CN116396688A - 一种光伏组件用抗pid型eva胶膜及其制备方法 - Google Patents
一种光伏组件用抗pid型eva胶膜及其制备方法 Download PDFInfo
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Abstract
Description
技术领域
本发明属于EVA胶膜领域,具体涉及一种光伏组件用抗PID型EVA胶膜及其制备方法。
背景技术
光伏EVA胶膜是一种热固性具有粘性的胶膜,由非极性的乙烯单体和极性的醋酸乙烯酯单体经过共聚反应而得到的高支化度无规共聚物,用于夹胶玻璃和硅晶片中间位置,由于其具有高透明性、易储存、易加工等优点,能适用于各种玻璃的夹胶工艺,在光伏组件或太阳能电池封装等领域被广泛应用。但是,光伏组件在工作运行过程中,EVA胶膜长期暴露在室外环境中,在紫外光、湿气、空气、温度的共同作用下,易出现黄变、老化降解现象,降低EVA胶膜透光率及粘附性能,使光伏电池的光电流下降,进而导致发电效率功率衰减(PID效应),严重时会导致功率衰减达50%以上。因此,如何提高EVA胶膜的抗老化、抗黄变性能对于抑制PID现象的发生及延长EVA胶膜的使用寿命具有重要意义。
目前,主要通过在EVA胶膜中物理添加紫外线吸收剂或受阻胺光稳定剂等以提高EVA胶膜的抗老化、耐黄变性能。如专利号为CN103897612B的发明专利,公开一种太阳能封装材料用抗PID的EVA封装胶膜,通过在EVA封装胶膜添加紫外线吸收剂2-羟基-4-正辛氧基二苯甲酮、3,5二叔丁基-4-羟基苯甲酸-2,4-二叔丁基苯酯以提高EVA封装胶膜的抗老化性能;如专利号为CN103937418B的发明专利,公开一种高反光率白色EVA胶膜及其制备工艺,在EVA胶膜中加入2-羟基-4-正辛氧基二苯甲酮、3,5-二叔丁基-4-羟基苯甲酸-2,4-二叔丁基苯酯的一种或两种以上的混成的紫外线吸收剂;如专利号为CN114716922A的发明专利,公开一种太阳能电池用EVA胶膜及其制备方法,在EVA胶膜中添加紫外线吸收剂和紫外线稳定剂。但是,由于紫外线吸收剂与EVA胶膜并不能完全相容,这种物理掺杂的方式存在紫外线吸收剂较易迁移与逸出等缺点,进而导致抗紫外、抗老化性能的减弱甚至丧失;同时,物理掺杂的方式对于紫外线吸收剂的用量较为严格,掺杂量过多影响EVA胶膜的粘结性能、致密性、力学性能等,掺杂量过少又无法有效抗光老化、耐黄变的效果。基于以上所述,如何使EVA胶膜能长期稳定抗老化及其封装的光伏组件具有良好抗PID性能,是亟待解决的技术问题。
发明内容
针对现有技术的不足之处,本发明的目的在于提供一种光伏组件用抗PID型EVA胶膜及其制备方法。
本发明的技术方案概述如下:
一种光伏组件用抗PID型EVA胶膜,包括以下质量份原料:
所述反应型紫外线吸收剂的化学结构式如式(I)所示:
进一步地,所述反应型紫外线吸收剂的制备方法为:将2,4-二羟基二苯甲酮加入丙酮中,再加入三乙胺,搅拌溶解后,再加入丙烯酰氯,于30-40℃搅拌反应12h,抽滤除去三乙胺盐,旋转蒸发去除丙酮溶剂后,得反应型紫外线吸收剂;
上述制备过程的反应方程式如式(II)所示:
进一步地,所述2,4-二羟基二苯甲酮、丙酮、三乙胺、甲基丙烯酰氯的用量比例为(0.01-0.025)mol∶50mL∶(0.01-0.025)mol∶(0.01-0.025)mol。
进一步地,所述抗PID助剂A包括乙烯-醋酸乙烯酯-乙烯醇三元共聚物、乙烯-醋酸乙烯酯-乙烯醇-马来酸乙烯醇单酯四元无规共聚物中的一种。
进一步地,所述抗PID助剂B为乙烯基改性金属磷酸盐,其制备方法为:将乙烯基硅烷偶联剂与金属磷酸盐按(1-2)∶10的质量比混合后,于35-45℃搅拌处理15-30min,对金属磷酸盐进行表面修饰改性,得抗PID助剂B。
进一步地,所述乙烯基硅烷偶联剂为乙烯基三乙酰氧硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三甲氧硅烷、乙烯基三乙氧硅烷中的一种或多种。
进一步地,所述金属磷酸盐为磷酸铝、磷酸钛、磷酸锌中的一种或多种。
进一步地,所述有机过氧化物交联剂过氧化二异丙苯、2,5-二甲基-2,5二叔丁基过氧化己烷、过氧化2-乙基己基碳酸叔丁酯、过氧化-2-乙基己基碳酸叔戊酯中的一种或多种。
本发明还进一步提供所述的光伏组件用抗PID型EVA胶膜制备方法:将季戊四醇四丙烯酸酯、反应型紫外线吸收剂、抗PID助剂A、抗PID助剂B、有机过氧化物交联剂依次加入乙烯-醋酸乙烯酯共聚物中,再于75-80℃混炼处理20-30min,再加入双螺杆挤出机中,流延挤出,经冷却成型、分切、收卷后,即得所述光伏组件用抗PID型EVA胶膜。
进一步地,所述流延挤出温度为100-110℃。
本发明的有益效果:
1.本发明利用2,4-二羟基二苯甲酮与甲基丙烯酰氯通过取代反应制出具有端乙烯基反应型紫外线吸收剂,在有机过氧化物产生的自由基引发作用下,该反应型紫外线吸收剂与乙烯-醋酸乙烯酯共聚物交联共聚,进而接枝到乙烯-醋酸乙烯酯共聚物分子链上,相比于传统物理掺杂紫外线吸收剂的形式,能明显提高紫外线吸收剂在EVA胶膜体系中的结合稳定性,克服与EVA胶膜相容性不高、易迁移逸出等缺点,进而使EVA胶膜具有长期抗光老化、抗黄变性能,有效抑制其封装的光伏组件发生PID现象;同时,通过化学交联共聚的形式引入紫外线吸收剂,形成稳定的EVA互穿网络结构,一定程度上提高了EVA胶膜的致密性,进而改善其阻水阻氧性能,当紫外线吸收剂用量稍过时,并不会造成EVA胶膜的粘结性能、致密性、力学稳定性的下降,更易控制使用剂量。
2.本发明利用有机抗PID助剂A与无机抗PID助剂B协同提高EVA胶膜封装的光伏组件的抗PID性能;其中,有机抗PID助剂A是乙烯类共聚物,其分子链中含有羟基结构,与EVA树脂的水解产物结构相似,其水解产物如下所示:-[CH2-CH2]n-…-[CH2-CHOH]m-,进而有效抑制EVA胶膜的水解,进一步阻止玻璃中的金属离子析出,并抑制金属离子在电场作用下迁移到电池表面,达到抗PID的作用;无机抗PID助剂B为乙烯基改性金属磷酸盐,金属磷酸盐能有效捕捉EVA胶膜中游离金属离子,进而达到抗PID的作用,同时,利用乙烯基硅烷对其进行表面修饰改性,提高金属磷酸盐在EVA胶膜中的分散稳定性。
3.本发明制出的EVA胶膜能长效抗黄变、抗光老化,粘结性能高,透光性、水汽阻隔性能良好,使光伏组件具有良好的抗衰减性能、光电转化性能。
附图说明
图1为本发明光伏组件用抗PID型EVA胶膜制备方法流程图。
具体实施方式
下面结合实施例对本发明做进一步的详细说明,以令本领域技术人员参照说明书文字能够据以实施。
本发明提供一实施例的光伏组件用抗PID型EVA胶膜,包括以下质量份原料:
所述反应型紫外线吸收剂的化学结构式如式(I)所示:
所述反应型紫外线吸收剂的制备方法为:将2,4-二羟基二苯甲酮加入丙酮中,再加入三乙胺,搅拌溶解后,再加入丙烯酰氯,于30-40℃搅拌反应12h,抽滤除去三乙胺盐,旋转蒸发去除丙酮溶剂后,得反应型紫外线吸收剂;所述2,4-二羟基二苯甲酮、丙酮、三乙胺、甲基丙烯酰氯的用量比例为(0.01-0.025)mol∶50mL∶(0.01-0.025)mol∶(0.01-0.025)mol;
上述制备过程的反应方程式如式(II)所示:
所述抗PID助剂A包括乙烯-醋酸乙烯酯-乙烯醇三元共聚物、乙烯-醋酸乙烯酯-乙烯醇-马来酸乙烯醇单酯四元无规共聚物中的一种;
所述抗PID助剂B为乙烯基改性金属磷酸盐,其制备方法为:将乙烯基硅烷偶联剂与金属磷酸盐按(1-2)∶10的质量比混合后,于35-45℃搅拌处理15-30min,对金属磷酸盐进行表面修饰改性,得抗PID助剂B;所述乙烯基硅烷偶联剂为乙烯基三乙酰氧硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三甲氧硅烷、乙烯基三乙氧硅烷中的一种或多种;所述金属磷酸盐为磷酸铝、磷酸钛、磷酸锌中的一种或多种;
所述有机过氧化物交联剂过氧化二异丙苯、2,5-二甲基-2,5二叔丁基过氧化己烷、过氧化2-乙基己基碳酸叔丁酯、过氧化-2-乙基己基碳酸叔戊酯中的一种或多种。
该实施例光伏组件用抗PID型EVA胶膜制备方法:将季戊四醇四丙烯酸酯、反应型紫外线吸收剂、抗PID助剂A、抗PID助剂B、有机过氧化物交联剂依次加入乙烯-醋酸乙烯酯共聚物中,再于75-80℃混炼处理20-30min,再加入双螺杆挤出机中,100-110℃流延挤出,经冷却成型、分切、收卷后,即得所述光伏组件用抗PID型EVA胶膜。
实施例1
一种光伏组件用抗PID型EVA胶膜制备方法,包括以下步骤:
(1)将乙烯基三乙酰氧硅烷与磷酸铝按1:10的质量比混合后,于35℃搅拌处理15min,对金属磷酸盐进行表面修饰改性,得乙烯基改性磷酸铝;
(2)将2,4-二羟基二苯甲酮加入丙酮中,再加入三乙胺,搅拌溶解后,再加入丙烯酰氯,于30℃搅拌反应12h,抽滤除去三乙胺盐,旋转蒸发去除丙酮溶剂后,得反应型紫外线吸收剂;所述2,4-二羟基二苯甲酮、丙酮、三乙胺、甲基丙烯酰氯的用量比例为0.01mol∶50mL∶0.01mol∶0.01mol;
上述反应方程式如下所示:
(3)按质量份将1份季戊四醇四丙烯酸酯、0.4份反应型紫外线吸收剂、1份乙烯-醋酸乙烯酯-乙烯醇三元共聚物、0.5份乙烯基改性磷酸铝、0.5份过氧化二异丙苯依次加入100份乙烯-醋酸乙烯酯共聚物中,再于75℃混炼处理20min,再加入双螺杆挤出机中,100℃流延挤出,经冷却成型、分切、收卷后,即得所述光伏组件用抗PID型EVA胶膜。
实施例2
一种光伏组件用抗PID型EVA胶膜制备方法,包括以下步骤:
(1)将甲基丙烯酰氧基丙基三甲氧基硅烷与磷酸钛按1.5∶10的质量比混合后,于40℃搅拌处理20min,对金属磷酸盐进行表面修饰改性,得乙烯基改性磷酸钛;
(2)将2,4-二羟基二苯甲酮加入丙酮中,再加入三乙胺,搅拌溶解后,再加入丙烯酰氯,于35℃搅拌反应12h,抽滤除去三乙胺盐,旋转蒸发去除丙酮溶剂后,得反应型紫外线吸收剂;所述2,4-二羟基二苯甲酮、丙酮、三乙胺、甲基丙烯酰氯的用量比例为0.015mol∶50mL∶0.015mol∶0.015mol;
上述反应方程式如下所示:
(3)按质量份将2份季戊四醇四丙烯酸酯、0.7份反应型紫外线吸收剂、1.5份乙烯-醋酸乙烯酯-乙烯醇-马来酸乙烯醇单酯四元无规共聚物、0.75份乙烯基改性磷酸钛、1份过氧化2-乙基己基碳酸叔丁酯依次加入100份乙烯-醋酸乙烯酯共聚物中,再于78℃混炼处理25min,再加入双螺杆挤出机中,105℃流延挤出,经冷却成型、分切、收卷后,即得所述光伏组件用抗PID型EVA胶膜。
实施例3
一种光伏组件用抗PID型EVA胶膜制备方法,包括以下步骤:
(1)将乙烯基三甲氧硅烷与磷酸锌按1.8∶10的质量比混合后,于45℃搅拌处理25min,对磷酸锌进行表面修饰改性,得乙烯基改性磷酸锌;
(2)将2,4-二羟基二苯甲酮加入丙酮中,再加入三乙胺,搅拌溶解后,再加入丙烯酰氯,于40℃搅拌反应12h,抽滤除去三乙胺盐,旋转蒸发去除丙酮溶剂后,得反应型紫外线吸收剂;所述2,4-二羟基二苯甲酮、丙酮、三乙胺、甲基丙烯酰氯的用量比例为0.02mol∶50mL0.02mol∶0.02mol;
上述反应方程式如下所示:
(3)按质量份将2.5份季戊四醇四丙烯酸酯、0.8份反应型紫外线吸收剂、1.8份乙烯-醋酸乙烯酯-乙烯醇-马来酸乙烯醇单酯四元无规共聚物、1份乙烯基改性磷酸锌、1.2份过氧化-2-乙基己基碳酸叔戊酯依次加入100份乙烯-醋酸乙烯酯共聚物中,再于80℃混炼处理25min,再加入双螺杆挤出机中,105℃流延挤出,经冷却成型、分切、收卷后,即得所述光伏组件用抗PID型EVA胶膜。
实施例4
一种光伏组件用抗PID型EVA胶膜制备方法,包括以下步骤:
(1)将乙烯基三乙氧硅烷与磷酸钛按2∶10的质量比混合后,于45℃搅拌处理30min,对金属磷酸盐进行表面修饰改性,得乙烯基改性磷酸钛;
(2)将2,4-二羟基二苯甲酮加入丙酮中,再加入三乙胺,搅拌溶解后,再加入丙烯酰氯,于40℃搅拌反应12h,抽滤除去三乙胺盐,旋转蒸发去除丙酮溶剂后,得反应型紫外线吸收剂;所述2,4-二羟基二苯甲酮、丙酮、三乙胺、甲基丙烯酰氯的用量比例为0.025mol∶50mL∶0.25mol∶0.25mol;
上述反应方程式如下所示:
(3)按质量份将3份季戊四醇四丙烯酸酯、1份反应型紫外线吸收剂、2份乙烯-醋酸乙烯酯-乙烯醇三元共聚物、1份乙烯基改性磷酸钛、1.5份过氧化二异丙苯依次加入100份乙烯-醋酸乙烯酯共聚物中,再于80℃混炼处理30min,再加入双螺杆挤出机中,110℃流延挤出,经冷却成型、分切、收卷后,即得所述光伏组件用抗PID型EVA胶膜。
对比例与实施例1相同,区别在于:对比例采用2,4-二羟基二苯甲酮代替实施例1中反应型紫外线吸收剂。
将实施例1-4及对比例制出的EVA胶膜与相同的多晶硅电池片、玻璃和背板采用相同工艺制成光伏组件,并根据IEC TS 62804-1:2015《光伏组件电压致衰减检测的试验方法》进行测定:在温度为85℃、相对湿度为90%的条件下,经240h后,测定光伏组件PID试验前后的功率衰减;并按照国家标准GB/T29848-2013《光伏组件封装用乙烯-醋酸乙烯酯共聚物(EVA)胶膜》测定实施例1-4及对比例制出的EVA胶膜的透光率、收缩率、紫外加速老化后黄变指数。试验结果如下表所示:
PID测试240h功率衰减/% | 透光率/% | 收缩率/% | 紫外加速老化后黄变指数 | |
实施例1 | 2.05 | 93.1 | 0.8 | 0.9 |
实施例2 | 1.68 | 92.6 | 0.7 | 0.8 |
实施例3 | 1.51 | 92.3 | 0.7 | 0.8 |
实施例4 | 1.33 | 92.1 | 0.6 | 0.7 |
对比例 | 4.56 | 92.7 | 0.9 | 1.2 |
由上表可知,实施例1在抗PID性能、透光率、收缩率、紫外加速老化后黄变指数方面均优于对比例,究其原因,实施例1中端乙烯基反应型紫外线吸收剂与EVA胶膜发生交联共聚反应,使端乙烯基反应型紫外线吸收剂稳定接枝或嵌合在EVA网络结构中,一定程度上提高了交联密度,提升EVA胶膜的致密性和结构稳定性,同时,保证了紫外线吸收剂的分布稳定性及分布均匀性,防止迁移、逸出,进而使EVA胶膜的综合性能都得到了不同程度的提高。
实施例1-4利用2,4-二羟基二苯甲酮与甲基丙烯酰氯通过取代反应制出具有端乙烯基反应型紫外线吸收剂,在有机过氧化物产生的自由基引发作用下,该反应型紫外线吸收剂与乙烯-醋酸乙烯酯共聚物交联共聚,进而接枝到乙烯-醋酸乙烯酯共聚物分子链上,相比于传统物理掺杂紫外线吸收剂的形式,能明显提高紫外线吸收剂在EVA胶膜体系中的结合稳定性,克服与EVA胶膜相容性不高、易迁移逸出等缺点,进而使EVA胶膜具有长期抗光老化、抗黄变性能,有效抑制其封装的光伏组件发生PID现象;同时,通过化学交联共聚的形式引入紫外线吸收剂,形成稳定的EVA互穿网络结构,一定程度上提高了EVA胶膜的致密性,进而改善其阻水阻氧性能,当紫外线吸收剂用量稍过时,并不会造成EVA胶膜的粘结性能、致密性、力学稳定性的下降,更易控制使用剂量。
实施例1-4利用有机抗PID助剂A与无机抗PID助剂B协同提高EVA胶膜封装的光伏组件的抗PID性能;其中,有机抗PID助剂A是乙烯类共聚物,其分子链中含有羟基结构,与EVA树脂的水解产物结构相似,其水解产物如下所示:-[CH2-CH2]n-…-[CH2-CHOH]m-,进而有效抑制EVA胶膜的水解,进一步阻止玻璃中的金属离子析出,并抑制金属离子在电场作用下迁移到电池表面,达到抗PID的作用;无机抗PID助剂B为乙烯基改性金属磷酸盐,金属磷酸盐能有效捕捉EVA胶膜中游离金属离子,进而达到抗PID的作用,同时,利用乙烯基硅烷对其进行表面修饰改性,提高金属磷酸盐在EVA胶膜中的分散稳定性。
实施例1-4制出的EVA胶膜能长效抗黄变、抗光老化,粘结性能高,透光性、水汽阻隔性能良好,使光伏组件具有良好的抗衰减性能、光电转化性能。
尽管本发明的实施方案已公开如上,但其并不仅仅限于说明书和实施方式中所列运用,它完全可以被适用于各种适合本发明的领域,对于熟悉本领域的人员而言,可容易地实现另外的修改,因此在不背离权利要求及等同范围所限定的一般概念下,本发明并不限于特定的细节。
Claims (10)
3.根据权利要求1所述一种光伏组件用抗PID型EVA胶膜,其特征在于,所述2,4-二羟基二苯甲酮、丙酮、三乙胺、甲基丙烯酰氯的用量比例为(0.01-0.025)mol∶50mL∶(0.01-0.025)mol∶(0.01-0.025)mol。
4.根据权利要求1所述一种光伏组件用抗PID型EVA胶膜,其特征在于,所述抗PID助剂A包括乙烯-醋酸乙烯酯-乙烯醇三元共聚物、乙烯-醋酸乙烯酯-乙烯醇-马来酸乙烯醇单酯四元无规共聚物中的一种。
5.根据权利要求1所述一种光伏组件用抗PID型EVA胶膜,其特征在于,所述抗PID助剂B为乙烯基改性金属磷酸盐,其制备方法为:将乙烯基硅烷偶联剂与金属磷酸盐按(1-2)∶10的质量比混合后,于35-45℃搅拌处理15-30min,对金属磷酸盐进行表面修饰改性,得抗PID助剂B。
6.根据权利要求5所述一种光伏组件用抗PID型EVA胶膜,其特征在于,所述乙烯基硅烷偶联剂为乙烯基三乙酰氧硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三甲氧硅烷、乙烯基三乙氧硅烷中的一种或多种。
7.根据权利要求5所述一种光伏组件用抗PID型EVA胶膜,其特征在于,所述金属磷酸盐为磷酸铝、磷酸钛、磷酸锌中的一种或多种。
8.根据权利要求1所述一种光伏组件用抗PID型EVA胶膜,其特征在于,所述有机过氧化物交联剂过氧化二异丙苯、2,5-二甲基-2,5二叔丁基过氧化己烷、过氧化2-乙基己基碳酸叔丁酯、过氧化-2-乙基己基碳酸叔戊酯中的一种或多种。
9.一种根据权利要求1-8任一项所述的光伏组件用抗PID型EVA胶膜制备方法,其特征在于:将季戊四醇四丙烯酸酯、反应型紫外线吸收剂、抗PID助剂A、抗PID助剂B、有机过氧化物交联剂依次加入乙烯-醋酸乙烯酯共聚物中,再于75-80℃混炼处理20-30min,再加入双螺杆挤出机中,流延挤出,经冷却成型、分切、收卷后,即得所述光伏组件用抗PID型EVA胶膜。
10.根据权利要求9所述的光伏组件用抗PID型EVA胶膜制备方法,其特征在于,所述流延挤出温度为100-110℃。
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