CN103897251B - 一种柔性或薄膜太阳能电池用光固化eva膜及其制备方法 - Google Patents

一种柔性或薄膜太阳能电池用光固化eva膜及其制备方法 Download PDF

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CN103897251B
CN103897251B CN201210589374.2A CN201210589374A CN103897251B CN 103897251 B CN103897251 B CN 103897251B CN 201210589374 A CN201210589374 A CN 201210589374A CN 103897251 B CN103897251 B CN 103897251B
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eva
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thin
solar cells
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张迎晨
吴红艳
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Zhongyuan University of Technology
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Abstract

一种柔性或薄膜太阳能电池用光固化EVA膜及其制备方法，由下述重量份的如下组分制成：EVA树脂100；纳米铝粉0.0001-0.1；光固化剂0.5-1.25；紫外光吸收剂0.1-0.2；增粘剂0-0.4；抗氧剂0.1-0.2；紫外吸收剂0.1-0.2；胺类光稳定剂0.1-0.2。利用螺杆式共混、挤出设备将乙烯-醋酸乙烯的共聚物（EVA）；纳米铝粉；光固化剂；增粘剂；紫外光吸收剂；抗氧剂；受阻胺类光稳定剂等共混，幷挤出经过滤导入流延模头，经冷却、欠伸、卷取等工序得到太阳能电池用光EVA膜。本发明所制作出来的产品，附于薄膜太阳能电池受光表面或做太阳能电池的上封装膜，直接提高柔性或薄膜太阳能电池的发电效率。

Description

一种柔性或薄膜太阳能电池用光固化EVA膜及其制备方法
技术领域
本发明涉及一种柔性或薄膜太阳能电池用光固化EVA膜及其制备方法，通过使用该膜封装在柔性或薄膜太阳能电池入光面的表面，直接提高柔性或薄膜太阳能电池的效率。
背景技术
在太阳能的有效利用项目当中：光电利用是近些年来发展最快，最具活力的研究领域。一般太阳能电池的制作主要是以半导体材料为基础，利用光电材料吸收光能后发生光电转换反应发电。根据所用材料的不同，太阳能电池可分为：1、硅太阳能电池；2、以无机盐如砷化镓III-V化合物、硫化镉、铜铟硒等多元化合物为材料的太阳能电池；3、以功能高分子材料制备的太阳能电池；4、纳米晶太阳能电池等。现有技术工作效率最高的是以III-V族半导体无机材料为原材料的产品。例如:砷化镓/锗单一接面型的量子井陷晶结构，其光电转换效率可达>18%；而多重接面量子井陷晶结构之太阳电池，例如:磷化铟镓/砷化镓/锗，其光电转换效率可高达>30%。目前应用最广，以硅为主：包括非晶硅，光电转换效率约9%；多晶硅，光电转换效率约14%；单晶硅，光电转换效率约17%。虽然在价格上，VI族元素Si要比III-V族半导体GaAs便宜，但其制造的价格，与高分子有机太阳能电池相比，还是昂贵许多；而在应用上，质轻又无破裂之虞的全塑化有机太阳能电池可经由印刷的加工实现，除价格降低外，更适合可携式电子产品的需求，且在室内或阴天均能正常使用（这是硅质太阳能电池所无法达到的），使得它的实用性及市场应用广度更加提升。
太阳能电池是一项关键技术，会推进更清洁的能源生产。但是太阳能电池的成本问题，降低了太阳能技术的经济竞争力。为克服这个问题，薄膜太阳能电池是目前广泛应用的技术，可以大量减少昂贵半导体材料的使用量，但薄膜太阳能电池的光吸收量较低，性能比不上传统的太阳能电池。
薄膜太阳能模块是由玻璃基板、金属层、透明导电层、电器功能盒、胶合材料、半导体层等所构成的。有机-无机复合太阳能电池是基于有机共轭高分子-无机纳米晶复合材料体系的太阳能电池，因同时具有机高分子材料成膜性好，能级结构及带隙易于调节，可以通过湿法制备低成本、大面积、柔性太阳能电池器件以及无机纳米晶材料高稳定性，高迁移率，可构筑有序纳米结构等优点，而成为近年来太阳能电池领域的研究热点。金属纳米粒子可以引导光更好地进入太阳能电池，防止光逃逸。在传统的“厚膜”太阳能电池中，纳米粒子没有什么效果，因为所有的光线吸收都是通过这种膜，这就依赖它的厚度。然而，对于薄膜而言，纳米粒子就可以发挥很大作用。它们的散射增加了光停留在薄膜中的时间，使总体吸收的光达到一种水平，可以媲美传统的太阳能电池。
铝与银纳米粒子在可见部分的频谱中，可以很好地聚焦光线进入太阳能电池。但是光学共振也会导致纳米粒子吸收光，这就意味着太阳能电池的效率会较低。银纳米粒子共振正好处在太阳能电池关键吸收光谱部分，所以光的吸收是相当可观的。铝纳米粒子共振超出了太阳能电池关键光谱部分。对能量的损耗较小，此外，铝粒子很容易钝化，虽然会改变形状和大小，钝化后纳米粒子属性变化很小。纳米粒子有凹凸不平的表面，散射光线会更多地进入广谱波长范围。这会带来更大的吸收，从而提高电池的整体效率。
太阳能电池板的需求上升推动乙烯一醋酸乙烯共聚物(EVA)需求增长。乙烯与醋酸乙烯共聚物是乙烯共聚物中最重要的产品，国外一般将其统称为EVA。EVA树脂的特点是具有良好的柔软性，橡胶般的弹性，在-50℃下仍能够具有较好的可挠性，透明性和表面光泽性好，化学稳定性良好，抗老化和耐臭氧强度好，无毒性。与填料的掺混性好，着色和成型加工性好。亚洲生产商近期目标是扩大醋酸乙烯含量30~33%的产量，以满足太阳能面板市场的需要。中国台湾和韩国的几家生产商目前正在着手建设30~33%醋酸乙烯含量的项目。该产品主要用作太阳能电池板封装原料，太阳能电池板广泛应用于住宅、商业、工业、农业和交通运输部门。
EVA膜本身为太阳能电池广泛应用的封装用膜，为适应以上工业需求，我们发明了纳米铝粉改性光固化EVA膜。该膜既可以使用于薄膜太阳能电池的背光板处，也可以使用于薄膜太阳能电池的入光膜表面，同时也可以使用于薄膜太阳能电池的中间层，提高太阳能电池的光吸收效率。提高太阳能电池的发电效率。
发明内容
本发明的目的是提供一种柔性或薄膜太阳能电池用光固化EVA膜及其制备方法，通过使用该膜封装在柔性或薄膜太阳能电池入光面的表面，直接提高柔性或薄膜太阳能电池的效率。并具经封装的柔性或薄膜太阳能电池具有自清洁的作用。
为实现上述目的，本发明采用的技术方案如下：
本发明的柔性或薄膜太阳能电池用光固化EVA膜，由下述重量份的如下组分制成：EVA树脂100；纳米铝粉0.0001-0.1；光固化剂0.5-1.25；紫外光吸收剂0.1-0.2；增粘剂0-0.4；抗氧剂0.1-0.2；紫外吸收剂0.1-0.2；胺类光稳定剂0.1-0.2。
所述的EVA树脂为氯化EVA、铕化EVA、氟化EVA或纳米改性乙烯一醋酸乙烯共聚物中的任意一种。
所述的EVA树脂中具有28-36%的醋酸乙烯的含量。
所述的胺类光稳定剂为双（1-辛氧基-2,2,6,6-四甲基-4-哌啶基）癸二酯、（2,2,6,6-四甲基-4-哌啶基）癸二酸酯、聚丁二酸（4羟基-2,2,6,6-四甲基-1哌啶乙醇酯）中的一种或几种的混合。
所述的黏度调节剂为钛酸酯偶联剂、r–氨丙基三乙氧基硅烷、r–缩水甘油醚氧丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、3–氨丙基三乙氧基硅烷中的一种或几种混合配比而成。
所述的光固化剂为芳香族羰基化合物，主要是苯基酮系化合物，如联苯甲酰，二苯甲酮，安息香及其醚类衍生物。
所述的紫外光吸收剂为2-羟基-4甲氧基二苯甲酮、2-羟基-4正辛氧基二苯甲酮或2-【4,5-双（2,4-二甲基苯基）-1,3,5-三嗪-2-基】-5-（辛氧基）酚中一种或多种。
所述的抗氧化剂为三（2，4-二叔丁基苯基）亚磷酸酯、二硬脂酸基季戊四醇二亚磷酸酯、亚磷酸三（单壬基苯和二壬基苯混合酯）、三（壬基苯）亚磷酸酯、四[B-（3，5-二叔丁基-4-羟基苯基）丙酸]季戊四醇酯、B-（4-羟基-3，5二叔丁基苯基）丙酸正十八碳醇酯中的一种或多种。
本发明的柔性或薄膜太阳能电池用光固化EVA膜的制备方法，包括如下步骤：
（1）将配方量的乙烯-醋酸乙烯的共聚物（EVA）；纳米铝粉；光固化剂；增粘剂；紫外光吸收剂；抗氧剂；受阻胺类光稳定剂等用搅拌器在-10~40℃温度环境下搅拌共混均匀；
（2）将以上共混物导入螺杆混合挤出机进行共混挤出，温度控制在80~90℃，挤出物经过滤、计量挤出、流延、冷却、欠伸、牵引、卷取等工序，得到太阳能封装用EVA膜。
纳米金属铝粒子很容易钝化，虽然会改变形状和大小，钝化后纳米粒子属性变化很小。纳米粒子有凹凸不平的表面，散射光线会更多地进入广谱波长范围。这会带来更大的吸收，从而提高电池的整体效率。金属铝纳米粒子的散射增加了光停留在薄膜中的时间，使总体吸收的光达到一种水平，可以媲美传统的太阳能电池。经使用本发明薄膜处理的薄膜太阳能电池比未经本薄膜处理的薄膜太阳能电池性能提高3-15%。薄膜太阳能电池使用该薄膜后，金属铝纳米粒子可以引导光较好地进入太阳能电池，防止光逃逸。解决传统的“厚膜”太阳能电池中，纳米粒子没有什么效果而所有的光线吸收必需依赖厚度解决的问题。
具体实施方式
实施例1
（1）将EVA（醋酸乙烯含量28%）（广州市协宇化工有限公司）100Kg；纳米铝粉0.0001Kg；交联固化剂（2,5-二甲基-2,5双（叔丁基过氧）己烷）0.8Kg；紫外光吸收剂（2-羟基-4甲氧基二苯甲酮）0.1Kg；抗氧剂（四[B-（3，5-二叔丁基-4-羟基苯基）丙酸]季戊四醇酯）0.1Kg；胺类光稳定剂（双（1-辛氧基-2,2,6,6-四甲基-4-哌啶基）癸二酯）0.2Kg，用搅拌器在-10-5℃温度环境下搅拌共混均匀；
（2）将以上共混物导入螺杆混合挤出机进行共混挤出，温度控制在80℃，挤出物经180目过滤器过滤、计量挤出（计量泵进出压力差为2MPa）、流延膜厚度50UM、10℃空气冷却、2倍牵伸率牵伸、离型纸覆膜、卷取等工序，得到一种柔性或薄膜太阳能电池用光固化EVA膜。经使用本薄膜的薄膜太阳能电池比未使用的薄膜太阳能电池性能提高3.6%。
实施例2
（1）将EVA（醋酸乙烯含量34%）（广州市协宇化工有限公司）100Kg；纳米铝粉0.1Kg；交联固化剂（2,5-二甲基-2,5双（叔丁基过氧）己烷）0.5Kg；紫外光吸收剂（2-羟基-4甲氧基二苯甲酮）0.12Kg；抗氧剂（三（壬基苯）亚磷酸酯）0.2Kg；胺类光稳定剂（双（1-辛氧基-2,2,6,6-四甲基-4-哌啶基）癸二酯）0.1Kg，用搅拌器在-10-40℃温度环境下搅拌共混均匀；
（2）将以上共混物导入螺杆混合挤出机进行共混挤出，温度控制在80-90℃，挤出物经180目过滤器过滤、计量挤出（计量泵进出压力差为2MPa）、流延膜厚度50UM、10℃空气冷却、2倍牵伸率牵伸、离型纸覆膜、卷取等工序，得到一种柔性或薄膜太阳能电池用光固化EVA膜。经使用本薄膜的薄膜太阳能电池比未使用的薄膜太阳能电池性能提高6.6%。
实施例3
（1）EVA100（醋酸乙烯含量36%）（广州市协宇化工有限公司）Kg；纳米铝粉,0.05Kg；交联固化剂（1,1-（双过氧化叔丁基）3，3,5-三甲基环己烷）1.25Kg；紫外光吸收剂（2-羟基-4正辛氧基二苯甲酮）0.16Kg；抗氧剂（亚磷酸三（单壬基苯和二壬基苯）混合酯）0.15Kg；胺类光稳定剂（（2,2,6,6-四甲基-4-哌啶基）癸二酸酯）0.15Kg,用搅拌器在0-10℃温度环境下搅拌共混均匀；
（2）将以上共混物导入螺杆混合挤出机进行共混挤出，温度控制在83℃，挤出物经180目过滤器过滤、计量挤出（计量泵进出压力差为2MPa）、流延膜厚度50UM、10℃空气冷却、2倍牵伸率牵伸、离型纸覆膜、卷取等工序，得到一种柔性或薄膜太阳能电池用光固化EVA膜。
经使用本薄膜的薄膜太阳能电池比未使用的薄膜太阳能电池性能提高14.8%。
实施例4
（1）将铕化EVA（EVA与乙酸乙烯酯-丙烯酸铕共聚物(VAA-Eu)的共混物(EVA/VAA-Eu)）100Kg；纳米铝粉0.008Kg；交联固化剂（1,1-（双过氧化叔丁基）3，3,5-三甲基环己烷）1.0Kg；紫外光吸收剂（2-[4,5-双（2,4-二甲基苯基）-1,3,5-三嗪-2-基]-5-（辛氧基）酚）0.18Kg；抗氧剂（二硬脂酸基季戊四醇二亚磷酸酯）0.18Kg；胺类光稳定剂（聚丁二酸（4羟基-2,2,6,6-四甲基-1哌啶乙醇）酯）0.12Kg,用搅拌器在10-20℃温度环境下搅拌共混均匀；
（2）将以上共混物导入螺杆混合挤出机进行共混挤出，温度控制在85℃，挤出物经180目过滤器过滤、计量挤出（计量泵进出压力差为2MPa）、流延膜厚度50UM、10℃空气冷却、2倍牵伸率牵伸、离型纸覆膜、卷取等工序，得到一种柔性或薄膜太阳能电池用光固化EVA膜。
经使用本薄膜的薄膜太阳能电池比未使用的薄膜太阳能电池性能提高8.2%。
实施例5
（1）将将纳米改性乙烯-醋酸乙烯共聚物（乙烯-乙酸乙烯酯共聚物—改性蒙脱石纳米复合材料）100Kg；纳米铝粉0.002Kg；交联固化剂（叔丁基过氧2-乙基己基碳酸酯）1.2Kg；紫外光吸收剂（2-[4,5-双（2,4-二甲基苯基）-1,3,5-三嗪-2-基]-5-（辛氧基）酚）0.2Kg；抗氧剂（三（2，4-二叔丁基苯基）亚磷酸酯）0.12Kg；胺类光稳定剂（聚丁二酸（4羟基-2,2,6,6-四甲基-1哌啶乙醇）酯）0.18Kg，用搅拌器在30-40℃温度环境下搅拌共混均匀；
（2）将以上共混物导入螺杆混合挤出机进行共混挤出，温度控制在90℃，挤出物经180目过滤器过滤、计量挤出（计量泵进出压力差为2MPa）、流延膜厚度50UM、10℃空气冷却、2倍牵伸率牵伸、离型纸覆膜、卷取等工序，得到一种柔性或薄膜太阳能电池用光固化EVA膜，经使用本薄膜的薄膜太阳能电池比未使用的薄膜太阳能电池性能提高11.3%。

Claims (5)

1.一种柔性或薄膜太阳能电池用光固化EVA膜，其特征在于，由下述重量份的如下组分制成：EVA树脂100；纳米铝粉0.0001-0.1；光固化剂0.5-1.25；紫外光吸收剂0.1-0.2；增粘剂0-0.4；抗氧剂0.1-0.2；胺类光稳定剂0.1-0.2；
所述的EVA树脂为氯化EVA、铕化EVA、氟化EVA或纳米改性乙烯一醋酸乙烯共聚物中的任意一种;所述的EVA树脂中具有28-36%的醋酸乙烯的含量;
所述的胺类光稳定剂为（2,2,6,6-四甲基-4-哌啶基）癸二酸酯、聚丁二酸（4-羟基-2,2,6,6-四甲基-1-哌啶乙醇）酯中的一种或几种的混合；
所述柔性或薄膜太阳能电池用光固化EVA膜的制备方法如下：
（1）将配方量的EVA；纳米铝粉；光固化剂；增粘剂；紫外光吸收剂；抗氧剂；受阻胺类光稳定剂用搅拌器在-10~40℃温度环境下搅拌共混均匀；
（2）将以上共混物导入螺杆混合挤出机进行共混挤出，温度控制在80~90℃，挤出物经过滤、计量挤出、流延、冷却、牵伸、牵引、卷取工序，得到太阳能电池用光固化EVA膜。
2.根据权利要求1所述的柔性或薄膜太阳能电池用光固化EVA膜，其特征在于：所述的增粘剂为钛酸酯偶联剂、γ–氨丙基三乙氧基硅烷、γ–缩水甘油醚氧丙基三甲氧基硅烷、乙烯基三乙氧基硅烷的一种或几种混合配比而成。
3.根据权利要求1所述的柔性或薄膜太阳能电池用光固化EVA膜，其特征在于：所述的光固化剂为联苯甲酰，二苯甲酮，安息香及其醚类衍生物中一种或多种。
4.根据权利要求1所述的柔性或薄膜太阳能电池用光固化EVA膜，其特征在于：所述的紫外光吸收剂为2-羟基-4-甲氧基二苯甲酮、2-羟基-4-正辛氧基二苯甲酮中的一种或多种。
5.根据权利要求2所述的柔性或薄膜太阳能电池用光固化EVA膜，其特征在于：所述的抗氧剂为三（2，4-二叔丁基苯基）亚磷酸酯、亚磷酸三（单壬基苯和二壬基苯混合酯）、三（壬基苯）亚磷酸酯、四[β-（3，5-二叔丁基-4-羟基苯基）丙酸]季戊四醇酯、β-（4-羟基-3，5-二叔丁基苯基）丙酸正十八碳醇酯中的一种或多种。
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