CN103915261A - 一种染料敏化太阳能电池固态电解质及其制备方法 - Google Patents
一种染料敏化太阳能电池固态电解质及其制备方法 Download PDFInfo
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- Y02E10/542—Dye sensitized solar cells
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Abstract
本发明涉及一种染料敏化太阳能电池固态电解质,包括以下组分:有机离子50~90wt%;碘盐10~50wt%;碘单质0~20wt%;添加剂0~10wt%;所述的有机离子化学结构通式为:,式中n为1、2或3。由于该有机离子中含有氰基官能团且该氰基官能团与吡咯烷紧仅隔1~3个亚甲基,使其具备了塑性晶体的性质,具有较宽的塑晶相温度范围(25~220℃),一方面提高了太阳能电池固态电解质相转变温度高,另一方面提高了太阳能电池固态电解质的电子和离子传输性能。
Description
技术领域
本发明属于太阳能电池领域,具体涉及一种染料敏化太阳能电池固态电解质及其制备方法。
背景技术
电解质是太阳能电池尤其是染料敏化太阳能电池的核心部件,主要起传输氧化还原对的作用,其性能的优劣直接影响太阳能电池效率。染料敏化太阳能电池用电解质存在液态、凝胶、固态等多种形式,其中液态电解质多以有机溶剂作为电解质,如乙腈、甲氧基丙腈。液体电解质存在易挥发、封装难、稳定性差、高毒性等缺点。凝胶电解质中一般含有大量的液态电解质,所以在高温下也容易发生电解质的挥发与泄漏,电池性能下降。由于固体电解质具有热稳定好、电导率高、呈固体不泄漏等的优点,被广泛应用于太阳能电池、超级电容器、锂离子电池等能源器件中,能够克服液体或凝胶电解质易燃烧泄漏、易挥发、难封装、高毒性、稳定性差等缺点,因此固态电解质的开发应用,正逐渐引起科技工作者的广泛关注。目前,固态电解质主要采用P-型无机半导体、有机空穴传输等材料,但是这类固态电解质的电子和离子传输性能比较低,导致电池效率较低。因此,提高固态电解质的染料敏化太阳能电池的效率成为重要的发展方向。另外,国外已有文献报道,电池在室外工作下的温度可能超过60 oC,但当前有些固态电解质在室温下是固态但60℃以上时却成液态。因此,固态电解质还必须具有较高的相转变温度,热稳定性,以防止高温下(>60oC)电解质的泄漏。
发明内容
本发明的目的是为了克服现有技术的不足而提供一种电子和离子传输性能高且相转变温度高的固态电解质,用于染料敏化太阳能电池。
为解决以上技术问题,本发明采取的一种技术方案是:一种染料敏化太阳能电池固态电解质,包括以下组分:
有机离子 50~90 wt%;
碘盐 10~50 wt%;
碘单质 0~20 wt%;
添加剂 0~10 wt%;
所述的有机离子化学结构通式为:
,式中n为1、2或3。
优化地,所述的碘盐为碘化锂、碘化钾、碘化钠、1-甲基-3-丙基甲基咪唑碘化盐、1-甲基-3-丁基甲基咪唑碘化盐、1-甲基-3-乙基甲基咪唑碘化盐的一种或两种以上组成的混合物。
优化地,所述添加剂为叔丁基吡啶、N-甲基苯并咪唑或N-丁基苯并咪唑。
本发明还提供一种染料敏化太阳能电池固态电解质的制备方法,包括以下步骤:
(a) 将碘盐加入有机离子中,加热熔融后搅拌均匀形成混合物;
(b) 向所述的混合物中再加入碘单质和添加剂,加热熔融后搅拌均匀,冷却固化即可。
优化地,所述步骤(a)中,加热温度为100~250℃。
由于上述技术方案运用,本发明与现有技术相比具有下列优点:本发明染料敏化太阳能电池固态电解质,引入了结构式为的有机离子,由于该有机离子中含有氰基官能团且该氰基官能团与吡咯烷紧仅隔1~3个亚甲基,使其具备了塑性晶体的性质,具有较宽的塑晶相温度范围(25~220℃),一方面提高了太阳能电池固态电解质相转变温度高,另一方面提高了太阳能电池固态电解质的电子和离子传输性能。
附图说明
图1 为实施例3的有机离子的核磁图;
图2为实施例1-3中制备的有机离子的差热扫描图;
图3为实施例2与不同比例的碘盐1-甲基-3-丙基甲基咪唑碘化盐(PMII)混合后的差热扫描图;
图4为实施例4的染料敏化太阳能的电流-电压曲线图;
图5为实施例4的染料敏化太阳能在100℃下的稳定性性能。
具体实施方式
本发明染料敏化太阳能电池固态电解质,包括以下组分:有机离子50~90 wt%(质量百分率);碘盐10~50 wt%;碘单质0~20 wt%;添加剂0~10 wt%;所述的有机离子化学结构通式为:
,式中n为1、2或3。由于该有机离子含有氰基官能团且该氰基官能团与吡咯烷紧仅隔1~3个亚甲基,使其具备了塑性晶体的性质,具有较宽的塑晶相温度范围(25~220℃),一方面提高了太阳能电池固态电解质相转变温度高,另一方面提高了太阳能电池固态电解质的电子和离子传输性能。
所述的碘盐优选为为碘化锂、碘化钾、碘化钠、1-甲基-3-丙基甲基咪唑碘化盐、1-甲基-3-丁基甲基咪唑碘化盐、1-甲基-3-乙基甲基咪唑碘化盐的一种或两种以上组成的混合物。所述的添加剂优选为叔丁基吡啶、N-甲基苯并咪唑或N-丁基苯并咪唑。
制备上述染料敏化太阳能电池固态电解质的制备方法,包括以下步骤:
(a) 将碘盐加入有机离子中,加热熔融后搅拌均匀形成混合物;
(b) 向所述的混合物中再加入碘单质和添加剂,加热熔融后搅拌均匀,冷却固化即可。其中所述步骤(a)中,加热温度优选为100~250℃。
下面结合具体实施例作详细说明:
实施例1
的合成:
在反应容器中依次加入20mL乙醇 、20mmol、22mmol碘甲烷,在50℃、惰性气体保护下,反应5小时后,经旋转蒸发除去乙醇、再用无水乙醚洗涤3-5次,得塑性晶体,产率85%。1HNMR(核磁谱图) (400 MHz, DMSO): 4.90 (s, 2H), 3.66 (m, 2H), 3.59 (m, 2H), 3.2 (s, 3H), 2.14 (m, 4H)。
固体电解质的配制:
取1g加入0.15g 1-甲基-3-丙基甲基咪唑碘化盐和0.05g碘,100℃下加热搅拌成均匀电解质。
实施例2
的合成:
在反应容器中依次加入20mL乙醇、20mmol、22mmol碘甲烷,在50℃、惰性气体保护下,反应10小时后,经旋转蒸发除去乙醇、再用无水乙醚洗涤3-5次,得塑性晶体,产率82%。1HNMR (400 MHz, DMSO): 3.71 (t, 2H), 3.52 (m, 2H), 3.48 (m, 2H), 3.20 (t, 2H), 3.03 (s, 3H), 2.08 (m, 4H)。
固体电解质的配制:
取1g加入0.3g 1-甲基-3-丙基甲基咪唑碘化盐和0.12g碘,110℃下加热搅拌成均匀电解质。
另外,本实施例中还将制备的有机离子与不同量的粘性离子液体(1-甲基-3-丙基甲基咪唑碘化盐)混合后进行差热扫描。即使粘性离子液体的质量分数达40%,的塑晶相和熔点也能够很好的保持,有利于制备高离子导电率的固态电解质,如图3所示。
实施例3
的合成:
在反应容器中依次加入20mL乙醇 、20mmol、22mmol碘甲烷,置于50℃、惰性气体保护下,反应10小时后,经旋转蒸发除去乙醇、再用无水乙醚洗涤3-5次,得塑性晶体,产率79%。1HNMR(核磁谱图) (400 MHz, DMSO): 2.85-3.52 (m, 6H), 3.05 (s, 3H), 2.64 (t, 2H), 2.09 (m, 6H)。具体核磁谱图见图1。
固体电解质的配制:
取1g加入0.3g 1-甲基-3-丙基甲基咪唑碘化盐,0.1g碘化锂和0.12g碘,100℃下加热搅拌成均匀电解质。
将实施例1至3中制备的有机离子分别进行差热扫描(DSC),可以发现通过改变有机离子的侧链长度可以有效调节塑性晶体塑晶相变温度和熔点,进而调节太阳能电池固态电解质相转变温度。
实施例4
取1g加入0.35g 1-甲基-3-丙基甲基咪唑碘化盐,0.05g1-甲基-3-乙基甲基咪唑碘化盐和0.25g碘,250℃下加热搅拌成均匀电解质。
实施例5
取1g加入0.35g 1-甲基-3-丙基甲基咪唑碘化盐,0.15g1-甲基-3-乙基甲基咪唑碘化盐,0.05g碘化钾,0.05gN-丁基苯并咪唑和0.16g碘,100℃下加热搅拌成均匀电解质。
实施例6
取1g加入0.20g 1-甲基-3-丙基甲基咪唑碘化盐,0.15g1-甲基-3-丁基甲基咪唑碘化盐,0.05g碘化钾,0.12g叔丁基吡啶和0.20g碘,100℃下加热搅拌成均匀电解质。
试验例1
将实施例1-6中的电解质在10~20MPa下压制成1cm*1cm的薄片,将这些薄片分别夹在两块不锈钢电极之间,使薄片与不锈钢电极的接触面积为1cm*1cm,用两电极法将其连接到电化学工作站上进行电导率测试,结果见表1所示。同时进行染料敏化太阳能电池组装,包括以下步骤:用超声波将FTO导电玻璃清洗干净,将其浸入在70℃40mM TiCl4水溶液中保持30min,从而在FTO导电玻璃表面形成一层致密的TiO2膜,随后取出FTO导电玻璃用乙醇冲洗后自然晾干;用刮涂技术,分别将P25浆料、P400浆料涂于TiO2膜上再形成厚度分别为8μm和3μm的TiO2涂层,加热至500℃煅烧,待FTO导电玻璃自然冷却到80℃时,浸入染料Z907溶液中12h,取出作为光阳极;用H2PtCl6溶液在另一块FTO导电玻璃涂一薄层做为对电极;通过热塑膜将光阳极和对电极封在一起,向对电极上预留的小孔内滴加数滴甲醇稀释后的电解质溶液,利用真空填充技术将该溶液浸润到光阳极上,同时加热至60~80℃除去甲醇,封住小孔即可。并进行性能测试,结果见表2所示。
表1 实施例7测试的各种固态电解质的电导率
实施例 | 电导率(Scm-1) |
实施例1 | 2.45×10-4 |
实施例2 | 3.08×10-4 |
实施例3 | 5.73×10-4 |
实施例4 | 6.43×10-4 |
实施例5 | 6.27×10-4 |
实施例6 | 6.16×10-4 |
由表1可以看出本发明中基于有机离子塑性晶体的固态电解质的电导率都比较高,适合用于制备染料敏化太阳能电池的电解质。
表2 利用实施例1-6中的电解质制备的染料敏化太阳能电池测试结果
注:测试条件:室温环境,使用氙灯模拟太阳光,光强100 mW/cm2条件下,测得电池(有效面积0.16cm2)。其中,,表示当电池具有最大输出功率(Pmax)时,对应的电流和电压的乘积与短路电流和开路电压乘积的比值。光电转化效率计算采用如下公式:。
由表2可以看出本发明中氰基结构的离子液体电解质制备的染料敏化太阳能电池效率较高,这是因为氰基官能团具有较强的吸电子能力,从而提高了的相转变温度高,使太阳能电池固态电解质的相转变温度提高,而且有利于电解质电导率的提高。而且对实施例4中的固体电解质测定了其电流-电压曲线图(图4)和在100℃下的稳定性(图5)。可以看出,固态电解质由于塑晶相的存在,电解质电导率较高,并有利于碘离子的迁移;制备的固态电解质具有高熔点的性能,组装成电池后能在高温下(大于100摄氏度)工作时仍保持固态,并且电池效率较高,长期稳定,应用前景广阔。
上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (5)
1. 一种染料敏化太阳能电池固态电解质,包括以下组分:
有机离子 50~90 wt%;
碘盐 10~50 wt%;
碘单质 0~20 wt%;
添加剂 0~10 wt%;
其特征在于:所述的有机离子化学结构通式为:
,式中n为1、2或3。
2.根据权利要求1所述的染料敏化太阳能电池固态电解质,其特征在于:所述的碘盐为碘化锂、碘化钾、碘化钠、1-甲基-3-丙基甲基咪唑碘化盐、1-甲基-3-丁基甲基咪唑碘化盐、1-甲基-3-乙基甲基咪唑碘化盐的一种或两种以上组成的混合物。
3.根据权利要求1所述的染料敏化太阳能电池固态电解质,其特征在于:所述添加剂为叔丁基吡啶、N-甲基苯并咪唑或N-丁基苯并咪唑。
4.权利要求1至3中任一所述染料敏化太阳能电池固态电解质的制备方法,其特征在于,包括以下步骤:
(a) 将碘盐加入有机离子中,加热熔融后搅拌均匀形成混合物;
(b) 向所述的混合物中再加入碘单质和添加剂,加热熔融后搅拌均匀,冷却固化即可。
5.根据权利要求4所述的染料敏化太阳能电池固态电解质的制备方法,其特征在于:所述步骤(a)中,加热温度为100~250℃。
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