CN102047442B - 具有低雾度包封层的太阳能电池模块 - Google Patents
具有低雾度包封层的太阳能电池模块 Download PDFInfo
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- CN102047442B CN102047442B CN200980120296.8A CN200980120296A CN102047442B CN 102047442 B CN102047442 B CN 102047442B CN 200980120296 A CN200980120296 A CN 200980120296A CN 102047442 B CN102047442 B CN 102047442B
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- solar cell
- carboxylic acid
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- sodium ionomer
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- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10743—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing acrylate (co)polymers or salts thereof
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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Abstract
本发明公开了一种太阳能电池模块，所述太阳能电池模块包括太阳能电池层和包含至少一个钠离聚物组合物层的片材，其中所述钠离聚物组合物基本上由钠离聚物组成，所述钠离聚物为前体α-烯烃羧酸共聚物的离子中和衍生物，其中存在于所述前体α-烯烃羧酸共聚物中的羧酸基团总含量的约10％至约35％已被钠离子中和，并且其中所述前体α-烯烃羧酸共聚物包含(i)具有2至10个碳原子的α-烯烃的共聚单元和(ii)按所述α-烯烃羧酸共聚物的总重量计为约20至约25重量％的具有3至8个碳原子的α，β-烯键式不饱和羧酸的共聚单元。
Description
发明领域
本发明涉及具有表现出低雾度的包封片层的太阳能电池模块。具体地讲，本发明涉及包括包封片材的太阳能电池模块，其中该包封片材包含至少一个钠离聚物组合物层。
发明背景
由于太阳能电池可提供可持续能源，因此其使用范围正在迅速扩大。根据所采用的光吸收材料，太阳能电池通常可分为两种，即，块状或晶片太阳能电池和薄膜太阳能电池。
单晶硅(c-Si)、多晶硅(poly-Si或mc-Si)和带状硅是用来形成较为传统的晶片太阳能电池的最常用材料。源自晶片太阳能电池的太阳能电池模块通常包括焊接在一起的一系列自承晶片(或电池)。这些晶片通常具有介于约180μm和约240μm之间的厚度。此类太阳能电池板称为太阳能电池层，并且其还可以包括电线，诸如连接各个电池单元的交叉带状线和一端连接至电池而另一端伸出模块的汇流条。然后，再将太阳能电池层层压到一个或多个包封层和一个或多个保护层上，从而形成可以最多使用25至30年的耐候性模块。一般来讲，源自一个或多个晶片太阳能电池的太阳能电池模块按从前受光面到后非受光面的位置顺序包括：(1)入射层，(2)前包封层，(3)太阳能电池层，(4)后包封层和(5)背衬层。
日益重要的可供选择的薄膜太阳能电池由通常由包括非晶硅(a-Si)、微晶硅(μc-Si)、碲化镉(CdTe)、铜铟硒化物(CuInSe2或CIS)、铜铟/镓二硒化物(CuInxGa(1-x)Se2或CIGS)、光吸收染料、以及有机半导体的材料形成。举例而言，薄膜太阳能电池公开于例如美国专利5,507,881、5,512,107、5,948,176、5,994,163、6,040,521、6,137,048和6,258,620以及美国专利公布20070298590、20070281090、20070240759、20070232057、20070238285、20070227578、20070209699和20070079866。通过将半导体层沉积到由玻璃或柔性膜形成的覆板或基板上来制备通常具有小于2μm的厚度的薄膜太阳能电池。制造过程通常包括激光划片工序，该工序能够使相邻的电池直接相互串联，而不需要在电池之间进行进一步焊料连接。与晶片电池一样，太阳能电池层还可包括诸如交叉带状线和汇流条的电线。同样地，再将薄膜太阳能电池层压到其他包封层和保护层上以制备耐候性和耐环境性模块。根据进行多层沉积的顺序，可将薄膜太阳能电池沉积到在最终模块中最终用作入射层的覆板上，或者可将电池沉积到在最终模块中最终用作背衬层的基板上。因此，源自薄膜太阳能电池的太阳能电池模块可具有两类构造中的一种。第一类构造按从前受光面到后非受光面的位置顺序包括：(1)太阳能电池层，其包括覆板和在非受光面处沉积在其上的一个或多个薄膜太阳能电池层；(2)(后)包封层；和(3)背衬层。第二类构造按从前受光面到后非受光面的位置顺序包括：(1)入射层；(2)(前)包封层；(3)太阳能电池层，其包括在其受光面处沉积在基板上的一个或多个薄膜太阳能电池层。
用于太阳能电池模块中的包封层被设计用于包封和保护易碎的太阳能电池。用于太阳能电池包封层的合适的聚合物材料通常具有以下特性的组合，诸如高抗冲击性、高耐穿透性、良好的耐紫外线(UV)性、良好的长期热稳定性、对玻璃和其他刚性聚合物片材具有足够的粘附强度、高防潮性以及良好的长期耐侯性。此外，前包封层应足够透明以使阳光可有效到达太阳能电池，从而使太阳能电池产生可能的最高功率输出。因此，非常期望用于前包封层的聚合物材料呈现出低雾度和高透明度的组合。
离聚物为通过使前体(也称为“母体”)酸共聚物酸部分的氢原子部分或完全由离子部分取代而制备的聚合物。这通常通过中和母体酸共聚物，例如包含α-烯烃和α，β-烯键式不饱和羧酸的共聚单元的共聚物来实现。存在于此类母体或前体共聚物中的羧酸基团的中和通常通过使共聚物与碱(例如氢氧化钠或氢氧化镁)反应来实现，通过该反应使得羧酸的氢原子被碱的阳离子取代。由此形成的离聚物为完全或部分中和的离子组合物，其包含具有源自羧酸与碱反应的阳离子的羧酸盐基团。离聚物在本领域中为人们所熟知，此类物质包括这样的聚合物：其中离聚物羧酸盐基团的阳离子为金属阳离子，包括碱金属阳离子、碱土金属阳离子以及过渡金属阳离子。可商购获得的离聚物包括具有钠阳离子、镁阳离子、铝阳离子、锌阳离子和铁阳离子的那些。
将离聚物组合物用作层压安全玻璃中的夹层在本领域中是已知的。参见例如美国专利3,344,014、3,762,988、4,663,228、4,668,574、4,799,346、5,759,698、5,763,062、5,895,721、6,150,028和6,432,522；美国专利公布20020155302、20020155302、20060182983、20070092706、20070122633、20070289693；以及PCT专利公布WO9958334、WO2006057771和WO2007149082。
近年来，还开发了某些离聚物组合物作为太阳能电池包封材料。参见例如美国专利5,476,553、5,478,402、5,733,382、5,741,370、5,762,720、5,986,203、6,114,046、6,187,448、6,353,042、6,320,116和6,660,930；以及美国专利公布20030000568和20050279401。例如，美国专利5,476,553公开了将尤其是诸如Surlyn1601树脂的钠离聚物用作包封材料。美国专利6,114,046公开了可用作包封材料的多层茂金属聚烯烃/离聚物层压结构。描述了多种类型的离聚物，包括钠离聚物和锌离聚物。
目前使用的离聚物包封材料以及本领域中所公开的那些包封材料的透明性并非最佳。期望存在具有更高透明性的可用离聚物组合物，从而使制备能够产生更高功率输出的太阳能电池成为可能。
发明概述
本发明提供太阳能电池模块，其包括太阳能电池层和包含至少一个钠离聚物组合物层的片材，其中(a)太阳能电池层选自包括单个太阳能电池的太阳能电池层和包括多个电互连太阳能电池的太阳能电池层；(b)该太阳能电池层具有受光面和非受光面；并且(c)钠离聚物组合物基本上由钠离聚物组成，该钠离聚物为前体α-烯烃羧酸共聚物的离子中和衍生物，其中存在于前体α-烯烃羧酸共聚物中的羧酸基团总含量的约10％至约35％已被钠离子中和，并且其中前体α-烯烃羧酸共聚物包含(i)具有2至10个碳原子的α-烯烃的共聚单元和(ii)具有3至8个碳原子的α，β-烯键式不饱和羧酸的共聚单元，其按α-烯烃羧酸共聚物的总重量计为约20至约25重量％。
在一个特定实施方案中，太阳能电池模块按位置顺序基本上由以下各层组成：(i)入射层；(ii)层压到太阳能电池层受光面上的前包封层；(iii)太阳能电池层；(iv)层压到太阳能电池层非受光面上的后包封层；以及(v)背衬层，其中前包封层和后包封层为包含钠离聚物组合物的片材。
在另一个实施方案中，太阳能电池模块按位置顺序基本上由以下各层组成：(i)入射层；(ii)前包封层，其包括具有至少一个钠离聚物组合物层的片材；和(iii)薄膜太阳能电池层，其中太阳能电池层还包括薄膜太阳能电池沉积在其上的基板，并且该基板被定位在太阳能电池层的非受光面上，使其成为模块的最外表面。
在另一个实施方案中，太阳能电池模块按位置顺序基本上由以下各层组成：(i)薄膜太阳能电池层；(ii)后包封层，其包括具有至少一个钠离聚物组合物层的片材；和(iii)背衬层，其中太阳能电池层还包括薄膜太阳能电池沉积在其上的覆板，并且该覆板被定位在太阳能电池层的受光面上，使其成为模块的最外表面。
本发明还提供了制备太阳能电池模块的方法，其包括：
(i)提供组合件，其包括太阳能电池层和具有至少一个钠离聚物组合物层的片材，其中(a)太阳能电池层选自包括单个太阳能电池的太阳能电池层和包括多个电互连太阳能电池的太阳能电池层；(b)该太阳能电池层具有受光面和非受光面；并且(c)钠离聚物组合物基本上由钠离聚物组成，该钠离聚物为前体α-烯烃羧酸共聚物的离子中和衍生物，其中存在于前体α-烯烃羧酸共聚物中的羧酸基团总含量的约10％至约35％已被钠离子中和，并且其中前体α-烯烃羧酸共聚物包含(i)具有2至10个碳原子的α-烯烃的共聚单元和(ii)具有3至8个碳原子的α，β-烯键式不饱和羧酸的共聚单元，其按α-烯烃羧酸共聚物的总重量计为约20至约25重量％；以及
(ii)层压该组合件，形成太阳能电池模块。
附图简述
图1为本文公开的晶片太阳能电池模块的剖面图(未按比例绘制)。
图2为本文公开的一个特定薄膜太阳能电池模块的剖面图(未按比例绘制)。
图3为本文所开的另一个薄膜太阳能电池模块的剖面图(未按比例绘制)。
发明详述
除非另有定义，本文所用的所有技术和科学术语的含义与本发明所属领域的普通技术人员所普遍理解的含义相同。如发生矛盾，以本说明书所包括的定义为准。
虽然与本文所述方法和材料类似或等同的方法和材料均可用于本发明的实践或检验，但合适的方法和材料是如本文所述的那些。
除非另行指出，否则所有百分数、份数、比率等均按重量计。
当数量、浓度或其他数值或参数以范围、优选范围或优选上限数值和优选下限数值的列表形式给出时，其应理解为具体地公开由任何范围上限或优选数值和任何范围下限或优选数值的任何一对所构成的所有范围，而不管所述范围是否被单独地公开。凡在本文中给出某一数值范围之处，该范围都旨在包括其端点，以及位于该范围内的所有整数和分数，除非另行说明。当定义一个范围时，不希望将本发明的范围限定于所列举的具体数值。
当术语“约”用于描述值或范围的端点时，本公开内容应被理解为包括具体的值或所涉及的端点。
如本文所用，术语“包含”、“包括”、“含有”、“特征在于”、“具有”或者它们的任何其他变型均旨在涵盖非排他性的包括。例如，包括要素列表的工艺、方法、制品、或设备不必只限于这些要素，还可包括其他没有明确列出的或此类工艺、方法、制品、或设备固有的要素。此外，除非另有明确的相反说明，“或”是指包含性的“或”而不是指排他性的“或”。
连接短语“基本上由…组成”将权利要求的范围限制为具体的材料或步骤以及不会显著影响受权利要求保护的本发明的基本和新型特征的那些要素。
当申请人用诸如“包括/包含”的开放式术语定义本发明或其一部分时，应容易理解，本说明书应被解释为也使用术语“基本上由…组成”对本发明进行描述，除非另行指出。
“一个”或“一种”用于描述本发明的要素和组分。这仅出于方便考虑并给出本发明的一般性意义。此描述应被理解为包括一个或至少一个、一种或至少一种，并且单数也包括复数，除非明显地另指他意。
在描述某些聚合物时，应当理解，有时申请人提及聚合物时使用的是制备该聚合物的单体或用于制备该聚合物的单体的量。虽然此类描述可能不包括用于描述最终聚合物的具体命名或者可能不包含以方法限定产品的术语，但是对单体和量的任何此类提及均应被解释为表示聚合物包含这些单体(即，这些单体的共聚单元)或这些单体的量，以及对应的聚合物及其组合物。
在描述本发明和/或提出本发明的权利要求时，术语“共聚物”用于指由两种或更多种单体共聚所形成的聚合物。此类共聚物包括二聚物、三元共聚物或更高阶共聚物。
如本文所用，术语“酸共聚物”是指包含α-烯烃、α，β-烯键式不饱和羧酸、和任选地其他合适的共聚单体(例如α，β-烯键式不饱和羧酸酯)的共聚单元的聚合物。
如本文所用，术语“离聚物”是指包含离子基团的聚合物，其中离子基团为金属离子羧酸盐，例如碱金属羧酸盐、碱土金属羧酸盐、过渡金属羧酸盐和/或此类羧酸盐的混合物。如本文所定义，此类聚合物通常通过部分或完全中和(例如通过与碱反应)前体或“母体”聚合物的羧酸基团来制备，其中前体或“母体”聚合物为酸共聚物。本文所用碱金属离聚物的实例为钠离聚物(或钠中和的离聚物)，例如乙烯和甲基丙烯酸的共聚物，其中共聚化的甲基丙烯酸单元的羧酸基团的全部或一部分为羧酸钠形式。
本发明提供太阳能电池模块，该太阳能电池模块包括a)至少一个为片材的层，该片材包括至少一个钠离聚物组合物层；和b)由一个或多个太阳能电池构成的太阳能电池层。片材用作太阳能电池模块中的包封层。也就是说，本发明的太阳能电池模块的特征在于具有包封层，该包封层具有至少一个钠离聚物组合物层。
本文所用的钠离聚物组合物基本上由钠离聚物组成，这些钠离聚物为前体酸共聚物的离子中和衍生物，其中该前体酸共聚物包含具有2至10个碳原子的α-烯烃的共聚单元，以及约20至约25重量％，或优选约21至约23重量％的具有3至8个碳原子的α，β-烯键式不饱和羧酸的共聚单元。
合适的α-烯烃共聚单体可包括但不限于乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、3-甲基-1-丁烯、4-甲基-1-戊烯等、以及它们中的两种或更多种的混合物。优选地，α-烯烃为乙烯。
合适的α，β-烯键式不饱和羧酸共聚单体可以包括但不限于丙烯酸、甲基丙烯酸、衣康酸、马来酸、马来酸酐、富马酸、单甲基马来酸以及它们中的两种或更多种的混合物。优选地，α，β-烯键式不饱和羧酸选自丙烯酸、甲基丙烯酸以及它们中的两种或更多种的混合物。
前体酸共聚物还可包含一个或多个其他共聚单体的共聚单元，该一个或多个其他共聚单体例如具有2至10个碳原子、或优选地具有3至8个碳原子的不饱和羧酸、或其衍生物。合适的酸衍生物包括酸酐、酰胺和酯。酯是优选的。不饱和羧酸的优选酯的具体实例包括但不限于：丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸异丙酯、甲基丙烯酸异丙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸异丁酯、甲基丙烯酸异丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、丙烯酸辛酯、甲基丙烯酸辛酯、丙烯酸十一酯、甲基丙烯酸十一酯、丙烯酸十八酯、甲基丙烯酸十八酯、丙烯酸十二酯、甲基丙烯酸十二酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、丙烯酸-2-羟乙基酯、甲基丙烯酸2-羟基乙酯、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、聚(乙二醇)丙烯酸酯、聚(乙二醇)甲基丙烯酸酯、聚(乙二醇)甲醚丙烯酸酯、聚(乙二醇)甲醚甲基丙烯酸酯、聚(乙二醇)山嵛醚丙烯酸酯、聚(乙二醇)山嵛醚甲基丙烯酸酯、聚(乙二醇)4-壬基苯基醚丙烯酸酯、聚(乙二醇)4-壬基苯基醚甲基丙烯酸酯、聚(乙二醇)苯基醚丙烯酸酯、聚(乙二醇)苯基醚甲基丙烯酸酯、马来酸二甲酯、马来酸二乙酯、马来酸二丁酯、富马酸二甲酯、富马酸二乙酯、富马酸二丁酯、富马酸二甲酯、乙酸乙烯酯、丙酸乙烯酯、以及它们中的两种或更多种的混合物。优选的合适共聚单体的实例包括但不限于丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸丁酯、甲基丙烯酸缩水甘油酯、乙酸乙烯酯、以及它们中的两种或更多种的混合物。然而，优选地是前体酸共聚物未掺入其他共聚单体。
前体酸共聚物可如美国专利3,404,134、5,028,674、6,500,888和6,518,365中公开的那样进行聚合。优选地，前体酸共聚物在使短链支化和长链支化最大化的工艺条件下聚合。此类工艺在以下文献中有所公开：例如P.Ehrlich和G.A.Mortimer的“Fundamentals of Free-RadicalPolymerization of Ethylene”(1970)，Adv.Polymer Sci.，第7卷第386至448页以及J.C.Woodley和P.Ehrlich的“The Free Radical，High PressurePolymerization of Ethylene II.The Evidence For Side Reactions from PolymerStructure and Number Average Molecular Weights”，J.Am.Chem.Soc.，第85卷第1580至1854页。
要获得可用于包封组件中钠离聚物组合物的钠离聚物(即，钠中和的离聚物)，需将前体酸共聚物用例如含钠离子的碱中和得到离聚物，其中前体酸羧酸基团的氢原子的约10％至约35％、或优选约15％至约30％被钠阳离子取代。也就是说，需将酸基中和至按前体酸共聚物的羧酸总含量计为约10％至约35％、或优选约15％至约30％的含量，其中该含量通过计算得到或通过测量未中和的前体酸共聚物得到。更优选和最优选的中和范围使得在片材形成过程中保持最优化的熔融流速的同时获得具有所期望的最终使用特性的离聚物片材，这些特性为本发明组合物的新特性，例如低雾度、高透明度和足够强的抗冲击性。包含除了钠之外的阳离子的离聚物可对用于本发明的包封层的透明度和低雾度特性产生不利影响。因此，优选的是离聚物组合物不包含除钠离聚物之外的其他离聚物；如果包含，则在每一百份钠离聚物组合物中含有的量小于5份。
前体酸共聚物可按例如美国专利3,404,134中公开的那样进行中和。
前体酸共聚物可以具有约60克/10分钟或更小、优选约45克/10分钟或更小，更优选约30克/10分钟或更小、最优选约25克/10分钟或更小的熔体流动速率(MFR)，其根据ASTM方法D1238在190℃和2.16kg下测得。钠离聚物优选地具有约10克/10分钟或更小，更优选约5克/10分钟或更小，并且最优选约3克/10分钟或更小的MFR。钠离聚物也可优选具有大于约40,000psi(276MPa)，更优选大于约50,000psi(345MPa)，并且最优选大于约60,000psi(414MPa)的挠曲模量，其根据ASTM方法D638测得。
相对于所期望的包含具有高羧酸含量的离聚物的离聚物片材而言，包含此类钠离聚物的聚合物片材表现出较大的韧性、较低的雾度以及较高的透明性。在不受任何具体理论束缚的情况下，据信与前体酸共聚物以及中和剂的特定阳离子(即钠)相关联的相对较低的MFR有助于改善韧性和透明性并降低雾度。美国专利公布20060182983中也公开了可用于本发明实践的一些示例性钠离聚物。
可用作聚合物片材的钠离聚物组合物还可包含不会影响片材光学性质的添加剂。例如，钠离聚物组合物可以包含这样的添加剂，其有效降低了树脂的熔融流动，并有助于制备热固性薄膜或片材，对其含量不作限制。使用此类添加剂将提高太阳能电池包封材料的最终使用温度上限，并减少材料在该温度上限时产生的蠕变。通常，最终使用温度可提高最多约20℃至约70℃。此外，包含此类材料的太阳能电池模块具有耐火性。具体地讲，通过在层压期间热固化离聚物树脂，可降低树脂熔融并流出层压板的趋势，继而减少在火灾中的可燃物。
可有效降低熔融流速的典型添加剂为有机过氧化物，诸如2，5-二甲基己烷-2，5-二氢过氧化物、2，5-二甲基-2，5-二(叔丁基过氧)己烷-3、二叔丁基过氧化物、过氧化叔丁基异丙苯、2，5-二甲基-2，5-二(叔丁基过氧)己烷、过氧化二异丙苯、α，α’-双(叔丁基过氧异丙基)苯、正丁基-4，4-双(叔丁基过氧)戊酸酯、2，2-双(叔丁基过氧)丁烷、1，1-双(叔丁基过氧)环己烷、1，1-双(叔丁基过氧)-3，3，5-三甲基-环己烷、叔丁基过氧苯甲酸酯、过氧化苯甲酰等、以及它们的混合物组合。优选地，有机过氧化物在约100℃或更高的温度下分解生成自由基。更优选地，有机过氧化物具有的分解温度应足够高，使其在约70℃或更高的温度下保持10小时后仍有一半量未分解，以改善其在共混操作中的稳定性。可将有机过氧化物以按钠离聚物组合物的总重量计为约0.01至约10重量％、或优选约0.5至约3重量％的量添加。
如果需要，诸如二月桂酸二丁基锡的引发剂还可以按钠离聚物组合物的总重量计约0.01至约0.05重量％的含量存在于离聚物组合物中。此外，如果需要，可添加诸如氢醌、氢醌单甲醚、对苯醌和甲基氢醌的引发剂，用于增强对反应和稳定性的控制。通常，引发剂可以按组合物的总重量计小于约5重量％的含量添加。
然而，为使工艺简便起见，优选地是钠离聚物组合物不掺入诸如上述过氧化物之类的交联添加剂。
钠离聚物组合物也可以包含本领域中已知的其他添加剂。这些添加剂可以包括但不限于加工助剂、流动增强剂、润滑剂、颜料、染料、阻燃剂、抗冲改性剂、成核剂、诸如二氧化硅的抗粘连剂、热稳定剂、紫外线吸收剂、紫外线稳定剂、分散剂、表面活性剂、螯合剂、偶联剂、诸如玻璃纤维的增强剂、填料等。一般来讲，将可降低组合物光学透明度的添加剂(诸如增强剂和填料)仅加入用作后包封的那些片材。
可使用热稳定剂，其在本领域中已广泛公开。任何已知的热稳定剂均可用于本发明。热稳定剂的优选普通种类包括但不限于酚类抗氧化剂、烷基化一元酚、烷硫基甲基苯酚、对苯二酚、烷基化对苯二酚、生育酚、羟基化硫代二苯醚、亚烷基双酚、O-、N-和S-苄基化合物、羟基苄基化丙二酸酯、芳香羟基苄基化合物、三嗪化合物、氨基酸类抗氧化剂、芳基胺、二芳基胺、聚芳基胺、酰氨基酚、草酰胺、金属减活化剂、亚磷酸盐、亚膦酸盐、苄基膦酸盐、抗坏血酸(维生素C)、清除过氧化物的化合物、羟胺、硝酮、硫代增效剂、苯并呋喃酮、吲哚酮等、以及它们的混合物。钠离聚物组合物可以包含任意有效量的热稳定剂。热稳定剂的使用是任选的，并且在某些情况下不是优选的。使用热稳定剂时，钠离聚物组合物包含按离聚物组合物的总重量计至少约0.05重量％，最多约10重量％，更优选最多约5重量％，并且最优选最多约1重量％的热稳定剂。
可使用紫外线吸收剂，其在本领域中也已广泛公开。任何已知的紫外线吸收剂均可用于本发明。紫外线吸收剂的优选普通种类包括但不限于苯并三唑、羟基二苯甲酮、羟基苯基三嗪、取代的和未取代的苯甲酸的酯等、以及它们的混合物。钠离聚物组合物可以包含任意有效量的紫外线吸收剂。紫外线吸收剂的使用是任选的，并且在某些情况下不是优选的。使用紫外线吸收剂时，钠离聚物组合物包含按离聚物组合物的总重量计至少约0.05重量％，最多约10重量％，更优选最多约5重量％，并且最优选最多约1重量％的紫外线吸收剂。
可使用受阻胺光稳定剂(HALS)，其在本领域中也已广泛公开。一般来讲，所公开的受阻胺光稳定剂为仲的或叔的、乙酰化的、N-烷氧基化取代的、羟基取代N-烷氧基化取代的或具有显著空间位阻效应的其他取代环胺，并且一般是得自邻近胺基的碳原子的脂族取代。钠离聚物组合物可以包含任意有效量的受阻胺光稳定剂。受阻胺光稳定剂的使用是任选的，并且在某些情况下不是优选的。使用受阻胺光稳定剂时，钠离聚物组合物包含按离聚物组合物的总重量计至少约0.05重量％，最多约10重量％，更优选最多约5重量％，并且最优选最多约1重量％的受阻胺光稳定剂。
可将硅烷偶联剂加入钠离聚物组合物中以改善其粘附强度。可用于本发明组合物的示例性硅烷偶联剂包括但不限于γ-氯丙基甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷、γ-乙烯基苄基丙基三甲氧基硅烷、N-β-(N-乙烯基苄基氨基乙基)-γ-氨基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三乙酰氧基硅烷、γ-环氧丙氧丙基三甲氧基硅烷、γ-环氧丙氧丙基三乙氧基硅烷、β-(3，4-环氧环己基)乙基三甲氧基硅烷、乙烯基三氯硅烷、γ-巯丙基甲氧基硅烷、γ-氨基丙基三乙氧基硅烷、N-β-(氨基乙基)-γ-氨基丙基三甲氧基硅烷、以及它们中的两种或更多种的混合物。优选将硅烷偶联剂以按离聚物组合物的总重量计约0.01至约5重量％，或更优选约0.05至约1重量％的含量掺入钠离聚物组合物中。
用作本发明太阳能电池模块的一个组件的片材可以为单层形式或多层形式。所谓“单层”是指该片材由钠离聚物组合物制成或基本上由其组成。当片材为多层形式时，至少一个亚层由钠离聚物组合物制成或基本上由其组成，而其他一个或多个亚层可由合适的其他任何一种或多种聚合材料制成，诸如本文前定义的酸共聚物、本文之前定义的离聚物、聚(乙烯乙酸乙烯酯)、聚(乙烯醇缩醛)(包括隔音级聚(乙烯醇缩醛))、聚氨酯、聚氯乙烯、聚乙烯(如线性低密度聚乙烯)、聚烯烃嵌段弹性体、α-烯烃与α，β-烯键式不饱和羧酸酯的共聚物(如乙烯丙烯酸甲酯共聚物和乙烯丙烯酸丁酯共聚物)、硅氧烷弹性体、环氧树脂、以及它们中的两种或更多种的组合。
包含至少一个钠离聚物组合物层的片材的总厚度可以在约10至约90密尔(约0.25至约2.3mm)的范围内、优选约10至约60密尔(约0.25至约1.5mm)，更优选约15至约55密尔(约0.38至约1.4mm)，更优选约15至约45密尔(约0.38至约1.14mm)，还更优选约15至约35密尔(约0.38至约0.89mm)，并且最优选约25至约35密尔(约0.64至约0.89mm)。组成总的多层包封层的各薄膜和片材组分的厚度并不重要，其可根据具体应用而独立地变化。
包含钠离聚物组合物的片材在一侧或两侧可以具有平滑表面或粗糙表面。优选地，该片材在两侧均具有粗糙表面以利于在层压过程中脱气。可在片材挤出过程中进行机械压花或融体破坏，然后让片材骤冷使其表面粗糙度在处理期间得以保持，通过这样的方式形成粗糙表面。可通过本领域的常用方法将表面图案施加到片材上。例如，可使刚挤出的片材从紧邻模头出口设置的模辊的特制表面上通过，从而赋予熔融聚合物的一侧所需的表面特性。因此，当此类模辊的表面具有微小的凹凸不平时，浇注在其上的聚合物片材在与辊接触的一侧上将生成粗糙表面，并且该粗糙表面上的凸起和凹陷一般分别适形于辊表面的凹陷和凸出。例如在美国专利4,035,549和美国专利公布20030124296中公开了此类模辊。
包含钠离聚物组合物的片材可通过任何合适的方法制备。例如，可通过浸涂、溶液浇注、压塑、注塑、层压、熔融挤出、吹膜、挤压涂布、串联挤压涂布或本领域技术人员知道的任何其他方法形成这些片材。优选地，通过熔融挤出、熔融共挤出、熔融挤出涂布或串联熔融挤出涂布方法形成这些片材。
本发明提供太阳能电池模块，其包括至少一个为片材的层(即包封层)，该片材包含至少一层上述钠离聚物组合物，以及由一个或多个太阳能电池构成的太阳能电池层。
术语“太阳能电池”旨在包括可将光转化为电能的任何制品。可用于本发明的太阳能电池包括但不限于晶片太阳能电池(例如单晶硅或多晶硅太阳能电池，如以上发明背景部分所述)和薄膜太阳能电池(例如非晶硅、微晶硅、碲化镉、铜铟硒或铜铟镓硒太阳能电池，如以上发明背景部分所述)。在太阳能电池层内，优选的是太阳能电池电互连和/或排列在平面中。此外，太阳能电池层还可包括电线，诸如交叉带状线和汇流条。
太阳能电池模块通常包括至少一个为片材的层，该片材包含被层压到太阳能电池层上并作为包封层的钠离聚物组合物。所谓“层压”是指在层压结构中，两个层直接(即两层之间无任何其他材料)或间接(即两层之间具有其他材料，诸如夹层或粘合剂材料)粘结。优选地，包含钠离聚物组合物的片材直接层压或粘结到太阳能电池层上。
太阳能电池模块还可包括其他包封层，这些包封层包含其他聚合材料，诸如本文之前定义的酸共聚物、本文之前定义的离聚物、聚(乙烯乙酸乙烯酯)、聚(乙烯醇缩醛)(包括隔音级聚(乙烯醇缩醛))、聚氨酯、聚(氯乙烯)、聚乙烯(如线性低密度聚乙烯)、聚烯烃嵌段弹性体、α-烯烃与α，β-烯键式不饱和羧酸酯的共聚物(如乙烯丙烯酸甲酯共聚物和乙烯丙烯酸丁酯共聚物)、硅氧烷弹性体、环氧树脂、以及它们中的两种或更多种的组合。
除了包含钠离聚物组合物的一个或多个片材之外，各包封层的厚度范围可独立地为约1密尔(0.026mm)至约120密尔(3mm)、或优选约1密尔至约40密尔(1.02mm)、或更优选约1密尔至约20密尔(0.51mm)。太阳能电池模块中所包括的任何或所有包封层可具有平滑表面或粗糙表面。优选地，这些包封层具有粗糙表面以利于在层压过程中脱气。
太阳能电池模块还可包括分别在太阳能电池模块的受光面和非受光面用作模块的一个或多个最外层的入射层和/或背衬层。
太阳能电池模块的外层，即入射层和背衬层，可源自任何合适的片材或薄膜。合适的片材可以为玻璃片材或塑料板，诸如聚碳酸酯、聚丙烯酸类、聚丙烯酸酯、环状聚烯烃(例如，乙烯降冰片烯聚合物)、聚苯乙烯(优选茂金属催化的聚苯乙烯)、聚酰胺、聚酯、含氟聚合物、或它们中的两种或更多种的组合。此外，可利用诸如铝、钢、镀锌钢之类的金属片材或陶瓷板来形成背衬层。
术语“玻璃”不仅包括窗玻璃、平板玻璃、硅酸盐玻璃、玻璃片、低铁玻璃、钢化玻璃、钢化无氧化铈玻璃和浮法玻璃，还包括彩色玻璃、特种玻璃(诸如那些包含控制太阳能加热的成分的玻璃)、镀膜玻璃(诸如那些溅射有金属(如银或氧化铟锡)以控制日照的玻璃)、电子玻璃、Toroglass、Solex
玻璃(PPG Industries(Pittsburgh，PA))和Starphire
玻璃(PPG Industries)。此类特种玻璃公开于例如美国专利4,615,989、5,173,212、5,264,286、6,150,028、6,340,646、6,461,736、和6,468,934中。然而应当理解，具体模块所选择的玻璃类型取决于其预期用途。
合适的薄膜层包含聚合物，这些聚合物包括但不限于聚酯(例如，聚(对苯二甲酸乙二醇酯)和聚(萘二甲酸乙二醇酯))、聚碳酸酯、聚烯烃(例如，聚丙烯、聚乙烯和环状聚烯烃)、降冰片烯聚合物、聚苯乙烯(例如，间同立构聚苯乙烯)、苯乙烯-丙烯酸酯共聚物、丙烯腈-苯乙烯共聚物、聚砜类(例如，聚醚砜、聚砜等)、尼龙、聚(氨基甲酸酯)、丙烯酸类、乙酸纤维素类(例如，乙酸纤维素、三醋酸纤维素等)、玻璃纸、聚(氯乙烯)(例如，聚(偏氯乙烯))、含氟聚合物(例如，聚氟乙烯、聚偏氟乙烯、聚四氟乙烯、乙烯-四氟乙烯共聚物等)、以及它们中的两种或更多种的组合。聚合物膜可以为双轴向的聚酯薄膜(优选聚(对苯二甲酸乙二醇酯)薄膜)或含氟聚合物薄膜(例如Tedlar
薄膜、Tefzel
薄膜和Teflon
薄膜，得自E.I.du Pont de Nemours and Company(DuPont)(Wilmington，DE))。就某些应用而言，含氟聚合物-聚酯-含氟聚合物(例如“TPT”)薄膜也是优选的。诸如铝箔之类的金属薄膜也可用作背衬层。
太阳能电池模块还可包括嵌入模块内的其他功能薄膜或片材层(例如，介电层或阻挡层)。此类功能层可源自任何上述聚合物膜或涂覆有其他功能涂层的那些。例如，涂覆有金属氧化物涂层的聚(对苯二甲酸乙二醇酯)薄膜(诸如美国专利6,521,825和6,818,819以及欧洲专利EP1182710中公开的那些)可以用作层压板中的氧气和水分阻挡层。
如果需要，太阳能电池层和包封材料之间还可存在一层非织造玻璃纤维(稀松布)，以利于在层压过程中脱气或起到加强包封材料的作用。例如美国专利5,583,057、6,075,202、6,204,443、6,320,115和6,323,416以及欧洲专利EP0769818中公开了此类稀松布层的用途。
设置在太阳能电池层受光面上的薄膜或片材层优选地由透明材料制成以使阳光有效透射到太阳能电池内。太阳能电池层的受光面有时可称为正面，并且在实际使用条件下通常面向光源。太阳能电池层的非受光面有时可称为下面或背面，并且在实际使用条件下通常背离光源。可以包括特殊的薄膜或片材以同时起到包封层和外层的作用。还可以想到，模块中包括的任何薄膜或片材层可为预成形的单层或多层薄膜或片材的形式。
如果需要，可在层压工序前对并入太阳能电池模块内的入射层薄膜和片材、背衬层薄膜和片材、包封层和其他层的一个表面或两个表面进行处理，以增强它们对其他层压层的粘附力。这种粘附力增强处理可采用本领域已知的任何形式，包括火焰处理(参见例如美国专利2,632,921、2,648,097、2,683,894和2,704,382)、等离子处理(参见例如美国专利4,732,814)、电子束处理、氧化处理、电晕放电处理、化学处理、铬酸处理、热空气处理、臭氧处理、紫外线处理、喷砂处理、溶剂处理、以及它们中的两种或更多种的组合。而且，还可通过将粘合剂或底漆涂层涂覆在一个或多个层压层的表面上来使粘附强度得到进一步改善。例如，美国专利4,865,711公开了具有改善的可粘结性的薄膜或片材，它们的一个或两个表面上沉积有薄的碳层。其他示例性粘合剂或底漆可以包括硅烷、聚(烯丙胺)基底漆(参见例如美国专利5,411,845、5,770,312、5,690,994和5,698,329)，以及丙烯酸基底漆(参见例如美国专利5,415,942)。粘合剂或底漆涂层可以呈粘合剂或底漆的单层形式并具有约0.0004至约1密尔(约0.00001至约0.03mm)，或优选约0.004至约0.5密尔(约0.0001至约0.013mm)，或更优选约0.004至约0.1密尔(约0.0001至约0.003mm)的厚度。
在一个特定实施方案(现在参见图1)中，其中太阳能电池源自晶片型自承太阳能电池单元，太阳能电池模块(20)按从前受光面到后非受光面的位置顺序包括：(a)入射层(10)；(b)前包封层(12)；(c)由一个或多个电互连的太阳能电池构成的太阳能电池层(14)；(d)后包封层(16)；和(e)背衬层(18)，其中前包封层和后包封层(12和16)的至少一者或两者包括由钠离聚物组合物构成的片材。
然而，优选地是太阳能电池模块源自薄膜太阳能电池，并且可以(i)在一个实施方案中(图2中30)按从前受光面到后非受光面的位置顺序包括：(a)太阳能电池层(14a)，其包括覆板(24)和在非受光面处沉积在其上的一个或多个薄膜太阳能电池层(22)；(b)包含构成片材的钠离聚物组合物的(后)包封层(16)；和(c)背衬层(18)，或(ii)在更优选的实施方案(图3中40)中，包括：(a)透明入射层(10)；(b)包括钠离聚物组合物构成的片材的(前)包封层(12)；和(c)太阳能电池层(14b)，其包括在其受光面处沉积在基板(26)上的一个或多个薄膜太阳能电池层(22)。
此外，可将上述一系列太阳能电池模块进一步连接以形成太阳能电池阵列，这可产生期望的电压和电流。
可以使用本领域内已知的任何层压方法(诸如热压方法或非热压方法)来制备太阳能电池模块。
在示例性工艺中，太阳能电池模块的组件层以期望的次序层叠在一起以形成预层压组合件。然后，将该组合件置于能够维持真空的袋子(“真空袋”)中，通过真空管线或其他装置将空气从袋子中抽出，在保持真空(例如，至少约27至28英寸汞柱(689至711毫米汞柱))的同时密封袋子，随后将密封袋置于压力为约150至约250psi(约11.3至约18.8巴)，温度为约130℃至约180℃、或约120℃至约160℃、或约135℃至约160℃、或约145℃至约155℃的高压釜中保持约10至约50分钟、或约20至约45分钟、或约20至约40分钟、或约25至约35分钟。可以用真空环代替真空袋。美国专利3,311,517公开了一种合适的真空袋。在加热和加压循环后，在不添加额外气体维持高压釜中压力的情况下使高压釜中的空气冷却。冷却约20分钟后，释放高压釜中过量气体并将层压板移出高压釜。
作为另外一种选择，可将预层压组合件置于烘箱中在约80℃至约120℃、或约90℃至约100℃的温度下加热约20至约40分钟，然后使加热后的组合件通过一组夹辊，通过这种方式挤出各层之间空隙内的空气、并密封组合件的边缘。此阶段的组合件称为预压件。
然后可将预压件置于高压釜中，使釜中空气的温度升至约120℃至约160℃、或约135℃至约160℃，压力为约100至约300psi(约6.9至约20.7巴)、或优选约200psi(13.8巴)。这些条件维持约15至约60分钟、或约20至约50分钟后，在不引入额外空气的情况下使高压釜中的空气冷却。冷却约20至约40分钟后，释放高压釜中过量气体并将层压产品移出高压釜。
还可通过非热压方法制备太阳能电池模块。例如美国专利3,234,062、3,852,136、4,341,576、4,385,951、4,398,979、5,536,347、5,853,516、6,342,116和5,415,909、美国专利公布20040182493、欧洲专利EP1235683B1、以及PCT专利公布WO9101880和WO03057478中公开了此类非热压方法。一般来讲，非热压方法包括加热预层压组合件并施加真空、压力或共同施加两者。例如，可使组合件相继通过加热烘箱和夹辊。
层压方法的这些实例并不旨在进行限制。基本上可以使用任何层压方法。
如果需要，可通过本领域公开的任何方式密封太阳能电池模块的边缘，以减少水分和空气侵入并使一个或多个太阳能电池效率下降和使用寿命缩短的潜在趋势减缓。合适的边缘密封材料包括但不限于丁基橡胶、多硫化物、硅酮、聚氨酯、聚丙烯弹性体、聚苯乙烯弹性体、嵌段弹性体、苯乙烯-乙烯-丁烯-苯乙烯(SEBS)等。
下面通过特定实施方案的实施例对本发明做进一步说明。
实施例
以下实施例旨在示例说明本发明，而并不旨在以任何方式限制本发明的范围。
材料和方法
离聚物树脂：
·离聚物A：乙烯和甲基丙烯酸共聚物的离聚物，其包含15重量％的甲基丙烯酸共聚单元，17％被锌离子中和，并具有5.9克/10分钟的MFR(根据ASTM D1238在190℃、2.16kg下测定)。前体乙烯甲基丙烯酸共聚物在中和前的MFR为25克/10分钟(190℃，2.16kg)。
·离聚物B：乙烯和甲基丙烯酸共聚物的离聚物，其包含21.7重量％的甲基丙烯酸共聚单元，15％被锌离子中和，并具有5.4克/10分钟的MFR(190℃，2.16kg)。前体乙烯甲基丙烯酸共聚物在中和前的MFR为23克/10分钟(190℃，2.16kg)。
·离聚物C：乙烯和甲基丙烯酸共聚物的离聚物，其包含21.7重量％的甲基丙烯酸共聚单元，15％被钠离子中和，并具有3.4克/10分钟的MFR(190℃，2.16kg)。前体乙烯甲基丙烯酸共聚物在中和前的MFR为23克/10分钟(190℃，2.16kg)。
·离聚物D：乙烯和甲基丙烯酸共聚物的离聚物，其包含21.7重量％的甲基丙烯酸共聚单元，20％被钠离子中和，并具有2.3克/10分钟的MFR(190℃，2.16kg)。前体乙烯甲基丙烯酸共聚物在中和前的MFR为23克/10分钟(190℃，2.16kg)。
·离聚物E：乙烯和甲基丙烯酸共聚物的离聚物，其包含21.7重量％的甲基丙烯酸共聚单元，25％被锌离子中和，并具有1.7克/10分钟的MFR(190℃，2.16kg)。前体乙烯甲基丙烯酸共聚物在中和前的MFR为23克/10分钟(190℃，2.16kg)。
·离聚物F：乙烯和甲基丙烯酸共聚物的离聚物，其包含21.7重量％的甲基丙烯酸共聚单元，25％被钠离子中和，并具有1.5克/10分钟的MFR(190℃，2.16kg)。前体乙烯甲基丙烯酸共聚物在中和前的MFR为23克/10分钟(190℃，2.16kg)。
·离聚物G：乙烯和甲基丙烯酸共聚物的离聚物，其包含21.7重量％的甲基丙烯酸共聚单元，26％被钠离子中和，并具有1.8克/10分钟的MFR(190℃，2.16kg)。前体乙烯甲基丙烯酸共聚物在中和前的MFR为23克/10分钟(190℃，2.16kg)。
·离聚物H：乙烯和甲基丙烯酸共聚物的离聚物，其包含19重量％的甲基丙烯酸共聚单元，39％被锌离子中和，并具有4克/10分钟的MFR(190℃，2.16kg)。前体乙烯甲基丙烯酸共聚物在中和前的MFR为250克/10分钟(190℃，2.16kg)。
·离聚物I：乙烯和甲基丙烯酸共聚物的离聚物，其包含19重量％的甲基丙烯酸共聚单元，36％被锌离子中和，并具有1克/10分钟的MFR(190℃，2.16kg)。前体乙烯甲基丙烯酸共聚物在中和前的MFR为60克/10分钟(190℃，2.16kg)。
·离聚物J：乙烯和甲基丙烯酸共聚物的离聚物，其包含19重量％的甲基丙烯酸共聚单元，37％被钠离子中和，并具有2.6克/10分钟的MFR(190℃，2.16kg)。前体乙烯甲基丙烯酸共聚物在中和前的MFR为60克/10分钟(190℃，2.16kg)。
·离聚物K：乙烯和甲基丙烯酸共聚物的离聚物，其包含21.7重量％的甲基丙烯酸共聚单元，30％被钠离子中和，并具有0.9克/10分钟的MFR(190℃，2.16kg)。前体乙烯甲基丙烯酸共聚物在中和前的MFR为23克/10分钟(190℃，2.16kg)。
压片方法：
将离聚物树脂装入采用表1所示温度特征图的25mm直径的Killion挤出机中。将这些树脂挤出浇铸成聚合物片材。
表1
| 挤出机区域 | 温度(℃) |
| 给料区域 | 环境温度 |
| 区域1 | 100-170 |
| 区域2 | 150-210 |
| 区域3 | 170-230 |
| 机颈 | 170-230 |
| 模头 | 170-230 |
通过调节螺杆转速可控制聚合物通过量并使其达到最大值。该挤出机装有具有2mm标称间隙的150mm狭槽冲模。将浇铸片材装在200mm直径的抛光镀铬冷却辊上，该冷却辊的温度保持在介于10℃和15℃之间并以1至2rpm的速度旋转。然后移除标称0.76mm(0.030英寸)厚的片材并将其切割成300mm×300mm的正方形。
用于玻璃层压板的层压方法1：
用50℃的磷酸三钠(5g/l)的去离子水溶液清洗退火的玻璃片材(100×100×3mm)5分钟，然后用去离子水充分冲洗并干燥。将三层各离聚物片材(每层约0.76mm厚)层叠在一起，并置于两片玻璃片材之间(以得到厚度为2.28mm的夹层)。通过最小化离聚物片材与室内环境(约35％的相对湿度)的接触时间，来将其水分含量保持在0.06重量％以下。然后，用聚酯胶带将预层压组合件在若干个位置处封在一起以保持各层与玻璃片材间的相对位置。环绕组合件周边设置尼龙织带以利于空气从各层内除去。将组合件置于尼龙真空袋内，密封，然后将真空袋连接至真空泵。施加真空以充分除去袋装组合件中的空气(袋子内的气压降至低于50毫巴的绝对压力)。然后，将袋装组合件置于对流空气烘箱中加热至120℃并保持这些条件30分钟。接着使用冷却风扇将组合件冷却至接近环境温度，然后断开真空源并移出袋子，从而得到玻璃和夹层的充分预压组合件。虽然组合件的周边已密封，但组合件的若干区域并未充分粘合，这些区域中存在气泡即说明了这一点。然后将组合件置于高压釜中，并在15分钟内将釜中空气的温度和压力从环境温度和环境压力升至135℃和13.8巴。保持此温度和压力30分钟，然后以2.5℃/分钟的冷却速率A或0.1℃/分钟的冷却速率B将温度降低至40℃，在降温过程中，压力在15分钟内降低至环境压力，然后将层压板移出高压釜。
雾度百分率测试：
使用Windex玻璃清洁剂和不起毛布料清洗玻璃层压板，确保其基本上不含气泡并且不存在可能妨碍进行有效光学测量的其他缺陷。然后使用Haze-gard Plus雾度计(BYK-Gardner(Columbia，MD))、并根据美国国家标准(ANSI Z26.1-1966)“Safety Code for Safety Glazing Materials for GlazingMotor Vehicles Operating on Land Highways”测定各层压板的雾度百分率。
用于太阳能电池模块的层压方法2：
将层压板的组件层堆叠在一起以形成预层压组合件。对于包含作为外表面层的聚合物薄膜层的组合件，需将盖玻璃片材置于薄膜层上。然后将预层压组合件置于Meier ICOLAM
10/08层压机(Meier层压机；MeierVakuumtechnik GmbH(Bocholt，Germany))内。层压循环包括5.5分钟的排空步骤(3英寸汞柱(76毫米汞柱)的真空)以及145℃温度下5.5分钟的压制阶段(1000毫巴的压力)。然后将得到的层压板移出层压机。
用于太阳能电池模块的层压方法3：
将层压板的组件层堆叠在一起以形成预层压组合件。对于包含作为外表面层的聚合物薄膜层的组合件，需将盖玻璃片材置于薄膜层上。然后将预层压组合件置于真空袋内，将该真空袋密封，并施加真空以除去袋内空气。将袋子置于烘箱中并加热至约90℃至约100℃，保持30分钟，以除去包含在组合件内的空气。然后将组合件置于空气压力为200psig(14.3巴)的高压釜中，使其在140℃下经受高压处理30分钟。不再向高压釜添加额外的空气，在此情况下使空气冷却。冷却20分钟后并当空气温度降至低于约50℃时，排出高压釜中的气体，将装有层压组合件的真空袋移出高压釜。然后将所得层压板移出真空袋。
比较实施例CE1-2和实施例E1-2
样品CE1-2和E1-2为通过上述层压方法1制备的玻璃层压板。采用下表2列出的离聚物树脂、并通过上述压片方法来制备用于各层压板的离聚物夹层片材。使用上述方法进一步测试玻璃层压板的雾度。结果在表2中示出。
结果表明，一般来讲，当冷却速率降低时，雾度百分率增加。结果还表明，在比较性酸含量(21.7重量％)和比较性中和水平(15％)下，与包含锌离聚物的玻璃层压板(CE2)相比，包含钠离聚物的玻璃层压板(E1)表现出较低的雾度百分率。
表2
比较实施例CE3和实施例E3-4
样品CE3和E3-4为通过上述层压方法1制备的玻璃层压板。采用下表3列出的离聚物树脂、并通过上述压片方法来制备用于各层压板的离聚物夹层片材。使用上述方法进一步测试玻璃层压板的雾度。结果在表3中示出。
结果还表明，在比较性酸含量(21.7重量％)和比较性的较高中和水平(25-26％)下，与包含锌离聚物的玻璃层压板(CE3)相比，包含钠离聚物的玻璃层压板(E3-4)表现出较低的雾度水平。
表3
比较实施例CE4-6和实施例5
样品CE4-6和E5为通过上述层压方法1制备的玻璃层压板。采用下表4列出的离聚物树脂、并通过上述压片方法来制备用于各层压板的离聚物夹层片材。使用上述方法测试玻璃层压板的雾度。结果在表4中示出。
结果表明，与包含锌离聚物的玻璃层压板(CE4-5)相比，包含钠离聚物的玻璃层压板(E5)表现出较低的雾度水平。此外，通过比较E5与CE6，结果表明钠离聚物中较高的酸含量(在E5中为21.7重量％)可进一步降低其雾度水平。
表4
实施例E6-25：
采用层压方法2(实施例E6-15)或层压方法3(实施例E16-25)对表5中描述的12英寸×12英寸(305mm×305mm)的太阳能电池模块进行组装和层压。层1和层2分别构成入射层和前板包封层，而层4和层5分别构成后板包封层和后板(在应用了这些层时)。
表5
·ACR 1为源自乙烯甲基丙烯酸共聚物的20密尔(0.51mm)厚压花片材，该共聚物包含18重量％的甲基丙烯酸共聚单元并具有2.5克/10分钟的MFR(根据ASTM D1238在190℃、2.16kg下测得)。
·FPF为经电晕表面处理的Tedlar薄膜(1.5密尔(0.038mm)厚)，E.I.du Pont de Nemours and Co.，Inc.出品。
·玻璃1为得自PPG Corporation的Starphire
玻璃。
·玻璃2为透明的退火浮法玻璃板层(2.5mm厚)。
·玻璃3为Solex
防阳光玻璃(3.0mm厚)。
·离聚物1为由离聚物K制成的60密尔(1.50mm)厚压花片材。
·离聚物2为由离聚物C制成的20密尔(0.51mm)厚压花片材。
·离聚物3为由离聚物F制成的35密尔(0.89mm)厚压花片材。
·离聚物4为由离聚物D制成的20密尔(0.51mm)厚压花片材。
·离聚物5为由离聚物F制成的20密尔(0.51mm)厚压花片材。
·离聚物6为由离聚物G制成的45密尔(1.14mm)厚压花片材。
·离聚物7为由离聚物G制成的20密尔(0.51mm)厚压花片材。
·离聚物8为由离聚物K制成的20密尔(0.51mm)厚压花片材。
·太阳能电池1具有为125μm厚不锈钢基板的10英寸×10英寸(254mm×254mm)非晶硅薄膜太阳能电池(美国专利6,093,581，实施例1)。
·太阳能电池2为10英寸×10英寸(254mm×254mm)的铜铟硒薄膜太阳能电池(美国专利6,353,042，第6栏第19行)。
·太阳能电池3为10英寸×10英寸(254mm×254mm)的碲化镉薄膜太阳能电池(美国专利6,353,042，第6栏第49行)。
·太阳能电池4为由10英寸×10英寸(254mm×254mm)的多晶EFG生长晶片制成的硅太阳能电池(美国专利6,660,930，第7栏第61行)。
·太阳能电池5为由12英寸×12英寸(305mm×305mm)玻璃片材支撑的薄膜太阳能电池(美国专利5,512,107、5,948,176、5,994,163、6,040,521、6,137,048、和6,258,620)。
Claims (13)
1.太阳能电池模块，所述太阳能电池模块包括太阳能电池层和包含至少一个钠离聚物组合物层的片材，其中(a)所述太阳能电池层选自包括单个太阳能电池的太阳能电池层和包括多个电互连的太阳能电池的太阳能电池层；(b)所述太阳能电池层具有受光面和非受光面；并且(c)所述钠离聚物组合物基本上由钠离聚物组成，所述钠离聚物为前体α-烯烃羧酸共聚物的离子中和衍生物，其中存在于所述前体α-烯烃羧酸共聚物中的羧酸基团总含量的25％至35％已被钠离子中和，并且其中所述前体α-烯烃羧酸共聚物包含(i)具有2至10个碳原子的α-烯烃的共聚单元和(ii)按所述α-烯烃羧酸共聚物的总重量计21至23重量％的具有3至8个碳原子的α,β-烯键式不饱和羧酸的共聚单元；并且所述钠离聚物组合物不掺入交联添加剂。
2.权利要求1的太阳能电池模块，其中所述前体α-烯烃羧酸共聚物包含按所述前体α-烯烃羧酸共聚物的总重量计21至23重量％的α，β-烯键式不饱和羧酸的共聚单元；或者
其中如根据ASTM D1238在190℃、2.16kg下所测定，所述前体α-烯烃羧酸共聚物具有60克／10分钟或更小的熔体流动速率；并且如根据ASTM D1238在190℃、2.16kg下所测定，所述钠离聚物具有10克／10分钟或更小的熔体流动速率；或者其中如根据ASTM D638所测定，所述钠离聚物具有大于40,000psi(276MPa)的挠曲模量；或其中(i)如根据ASTM D1238在190℃、2.16kg下所测定，所述前体α-烯烃羧酸共聚物具有25克／10分钟或更小的熔体流动速率；(ii)所述前体α-烯烃羧酸共聚物包含21至23重量％的α,β-烯键式不饱和羧酸的共聚单元；(iii)存在于所述前体α-烯烃羧酸中的羧酸基团总含量的20％至35％已被钠离子中和；并且(iv)如根据ASTM D1238在190℃、2.16kg下所测定，所述钠离聚物具有5克／10分钟或更小的熔体流动速率。
3.权利要求1的太阳能电池模块，其中包含所述钠离聚物组合物的片材为基本上由所述钠离聚物组合物组成的单层的形式；或者
其中包含所述钠离聚物组合物的片材为多层片材的形式并具有两个或更多个亚层，并且其中至少一个所述亚层基本上由所述钠离聚物组合物组成，并且存在于所述多层片材中的每一个其他亚层均包含至少一种聚合物，所述聚合物选自酸共聚物、离聚物、聚(乙烯乙酸乙烯酯)、聚(乙烯醇缩醛)、聚氨酯、聚氯乙烯、聚乙烯、聚烯烃嵌段弹性体、α-烯烃和α，β-烯键式不饱和羧酸的共聚物、硅酮弹性体、环氧树脂、以及它们中的两种或更多种的组合；或者
其中包含所述钠离聚物组合物的片材具有0.25至1.5mm的总厚度；或者
其中包含所述钠离聚物组合物的片材直接层压到所述太阳能电池层上。
4.权利要求1的太阳能电池模块，所述太阳能电池模块包括层压到所述太阳能电池层的受光面上的前包封层和层压到所述太阳能电池层的非受光面上的后包封层，其中所述前包封层和所述后包封层中的一者为包含权利要求1所述的钠离聚物组合物的片材，并且所述前包封层和所述后包封层中的另一者包含聚合材料，所述聚合材料选自α-烯烃和α，β-烯键式不饱和羧酸的共聚物、α-烯烃和α，β-烯键式不饱和羧酸的共聚物的离聚物、聚(乙烯乙酸乙烯酯)、聚(乙烯醇缩醛)、聚氨酯、聚氯乙烯、聚乙烯、聚烯烃嵌段弹性体、α-烯烃和α，β-烯键式不饱和羧酸的共聚物、硅酮弹性体、环氧树脂、以及它们中的两种或更多种的组合。
5.权利要求7的太阳能电池模块，所述太阳能电池模块包括包含权利要求1所述的钠离聚物组合物的片材中的两者，其中所述前包封层和所述后包封层中的每一者为两个钠离聚物构成的片材中的一者。
6.权利要求1的太阳能电池模块，所述太阳能电池模块还包括入射层，其中所述入射层为所述模块的最外表面层并定位在所述太阳能电池层的受光面上；或还包括背衬层，其中所述背衬层为所述模块的最外表面层并定位在所述太阳能电池层的非受光面上。
7.权利要求6的太阳能电池模块，其中所述入射层选自(i)玻璃片材；(ii)聚合物片材，所述聚合物片材包含选自聚碳酸酯、丙烯酸类、聚丙烯酸酯、环状聚烯烃、聚苯乙烯、聚酰胺、聚酯、含氟聚合物以及它们中的两种或更多种的组合的聚合物；和(iii)聚合物膜，所述聚合物膜包含选自聚酯、聚碳酸酯、聚烯烃、降冰片烯聚合物、聚苯乙烯、苯乙烯-丙烯酸酯共聚物、丙烯腈-苯乙烯共聚物、聚砜、尼龙、聚氨酯、丙烯酸类、醋酸纤维素、玻璃纸、聚(氯乙烯)、含氟聚合物以及它们中的两种或更多种的组合的聚合物；或其中所述背衬层选自(i)玻璃片材；(ii)聚合物片材；(iii)聚合物膜；(iv)金属片材；和(v)陶瓷板，并且其中所述聚合物片材包含选自聚碳酸酯、丙烯酸类、聚丙烯酸酯、环状聚烯烃、聚苯乙烯、聚酰胺、聚酯、含氟聚合物以及它们中的两种或更多种的组合的聚合物；并且所述聚合物膜包含选自聚酯、聚碳酸酯、聚烯烃、降冰片烯聚合物、聚苯乙烯、苯乙烯-丙烯酸酯共聚物、丙烯腈-苯乙烯共聚物、聚砜、尼龙、聚氨酯、丙烯酸类、醋酸纤维素、玻璃纸、聚(氯乙烯)、含氟聚合物以及它们中的两种或更多种的组合的聚合物。
8.权利要求1的太阳能电池模块，其中所述太阳能电池为选自晶体硅(c-Si)和多晶硅(mc-Si)太阳能电池的晶片太阳能电池。
9.权利要求8的太阳能电池模块，所述太阳能电池模块按位置顺序基本上由以下各层组成：(i)入射层；(ii)层压到所述太阳能电池层的受光面上的前包封层；(iii)所述太阳能电池层；(iv)层压到所述太阳能电池层的非受光面上的后包封层；和(v)背衬层，其中所述前包封层和所述后包封层中的一者为包含权利要求1所述的钠离聚物组合物的片材；或
所述太阳能电池模块包括两个片材，每个片材均包含权利要求1所述的钠离聚物组合物，其中所述前包封层和所述后包封层中的每一者包括包含所述钠离聚物组合物的两个片材中的一者。
10.权利要求1的太阳能电池模块，其中所述太阳能电池为薄膜太阳能电池，所述薄膜太阳能电池选自非晶硅(a-Si)、微晶硅(μc-Si)、碲化镉(CdTe)、铜铟硒(CIS)、铜铟／镓二硒化物(CIGS)、光吸收染料和有机半导体太阳能电池。
11.权利要求10的太阳能电池模块，所述太阳能电池模块按位置顺序基本上由以下各层组成：(i)入射层；(ii)前包封层，所述前包封层包括包含权利要求1所述的钠离聚物组合物的片材；和(iii)所述太阳能电池层，其中所述太阳能电池层还包括其上沉积有薄膜太阳能电池的基板，并且所述基板被定位成使得所述基板为所述模块的最外表面并定位在所述太阳能电池层的非受光面上；或者
所述太阳能电池模块按位置顺序基本上由以下各层组成：(i)所述太阳能电池层；(ii)后包封层，所述后包封层包括包含权利要求1所述的钠离聚物组合物的片材；和(iii)背衬层，其中所述太阳能电池层还包括其上沉积有薄膜太阳能电池的覆板，并且所述覆板被定位成使得所述覆板为所述太阳能电池层的受光面上的模块的最外表面。
12.制备太阳能电池模块的方法，所述方法包括：(i)提供包括权利要求1至11中任一项所提及的所有组件层的组合件，和(ii)层压所述组合件以形成所述太阳能电池模块。
13.权利要求12的方法，其中所述层压步骤通过对所述组合件进行加热来实施，并且任选地是其中所述层压步骤还包括使所述组合件经受真空或压力。
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Effective date of registration: 20220302 Address after: Michigan, USA Patentee after: THE DOW CHEMICAL Co. Address before: Michigan, USA Patentee before: Performance Materials North America, Inc. Effective date of registration: 20220302 Address after: Michigan, USA Patentee after: Dow Global Technologies Llc Address before: Michigan, USA Patentee before: THE DOW CHEMICAL Co. |
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