CN101933160B - 带有低吸湿性的包含增塑剂的膜的光电模块 - Google Patents
带有低吸湿性的包含增塑剂的膜的光电模块 Download PDFInfo
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- 238000010521 absorption reaction Methods 0.000 title description 5
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 39
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 38
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- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 claims description 5
- HORIEOQXBKUKGQ-UHFFFAOYSA-N bis(7-methyloctyl) cyclohexane-1,2-dicarboxylate Chemical class CC(C)CCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCC(C)C HORIEOQXBKUKGQ-UHFFFAOYSA-N 0.000 claims description 5
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- WTTWSMJHJFNCQB-UHFFFAOYSA-N 2-(dibenzylamino)ethanol Chemical compound C=1C=CC=CC=1CN(CCO)CC1=CC=CC=C1 WTTWSMJHJFNCQB-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
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- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
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- 239000011654 magnesium acetate Substances 0.000 description 1
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- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及基于聚乙烯醇缩醛的包含增塑剂的膜的用途,其用于生产光电模块,该聚乙烯醇缩醛的聚乙烯醇含量小于20重量%。该膜优选的玻璃化转变温度Tg至少为20℃和/或增塑剂最大含量为26重量%。
Description
技术领域
本发明涉及光电模块的生产,该生产使用了低吸湿性的基于聚乙烯醇缩醛的包含增塑剂的膜。
现有技术
光电模块由光敏半导体层组成,其带有透明的覆盖层来保护其免遭外来影响。作为光敏半导体层,可以使用单晶太阳能电池或者带有载体的多晶薄半导体层。薄膜太阳能模块由光敏半导体层组成,该半导体层依靠例如蒸发、气相沉积、溅射或者湿沉积来施加到基本透明的片上。
两种系统通常都层压到玻璃板和硬的后覆盖层板之间,该后覆盖层板例如是由玻璃或者塑料依靠透明的粘接剂来制成的。
该透明的粘接剂必须完全地包封光敏半导体层和它的连接线路,必须是UV稳定的和湿气不敏感的,并且在层压加工后必须是完全无气泡的。
作为透明粘接剂,经常使用的是热固性流延树脂或者可交联的基于乙烯乙酸乙烯酯(EVA)的体系,例如诸如DE4122721C1或者DE4128766A1中所公开的那样。在未固化状态时,这些粘接剂体系可以调整到这样低的粘度,以使得它们无气泡的包封太阳能电池单元。在加入固化剂或者交联剂之后,获得了机械耐受性的粘接剂层。这些粘接剂体系的一个缺点是在固化加工过程中,经常会释放出侵蚀性物质例如酸,其会损害光敏半导体层,特别是薄膜模块。另外,在几年之后,由于UV辐照的结果,一些流延树脂倾向于形成气泡或者脱层。
作为热固性粘接剂体系的一种备选方案是使用包含增塑剂的基于聚乙烯醇缩醛例如聚乙烯醇缩丁醛(PVB)(其是复合玻璃制造中已知的)的膜。太阳能电池单元用一个或多个PVB膜覆盖,并且在升高压力和升高温度下将该膜用期望的覆盖材料结合成为层压制件。
使用PVB膜生产太阳能模块的方法例如是从DE4026165C2,DE4227860A1,DE2923770C2,DE3538986C2或者US4321418中已知的。在太阳能模块中使用PVB膜作为复合安全玻璃公开在例如DE20302045U1,EP1617487A1和DE3538986C2中。但是,这些文献没有包含任何关于所用的PVB膜的机械、化学和电学性能的信息。
特别地,随着光敏半导体层日益提高的效率和太阳能模块的全球普及,粘接剂膜的电学性能变得越来越重要。在所述模块的整个使用寿命内,在极端的气候条件下例如热带温度、高空气湿度或者强烈UV辐照下,还必须避免半导体层的电荷损失或者甚至短路。根据CEI 61215,对光电模块进行众多的测试(湿热测试,湿泄漏电流测试),目的是降低该模块的泄漏电流。
已知的是PVB膜的电阻随着含水量的提高而急剧下降,其强烈促使光电模块中泄漏电流的出现。在光电模块的边缘区域中,作为包封材料的膜经常暴露于高的环境湿度。在这里,膜的含水量会大大增加并且达到高到平衡湿度的值(大约3重量%)。在膜边缘区域中含水量的增加大大降低了这个区域的电阻。朝着该膜的中间,含水量会再次降低,但是为了避免泄漏电流,光敏半导体层因此不能放置到直至所述膜或者模块的边缘区域。这降低了面密度(),以及因此降低了该模块的电流效率。
用于光电模块的粘接剂膜因此应当具有尽可能低的吸湿性。
目标
因此,本发明的目标是提供具有低吸湿性的基于聚乙烯醇缩醛的包含增塑剂的膜,用于生产光电模块。
已经发现基于包含增塑剂的聚乙烯醇缩醛的具有低聚乙烯醇含量的膜表现出足够低的吸湿性。另外,可以使用低极性的增塑剂,这进一步提高了所述膜的耐潮湿性。
发明内容
本发明的主题因此是光电模块,其包含由下列组成的层压制件:
a)透明的前覆盖层
b)一个或多个光敏半导体层
c)至少一个基于聚乙烯醇缩醛的包含增塑剂的膜,和
d)后覆盖层,
其中该聚乙烯醇缩醛的聚乙烯醇含量小于20重量%。
即使在潮湿条件下,适于生产光电模块的膜优选在边缘区域具有下面的含水量或者含水量:最大2.3重量%,最大2.0重量%,最大1.8重量%,和特别优选最大1.5重量%。距离模块棱边不超过3cm的区域被认为是边缘区域。在该区域中,所述膜经由暴露的棱边吸湿,在模块内部含水量以一种扩散受控的方式降低。具有这种类型膜的光电模块可以非常接近于该膜边缘用光敏半导体层来覆盖,并因此具有提高的面积产量和电流产量。
具有提高的玻璃化转变温度Tg的聚乙烯醇缩醛膜也具有提高的电阻系数。不受该理论的正确性的束缚,这归因于降低了在玻璃状或者高粘度环境中的离子迁移率。
为了生产光电模块,本发明所用的膜c)的玻璃化转变温度Tg进一步优选在每种情况中为至少20℃,22℃,24℃,26℃,27℃,30℃或者35℃。可以规定40℃为最大的玻璃化转变温度Tg。
本发明所用的膜优选在85%相对湿度的环境湿度和23℃表现出下面的电阻系数:至少1E+11ohm×cm,优选至少5E+11ohm×cm,优选1E+12ohm×cm,优选5E+12ohm×cm,优选1E+13,优选5E+13ohm×cm,优选1E+14ohm×cm。这些值应当在膜的任何位置上实现,特别是在模块的边缘区域中。
该基于包含增塑剂的聚乙烯醇缩醛的膜优选包含未交联的聚乙烯醇缩丁醛(PVB),其通过将聚乙烯醇用丁醛进行缩醛化获得。
使用交联的聚乙烯醇缩醛,特别是交联的聚乙烯醇缩丁醛(PVB)同样是可能的。合适的交联聚乙烯醇缩醛描述在例如EP 1527107B1和WO2004/063231 A1(含羧基的聚乙烯醇缩醛的加热自交联),EP 1606325A1(用多醛交联的聚乙烯醇缩醛)和WO 03/020776 A1(用二羟乙酸交联的聚乙烯醇缩醛)中。这些专利申请的公开内容在此全部引入作为参考。
还可以使用具有5-10个碳原子的其它或者另外的醛类(例如诸如戊醛)来进行缩醛化。
来自水解的乙酸乙烯酯/乙烯共聚物的三元共聚物也可以用作本发明范围内的聚乙烯醇。这些化合物通常水解到大于98%,并且包含1-10重量%的基于乙烯的单元(例如Kuraray Europe GmbH的“Exceval”类型)。
除了缩醛单元之外,聚乙烯醇缩醛还包含由乙酸乙烯酯和乙烯醇所形成的单元。本发明所用的聚乙烯醇缩醛优选具有下面的聚乙烯醇含量:小于18重量%,小于16重量%或者特别是小于14重量%。聚乙烯醇含量应当不低于12重量%。
聚乙酸乙烯酯含量优选低于5重量%,优选低于3重量%和最优选低于2重量%。由聚乙烯醇含量和残留的乙酸酯含量能够计算缩醛化程度。
基于聚乙烯醇缩醛的包含增塑剂的膜的耐湿性和玻璃化转变温度Tg另外取决于所用的增塑剂的含量和极性或者增塑效果。结果,该膜的吸湿性和电阻系数可以通过增塑剂以简单的方式来调整。
所述的膜优选具有下面的增塑剂含量:最大26重量%,更优选最大24重量%,和特别是最大22重量%;因为该膜的加工性原因,增塑剂含量应当不低于15重量%。本发明的膜或者光电模块可以包含一种或多种增塑剂。
根据本发明,特别合适的是这样的增塑剂,它用式100xO/(C+H)表示的极性小于/等于9.4;其中O、C和H表示在各自分子中的氧,碳和氢原子的数目。下面的表格表示了可用于本发明的增塑剂以及其根据式100xO/(C+H)的极性值。
名称 缩写 100xO/(C+H)
二-2-乙基己基癸二酸酯 (DOS) 5.3
二-2-乙基己基己二酸酯 (DOA) 6.3
二-2-乙基己基邻苯二甲酸酯 (DOP) 6.5
二己基己二酸酯 (DHA) 7.7
二丁基癸二酸酯 (DBS) 7.7
二-2-丁氧基-乙基癸二酸酯 (DBES) 9.4
三甘醇双-2-乙基己酸酯 (3G8) 9.4
1,2-环己烷二羧酸二异壬基酯 (DINCH) 5.4
次适合的是下面的增塑剂
名称 缩写 100xO/(C+H)
三甘醇双正庚酸酯 3G7 10.3
四甘醇双正庚酸酯 4G7 10.9
二-2-丁氧基-乙基己二酸酯 DBEA 11.5
二-2-丁氧基-乙氧基-乙基己二酸酯 DBEEA 12.5
聚乙烯醇缩醛膜在玻璃上的附着性通常是通过加入粘附调节剂例如诸如WO 03/033583 A1中所公开的有机酸的碱金属和/或碱土金属盐来进行调整的。乙酸钾和/或乙酸镁经证实是特别合适的。此外,来自生产过程的聚乙烯醇缩醛经常包含无机酸的碱金属和/或碱土金属盐,例如诸如氯化钠。
因为盐还影响电阻系数,因此合乎目的的是使用具有下面含量的金属离子的基于聚乙烯醇缩醛的包含增塑剂的膜:小于50ppm,更优选小于30ppm和特别是小于20ppm。这可以如下来实现:通过聚乙烯醇缩醛适当的清洗加工和通过使用特别有效的防结块剂例如本领域技术人员已知的有机酸的镁、钙和/或锌盐(例如乙酸盐)。
基于聚乙烯醇缩醛的膜的基本生产和组成描述在例如EP185863B1,EP1118258B1,WO02/102591A1,EP1118258B1或者EP387148B1中。
光电模块的层压是通过熔合所述膜来进行的,使得用所述膜获得了无气泡的和无波纹地包封光敏半导体层。
在本发明光电模块的一种变型方案中,将光敏半导体层施加到覆盖层d)(例如通过蒸发、气相沉积、溅射或者湿沉积)上并通过膜c)与所述覆盖层a)相粘合。
备选地,该光敏半导体层可以嵌入到两个膜c)之间,并且以此方式与覆盖层a)和d)相粘合。
该基于聚乙烯醇缩醛的包含增塑剂的膜的厚度通常是0.38,0.51,0.76,1.14,1.52或者2.28mm。
在层压加工过程中,本发明所用的膜填充了存在于光敏半导体层或者其电连接线路的空隙。
透明的前覆盖层a)通常由玻璃或者PMMA组成。本发明光电模块的后覆盖层(所谓的背片)a)可以由玻璃、塑料或者金属或者其复合材料组成,其中至少一个载体可以是透明的。还可以将所述覆盖层的一个或者两个设计成复合玻璃(即,作为由至少两个玻璃板和至少一个PVB膜制成的层压制件)或者作为带有气体间隙的绝缘玻璃板。当然,这些措施的组合也是可能的。
模块中所用的光敏半导体层不必具有任何特定的性能。可以使用单晶,多晶或者无定形体系。
在薄膜太阳能模块的情况中,将光敏半导体层直接施加到载体上。这里封装是不可能的。因此,层合件()是由载体(例如后覆盖层)与光敏半导体层和透明的前覆盖层,使用至少一个夹入其中的本发明的基于聚乙烯醇缩醛的包含增塑剂的膜,并且依靠这种膜在升高温度下粘合来组装的。备选地,光敏半导体层可以施加到作为载体的透明前覆盖层上,并且依靠至少一个夹入其中的本发明的基于包含增塑剂的聚乙烯醇缩醛的膜来粘合到后覆盖层上。
为了层压这样获得的层合件,可以使用本领域技术人员已知的方法,进行或者不进行预制复合件的预先制备。
所谓的高压釜方法是在大约10-15bar的升高压力和130-145℃的温度在大约2小时的期间进行的。真空袋或者真空环方法(例如根据EP1235683B1)在大约200mbar和130-145℃运行。
真空层压机优选用于生产本发明的光电模块。它们由可加热的和可排空的腔室组成,其中复合玻璃可以层压30-60分钟。0.01-300mbar的减压和100-200℃,特别是130-160℃的温度已经被证实在实践中具有价值。
备选地,如上所述组装的层合件可以在至少一对60-150℃温度的辊子之间压制成本发明的模块。这种装置是复合玻璃生产中已知的,并且通常具有至少一个加热通道,该通道处于具有两个挤压设备的装置的第一挤压设备的上游或者下游。
本发明另外一个主题是基于聚乙烯醇缩醛的包含增塑剂的膜用于生产光电模块的用途,其中该聚乙烯醇缩醛的聚乙烯醇含量少于20重量%。
本发明的光电模块可以用作房屋立面元件,屋顶区域,温室遮盖物,隔音壁,阳台或者栏杆元件,或者作为窗户区域的部件。
测量方法
所述膜的玻璃化转变温度的测量是依靠动态差示扫描量热法(DSC),根据DIN53765,使用10K/min的加热速率,在-50℃到150℃的温度间隔内进行的。使用第一加热爬坡,随后是冷却爬坡,随后是第二加热爬坡。玻璃化转变温度的位置是由与根据DIN51007的第二加热爬坡相关的测量曲线来确定的。该DIN中点(Tg DIN)定义为水平线在半步幅高度与测量曲线的交叉点。该步幅高度是通过在玻璃化转变之前和之后,与测量曲线的基线中间相切的两个交叉点的垂直距离来定义的。
所述膜流动行为的测量是作为熔融流动指数(熔体质量流动速率:MFR),根据ISO1133,在合适的仪器例如来自公司的MI2型号仪器上进行的。该MFR值规定为在100℃和140℃,使用2mm喷嘴和21.6kg的重量负载时的每10分钟的克数(g/10min)。
所述膜的容积电阻系数的测量是根据DIN IEC 60093,在规定的温度和环境湿度(23℃和85%相对空气湿度),在该膜已经在这些条件下整理了至少24h之后进行的。为了进行该测量,使用来自Fetronic GmbH公司的型号为302132的平板电极和来自Amprobe公司的电阻测量仪ISO-Digi 5kV。测量电压是2.5kV,施加测试电压之后直到获得测量数据的等待时间是60秒。为了保证测量电极的平板与膜之间足够的接触,当根据DIN EN ISO 4287测量时,所述膜的表面粗糙度Rz应当不大于10μm;即,在测量电阻系数,任选地,PVB膜的初始表面必须通过热再模压来光滑化。
聚乙烯醇缩醛的聚乙烯醇和聚乙酸乙烯酯含量是根据ASTM D1396-92来测量的。金属离子含量的分析是依靠原子吸收光谱(AAS)来进行的。
所述膜的含水量或者含水量是通过卡尔-费歇尔(Karl Fischer)方法来测量的。为了模拟在潮湿条件下的润湿行为,将所述膜预先在23℃和85%相对湿度存储24h。该方法可以在未层压的膜和层压的光电模块二者上进行,具体取决于到膜边缘的距离。
实施例
生产下表所列出的组成的混合物,并且测试玻璃化转变温度Tg,离子含量,增塑剂含量和电阻。
3G8表示三甘醇-双-2-乙基己酸酯
DOS表示二-2-乙基己基癸二酸酯
DOA表示二-2-乙基己基己二酸酯
DOP表示二-2-乙基己基邻苯二甲酸酯
DHA表示二己基己二酸酯
DBS表示二丁基癸二酸酯
DBES表示二-2-丁氧基乙基癸二酸酯
DINCH表示1,2-环己烷二羧酸二异壬基酯
很显然在所用的PVB中具有高聚乙烯醇含量的标准膜(对比例1-对比例6)表现出对于光伏应用来说过低的阻抗。
减少PVB中聚乙烯醇含量(实施例1-20)导致了电阻系数的明显增加。除了增加流动性之外,这可以通过使用低极性增塑剂来进一步提高。
此外,依靠增塑剂的选择和含量,可以获得这样的具有一般大于20℃的Tg的膜,该膜具有对于太阳能电池或者电路的封装来说足够的柔性。
Claims (10)
1.光电模块,其包含由下列组成的层压制件:
a)透明的前覆盖层
b)一个或多个光敏半导体层
c)至少一个基于聚乙烯醇缩醛的包含增塑剂的膜,和
d)后覆盖层,
特征在于该聚乙烯醇缩醛的聚乙烯醇含量小于20重量%。
2.根据权利要求1的光电模块,特征在于该基于聚乙烯醇缩醛的包含增塑剂的膜c)的增塑剂含量最大为26重量%。
3.根据权利要求1或2的光电模块,特征在于基于聚乙烯醇缩醛的包含增塑剂的膜c)的玻璃化转变温度Tg至少为20℃。
4.根据权利要求1或2的光电模块,特征在于该聚乙烯醇缩醛的聚乙酸乙烯酯含量小于5重量%。
5.根据权利要求1或2的光电模块,特征在于作为增塑剂使用这样的一种或多种化合物,该化合物用式100xO/(C+H)表示的极性小于/等于9.4,其中O、C和H表示在各自分子中的氧、碳和氢原子的数目。
6.根据权利要求1或2的光电模块,特征在于将选自下面的一种或多种化合物用作增塑剂:二-2-乙基己基癸二酸酯、二-2-乙基己基己二酸酯、二-2-乙基己基邻苯二甲酸酯、二己基己二酸酯、二丁基癸二酸酯、二-2-丁氧基乙基癸二酸酯、1,2-环己烷二羧酸二异壬基酯和三甘醇-双-2-乙基己酸酯。
7.根据权利要求1或2的光电模块,特征在于该基于聚乙烯醇缩醛的包含增塑剂的膜包含小于50ppm的金属离子。
8.根据权利要求1或2的光电模块,特征在于该基于聚乙烯醇缩醛的包含增塑剂的膜包含0.001-5重量%的SiO2。
9.根据权利要求1或2的光电模块,特征在于将聚乙烯醇缩丁醛用作聚乙烯醇缩醛。
10.基于聚乙烯醇缩醛的包含增塑剂的膜用于生产光电模块的用途,其中该聚乙烯醇缩醛的聚乙烯醇含量小于20重量%。
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Also Published As
Publication number | Publication date |
---|---|
EP2206162A2 (de) | 2010-07-14 |
CN101933160A (zh) | 2010-12-29 |
RU2010117695A (ru) | 2011-11-10 |
DE102007000818A1 (de) | 2009-04-09 |
TW200934819A (en) | 2009-08-16 |
WO2009047223A2 (de) | 2009-04-16 |
WO2009047223A3 (de) | 2010-05-27 |
JP2010541270A (ja) | 2010-12-24 |
JP5832092B2 (ja) | 2015-12-16 |
TWI457391B (zh) | 2014-10-21 |
US20100193024A1 (en) | 2010-08-05 |
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