CN108461637B - 一种用于聚合物太阳能电池电子传输层的杂化物及其制备方法 - Google Patents
一种用于聚合物太阳能电池电子传输层的杂化物及其制备方法 Download PDFInfo
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- H—ELECTRICITY
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Abstract
本发明涉及一种可用于聚合物太阳能电池电子传输层的杂化物及其制备方法,先合成水/醇溶性共轭聚合物,然后制备TiO2纳米分散液,进一步将水/醇溶性共轭聚合物与TiO2纳米分散液分散混合,得到共轭聚合物/TiO2杂化材料,并进一步用于聚合物太阳能电池电子传输层。本发明的有益效果是:提供了侧链含有氨基的水/醇溶性共轭聚合物的合成方法;并且提供了一种用于聚合物太阳能电池电子传输层的共轭聚合物/TiO2杂化材料及其制备方法。
Description
技术领域
本发明涉及太阳能电池技术领域,特别涉及一种可用于聚合物太阳能电池电子传输层的杂化物及其制备方法。
背景技术
近年来,人们正在严重的遭受着地球上能源消耗所带来的环境污染以及温室效应。因此,现在人们最重要的目标就是发展清洁、干净、便宜的能源。太阳能就是这些能源中最有前途、可用的和可再生的能源。太阳能电池是一种可以将太阳光转化为电能的光伏器件。无机硅系电池在过去几十年发展的很迅速,它占了大约70%的光伏市场,拥有当前最成熟的技术。然而高成本的原材料和复杂的加工工艺,限制了其大规模的商业发展。因此人们有必要在将来改进这种技术从而降低成本。与无机太阳能电池相比较,聚合物太阳能电池(PSCs)凭借易于制造、操纵、灵活性、重量轻、成本低等潜在优势受到了很大的关注。
聚合物太阳能电池经过了多年的快速发展,虽然光电转化效率得到了很大的提高,但是距离商业化还有很大的距离,主要是电池的性能和稳定性没有得到决定性的改善。为了提高聚合物太阳能电池的稳定性和能量转化效率,大家使用了无机金属化合物或者水/醇溶性的小分子/高分子材料作为聚合物太阳能电池的电子传输层,特别是可溶液加工的水/醇溶性的小分子/高分子材料的开发和使用,使得聚合物太阳能电池的制备工艺得到了简化,并且大幅度提高了器件的性能。
但目前常用的无机金属化合物TiO2需要高温处理(大于450℃)才能得到高电子迁移率的薄膜,且成膜性较差。而水/醇溶性的小分子/高分子材料,其可加工性良好,但其电子迁移率相对于无机金属化合物TiO2仍有待提高。
在这里,我们将共轭聚合物与无机半导体材料进行复合,得到共轭聚合物/无机半导体杂化材料,该杂化材料同时结合了共轭聚合物、无机半导体材料以及纳米材料的优越性,既具有共轭聚合物材料良好的柔性和可加工性,又保留了无机半导体材料较高的载流子迁移率和高化学稳定性。将其用作聚合物太阳能电子传输层,优化薄膜间的界面接触,提高电池的光电转换效率。全溶液法的制备方式,为商业化生产提供了基础。
发明内容
本发明所要解决的技术问题:提供一种用于聚合物太阳能电池电子传输层的杂化物及其制备方法。
本发明通过下面所述技术方案实现:
一种聚合物太阳能电池电子传输层杂化物,其特征在于:由水/醇溶性共轭聚合物与纳米 TiO2形成的杂化材料。
其中,水/醇溶性共轭聚合物结构式如下:
式中Ra为氢原子,或C1~C12的饱和烷烃或者不饱和烃基;Rb选自丙酸二甲氨基乙酯基、丙酸二乙氨基乙酯基、甲基丙酸二甲氨基乙酯基或甲基丙酸二乙氨基乙酯基;X值为0.00~0.99。
其中,共轭聚合物与TiO2质量比为100:1~1:100。
一种共轭聚合物/TiO2杂化材料薄膜,其制作方法包括以下步骤:
(1)水/醇溶性共轭聚合物的合成:
在反应器中,加入二溴芴单体、A1的二硼酸酯物、A2的二溴代物、催化剂、配体、弱碱以及溶剂,在氮气氛围下,加热至85~95℃,反应12~24h后,加入苯硼酸反应2~3h,最后加入溴代苯,反应2~3h。反应结束之后,沉淀,过滤,烘干产物,然后将所得产物经层析柱提纯,将提纯的产物溶液用旋蒸仪进行浓缩,再次沉淀,过滤,烘干产物即可。
其中,二溴芴单体选自2,7-二溴-9,9-二(丙酸二甲氨基乙酯)芴、2,7-二溴-9,9-二(丙酸二乙氨基乙酯)芴、2,7-二溴-9,9-二(甲基丙酸二甲氨基乙酯)芴、2,7-二溴-9,9-二(甲基丙酸二乙氨基乙酯)芴中的一种或几种。
其中,A1的二硼酸酯物的结构式为:
其中,R2为氢原子,或C1~C12的饱和烷烃或者不饱和烃基。
其中,A2的二溴代物的结构式为:
其中,R2为氢原子,或C1~C12的饱和烷烃或者不饱和烃基。
其中,二溴芴单体与A2的二溴代物的总摩尔数与A1的二硼酸酯物的摩尔数比例为0.5:1~1:1.5。二溴芴单体与A2的二溴代物的比例为1:100~100:1。
其中,催化剂为钯催化剂,选自Pd(OAc)2、PdCl2(dppf)或者Pd(PPh3)4中的一种或几种;其摩尔数与二溴芴单体、A1的二硼酸酯物、A2的二溴代物这三种物质的总摩尔数的比例为 0.001:1~0.6:1。
其中,配体选自三环己基膦氟硼酸盐、三吡咯烷基膦、三苯基膦、三叔丁基膦、三环己基膦或三乙烯二胺的一种或几种;配体与催化剂的摩尔比例为1:1~12:1。
其中,弱碱选自质量分数为5%~50%的四甲基氢氧化铵水溶液、四乙基氢氧化铵水溶液、四丙基氢氧化铵水溶液、四丁基氢氧化铵水溶液、四己基氢氧化铵水溶液、四辛基氢氧化铵水溶液、碳酸钾水溶液、碳酸钠水溶液或醋酸钾水溶液中的一种或几种;弱碱的摩尔数与二溴芴单体、A1的二硼酸酯物、A2的二溴代物这三种物质的总摩尔数的比例为1:1~12:1。
其中,溶剂选自甲苯、二甲苯、二甲基亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAc)、N-甲基吡咯烷酮(NMP)中的一种或几种。
其中,加入的苯硼酸和溴代苯为封端剂,用量均为二溴芴单体、A1的二硼酸酯物、A2 的二溴代物这三种物质的总摩尔数的0.5~1。
(2)TiO2纳米分散液的制备:
在室温下取溶剂S、钛酸酯和适量的酸于烧杯中混合,磁力搅拌10~20min后得到溶液A。另取溶剂S和去离子水于烧杯中混合,得到溶液B。在磁力搅拌的条件下将溶液B缓慢滴加到溶液A中,滴加完毕后继续搅拌20~30min,得到半透明状的TiO2溶胶。最后将TiO2溶胶倒入内衬聚四氟乙烯的不锈钢反应釜中,将反应釜密封后放入140~160℃的烘箱中反应5~8h,反应结束后冷却至室温,即得到半透明的TiO2纳米分散液,平均粒径≤150nm。
其中,溶剂S选自甲醇、乙醇、乙二醇、丙二醇、丙三醇、异丙醇、丁醇、戊醇以及己醇中的一种或几种;
其中,钛酸酯选自钛酸四乙酯、钛酸四丁酯、钛酸四丙酯、钛酸四异丙酯、钛酸四异辛酯以及钛酸四(十八烷基)酯中的一种或几种;
其中,酸选自冰醋酸、盐酸、硫酸、硝酸以及碳酸中的一种或几种;
其中,溶液A和溶液B中所使用的酸与钛酸酯的体积比为1:1~1:20;酸与水的体积比为 1:1~1:5;
其中,所制备的TiO2纳米分散液浓度为3mg/mL~40mg/mL。
(3)电子传输层的制备:
将步骤(2)制备的TiO2纳米分散液,用滤头过滤后置于玻璃瓶中。随后称取步骤(1) 制备的醇溶性共轭聚合物溶于有机溶剂中,待聚合物溶解完全后用滤头过滤,并将滤液与TiO2纳米分散液进行共混,共混液经超声处理10~15min后得到稳定的、半透明状的醇溶性共轭聚合物/TiO2分散液。将所制得的醇溶性共轭聚合物/TiO2分散液旋涂在经等离子处理后的玻璃基底上,得到醇溶性共轭聚合物/TiO2杂化材料薄膜,最后将杂化膜在150℃的烘箱中干燥即可。
其中,共轭聚合物与TiO2质量比为100∶1~1∶100。
其中,有机溶剂选自甲醇、乙醇、乙二醇、丙二醇、丙三醇、异丙醇、丁醇、丙二醇甲醚以及乙二醇甲醚中的一种或几种;
一种用上述醇溶性共轭聚合物/TiO2杂化材料制备而成的聚合物太阳能电池器件,所述聚合物太阳能电池器件结构由下到上依次为阳极层、空穴传输层、有机活性层、电子传输层和阴极层,其结构示意如下:
Ag |
电子传输层 |
有机活性层 |
空穴传输层 |
ITO玻璃 |
其中,阳极层为刻蚀好的ITO玻璃或者FTO玻璃。
其中,空穴传输层为聚乙撑二氧噻吩和聚苯乙烯磺酸钠(PEDOT:PSS)薄膜。
其中,有机活性层为聚三己基噻吩(P3HT)和C60衍生物PCBM的混合物。
其中,电子传输层为醇溶性共轭聚合物/TiO2杂化材料薄膜。
其中,阴极为用银、金或者铝蒸镀的金属电极。
与现有技术相比,本发明具有以下优点及有益效果:
本发明提供了侧链含有氨基的水/醇溶性共轭聚合物的合成方法;并且提供了一种用于聚合物太阳能电池电子传输层的共轭聚合物/TiO2杂化物及其制备方法。
具体实施方式
现在结合具体实施例对本发明作进一步说明,以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例1:
醇溶性共轭聚合物聚[9,9-二辛基芴-co-9,9-二(丙酸二甲氨基乙酯)芴]的合成:
依次将0.304g(0.5mmol)2,7-二溴-9,9-二(丙酸二甲氨基乙酯)芴、0.3208g(0.5mmol) 2,7-双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-二基)-9,9-二辛基芴、0.01g四(三苯基膦)钯 [Pd(PPh3)4]、0.56gK2CO3、10mL甲苯、3mL水加入装有磁力搅拌子的100mL三口烧瓶,抽真空通氮气,恒温90℃在氮气氛围下反应24h,溶液有淡蓝色荧光出现。先后加入0.061g 苯硼酸和52μL溴代苯封端,各反应2h。反应结束,将温度降至室温,过滤,滤液用正己烷沉淀,过滤,烘干,所得的产物经柱层析进行提纯(固定相为中性氧化铝,流动相为THF)得到含50%胺基芴结构单元的黄色聚合物,产率为51.8%。其核磁图见附图1,聚[9,9-二辛基芴-co-9,9-二(丙酸二甲氨基乙酯)芴]的核磁图。通过核磁图分析确认目标产物。通过GPC 分析,测得其数均分子量为17000,重均分子量为54600,分子量分布为3.21。
实施例2:
醇溶性共轭聚合物聚[9,9-二己基芴-co-9,9-二(丙酸二乙氨基乙酯)芴]的合成:
依次将0.2657g(0.4mmol)2,7-二溴-9,9-二(丙酸二乙氨基乙酯)芴、0.049g(0.1mmol) 2,7-二溴-9,9-二己基芴、0.2932g(0.5mmol)2,7-双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-二基) -9,9-二己基芴、0.01g四(三苯基膦)钯[Pd(PPh3)4]、0.56gK2CO3、10mL甲苯、3mL水加入装有磁力搅拌子的100mL三口烧瓶,抽真空通氮气,恒温90℃在氮气氛围下反应24h,溶液有淡蓝色荧光出现。先后加入0.061g苯硼酸和52μL溴代苯封端,各反应2h。反应结束,将温度降至室温,过滤,滤液用正己烷沉淀,过滤,烘干,所得的产物经柱层析进行提纯(固定相为中性氧化铝,流动相为THF)得到含40%胺基芴结构单元的聚合物。
实施例3:
醇溶性共轭聚合物聚[9,9-二辛基芴-co-9,9-二(甲基丙酸二甲氨基乙酯)芴]的合成:
依次将0.1908g(0.3mmol)2,7-二溴-9,9-二(甲基丙酸二甲氨基乙酯)芴、0.1096g(0.2mmol) 2,7-二溴-9,9-二辛基芴、0.3208g(0.5mmol)2,7-双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-二基) -9,9-二辛基芴、0.01g四(三苯基膦)钯[Pd(PPh3)4]、0.56gK2CO3、10mL甲苯、3mL水加入装有磁力搅拌子的100mL三口烧瓶,抽真空通氮气,恒温90℃在氮气氛围下反应24h,溶液有淡蓝色荧光出现。先后加入0.061g苯硼酸和52μL溴代苯封端,各反应2h。反应结束,将温度降至室温,过滤,滤液用正己烷沉淀,过滤,烘干,所得的产物经柱层析进行提纯(固定相为中性氧化铝,流动相为THF)得到含30%胺基芴结构单元的聚合物。
实施例4:
含量为3mg/mL的TiO2纳米分散液的制备:
采用溶剂热法制备二氧化钛纳米分散液。在室温下取25mL无水异丙醇、0.5mL钛酸四丙酯和0.05mL硝酸于50mL的烧杯中混合,磁力搅拌10min后得到溶液A。另取5mL无水异丙醇和0.15mL去离子水于10mL的烧杯中混合,超声处理5min后得到溶液B。在磁力搅拌的条件下将溶液B缓慢滴加到溶液A中,滴加完毕后继续搅拌20min,得到半透明状的TiO2溶胶。最后将TiO2溶胶倒入内衬聚四氟乙烯的不锈钢反应釜中,将反应釜密封后放入 150℃的烘箱中反应6h,反应结束后冷却至室温,即得到半透明的TiO2纳米分散液。通过固含量的测试,分散液中TiO2的含量为3mg/mL。通过激光粒度仪检测,其平均粒径为71nm,粒径分布为0.258。
实施例5:
含量为30mg/mL的TiO2纳米分散液的制备:
采用溶剂热法制备二氧化钛纳米分散液。在室温下取25mL无水甲醇、4mL钛酸四丁酯和0.4mL冰醋酸于50mL的烧杯中混合,磁力搅拌10min后得到溶液A。另取5mL无水甲醇和1.3mL去离子水于10mL的烧杯中混合,超声处理5min后得到溶液B。在磁力搅拌的条件下将溶液B缓慢滴加到溶液A中,滴加完毕后继续搅拌20min,得到半透明状的TiO2溶胶。最后将TiO2溶胶倒入内衬聚四氟乙烯的不锈钢反应釜中,将反应釜密封后放入150℃的烘箱中反应6h,反应结束后冷却至室温,即得到半透明的TiO2纳米分散液。通过固含量的测试,分散液中TiO2的含量为30mg/mL。通过激光粒度仪检测,其平均粒径为49nm,粒径分布为0.246。
实施例6:
含量为40mg/mL的TiO2纳米分散液的制备:
采用溶剂热法制备二氧化钛纳米分散液。在室温下取25mL无水乙醇、6mL钛酸四乙酯和0.6mL盐酸于50mL的烧杯中混合,磁力搅拌10min后得到溶液A。另取5mL无水乙醇和2mL去离子水于10mL的烧杯中混合,超声处理5min后得到溶液B。在磁力搅拌的条件下将溶液B缓慢滴加到溶液A中,滴加完毕后继续搅拌20min,得到半透明状的TiO2溶胶。最后将TiO2溶胶倒入内衬聚四氟乙烯的不锈钢反应釜中,将反应釜密封后放入150℃的烘箱中反应6h,反应结束后冷却至室温,即得到半透明的TiO2纳米分散液。通过固含量的测试,分散液中TiO2的含量为40mg/mL。通过激光粒度仪检测,其平均粒径为47nm,粒径分布为 0.224。
实施例7:
电子传输层的制备:
以实施例1所制备的醇溶性共轭聚合物聚[9,9-二辛基芴-co-9,9-二(丙酸二甲氨基乙酯)芴] (PFDMAEA)和实施例5所制备的TiO2纳米醇分散液制备电子传输层杂化物。
取TiO2纳米分散液0.1mL,用0.45μm的滤头过滤后置于1mL的玻璃瓶中。随后称取15 mg的PFDMAEA溶于5mL的甲醇溶液中,待聚合物溶解完全后用0.45μm的滤头过滤,并将滤液与TiO2纳米分散液进行共混,共混液经超声处理10min后得到稳定的、半透明状的PFDMAEA/TiO2分散液。将所制得的PFDMAEA/TiO2分散液以4000rpm的转速旋涂在经等离子处理后的玻璃基底上,旋涂时间为30s,得到TiO2含量为共轭聚合物质量20%的 PFDMAEA/TiO2杂化材料薄膜,最后将杂化膜在150℃的烘箱中干燥。
实施例8:
以实施例7所制备的PFDMAEA/TiO2杂化材料薄膜制备聚合物太阳能电池:
将5cm×5cm的ITO导电玻璃刻蚀并切割成1.25×1.25cm2大小。随后将切割后的ITO导电玻璃依次用洗涤剂、蒸馏水、丙酮和异丙醇进行超声清洗,清洗完毕后放入真空干燥箱烘干。ITO导电玻璃烘干后用等离子体清洗机对玻璃表面进行处理。然后在ITO导电玻璃表面旋涂一层PEDOT:PSS,再150℃真空热处理20min。预先将聚合物P3HT与PCBM以1:1的重量比分别加入到一定量邻二氯苯溶剂中,配成40mg/mL的混合溶液,并搅拌过夜备用。旋涂时,先用氯仿溶剂将PEDOT:PSS表面清洗一遍,再将配制的活性层溶液旋涂于 PEDOT:PSS表面,将其放置于真空烘箱中150℃退火20min待用。然后,将PFDMAEA溶于无水甲醇中,加入TiO2纳米分散液,配制PFDMAEA/TiO2分散液,其中TiO2含量为20%、 30%、40%。随后将配制的PFDMAEA/TiO2分散液旋涂在活性层的表面。用棉签擦去部分薄膜,使两端露出ITO,将其放置于真空烘箱中退火待用。最后,以Ag作为阴极材料,采用真空热蒸发镀膜机将银沉积在电子传输层表面,热蒸发时,其真空度为1.5×10-3Pa,沉积速率为沉积厚度为
其性能参数见表1,器件的J-V曲线图见图2,PFDMAEA/TiO2杂化膜中TiO2含量不同时电池的J-V曲线。
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做的改变、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。
表1PFDMAEA/TiO2杂化膜中TiO2含量不同时电池的器件性能
附图说明:
图1聚[9,9-二辛基芴-co-9,9-二(丙酸二甲氨基乙酯)芴]的核磁图
图2PFDMAEA/TiO2杂化膜中TiO2含量不同时电池的J-V曲线。
Claims (8)
1.一种聚合物太阳能电池电子传输层杂化材料的制备方法,其特征是包括以下步骤:
(1)在装有磁子和温度计的四口圆底烧瓶中,加入二溴芴单体、A1二硼酸酯物、A2二溴代物、催化剂、配体、弱碱以及溶剂,在氮气氛围下,加热至85~95℃,反应12~24h后,加入苯硼酸反应2~3h,最后加入溴代苯,反应2~3h;反应结束之后,将反应物沉淀,过滤,然后将所得产物经层析柱提纯,再次沉淀,过滤,烘干即得醇溶性共轭聚合物;其中,二溴芴单体为2,7-二溴-9,9-二(丙酸二甲氨基乙酯)芴、2,7-二溴-9,9-二(丙酸二乙氨基乙酯)芴、2,7-二溴-9,9-二(甲基丙酸二甲氨基乙酯)芴、2,7-二溴-9,9-二(甲基丙酸二乙氨基乙酯)芴中的一种或几种;A1二硼酸酯物的结构式为:
式中R2为氢原子,或C1~C12的饱和烷烃或者不饱和烃基;A2二溴代物的结构式为:
式中R2为氢原子,或C1~C12的饱和烷烃或者不饱和烃基;
(2)在室温下取溶剂S、钛酸酯和酸于烧杯中混合,搅拌10~20min后得到溶液A;另取溶剂S和去离子水于烧杯中混合,得到溶液B;在搅拌下将溶液B缓慢滴加到溶液A中,滴加完毕后继续搅拌20~30min,得到半透明状的TiO2溶胶;最后将TiO2溶胶倒入内衬聚四氟乙烯的不锈钢反应釜中,放入140~160℃的烘箱中反应5~8h,反应结束后冷却至室温,即得到半透明的TiO2纳米分散液,平均粒径≤150nm;
(3)将步骤(2)制备的TiO2纳米分散液,用滤头过滤后置于玻璃瓶中;随后称取步骤(1)制备的醇溶性共轭聚合物溶于有机溶剂中,待聚合物溶解完全后用滤头过滤,并将滤液与TiO2纳米分散液进行共混,共混液经超声处理10~30min后得到稳定的、半透明状的醇溶性共轭聚合物/TiO2分散液;将所制得的醇溶性共轭聚合物/TiO2分散液旋涂于相应的基材上,干燥后得到可用于聚合物太阳能电池电子传输层共轭聚合物/TiO2杂化材料薄膜。
2.根据权利要求1所述的一种聚合物太阳能电池电子传输层杂化材料的制备方法,其特征是:所述的步骤(1)中二溴芴单体与A2二溴代物的总摩尔数与A1二硼酸酯物的摩尔数比例为0.5:1~1:1.5;二溴芴单体与A2二溴代物的摩尔比例为1:100~100:1。
3.根据权利要求1所述的一种聚合物太阳能电池电子传输层杂化材料的制备方法,其特征是:所述的步骤(1)中催化剂为钯催化剂,选自Pd(OAc)2、PdCl2(dppf)或者Pd(PPh3)4中的一种或几种;催化剂摩尔数与二溴芴单体、A1二硼酸酯物、A2二溴代物这三种物质的总摩尔数的比例为0.001:1~0.6:1;所述的步骤(1)中配体选自三环己基膦氟硼酸盐、三吡咯烷基膦、三苯基膦、三叔丁基膦、三环己基膦或三乙烯二胺的一种或几种;配体与催化剂的摩尔比例为1∶1~12∶1。
4.根据权利要求1所述的一种聚合物太阳能电池电子传输层杂化材料的制备方法,其特征是:所述的步骤(1)中弱碱选自质量分数为5%~50%的四甲基氢氧化铵水溶液、四乙基氢氧化铵水溶液、四丙基氢氧化铵水溶液、四丁基氢氧化铵水溶液、四己基氢氧化铵水溶液、四辛基氢氧化铵水溶液、碳酸钾水溶液、碳酸钠水溶液或醋酸钾水溶液中的一种或几种;弱碱的摩尔数与二溴芴单体、A1二硼酸酯物、A2二溴代物这三种物质的总摩尔数的比例为1∶1~12∶1;所述的步骤(1)中溶剂选自甲苯、二甲苯、二甲基亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAc)、N-甲基吡咯烷酮(NMP)中的一种或几种。
5.根据权利要求1所述的一种聚合物太阳能电池电子传输层杂化材料的制备方法,其特征是:所述的步骤(2)中溶剂S选自甲醇、乙醇、乙二醇、丙二醇、丙三醇、异丙醇、丁醇、戊醇以及己醇中的一种或几种;所述的步骤(2)中钛酸酯选自钛酸四乙酯、钛酸四丁酯、钛酸四丙酯、钛酸四异丙酯、钛酸四异辛酯以及钛酸四(十八烷基)酯中的一种或几种;所述的步骤(2)中酸选自冰醋酸、盐酸、硫酸、硝酸以及碳酸中的一种或几种。
6.根据权利要求1所述的一种聚合物太阳能电池电子传输层杂化材料的制备方法,其特征是:所述的步骤(2)中酸与钛酸酯的体积比为1∶1~1∶20;酸与水的体积比为1∶1~1∶5;TiO2纳米分散液浓度为3mg/mL~40mg/mL。
7.根据权利要求1所述的一种聚合物太阳能电池电子传输层杂化材料的制备方法,其特征是:所述的步骤(3)中有机溶剂选自甲醇、乙醇、乙二醇、丙二醇、丙三醇、异丙醇、丁醇、丙二醇甲醚以及乙二醇甲醚中的一种或几种;醇溶性共轭聚合物与TiO2质量比为100∶1~1∶100。
8.一种聚合物太阳能电池电子传输层杂化材料,其特征在于:权利要求1中所述的由共轭聚合物与纳米TiO2形成的杂化材料;所述的聚合物太阳能电子传输层为具有如下结构的聚合物太阳能电池中的电子传输层:
其中,空穴传输层为聚乙撑二氧噻吩和聚苯乙烯磺酸钠(PEDOT:PSS)薄膜;有机活性层为聚3-己基噻吩(P3HT)和C60衍生物PCBM的混合物;电子传输层为所述的醇溶性共轭聚合物与纳米TiO2形成的杂化材料的薄膜。
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