CN111978515B - 含苄醇基团的空穴传输高分子及其应用 - Google Patents
含苄醇基团的空穴传输高分子及其应用 Download PDFInfo
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- CN111978515B CN111978515B CN201910425043.7A CN201910425043A CN111978515B CN 111978515 B CN111978515 B CN 111978515B CN 201910425043 A CN201910425043 A CN 201910425043A CN 111978515 B CN111978515 B CN 111978515B
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- hole transport
- benzyl alcohol
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- perovskite
- alkoxy
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- 125000002541 furyl group Chemical group 0.000 claims description 2
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—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
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/84—Layers having high charge carrier mobility
- H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G2261/10—Definition of the polymer structure
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Abstract
本发明涉及一种含有苄醇基团的空穴传输高分子及其在钙钛矿太阳能电池中的应用，属于钙钛矿太阳能电池领域。本发明的目的是提供一种含苄醇基团的高分子空穴传输材料。此材料的高分子主链由三芳胺类重复单元构成，以保证其具有合适的HOMO能级和空穴迁移率；侧链引入苄醇基团以提高高分子的亲水性，可以实现钙钛矿层在其薄膜表面的完整均匀覆盖。此外，该高分子的重复单元合成简单，原料价格便宜，降低了材料的开发成本。这些有利于此类高分子空穴传输材料在高效、大面积器件中的应用，具有很好的应用前景。
Description
技术领域
本发明涉及钙钛矿太阳能电池领域，具体涉及一种含有苄醇基团的空穴传输高分子的制备方法及其在钙钛矿太阳能电池中的应用。
背景技术
近年来，“能源危机”以及化石能源燃烧所带来的环境问题越来越受到人们的重视，发展可再生、环境友好的新能源势在必行。其中，太阳能是“取之不尽、用之不竭”的清洁能源，对人类社会的可持续发展至关重要。开发低成本、高效率的新型太阳能电池已成为了近年来的研究热点。其中钙钛矿太阳能电池(PSC)发展迅速，器件效率已从2009年的3.8％[1]提升至2018年的23.7％[2]，成为目前新型太阳能电池领域的研究热门之一。
CH3NH3PbI3(MAPbI3)等有机-无机杂化钙钛矿材料具有诸多优点，比如，消光系数高且带隙合适[3]、激子束缚能低[4]、电荷扩散距离长[5]、载流子迁移率高[6]、光谱吸收范围宽[7]等，非常适合作为太阳能电池的吸光材料。PSC效率迅速提高得益于钙钛矿材料组分的调控、制备方法的优化[8]以及新型高效电荷收集材料的发展[9]。电荷收集材料包括电子传输材料和空穴传输材料(HTM)，是实现PSC更高效率和稳定性必不可少的部分[10]。
相比于无机和有机小分子HTM，高分子HTM具有更好的成膜性和形貌稳定性，更适合未来稳定、大面积器件制备。PTAA是一种经典的高分子HTM，结合优异的钙钛矿薄膜制备方法，已经实现了超过20％的器件效率[11]。然而，作为反式PSC器件中的空穴传输层时，PTAA本身的疏水性质使得钙钛矿前驱液在其表面的浸润性差，造成钙钛矿层覆盖不完整[12]。这不仅不利于电池效率的提升，更限制了大面积器件的制备。此外，PTAA本身价格昂贵[13]，同样限制了其未来的大规模应用。因此开发浸润性好、效率高且成本低廉的新型HTM具有重要的意义。
发明内容
本发明的目的之一，提供一种含苄醇基团的高分子HTM。本发明的HTM，高分子主链由三芳胺类重复单元构成，以保证其具有合适的HOMO能级和空穴迁移率；侧链引入苄醇基团以提高高分子的亲水性，可以实现钙钛矿层在其薄膜表面的有效铺展。此外，该高分子重复单元合成简单，原料价格便宜，降低了材料的开发成本。这些有利于此类高分子HTM在高效、大面积器件中的应用。
为了实现上述目的，本发明的技术方案具体如下：
一种含有苄醇基团的高分子，其特征在于，其化学结构式通式如下：
通式中圆括号间的结构单元(下标分别为X和1-X)的共聚方式是无规共聚，涉及的符号和系数具有如下含义：
R1为H、C1-C20的烷氧基或者C1-C20的烷基；
x是0到1；
n是2-500；
＊是常见封端单元，包括苯基、联苯基、噻吩基、联噻吩基、呋喃基、咔唑基、三苯胺基等；
Ar1、Ar2是相同或者不同的，并为如下所示结构:
其中的符号和系数具有如下含义：
结构式(1)中R2是相同或者不同的，并为H、-CH2OH、C1-C20的烷氧基或者C1-C20的烷基中的一种或二种以上；
当x不为0时，R3、R4、R5是相同或者不同的，并分别为H、-CH2OH、C1-C20的烷氧基或者C1-C20的烷基中的一种或二种以上；
当x为0时，Ar2选择结构式(2)(3)中的一种或二种；Ar2选择结构式(2)时，R3、R4分别为H、-CH2OH、C1-C20的烷氧基或者C1-C20的烷基中的一种或二种以上，且其中至少有一个取代基为-CH2OH；Ar2选择结构式(3)时，R5为-CH2OH；Ar2选择结构式(2)(3)中的二种时，R3、R4、R5分别为H、-CH2OH、C1-C20的烷氧基或者C1-C20的烷基中的一种或二种以上，且其中至少有一个取代基为-CH2OH。
本发明的目的之二，提供上述含苄醇基团的高分子HTM的应用。本发明的高分子HTM可用于PSC的空穴传输层，使其表现出较高的光电转换效率和更好的器件重复性。以实施例1中的高分子材料P1为例，以其作为空穴传输层，制备出的反式器件光电转换效率达到20.10％。
本发明解决上述问题的技术方案如下：一种如上所述的含苄醇基团的高分子空穴传输材料在钙钛矿太阳能电池器件中的应用。
术语：
“PTAA”，指的是聚[双(4-苯基)(2,4,6-三甲基苯基)胺]。
“Pd2dba3”，指的是三(二卞叉丙酮)二钯。
“Xantphos”，指的是4,5-双(二苯基膦)-9,9-二甲基氧杂蒽。
“NBS”，指的是N-bromosuccinimide，N-溴代丁二酰亚胺。
“DMF”，指的是N,N-Dimethylformamide，N,N-二甲基甲酰胺。
“Pd(OAc)2”，指的是醋酸钯。
“Pd(dppf)Cl2”，指的是1,1'-二(二苯膦基)二茂铁二氯化钯(II)。
“Sphos”，指的是2-双环己基膦-2',6'-二甲氧基联苯。
“Aliquat 336”，指的是甲基三辛基氯化铵。
“PCBM”，指的是(6,6)-苯基-C61-丁酸异甲酯。
“DMSO”，指的是二甲基亚砜。
本发明的有益效果是：
1、相比经典材料PTAA，本发明的空穴传输材料，利用三芳胺类单元来构建高分子主链，以保证其具有合适的能级和空穴迁移率；引入烷基侧链保证高分子的溶解性；苄醇类侧链可以降低其薄膜的接触角(图1)，增加了其薄膜的亲水性，这不仅有利于钙钛矿层在其表面的铺展，进而实现在完整钙钛矿层的形成(图2)，同时苄醇基团的羟基还能加强与钙钛矿层的相互作用，有利于电荷的有效提取。
2、本发明中高分子重复单元的合成路线简单、收率高、提纯容易，反应条件温和；所有涉及的反应均为常压反应，所有反应温度均在0～110℃之间，易于大规模制备；所需原料廉价易得，均为市售商品。
3、本发明的空穴传输材料用于钙钛矿太阳能电池器件，器件具有较高的光电转换效率。以材料实施例1中的高分子P1为例，以其作为空穴传输层，制备出的反式器件光电转换效率达到20.10％。
4、本发明的钙钛矿太阳能电池器件的制备方法，操作步骤简单易行，所需原料和设备均容易购买。
5、本发明的高分子空穴传输材料同样实现了钙钛矿层在其表面大面积的有效覆盖(1cm2)(图2)，说明本发明所提出的含苄醇基团的空穴传输高分子在大尺寸钙钛矿电池器件方面具有良好的应用前景。
此材料的高分子主链由三芳胺类重复单元构成，以保证其具有合适的HOMO能级和空穴迁移率；侧链引入苄醇基团以提高高分子的亲水性，可以实现钙钛矿层在其薄膜表面的完整均匀覆盖。此外，该高分子的重复单元合成简单，原料价格便宜，降低了材料的开发成本。这些有利于此类高分子空穴传输材料在高效、大面积器件中的应用，具有很好的应用前景。
附图说明
图1为实施例1中的高分子P1和PTAA薄膜表面的水滴的接触角测试结果，
图2为在同样制备条件下，在1cm2面积大小时钙钛矿层(黑色)在实施例1中的高分子P1和PTAA薄膜表面分布情况的对比，具体为在P1和PTAA薄膜表面旋涂制备同样厚度(400nm)钙钛矿层，钙钛矿层的形成情况对比，
图3为本发明提供的钙钛矿太阳能电池的器件结构图，涉及钙钛矿电池器件各层分布情况。
附图中，各标号所代表的部件依次为玻璃基底1、ITO阳极2、空穴传输层3、钙钛矿层4、电子传输层5和Ag电极6。
图4为以实施例1中的高分子P1作为空穴传输材料制成的钙钛矿太阳能电池器件的电流-电压曲线。
具体实施方式
以下这些实施例更详细地说明本发明，而不是要把本发明限于这些实施例。
合成实施例所需的中间体化合物的合成过程如下：
化合物2的合成：
氩气条件下，将14.15g(50.00mmol)化合物1、4.60g(50.00mmol)苯胺、0.23g(0.25mmol)Pd2(dba)3、0.58g(1.00mmol)膦配体Xantphos、7.21g(75.00mmol)叔丁醇钠和50mL甲苯混合搅拌，升温至110℃回流15分钟。反应结束后过滤，蒸干甲苯后补加二氯甲烷，水洗三次后用无水硫酸钠干燥。硅胶柱分离得油状液体9.92g(收率80％)。LC-MS：C12H10BrN，计算值：248.12；实测值：[M]+＝248.12。1H NMR(300MHz,CDCl3)δ7.48(dd,J＝1.5,1.8Hz,1H),7.31-7.10(m,6H),7.0(t,J＝7.3Hz,1H),6.69(dt,J＝1.7,8.1Hz,1H),6.03(bs,1H).合成路线如下：
化合物3的合成：
将12.41g(50.00mmol)化合物2、10.62g(55.00mmol)溴辛烷、2.00g(50.00mmol)氢氧化钠和100mL DMSO室温搅拌24小时。反应结束后将反应液倒入到2000mL水中，二氯甲烷萃取三次，所得有机相水洗三次，干燥、浓缩后柱分离得无色油状液体15.00g(收率83％)。LC-MS：C20H26BrN，计算值：360.34；实测值：[M]+＝360.34。1H NMR(400MHz,CDCl3)δ7.45(dd,J＝7.9,1.4Hz,1H),7.12–7.03(m,3H),6.92(dd,J＝8.2,1.4Hz,1H),6.89–6.84(m,2H),6.81–6.77(m,1H),6.62(td,J＝7.9,1.5Hz,1H),3.92(t,J＝6.6Hz,2H),1.76(dd,J＝14.7,6.8Hz,2H),1.44(dd,J＝14.8,7.0Hz,2H),1.32(dd,J＝13.5,8.0Hz,8H),0.92–0.86(m,3H).合成路线如下：
化合物4的合成：
氩气条件下，将28.83g(80.00mmol)化合物3的四氢呋喃溶液(200mL)缓慢滴入到2.14g(88.00mmol)镁屑中，滴完后在50℃搅拌3小时。在冰水浴条件下，向反应溶液中加入27.04g(80.00mmol)2,7-二溴-9-芴酮，室温搅拌12小时。反应结束后，蒸干溶剂，加入二氯甲烷和饱和氯化铵水溶液，经过萃取、分液、无水硫酸钠干燥、硅胶柱分离得中间体粗产品。将粗产品加入到200mL乙酸中搅拌溶解，再加入20mL浓盐酸，70℃搅拌过夜。反应结束后，加入二氯甲烷，然后水洗至中性，所得粗产品经过乙醇重结晶得针状晶体28.87g(收率60％)。LC-MS：C33H31Br2N，计算值：601.43，实测值：[M]+＝601.43。1H NMR(400MHz,CDCl3)δ7.58(d,J＝8.1Hz,2H),7.46(dd,J＝8.1,1.8Hz,2H),7.36(d,J＝1.7Hz,2H),7.23–7.18(m,2H),7.06(d,J＝8.1Hz,2H),6.64(t,J＝7.4Hz,2H),6.37(dd,J＝7.7,1.5Hz,2H),4.08–3.98(m,2H),1.95(dd,J＝15.8,7.9Hz,2H),1.53(m,4H),1.45–1.31(m,6H),0.93(t,J＝6.8Hz,3H).合成路线如下：
化合物5的合成：
在氩气条件下，将4.81g(8.00mmol)化合物4、5.28g(20.80mmol)双联频哪醇硼酸酯、0.39g(0.48mmol)Pd(dppf)Cl2、5.18g(52.80mmol)醋酸钾和70mL无水DMF混合搅拌，升温至90℃反应24小时。反应结束后，加入2000mL水，二氯甲烷萃取后水洗三次、无水硫酸钠干燥，柱分离得粗产物，再经过乙醇重结晶得无色针状晶体4.45g(收率80％)。LC-MS：C45H55B2NO4，计算值：695.56；实测值：[M]+＝695.56。1H NMR(400MHz,CDCl3)δ7.83–7.76(m,4H),7.63(s,2H),7.20–7.08(m,2H),7.02(d,J＝8.2Hz,2H),6.54(t,J＝7.3Hz,2H),6.32(dd,J＝7.7,1.5Hz,2H),4.11–3.97(m,2H),2.06–1.93(m,2H),1.64–1.32(m,10H),1.30–1.24(m,24H),0.98–0.90(m,3H).合成路线如下：
化合物6的合成：
在氩气条件下，将3.01g(5.00mmol)化合物4和9.53g(130.00mmol)的无水DMF混合搅拌。在0℃下，滴入15.33g(100.00mmol)POCl3,滴完后0℃搅拌0.5小时，再升温至105℃搅拌4小时。反应结束后，加入500mL水，二氯甲烷萃取后水洗三次、无水硫酸钠干燥，柱分离得浅黄色固体2.63g(收率80％)。LC-MS：C35H31Br2NO2，计算值：657.45；实测值：[M]+＝657.45。1H NMR(400MHz,CDCl3)δ9.59(s,2H),7.78(dd,J＝8.7,1.9Hz,2H),7.67(d,J＝8.2Hz,2H),7.55(dd,J＝8.2,1.8Hz,2H),7.23(d,J＝8.7Hz,2H),6.85(d,J＝1.9Hz,2H),4.22–4.07(m,2H),2.01(m,2H),1.67–1.58(m,2H),1.56–1.48(m,2H),1.39(m,6H),0.93(t,J＝6.9Hz,3H).合成路线如下：
化合物8的合成：
将2.73g(10.00mmol)化合物7溶解于70mL四氢呋喃中。在0℃下，将3.92g(22.00mmol)NBS分批加入到反应液中，加完后继续搅拌4小时，再室温搅拌10小时。反应结束后，蒸干溶剂，加入二氯甲烷溶解产物，再经过水洗、无水硫酸钠干燥，乙醇重结晶得黄色块状晶体4.60g(收率90％)。LC-MS：C19H13Br2NO,计算值：431.13；实测值：[M]+＝431.13。1HNMR(400MHz,CDCl3)δ9.84(s,1H),7.74–7.69(m,2H),7.47–7.43(m,4H),7.08–6.99(m,6H).合成路线如下：
化合物9的合成：
在氩气条件下，将2.15g(5.00mmol)化合物8、3.81g(15.00mmol)双联频哪醇硼酸酯、0.12g(0.15mmol)Pd(dppf)Cl2、3.93g(40.00mmol)醋酸钾和50mL无水二氧六环混合搅拌，升温至80℃反应8小时。反应结束后，蒸干溶剂，二氯甲烷萃取后水洗三次、无水硫酸钠干燥，柱分离得粗产物，再经过乙醇重结晶得黄色块状晶体2.10g(收率80％)。LC-MS：C31H37B2NO5，计算值：525.26；实测值：[M]+＝525.26。1H NMR(400MHz,CDCl3)δ9.84(s,1H),7.75(d,J＝5.0Hz,4H),7.70(d,J＝8.8Hz,2H),7.11(t,J＝8.9Hz,6H),1.35(s,24H).合成路线如下：
实施例1
高分子P1的合成：
在氩气条件下，将0.1078g(0.25mmol)化合物5、0.1739g(0.25mmol)化合物8、0.46mg Pd(OAc)2、1.64mg膦配体Sphos、5.00mg相转移催化剂Aliquat 336和5mL无水甲苯混合搅拌，升温至95℃后加入无氧碳酸钾水溶液(2M，0.8mL)，然后95℃搅拌5小时。依次加入15.00mg苯硼酸反应5小时和0.50mL溴苯反应5小时。降温至80℃加入1.00g二乙基二硫代氨基甲酸钠，继续搅拌24小时。反应结束后，二氯甲烷萃取后水洗三次、无水硫酸钠干燥。过滤、浓缩后，将产物沉降到150mL甲醇中。将所得固体、12.58mg(0.33mmol)的硼氢化钠和60mL二氯甲烷在氩气氛围回流搅拌4小时。反应结束后蒸干溶剂，二氯甲烷萃取后水洗一次、无水硫酸钠干燥。浓缩至5mL，加入100mL正己烷后得黄绿色固体134mg(收率75％)。1HNMR(400MHz,DMSO)δ7.99(m,2H),7.73–7.63(m,2H),7.43(m,6H),7.21(m,6H),6.99(m,6H),6.62(m,2H),6.36(m,2H),5.18–5.07(m,1H),4.45(s,2H),4.19–4.06(m,2H),1.83(s,2H),1.49(s,2H),1.35(s,2H),1.16(m,6H),0.76(s,3H).合成路线如下：其中n为10-30，平均值为20。
实施例2
高分子P2的合成：
在氩气条件下，将0.1644g(0.25mmol)化合物6、0.1278g(0.25mmol)化合物10、0.46mg Pd(OAc)2、1.64mg膦配体Sphos、5.00mg相转移催化剂aliquat 336和5mL无水甲苯混合搅拌，升温至95℃后加入无氧碳酸钾水溶液(2M，0.8mL)，然后95℃搅拌5小时，再依次加入15.00mg苯硼酸反应5小时和0.50mL溴苯反应5小时。降温至80℃，加入1.00g二乙基二硫代氨基甲酸钠，继续搅拌24小时。反应结束后，二氯甲烷萃取后水洗三次、无水硫酸钠干燥。过滤、浓缩，将产物沉降到150mL甲醇中。将所得固体、12.58mg(0.33mmol)的硼氢化钠和60mL二氯甲烷在氩气氛围回流搅拌4小时。反应结束后蒸干溶剂，二氯甲烷萃取后水洗一次、无水硫酸钠干燥。浓缩至5mL，加入100mL正己烷得黄绿色固体142mg(收率75％)。1H NMR(400MHz,CDCl3)δ7.78(s,2H),7.57(m,2H),7.45(s,2H),7.36(d,J＝8.0Hz,4H),7.20(d,J＝7.7Hz,2H),7.09–6.93(m,10H),6.45(m,2H),4.29(d,J＝8.0Hz,4H),4.04(s,2H),2.31(s,3H),1.96(d,J＝5.7Hz,2H),1.60–1.19(m,10H),0.88(t,J＝6.6Hz,3H).合成路线如下：其中n为14-34，平均值为24。
实施例3
高分子P3的合成：
在氩气条件下，将0.1644g(0.25mmol)化合物6、0.1313g(0.25mmol)化合物9、0.46mg Pd(OAc)2、1.64mg膦配体Sphos、5.00mg相转移催化剂aliquat 336和5mL无水甲苯混合搅拌，升温至95℃后加入无氧碳酸钾水溶液(2M，0.8mL)，然后95℃搅拌5小时，再依次加入15.00mg苯硼酸反应5小时和0.50mL溴苯反应5小时。降温至80℃加入1.00g二乙基二硫代氨基甲酸钠，继续搅拌24小时。反应结束后，二氯甲烷萃取后水洗三次、无水硫酸钠干燥。过滤、浓缩后，将产物沉降到150mL甲醇中。将所得固体、12.58mg(0.33mmol)硼氢化钠和60mL二氯甲烷在氩气氛围回流搅拌4小时。反应结束后蒸干溶剂，二氯甲烷萃取后水洗一次、无水硫酸钠干燥。浓缩至5mL，加入100mL正己烷得黄绿色固体144mg(收率75％)。1H NMR(400MHz,DMSO)δ7.99(m,2H),7.69(m,2H),7.43(m,6H),7.25(m,2H),7.19–7.09(m,4H),6.99(m,6H),6.35(s,2H),5.14(s,0.15H),4.80(s,0.35H),4.44(s,2H),4.10(s,6H),1.83(s,2H),1.49(s,2H),1.35(s,2H),1.16(m,6H),0.76(s,3H).合成路线如下：其中n为12-34，平均值为23。
实施例4
高分子P4的合成：
在氩气条件下，将0.1078g(0.25mmol)化合物8、0.1383g(0.25mmol)化合物11、0.46mg Pd(OAc)2、1.64mg膦配体Sphos、5.00mg相转移催化剂aliquat 336和5mL无水甲苯混合搅拌，升温至95℃后加入无氧碳酸钾水溶液(2M，0.8mL)，然后95℃搅拌5小时，再依次加入15.00mg苯硼酸反应5小时和0.50mL溴苯反应5小时。降温至80℃，加入1.00g二乙基二硫代氨基甲酸钠，继续搅拌24小时。反应结束后，二氯甲烷萃取后水洗三次、无水硫酸钠干燥。过滤、浓缩后将产物沉降到150mL甲醇中。将所得固体、12.58mg(0.33mmol)硼氢化钠和60mL二氯甲烷在氩气氛围回流搅拌4小时。反应结束后蒸干溶剂，二氯甲烷萃取后水洗一次、无水硫酸钠干燥。浓缩至5mL，加入100mL正己烷得黄绿色固体107mg(收率75％)。1H NMR(400MHz,CDCl3)δ7.58(d,J＝7.7Hz,1H),7.44(m,8H),7.32–7.26(m,5H),7.13(m,8H),6.97–6.88(m,2H),4.66(s,1H),3.81(s,2H),1.43–1.18(m,9H).合成路线如下：其中n为14-36，平均值为25。
实施例5
高分子P5的合成：
在氩气条件下，将0.1078g(0.25mmol)化合物5、0.1652g(0.2375mmol)化合物8、0.0052g(0.0125mmol)化合物12、0.46mg Pd(OAc)2、1.64mg膦配体Sphos、5.00mg相转移催化剂Aliquat 336和5mL无水甲苯混合搅拌，升温至95℃后加入无氧碳酸钾水溶液(2M，0.8mL)，然后95℃搅拌5小时。依次加入15.00mg苯硼酸反应5小时和0.50mL溴苯反应5小时。降温至80℃加入1.00g二乙基二硫代氨基甲酸钠，继续搅拌24小时。反应结束后，二氯甲烷萃取后水洗三次、无水硫酸钠干燥。过滤、浓缩后，将产物沉降到150mL甲醇中。将所得固体、12.58mg(0.33mmol)的硼氢化钠和60mL二氯甲烷在氩气氛围回流搅拌4小时。反应结束后蒸干溶剂，二氯甲烷萃取后水洗一次、无水硫酸钠干燥。浓缩至5mL，加入100mL正己烷后得黄绿色固体134mg(收率75％)。1H NMR(400MHz,DMSO)δ7.99(m,2H),7.73–7.63(m,2H),7.43(m,6H),7.21(m,6H),6.99(m,6H),6.62(m,2H),6.36(m,2H),5.18–5.07(m,1H),4.45(s,2H),4.19–4.06(m,2H),1.83(s,2H),1.49(s,2H),1.35(s,2H),1.16(m,6H),0.76(s,3H).合成路线如下：其中n为11-31，平均值为21。
实施例6
含苄醇基团的高分子空穴传输材料在钙钛矿太阳能电池器件中的应用。
本发明制备的钙钛矿太阳能电池的器件结构如图3所示，各层依次为玻璃基底1、ITO阳极2、空穴传输层3、钙钛矿层4、电子传输层5和Ag电极6。所述空穴传输层3由如上所述的高分子材料(如高分子P1)制备而成。
所述钙钛矿太阳能电池的制备流程：
(1)清洗：用丙酮、异丙醇、乙醇依次超声清洗ITO玻璃基底，然后用氮气吹干。使用前用紫外-臭氧处理20分钟，进一步去除表面的有机物等；
(2)空穴传输层的制备：将处理好的ITO玻璃基底转移至手套箱中，旋涂P1的溶液(浓度为1.5mg/mL，溶剂为甲苯和DMF体积比为1：4的混合溶剂)，膜厚为8nm；
(3)钙钛矿活性层的制备：在空穴传输层上旋涂浓度为1mol/L的钙钛矿前驱体溶液(混合溶剂，其组分为DMF与DMSO的体积比为4：1)，以制备约400nm厚的钙钛矿活性层，所用钙钛矿材料的组分为Cs0.04[CH(NH2)2]0.80(CH3NH3)0.16Pb(I0.84Br0.16)3，旋涂后100℃退火10分钟；
(4)电子传输层的制备：钙钛矿层冷却后，旋涂PCBM的氯苯溶液(浓度为20mg/mL)，膜厚为50nm；
(5)Ag电极的制备：将旋涂完电子传输层的基底置于真空蒸镀室内，蒸镀厚度约100nm的金属Ag，完成钙钛矿太阳能电池的制备。
以实施例1中制备的高分子P1作为上述太阳能电池的空穴传输层为例进行说明，所述钙钛矿太阳能电池的器件结构为：玻璃基片/ITO/空穴传输层(P1)/钙钛矿层/电子传输层/Ag电极。对上述完成的钙钛矿太阳能电池进行I-V测试，如图4所示，器件的短路电流是20.81mA/cm2，填充因子是84％，开路电压是1.15V，能量转换效率是20.10％。
同上述操作过程，以实施例2、3、4和5中制备的高分子P2、P3、P4和P5分别作为上述太阳能电池的空穴传输层，采用上述相同的器件结构。对上述完成的钙钛矿太阳能电池进行I-V测试，能量转换效率均在18％到20％之间。
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显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (3)
1.一种含有苄醇基团的空穴传输高分子，其特征在于，其化学结构式通式如下：
通式中圆括号间的结构单元的共聚方式是无规共聚，涉及的符号和系数具有如下含义：
R1为H、C1-C20的烷氧基或者C1-C20的烷基；
x是0到1；
n是2-500；
结构式（1）中＊是常见封端单元，包括苯基、联苯基、噻吩基、联噻吩基、呋喃基、咔唑基、三苯胺基中的一种或二种以上；
Ar1、Ar2是相同或者不同的，并为如下所示结构:
其中的符号和系数具有如下含义：
结构式（2）中R2是相同或者不同的，并为H、-CH2OH、C1-C20的烷氧基或者C1-C20的烷基中的一种或二种以上；
当x不为0时，R3、R4、R5是相同或者不同的，并分别为H、-CH2OH、C1-C20的烷氧基或者C1-C20的烷基中的一种或二种以上；
当x为0时，Ar2选择结构式（2）（3）中的一种或二种；Ar2选择结构式（2）时，R3、R4分别为H、-CH2OH、C1-C20的烷氧基或者C1-C20的烷基中的一种或二种以上，且其中至少有一个取代基为-CH2OH；Ar2选择结构式（3）时，R5为-CH2OH；Ar2选择结构式（2）（3）中的二种时，R3、R4、R5分别为H、-CH2OH、C1-C20的烷氧基或者C1-C20的烷基中的一种或二种以上，且其中至少有一个取代基为-CH2OH。
2.一种权利要求1所述的含有苄醇基团的空穴传输高分子作为空穴传输材料在钙钛矿太阳能电池中的应用。
3.如权利要求2所述的应用，其特征在于，所述钙钛矿太阳能电池由依次层叠的玻璃基底层、ITO阳极层、空穴传输层、钙钛矿层、电子传输层和Ag电极层组成，所述空穴传输层以所述的含有苄醇基团的空穴传输高分子材料作为功能材料制备而成。
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