CN107403853B - 一种ZTO-ZnO/CBS-GSs柔性薄膜太阳能电池及其制备方法 - Google Patents
一种ZTO-ZnO/CBS-GSs柔性薄膜太阳能电池及其制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
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- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical class Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
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Abstract
本发明以不锈钢滤网(SSM)为柔性衬底,制备ZTO纳米线与ZnO纳米线复合光阳极(ZTO‑ZnO)、Cu4Bi4S9纳米带与石墨烯片复合光敏层(CBS‑GSs)以及薄膜结构(ZTO‑ZnO/CBS‑GSs),并组装成太阳能电池。该太阳能电池所需原料储量丰富、制备方法简单、重复性好、安全环保,在实验室阶段平均光电转换效率已达10.3%,最佳光电转换效率已超过11%。用平镊1000次折弯以后仍然呈现出良好的柔韧性和可弯曲性,光电转换效率仍保持在95%以上。该新型薄膜太阳能电池柔性好、应用弹性大、适应性强,如果应用到新能源领域,将大大缓解能源危机和环境污染等问题,因此具有非常广泛的应用前景。
Description
技术领域
本发明属于太阳能电池技术领域,具体涉及一种ZTO-ZnO/CBS-GSs柔性薄膜太阳能电池及其制备方法。
背景技术
随着世界能源危机和环保问题日益突出,需要不断探索绿色安全、可持续再生新型能源来替代传统能源,太阳能电池是通过光电效应或光化学效应直接把光能转化成电能的装置,也是缓解经济发展与能源及环境之间矛盾的“绿色”新技术。利用光敏材料对可见光的敏感效应与光阳极制备成薄膜太阳能电池,是近年来迅速发展起来的一种新型太阳能电池。2014年Jeon和Zhou等人把钙钛矿太阳能电池转换效率分别提高到了16.2%和19.3%,但还不能与结晶硅基太阳能电池相比拟,而且稳定性较差;此外,影响和制约薄膜太阳能电池光电转换效率的因素很多,其一,需设计和优化内部微纳结构,提高其光吸收效率、光电转换效率和总发电效率;其二,需寻找廉价、清洁、光电转换效率高的新型薄膜材料及制备方法,其三,需分析光生电荷在界面的产生、分离、传输、复合、萃取和收集等过程对光生电荷分离效率的影响机制,为光电材料选择和电池结构优化提供理论依据。近年来,柔性太阳能电池因具备轻便、可折叠、可穿戴、成本低等特点受到了研究者的广泛关注。因此,制备一种新型柔性薄膜太阳能电池不但可以提高其适应性和应用范围,还可以大大缓解能源危机和环境污染等问题。
发明内容
本发明的目的在于提供一种ZTO-ZnO/CBS-GSs柔性薄膜太阳能电池,该太阳能电池资源储量丰富、制备方法简单、柔韧性好、适应性强、安全环保、成本低、且具有优越的光电性质,本发明还提供一种ZTO-ZnO/CBS-GSs柔性薄膜太阳能电池的制备方法,该方法可实现规模化生产,在缓解能源危机和环境污染等方面具有广泛的应用前景。
本发明是通过以下技术方案来实现的:
一种ZTO-ZnO/CBS-GSs柔性薄膜太阳能电池的制备方法,包括如下步骤:
(1)制备ZTO-ZnO纳米线:按照现有技术制备ZnO胶体溶液,在柔性衬底上生长ZTO纳米线,将生长有ZTO纳米线的柔性衬底浸没在ZnO胶体溶液中,以使在ZTO纳米线上沉积一层ZnO种子层,然后于450 ℃~550 ℃下保持10~30分钟使其结晶,再将带有ZnO种子层的ZTO纳米线放入硝酸锌的六次甲基四胺溶液中,在位生长ZnO纳米线,获得ZTO-ZnO纳米线;
(2)制备CBS-GSs混合溶液:按照现有技术先制备CBS胶体溶液,将预处理过的GSs加入CBS胶体溶液中搅拌至少12 小时;
(3) 最后,将CBS-GSs混合溶液旋转涂覆在ZTO-ZnO纳米线上,180 ±10℃下保持至少30 小时使CBS结晶成纳米带,即得一种表面覆盖有CBS-GSs光敏层的ZTO-ZnO薄膜结构,按照现有技术组装成薄膜太阳能电池,即可;其中,ZTO是指Zn2SnO4,CBS是指Cu4Bi4S9,GSs是指石墨烯纳米片。
其中,步骤(1)中ZnO胶体溶液的浓度为0.75 mol/L,硝酸锌的六次甲基四胺溶液浓度为2.5 × 10-3 mol/L,在位生长ZnO纳米线的温度为65~75 ℃,时间至少为8 小时。
步骤(2)中预处理过的GSs是指将GSs在体积比3:1的浓硫酸和浓硝酸中搅拌至少48 小时,间断超声至少36 小时;GSs占GSs和CBS两者总质量比为0.5~2.5 wt%。
利用上述方法即可制得ZTO-ZnO/CBS-GSs柔性薄膜太阳能电池。
为制备ZTO-ZnO/CBS-GSs柔性薄膜太阳能电池,首先,在柔性衬底(本发明采用的是不锈钢滤网,简称SSM,尺寸为:2×2.5 cm2)上生长ZTO纳米线,然后在ZTO纳米线上沉积一层ZnO种子层,并于450~550 ℃下保持10~30分钟(退火结晶处理),随后在位生长ZnO纳米线;其次,CBS纳米带虽有较宽光伏响应区域,但光生电荷分离效率较低,在CBS纳米带中引入适量GSs,可提供丰富异质分离界面(CBS/GSs);最后,在ZTO-ZnO光阳极上涂覆CBS-GSs复合光敏层,形成ZTO-ZnO/CBS-GSs薄膜结构,并组装成薄膜太阳能电池。
本发明在SSM柔性衬底上以ZTO-ZnO为光阳极、CBS-GSs为光敏层,不但可以提高CBS中光生载流子分离效率,还可以满足ZnO与GSs间良好能级匹配,促进光生电子快速迁移和收集;同时该柔性电池还具备原料储量丰富、光电性质优越、制备方法简单、重复性好、应用弹性大、适应性强、安全环保等特点。应用到新能源领域,可大大缓解能源危机和环境污染等问题,具有非常广泛的应用前景。
所制备ZTO-ZnO/CBS-GSs柔性薄膜太阳能电池实验室阶段平均光电转换效率已达10.3%,最佳光电转换效率已超过11%。用平镊1000次折弯以后仍然呈现出良好的柔韧性和可弯曲性,光电转换效率仍保持在95%以上。
附图说明
图1中,(a) 为SSM上生长ZTO纳米线的扫描电子形貌图,(b) 为ZTO纳米线上沉积ZnO种子层、并退火结晶后的扫描电子形貌图, (c) 为ZTO纳米线的ZnO种子层上在位生长ZnO纳米线后的扫描电子形貌图,(d) CBS-GSs混合溶液180 ℃下保持30 小时后的扫描电子形貌图;
图2中,(a) 为薄膜结构ZTO-ZnO/CBS-GSs随厚度最大光伏响应强度(483 nm处)变化曲线(薄膜厚度分别为3.0、3.5、4.0、4.5、5.0、5.5 和6.0 µm),(b) 为ZTO-ZnO/CBS-GSs最大表面光伏响应曲线(薄膜厚度为4.5 µm);
图3中,(a) 为薄膜太阳能电池ZTO-ZnO/CBS-GSs光电转换效率(IPCE),(b) 为ZTO-ZnO/CBS-GSs薄膜太阳能电池I-V曲线;
图4 为ZTO-ZnO/CBS-GSs薄膜太阳能电池随厚度总光电转换效率变化曲线(薄膜厚度分别为3.0、3.5、4.0、4.5、5.0、5.5 和6.0 µm);
图5 为ZTO-ZnO/CBS-GSs薄膜太阳能电池随GSs质量百分含量变化对应总光电转换效率曲线(质量百分含量分别为:0、0.5、1.0、1.5、2.0 和2.5 wt%)。
具体实施方式
以下以具体实施例来说明本发明的技术方案,但本发明的保护范围不限于此。
实施例1
一种ZTO-ZnO/CBS-GSs柔性薄膜太阳能电池的制备方法,具体步骤如下:
(1) 在柔性衬底SSM上生长ZTO纳米线:将0.21 g四氯化锡、0.263 g醋酸锌溶入到10 ml乙二胺和10 ml水的混合溶液中,搅拌30 分钟后缓慢添加0.29 g氢氧化钠,继续搅拌30 分钟使其均匀分散,然后将分散均匀后的溶液转移至不锈钢反应釜中,并将SSM片(不锈钢滤网片,2 × 2.5 cm2)斜靠在不锈钢反应釜内衬壁上,在烘箱中200 ℃下保持24 小时,自然冷却至室温,用去离子水清洗干净即可得到ZTO纳米线,如图1(a)所示,该纳米线具有良好的取向性,长度分布在1.5 -2.0 µm,直径分布在30-100 nm。
(2) ZTO-ZnO纳米线的制备:将8.26 g醋酸锌溶解到30 mL乙醇溶剂中,70 ℃下搅拌10分钟,再添加4.6 mL乙醇胺为稳定剂,再滴定适量乙醇制备成0.75 mol L-1ZnO胶体溶液,在70 ℃下搅拌1小时,陈化2天后待用。将步骤(1)制备的ZTO纳米线浸没在已制备好的0.75 mol L-1的ZnO胶体溶液中,保持10分钟即可在ZTO纳米线上沉积一层ZnO种子层,在500℃下保持20分钟(退火结晶处理)就可以得到结晶良好的ZnO种子层,如图1(b)所示,ZnO纳米颗粒分布均一,粒径分布在20-50 nm;将带有ZnO种子层的ZTO纳米线放置到2.5×10-3mol L-1硝酸锌溶液(溶剂为六次甲基四胺)中,将硝酸锌溶液缓慢加热到70 ℃,并保持8 小时,自然冷却至室温,用去离子水清洗干净即可得到ZTO-ZnO复合纳米线,如图1(c)所示,ZnO纳米线也具有良好的取向性,长度分布为400-800 nm,直径分布为20-60 nm。
(3)同时制备两组相同的CBS-GSs混合溶液,制备过程如下:将0.5 mmol氯化铋、0.5 mmol氯化亚铜、0.7 g十二胺溶解到30 ml的甲苯中,将溶液加热至70 ℃,并搅拌30分钟,在搅拌下将250 µL的二硫化碳缓慢滴加到上述溶液中即可得到CBS(Cu4Bi4S9)胶体(深棕色)溶液;将预处理过的GSs(以CBS和GSs总质量计,GSs质量百分含量:1.5 wt%)添加到CBS胶体溶液中,连续搅拌12小时就可以得到两组相同的CBS-GSs均匀混合溶液,其中一组直接进入下一步;将另一组混合溶液转移至不锈钢反应釜中,并在180 ℃下保持30 小时就可以得到结晶良好的CBS-GSs,其扫描电子形貌图如图1(d)所示,表明两组分已均匀混合在一起,且具有丰富界面,其中CBS纳米带表面光滑,长度分布为几微米到数十微米,直径为20-150 nm;GSs由多片纳米片堆叠在一起,且有丰富的褶皱。其中,GSs(石墨烯纳米片)购置于上海甄准生物科技有限公司,使用前需将GSs在体积比为3:1的浓硫酸和浓硝酸中搅拌至少48 小时,间断超声至少36 小时。
(4)对于其中一组CBS-GSs溶液,利用旋转涂覆的方法将CBS-GSs混合溶液涂覆到ZTO-ZnO纳米线上,并在手套箱中自然干燥,再次将CBS-GSs混合溶液涂覆到ZTO-ZnO纳米线上,如此重复,直至得到合适涂层厚度,涂覆结束后,将薄膜结构放置到不锈钢反应釜中,在180 ℃下保持30 小时就可以得到结晶良好的CBS-GSs光敏层以及ZTO-ZnO/CBS-GSs薄膜结构,并按照现有技术组装成ZTO-ZnO/CBS-GSs柔性薄膜太阳能电池。涂覆不同次数就可以得到不同厚度ZTO-ZnO/CBS-GSs薄膜结构, CBS-GSs的涂覆次数分别为1、2、3、4、5、6、7对应薄膜厚度分别为3.0、3.5、4.0、4.5、5.0、5.5和6.0 µm,ZTO-ZnO/CBS-GSs薄膜结构随涂层厚度最大光伏响应强度(483 nm)如图2(a)所示,其中在最佳厚度4.5 µm时最大光伏响应强度为715 µV。该薄膜结构在最佳厚度4.5 µm时对应表面光伏响应曲线如图2(b)所示,同样在483nm处达到最大光伏响应值,约为716 µV。ZTO-ZnO/CBS-GSs太阳能电池对应光电转换效率随入射波长关系曲线如图3(a)所示,从图中可以看出在483 nm达到最大转换效率值,约为70.5%。此外,ZTO-ZnO/CBS-GSs太阳能电池的I-V关系曲线如图3(b)所示,其对应开路电压和短路电流密度分别为0.83 V和18.2 mA cm-2。ZTO-ZnO/CBS-GSs太阳能电池光电转换效率随厚度变化规律如图4所示,表明光电转换效率随厚度增加而增加,在最佳厚度4.5 µm时达到最大光电转换效率11.8%,随后,随厚度增加逐渐减弱。
本实施例制备的ZTO-ZnO/CBS-GSs薄膜结构用平镊1000次折弯以后仍然呈现出良好的柔韧性和可弯曲性,光电转换效率仍保持在95%以上。
实施例2
基于实例1中优化的ZTO-ZnO/CBS-GSs最佳薄膜厚度(4.5 µm),改变GSs在CBS-GSs中的质量百分含量(0、0.5、1.0、1.5、2.0、2.5 wt%)就可以得到一系列ZTO-ZnO/CBS-GSs薄膜结构太阳能电池,其对应光电转换效率也在不断发生变化,合成方法如实施例1,添加GSs不同质量百分含量太阳能电池光电转换效率变化规律如图5所示。表明光电转换效率随GSs质量百分含量增加而增加,在最佳质量百分含量1.5 wt%时达到最大光电转换效率11.8%,随后,随质量百分含量增加逐渐减弱。
Claims (3)
1.一种ZTO-ZnO/CBS-GSs柔性薄膜太阳能电池的制备方法,其特征在于,包括如下步骤:
(1)制备ZTO-ZnO纳米线:在柔性衬底上生长ZTO纳米线,将生长有ZTO纳米线的柔性衬底浸没在ZnO胶体溶液中,以使在ZTO纳米线上沉积一层ZnO种子层,然后于450 ℃~550 ℃下保持10~30分钟使其结晶,再将带有ZnO种子层的ZTO纳米线放入硝酸锌的六次甲基四胺溶液中,在位生长ZnO纳米线,获得ZTO-ZnO纳米线;
(2)制备CBS-GSs混合溶液:先制备CBS胶体溶液,将预处理过的GSs加入CBS胶体溶液中搅拌至少12 小时;预处理过的GSs是指将GSs在体积比3:1的浓硫酸和浓硝酸中搅拌至少48小时,间断超声至少36 小时;GSs占GSs和CBS两者总质量的0.5~2.5 wt%;
(3) 最后,将CBS-GSs混合溶液旋转涂覆在ZTO-ZnO纳米线上,于180 ±10℃下保持至少30 小时使CBS结晶成纳米带,即得一种表面覆盖有CBS-GSs光敏层的ZTO-ZnO薄膜结构,按照现有技术组装成薄膜太阳能电池,即可;其中,ZTO是指Zn2SnO4,CBS是指Cu4Bi4S9,GSs是指石墨烯纳米片。
2.根据权利要求1所述的ZTO-ZnO/CBS-GSs柔性薄膜太阳能电池的制备方法,其特征在于,步骤(1)中ZnO胶体溶液的浓度为0.75 mol/L,硝酸锌的六次甲基四胺溶液浓度为2.5×10-3 mol/L,在位生长ZnO纳米线的温度为65~75 ℃,时间至少为8 小时。
3.权利要求1或2所述的制备方法制得的ZTO-ZnO/CBS-GSs柔性薄膜太阳能电池。
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