CN111484416A - 新型空穴传输材料应用于固态染料敏化太阳能电池 - Google Patents
新型空穴传输材料应用于固态染料敏化太阳能电池 Download PDFInfo
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Abstract
本发明设计将三芴氨类化合物作为空穴传输材料应用于固态染料敏化太阳能电池。与常用的Spiro‑OMeTAD相比，该类化合物具有分子结构简单、有机溶剂中的溶解度好、化合物及阳离子与光敏剂不发生光谱竞争等特点。并且该类化合物具有合适的HOMO能级可以作为空穴传输材料应用于固态染料敏化太阳能电池中。
Description
技术领域：
本发明涉及可用于固态染料明化太阳能电池的空穴传输材料及其合成方法。
背景技术：
在染料敏化太阳能电池中，液态电解质(如I-/I3 -的液态电解质)存在着泄漏、腐蚀性、与光敏剂发生光谱竞争能缺点，限制了大规模的民用化生产。而基于空穴传输材料的固态染料敏化太阳能电池可以有效地避免以上缺陷，因此得到人们的广泛研究。
Spiro-OMeTAD作为一类成功的空穴传输材料，以其优良的电子传输性能和稳定的氧化还原性能在固态染料敏化太阳能电池领域得到广泛应用[Poplavskyy D.,NelsonJ.Nondispersive hole transport in amorphous films of methoxy-spirofluorene-arylamine organic compound[J].J.Appl.Phys.2003,93:341-346]。虽然基于Spiro-OMeTAD的固态染料敏化太阳能电池具有很好的光电性能，但是其仍然存在一定的缺陷：例如其氧化态在可见光区有一定的吸收，这样势必会与光敏剂发生光谱竞争；分子结构复杂，合成比较困难；在有机溶剂中的溶解性较差，这样就会限制其在TiO2膜中的空穴填充率等。因此为了弥补以上缺陷，开发具有结构简单溶解性更好的空穴传输材料对于固态染料敏化太阳能电池的发展具有重要的意义。
芳胺类、芴类等衍生物由于自身的结构特点常被作为空穴传输材料应用于OLED领域，并且该类化合物具有较好的电化学稳定性及适合的氧化还原电位，符合固态染料敏化太阳能电池对空穴传输材料的要求，因此本发明设计基于不同烷基取代的三芴氨类化合物，并在化合物的结构中引入不同的烷基链来改善其溶解性，可以作为空穴传输材料应用于固态染料敏化太阳能电池中[Leijtens T.,Ding I.K.,Giovenzana T.et al.HoleTransport Materials with Low Glass Transition Temperatures and HighSolubility for Application in Solid-State Dye-Sensitized Solar Cells[J].ACSNano,2012,6:1455-1462]。
发明内容：
本发明的目的之一在于提供一类可以应用于固态染料敏化太阳能电池的空穴传输材料。
本发明的目的之二在于提供一种三芴胺类空穴传输材料的合成方法。
本发明的可用于固态染料敏化太阳能电池的空穴传输材料具有图1所示的结构:
其中，图1中的R可以为甲基、乙基、正丙基、正丁基等烷基类取代基。
1.根据权利要求1所述的三芴胺类空穴传输材料其特征是：
所述的空穴传输材料具有如结构1、2、3、4之一：
本发明的三芴胺类空穴传输材料可以参照如下给出的合成路线和合成方法得到。
具体合成路线如图2所示：
合成方法：
室温下，将起始原料2-溴芴和氢氧化钾以1:2～1:2.5的比例加入DMSO中，搅拌溶清后滴加R-I(3eq)。室温搅拌1h，补加R-I(1eq)，继续搅拌反应18h。反应结束后将反应液倒入水中，乙酸乙酯萃取，有机相用无水Na2SO4干燥，除去有机溶剂后硅胶层析柱分离得到化合物1的白色固体。
室温氮气下将化合物1，Pd2(dba)3·CHCl3及2-(二环己基膦基)联苯以1:0.01:0.02的比例加入干燥的THF中溶解。后加入双三甲基硅基胺基锂的THF溶液(2.4eq)，65℃油浴中搅拌反应15h。反应结束后冷至室温用1M HCl调节反应液的pH至酸性，搅拌5min后，用1M NaOH水溶液中和，分出有机层，水层用CH2Cl2萃取，合并有机相，无水Na2SO4干燥，除去有机溶剂后硅胶层析柱分离得到化合物2的浅黄色固体。
室温氮气下将化合物1、化合物2、叔丁醇钾、Pd2(dba)3·CHCl3以及三叔丁基膦以1:0.4:3.3:0.01:0.03的比例加入干燥的甲苯中溶解。升温至110℃搅拌反应10h。反应结束后，冷至室温，加入CH2Cl2，后依次用水，饱和食盐水，水洗涤，无水Na2SO4干燥，除去有机溶剂后硅胶层析柱分离得到目标空穴传输材料。
所得到的化合物的结构如图1所示：
结构式中的R可以为甲基、乙基、正丙基、正丁基等烷基类取代基。该方法可以得到上述结构式1-4的化合物。
本发明的三芴胺类空穴传输材料具有结构简单，光物理性能方面该类化合物及其阳离子可以有效地避免与光敏染料发生光谱竞争，电化学性能方面又可以提供适合的HOMO能级。因此作为空穴传输材料，这类化合物在固态染料敏化太阳能电池领域具有良好的开发和应用前景。
附图说明：
图1本发明所涉及的空穴传输材料化学结构式；
结构式1,2,3,4分别为本发明所涉及的空穴传输材料中当R为甲基，乙基，正丙基及正丁基时所对应的结构式；
图2本发明所涉及空穴传输材料合成路线；
图3本发明所涉及空穴传输材料结构式2的合成路线；
图4本发明所涉及空穴传输材料结构式4的合成路线。
具体实施方式
下面以结构式2和结构式4为例，通过具体实施例对本发明做进一步说明，但本发明并不局限于此。
下述实施例中，如无特殊说明均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。
实施例1：
结构式2的空穴传输材料的制备及其光物理和电化学性能测试：
合成路线如图3所示：
(1)于圆底瓶中加入2-溴芴(10g，41mmol)，KOH(5.2g，100mmol)和50mL的DMSO，室温搅拌至澄清后滴加碘乙烷(19.1g，122mmol)。室温搅拌1h，补加碘乙烷(6g，38mmol)，继续搅拌反应18h。反应结束后将反应液倒入200mL水中，乙酸乙酯萃取，有机相用无水Na2SO4干燥，除去有机溶剂后柱分离(流动相：石油醚)得到化合物1的白色固体(10.58g，收率：86％)。GC/TOF HRMS-EI(m/z):[M]+calcd.for C17H17Br,300.0514；found,300.0517.
(2)于圆底瓶中加入化合物1(1.2g，4mmol)，Pd2(dba)3·CHCl3(42mg，0.04mmol)，2-(二环己基膦基)联苯(34mg，0.088mmol)，后抽真空置换N2数次，后加入蒸过的THF溶解。加入双三甲基硅基胺基锂的THF溶液(1M，9.6mL，9.6mmol)，65℃油浴中搅拌反应15h。反应结束后冷至室温用1M HCl调节反应液的pH至酸性，搅拌5min后，用1M NaOH水溶液中和，分出有机层，水层用CH2Cl2萃取，合并有机相，无水Na2SO4干燥，除去有机溶剂后柱分离(洗脱剂：乙酸乙酯/石油醚＝1：1，加入1％体积的三乙胺)得到化合物2的浅黄色固体(0.56g，收率：59％)。GC/TOF HRMS-EI(m/z):[M]+calcd.for C17H19N,237.1517；found,237.1512.
(3)于圆底瓶中加入化合物1(0.36g，1.2mmol)，化合物3(0.12g，0.5mmol)，叔丁醇钾(0.45g，4mmol)，Pd2(dba)3·CHCl3(11mg，0.01mmol)，三叔丁基膦(10mg，0.04mmol)，抽真空置换N2数次，加入蒸过的甲苯溶解，于110℃搅拌反应10h。反应结束后，冷至室温，加入20mL CH2Cl2，依次用水，饱和食盐水，水洗涤，无水Na2SO4干燥，除去有机溶剂后柱分离(洗脱剂：二氯甲烷/石油醚＝1：15)得到化合物TFA(n＝2)的乳白色固体(0.18g，收率：53％)。1H NMR(400MHz,CDCl3,δ):7.65(d,3H),7.58(d,3H)；7.26(m,9H),7.16(s,3H),7.06(d,J＝7.5,3H),1.90(m,12H),0.35(t,18H).GC/TOF HRMS-EI(m/z):[M]+calcd.for C51H51N,677.4022；found,677.4011.
对上述制备的空穴传输材料结构式2进行了光物理和电化学性能研究。
光物理性能通过空穴传输材料的溶液紫外进行测定。将空穴传输材料于室温下在CH2Cl2溶液中(2×10-5M)进行紫外测试，得到空穴传输材料结构式2的最大吸收波长为375nm，(对比常用的Spiro-OMeTAD的最大吸收波长为395nm)通过将空穴传输材料用四氟硼酸亚硝氧化后进行紫外测试得到空穴传输材料结构式2的阳离子的最大吸收波长分别为442nm，788nm和953nm(对比常用的Spiro-OMeTAD阳离子的最大吸收波长分别为422nm，511nm，700nm)[Poplavskyy D.,Nelson J.Nondispersive hole transport in amorphousfilms of methoxy-spirofluorene-arylamine organic compound[J].J.Appl.Phys.2003,93:341-346]。
电化学性能通过循环伏安测得，具体方法为将空穴传输材料溶解在在干燥的CH2Cl2中，支持电解质为四丁基六氟磷酸铵(TBAPF6，0.1M)，工作电极为玻璃碳电极，参比电极为Ag/Ag+电极，对电极为铂丝电极，估算时以二茂铁电对(Fc/Fc+)作为内标通过加上440mV进行校正。通过循环伏安测试，上述空穴传输材料结构式2的HOMO能级为0.77V(对比Spiro-OMeTAD的HOMO能级为0.59V)[Poplavskyy D.,Nelson J.Nondispersive holetransport in amorphous films of methoxy-spirofluorene-arylamine organiccompound[J].J.Appl.Phys.2003,93:341-346]。
实施例2：
结构式4的空穴传输材料的制备及其光物理和电化学性能测试：
合成路线如图4所示：
(1)于圆底瓶中加入2-溴芴(10g，41mmol)，KOH(5.2g，100mmol)和50mL的DMSO，室温搅拌至澄清后滴加碘代正丁烷(22.45g，122mmol)。室温搅拌1h，补加碘代正丁烷(7g，38mmol)，继续搅拌反应18h。反应结束后将反应液倒入200mL水中，乙酸乙酯萃取，有机相用无水Na2SO4干燥，除去有机溶剂后柱分离(流动相：石油醚)得到化合物1的白色固体(12.10g，收率：83％)GC/TOF HRMS-EI(m/z):[M]+calcd.for C21H25Br,356.1140；found,356.1144.
(2)于圆底瓶中加入化合物1(1.43g，4mmol)，Pd2(dba)3·CHCl3(42mg，0.04mmol)，2-(二环己基膦基)联苯(34mg，0.088mmol)，后抽真空置换N2数次，后加入蒸过的THF溶解。加入双三甲基硅基胺基锂的THF溶液(1M，9.6mL，9.6mmol)，65℃油浴中搅拌反应15h。反应结束后冷至室温用1M HCl调节反应液的pH至酸性，搅拌5min后，用1M NaOH水溶液中和，分出有机层，水层用CH2Cl2萃取，合并有机相，无水Na2SO4干燥，除去有机溶剂后柱分离(洗脱剂：乙酸乙酯/石油醚＝1：1，加入1％体积的三乙胺)得到化合物2的浅黄色固体(0.74g，收率：63％)。GC/TOF HRMS-EI(m/z):[M]+calcd.for C21H27N,293.2144；found,293.2144.
(3)于圆底瓶中加入化合物1(0.43g，1.2mmol)，化合物3(0.15g，0.5mmol)，叔丁醇钾(0.45g，4mmol)，Pd2(dba)3·CHCl3(11mg，0.01mmol)，三叔丁基膦(10mg，0.04mmol)，抽真空置换N2数次，加入蒸过的甲苯溶解，于110℃搅拌反应10h。反应结束后，冷至室温，加入20mL CH2Cl2，依次用水，饱和食盐水，水洗涤，无水Na2SO4干燥，除去有机溶剂后柱分离(洗脱剂：二氯甲烷/石油醚＝1：15)得到空穴传输材料结构式4的乳白色固体(0.26g，收率：61％)。1H NMR(400MHz,CDCl3,δ):7.68(d,3H),7.54(d,3H)；7.29(m,9H),7.15(s,3H),7.03(d,3H),1.92(m,12H),1.35(m,24H),0.85(m,18H).GC/TOF HRMS-EI(m/z):[M]+calcd.forC63H75N,845.5900；found,845.5919.
对上述制备的空穴传输材料结构式4进行了光物理和电化学性能研究。
光物理性能通过空穴传输材料的溶液紫外进行测定。将空穴传输材料于室温下在CH2Cl2溶液中(2×10-5M)进行紫外测试，得到空穴传输材料结构式4的最大吸收波长为373nm，(对比常用的Spiro-OMeTAD的最大吸收波长为395nm)通过将空穴传输材料用四氟硼酸亚硝氧化后进行紫外测试得到空穴传输材料结构式2的阳离子的最大吸收波长分别为446nm，790nm和966nm(对比常用的Spiro-OMeTAD阳离子的最大吸收波长分别为422nm，511nm，700nm)[Poplavskyy D.,Nelson J.Nondispersive hole transport in amorphousfilms of methoxy-spirofluorene-arylamine organic compound[J].J.Appl.Phys.2003,93:341-346]。
电化学性能通过循环伏安测得，具体方法为将空穴传输材料溶解在在干燥的CH2Cl2中，支持电解质为四丁基六氟磷酸铵(TBAPF6，0.1M)，工作电极为玻璃碳电极，参比电极为Ag/Ag+电极，对电极为铂丝电极，估算时以二茂铁电对(Fc/Fc+)作为内标通过加上440mV进行校正。通过循环伏安测试，上述空穴传输材料结构式2的HOMO能级为0.76V(对比Spiro-OMeTAD的HOMO能级为0.59V)[Poplavskyy D.,Nelson J.Nondispersive holetransport in amorphous films of methoxy-spirofluorene-arylamine organiccompound[J].J.Appl.Phys.2003,93:341-346]。
通过紫外测试发现本发明所涉及的空穴传输材料与Spiro-OMeTAD相比可以更加有效地避免与光敏染料发生光谱竞争。通过循环伏安测试，本发明所涉及的空穴传输材料也具有合适的HOMO能级。因此可以作为空穴传输材料应用于固态染料敏化太阳能电池中。
本发明通过以上实例加以具体说明。需要指出的是，在本发明的思想和所声明的范围内可以做多种变化和修改，因此，上述各实例并非用于限制本发明。
Claims (2)
1.一类三芴胺类空穴传输材料，其特征是：所述的空穴传输材料具有如下所示的结构：
其中，R可以为甲基、乙基、正丙基、正丁基等烷基类取代基。
2.根据权利要求1所述的三芴胺类空穴传输材料其特征是：
所述的空穴传输材料具有如下结构之一：
化学结构式1：
化学结构式2：
化学结构式3：
化学结构式4：
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