CN109964320B - 包含面向背面封装剂的基于聚烯烃的功能层的背板 - Google Patents

包含面向背面封装剂的基于聚烯烃的功能层的背板 Download PDF

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CN109964320B
CN109964320B CN201780069434.9A CN201780069434A CN109964320B CN 109964320 B CN109964320 B CN 109964320B CN 201780069434 A CN201780069434 A CN 201780069434A CN 109964320 B CN109964320 B CN 109964320B
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polypropylene
layer
copolymer
solar cell
functional layer
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CN109964320A (zh
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弗拉其苏斯·格拉尔杜斯·亨利克斯·范杜伊霍文
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Yingrun Solar Solutions Co ltd
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Abstract

本发明涉及太阳能电池背板，其包含功能层，其中功能层包含聚乙烯合金和半结晶聚合物(例如聚丙烯)，基于功能层中聚合物的总重量，优选地至少10wt％的聚丙烯。聚丙烯选自聚丙烯均聚物或共聚物，所述共聚物是无规共聚物或嵌段共聚物。聚乙烯合金包含含有乙烯链段(‑CH2‑CH2‑)的共聚物，所述乙烯链段选自乙烯丙烯酸酯共聚物、乙烯‑己烯共聚物、乙烯‑辛烯共聚物、乙烯‑乙酸乙烯酯共聚物中的一种或多种。功能层还包含选自碳酸钙、二氧化钛、硫酸钡、云母、滑石、高岭土、玻璃微珠和玻璃纤维中的一种的无机填料。本发明还涉及包含根据本发明的背板的光伏模组。

Description

包含面向背面封装剂的基于聚烯烃的功能层的背板
本发明涉及用于太阳能电池模组的背板。本发明具体涉及背板，其包含直接面朝背面封装剂的基于聚烯烃的功能层。本发明还涉及包含背板的光伏模组。
太阳能电池或光伏模组用于从太阳光产生电能。光伏模组是可再生能量的重要来源。特别是，它们包含当暴露于阳光下时释放电子的太阳能电池。这些太阳能电池通常是易碎的半导体材料，通常被封装在聚合物材料中，以保护它们免受物理冲击和划伤。经封装的太阳能电池通常进一步受到玻璃或另外的外层的保护，该外层耐风化、磨损或其他物理损伤。
传统上，光伏模组安装在室外屋顶上或者在广阔的空间中，在那里它们对太阳光的暴露最大化。当太阳光强度增加时，光伏模组的电输出也增加。然而，光伏模组将太阳光转换成电能的效率通常仅为约20％。剩下的大约80％的阳光被模组反射回来或吸收。吸收的能量导致模组的工作温度升高。过热会降低光伏模组将太阳光转化为电能的效率。
太阳能电池模组具有设置在太阳光入射一侧上的前表面保护板，以保护表面。该层例如是玻璃层，其是保护PV电池和电子器件免受环境影响，同时允许光能穿过并转换成电能的刚性外层。太阳能电池模组还具有称为背板的太阳能电池背面保护板，其设置在相对侧上以保护发电电池。
通过使用所谓的封装剂进一步保护脆弱的太阳能电池。封装剂用于提供PV模组的太阳能电池、前表面和后表面或背板之间的粘合。用于太阳能电池封装剂的合适的聚合物材料通常具有如下特性的组合：诸如高抗冲击性，高抗穿透性，良好的耐紫外(UV)光性，良好的长期热稳定性，对玻璃和/或其它刚性聚合物板的足够粘合强度，高耐湿性，以及良好的长期耐候性。封装剂的示例是离聚物、乙烯醋酸乙烯酯(EVA)、聚(乙烯醇缩醛)、聚乙烯醇缩丁醛(PVB)、热塑性聚氨酯(TPU)、聚氯乙烯(PVC)、茂金属催化的线性低密度聚乙烯、聚烯烃嵌段弹性体、聚(乙烯-共聚-丙烯酸甲酯)和聚(乙烯-共聚-丙烯酸丁酯)、有机硅弹性体或环氧树脂。EVA是最常用的封装剂材料。EVA板通常插入太阳能电池和顶表面之间(称为前封装剂)以及太阳能电池和后表面之间(称为背面封装剂)。
背板是一种光伏层压板，其保护PV模组免受紫外线、潮湿和天气的影响，同时充当电绝缘体。背板通常包含若干聚合物层，以提供上述性能并使太阳能电池模组的长期性能的劣化最小。此若干聚合物层在背板中具有它们自己的功能。通常，背板包括面向电池的功能层、结构增强层、耐候层以及在功能层与结构增强层之间和/或结构增强层与耐候层之间的粘合剂层。用于上述层的聚合物的实例是聚丙烯、聚氯乙烯、聚酯(例如PET或PBT)、氟树脂(例如PTFE或PVDF)和丙烯酸类树脂。
包含直接面向背面封装剂的聚烯烃层的背板在本领域中是已知的。这些背板例如在WO2014083604中公开。WO2014083604公开了一种耐湿热太阳能电池背板，其由耐风雨层、第一连接层、结构增强层和反射层组成。反射层面向电池并包含聚乙烯、含有乙烯链段-CH2-CH2-的共聚物、抗UV稳定剂和白色无机颜料。所描述的包含这种基于聚乙烯和含有乙烯链段(-CH2-CH2-)的共聚物的反射层的背板的一个缺点是在层压过程中的不完整性，导致过多的收缩并因此在层压后冷却时产生应力，这可能导致背板在边缘处卷曲。此外，这些背板显示出朝向粘合剂层的相对低的层间粘合，所述粘合剂层附着于结构增强层。另一个缺点是聚乙烯的高氧传输，这可能导致在PV模组中的接触点处腐蚀。
本发明的目标是克服上述缺点。
实现本发明的目的在于：提供太阳能电池背板，其具有面向背面封装剂的功能层，其中功能层包括聚乙烯合金和熔点高于140℃的半结晶聚合物。
已经发现，在层压过程中上述背板的完整性增加，因此提供了减少的残余应力，因而实现了改善的耐久性。改善的耐久性防止形成表面平坦性缺陷，例如卷曲或起伏，并防止在硅电池中和焊料中形成微裂纹生长。此外还发现，在功能层中添加半结晶聚合物改善了朝向粘合剂层的层间粘合，该粘合剂层附着于结构增强层。令人惊奇的是，包含半结晶聚合物的功能层与背面密封剂的粘合仍然很好。
在PV模组的层压过程中，通常背板突出PV模组堆叠物，该PV模组堆叠物位于层压机中的带上并且具有面向带的经AR涂覆的玻璃。当在高温下在堆叠物上施加压力时，背板可以被压贴到带上，因而功能层与带接触。当功能层和结构层之间的粘合过低时，功能层的一部分将留在带上，在下一个层压循环中污染经AR涂覆的玻璃的前侧。需要去除这些污染物并且可能在清洁期间损坏AR涂层。结构层和功能层之间增加的粘合防止了这种污染，并且不需要清洁以防止AR涂层被损坏。
半结晶聚合物优选地选自由聚烯烃、聚酰胺或聚酯组成的组。
半结晶聚烯烃的实例是例如聚乙烯、聚丙烯均聚物和共聚物、马来酸酐接枝的聚丙烯和/或聚丁烯，其中最优选的是聚丙烯共聚物。
在聚丙烯共聚物的情况下，丙烯是主要的单体单元，其可以含有其他α-烯烃，例如乙烯和丁烯-1。这些聚丙烯可以使用Zieger-Natta催化剂或茂金属催化剂获得。
术语“半结晶”应理解为聚合物的结晶度通常为10-80％。优选地，聚合物的结晶度大于30％。使用差示扫描量热法(DSC)可以最容易地评估聚合物的结晶度，差示扫描量热法测量在加热、冷却或等温情况下流入样品或流出样品的热量。例如来自PerkinElmer的Pyris 6,DSC提供了测量热塑性材料的结晶度百分比的工具。DSC测量在本领域中是众所周知的。
无论怎样测量结晶聚丙烯的结晶度，聚合物的性质将决定给定的聚合物是否是如本文所用的术语“半结晶”。第一个性质是熔点。在使用Zieger-Natta催化剂制备半结晶聚丙烯的情况下，半结晶聚丙烯可具有高于140℃的熔点。优选地，熔点高于145℃，最优选熔点为150-170℃。第二个决定性的性质是熔化热。当聚丙烯是Ziegler-Natta获得的聚合物时，它们可具有至少100焦耳/克、至少115焦耳/克或至少120焦耳/克的熔化热。使用差示扫描量热计和诸如ASTM D-3417-99中描述的方法测定熔化热，其中将5至10mg样品以10℃的速率加热并冷却。
如果通过使用茂金属催化剂获得半结晶聚丙烯，则聚丙烯会具有至少约158℃的熔点和至少90焦耳/克的熔化热。对于Ziegler-Natta获得的聚丙烯，还可以使用DSC评估茂金属催化的聚丙烯的结晶性质。可用于本发明的半结晶聚丙烯的实例是来自ATOFINATM的3270 9119、BPTM Accpro 9346、BASELLADSTIFTM HA722J、Sinopec K8003和SUNOCOTM PPF-050-HC。
基于功能层中聚合物的总重量，功能层包含至少5wt％的半结晶聚合物，优选地至少10wt％的半结晶聚合物。更优选地，基于功能层中聚合物的总重量，功能层包含10-49wt％的半结晶聚合物。
本发明的功能层中的聚乙烯(PE)合金或共混物优选地包含聚乙烯和“极性”聚乙烯。“极性”聚乙烯是指例如，与极性共聚单体共聚的乙烯，极性共聚单体选自乙酸乙烯酯、丙烯酸酯和甲基丙烯酸酯，例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯或丙烯酸乙基己酯。优选地，聚乙烯(PE)合金是聚乙烯和乙烯-甲基丙烯酸酯共聚物和/或乙烯-乙酸乙烯酯共聚物的共混物。
半结晶聚酰胺在加热下具有高尺寸稳定性、较低的水吸收、改善的水解稳定性和在湿汽作用下增加的尺寸稳定性。在高湿度环境下，低吸湿性可确保良好的电绝缘性。半结晶聚酰胺的示例是聚酰胺6；聚酰胺6,6；聚酰胺4,6；聚酰胺4,10,聚酰胺6,10；聚酰胺6,12；聚酰胺6,14；聚酰胺6,13；聚酰胺6,15；聚酰胺6,16；聚酰胺11；聚酰胺12；聚酰胺10；聚酰胺9,12；聚酰胺9,13；聚酰胺9,14；聚酰胺9,15；聚酰胺6,16；聚酰胺10,10；聚酰胺10,12；聚酰胺10,13；聚酰胺10,14；聚酰胺12,10；聚酰胺12,12；聚酰胺12,13；聚酰胺12,14；己二酰胺聚对苯二甲酸乙二醇酯(adipamide polyethylene terephthalate)，聚对苯二甲酸乙二醇酯壬二酰胺(polyethylene terephthalate azelaic acid amide)，聚乙烯癸二酰胺(polyethylene sebacic acid amide)，聚对苯二甲酸乙二醇酯十二二酰胺(polyethyleneterephthalate twelve diamide)，己二酸己二酰胺/对苯二甲酸己二酰胺共聚酰胺，对苯二甲酸己二酰胺/间苯二甲酸己二酰胺共聚酰胺(adipamide terephthalate/isophthalate copolymerized adipamide amide)，聚己二酸间二甲苯酰胺，对苯二甲酸己二酰胺/对苯二甲酸甲基戊二酰胺，己二酸己二酰胺/对苯二甲酸酯己二酰胺/间苯二甲酸己二酰胺共聚酰胺，聚己内酰胺，聚己内酰胺-对苯二甲酸己二酰胺，聚酰胺12，及其任意混合物。优选的聚酰胺具有有限的吸湿性，例如聚酰胺11、聚酰胺12或聚酰胺4,10。
半结晶聚酯的示例包括聚(反式-1,4-亚环己基烷二羧酸酯)，例如聚(反式-1,4-亚环己基琥珀酸酯)和聚(反式-1,4-亚环己基己二酸酯)；聚(顺式或反式-1,4-环己烷二亚甲基)烷二羧酸酯，例如聚(顺式1,4-环己烷二亚甲基)草酸酯和聚(顺式1,4-环己烷二亚甲基)琥珀酸酯；聚(对苯二甲酸亚烷基酯)例如聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯；聚(间苯二甲酸亚烷基酯)，例如聚间苯二甲酸乙二醇酯和聚间苯二甲酸丁二醇酯；聚(对亚苯基烷二羧酸酯(poly(p-phenylene alkanedicarboxylates)，例如聚(对亚苯基戊二醇酯)和聚(对亚苯基己二酸酯)，聚(对二甲苯草酸酯)，聚(邻二甲苯草酸酯)；聚(对亚苯基二亚烷基对苯二甲酸酯)(poly(p-phenylenedialkylene terephthalates))，例如聚(对亚苯基二亚甲基对苯二甲酸酯)和聚(对亚苯基-二-1,4-亚丁基对苯二甲酸酯；聚(亚烷基-1,2-亚乙基二氧-4,4'-二苯甲酸酯)，例如聚(亚乙基-1,2亚乙基二氧-4,4'-二苯甲酸酯)，聚(四亚甲基-1,2-亚乙基二氧-4,4'-二苯甲酸酯)和聚(六亚甲基-1,2-亚乙基二氧-4,4'-二苯甲酸酯)；聚(亚烷基-4,4'-二苯甲酸酯)，例如聚(五亚甲基-4,4'-二苯甲酸酯)，聚(六亚甲基-4,4'-二苯甲酸酯)和聚(十亚甲基-4,4'-二苯甲酸酯)，聚(亚烷基-2,6-萘二羧酸酯)，例如聚(亚乙基-2,6-萘二羧酸酯)，聚(三亚甲基-2,6-萘二羧酸酯)和聚(四亚甲基-2,6-萘二羧酸酯)；和聚(亚烷基磺酰基-4,4'-二苯甲酸酯)，例如聚(八亚甲基磺酰基-4,4'-二苯甲酸酯)，和聚(十亚甲基磺酰基-4,4'-二苯甲酸酯)。优选的聚酯是聚(对苯二甲酸亚烷基酯)，例如聚对苯二甲酸乙二醇酯(PET)或聚对苯二甲酸丁二醇酯(PBT)。
根据本发明的功能层还可以包含无机填料和其他添加剂。这些无机填料的示例是碳酸钙、二氧化钛、硫酸钡、云母、滑石、高岭土、ZnO、ZnS、玻璃微珠和玻璃纤维。当使用这类填料时，功能层包含基于功能层中聚合物的总重量0.05-20wt.％的填料，优选地功能层包含基于功能层中聚合物的总重量5-15wt.％的填料。添加剂的实例选自UV稳定剂、紫外线吸收剂、抗氧化剂、热稳定剂和/或水解稳定剂。当使用这种稳定剂时，功能层包含基于功能层中聚合物的总重量0.05-10wt.％、更优选5wt.％的添加剂。
可以将诸如TiO2、ZnO或ZnS的白色颜料添加到功能层中以增加太阳光的后向散射，从而提高太阳能模组的效率。出于审美原因，也可加入炭黑等黑色颜料。
根据本发明的太阳能背板可进一步包含其他层，例如结构增强层和/或耐候层。结构增强层和/或耐候层可进一步包含上述段落中提到的无机填料或添加剂。
根据本发明的太阳能背板可进一步包含粘合剂层，其可以布置在功能层和结构增强层之间和/或结构增强层和耐候层之间。粘合剂层例如包含马来酸酐接枝的聚烯烃，例如马来酸酐接枝的聚乙烯或马来酸酐接枝的聚丙烯、乙烯-丙烯酸共聚物或乙烯-丙烯酸酯-马来酸酐三元共聚物。优选地，粘合剂层包含马来酸酐接枝的聚烯烃，例如马来酸酐接枝的聚乙烯或马来酸酐接枝的聚丙烯。
耐候层包含例如聚酰胺或氟树脂，例如PTFE或PVDF。聚酰胺例如选自如下材料中的一种或多种：聚酰胺6，聚酰胺6,6；聚酰胺4,6；聚酰胺4,10,聚酰胺6,10；聚酰胺6,12；聚酰胺6,14；聚酰胺6,13；聚酰胺6,15；聚酰胺6,16；聚酰胺11；聚酰胺12，聚酰胺10，聚酰胺9,12，聚酰胺9,13，聚酰胺9,14，聚酰胺9,15，聚酰胺6,16，聚酰胺10,10，聚酰胺10,12，聚酰胺10,13，聚酰胺10,14，聚酰胺12,10，聚酰胺12,12，聚酰胺12,13，聚酰胺12,14，己二酸己二酰胺/对苯二甲酸己二酰胺共聚酰胺,对苯二甲酸己二酰胺/间苯二甲酸己二酰胺共聚酰胺，聚(己二酸间二甲基苯甲酰胺，对苯二甲酸己二酰胺/对苯二甲酸2-甲基戊二酰胺，己二酸己二酰胺/对苯二甲酸己二酰胺/间苯二甲酸己二酰胺共聚酰胺和聚己内酰胺-对苯二甲酸己二酰胺。耐候层可进一步包含二氧化钛或硫酸钡、UV稳定剂和热稳定剂。
结构增强层例如包含工程塑料，例如聚丙烯或改性聚丙烯或者聚丙烯的共混物，聚酯例如PET，或者上文所述的聚酰胺。
包含结构增强层和/或耐候层和/或粘合剂层的本发明的背板可进一步包含无机填料和其他添加剂。填料和添加剂的示例和可能的用量如上所述。
可以使用多层共挤出工艺制备根据本发明的太阳能背板。该工艺包括包含如下步骤：将包含无机填料、添加剂和稳定剂的功能层和其他层(例如结构增强层和/或耐候层和/或粘合剂层)的各个配方混合，然后将不同的层挤出并对它们进行层压。
或者，还可以通过如下方法制造根据本发明的太阳能背板：
第一种方法包括如下步骤：(1)在挤出机中分别将耐风雨层材料、粘合剂层材料、结构增强层材料和功能层材料造粒，以获得耐风雨层塑料颗粒、粘合层塑料颗粒、结构增强层塑料颗粒和功能层塑料颗粒，并且(2)将步骤(1)中制备的耐风雨层塑料颗粒、粘合剂层塑料颗粒、结构增强层塑料颗粒和功能层塑料颗粒熔融并共挤出成多层共挤出的膜。
另一种方法包括如下步骤：(1)将粘合剂层材料、结构增强层材料和功能层材料分别挤出机中造粒，以获得粘合层塑料颗粒、结构增强层塑料颗粒和功能层塑料颗粒，并且(2)将步骤(1)中制备的粘合层塑料颗粒、结构增强层塑料颗粒和功能层塑料颗粒熔融并共挤出穿过挤出机，并将共挤出多层膜挤出层压在耐风雨层上。
还可以通过挤出背板的各单独的层并用粘合剂(例如环氧树脂、丙烯酸酯或聚氨酯粘合剂)将这些层层压而获得背板。
本发明还涉及包含根据本发明的太阳能背板的光伏模组。光伏模组(简称PV模组)按照从前朝阳侧到背面非朝阳侧的位置顺序至少包括以下层：(1)透明窗格(代表前板)，(2)前封装剂，(3)太阳能电池层，(4)背面封装剂和(5)根据本发明的背板。
前板通常是玻璃板，或者在柔性模组的情况下，是由氟化聚合物诸如ETFE(乙烯四氟乙烯)或PVDF(聚偏二氟乙烯)形成的层。
本发明还涉及制备这种太阳能电池模组的方法，该方法包括：(a)提供包含上文所述的一个或多个聚合物层的组件，和(b)将组件层压，以形成太阳能电池模组。该方法的层压步骤可以通过使组件经受加热和任选的真空或压力来进行。
现在通过一系列实施例和对比实验来说明本发明。
实施例
制造下部太阳能背板的方法包括如下步骤：
通过挤出机将耐候层、粘合剂层、结构增强层和功能层的材料分别造粒，以获得各层的塑料粒料。
通过多层共挤出工艺制备背板，其中将各层的粒料加入多个挤出机中，在高温下熔融挤出，流经接头和模头，通过冷却辊冷却并成形，以制造多层背板。多层背板中不同层的组成在表1中给出。
测量
在功能层和结构增强层之间以及功能层和作为封装剂的EVA之间测量剥离强度。
测量老化：在HAST高压加速老化试验机中老化(121℃，100％湿度)48小时后的外观。
在通过120KWH紫外线辐射老化后测量外观和黄变。
表2中给出了对比例I和II以及实施例1-5的多层背板的这些测量结果。
对比例I(CE-I)
使用PVDF氟聚合物作为耐候层，使用马来酸酐接枝的聚丙烯和EMA乙烯丙烯酸甲酯的聚合物的共混物作为粘合剂层，其可以粘附氟聚合物和马来酸酐接枝聚丙烯。在功能层中没有添加半结晶聚合物。
对比例II(CE-II)
使用尼龙12(PA12)聚合物作为耐候层，使用马来酸酐接枝的聚丙烯作为粘合剂层。在功能层中没有添加半结晶聚合物。
实施例1-4
在实施例1-4中，分别向功能层中添加半结晶聚合物(例如聚丙烯或马来酸酐接枝的聚丙烯)。
表1
在表1中，各层是多组分层，每种组分的比例是重量份。
Elvaloy AC1224是从DuPont获得的乙烯和丙烯酸甲酯的共聚物；
表2
从表2中的数据可以看出，向功能层中加入5-15份聚丙烯(PP)，导致功能层与结构增强层之间的粘合力显着提高，同时功能层与EVA封装层之间的粘合力略有减少。通过添加10重量份的聚丙烯PP和15重量份的马来酸酐接枝的聚丙烯(MPP)，功能层与结构增强层之间的粘合力增加。从HAST和耐紫外线老化性的试验结果可以看出，在功能层中加入聚丙烯或马来酸酐接枝的聚丙烯对耐水解性和耐紫外线老化性几乎没有影响
从表1和2中可以看出，相对于对比例I和II的背板，实施例1-4的背板中的功能层与结构增强层之间的粘合力显著改善。此外，对封装层的剥离强度也可以保持在良好的水平，在背板之间的粘合力和对封装层的粘合力方面没有弱点，这意味着背板的整体耐久性得到改善。

Claims (12)

1.太阳能电池背板，其包含面向背面封装剂的功能层，其中所述功能层包括聚乙烯合金和熔点高于140℃的半结晶聚合物，基于功能层中聚合物的总重量，所述功能层包含5至10wt%的半结晶聚合物，所述半结晶聚合物为聚丙烯均聚物或聚丙烯共聚物，其中所述聚乙烯合金包括聚乙烯和共聚物，所述聚乙烯合金中的共聚物选自乙烯丙烯酸酯共聚物、乙烯甲基丙烯酸酯共聚物、乙烯-己烯共聚物、乙烯-辛烯共聚物中的一种或多种。
2.根据权利要求1所述的太阳能电池背板，其中所述聚丙烯共聚物选自聚丙烯无规共聚物、聚丙烯嵌段共聚物或马来酸酐接枝的聚丙烯。
3.根据权利要求1所述的太阳能电池背板，其中所述聚乙烯合金中的共聚物包含乙烯丙烯酸酯共聚物。
4.根据权利要求1所述的太阳能电池背板，其中所述功能层还包含无机填料。
5.根据权利要求4所述的太阳能电池背板，其中所述无机填料选自碳酸钙、二氧化钛、硫酸钡、云母、滑石、高岭土、玻璃微珠和玻璃纤维中的一种。
6.根据权利要求1-5中任一项所述的太阳能电池背板，其还包含结构增强层和/或耐候层和/或粘合剂层。
7.根据权利要求6所述的太阳能电池背板，其中所述耐候层包含氟树脂或聚酰胺。
8.根据权利要求6所述的太阳能电池背板，其中所述结构增强层包含选自聚丙烯、改性聚丙烯、马来酸酐接枝的聚丙烯、PET、PBT或其与另外的工程塑料的共混物的层。
9.根据权利要求6所述的太阳能电池背板，其中所述粘合剂层包含马来酸酐接枝的聚烯烃。
10.根据权利要求9所述的太阳能电池背板，其中所述马来酸酐接枝的聚烯烃选自马来酸酐接枝的聚乙烯、马来酸酐接枝的聚丙烯、乙烯-丙烯酸共聚物或乙烯-丙烯酸酯-马来酸酐三元共聚物。
11.根据权利要求6所述的太阳能电池背板，其中所述结构增强层和/或所述耐候层和/或所述粘合剂层还包含无机填料。
12.光伏模组，其包含根据权利要求1-11所述的背板。
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JP2023052164A (ja) 2023-04-11
EP3539162A1 (en) 2019-09-18

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