CN113736374B - 一种高分散抗电势诱导衰减光伏封装胶膜及制备方法 - Google Patents
一种高分散抗电势诱导衰减光伏封装胶膜及制备方法 Download PDFInfo
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- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 3
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 claims description 2
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开了一种高分散抗电势诱导衰减光伏封装胶膜及制备方法,在基料乙烯醋酸乙烯共聚物中加入交联剂、助交联剂、硅烷偶联剂、抗PID助剂、高分子分散剂、紫外光吸收剂和抗氧剂,具体制备步骤为:将EVA基料及改性添加剂溶于有机溶剂,溶解、超声后倒入模具,经烘干后得到粗膜;粗膜经层压,得到所需光伏封装胶膜。本发明采用溶剂法制备封装胶膜,通过超声可使添加剂与基料充分结合,增加助剂的分散度,提高极性基团在胶膜内部的分散性,延长封装胶膜的存储时间;筛选出合适的配方可以显著提高添加剂的协同作用效果,添加合适的助剂可以明显提升胶膜的抗PID性能。
Description
技术领域
本发明属于光伏组件用封装胶膜,具体涉及一种高分散抗电势诱导衰减光伏封装胶膜及制备方法。
背景技术
当今社会发展的主要问题归根到底就是能源问题,所有能源中,太阳能被认为是最清洁、环保及长久的可再生能源。作为常用的太阳能利用技术,太阳能发电主要是指太阳能光伏发电,绝大部分光伏发电系统以晶体硅太阳能电池作为光电转换器件,以其成熟的生产工艺及高光电转换效率获得了投资者的青睐,现已在全国各地大规模生产。
近年来随着太阳能光伏电池技术的发展,双面电池组件的产能有了更进一步的增长。常见封装材料EVA、POE相比,POE的缺点在于其结构有限制,成本较高,导致组件成本较高、生产良率相对偏低。尽管EVA在抗诱导电势差衰减(PID)性能方面相对较弱,但仍具光伏电池封装材料的实际应用价值。通过添加抗PID助剂的方式提高EVA封装胶膜的抗PID性能是解决这一问题的有效途径。
日本京瓷的研究(CN101978511A)表明,加入氢氧化镁作为酸吸收剂可以提高胶膜的抗PID性能;海优威的研究(CN109554141A)中提到,主链是碳链、支链含有若干羟基的树脂可以一定程度上抑制EVA水解反应的进行,保证EVA膜的交联密度,有效阻隔EVA和玻璃表面的离子聚集到电池表面,从而抑制组件PID问题的发生,但是上述的研究均存在PID测试后功率大幅衰减的问题。因此,需要寻求有效的抗PID助剂及配方改性EVA封装胶膜,以此来提高EVA封装胶膜的抗PID性能。
发明内容
发明目的:本发明的目的在于提供一种具有高分散性和抗电势诱导衰减的光伏封装胶膜;本发明的第二目的在于提供一种通过溶剂法来制备上述高分散抗电势诱导衰减光伏封装胶膜的方法。
技术方案:本发明提供的一种高分散抗电势诱导衰减光伏封装胶膜,所述胶膜按重量份包括以下组分:
其中,所述抗PID助剂为金属磷酸盐、金属氧化物、氢氧化物中的一种或多种。
进一步的,所述抗PID助剂为磷酸氢锆、磷酸锌或氢氧化镁中的一种或多种。
进一步的,所述高分子分散剂为2-丙烯酰胺-2-甲基丙磺酸、甲基丙烯酸甲酯、丙烯酸丁酯、马来酸酐及其酯化物、甲基丙烯酸丁酯、苯乙烯中的一种或多种。
进一步的,所述交联剂为1,1-双(叔丁基过氧基)-3,3,5-三甲基环己烷、2,5-二甲基-2,5-双(过氧化叔丁基)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、过氧化苯甲酰中的一种或多种;所述的助交联剂为三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、邻苯二甲酸二烯丙酯中的一种或多种。
进一步的,所述硅烷偶联剂为3-(甲基丙烯酰氧)丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(2-甲氧乙氧基)硅烷中的一种或多种。
进一步的,所述的紫外光吸收剂为二苯甲酮、双(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)酯中的一种或多种。
进一步的,所述抗氧剂为2,6-二叔丁基对甲酚、硫代二丙酸双十八酯、亚磷酸酯中的一种或多种。
本发明还保护上述封装胶膜的制备方法,具体为溶剂法,制备步骤为将各组分溶于有机溶剂中,并超声处理后倒入模具,经烘干后得到EVA粗膜;采用玻璃板-离型膜-EVA粗膜-离型膜-玻璃板的放置,于层压机中真空层压,冷却得到所需光伏封装胶膜。
进一步的,超声功率为180~220W,超声温度为25~40℃,超声时间为20~40min;真空层压的温度为140~155℃,真空度0.05~0.08MPa,压强为0.6~0.7MPa。
进一步的,所述有机溶剂为甲苯、氯仿、N,N-二甲基甲酰胺中的一种或多种。
本发明的组分中,含有用于成膜的主要助剂,其中交联剂和助交联剂起到交联作用,过氧化物交联剂分解后产生自由基,引发长链分子结合,使得EVA由线性结构交联固化成稳定的三维网状结构;硅烷偶联剂主要起增强EVA极性,提高其与无机玻璃和背板的粘结性;紫外光吸收剂、抗氧剂起到抵抗紫外线,抗老化的作用。此外,本发明的组分中还含有抗PID助剂和高分子分散剂,其中抗PID助剂可吸附化合EVA胶膜中的羧酸,提高封装胶膜的抗PID性能。交联剂与助交联剂有协同作用。随着助交联剂含量增加,交联剂的含量即使减少,交联度反而升高。这是因为助交联剂的存在可以延长交联剂过氧化物自由基的寿命,减少自由基的猝灭,过氧化物的用量自然就减少了,层压后胶膜中过氧化物的残留量就会减少。因此,适当调节交联剂与助交联剂的配比可以提高封装胶膜的稳定性。
本发明的制备工艺采用溶剂法制备胶膜,通过超声可使添加剂与基料充分结合,提高极性基团在胶膜内部的分散性;改性后,极性基团不易迁移至封装胶膜表面,可延长封装胶膜的存储时间;筛选出合适的配方可以显著提高添加剂的协同作用效果,添加合适的助剂可以明显提升胶膜的抗PID性能。
有益效果:与现有技术相比,本发明的具有如下显著优点:本发明在基料乙烯醋酸乙烯共聚物(EVA)中加入不同类型的助剂,特别添加了抗PID助剂,以提升光伏组件抗PID性能;同时添加高分子分散剂以进一步提升助剂的分散度,提高胶膜的稳定性;本采用有机溶剂溶解助剂,有利于助剂更好的存储于封装胶膜中;在制备过程中采用超声,提高助剂的分散度;与现有技术相比,本发明所提到的制备方法和配方下的胶膜,其优势在于添加剂在胶膜内部有更好的分散性和稳定性,测试结果表明PID测试后封装胶膜功率衰减降低到2%,抗PID改性效果显著。
附图说明
图1为实施例3所制备产品的红外测试图。
具体实施方式
下面结合附图和实施例对本发明的技术方案做进一步详细说明。
实施例1
本实施例包括A组和B组,两组高分散抗PID光伏封装胶膜的配方组分如下:
将上述两组的组分置于甲苯溶剂中,EVA:有机溶剂=1:7(重量比),溶解、超声一定时间,超声功率为200W,超声时间为25min,超声温度为25℃;将该溶液倒入表面光滑且尺寸固定的玻璃模具中,以保证制备的EVA膜膜厚基本一致,放置于鼓风干燥箱干燥,取出静置自然冷却得到EVA粗膜,膜厚在0.85mm左右。
采用“玻璃板-离型膜-EVA粗膜-离型膜-玻璃板”的放置,于层压机中145℃真空层压,真空度0.08MPa、压力0.6MPa、时间15min,层压结束后冷却得到A组层压件和B组层压件。
A组层压件在PID实验(湿度85%、温度85℃,电压-1000V,时间192h)中,测得功率衰减3.0%;B组层压件在PID实验(湿度85%、温度85℃,电压-1000V,时间192h)中,测得功率衰减15%。
由此可知,加入高分子分散剂可显著提高助剂的分散度,进而胶膜的稳定性,提高胶膜抗PID性能。
实施例2
本实施例包括A组和B组,两组高分散抗PID光伏封装胶膜的配方组分如下:
将上述两组的组分置于氯仿溶剂中,EVA:有机溶剂=1:7(重量比),溶解、超声一定时间,超声功率为200W,超声时间为30min,超声温度为30℃;将该溶液倒入表面光滑且尺寸固定的玻璃模具中,以保证制备的EVA膜膜厚基本一致,放置于鼓风干燥箱干燥,取出静置自然冷却得到EVA粗膜,膜厚在0.85mm左右。
采用“玻璃板-离型膜-EVA粗膜-离型膜-玻璃板”的放置,于层压机中145℃真空层压,真空度0.07MPa、压力0.7MPa、时间16min,层压结束后冷却可得A组层压件和B组层压件。
A组层压件在PID实验(湿度85%、温度85℃,电压-1000V,时间192h)中,测得功率衰减10%;B组层压件在PID实验(湿度85%、温度85℃,电压-1000V,时间192h中,测得功率衰减28%。
由此可知,当添加剂含量相对基料EVA太低时,胶膜的抗PID性能差;分散性差导致胶膜抗PID性能大幅下降。
实施例3
本实施例包括A组和B组,两组高分散抗PID光伏封装胶膜的配方组分如下:
成分 | A组(重量份) | B组(重量份) |
EVA树脂,VA含量28% | 86.64 | 90.64 |
2,5-二甲基-2,5-双(过氧化叔丁基)己烷 | 3 | 3 |
邻苯二甲酸二烯丙酯 | 1.5 | 1.5 |
乙烯基三(2-甲氧乙氧基)硅烷 | 0.3 | 0.3 |
磷酸氢锆 | 4 | 0 |
2-丙烯酰胺-2-甲基丙磺酸 | 0.5 | 0.5 |
甲基丙烯酸甲酯 | 3 | 3 |
丙烯酸丁酯 | 0.5 | 0.5 |
二苯甲酮 | 0.5 | 0.5 |
亚磷酸酯 | 0.06 | 0.06 |
将上述两组的组分置于N,N-二甲基甲酰胺溶剂中,EVA:有机溶剂=1:7(重量比),溶解、超声一定时间,超声功率为200W,超声时间为35min,超声温度为35℃;将该溶液倒入表面光滑且尺寸固定的玻璃模具中,以保证制备的EVA膜膜厚基本一致,放置于鼓风干燥箱干燥,取出静置自然冷却得到EVA粗膜,膜厚在0.85mm左右。
采用“玻璃板-离型膜-EVA粗膜-离型膜-玻璃板”的放置,于层压机中140℃真空层压,真空度0.08MPa、压力0.6MPa、时间20min,层压结束后冷却可得得到A组层压件和B组层压件。
A组层压件在PID实验(湿度85%、温度85℃,电压-1000V,时间192h)中,测得功率衰减2%;B组层压件在PID实验(湿度85%、温度85℃,电压-1000V,时间192h中,测得功率衰减42%。
由此可知,合理的配比可使得胶膜具备良好的抗PID性能,磷酸氢锆作为抗PID助剂对提高封装胶膜抗PID性能效果显著。
对原始的EVA膜以及A组层压件分别进行红外测试,参见图1可知,3445cm-1处吸收峰为羧酸中游离的-OH伸缩振动,1250cm-1附近有强吸收峰为羧酸中C=O和C-O伸缩振动耦合的结果;1646cm-1和1552cm-1处特征峰为羧酸盐中C=O和C-О偶合所产生的反对称伸缩振动;经过对比可知,老化192h后,EVA膜中无羧酸盐,EVA/Zr(HPO4)2膜中含有羧酸盐,EVA中的VA脱羧反应生成的羧酸基团被磷酸锆吸附化合生成羧酸盐,此外,磷酸氢锆作为填料能提升胶膜的导热性能,避免了过热,故羧酸基团无论是挥发还是转化为小分子物质的速度都减小,这正说明磷酸氢锆之所以可提高EVA胶膜的抗PID性能,是因为磷酸氢锆可吸附化合EVA胶膜中的羧酸。
实施例4
本实施例包括A组和B组,各两高分散抗PID光伏封装胶膜的配方组分如下:
将上述两组的组分置于甲苯溶剂中,EVA:有机溶剂=1:7(重量比),溶解、超声一定时间,超声功率为200W,超声时间为40min,超声温度为25℃;将该溶液倒入表面光滑且尺寸固定的玻璃模具中,以保证制备的EVA膜膜厚基本一致,放置于鼓风干燥箱干燥,取出静置自然冷却得到EVA粗膜,膜厚在0.85mm左右。
采用“玻璃板-离型膜-EVA粗膜-离型膜-玻璃板”的放置,于层压机中145℃真空层压,真空度0.08MPa、压力0.6MPa、时间17min,层压结束后冷却可得A组层压件和B组层压件。
A组层压件在PID实验(湿度85%、温度85℃,电压-1000V,时间192h)中,测得功率衰减2.7%;B组层压件在PID实验(湿度85%、温度85℃,电压-1000V,时间192h中,测得功率衰减37%。
由此可知,磷酸锌作为抗PID助剂对提高封装胶膜抗PID性能效果显著。
实施例5
本实施例包括A组和B组,两组高分散抗PID光伏封装胶膜的配方组分如下:
成分 | A组(重量份) | B组(重量份) |
EVA树脂,VA含量28% | 87.9 | 92.9 |
过氧化碳酸-2-乙基己基碳酸叔戊酯 | 3 | 3 |
三羟甲基丙烷三丙烯酸酯 | 1 | 1 |
3-(甲基丙烯酰氧)丙基三甲氧基硅烷 | 0.8 | 0.8 |
氧化镁 | 5 | 0 |
马来酸酐 | 0.6 | 0.6 |
甲基丙烯酸丁酯 | 0.2 | 0.2 |
苯乙烯 | 0.4 | 0.4 |
双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯 | 1 | 1 |
2,6-二叔丁基对甲酚 | 0.1 | 0.1 |
将上述两组的组分置于甲苯溶剂中,EVA:有机溶剂=1:7(重量比),溶解、超声一定时间,超声功率为200W,超声时间为20min,超声温度为40℃;将该溶液倒入表面光滑且尺寸固定的玻璃模具中,以保证制备的EVA膜膜厚基本一致,放置于鼓风干燥箱干燥,取出静置自然冷却得到EVA粗膜,膜厚在0.85mm左右。
采用“玻璃板-离型膜-EVA粗膜-离型膜-玻璃板”的放置,于层压机中155℃真空层压,真空度0.05MPa、压力0.7MPa、时间17min,层压结束后冷却可得A组层压件和B组层压件。
A组层压件在PID实验(湿度85%、温度85℃,电压-1000V,时间192h)中,测得功率衰减3.9%;B组层压件在PID实验(湿度85%、温度85℃,电压-1000V,时间192h中,测得功率衰减40%。
由此可知,氧化镁作为抗PID助剂对提高封装胶膜抗PID性能效果显著。
对比例1
具体配方同实施例1,不同之处在于,制备工艺中不采用超声处理。
本实施例包括C组和D组,两组高分散抗PID光伏封装胶膜的配方组分如下:
成分 | C组(重量份) | D组(重量份) |
EVA树脂,VA含量28% | 85 | 85 |
过氧化-2-乙基己基碳酸叔丁酯 | 5 | 5 |
三羟甲基丙烷三丙烯酸酯 | 1 | 3 |
3-(甲基丙烯酰氧)丙基三甲氧基硅烷 | 1 | 3 |
氢氧化镁 | 2 | 2 |
2-丙烯酰胺-2-甲基丙磺酸 | 0.5 | 0 |
甲基丙烯酸甲酯 | 3.98 | 0 |
丙烯酸丁酯 | 0.5 | 0 |
二苯甲酮 | 1 | 1 |
2,6-二叔丁基对甲酚 | 0.02 | 1 |
将上述两组的组分置于甲苯溶剂中,EVA:有机溶剂=1:7(重量比),溶解;将该溶液倒入表面光滑且尺寸固定的玻璃模具中,以保证制备的EVA膜膜厚基本一致,放置于鼓风干燥箱干燥,取出静置自然冷却得到EVA粗膜,膜厚在0.85mm左右。
采用“玻璃板-离型膜-EVA粗膜-离型膜-玻璃板”的放置,于层压机中150℃真空层压,真空度0.07MPa、压力0.7MPa、时间16min,层压结束后冷却可得C组层压件和D组层压件。
C组层压件在PID实验(湿度85%、温度85℃,电压-1000V,时间192h)中,测得功率衰减10%;D组层压件在PID实验(湿度85%、温度85℃,电压-1000V,时间192h中,测得功率衰减40%。
与实施例1的数据对比可知,C、D组的对照实验说明制备工艺采用超声法可显著提高助剂的分散度,提高胶膜的稳定性。
Claims (8)
2.根据权利要求1所述的高分散抗电势诱导衰减光伏封装胶膜,其特征在于:所述抗PID助剂为磷酸氢锆、磷酸锌或氢氧化镁中的一种或多种。
3.根据权利要求1所述的高分散抗电势诱导衰减光伏封装胶膜,其特征在于:所述交联剂为1,1-双(叔丁基过氧基)-3,3,5-三甲基环己烷、2,5-二甲基-2,5-双(过氧化叔丁基)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、过氧化苯甲酰中的一种或多种;所述助交联剂为三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、邻苯二甲酸二烯丙酯中的一种或多种。
4.根据权利要求1所述的高分散抗电势诱导衰减光伏封装胶膜,其特征在于:所述硅烷偶联剂为3-(甲基丙烯酰氧)丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(2-甲氧乙氧基)硅烷中的一种或多种。
5.根据权利要求1所述的高分散抗电势诱导衰减光伏封装胶膜,其特征在于:所述的紫外光吸收剂为二苯甲酮、双(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)酯中的一种或多种。
6.权利要求1所述的高分散抗电势诱导衰减光伏封装胶膜的制备方法,其特征在于:封装胶膜的制备方法为溶剂法,制备步骤为将各组分溶于有机溶剂中,并超声处理后倒入模具,经烘干后得到EVA粗膜;采用玻璃板-离型膜-EVA粗膜-离型膜-玻璃板的放置,于层压机中真空层压,冷却得到所需光伏封装胶膜。
7.根据权利要求6所述的制备方法,其特征在于:超声功率为180~220W,超声温度为25~40℃,超声时间为20~40min;真空层压的温度为140~155℃,真空度0.05~0.08MPa,压强为0.6~0.7MPa。
8.根据权利要求7所述的制备方法,其特征在于:所述有机溶剂为甲苯、氯仿、N,N-二甲基甲酰胺中的一种或多种。
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