CN103366967B - 一种柔性敏化太阳能电池光阳极的制备方法 - Google Patents
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Abstract
本发明属于太阳能电池和能源技术领域,特别涉及一种柔性敏化太阳能电池光阳极的制备方法。本发明采用氧化铟‑聚对苯二甲酸乙二醇酯(ITO/PET)或氧化铟‑聚萘二甲酸乙二醇酯(ITO/PEN)透明导电塑料薄膜为基底,将浓度为20%~50%的纳米氧化物(TiO2、ZnO或SnO2)浆料通过刮涂法或丝网印刷发涂覆在基底上,然后利用温压技术(温度为25~150℃、压力为50~300MPa和保压时间为30~120s)获得纳米氧化物厚度为5~25μm的薄膜,吸附染料敏化剂或量子点敏化剂得到柔性敏化太阳能电池光阳极。本发明制备工艺简单、成本较低、能批量化生产且光电转换效率高,因此具有广泛的应用前景和研究价值。
Description
技术领域
本发明属于太阳能电池和能源技术领域,涉及一种柔性敏化太阳能电池光阳极的制备方法。
背景技术
随着世界经济的快速发展,人们对能源的需求量与日俱增,化石能源作为不可再生能源,已无法满足全球的能源消耗;另一方面,化石能源的大量使用会造成全球变暖和环境污染问题。因而,寻求可高效利用并且对环境友好的可再生能源是世界各国的共同目标。太阳能作为一种清洁的可再生能源,已经引起了广泛的关注,被认为是传统能源的最佳替代者。
根据所用材料的不同,太阳能电池可分为:硅基太阳能电池、化合物薄膜太阳能电池、光化学太阳能电池(包括染料敏化太阳能电池和量子点敏化太阳能电池)、有机太阳能电池和多结太阳能电池等。染料敏化太阳能电池是一类以染料分子敏化纳米多孔半导体薄膜为光阳极的光化学太阳能电池,由瑞士洛桑联邦理工(EPFL)的等人于1991年发明(O’Regan B andM.Nature,1991,353:737-740),当时的光电转换效率在AM1.5模拟日光照射下可达7.1~7.9%。量子点敏化太阳能电池是在染料敏化太阳能电池基础上发展起来的又一类光化学太阳能电池。1998年Nozik首先进行了利用磷化铟(InP)半导体量子点取代染料敏化太阳能电池中染料分子(Zaban A,O I and A J Nozik,et al.Langmuir,1998,14:3153-3156),开创了量子点敏化太阳能电池的先河。
至今为止,报道的最高效的染料敏化和量子点敏化太阳能电池的光阳极是高温下(通常在500℃左右)在FTO(掺氟的氧化锡)导电玻璃基板上烧结TiO2制成的。玻璃因具有质量大、易破碎等缺点无应用于要求轻便和异形的器件上。用柔性透明导电塑料基底代替导电玻璃组装成的柔性敏化太阳能电池具有质量轻、挠性好、抗冲击强、成本低、可进行各种形状或表面设计等优点,使得这种太阳能电池具有强大的竞争力,成为近年来研究的热点。
传统玻璃基底敏化太阳能电池采用高温烧结法对光阳极进行处理,能够除去浆料制备过程中的有机物,并加强了TiO2颗粒之间以及TiO2颗粒和基底之间的连接力。制备以柔性透明导电塑料薄膜为基底的敏化太阳能电池光阳极,要求采用不高于150℃的低温制备技术。因此近年来,许多研究集中于纳米晶TiO2薄膜的低温制备方法,包括低温烧结法(Pichot F,Pitts J R,Gregg B A,et al.Langmuir,2000,16:5626)、微波烧结法(Uchida S,Tomiha M,Takizawa H,et al.J PhotochemPhotobiol A:Chem,2004,164:93)、水热法(Zhang D S,Yoshida T,Yoshida T,et al.JPhotochem Photobiol A:Chem,2004,164:159)、紫外光照射法(Zhang D S,YoshidaT,Oekermann T,et al.Adv Funct Mater,2006,16:1228)、辊轧法(Lindstrom H,Holmberg A,Magnusson E,et al.J Photochem Photobiol A:Chem,2001,145:107)、冷等静压法(Weerasinghe H C,Sirimanne P M,Simon G P,et al.Progress inPhotovoltaics,2011,20(3):321-332)等。
上述方法中,辊轧法和冷等静压法均是在常温下进行,通过对TiO2薄膜施加压力,增强TiO2颗粒之间以及TiO2颗粒和基底之间的连接性能,能够获得均一致密的光阳极,因此,在一定程度上提高了柔性敏化太阳能电池的光电转换效率。但是这种方法所获得的电池光电转换效率低或者成本偏高,主要原因是TiO2颗粒在基体的连接强度还是偏低。
发明内容
本发明的目的是提供一种柔性敏化太阳能电池光阳极的制备方法,该方法采用温压技术对涂覆有纳米氧化物薄膜的柔性透明导电塑料基底进行处理,在适当温度下,加压后进一步使纳米氧化物颗粒均匀紧密的附着在基底上,获得高转换效率的太阳能电池光阳极。该方法具有制备工艺简单、成本低、可批量化生产等优点,因此具有广阔的发展前景和研究价值。
本发明采用刮涂法或丝网印刷法将浓度为20%~50%的纳米氧化物浆料,涂覆在透明导电塑料基底上,然后利用温压技术获得厚度为5~25μm的纳米氧化物薄膜,吸附染料敏化剂或量子点敏化剂得到柔性敏化太阳能电池光阳极,具体步骤如下:
a)将柔性透明导电塑料基底依次用去离子水、无水乙醇分别超声清洗5~15min,然后烘干;
b)将平均粒度为10~80nm的氧化物粉末与溶剂(去离子水或无水乙醇)配置成质量浓度为20%~50%的浆料;
c)采用刮涂法或丝网印刷法将浆料均匀涂覆在柔性透明导电塑料基底上,然后在20~100℃下烘干;
d)对涂覆有纳米氧化物薄膜的基底进行温压处理(压力为50~300MPa、温度为25~150℃和保压时间为30~120s),获得5~25μm的纳米氧化物薄膜;
e)将温压后的薄膜基底烘干,浸入敏化剂溶液中吸附敏化剂,吸附时间为3~20h,取出后用无水乙醇清洗后,烘干,得到柔性敏化太阳能电池光阳极。
柔性透明导电塑料基底为氧化铟-聚对苯二甲酸乙二醇酯(ITO/PET)或氧化铟-聚萘二甲酸乙二醇酯(ITO/PEN)。
纳米氧化物为氧化钛(TiO2)、氧化锌(ZnO)或氧化锡(SnO2)。
染料敏化剂为钌联吡啶类染料,为N3染料(顺式-双(异硫氰基)双(2,2'-联吡啶基-4,4'-二羧基)钌(II))、N719染料(双(四丁基铵)-顺式-双(异硫氰基)双(2,2'-联吡啶基-4,4'-二羧基)钌(II))和黑色染料(三(四丁基铵)-三(异硫氰基)(2,2':6',2''-三联吡啶基-4,4',4''-三羧基)钌(II))中一种。
量子点敏化剂为硒化镉(CdSe)、硫化镉(CdS)、硒化铅(PbSe)或硫化铅(PbS)。
本发明方法的优点:有利于提高氧化物薄膜与柔性基底的结合性能、增强薄膜中颗粒之间结合力、消除薄膜中裂纹的产生,太阳能电池效率较高;此外,制备工艺简单、成本较低、能批量化生产,具有广泛的应用前景和研究价值。
附图说明
图1是本发明的工艺流程图;
图2(a)是未经温压处理的柔性光阳极的光学显微镜照片,
图2(b)是经过温压处理的柔性光阳极的光学显微镜照片;
图3是用本发明方法制备的柔性光阳极的扫面电子显微镜照片;
图4是用本发明方法制备的敏化太阳能电池的I-V特性曲线图。
具体实施方式
实施例1
研究不同柔性基底对敏化太阳能电池性能的影响:
a)将ITO-PEN柔性基底或ITO-PET柔性基底依次用去离子水、无水乙醇分别超声清洗5~15min,然后烘干;b)将平均粒度为50nm的TiO2粉末与溶剂配置成浓度为25%浆料;c)采用刮涂法将上述浆料均匀涂覆在柔性基底上,然后在60℃下烘干;d)将上述涂覆有纳米TiO2薄膜的柔性基底,用温压技术进行处理,压力为100MPa,温度为50℃,保压时间为60s;e)将用温压技术处理过的涂覆有纳米TiO2薄膜的柔性基底在在60℃下烘干2.5h,然后浸入N719染料敏化剂溶液中,密封避光放置15h,使其充分吸收敏化剂分子后,取出在室温下干燥,得到柔性敏化太阳能电池光阳极。
表1不同柔性基底对敏化太阳能电池性能的影响
实施例2
研究不同浆料对敏化太阳能电池性能的影响:
a)将ITO-PEN柔性基底依次用去离子水、无水乙醇分别超声清洗10min,然后烘干;b)将平均粒度为10~80nm的氧化物(包括TiO2、ZnO、SnO2)粉末与溶剂配置成不同浓度的浆料;c)采用刮涂法将上述浆料均匀涂覆在ITO-PEN柔性基底上,然后在60℃下烘干;d)将上述涂覆有纳米氧化物薄膜的ITO-PEN柔性基底,用温压技术进行处理,压力为100MPa,温度为50℃,保压时间为60s;e)将用温压技术处理过的涂覆有纳米氧化物薄膜的ITO-PEN柔性基底在在60℃下烘干2.5h,然后浸入N719染料敏化剂溶液中,密封避光放置15h,使其充分吸收敏化剂分子后,取出在室温下干燥,得到柔性敏化太阳能电池光阳极。
表2不同浆料对敏化太阳能电池性能的影响
实施例3
研究不同制备工艺对敏化太阳能电池性能的影响:
a)将ITO-PEN柔性基底依次用去离子水、无水乙醇分别超声清洗10min,然后烘干;b)将平均粒度为50nm的TiO2粉末与溶剂配置成浓度为25%的浆料;c)采用刮涂法或丝网印刷法将上述浆料均匀涂覆在ITO-PEN柔性基底上,然后在20~100℃下烘干;d)将上述涂覆有纳米TiO2薄膜的ITO-PEN柔性基底,用温压技术进行处理,压力为100MPa,温度为50℃,保压时间为60s;e)将用温压技术处理过的涂覆有纳米TiO2薄膜的ITO-PEN柔性基底在在60℃下烘干2.5h,然后浸入N719染料敏化剂溶液中,密封避光放置15h,使其充分吸收敏化剂分子后,取出在室温下干燥,得到柔性敏化太阳能电池光阳极。
表3不同制备工艺对敏化太阳能电池性能的影响
实施例4
研究不同温压处理工艺对敏化太阳能电池性能的影响:
a)将ITO-PEN柔性基底依次用去离子水、无水乙醇分别超声清洗10min,然后烘干;b)将平均粒度为50nm的TiO2粉末与溶剂配置成浓度为25%的浆料;c)采用刮涂法将上述浆料均匀涂覆在ITO-PEN柔性基底上,然后在60℃下烘干;d)将上述涂覆有纳米TiO2薄膜的ITO-PEN柔性基底,用温压技术进行处理,压力为50~300MPa,温度为25~150℃,保压时间为30~120s;e)将用温压技术处理过的涂覆有纳米TiO2薄膜的ITO-PEN柔性基底在在60℃下烘干2.5h,然后浸入N719染料敏化剂溶液中,密封避光放置15h,使其充分吸收敏化剂分子后,取出在室温下干燥,得到柔性敏化太阳能电池光阳极。
表4不同温压处理工艺对敏化太阳能电池性能的影响
实施例5
研究不同染料敏化剂对敏化太阳能电池性能的影响:
a)将ITO-PEN柔性基底依次用去离子水、无水乙醇分别超声清洗10min,然后烘干;b)将平均粒度为50nm的TiO2粉末与溶剂配置成浓度为25%的浆料;c)采用刮涂法将上述浆料均匀涂覆在ITO-PEN柔性基底上,然后在60℃下烘干;d)将上述涂覆有纳米TiO2薄膜的ITO-PEN柔性基底,用温压技术进行处理,压力为100MPa,温度为50℃,保压时间为60s;e)将用温压技术处理过的涂覆有纳米TiO2薄膜的ITO-PEN柔性基底在在50~70℃下烘干2~3h,然后浸入染料敏化剂(包括N3、N719、N749染料)溶液中,密封避光放置10~20h,使其充分吸收敏化剂分子后,取出在室温下干燥,得到柔性敏化太阳能电池光阳极。
表5不同染料敏化剂对敏化太阳能电池性能的影响
实施例6
研究不同量子点敏化剂对敏化太阳能电池性能的影响:
a)将ITO-PEN柔性基底依次用去离子水、无水乙醇分别超声清洗10min,然后烘干;b)将平均粒度为50nm的TiO2粉末与溶剂配置成浓度为25%的浆料;c)采用刮涂法将上述浆料均匀涂覆在ITO-PEN柔性基底上,然后在60℃下烘干;d)将上述涂覆有纳米TiO2薄膜的ITO-PEN柔性基底,用温压技术进行处理,压力为100MPa,温度为100℃,保压时间为60s;e)将用温压技术处理过的涂覆有纳米TiO2薄膜的ITO-PEN柔性基底在在50~70℃下烘干2~3h,然后浸入量子点敏化剂(包括CdSe、CdS、PbSe、PbS量子点)溶液中,敏化30~90s,使其充分吸收敏化剂分子后,取出在室温下干燥,得到柔性敏化太阳能电池光阳极。
表6不同量子点敏化剂对敏化太阳能电池性能的影响
实施例7
研究不同氧化物膜厚对敏化太阳能电池性能的影响:
a)将ITO-PEN柔性基底依次用去离子水、无水乙醇分别超声清洗10min,然后烘干;b)将平均粒度为50nm的TiO2、ZnO和SnO2粉末与溶剂配置成浓度为25%的浆料;c)采用刮涂法将上述浆料均匀涂覆在ITO-PEN柔性基底上,然后在60℃下烘干;d)将上述涂覆有纳米TiO2、ZnO和SnO2薄膜的ITO-PEN柔性基底,用温压技术进行处理,压力为100MPa,温度为100℃,保压时间为60s;e)将用温压技术处理过的涂覆有纳米薄膜的ITO-PEN柔性基底在在50~70℃下烘干2~3h,然后浸入N719染料敏化剂溶液中,密封避光放置10~20h,使其充分吸收敏化剂分子后,取出在室温下干燥,得到柔性敏化太阳能电池光阳极。表7不同膜厚太阳能电池性能的影响
Claims (1)
1.一种柔性敏化太阳能电池光阳极的制备方法,其特征在于:采用刮涂法或丝网印刷法将浓度为20%~50%的纳米氧化物浆料,涂覆在氧化铟-聚对苯二甲酸乙二醇酯即ITO/PET透明导电塑料基底上,然后利用温压技术获得厚度为5~25μm的二氧化钛纳米氧化物薄膜,吸附N719染料即双(四丁基铵)-顺式-双(异硫氰基)双(2,2'-联吡啶基-4,4'-二羧基)钌(II)敏化剂或硒化镉量子点敏化剂得到柔性敏化太阳能电池光阳极,具体步骤如下:
a)将ITO/PET柔性透明导电塑料基底依次用去离子水、无水乙醇分别超声清洗5~15min,然后烘干;
b)将平均粒度为10~80nm的二氧化钛粉末与溶剂配置成质量浓度为20%~50%的浆料,溶剂为去离子水或无水乙醇;
c)采用刮涂法或丝网印刷法将浆料均匀涂覆在ITO/PET柔性透明导电塑料基底上,然后在20~100℃下烘干;
d)对涂覆有纳米二氧化钛薄膜的基底进行温压处理,获得5~25μm的纳米二氧化钛薄膜,处理条件为;压力为100MPa、温度为50℃和保压时间为60s;
e)将温压后的薄膜基底烘干,浸入敏化剂溶液中吸附N719染料敏化剂,吸附时间为3~20h,取出后用无水乙醇清洗后,烘干,得到柔性染料敏化太阳能电池光阳极;
g)将温压后的薄膜基底烘干,浸入敏化剂溶液中吸附硒化镉量子点溶液中,吸附时间为3~20h,取出后用无水乙醇清洗后,烘干,得到柔性量子点敏化太阳能电池光阳极。
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