CN105845443B - 一种原位制备的碳量子点敏化太阳能电池 - Google Patents
一种原位制备的碳量子点敏化太阳能电池 Download PDFInfo
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Abstract
本发明公开了一种原位制备的碳量子点敏化太阳能电池。太阳能电池由光阳极、对电极和电解液组成;其中光阳极以碳量子点为敏化剂;对电极为催化活性材料;电解液为多硫化物氧化还原电对电解液;本发明成本低,方法简单,适于制作大面积量子点敏化太阳能电池;清洁无污染,提高了量子点敏化太阳能电池应用前景。
Description
技术领域
本发明属于太阳能电池制造领域,具体涉及一种原位制备的碳量子点敏化太阳能电池。
背景技术
面对全球化石能源日益枯竭,取之不尽用之不竭的太阳能可以替代化石能源解决日益严重的能源危机问题。在各类新型太阳能电池中,染料敏化太阳能电池(DSCs)以成本低廉、制作工艺简单、相对较高的光电转换效率而成为研究热点(O’Regan, B., Grätzel,M., Nature, 1991, 353, 737)。但是它们的缺点也不容忽视:一方面染料的稳定性还有待进一步提高,另一方面价格相对较高,限制了染料敏化太阳能电池成本的进一步降低。而采用价格便宜的窄禁带无机半导体纳米晶即量子点,作为敏化剂,可以进一步降低电池成本。并且,与一般染料吸收一个光子最多产生1个电子不同,量子点可以由1个高能光子产生多个电子,使量子产率将大大提高(Nozik, A. J., Physica E, 2002, 14, 115)。
通常用于量子点敏化太阳能电池的敏化剂主要包括硫化镉(Lin, S. C., Lee,Y. L., etc, Appl. Phys. Lett. 2007, 90, 143517)、硒化镉(Lee, Y. L., Lo, Y. S.,Adv. Funct. Mater. 2009, 19,604)和硫化铅(Toyoda, T.,Bisquert, J.,etc,Nanotechnology 2009, 20, 295204)量子点等。这些量子点都存在对环境和人体的毒害问题,很难符合太阳能电池的清洁能源发展趋势。碳量子点不仅具有碳材料特有的毒性小和生物相容性好的优点,还拥有化学性质稳定、水溶性好、光稳定性强、无光闪烁、易于功能化和廉价等无可比拟的优势。发展碳量子点敏化太阳能电池,将引领量子点敏化太阳能电池的发展方向,拓展量子点敏化太阳能电池的应用前景(Li, Xiaoming,Zeng, Haibo, etc,Adv. Funct. Mater. 2015, 25,4929)。
目前,实现量子点在光阳极上沉积主要有两种常规方法:(1)原位沉积法:化学浴沉积(CBD)或连续离子层吸附和反应(SILAR)直接在TiO2光阳极生长量子点;(2)预先制备胶体量子点,然后直接或通过功能连接分子将量子点连接到光阳极上。到现在为止,没有文献或专利报道采用原位沉积得到的碳量子点敏化太阳能电池。
发明内容
本发明的目的在于克服上述现有技术的缺陷,提供一种原位制备的碳量子点敏化太阳能电池。
一种原位制备的碳量子点敏化太阳能电池,其特征在于太阳能电池由光阳极、对电极和电解液组成;其中光阳极以碳量子点为敏化剂;对电极为催化活性材料;电解液为多硫化物氧化还原电对电解液;碳量子点的沉积方式为原位沉积方式。
所述量子点可以与其它类型量子点形成复合量子点。
所述其它类型量子点为金属硫化物量子点或硒化物量子点。
所述金属硫化物量子点为PbS或CuInS2,所述硒化物量子点为CdSe或PbSe。
所述碳量子点不经过任何后处理措施或者经过烧结或表面钝化的后处理措施。
所述碳量子点的制备方法为水热/溶剂热法、溶胶凝胶法或微波加热法。
所述催化活性材料为贵金属、金属硫化物或碳材料。
所述贵金属为金、银或铂;所述金属硫化物为硫化亚铜、硫化铅和硫化亚铁的一种或多种;所述碳材料为活性炭、鳞片状石墨、石墨烯、球形石墨、单壁碳纳米管、多壁碳纳米管、碳纤维和硬碳材料中的一种或多种。
所述碳材料为活性炭或单壁碳纳米管。
所述多硫化物氧化还原电对电解液为二硫化物氧化还原电对电解液,其浓度为0.1~5M。
与现有的量子点敏化染料敏化太阳能电池相比,本发明的优点在于:
1、成本低,方法简单,适于制作大面积量子点敏化太阳能电池;
2、清洁无污染,提高了量子点敏化太阳能电池应用前景。
附图说明
图1:1M 柠檬酸10mL,加入0.3mL的乙二胺水热150度形成的碳量子点敏化太阳能电池的光电转化效率曲线。
图2:沉积碳量子点前(a)和沉积量子点后(b)的光阳极形貌图(水热条件:1M 柠檬酸10mL,加入0.3mL的乙二胺水热150度)。
图3:粉末碳量子点的XRD图。
图4:经过ZnS钝化的碳量子点敏化太阳能电池的光电转化效率曲线。
图5:经过烧结后处理的碳量子点敏化太阳能电池的光电转化效率曲线。
图6:形成CdS/CdSe/碳量子点的复合量子点敏化太阳能电池的光电转化效率曲线。
具体实施方式
本发明所采用的测量电池的方法:将本发明所制备的光阳极、电解质和碳对电极组装成电池,进行测量;电池的光电性能用计算机控制的恒电位/恒电流仪(Keithley2400)在室温下测量;光源使用500W 氙灯,入射光强为100 mw/cm2,光照面积为0.20 cm2 。除非另有说明,以下各实施例中的本发明光电性能的测量都是在室温下进行的。
按照本领域技术人员所熟知的常规方法将经过量子点敏化的TiO2光阳极、含S2-/S2 2-电解液溶液和硫化亚铜对电极组装成量子点敏化太阳能电池。
实施例1
配制1M 柠檬酸10mL,加入0.3mL的乙二胺后转移到水热釜中,在室温下将TiO2多孔膜垂直浸入溶液中,150度水热反应48h。水热反应完后,将Na2S2电解质溶液,原位制备的碳量子点敏化的TiO2多孔膜为光阳极和碳对电极,组装成碳量子点敏化太阳能电池。电池的光电化学性能测试结果见图1;沉积碳量子点前后光阳极形貌的变化见图2;粉末碳量子点的XRD图谱见图3。
实施例2
在实施例1的基础上,对原位沉积的碳量子点敏化光阳极进行ZnS钝化处理,方法是将光阳极交替浸入到1M的Zn(CH3COO)2和Na2S溶液中1min,用纯净水清洗后吹干。这种经过ZnS钝化后的碳量子点敏化电池的光电化学性能测试结果见图4。
实施例3
在实施例1的基础上,对原位沉积的碳量子点敏化光阳极进行烧结后处理,方法是将光阳极在N2保护下,在马弗炉中400度烧结10min,自然降温后取出。这种经过烧结后处理的碳量子点敏化电池的光电化学性能测试结果见图5。
实施例4
采用化学浴沉积技术(CBD),在光阳极上先沉积CdS量子点,再沉积CdSe量子点。量子点的沉积在10 ºC下进行。具体操作步骤如下:将TiO2薄膜浸泡在含有20 mM CdCl2、66 mMNH4Cl、140 mM 硫脲和230 mM 氨水的PH约为9.5的水溶液中,CdS沉积时间为30min,用水反复清洗。再将已经沉积了CdS量子点的TiO2薄膜浸泡在含有26 mM CdSO4、40 mM N(CH2COONa)3和26 mM Na2SeSO3的混合溶液中,CdSe的沉积时间为5.5h。在连续沉积CdS和CdSe量子点后,在实施例1的基础上沉积碳量子点。这种形成复合量子点的碳量子点敏化电池的光电化学性能测试结果见图6。
从以上内容可以看出,在本发明的原位制备的碳量子点敏化太阳能电池中,原位制备的方式是化学浴沉积(CBD)方式。碳量子点的制备方法为水热/溶剂热法、溶胶凝胶法和微波加热法,溶剂可以为水、乙醇、甲醇、乙腈、甲氧基丙腈、丙酮中的一种或多种。碳量子点的制备原料包括柠檬酸等的不同种类无机酸,甘氨酸等的不同种类氨基酸,乙二胺等的不同种类无机胺类,氨基咪唑等的不同种类的有机胺类。
在本发明的原位制备的碳量子点敏化太阳能电池中,可以采用贵金属为对电极材料,贵金属包括金、银和铂;也可以采用金属硫化物作为对电极材料,包括硫化亚铜、硫化铅和硫化亚铁的一种或多种;可以采用碳材料作为对电极,例如碳黑、鳞片状石墨、石墨烯、球形石墨、单壁碳纳米管、多壁碳纳米管、碳纤维或硬碳材料中的一种或多种,优选为活性炭、单壁碳纳米管,这是因为活性炭比表面积大,有利于氧化态电解液的还原,并且性质稳定,而单壁碳纳米管电子传输性能更好;所述碳材料的颗粒尺寸可以在10~500nm之间,所制成的碳薄膜的厚度可以在0.5μm~50μm之间,优选为3μm~20μm,更优选为8-12μm,从而得到更好的光电转换效率。在本发明中可以采用多硫化物氧化还原电对溶液作为电解质溶液(除非另外说明,本文中的“多硫化物”指的是M2SX,其中X=2、3、4,M= Na+, K+, NH4 +),但因为二硫化物的稳定性比三硫化物或四硫化物高,所以优选为二硫化物氧化还原电对电解质溶液,该电解液的浓度可以在0.1~5M之间。对于本领域不同技术人员应该理解,多硫化物氧化还原电对电解液的溶剂可以为水、乙醇、甲醇、乙腈、甲氧基丙腈、丙酮中的一种或多种。尽管在实施例中仅列举TiO2作为量子点敏化太阳能电池的光阳极中多孔层的材料,但本发明并不局限于此,所述多孔层的材料还可以是TiO2、Nb2O5、ZnO、SrO、SiO2、ZrO2、Al2O3中的一种或多种;另外,所采用的导电玻璃基底仅为一种优选,还可以采用其他无机非金属材料作为光阳极和对电极的基底。
Claims (9)
1.一种原位制备的碳量子点敏化太阳能电池,其特征在于太阳能电池由光阳极、对电极和电解液组成;其中光阳极以碳量子点为敏化剂;对电极为催化活性材料;电解液为多硫化物氧化还原电对电解液;碳量子点的沉积方式为原位沉积方式;配制柠檬酸,加入乙二胺后转移到水热釜中,在室温下将TiO2多孔膜垂直浸入溶液中,水热反应即得原位制备的碳量子点敏化的TiO2多孔膜光阳极。
2.如权利要求1所述的电池,其特征在于所述量子点可以与其它类型量子点形成复合量子点。
3.如权利要求2所述的电池,其特征在于所述其它类型量子点为金属硫化物量子点或硒化物量子点。
4.如权利要求3所述的电池,其特征在于所述金属硫化物量子点为PbS或CuInS2,所述硒化物量子点为CdSe或PbSe。
5.如权利要求1所述的电池,其特征在于所述碳量子点不经过任何后处理措施或者经过烧结或表面钝化的后处理措施。
6.如权利要求1所述的电池,其特征在于所述碳量子点的制备方法为水热法、溶剂热法、溶胶凝胶法或微波加热法。
7.如权利要求1所述的电池,其特征在于所述催化活性材料为贵金属、金属硫化物或碳材料。
8.如权利要求7所述的电池,其特征在于所述贵金属为金、银或铂;所述金属硫化物为硫化亚铜、硫化铅和硫化亚铁的一种或多种;所述碳材料为活性炭、鳞片状石墨、石墨烯、球形石墨、单壁碳纳米管、多壁碳纳米管、碳纤维和硬碳材料中的一种或多种。
9.如权利要求1所述的电池,其特征在于所述多硫化物氧化还原电对电解液为二硫化物氧化还原电对电解液,其浓度为0.1~5M。
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