CN111403547B - 一种钙钛矿太阳能电池及其制备方法 - Google Patents
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Abstract
本发明提供一种钙钛矿太阳能电池的制备方法,该方法,包括以下步骤:1)在FTO导电玻璃基板上,采用TiCl4化学浴沉积法制得TiO2薄膜后,经过退火处理,得到TiO2电子传输层;2)采用真空辅助刮涂法在所述TiO2电子传输层上制得钙钛矿吸光层后,在所述钙钛矿吸光层上制备C电极,得到钙钛矿太阳能电池。本发明通过化学浴沉积法在FTO导电玻璃基板上制备TiO2电子传输层,在TiO2电子传输层上采用真空辅助刮涂法制备钙钛矿吸光层,舍弃传统的空穴传输层,直接在钙钛矿吸光层表面印刷碳电极,可大面积制备均匀、平整度高、晶粒尺寸大的钙钛矿薄膜,且所得的钙钛矿薄膜材料具有较高的能量转化效率和较好的稳定性,其在钙钛矿太阳能电池领域具有良好的应用前景。
Description
技术领域
本发明涉及太阳能电池技术领域,特别涉及一种钙钛矿太阳能电池及其制备方法。
背景技术
钙钛矿太阳能电池由于其不断提高的光电转换效率,来源丰富且价格低廉的材料组分以及简单的制造工艺而引起了人们的广泛关注。2009年,钙钛矿太阳能电池的光电转化效率仅为3.8%,现今已在实验室规格实现了25.2%的的光电转化效率,可与商用多晶硅太阳能电池以及铜铟镓硒(CIGS)、碲化镉(CdTe)薄膜太阳能电池媲美。
钙钛矿太阳能一般是在特定的基板上,直接制备一层平面钙钛矿薄膜,与两侧的p、n型半导体组成n-i-p型三明治结构。其中光吸收层在钙钛矿太阳能电池中起着至关重要的作用,制备高效的钙钛矿太阳能电池,一般使用有机无机杂化钙钛矿材料,通过旋涂法制备,并应用氯苯等有机溶剂通过反溶剂萃取的方式诱导钙钛矿。其中最大的障碍是这种钙钛矿材料的稳定性差,且旋涂工艺只实用于小面积制备,无法大面积生产。
在前驱体溶液中加入极少量的表面活性剂可以有效控制成膜过程,有学者将卵磷脂加入到CH3NH3PbI3的前驱体溶液中,改变了溶液流体动力学并提高了钙钛矿溶液的附着力,显著改善了刮涂制备钙钛矿的薄膜质量。除了提高前驱体溶液的附着力,获得高均匀性的薄膜和高致密性的晶体也是至关重要的,有学者通过真空辅助去溶剂快速且良好的控制溶剂的去除,促进了钙钛矿材料的快速结晶,为大面积生产高质量的钙钛矿薄膜提供支持。真空处理可以产生一个固态的中间相,退火后可以转变为钙钛矿。但是如何在大面积制备高均匀性薄膜的同时提高钙钛矿薄膜的稳定性却没有有效的解决方法。
因此,本文开发一种通过刮涂法真空辅助制备钙钛矿太阳能电池器件以提高器件的稳定性,对钙钛矿未来的发展尤其重要。
发明内容
有鉴于此,本发明旨在提出一种钙钛矿太阳能电池的制备方法,以解决现有钙钛矿太阳能电池在制备时无法兼具大面积和稳定性的问题。
为达到上述目的,本发明的技术方案是这样实现的:
一种钙钛矿太阳能电池的制备方法,包括以下步骤:
1)在FTO导电玻璃基板上,采用TiCl4化学浴沉积法制得TiO2薄膜后,经过退火处理,得到TiO2电子传输层;
2)采用真空辅助刮涂法在所述TiO2电子传输层上制得钙钛矿吸光层后,在所述钙钛矿吸光层上制备C电极,得到钙钛矿太阳能电池。
可选地,所述步骤1)中所述退火处理,包括:30min升温至450℃,保温30min,自然冷却。
可选地,所述步骤2)中采用真空辅助刮涂法在所述TiO2电子传输层上制得钙钛矿吸光层,包括:
将碘化铯和溴化铅混合后,溶于溶剂中,然后,加入表面活性剂,得到钙钛矿前驱体溶液;
采用刮涂法将所述钙钛矿前驱体溶液刮涂在所述TiO2电子传输层上后,抽真空,然后,进行退火处理,得到钙钛矿吸光层。
可选地,所述碘化铯和所述溴化铅的摩尔比为1∶1。
可选地,所述溶剂为二甲基亚砜;所述二甲基亚砜的浓度为0.4mol/L。
可选地,所述表面活性剂为吐温-80;所述吐温-80的浓度为0.72g/L。
可选地,所述退火处理,包括:在160℃下退火10min。
可选地,所述步骤2)中在所述钙钛矿吸光层上制备C电极,包括:采用丝网印刷法在所述钙钛矿吸光层上制备C电极。
本发明的第二目的在于提供一种钙钛矿太阳能电池,该钙钛矿太阳能电池由上述钙钛矿太阳能电池的制备方法制得。
相对于现有技术,本发明所述的钙钛矿太阳能电池的制备方法具有以下优势:
1、本发明通过化学浴沉积法在FTO导电玻璃基板上制备TiO2电子传输层,在TiO2电子传输层上采用真空辅助刮涂法制备钙钛矿吸光层,舍弃传统的空穴传输层,直接在钙钛矿吸光层表面印刷碳电极,可大面积制备均匀、平整度高、晶粒尺寸大的钙钛矿薄膜,且所得的钙钛矿薄膜材料具有较高的能量转化效率和较好的稳定性,将本发明制得钙钛矿太阳能电池用于太阳能电池器件时,可使所得的太阳能电池器件具有较高效率。
2、本发明在钙钛矿的前驱体溶液中加入一种非离子型表面活性剂吐温-80,有效控制溶液的流体动力学,提高了溶液与基体的附着力,从而消除岛状结晶现象,可进一步提高钙钛矿薄膜的均匀性和致密性,从而有利于进一提高钙钛矿薄膜材料的能量转化效率和稳定性。
3、本发明采用碘化铯和溴化铅成功制得全无机钙钛矿太阳能电池,可有效解决现有有机无机杂化钙钛矿太阳能电池易分解的问题,从而可更进一步提高本发明所得钙钛矿太阳能电池的稳定性。
4、本发明用真空辅助的刮涂工艺制备钙钛矿吸光层的方法,过程简单,易于操作,可重复性好,且制备成本低,在钙钛矿太阳能电池领域具有良好的应用前景。
附图说明
构成本发明的一部分的附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。在附图中:
图1为本发明实施例1制备的平面型CsPbIBr2钙钛矿太阳能电池结构示意图;
图2为本发明实施例1采用真空辅助刮涂法制备的CsPbIBr2薄膜的扫描电子显微镜图;
图3为本发明实施例1的钙钛矿太阳能电池的电流密度—电压的性能图像;
图4为本发明实施例1采用的刮涂装置结构示意图。
附图标记:1-刮涂基底,2-刮刀,3-沉积有TiO2电子传输层的FTO导电玻璃基板,4-钙钛矿前驱体溶液。
具体实施方式
需要说明的是,在不冲突的情况下,本发明中的实施例及实施例中的特征可以相互组合。
下面将结合附图和实施例来详细说明本发明。
实施例1
一种钙钛矿太阳能电池的制备方法,具体包括以下步骤:
1)对FTO导电玻璃基板分别用洗涤剂、超纯水和酒精进行清洗,再对FTO导电玻璃基板紫外臭氧处理15分钟后,在FTO导电玻璃基板(阴极)上,利用烘箱在70℃条件下通过TiCl4化学浴沉积法制得TiCl4薄膜,并30分钟升温至450℃退火30分钟,自然冷却,制得TiO2电子传输层;
2)对沉积有TiO2电子传输层的FTO导电玻璃基板3进行紫外臭氧处理15分钟,在TiO2电子传输层上利用真空辅助刮涂法制备钙钛矿吸光层,具体为:
将碘化铅和碘化铯以1∶1的摩尔比混合,并用二甲基亚砜(DMSO)溶解后,加入适量浓度为0.72g/L的吐温-80(表面活性剂),得到0.4mol/L的钙钛矿前驱体溶液;
将沉积有TiO2电子传输层的FTO导电玻璃基板放于刮涂机器的刮涂基底1上,用移液枪量取25ml钙钛矿前驱体溶液滴加于刮刀与沉积有TiO2电子传输层的FTO导电玻璃基板的缝隙中,运行刮刀2,将钙钛矿前驱体溶液4刮涂在TiO2电子传输层上,制得钙钛矿液态薄膜,具体刮涂装置如图4所示;
将刮涂有钙钛矿液态薄膜,且沉积有TiO2电子传输层的FTO导电玻璃基板在40℃下抽真空1min后,在160℃下退火10分钟,冷却至室温,得到500nm左右厚度的钙钛矿吸光层;
3)采用丝网印刷法在钙钛矿吸光层上印刷碳电极,得到钙钛矿太阳能电池。
在本实施例中,吐温-80的结构式为:
本实施例制得的钙钛矿太阳能电池的结果示意图如图1所示,其由上至下依次为碳电极(C)、钙钛矿吸光层(CsPbIBr2)、TiO2电子传输层(TiO2)、FTO导电玻璃基板(FTO)。
对本实施例制得的CsPbIBr2薄膜(钙钛矿吸光层)进行SEM测试,测试结果如图2所示。
由图2可知,本发明实施例1制得的CsPbIBr2薄膜致密,没有孔洞缺陷,且晶体呈明显的六边形,尺寸较大,达到1.3um。
对本实施例制得的钙钛矿太阳能电池的电流密度—电压性能进行测试,测试结果如图3和表1所示,RS:反扫曲线FS:正扫曲线。
由图3和表1可知,本实施例制得的钙钛矿太阳能电池的转化效率达到4.7%,短路电流为9mA/cm2,开路电压为1.063V,填充因子为0.491。
表1
以上仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (5)
1.一种钙钛矿太阳能电池的制备方法,其特征在于,包括以下步骤:
1)在FTO导电玻璃基板上,采用TiCl4化学浴沉积法制得TiO2薄膜后,经过退火处理,得到TiO2电子传输层;
2)采用真空辅助刮涂法在所述TiO2电子传输层上制得钙钛矿吸光层后,在所述钙钛矿吸光层上制备C电极,得到钙钛矿太阳能电池;
所述步骤2)中采用真空辅助刮涂法在所述TiO2电子传输层上制得钙钛矿吸光层,包括:
将碘化铯和溴化铅混合后,溶于溶剂中,然后,加入表面活性剂,得到钙钛矿前驱体溶液;
采用刮涂法将所述钙钛矿前驱体溶液刮涂在所述TiO2电子传输层上后,抽真空,然后,进行退火处理,得到钙钛矿吸光层;
所述碘化铯和所述溴化铅的摩尔比为1∶1;
所述表面活性剂为吐温-80;所述吐温-80的浓度为0.72g/L;
所述退火处理,包括:在160℃下退火10min,冷却至室温。
2.根据权利要求1所述的钙钛矿太阳能电池的制备方法,其特征在于,所述步骤1)中所述退火处理,包括:30min升温至450℃,保温30min,自然冷却。
3.根据权利要求1所述的钙钛矿太阳能电池的制备方法,其特征在于,所述溶剂为二甲基亚砜;所述二甲基亚砜的浓度为0.4mol/L。
4.根据权利要求1所述的钙钛矿太阳能电池的制备方法,其特征在于,所述步骤2)中在所述钙钛矿吸光层上制备C电极,包括:采用丝网印刷法在所述钙钛矿吸光层上制备C电极。
5.一种钙钛矿太阳能电池,其特征在于,由权利要求1至4任一项所述的钙钛矿太阳能电池的制备方法制得。
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