CN113113497B - 一种使用有机增效剂的太阳能电池及其制备方法 - Google Patents
一种使用有机增效剂的太阳能电池及其制备方法 Download PDFInfo
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Abstract
本发明提供使用有机增效剂的太阳能电池及其制备方法,特别是提供一种减少分层和粉化现象的太阳能电池及其制备方法,包括以AZO@TiO2为原料制成的第一减反射层和有机增效剂为原料制成的第二减反射层;所述AZO@TiO2/SiO2为采用TiO2/SiO2为核,AZO为外壳的核壳结构;有机增效剂由有机硅树脂、带活性官能团的纳米中空二氧化硅和有机溶剂组成,AZO@TiO2/SiO2包覆结构中,部分SiO2纳米颗粒未被完全包覆的部分,作为“钉扎效应”的连接结构,连接第一减反射层和第二减反射层,能够有效的避免第一减反射层和第二减反射层之间的分层具有极强的耐候性。
Description
一种使用有机增效剂的太阳能电池及其制备方法
技术领域
本发明涉及太阳能电池技术领域,具体涉及一种使用有机增效剂的太阳能电池及其制备 方法。
背景技术
太阳能由于其“取之不尽、用之不竭”是一种真正意义上的“绿色”能源,而成为世界 各国政府可持续发展的能源战略。太阳能电池技术作为新兴绿色能源近几年得到了迅猛的发 展。太阳能电池被广泛用于。目前实验室中太阳能电池的转化率已经能够满足空间飞行器, 例如导航卫星、通讯卫星,空间站,空间探测器等需求。
但是实际用于过程中太阳能电池减反射膜的质量与实际服务寿命严重制约着电池的效 率和使用寿命,这是因为太阳能电池在大气环境中,减反射膜逐渐为灰尘或工业污染物覆盖, 降低了玻璃透光率,使太阳能电池效率下降。太阳能电池表面在恶劣的湿热环境中,会出现 分层或粉化现象,太阳能电池玻璃减反射膜的寿命明显缩短,对入射太阳光有显著阻挡和吸 收作用。
现有技术中已经有使用ITO或者AZO或其叠层作为反射膜,避免减反射膜的纳米二氧 化硅水解形成的硅酸盐。但是目前ITO或者AZO或其叠层减反射膜的透射率与导电性相互 制约,会增加减反射膜的厚度,此外叠层结构的反射膜在长期使用过程中,由于层间应力的 不同,会出现分层或粉化现象,造成减反射膜实际服务寿命的降低。CN108155253 A公开了 一种导电玻璃减反射膜的设计和制备方法,具体常温固化的减反射镀膜液由有机硅树脂、带 活性官能团的纳米中空二氧化硅和有机溶剂组成,但是直接使用上述有机材料作为反射膜与 现有的反射膜直接容易分层,使用寿命低。
发明内容
针对以上问题,本发明的目的是提供一种使用有机增效剂的太阳能电池及其制备方法, 特别是提供一种减少分层和粉化现象的太阳能电池及其制备方法。
本发明的使用有机增效剂的太阳能电池,包括下电极,下电极上的衬底层,衬底层上的 外延层结构、以及位于外延层之上的上电极,其特征在于:还包括上电极上的减反射膜,所 述减反射膜为双层结构,包括以AZO@TiO2为原料制成的第一减反射层和有机增效剂为原料 制成的第二减反射层;所述AZO@TiO2/SiO2为采用TiO2/SiO2为核,AZO为外壳的核壳结构; 有机增效剂由有机硅树脂、带活性官能团的纳米中空二氧化硅和有机溶剂组成。
本发明中有机硅树脂是由甲基三乙氧基硅烷和二氧化硅水溶胶以摩尔比为1:1.5-2共聚形 成的乙醇溶胶,溶胶粒径为5-10nm。
本发明中带活性官能团的纳米中空二氧化硅是由正硅酸乙酷和带有环氧基或氨基的有机 硅偶联剂以摩尔比为1:0.1-0.3共聚形成的乙醇溶胶,溶胶粒径为20-50nm,溶胶粒子壁厚为 5-10nm。
正硅酸乙酷水解均聚反应形成的纳米中空二氧化硅增透率高,但强度不足;与有机硅偶联 剂水解共聚可弥补形成的纳米中空二氧化硅强度不足的缺陷。
典型的带有环氧基或氨基的有机硅偶联剂分别是γ―(2,3-环氧丙氧)丙基三甲氧基硅烷 和3-氨基丙基三乙氧基硅烷。
正硅酸乙酯和有机硅偶联剂的比例影响膜层的增透率、附着力和固化速度。当有机硅偶 联剂比例升高时,增透率下降,附着力提高,固化速度提高。有机硅偶联剂分子中含有环氧 基或氨基活性基团,它们与有机硅分子中的羟基反应速度很快,可作为有机硅树脂的快速固 化剂,所以,其添加比例不能过大,也不能混合添加。
本发明中采用的AZO@TiO2/SiO2纳米颗粒通过溶液法制备,将TiO2纳米颗粒与SiO2纳 米颗粒进行球磨混合加入有机溶剂制成悬浊液后,加入一定比例的AlCl3和ZnCl2混合溶液, 同时控制混合溶液的pH值保持恒定,反应结束后,进行洗涤、过滤、干燥、煅烧处理,即可得到表面包覆AZO的导电AZO@TiO2/SiO2纳米颗粒。
本发明中采用的有机溶剂是乙醇、乙二醇二丁醚、乙酰丙酮之一或其混合物。
本发明中AZO@TiO2/SiO2,TiO2的粒径为20-30nm,SiO2的粒径为20-30nm,AZO包 覆层的厚度为10-50nm。优选地,AZO包覆层的厚度小于SiO2的粒径,使部分SiO2的粒径 未被完全包覆。
本发明中第一减反射层和/或第二减反射层,通过固化获得,可采用辊涂、喷涂、刷涂、 离心或提拉方法涂布,根据涂布方式不同用有机溶剂稀释到合适粘度后使用。
本发明中衬底层为聚合物非导电性衬底或其他衬底。
本发明中外延层包含但不限于单结或多结GaAs基、硅基电池、有机电池、染料敏化电 池、量子点、铜铟镓硒、铜锌锡硫、碲化镉或以上任何二种以上电池的复合型电池。
根据本发明的第二个方面,一种使用有机增效剂的太阳能电池的制造方法,包括如下步 骤:
(1)在衬底层上生长外延层;
(2)在具有外延层的衬底上表面和下表面分别制备上电极和下电极,其中下电极位于衬 底层一侧,上电极位于外延层外表面;
(3)在上电极上制备AZO@TiO2/SiO2层作为第一反射层;其中,AZO@TiO2/SiO2层 通过涂布干燥获得。
(4)在AZO@TiO2/SiO2层通过涂布制备有机增效剂层作为第二减反射层,其中有机增 效剂层通过涂布含有有机硅树脂、带活性官能团的纳米中空二氧化硅和有机溶剂组成的溶液 后干燥获得。
本发明的有益效果在于:
首先,本发明采用了AZO@TiO2/SiO2核壳纳米结构作为减反射层材料,避免了常规AZO、TiO2、SiO2叠层结构因为层间应力造成的分层问题,其次,有机增效剂中具有不同 粒径的二氧化硅混合,例如 以甲基三乙氧基硅烷水解形成的甲基二氧化硅、二氧化硅水溶胶粒子,纳米中空二氧化硅, 且发明中纳米中空二氧化硅带有活性官能团,容易与有机硅树脂结合增加了外层反射层的强 度。最重要的是本发明中的AZO@TiO2/SiO2包覆结构中,部分SiO2纳米颗粒未被完全包覆 的部分,作为“钉扎效应”的连接结构,连接第一减反射层和第二减反射层,能够有效的避 免第一减反射层和第二减反射层之间的分层具有极强的耐候性。
具体实施方式
下面结合实施例对本发明作进一步描述,但不应以此限制本发明的保护范围。
一种使用有机增效剂的太阳能电池的制造方法,包括如下步骤:
S10:提供p型Ge单晶衬底,所述Ge衬底的厚度为300um-600um;
S20:在p型Ge单晶衬底上生长外层结构;
S30:在电池上表面及背面通过真空蒸发的方法制备上电极与下电极,其中电极材料为Pd 或Ag或Au,电极结构为单层或叠层结构;
S40:在上电极层上涂布一层在AZO@TiO2/SiO2浆料并干燥后获得第一反射层;
S50:在第一反射层上涂布一层有机增效剂并干燥后获得第二反射层,有机增效剂由有机 硅树脂、带活性官能团的纳米中空二氧化硅和有机溶剂组成。
所述S10包括以下步骤:对p型Ge单晶衬底依次用丙酮、乙醇以及超纯水对衬底片进 行5分钟的超声清洗,其后用10%的盐酸浸泡3分钟,随后用去离子水冲洗衬底表面的盐酸; 最后用乙醇对衬底片进行5分钟的超声清洗以洗去表面水分。
所述S20包括以下步骤:在p型Ge单晶衬底上生长n型Ge外延层;在n型Ge外延层 上生长一层n型GaAs作为过渡层;再外延生长重掺杂的n型与p型GaAs作为下隧穿结在 下隧穿结上按先后顺序依次生长中间电池的p型GaAs,InGaAs/GaInP量子阱结构、n型GaAs, 其中InGaAs作为量子阱层,厚度为15nm,GaInP作为势垒层,厚度为21nm;生长重掺杂的 n型与p型GaAs作为上隧穿结;在上隧穿结上按先后顺序生长顶电池的p型GaInP与n型 GaInP;
所述S30包括以下步骤:通过电子束蒸镀系统在背面和上表面蒸镀一层Pd或Ag或Au 作为电极,优选为Au,蒸镀速率为1.2nm/s,厚度为100nm,其中采用lift-off剥离工艺得到 上电极的栅线结构。
所述S40包括以下步骤:
S401:将TiO2纳米颗粒与SiO2纳米颗粒进行球磨混合,使TiO2的粒径为20-30nm,SiO2 的粒径为20-30nm。
S402:将TiO2纳米颗粒与SiO2纳米颗粒加入乙醇制成悬浊液后并超声30min,将悬浊液 倒入三口烧瓶中匀速搅拌,一侧插入温度计监测反应温度,待悬浊液温度保持恒定后,在另 一侧缓慢滴入一定比例的AlCl3和ZnCl2混合溶液,同时控制混合溶液的pH值保持恒定,反 应结束后,对浆液进行洗涤、过滤、干燥、煅烧处理,即可得到AZO表面包覆的TiO2/SiO2; 一定比例具体为质量比为1:1-1.5。AZO包覆层的厚度为10-15nm。AZO@TiO2/SiO2纳米颗 粒的包覆率为67%。
S403:将AZO@TiO2/SiO2纳米颗粒加入乙醇、乙二醇二丁醚、乙酰丙酮之一或其混合物 中获得AZO@TiO2/SiO2浆料。
S404:常温下,在上电极层上涂布一层在AZO@TiO2/SiO2浆料并干燥后获得第一反射层。
所述S50包括以下步骤:
S501:十六烷基三甲基溴化铵2g、去离子水600g,乙二醇二丁醚300g和质量百分浓度 为20%的氨水5g,强烈搅拌30分钟,然后加入正硅酸乙酯104g和3-氨基丙基三乙氧基硅烷 11.1g的混合物,在20-30℃下反应12小时生成半透明溶胶。
S502:用磷酸水溶液调节溶胶pH为1-2,使有机硅化合物完全水解,然后升温到100℃ 蒸出大部分有机溶剂和水,冷却后加入无水乙醇稀释得到质量百分浓度为20%的带氨基官能 团的纳米中空二氧化硅溶胶240g,溶胶粒径为30-60nm。
S503:将质量百分浓度为40%的有机硅树脂乙醇溶胶10g和质量百分浓度为20%的带氨 基官能团的纳米中空二氧化硅溶胶20g混合,用乙二醇二丁醚和无水乙醇等量混合的有机溶 剂170g稀释后陈化12h,得到质量百分浓度为4%的能够常温固化的有机增效剂。
S603:在第一反射层上涂布一层有机增效剂并干燥后获得第二反射层。
测得本实施例与AZO@TiO2作为第一反射层的结构相比耐候性(耐候时间)提高了30%。
最后应当说明的是:以上实施例仅用以说明本申请的技术方案而非对其限制;尽管参照 较佳实施例对本申请进行了详细的说明,所属领域的普通技术人员应当理解:依然可以对本 申请的具体实施方式进行修改或者对部分技术特征进行等同替换,其均应涵盖在本申请请求 保护的技术方案范围当中。
Claims (7)
1.一种使用有机增效剂的太阳能电池,包括下电极,下电极上的衬底层,衬底层上的外延层结构、以及位于外延层之上的上电极,其特征在于:还包括上电极上的减反射膜,所述减反射膜为双层结构,包括以AZO@TiO2为原料制成的第一减反射层和有机增效剂为原料制成的第二减反射层;所述AZO@TiO2/SiO2为采用TiO2/SiO2为核,AZO为外壳的核壳结构;有机增效剂由有机硅树脂、带活性官能团的纳米中空二氧化硅和有机溶剂组成;所述有机增效剂中具有不同粒径的二氧化硅混合;所述AZO@TiO2/SiO2包覆结构存在部分SiO2纳米颗粒未被完全包覆,以连接第一减反射层和第二减反射层,所述有机硅树脂是由甲基三乙氧基硅烷和二氧化硅水溶胶以摩尔比为1:1.5-2共聚形成的乙醇溶胶,溶胶粒径为5-10nm;所述带活性官能团的纳米中空二氧化硅是由正硅酸乙酷和带有环氧基或氨基的有机硅偶联剂以摩尔比为1:0.1-0.3共聚形成的乙醇溶胶,溶胶粒径为20-50nm,溶胶粒子壁厚为5-10nm;所述AZO包覆层的厚度小于SiO2的粒径,使部分SiO2的粒径未被完全包覆。
2.根据权利要求1所述的使用有机增效剂的太阳能电池,其特征是,AZO@TiO2/SiO2纳米颗粒通过溶液法制备,将TiO2纳米颗粒与SiO2纳米颗粒进行球磨混合加入有机溶剂制成悬浊液后,加入AlCl3和ZnCl2混合溶液,所述AlCl3与ZnCl2的质量比为1:1-1.5,同时控制混合溶液的pH值保持恒定,反应结束后,进行洗涤、过滤、干燥、煅烧处理,得到表面包覆AZO的导电AZO@TiO2/SiO2纳米颗粒。
3.根据权利要求1所述的使用有机增效剂的太阳能电池,其特征是,有机溶剂是乙醇、乙二醇二丁醚、乙酰丙酮之一或其混合物。
4.根据权利要求1所述的使用有机增效剂的太阳能电池,其特征是,第一减反射层和/或第二减反射层,通过固化获得,采用辊涂、喷涂、刷涂、离心或提拉方法涂布。
5.一种如权利要求1所述的使用有机增效剂的太阳能电池的制造方法,包括如下步骤:
(1)在衬底层上生长外延层;
(2)在具有外延层的衬底上表面和下表面分别制备上电极和下电极,其中下电极位于衬底层一侧,上电极位于外延层外表面;
(3)在上电极上制备AZO@TiO2/SiO2层作为第一反射层;其中,AZO@TiO2/SiO2层通过涂布干燥获得;
(4)在AZO@TiO2/SiO2层通过涂布制备有机增效剂层作为第二减反射层,其中有机增效剂层通过涂布含有有机硅树脂、带活性官能团的纳米中空二氧化硅和有机溶剂组成的溶液后干燥获得。
6.一种如权利要求1所述的使用有机增效剂的太阳能电池的制造方法,包括如下步骤:S10:提供p型Ge单晶衬底,所述Ge单晶衬底的厚度为300um-600um;
S20:在p型Ge单晶衬底上生长外层结构;
S30:在电池上表面及背面通过真空蒸发的方法制备上电极与下电极,其中电极材料为Pd或Ag或Au,电极结构为单层或叠层结构;
S40:在上电极层上涂布一层在AZO@TiO2/SiO2浆料并干燥后获得第一反射层;
S50:在第一反射层上涂布一层有机增效剂并干燥后获得第二反射层,有机增效剂由有机硅树脂、带活性官能团的纳米中空二氧化硅和有机溶剂组成;
所述S10包括以下步骤:对p型Ge单晶衬底依次用丙酮、乙醇以及超纯水对衬底片进行5分钟的超声清洗,其后用10%的盐酸浸泡3分钟,随后用去离子水冲洗衬底表面的盐酸;最后用乙醇对衬底片进行5分钟的超声清洗以洗去表面水分。
7.根据权利要求6所述的一种使用有机增效剂的太阳能电池的制造方法,其特征是,所述S40包括以下步骤:
S401:将TiO2纳米颗粒与SiO2纳米颗粒进行球磨混合,使TiO2的粒径为20-30nm,SiO2的粒径为20-30nm;
S402:将TiO2纳米颗粒与SiO2纳米颗粒加入乙醇制成悬浊液后并超声30min,将悬浊液倒入三口烧瓶中匀速搅拌,一侧插入温度计监测反应温度,待悬浊液温度保持恒定后,在另一侧缓慢滴入AlCl3和ZnCl2混合溶液,同时控制混合溶液的pH值保持恒定,反应结束后,对浆液进行洗涤、过滤、干燥、煅烧处理,即可得到AZO表面包覆的TiO2/SiO2,AZO包覆层的厚度为10-15nm,AZO@TiO2/SiO2纳米颗粒的包覆率为67%;
S403:将AZO@TiO2/SiO2纳米颗粒加入乙醇、乙二醇二丁醚、乙酰丙酮之一或其混合物中获得AZO@TiO2/SiO2浆料;
S404:常温下,在上电极层上涂布一层在AZO@TiO2/SiO2浆料并干燥后获得第一反射层。
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