CN113937169A - 一种用于bipv的铜铟镓硒太阳能电池 - Google Patents

一种用于bipv的铜铟镓硒太阳能电池 Download PDF

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CN113937169A
CN113937169A CN202111124682.3A CN202111124682A CN113937169A CN 113937169 A CN113937169 A CN 113937169A CN 202111124682 A CN202111124682 A CN 202111124682A CN 113937169 A CN113937169 A CN 113937169A
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zinc oxide
film layer
oxide film
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plate glass
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李刚
夏申江
甘治平
杨扬
姚婷婷
王东
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CNBM Bengbu Design and Research Institute for Glass Industry Co Ltd
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Abstract

本发明提供了一种用于BIPV的铜铟镓硒太阳能电池，包括背板玻璃，自所述背板玻璃表面向外依次为铜铟镓硒电池功能层/胶膜层/紫外电池功能层/盖板玻璃/减反射膜层。与现有电池相比，本发明具有以下优点和效果：采用化学溶液法制备p型氧化锌膜层与n型氧化锌膜层，以此在盖板玻璃内表面形成紫外电池功能层，这样，通过紫外电池功能层吸收紫外光，并可利用紫外光发电，提高太阳光谱的利用率，且能有效降低紫外线的伤害，延长铜铟镓硒电池使用寿命；同时通过控制p型与n型氧化锌膜层材料折射率和膜层厚度，使反射光产生干涉的波长不同，并同黑色电池功能层相结合，从而获得具有与环境、建筑外观匹配的多种颜色的铜铟镓硒太阳能电池。

Description

一种用于BIPV的铜铟镓硒太阳能电池
技术领域
本发明涉及薄膜太阳能电池技术领域，具体是指一种用于BIPV的铜铟镓硒太阳能电池。
背景技术
近年来由于我国城市化进程的加快，建筑能耗逐年增长，因此加快可再生能源在建筑领域中规模化应用，是降低建筑能耗、调整建筑用能结构的关键措施之一。太阳能系统建筑一体化技术（简称“BIPV”）是将太阳能系统产品有机结合到建筑领域，既可以使太阳能系统具有建筑功能，同时又利用建筑表面产生的能量，实现提供清洁能源和降低建筑能耗的双重效果。
与传统晶硅、非晶硅电池相比，铜铟镓硒(CIGS)薄膜太阳能电池作为新一代的薄膜电池，具备弱光发电性能好、成本低、温度系数低、能源回收期短、寿命长、发电稳定、抗辐射能力强、生产工艺无污染等优势，市场前景巨大。CIGS是一种直接带隙的P型半导体材料，其吸收系数高达105/cm，2μm厚的CIGS薄膜就可吸收90％以上的太阳光，CIGS电池转换效率在薄膜太阳能电池中也是最高的，CIGS太阳能电池的优点非常符合“光伏建筑一体化”的应用实施。
但常规太阳能电池在建筑物上的应用受到一个根本性制约，因为建筑作为环境和城市景观，对外观色彩的要求非常高。CIGS太阳能电池是将电池功能层以多层薄膜的形式涂镀在背板玻璃上，然后与胶膜、光伏盖板玻璃层压合片，以组件的形式投入应用，由于电池功能层为黑色，而胶膜和光伏盖板玻璃都是无色透明的，所以CIGS电池的颜色通常显示为黑色。因而传统CIGS电池难以满足建筑作为环境和城市景观，对外观色彩的特殊要求。
此外，CIGS太阳能电池主要利用可见光和红外波段光的能量，紫外线对电池组件是有害的，这是因为紫外线具有较短的波长和较高的能量，而目前封装用的胶膜多为高分子材料，所以紫外线对胶膜具有很强的破坏性，严重影响光伏电池组件的使用寿命；同时紫外光穿透玻璃被电池吸收转化为热能，使组件工作温度过高，从而降低了组件实际发电量。
由此可见，BIPV的概念需要新的内涵，开发出一种既能与环境、建筑完美融合，外表美观，又能利用紫外线，拥有长使用寿命的彩色铜铟镓硒太阳能电池，具有重要的现实意义。
发明内容
本发明的目的就是为了克服现有技术中的不足，提供了一种用于BIPV的铜铟镓硒太阳能电池。
为了达到上述目的，本发明采用如下技术方案：
一种用于BIPV的铜铟镓硒太阳能电池，所述铜铟镓硒太阳能电池，包括自背板玻璃表面向外依次制有的铜铟镓硒电池功能层和胶膜层，在胶膜层外层依次设置盖板玻璃和减反射膜层，其特征在于：在胶膜层和盖板玻璃之间制有紫外电池功能层。
在上述技术方案的基础上，有以下进一步的技术方案：
所述的紫外电池功能层，其结构自盖板玻璃内表面向外依次为透明电极层/n型氧化锌膜层/p型氧化锌膜层/金属栅电极层；
制备透明电极层的材料，包括但不限制于透明导电氧化物、氧化物/金属/氧化物叠层、银纳米线；
制备n型氧化锌膜层的材料，包括但不限制于未掺杂氧化锌、铝掺杂氧化锌、镓掺杂氧化锌、铟掺杂氧化锌、硼掺杂氧化锌；
所述n型氧化锌膜层的制备方法：采用化学溶液法，具体包括以乙酸锌作为前躯体，硝酸铝或硝酸镓或硝酸铟或硼酸三甲酯作为掺杂物，乙醇或乙二醇甲醚作为溶剂，配制成胶体溶液后，利用提拉、旋涂、喷涂等方法沉积到已镀有透明电极层的盖板玻璃上，然后在空气中热解，最后在氧气或空气或依次在空气/还原气氛中退火晶化，得到所述的n型氧化锌膜层；
制备p型氧化锌膜层的材料，包括但不限制于锑掺杂氧化锌、氮掺杂氧化锌；
所述P型氧化锌膜层的制备方法：采用化学溶液法，具体包括以乙酸锌作为前躯体，三氯化锑或乙酸铵作为掺杂物，乙醇或乙二醇甲醚作为溶剂，配制成胶体溶液后，利用提拉、旋涂、喷涂等方法沉积到n型氧化锌膜层上，然后在空气中热解，最后在氧气或依次在氧气/真空或空气/氧气中退火晶化，得到所述的p型氧化锌膜层；
制备所述减反膜层材料，包括但不限制于氧化硅、氮氧化硅、氟化镁；
背板玻璃为中铝玻璃，盖板玻璃为超白玻璃；
铜铟镓硒电池功能层结构自背板玻璃外表面向外依次为钼电极层/铜铟镓硒吸收层/缓冲层/窗口层/铝掺杂氧化锌膜层/金属栅电极层；
制备胶膜层的材料为PVB、PO、EVA。
本发明提供了一种用于BIPV的铜铟镓硒太阳能电池具有宽色系、长寿命的特点，与现有电池相比，其具有以下优点和效果：本发明采用化学溶液法制备p型氧化锌膜层与n型氧化锌膜层，并以此在盖板玻璃内表面形成紫外电池功能层，这样，一方面，通过紫外电池功能层吸收紫外光，并可利用紫外光发电，提高太阳光谱的利用率，且有效降低紫外线的伤害，提升铜铟镓硒电池稳定性及使用寿命；另一方面，通过控制p型与n型氧化锌膜层材料折射率和膜层厚度，使反射光产生干涉的波长不同，并同黑色电池功能层相结合，从而获得多种色彩反射的铜铟镓硒太阳能电池。同时，盖板玻璃外表面的减反膜层可以显著提高盖板玻璃的透光率，从而弥补紫外电池功能层对可见光和红外波段光透光率造成的损失。因此，本发明实现了铜铟镓硒太阳能电池具有与环境、建筑外观匹配的多种颜色及长使用寿命的目的。
以下结合附图，通过示例说明本发明主旨的描述，以清楚本发明的其它方面和优点。
附图说明
结合附图，通过下文的详细说明，可更清楚地理解本发明的上述及其它特征和优点，其中：
图1为本发明提供的一种用于BIPV的铜铟镓硒太阳能电池的结构示意图；
图2为本发明提供的铜铟镓硒电池功能层的结构示意图；
图3为本发明提供的紫外电池功能层的结构示意图；
图4为本发明实施例1提供的增加紫外电池功能层前后，CIGS电池盖板玻璃透过率的对比图；
图5为本发明实施例4提供的增加紫外电池功能层前后，CIGS电池盖板玻璃透过率的对比图。
具体实施方式
参见本发明具体实施例的附图，下文将更详细地描述本发明。然而，本发明可以以许多不同形式实现，并且不应解释为受在此提出之实施例的限制。相反，提出这些实施例是为了达成充分及完整公开，并且使本技术领域的技术人员完全了解本发明的范围。
现参考附图详细说明本发明实施例提供的一种用于BIPV的铜铟镓硒太阳能电池。
如图1所示，本发明提供的一种用于BIPV的铜铟镓硒太阳能电池，包括背板玻璃，自所述背板玻璃表面向外依次为铜铟镓硒电池功能层、胶膜层、紫外电池功能层、盖板玻璃、减反射膜层。
其中，所述背板玻璃为中铝玻璃，盖板玻璃为超白玻璃。
其中，所述铜铟镓硒电池功能层结构自背板玻璃外表面向外依次为钼电极层/铜铟镓硒吸收层/缓冲层/窗口层/铝掺杂氧化锌膜层/金属栅电极层，如图2所示。
其中，所述胶膜层为PVB、PO、EVA。
其中，所述减反膜层材料包括但不限制于氧化硅、氮氧化硅、氟化镁。
其中，所述紫外电池功能层结构自盖板玻璃内表面向外依次为透明电极层/n型氧化锌膜层/p型氧化锌膜层/金属栅电极层，如图3所示。
优选的，所述透明电极层材料包括但不限制于透明导电氧化物、氧化物/金属/氧化物叠层、银纳米线。
优选的，所述n型氧化锌膜层材料包括但不限制于未掺杂氧化锌、铝掺杂氧化锌、镓掺杂氧化锌、铟掺杂氧化锌、硼掺杂氧化锌。
进一步的，采用化学溶液法制备所述的n型氧化锌膜层，具体包括以乙酸锌作为前躯体，硝酸铝或硝酸镓或硝酸铟或硼酸三甲酯作为掺杂物，乙醇或乙二醇甲醚作为溶剂，配制成胶体溶液后，利用提拉、旋涂、喷涂等方法沉积到已镀有透明电极层的玻璃基板上，然后在空气中热解，最后在氧气或空气或依次在空气/还原气氛中退火晶化，得到所述的n型氧化锌膜层。
优选的，所述p型氧化锌膜层材料包括但不限制于锑掺杂氧化锌、氮掺杂氧化锌。
进一步的，采用化学溶液法制备所述的p型氧化锌膜层，具体包括以乙酸锌作为前躯体，三氯化锑或乙酸铵作为掺杂物，乙醇或乙二醇甲醚作为溶剂，配制成胶体溶液后，利用提拉、旋涂、喷涂等方法沉积到n型氧化锌膜层上，然后在空气中热解，最后在氧气或依次在氧气/真空或空气/氧气中退火晶化，得到所述的p型氧化锌膜层。
本发明实施例提供的铜铟镓硒太阳能电池，可以克服现有产品中的不足，实现铜铟镓硒太阳能电池具有与环境、建筑外观匹配的多种颜色及长使用寿命的目的。
以下详细描述了本发明的较佳具体实施例。应当理解，本领域的普通技术人员无需创造性劳动就可以根据本发明的构思做出诸多修改和变化。凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在由权利要求书所确定的保护范围内。
实施例1
本实施例中，减反膜层材料为氧化硅；透明电极层材料为氧化铟锡；n型氧化锌膜层材料为未掺杂氧化锌，具体工艺参数为：以乙酸锌作为前躯体，乙二醇甲醚作为溶剂，乙酸锌与乙二醇甲醚的比例为1:1，采用旋涂法沉积到已镀有氧化铟锡膜层的超白玻璃上，然后在300℃空气中热解，最后在550℃氧气中退火晶化；p型氧化锌膜层材料为锑掺杂氧化锌，具体工艺参数为：以乙酸锌作为前躯体，三氯化锑作为掺杂物，乙二醇甲醚作为溶剂，乙酸锌与乙二醇甲醚的比例为1:1，按Sb/Zn比例为4:1000配制成胶体溶液，采用旋涂法沉积到未掺杂氧化锌膜层上，然后在300℃空气中热解，最后依次在550℃氧气/真空中退火晶化，得到锑掺杂氧化锌膜层，如图3所示。
从图4中可以看出，本实施例增加紫外电池功能层后，320-380nm波长范围的紫外光被有效吸收，从而实现了CIGS电池提高太阳光谱的利用率，且降低紫外线伤害的目的。
实施例2~3
除了膜层厚度之外，实施例2~3的制备工艺参数与实施例1基本相同，实施例1~3中未掺杂氧化锌、锑掺杂氧化锌和氧化硅膜层的折射率、膜层厚度及铜铟镓硒太阳能电池在CIE-D65发光体下的1931 CIE(x,y)色彩坐标列于表1中。
表1
Figure 73086DEST_PATH_IMAGE002
从表1中反射光色彩坐标可以得知，实施例1~3依次得到的是紫色、绿灰色、蓝灰色反射的铜铟镓硒太阳能电池。
实施例4
本实施例中，减反膜层材料为氧化硅；透明电极层材料为氧化铟锡；n型氧化锌膜层材料为铝掺杂氧化锌，具体工艺参数为：以乙酸锌作为前躯体，硝酸铝作为掺杂物，乙二醇甲醚作为溶剂，乙酸锌与乙二醇甲醚的比例为1:1，按Al/Zn比例为5:1000配制成胶体溶液，采用旋涂法沉积到已镀有氧化铟锡膜层的超白玻璃上，然后在300℃空气中热解，最后在600℃空气中退火晶化；p型氧化锌膜层材料为氮掺杂氧化锌，具体工艺参数为：以乙酸锌作为前躯体，乙酸铵作为掺杂物，乙二醇甲醚作为溶剂，乙酸锌与乙二醇甲醚的比例为1:1，按N/Zn比例为3:1配制成胶体溶液，采用旋涂法沉积到铝掺杂氧化锌膜层上，然后在300℃空气中热解，最后依次在550℃空气/氧气中退火晶化。
从图5中可以看出，本实施例增加紫外电池功能层后，320-380nm波长范围的紫外光被有效吸收，从而实现了CIGS电池提高太阳光谱的利用率，且降低紫外线伤害的目的。
实施例5~6
除了膜层厚度之外，实施例5~6的制备工艺参数与实施例4基本相同，实施例4~6中铝掺杂氧化锌、氮掺杂氧化锌和氧化硅膜层的折射率、膜层厚度及铜铟镓硒太阳能电池在CIE-D65发光体下的1931 CIE(x,y)色彩坐标列于表2中。
表2
Figure 426445DEST_PATH_IMAGE004
从表2中反射光色彩坐标可以得知，实施例4~6依次得到的是灰绿色、紫色、粉紫色反射的铜铟镓硒太阳能电池。

Claims (9)

1.一种用于BIPV的铜铟镓硒太阳能电池，所述铜铟镓硒太阳能电池，包括自背板玻璃表面向外依次制有铜铟镓硒电池功能层和胶膜层，在胶膜层外层依次设置盖板玻璃和减反射膜层，其特征在于：在胶膜层和盖板玻璃之间制有紫外电池功能层。
2.根据权利要求1所述的一种用于BIPV的铜铟镓硒太阳能电池，其特征在于：所述的紫外电池功能层，其结构自盖板玻璃内表面向外依次为透明电极层、n型氧化锌膜层、p型氧化锌膜层、金属栅电极层。
3.根据权利要求2所述的一种用于BIPV的铜铟镓硒太阳能电池，其特征在于：制备透明电极层的材料包括但不限制于透明导电氧化物、氧化物、金属、氧化物叠层、银纳米线。
4.根据权利要求3所述的一种用于BIPV的铜铟镓硒太阳能电池，其特征在于：制备n型氧化锌膜层的材料包括但不限制于未掺杂氧化锌、铝掺杂氧化锌、镓掺杂氧化锌、铟掺杂氧化锌、硼掺杂氧化锌；
所述n型氧化锌膜层的制备方法：采用化学溶液法，具体包括以乙酸锌作为前躯体，硝酸铝或硝酸镓或硝酸铟或硼酸三甲酯作为掺杂物，乙醇或乙二醇甲醚作为溶剂，配制成胶体溶液后，利用提拉、旋涂、喷涂等方法沉积到已镀有透明电极层的盖板玻璃上，然后在空气中热解，最后在氧气或空气或依次在空气/还原气氛中退火晶化，得到所述的n型氧化锌膜层。
5.根据权利要求3或4所述的一种用于BIPV的铜铟镓硒太阳能电池，其特征在于：制备p型氧化锌膜层的材料包括但不限制于锑掺杂氧化锌、氮掺杂氧化锌；
所述P型氧化锌膜层的制备方法：采用化学溶液法，具体包括以乙酸锌作为前躯体，三氯化锑或乙酸铵作为掺杂物，乙醇或乙二醇甲醚作为溶剂，配制成胶体溶液后，利用提拉、旋涂、喷涂等方法沉积到n型氧化锌膜层上，然后在空气中热解，最后在氧气或依次在氧气/真空或空气/氧气中退火晶化，得到所述的p型氧化锌膜层。
6.根据权利要求1所述的一种用于BIPV的铜铟镓硒太阳能电池，其特征在于：所述减反膜层材料包括但不限制于氧化硅、氮氧化硅、氟化镁。
7.根据权利要求1所述的一种用于BIPV的铜铟镓硒太阳能电池，其特征在于：背板玻璃为中铝玻璃，盖板玻璃为超白玻璃。
8.根据权利要求1所述的一种用于BIPV的铜铟镓硒太阳能电池，其特征在于铜铟镓硒电池功能层结构自背板玻璃外表面向外依次为钼电极层/铜铟镓硒吸收层/缓冲层/窗口层/铝掺杂氧化锌膜层/金属栅电极层。
9.根据权利要求1所述的一种用于BIPV的铜铟镓硒太阳能电池，其特征在于：制备胶膜层的材料为PVB、PO、EVA。
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