池中的用途。
9.如权利要求8所述的用途，其特征在于，所述不对称有机聚合物用于制备钙钛矿电池的光活性层中的空穴传输层。
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