CN108538605B - 一种金属凝胶电解质及其制备方法 - Google Patents
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- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
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Abstract
本发明公开了一种金属凝胶电解质及其制备方法。本发明的金属凝胶电解质利用金属阳离子与有机配体形成凝胶框架,然后吸附液态电解质形成准固态电解质。本发明具有成本廉价、制备简单等特点,本发明可应用于染料敏化太阳电池及其它电池领域。
Description
技术领域
本发明属于化学、化工、材料及物理技术的交叉领域,涉及一种金属凝胶电解质、制备方法及其在染料敏化太阳电池中的应用。
背景技术
染料敏化太阳电池因其成本低廉、制备工艺简单、转换效率高等特点,得到了广泛的关注并迅速发展起来。
DSSC的经典结构是“三明治”夹心结构,主要由导电基底、半导体纳米多孔薄膜(多为TiO2、ZnO等)、染料敏化剂(N719、C101等)、含有氧化还原电对(I-/I3 -,或Br-/Br3 -,SeCN-/(SeCN)2,SCN-/(SCN)2等)的电解质,和对电极(如涂有Pt的导电玻璃)几个主要部分组成,其中电解质作为其重要的组成部分之一,对电池的效率及其稳定性具有重要影响。液态电解质具有扩散速率快、良好的浸润性、光电转换效率高等特点而被广泛应用。
然而随着光电效率超过14%的液态电解质DSSC的诞生,虽然液态电解质DSSC的光电效率虽然较高,但同时存在电解质溶剂易挥发泄露、电池封装困难等问题,固态电解质和准固态电解质可有效改善上述问题,固态电解质由于离子导电性能差,且不能有效浸润TiO2多孔薄膜,导致其组装的固态DSSC光电转换效率较低,而准固态电解质因其良好的界面浸润性,在提高DSSC的长期稳定性的同时,能够保证DSSC的光电性能因而受到研究学者的广泛关注。
发明内容
本发明的目的是提供一种金属凝胶电解质及其制备方法。金属凝胶在近些年来发展为功能性纳米材料,是一类重要的准固态材料,具有种类丰富、制备简单、成本低廉等特点。此外,金属凝胶一般具有优秀的孔隙率,离子能够在其中高效传输,使得其具备充当准固态材料的条件。
本发明是通过以下技术方案实现的:
一种金属凝胶电解质利用金属阳离子与有机配体形成凝胶框架,然后吸附液态电解质形成准固态电解质。
一种金属凝胶电解质,所述金属阳离子为Ti4+、Zr4+、V4+、Mn4+等金属元素离子,优先选择含Ti4+、Zr4+、V4+、Mn4+的盐或者盐溶液。
一种金属凝胶电解质,所述有机配体为一种或者多种酸类配体,如单宁酸。
一种金属凝胶电解质,所述吸附的液态电解质为含有I-/I3 -氧化还原电对的染料敏化太阳电池电解液。
一种金属凝胶电解质,其制备步骤如下:
(1)将金属盐或金属盐溶液与有机配体溶解在有机溶剂中,搅拌或者超声分散均匀;(2)加热或者室温静置使其形成凝胶;(3)将制备的金属凝胶去吸附含有I-/I3 -氧化还原电对的液态电解液形成所述金属凝胶电解质。
一种金属凝胶电解质的制备方法,所述有机溶剂可以为N-甲基-2-吡咯烷酮、二甲基甲酰胺、乙醇、乙腈、3-甲氧基丙腈等中的一种或多种混合。
一种金属凝胶电解质的制备方法,所述金属阳离子与有机配体的摩尔比为1:1~1:10。
一种金属凝胶电解质的制备方法,所述金属凝胶反应的温度为室温~100℃,反应时间为1min~24h,金属凝胶吸附电解液的时间为1~50h。
一种金属凝胶电解质的制备方法,所述液态电解质的配方通式可以为:
aA+bB+cC+dD+eE;
通式中:
A表示卤素氟、氯、溴、碘或拟卤素氰根、硫氰根,如I2、(SeCN)2、(SCN)2等;
B表示卤素氟、氯、溴、碘或拟卤素氰根、硫氰根、高氯酸根的一价、二价或三价金属阳离子或非金属阳离子盐类及其这些盐类的水合物,如碘化锂、碘化钠、碘化钾、氯化钠、氯化钾等;
C表示卤素(氟、氯、溴、碘)、拟卤素(氰根、硫氰根)、硒氰根的咪唑类阳离子盐类,如1,3-二甲基-3-咪唑碘;
D表示一种有机溶剂或者几种有机溶剂的混合物,离子液体或者几种离子液体的混合物,离子液体与有机溶剂的混合物,水或者水与有机溶剂或离子液体的混合物,如水、腈类、酰胺类溶剂、醇类、1-甲基-3-丙基咪唑碘等;
E表示N-甲基苯并咪唑、苯并咪唑等暗电流抑制剂或者添加剂的一种或多种;
a,b,c,d,e分别表示A、B、C、D、E的质量分数,并且其范围为:0≤a≤70%,0≤b≤70%,0≤c≤70%,0.01%≤d≤99.99%,0≤e≤70%。
本发明的优点是:
本金属凝胶电解质具有物料丰富、成本廉价、制备简单等特点,且其应用在染料敏化太阳电池中具有较高效的光电性能。
附图说明
图1为基于金属凝胶电解质的染料敏华太阳电池的J-V曲线。
具体实施方式
以下结合具体实施例来进一步解释本发明,但实施例不对本发明做任何形式的限定。
实施例1
金属凝胶电解质的制备:分别称取18mg单宁酸、20mg二(乙酰丙酮基)钛酸二异丙酯和0.45ml二甲基甲酰胺于样品瓶中,超声20min使其分散,然后室温静置1h使其形成金属凝胶,随后向金属凝胶中添加0.8ml的液态电解质,吸附1day后,倒出未吸附完的液态电解质,样品瓶中即为金属凝胶电解质。所述液态电解质包括:1mol/L 1,3-二甲基-3-咪唑碘(DMII),0.1mol/L碘化锂,0.13mol/L硫氰酸胍,0.11mol/L碘,0.7mol/L4-叔丁基吡啶,溶剂为体积比为85:15的乙腈和戊腈的混合溶液。
实施例2
基于金属凝胶电解质的准固态染料敏化太阳能电池的制备:
利用丝网印刷技术将TiO2纳米颗粒印刷在洗净的FTO导电玻璃上,控制其厚度11μm左右,在程序控温马弗炉中510℃热处理30min,待冷去至室温后,于70℃下浸泡于30mMTiCl4的水溶液中20min,然后510℃高温烧结30min,冷却到120℃时,将其浸泡于N719染料中16小时,取出即可得到吸附N719染料的光阳极。用含氯铂酸的异丙醇溶液涂在另一块洗净的FTO导电玻璃上,在410℃高温煅烧30min,冷却到室温得到含Pt的对电极。最后利用三明治的方法将所属金属凝胶电解质置于光阳极和对电极之间,组装成电池。如图1所示为基于金属凝胶电解质的染料敏华太阳电池的J-V曲线。
本发明不局限于上述实施方式,如果对本发明的各种改动不脱离本发明的精神和范围,倘若这些改动属于本发明权利要求和等同技术范围内,则本发明也试图包含这些改动。
Claims (3)
1.一种金属凝胶电解质及其制备方法,其特征在于:利用金属阳离子与有机配体形成凝胶框架,然后吸附液态电解质形成准固态电解质,所述金属阳离子包括Ti4+、Zr4+、V4+、Mn4 +,所述有机配体为一种或者多种酸类配体,所述吸附液态电解质为含有I-/I3 -氧化还原电对的染料敏化太阳电池电解液;所述金属凝胶电解质的制备方法,包括以下步骤:
(1)将金属盐或金属盐溶液与有机配体溶解在有机溶剂中,搅拌或者超声分散均匀;所述有机溶剂可以为N-甲基-2-吡咯烷酮、二甲基甲酰胺、乙醇、乙腈、3-甲氧基丙腈等中的一种或多种混合;所述金属阳离子与有机配体的摩尔比为1:1~1:10;
(2)加热或者室温静置使其形成凝胶;金属凝胶反应的温度为室温~100℃,反应时间为1min~24h,金属凝胶吸附电解液的时间为1~50h;
(3)将制备的金属凝胶去吸附含有I-/I3 -氧化还原电对的液态电解液形成所述金属凝胶电解质。
2.根据权利要求1所述的金属凝胶电解质及其制备方法,其特征在于所述液态电解质的配方通式可以为:
aA+bB+cC+dD+eE;
通式中:
A表示卤素氟、氯、溴、碘或拟卤素氰根、硫氰根;
B表示卤素氟、氯、溴、碘或拟卤素氰根、硫氰根、高氯酸根的一价、二价或三价金属阳离子或非金属阳离子盐类;
C表示卤素、拟卤素、硒氰根的咪唑类阳离子盐类;
D表示一种有机溶剂或者几种有机溶剂的混合物,离子液体或者几种离子液体的混合物,离子液体与有机溶剂的混合物,水或者水与有机溶剂或离子液体的混合物;
E表示N-甲基苯并咪唑、苯并咪唑等暗电流抑制剂或者添加剂的一种或多种;
a,b,c,d,e分别表示A、B、C、D、E的质量分数,并且其范围为:0≤a≤70%,0≤b≤70%,0≤c≤70%,0.01%≤d≤99.99%,0≤e≤70%。
3.一种染料敏化太阳能电池的制备方法,其特征在于:利用丝网印刷将TiO2浆料印刷在提前洗干净的FTO导电玻璃上,经过热处理,降温到一定温度后浸泡于N719染料中12~24h,取出后即为工作电极;利用热分解法将氯铂酸溶液涂抹在另外块洗净的FTO上,经过热处理形成pt对电极;然后将权利要求1至2中任一项所述金属凝胶电解质置于工作电极和对电极之间形成三明治结构电池。
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