CN106833406A - 一种高折射率纳米无机物杂化光伏封装材料 - Google Patents

一种高折射率纳米无机物杂化光伏封装材料 Download PDF

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CN106833406A
CN106833406A CN201710096221.7A CN201710096221A CN106833406A CN 106833406 A CN106833406 A CN 106833406A CN 201710096221 A CN201710096221 A CN 201710096221A CN 106833406 A CN106833406 A CN 106833406A
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thiophenol
refractive index
double
high refractive
inorganic matter
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周欣蕊
熊曦
侯宏兵
周光大
林建华
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Hangzhou First PV Material Co Ltd
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Hangzhou First PV Material Co Ltd
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Abstract

本发明公开了一种高折射率纳米无机物杂化光伏封装材料。该材料由封装胶膜基体材料、高折射率纳米无机物等组成，通过加入高折射率纳米无机物，可实现提高光伏封装材料折射率并可调的作用，从而达到玻璃、封装材料、晶硅电池片三者折射率完美匹配，将硅片对入射太阳光的吸收最优化，提高太阳能电池效率；并通过对高折射率纳米无机物进行包覆，改善其在聚合物中的分散性；通过其他助剂的加入，保证高折射率纳米无机物杂化光伏封装材料的绝缘性、耐候性等满足光伏封装领域的要求。

Description

一种高折射率纳米无机物杂化光伏封装材料
技术领域
本发明属于光伏封装胶膜领域，尤其涉及一种高折射率纳米无机物杂化光伏封装材料。
背景技术
在资源紧缺，环境污染日趋严重的全球问题下，人们愈发迫切地需求一种环境友好、可再生的绿色能源。太阳能技术应运而生，太阳能也成为了目前被广泛认可的清洁能源，而光伏发电是太阳能利用的一种主要形式。在恶劣的条件下，为保证太阳能电池组件的整体性和持久性，确保硅晶片不被破坏，一般先用两层高分子封装胶膜密封晶硅电池片，再和上层保护材料钢化玻璃和下层保护背板粘结。
太阳光在组件中的吸收和损耗受组件各层物质的折射率影响很大，光照射到晶硅片上时一部分光被反射，根据反射最小值公式：
阳光透光上层钢化玻璃，透过封装胶膜，在晶硅片上由光能转化为电能，如果钢化玻璃和电池片之间的封装材料的折射率是其两边材料的几何平均值则反射率为0，电池片对太阳光的利用效率达到最大值。其中玻璃的折射率n0＝1.52，硅电池片的折射率n2＝3.8。根据公式所需封装胶膜的折射率为n1＝2.3。而常用封装材料折射率都不足1.5，远达不到要求，大大影响了光利用率。
若采用直接分散法或共混法加入高折射率纳米材料，由于纳米粒子表面能较高、极性不匹配等原因，容易团聚或沉积造成相分离，使粒子失去或部分失去其特有的功能和作用。
鉴于上述情况，目前急需一种具有高折射率的封装胶膜，提高光伏组件的整体效率。同时，需要对纳米粒子进行表面修饰，设计纳米粒子的表面结构降低其与有机基体间的界面能，提高纳米粒子与聚合物之间的相容性。
发明内容
本发明的目的是针对现有技术的不足，提供一种高折射率纳米无机物杂化光伏封装材料。
本发明的目的是通过以下技术方案实现的：一种高折射率纳米无机物杂化光伏封装材料，它通过以下方法制备得到：将100～120质量份封装胶膜基体、5～20质量份高折射率纳米无机物、0.1～5质量份交联剂、0.01～2质量份紫外光吸收剂、0.01～5质量份光稳定剂混合均匀，然后用双螺杆挤出机挤出造粒，将造好的粒子用单螺杆挤出机挤出，挤出物经流延成膜。
进一步地，所述高折射率纳米无机物为粒径尺寸小于25纳米的粉体，选自非晶硅、金属单质锗(Ge)、二氧化钛(TiO2)、氧化锆(ZrO2)、氧化铪(HfO2)、氧化铌(Nb2O5)、氧化锌(ZnO)、氧化铈(CeO2)、五氧化二钽(Ta2O5)、碲化铅(PbTe)、硫化铅(PbS)、硫化锌(ZnS)、硫化铁(FeS)、硒化锌(ZnSe)、磷化镓(GaP)、磷化铟(InP)；所述二氧化钛、氧化锆、氧化铪、氧化铌、氧化锌、氧化铈、五氧化二钽通过与硅烷偶联剂表面的羟基发生溶胶凝胶反应实现表面包覆，所述碲化铅、硫化铅、硫化锌、硫化铁、硒化锌用硫酚类的化合物来包覆。
进一步地，所述硅烷偶联剂选自γ-甲基丙烯酰氧丙基-三甲氧基硅烷、3一氨基丙基三乙氧基硅烷、异氰酸丙基三乙氧基硅烷、异丁基三乙氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷、γ-缩水甘油丙基-三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基-三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基-甲基-三甲氧基硅烷、γ-氯丙基-三甲氧基硅烷、γ-巯丙基-三甲氧基硅烷、γ-氨丙基-三甲氧基硅烷。
进一步地，所述硫酚类化合物选自2-硝基硫酚、4-硝基硫酚、4-乙基硫酚、2-乙氧基硫酚、3-乙氧基硫酚、4-苯氧基硫酚、3-羟基硫酚、2，5-二乙氧基硫酚、3，4-二甲氧基硫酚、2，5-二甲氧基硫酚、2，5-二羟基硫酚、2，6-二甲基-4-硫酚、2-氯-4-氟硫酚、4-甲氧基-2-甲基硫酚、3-氟-4-甲氧基硫酚、4-氯-2，5-甲基硫酚、对羟基硫酚、2-羟基硫酚、氯硫酚、氟硫酚、溴硫酚、二氯硫酚、、二氟硫酚、三氯硫酚、三氟硫酚、四氟硫酚、五氟硫酚。
进一步地，所述封装胶膜基体由乙烯-醋酸乙烯酯共聚物、低密度聚乙烯、聚丙烯、聚丁烯、聚乙烯醇缩丁醛、聚氨酯弹性体、有机硅橡胶、茂金属催化聚乙烯、乙烯辛烯共聚物、乙烯戊烯共聚物中的一种或两种以上按任意配比混合组成。
进一步地，所述交联剂为自由基热引发交联剂，由以下物质中的一种或几种按照任意配比混合组成：叔丁基过氧化碳酸异丙酯、2，5-二甲基-2，5－双(叔丁过氧基)己烷、1-双(过氧化叔丁基)-3，3，5-三甲基环己烷、叔丁基过氧化碳酸-2-乙基己酯、1，1-双(叔丁基过氧)-3，3，5-三甲基环己烷、1，1-双(叔戊基过氧)-3，3，5-三甲基环己烷、1，1-双(叔戊基过氧)环己烷、1，1-双(叔丁基过氧)环己烷、2，2-双(叔丁基过氧)丁烷、过氧化2-乙基己基碳酸叔戊酯、2，5-二甲基2，5-双(苯甲酰过氧)-己烷、过氧化碳酸叔戊酯、过氧化3，3，5三甲基己酸叔丁酯。
进一步地，所述紫外光吸收剂由以下物质中的一种或多种按照任意配比混合组成：2-羟基-4-正辛氧基二苯甲酮、2，2-四亚甲基双(3，1-苯并噁嗪-4-酮)、2-(2’-羟基-5-甲基苯基)苯并三唑、2，2’-二羟基-4，4’-二甲氧基二苯甲酮。
进一步地，所述光稳定剂为受阻胺类光稳定剂，由以下物质中的一种或多种按照任意配比混合组成：3，5-二叔丁基-4-羟基-苯甲酸十六烷基酯、三(1，2，2，6，6-五甲基-4-哌啶基)亚磷酸酯、癸二酸双-2，2，6，6-四甲基哌啶醇酯、双-1-癸烷氧基-2，2，6，6-四甲基哌啶-4-醇癸二酸酯、丁二酸和4-羟基-2，2，6，6-四甲基-1-哌啶醇的聚合物、N，N’-双(2，2，6，6-四甲基-4-哌啶基)-1，6-己二胺和2，4-二氯-6-(1，1，3，3-四甲基丁基)氨基-1，3，5-三嗪的聚合物、N，N’-双(2，2，6，6-四甲基-4-哌啶基)-1，6-己二胺和吗啉-2，4，6-三氯-1，3，5-三嗪的聚合物。
本发明的有益效果是：本发明通过加入高折射率纳米无机物，可实现提高光伏封装材料折射率并可调的作用，从而达到玻璃、封装材料、晶硅电池片三者折射率完美匹配，将硅片对入射太阳光的吸收最优化，提高太阳能电池效率。
具体实施方式
下面结合实施例对本发明作进一步描述，但本发明的保护范围不仅局限于实施例：
实施例1：
以质量份数计，向100份乙烯-醋酸乙烯酯共聚物(醋酸乙烯VA的质量含量为31％)中，加入粒径尺寸小于25nm，经γ-甲基丙烯酰氧丙基-三甲氧基硅烷包覆后的纳米二氧化铪和经4-硝基硫酚包覆后的纳米硫化锌各5份，加入0.3份交联剂叔丁基过氧化碳酸异丙酯和0.3份交联剂1-双(过氧化叔丁基)-3，3，5-三甲基环己烷，0.01份紫外光吸收剂2-羟基-4-正辛氧基二苯甲酮，0.1份光稳定剂癸二酸双-2，2，6，6-四甲基哌啶醇酯，混合均匀后用双螺杆挤出机挤出造粒。将造好的粒子用单螺杆挤出机挤出，挤出物经流延成膜，冷却后收卷得到厚度为0.5mm的胶膜，记为S1。
实施例2：
以质量份数计，向105份乙烯辛烯共聚物中，加入粒径尺寸小于25nm的纳米碲化铅10份，加入0.1份交联剂2，5-二甲基-2，5－双(叔丁过氧基)己烷，2份紫外光吸收剂2，2-四亚甲基双(3，1-苯并噁嗪-4-酮)，0.5份光稳定剂3，5-二叔丁基-4-羟基-苯甲酸十六烷基酯，混合均匀后用双螺杆挤出机挤出造粒。将造好的粒子用单螺杆挤出机挤出，挤出物经流延成膜，冷却后收卷得到厚度为0.5mm的胶膜，记为S2。
实施例3：
以质量份数计，向120份乙烯-甲基丙烯酸甲酯共聚物中，加入粒径尺寸小于25nm的纳米磷化镓5份，加入5份交联剂过氧化3，3，5三甲基己酸叔丁酯，0.5份紫外光吸收剂2-羟基-4-正辛氧基二苯甲酮，5份光稳定剂双-1-癸烷氧基-2，2，6，6-四甲基哌啶-4-醇癸二酸酯，混合均匀后用双螺杆挤出机挤出造粒。将造好的粒子用单螺杆挤出机挤出，挤出物经流延成膜，冷却后收卷得到厚度为0.5mm的胶膜，记为S3。
实施例4：
以质量份数计，向100份聚乙烯醇缩丁醛中，加入粒径尺寸小于25nm，经N-(β-氨乙基)-γ-氨丙基-三甲氧基硅烷包覆的纳米五氧化二钽20份，加入3份交联剂叔丁基过氧化碳酸-2-乙基己酯，1份紫外光吸收剂2，2-四亚甲基双(3，1-苯并噁嗪-4-酮)，0.5份光稳定剂三(1，2，2，6，6-五甲基-4-哌啶基)亚磷酸酯和0.3份光稳定剂双-1-癸烷氧基-2，2，6，6-四甲基哌啶-4-醇癸二酸酯，混合均匀后用双螺杆挤出机挤出造粒。将造好的粒子用单螺杆挤出机挤出，挤出物经流延成膜，冷却后收卷得到厚度为0.5mm的胶膜，记为S4。
实施例5：
以质量份数计，向105份茂金属催化聚乙烯中，加入粒径尺寸小于25nm，经2，6-二甲基-4-硫酚包覆的纳米硫化铁15份，加入1.5份交联剂1，1-双(叔戊基过氧)环己烷，1份紫外光吸收剂2-羟基-4-正辛氧基二苯甲酮和1份紫外光吸收剂2-(2’-羟基-5-甲基苯基)苯并三唑，0.5份光稳定剂丁二酸和4-羟基-2，2，6，6-四甲基-1-哌啶醇的聚合物，混合均匀后用双螺杆挤出机挤出造粒。将造好的粒子用单螺杆挤出机挤出，挤出物经流延成膜，冷却后收卷得到厚度为0.5mm的胶膜，记为S5。
实施例6：
以质量份数计，向100份聚氨酯弹性体中，加入粒径尺寸小于25nm，经异丁基三乙氧基硅烷包覆的纳米氧化锆3份和纳米磷化铟5份，加入2份交联剂叔丁基过氧化碳酸-2-乙基己酯，0.5份紫外光吸收剂2，2’-二羟基-4，4’-二甲氧基二苯甲酮，0.01份光稳定剂双-1-癸烷氧基-2，2，6，6-四甲基哌啶-4-醇癸二酸酯，混合均匀后用双螺杆挤出机挤出造粒。将造好的粒子用单螺杆挤出机挤出，挤出物经流延成膜，冷却后收卷得到厚度为0.5mm的胶膜，记为S6。
比较例1：
以质量份数计，向100份乙烯-醋酸乙烯酯共聚物(醋酸乙烯VA的质量含量为31％)中，加入0.3份交联剂叔丁基过氧化碳酸异丙酯和0.3份交联剂1-双(过氧化叔丁基)-3，3，5-三甲基环己烷，0.01份紫外光吸收剂2-羟基-4-正辛氧基二苯甲酮，0.1份光稳定剂癸二酸双-2，2，6，6-四甲基哌啶醇酯，混合均匀后用双螺杆挤出机挤出造粒。将造好的粒子用单螺杆挤出机挤出，挤出物经流延成膜，冷却后收卷得到厚度为0.5mm的胶膜，记为C1。
比较例2：
以质量份数计，向100份聚乙烯醇缩丁醛中，加入3份交联剂叔丁基过氧化碳酸-2-乙基己酯，1份紫外光吸收剂2，2-四亚甲基双(3，1-苯并噁嗪-4-酮)，0.5份光稳定剂三(1，2，2，6，6-五甲基-4-哌啶基)亚磷酸酯和0.3份光稳定剂双-1-癸烷氧基-2，2，6，6-四甲基哌啶-4-醇癸二酸酯，混合均匀后用双螺杆挤出机挤出造粒。将造好的粒子用单螺杆挤出机挤出，挤出物经流延成膜，冷却后收卷得到厚度为0.5mm的胶膜，记为C2。
通过上述实施例和比较例得到的封装胶膜，经下述测试方法进行评估，评估结果列于表1：1、封装胶膜折射率
样品制作：取封装胶膜，按离形膜/胶膜/离形膜次序放入真空层压机内，在150℃，层压固化15分钟。将层压后的胶膜取出测试。
用阿贝折光仪测得胶膜折射率。
2、玻璃/封装胶膜粘结强度
测试方法参考国家标准GB/T2790《胶粘剂180°剥离强度试验方法挠性材料对刚性材料》。
样品制作：取3mm厚玻璃、封装胶膜、TPT背板，按玻璃/胶膜/背板次序放入真空层压机内，在150℃，层压固化15分钟。对于表面预交联封装胶膜，剥离样品在制作时非预交联侧朝向玻璃。
在拉力机上进行测试，剥离速度为100mm/min，记录拉伸强度数值。
3、组件功率测试
将上述实施例和比较例得到的封装胶膜，按照相同的工艺进行封装太阳能电池组件。同一种胶膜封装四块组件，为一个模块。所封装的组件为标准的60片15.6cm×15.6cm多晶硅电池，且为同一厂家，同一批次，同一档次。
将制作好的组件模块用功率模拟器测量功率。
表1：实施例与比较例所得的封装胶膜性能对比
胶膜样品 折射率 与玻璃粘结强度(N/cm) 组件功率(w)
S1 1.56 153 261
S2 1.53 126 258
S3 1.52 138 256
S4 1.62 103 270
S5 1.60 124 265
S6 1.54 132 259
C1 1.47 136 251
C2 1.48 108 252
本发明方案可以给光伏组件提供高折射率的封装胶膜，从而提高组件功率。
最后应该说明的是：以上实施例仅用以说明本发明而非限制本发明所描述的技术方案；因此，尽管本说明书参照上述的各个实施例对本发明已进行了详细的说明，但是，本领域的普通技术人员应当理解，仍然可以对本发明进行修改或等同替换；而一切不脱离本发明精神和范围的技术方案及其改进，其均应覆盖在本发明的权利要求范围中。

Claims (8)

1.一种高折射率纳米无机物杂化光伏封装材料，其特征在于，它通过以下方法制备得到：将100～120质量份封装胶膜基体、5～20质量份高折射率纳米无机物、0.1～5质量份交联剂、0.01～2质量份紫外光吸收剂、0.01～5质量份光稳定剂等混合均匀，然后用双螺杆挤出机挤出造粒，将造好的粒子用单螺杆挤出机挤出，挤出物经流延成膜。
2.根据权利要求1所述的高折射率纳米无机物杂化光伏封装材料，其特征在于，所述高折射率纳米无机物为粒径尺寸小于25纳米的粉体，选自非晶硅、金属单质锗(Ge)、二氧化钛(TiO2)、氧化锆(ZrO2)、氧化铪(HfO2)、氧化铌(Nb2O5)、氧化锌(ZnO)、氧化铈(CeO2)、五氧化二钽(Ta2O5)、碲化铅(PbTe)、硫化铅(PbS)、硫化锌(ZnS)、硫化铁(FeS)、硒化锌(ZnSe)、磷化镓(GaP)、磷化铟(InP)；所述二氧化钛、氧化锆、氧化铪、氧化铌、氧化锌、氧化铈、五氧化二钽通过与硅烷偶联剂表面的羟基发生溶胶凝胶反应实现表面包覆，所述碲化铅、硫化铅、硫化锌、硫化铁、硒化锌用硫酚类的化合物来包覆。
3.根据权利要求2述的高折射率纳米无机物杂化光伏封装材料，其特征在于，所述硅烷偶联剂选自γ-甲基丙烯酰氧丙基-三甲氧基硅烷、3一氨基丙基三乙氧基硅烷、异氰酸丙基三乙氧基硅烷、异丁基三乙氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷、γ-缩水甘油丙基-三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基-三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基-甲基-三甲氧基硅烷、γ-氯丙基-三甲氧基硅烷、γ-巯丙基-三甲氧基硅烷、γ-氨丙基-三甲氧基硅烷等。
4.根据权利要求2所述的高折射率纳米无机物杂化光伏封装材料，其特征在于，所述硫酚类化合物选自2-硝基硫酚、4-硝基硫酚、4-乙基硫酚、2-乙氧基硫酚、3-乙氧基硫酚、4-苯氧基硫酚、3-羟基硫酚、2，5-二乙氧基硫酚、3，4-二甲氧基硫酚、2，5-二甲氧基硫酚、2，5-二羟基硫酚、2，6-二甲基-4-硫酚、2-氯-4-氟硫酚、4-甲氧基-2-甲基硫酚、3-氟-4-甲氧基硫酚、4-氯-2，5-甲基硫酚、对羟基硫酚、2-羟基硫酚、氯硫酚、氟硫酚、溴硫酚、二氯硫酚、、二氟硫酚、三氯硫酚、三氟硫酚、四氟硫酚、五氟硫酚等。
5.根据权利要求1所述的高折射率纳米无机物杂化光伏封装材料，其特征在于：所述封装胶膜基体由乙烯-醋酸乙烯酯共聚物、低密度聚乙烯、聚丙烯、聚丁烯、聚乙烯醇缩丁醛、聚氨酯弹性体、有机硅橡胶、茂金属催化聚乙烯、乙烯辛烯共聚物、乙烯戊烯共聚物中的一种或两种以上按任意配比混合组成。
6.根据权利要求1所述封装材料，其特征在于，所述交联剂为自由基热引发交联剂，由以下物质中的一种或几种按照任意配比混合组成：叔丁基过氧化碳酸异丙酯、2，5-二甲基-2，5－双(叔丁过氧基)己烷、1-双(过氧化叔丁基)-3，3，5-三甲基环己烷、叔丁基过氧化碳酸-2-乙基己酯、1，1-双(叔丁基过氧)-3，3，5-三甲基环己烷、1，1-双(叔戊基过氧)-3，3，5-三甲基环己烷、1，1-双(叔戊基过氧)环己烷、1，1-双(叔丁基过氧)环己烷、2，2-双(叔丁基过氧)丁烷、过氧化2-乙基己基碳酸叔戊酯、2，5-二甲基2，5-双(苯甲酰过氧)-己烷、过氧化碳酸叔戊酯、过氧化3，3，5三甲基己酸叔丁酯等。
7.根据权利要求1所述封装材料，其特征在于，所述紫外光吸收剂由以下物质中的一种或多种按照任意配比混合组成：2-羟基-4-正辛氧基二苯甲酮、2，2-四亚甲基双(3，1-苯并噁嗪-4-酮)、2-(2’-羟基-5-甲基苯基)苯并三唑、2，2’-二羟基-4，4’-二甲氧基二苯甲酮。
8.根据权利要求1所述封装材料，其特征在于，所述光稳定剂为受阻胺类光稳定剂，由以下物质中的一种或多种按照任意配比混合组成：3，5-二叔丁基-4-羟基-苯甲酸十六烷基酯、三(1，2，2，6，6-五甲基-4-哌啶基)亚磷酸酯、癸二酸双-2，2，6，6-四甲基哌啶醇酯、双-1-癸烷氧基-2，2，6，6-四甲基哌啶-4-醇癸二酸酯、丁二酸和4-羟基-2，2，6，6-四甲基-1-哌啶醇的聚合物、N，N’-双(2，2，6，6-四甲基-4-哌啶基)-1，6-己二胺和2，4-二氯-6-(1，1，3，3-四甲基丁基)氨基-1，3，5-三嗪的聚合物、N，N’-双(2，2，6，6-四甲基-4-哌啶基)-1，6-己二胺和吗啉-2，4，6-三氯-1，3，5-三嗪的聚合物等。
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