CN103314066A - 反应性导电压敏胶带 - Google Patents
反应性导电压敏胶带 Download PDFInfo
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- CN103314066A CN103314066A CN2011800653197A CN201180065319A CN103314066A CN 103314066 A CN103314066 A CN 103314066A CN 2011800653197 A CN2011800653197 A CN 2011800653197A CN 201180065319 A CN201180065319 A CN 201180065319A CN 103314066 A CN103314066 A CN 103314066A
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- Prior art keywords
- reactive
- sensitive adhesive
- conductive tape
- group
- photovoltaic cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
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Abstract
本发明披露了反应性压敏胶粘剂组合物。还披露了使用反应性压敏胶粘剂形成的胶带。与常规的非可固化电荷收集胶带相比,压敏胶粘剂在其的固化状态显示更好的机械和电性质。所述胶带具有预先选择的固化特征,以对应于光伏电池制造过程的固化特征,使得固化可在电池制造期间进行,并可与电池制造中使用的一个或者多个其它固化步骤同时发生。
Description
相关申请的交叉引用
本申请要求2010年11月23日提交的美国申请61/416,385的优先权,将其全部内容并入本文作为参考。
背景技术
导电性胶粘剂可用于在两种导电材料之间形成电互连物(electricalinterconnection)。这种胶粘剂存在许多应用,包括手持设备的电接地、电磁屏蔽和芯片连接胶粘剂(die attach adhesives)。对于许多这种应用,可使用导电浆糊(paste)或者导电膜,取决于具体性能和应用细节。
然而,在任何导电接合中,无论是由导电胶粘剂形成,还是由其它材料形成,电可靠性是个问题。稳定的电性能应该长期呈现,甚至在暴露于苛刻条件的情况下也应该呈现,所述苛刻条件可通过使用偏置(bias)湿度测试、湿热老化,和热循环的加速适应(accelerated conditioning)以受控的设置条件重现。可靠的电互连物应该在苛刻条件下随时间推移呈现很少的电阻变化或者无电阻变化。
依靠高电可靠性和低电接合电阻的应用的一个实例是用于光伏(例如,太阳能)电池中的电荷收集胶带(charge collection tape)。这种胶带可用于捕获电池中产生的电荷,然后将捕获的电荷携带至外部电路。在光伏电池中可使用电荷收集带的区域的实例包括集电栅(charge collection grid)、在电池之间的带连接(ribbon connections between cells),和使正电荷和负电荷集电极与外部电路连接的公用电源线(busbars)。导电胶带的益处是通常良好限定的粘合层、有效和快速的胶带施用(经常以卷至卷/幅的方法),和成本效率。
在太阳能电池中电互连物的高可靠性是重要的,以维持这种设备的长的期望的功能寿命。大部分太阳能电池板额定以高效率工作20-30年。因此,高度可靠/结实的电互连物和导电性胶粘剂对于在整个长寿命中维持性能目标或许是重要的。
在电互连物中使用的一类导电胶粘剂是导电压敏胶带。典型的胶带利用涂有导电胶粘剂组合物的金属箔片背衬。典型的导电胶粘剂组合物包含填充有导电粒子的压敏胶粘剂(PSA)树脂基质,所述导电粒子单独桥接粘合层或者形成桥接粘合层的渗透网络。通常将这种衬有金属的导电PSA胶带称为"电荷收集胶带"。
用于导电PSA的树脂是当以1弧度/秒的速率测量时剪切模量低于约3x105Pa的软材料,这与它们用作压敏组合物的能力有关。因此,PSA树脂是呈现一定程度的分子水平流动/粘性特征的粘弹性体系。当在导电PSA胶带中使用时,如果胶带充分受到应力,则常规非反应性PSA的粘性特征可影响接合电阻和接合可靠性。特别地,高温进一步软化已知的导电PSA,从而提高它们的流动倾向。
因为多种原因,其它已知措施也是不令人满意的。浆糊无法提供足够的处理强度,直到它们热固化。热密封需要热粘着(heat tacking)或者用压力充分热固化,以形成显著的粘合强度。
对于经受极端环境条件的应用,需要更加电可靠的材料。因此,仍需要在苛刻条件和高温下呈现高可靠性和高导电性(即,低接合电阻)的材料。
发明内容
在一种实施方式中,反应性导电胶带包含反应性胶粘剂层和导电基底。所述胶粘剂层包含可固化压敏胶粘剂和导电填料,并且所述层层合在所述导电基底上并与所述导电基底接触。预先选择所述胶粘剂层的固化特征(cureprofile),以对应于光伏电池制造过程的固化特征。
在另一实施方式中,反应性导电压敏胶粘剂组合物包含可固化压敏胶粘剂和导电填料,其中胶粘剂组合物在室温施用后在未固化状态具有大于约25盎司(oz)/英寸宽度(约2.7N/cm)的剥离强度。
在又一实施方式中,构建光伏电池的方法包括将本申请所述的反应性导电胶带作为电互连物施用至光伏电池,然后在光伏电池制造期间固化所述胶带的胶粘剂层。
示例性实施方式的一个优点是提供与常规导电性压敏电荷收集胶带相比可产生更可靠的电互连物的化学反应性导电PSA胶带,同时仍然提供即时的,低压室温粘合形成的PSA益处。
另一个优点是,提供根据示例性实施方式的反应性导电PSA胶带,其固化至与典型导电PSA胶带相比更有弹性的较低粘性的状态,并由此当在光伏电池和其它设备中使用时可产生改善的电可靠性。
另一个优点是,根据示例性实施方式的反应性导电PSA胶带具有与光伏电池制造过程固化特征相对应的固化特征,使得固化步骤不需要暴露于会导致光伏电池或者它的组件损坏的固化条件。它可进一步允许PSA与一个或者多个在电池制造过程中的其它固化步骤同时固化,从而减少构建电池所需要的总时间和制造步骤的数目。不需要另外的单独固化和/或热粘着步骤。
根据下面的示例性实施方式的更详细的描述,并结合示例性示出本发明原理的附图,本发明的其它特征和优点将显而易见。
附图说明
图1图示了根据示例性实施方式的胶带和常规电荷收集胶带在热循环期间相对于时间的电阻变化。
图2图示了模拟包封的光伏电池随时间推移的重叠接合电阻与热循环的关系曲线。
具体实施方式
对于光伏电池应用,反应性导电PSA胶带可用作电荷载体胶带,并可在电池制造期间固化,而无需单独的加工步骤。提供具有压敏胶粘剂制剂的胶带,所述压敏胶粘剂制剂可在已经作为电池制造的一部分存在的加工步骤的条件下固化,例如用于固化电池包封材料的步骤。提供根据示例性实施方式的反应性导电PSA胶带,其在电池制造期间使用的这些和/或其它包封热特征下固化。与已知的非可固化导电电荷收集胶带相比,这种胶带也提供改善的电可靠性。
用于根据示例性实施方式的反应性导电PSA胶带的反应性胶粘剂制剂为可固化制剂,其包含与导电填料混合的一种或者多种作为压敏胶粘剂的基础聚合物。在一些实施方式中,PSA制剂的预固化玻璃化转变温度(Tg)为约-50°C至约-10°C。保持低的后固化Tg,通常低于0°C。结果,固化的胶粘剂呈现良好的剥离强度,但是仍然足够柔软坚韧以历经长时间经受热循环和其它苛刻的环境条件,例如光伏电池经历的那些。根据示例性实施方式的反应性导电PSA胶带的使用进一步提供如下益处,如在室温即时的低压组装和固定,这是用导电性浆糊或者热封不能实现的。
压敏胶粘剂可包含本身或者在一种或者多种交联组分的存在下可固化的任何适合的反应性聚合物。可选择地,压敏胶粘剂可包含与一种或者多种交联组分(例如,多官能单体、低聚物,或者聚合物)共混的非反应性聚合物,以形成可固化PSA制剂。也可使用这种反应性和非反应性聚合物的共混物。
可用作胶粘剂制剂的基础聚合物的示例性反应性聚合物包括将环氧基团、羧酸、胺、硫醇、酰胺、异氰酸酯、氰酸酯、烯丙基、马来酰亚胺、丙烯酸酯、环氧丙烷、氢化有机硅、烷氧基硅烷基团,或者其它反应性基团悬垂地(pendant)结合至聚合物主链或者结合在聚合物主链中的丙烯酸类共聚物。用于丙烯酸类PSA聚合物的示例性反应性单体包括甲基丙烯酸缩水甘油基酯、丙烯酸羟基乙基酯、甲基丙烯酸烯丙酯、丙烯酸异氰酸基丙基酯、N-乙烯基吡咯烷酮,和丙烯酸。也可使用其它公知的官能丙烯酸酯单体。
示例性非反应性聚合物包括由丙烯酸酯如丙烯酸丁酯、丙烯酸甲酯、丙烯酸乙基己基酯、丙烯酸异辛酯,和甲基丙烯酸甲酯形成的聚合物。
胶粘剂制剂也可包含单独的或者与丙烯酸类聚合物组合的非丙烯酸类聚合物作为基础聚合物。反应性和非反应性的非丙烯酸类聚合物可在制剂中使用。根据示例性实施方式使用的适合的非丙烯酸类聚合物包括但不限于酚醛树脂、脂族聚酯、芳族聚酯、聚醚多元醇、聚酯多元醇、胺官能的丙烯腈丁二烯共聚物、羧酸官能的丙烯腈丁二烯共聚物、聚氨酯、聚酰胺、橡胶化的环氧预聚物如羧基-末端的液体丁二烯丙烯腈(CTBN)-环氧加合物,和羟基官能的丙烯腈丁二烯聚合物。
反应性或者非反应性基础聚合物可商购得到或者可合成。例如,丙烯酸类反应性聚合物可通过在溶剂存在下的单体自由基聚合合成。在这种情况中,可使用任何适合的自由基引发剂;示例性引发剂包括但不限于过氧和/或偶氮化合物。类似地,聚酯、聚氨酯、CTBN-环氧加合物、烯属和橡胶聚合物、橡胶嵌段共聚物,和其它基础聚合物可商购或者通过已知方法合成。
将交联组分与非反应性基础聚合物共混以提供反应性胶粘剂制剂,不过,也可将交联组分与反应性基础聚合物组合使用,以提供可固化制剂。典型的交联组分是包含环氧化基、丙烯酸酯、环氧丙烷、马来酰亚胺、醇、硫醇、异氰酸酯、氰酸酯、烷氧基硅烷、氢化有机硅(silicon-hydride)、烯丙基,和苯并噁嗪官能团的交联组分。含有这种反应性基团的交联组分可作为单体、多官能树脂、低聚物,或者聚合物存在。
一类适合的交联组分包括低聚物如脂族和芳族氨基甲酸酯丙烯酸酯(urethane acrylate)。另一类适合的交联组分包括脂族和芳族环氧树脂。在一些情况中,可使用在基础聚合物中不可溶,并因此呈现改善的潜伏期的环氧树脂。用作交联组分的其它反应性组分包括但不限于多官能醇、多官能丙烯酸酯树脂,和多官能异氰酸酯(有时为化学封端异氰酸酯的形式)。尽管交联组分的选择不限于特定固化化学,但是示例性实施方式具体地涵盖例如可通过自由基固化、羟基封端的异氰酸酯固化、环氧-潜在的胺固化(epoxy-latentamine cure),和不溶性环氧-胺固化(insoluble epoxy-amine cure)来固化的制剂。
交联组分的量可为制剂的有机固体含量的约0.1重量%至约70重量%(即,不包括溶剂和填料),取决于应实现的固化水平和交联组分是否与已经反应性聚合物或者与非反应性聚合物组合使用。更典型地,交联组分为制剂的有机固体含量的约0.5重量%至约20重量%。
用于根据示例性实施方式的特定制剂的一种或多种反应性或者非反应性聚合物和/或一种或多种交联组分可取决于将使用的和反应性导电PSA胶带将经受的固化条件。如所讨论的,可预先选择固化特征,以对应于光伏电池制造过程和/或制造过程中的特定步骤的固化特征。在一些情况中,可具有多重场合,例如在利用可导致固化的热特征的光伏电池制造期间,这取决于用于制造胶带的胶粘剂制剂的固化特征。在这种情况中,可选择制剂,使得与将在制造期间内的特定点使用的特定热特征结合发生固化。一个这种实例是在电池制造期间已经用于固化电池包封材料如乙烯乙酸乙烯酯(EVA)或者聚乙烯醇缩丁醛(PVB)的热特征,其通常包括在150-170°C10-15分钟的热固化特征。
将胶粘剂制剂的PSA组分(包括任何交联组分)与导电填料充分混合,任选使用溶剂以促进混合,以形成将施用于胶带的反应性导电胶粘剂制剂。导电填料可作为总胶粘剂制剂的约0.1重量%至约90重量%固体(即,不包括任何任选溶剂的质量)存在。导电填料包括金属如银、金、镍、铜;炭黑;碳纤维;金属化碳纤维,以及金属包覆的玻璃珠粒、金属包覆的玻璃片/纤维,和金属包覆的镍粒子,所有物质均为举例。金属涂层可为任何导电金属材料如银、金、铜等。粒子形状不限制,并且可包括球形、片状,和不规则形状的粒子。同样,粒度不限制,并且可包括远低于胶粘剂膜的厚度的粒度至足够大以跨越胶粘剂膜的整个粘合层厚度的粒子。
应理解的是,也可使用出于各种目的而用于其它已知PSA制剂的常规添加剂。
如果使用溶剂,则使用的溶剂通常为常用溶剂。如果希望,出于加工目的,可通过添加或者除去溶剂来调节制剂的粘度。如果使用溶剂,那么可使用任何适合的溶剂,包括乙酸乙酯、甲苯、烃如庚烷或者己烷、醇,及其组合,所有物质均仅为举例。
然后可将胶粘剂制剂(包含基础聚合物、任何交联组分、导电填料、任何其它填料,和任选的溶剂)涂布在任何适合的基底上,所述基底包括聚对苯二甲酸乙二醇酯(PET)膜、聚酰亚胺膜、聚氨酯膜,和聚乙烯膜,所有物质均仅为举例。然而,对于电气应用如光伏电池制造,通常将胶粘剂制剂与金属或者其它导电基底如锡涂覆的铜箔组合使用。其它适合的导电基底包括铝箔、铜箔、金属化塑料和导电斯克林布(scrim),所有物质均仅为举例。
然后可将剥离衬如有机硅剥离衬层合在整个胶粘剂上,直到所述膜准备施用,在该点可将剥离衬除去以暴露胶粘剂。通常,在胶粘剂与金属箔片组合使用的实施方式中,可为理想的是,首先将胶粘剂溶液施用至剥离衬,然后干燥以除去过量溶剂,然后使用辊或者类似设备将胶粘剂/衬的组合层合至箔片,形成反应性导电PSA胶带。
然后可将所述胶带在室温和普通压力与光伏电池或者其它互连电设备连接,然后固化以开始并进行制剂内的交联,同时导电填料仍然悬浮在制剂中。可将根据示例性实施方式形成的胶带用于各种类型的光伏电池/太阳能电池中,包括结晶Si光伏电池、多晶Si光伏电池、无机薄膜(例如,CdTe、CIGS等)光伏电池,和有机光伏电池。这些电池可为刚性的或者柔性的,取决于电池的预期最终用途。光伏电池的类型和它的预期最终用途可对于电池制造期间使用的热特征具有影响,所述热特征进而可导致预先选择胶带的特定聚合物和交联组分,使得胶粘剂的固化特征与电池制造的热特征相对应。
在根据示例性实施方式的胶带中使用压敏胶粘剂导致在未固化状态的强烈粘性。所述胶带在施用时(即,在固化之前)的剥离强度为至少25盎司/英寸宽度(约2.7N/cm宽度),通常大于约40盎司/英寸宽度(约4.3N/cm宽度)。结果,一旦施用,在固化之前的其它电池制造步骤中几乎没有胶带移动或者松开的危险,即使电池经受明显的处理和/或操纵。在固化后,胶粘剂仍呈现良好的剥离强度,后固化剥离强度通常为至少25盎司/英寸宽度(约2.7N/cm宽度)。因为固化的胶粘剂保留低Tg,所述胶带也可经受重复的热循环。因此,除了在下面实施例的上下文中更详细显示的在苛刻环境中随时间推移表现一贯的电性能之外,示例性实施方式提供了在苛刻环境中使用的希望的机械性质。
实施例
通过以下实施例进一步描述本发明,提供这些实施例用于说明,而非限制。
实施例1
实施例1说明基于可固化丙烯酸类基础聚合物和自由基可固化交联组分的反应性导电PSA的实施方式。压敏胶粘剂组合物如表1中所述配制,其中份数为重量份。
表1
项目描述 | 数量(ppH) |
环氧基,羧酸官能的丙烯酸类聚合物 | 41.0 |
疏水的脂族氨基甲酸酯丙烯酸酯低聚物 | 3.7 |
氨基甲酸酯丙烯酸酯低聚物 | 10.3 |
过氧化二苯甲酰 | 0.1 |
银包覆的镍粒子 | 21.9 |
乙酸乙酯 | 23.0 |
通过差示扫描量热法(DSC)测定,这样配制的胶粘剂的玻璃化转变温度(Tg)在未固化状态为-23°C,在固化状态的Tg为-24°C,其对于在苛刻条件下使用的光伏电池中发生的热循环期间的可靠性能是有利的。低Tg的柔性胶粘剂可变形并补偿在热循环和一般使用期间形成的应力(例如,由于热膨胀系数(CTE)不匹配)。然而,在固化后,它不会永久流动或者蔓延,如非反应性PSA可发生的那样。
将表1中所示的胶粘剂制剂施用于2密耳(0.002英寸)有机硅剥离衬并在65°C干燥5分钟,在剥离衬上得到1.5密耳(0.0015英寸)厚的胶粘剂层。然后将胶粘剂使用层压辊以约80-100psi层合至1.4密耳(0.0014英寸)锡涂覆的铜箔,形成反应性导电PSA胶带构造。
将这种构造的试条在150°C烘箱中放置10分钟,并使剥离衬保持在适当位置以排除氧。然后将样品除去并冷却至室温。在热暴露之前和之后评价这些样品的粘性,并观察到以下:
实施例1在热固化之前–非常强烈的粘性
实施例1在热固化之后–轻微粘性至无粘性
重叠接合通过以下方法制备:使0.5英寸×1.4密耳厚的锡涂覆的铜箔与根据实施例1制造的胶带构造的0.25英寸宽的试条重叠。将样品在150°C在25psi下固化10分钟,模拟用于光伏模块的典型的EVA包封条件。将样品冷却至室温。
在固化后,然后通过针对施加的电流测量电阻来测试样品。将电流逐渐从1安培增加至10安培,在10安培保持2分钟,然后返回至1安培。在测试期间,以1、5和10安培间隔记录跨越接合的电压,然后根据欧姆定律计算电阻。用市售非反应性电荷收集胶带进行了相同的试验。结果在表2中示出。
表2
使用相同实验设置和固化条件,将实施例1的胶带构造的样品和常规电荷收集胶带的样品置于120°C烘箱中,同时通过10安培的连续电流。在一段时间内测量并记录电压。然后根据欧姆定律计算随时间推移电阻的变化,结果在表3中示出。
表3
使用相同实验设置和固化条件,将实施例1的胶带构造的样品和常规电荷收集胶带的样品置于环境室中,并根据国际电工委员会(InternationalElectrotechnical Commission)的用于薄膜地面光伏模块–设计鉴定和类型批准的标准试验(标识为IEC61646),进行-40°C至85°C之间的热循环,同时通过1.5安培的连续电流。在一段时间内测量并记录电压。根据欧姆定律计算电阻,并将电阻变化相对于时间作图,结果在图1中示出。
如表2和3中所述和图1中所示,与常规可替换物-具有非可固化压敏胶粘剂的电荷收集胶带相比,示例性实施方式历经改变电流条件、温度循环,和随时间推移显示显著较低的电阻增加。显著的电阻变化(例如在对比例中显示)暗示在重叠接合处的不稳定。在这种情况中电阻的降低被认为是胶粘剂制剂在受热时流动性增加和所得的表面湿润改善的作用。对比例的未固化胶粘剂在升高的温度非常易于流动的事实暗示,它在受热时是较不稳定的和不太能够维持电互连。相反,实施例1的构造显示很少的电阻变化,这暗示它的机械和电性质是稳定的,甚至在调适后也是如此。
实施例2
实施例2说明由羟基官能丙烯酸类PSA聚合物基础树脂和封端的异氰酸酯交联组分形成的反应性导电PSA。溶剂型导电PSA通过以下方法形成:将羟基官能的丙烯酸类聚合物(27g,90重量份丙烯酸乙基己酯,10重量份丙烯酸羟基乙基酯,Mn~250K,Mw~550K)和封端异氰酸酯溶液TrixeneBI-7982(4g,DMP-封端的HDI三聚体,来自Baxenden Chemical)溶解在乙酸乙酯(70g)中。向此溶液缓慢添加标称35μm的Ag包覆的玻璃珠粒(15g,Conduct-O-Fil TP35-S12,来自Potters Industries),并使用机械桨叶混合机搅拌。
将这种溶液使用棒拉伸涂布机(bar drawdown coater)涂布在2密耳PET剥离衬上,在65°C干燥5分钟后形成约38μm厚的膜,在剥离衬上得到粘性的,未固化的PSA膜。
将这种膜使用40psi的层合压力层合至36微米锡涂覆的铜箔基底。将剥离衬从所得的胶粘剂涂覆的箔片除去,并将衬有箔片的PSA使用在150°C15分钟的固化特征固化,以模拟典型的EVA包封物热固化特征。在此固化步骤中,将封端的异氰酸酯脱保护,生成与丙烯酸类聚合物的羟基官能团反应的多官能异氰酸酯树脂。在热固化后,反应性PSA在交联状态显示基本无粘性。
实施例3
如同实施例2一样,实施例3是由羟基官能的丙烯酸类PSA聚合物基础树脂和封端的异氰酸酯交联组分形成的反应性导电PSA的另一实例。与实施例2中所述的可固化导电性PSA相似的可固化导电性PSA通过以下方法配制:组合羟基官能的丙烯酸类PSA基础树脂(8.9g聚合物,在13.4g乙酸乙酯溶剂中)、二甲基吡唑(DMP)-六亚甲基二异氰酸酯(HDI)三聚体加合物封端的异氰酸酯固化剂(1.1g加合物,在1.1g甲基乙基酮溶剂中),和Ag包覆的玻璃珠粒(2.1g),并使用旋涡混合器搅拌。将这种胶粘剂使用拉伸棒(drawdown bar)涂覆在剥离衬上并在对流烘箱中干燥,得到1.7密耳厚的干燥的胶粘剂膜。将这种膜使用实验室辊层合至Sn涂覆的Cu箔片背衬。
切割这种层合物的一英寸宽试条,除去剥离衬,并将试条根据PSTC方法PSTC-101和ASTM方法D-3330层合至不锈钢试验板,并随后使用12英寸/分钟的剥离速率剥离。在环境条件停留1小时后,测试一组样品的1小时剥离力(未固化样品)。随后,将第二组样品在对流烘箱中在170°C固化15分钟,然后测量剥离力(固化样品)。
未固化胶粘剂的平均剥离力为58盎司/英寸宽度。固化样品的平均剥离力为26盎司/英寸宽度。未固化剥离力对于填充的导电性PSA而言是高的,并促进在光伏电池组装过程中未固化材料的固定和处理。尽管固化胶粘剂的剥离强度低于未固化的值,但是在包封的太阳电池板中足以以高可靠性使用。剥离力的变化显示,胶粘剂在模拟的光伏电池包封热特征期间广泛固化。
实施例3的胶粘剂的玻璃化转变温度(Tg)也通过差示扫描量热法(DSC)测定。经测定,在未固化状态的Tg为-31°C,并且在固化后维持-31°C的Tg。如实施例1中所述,在固化后低Tg的保留对于在苛刻条件下使用的光伏电池中发生的热循环期间的可靠性能是有利的,允许它变形和补偿在热循环期间形成的应力,但是不呈现永久性流动或者蔓延。
实施例4
实施例4说明使用反应性导电PSA的实施方式,所述反应性导电PSA由丙烯酸类聚合物PSA基础树脂形成并使用潜在不溶性固体环氧交联组分。溶剂型导电性PSA通过以下方法形成:将10g三(环氧丙基)异氰酸酯(tris(epoxypropyl)isocyanurate)粉末(TEPIC)(得自TCI America)和5g双氰胺固体粉末(DICY)(从Air Products作为Dicyanex1400B得到)溶解在具有85g聚合物固体的环氧官能的丙烯酸类压敏胶粘剂在乙酸乙酯中的212.5g溶液中,在所述丙烯酸类聚合物合成期间在单体进料中包含5重量%甲基丙烯酸缩水甘油基酯。向此分散体缓慢添加标称35μm Ag包覆的玻璃珠粒(30g,Conduct-O-Fil TP35-S12,来自Potters Industries),并使用机械桨叶混合机搅拌。
将这种分散体使用棒拉伸涂布机涂覆在2密耳PET剥离衬上,形成约38μm厚的膜,然后在65°C干燥5分钟,在剥离衬上得到粘性的,未固化的PSA膜。TEPIC/DICY反应性组分在干燥过程(dry-down process)中不固化,这是由于使用低干燥温度和这些组分在丙烯酸类聚合物中不溶。
然后将膜使用40psi的层合压力层合至36微米锡涂覆的铜箔载体。从所得的胶粘剂涂覆箔片除去剥离衬,并将衬有箔片的PSA使用在170°C15分钟的固化特征固化,以模拟典型的EVA包封物热固化特征。在此固化步骤中,TEPIC和DICY可在固化时溶解/熔融进入基础环氧官能的丙烯酸类树脂体系,在固化后得到热固性基质。在热固化后,导电胶粘剂在交联的(即,固化的)状态呈现低粘性。
实施例5
通过生成包封的重叠接合,将在实施例2中制造的反应性导电胶带与非反应性电荷载体胶带基准(benchmark)对比。在玻璃基底上通过以下方法制备接合:将0.5英寸宽×1.4密耳厚的锡涂覆的铜箔与根据实施例2制造的反应性胶带构造的0.25英寸宽试条重叠。将聚合物包封物层置于该接合上,接着是第二玻璃板。将多层结构在压力下在150°C热层合10分钟,以模拟太阳能电池包封过程。类似的重叠接合使用非反应性电荷载体胶带基准构建。将样品冷却至室温。在1、5,和10安培电流("逐渐增加的"数据)下测量重叠接合的电阻,接着将接合在10安培电流保持60分钟。然后随着电流从10至5至1安培("逐渐下降的"数据)逐步下降,再次测量接合的电阻。结果显示在下表4中。
表4
在所有研究的条件下,根据示例性实施方式制造的反应性胶带显示具有较低总电阻的接合。此外,接合的稳定性/可靠性可通过在10安培偏置(bias)下处理一小时后电阻变化的多少来评价。在此偏置测试中,实施例2的胶带呈现5.1%的电阻增加,而非反应性常规电荷收集胶带电阻增加6.1%。这些结果表明,与非反应性胶粘剂基准相比,使用实施例2的胶粘剂形成的固化接合在高偏置条件下更稳定。
实施例6
将在实施例1的表1中显示的胶粘剂制剂施用至2密耳(0.002英寸)有机硅剥离衬,并在65°C干燥5分钟,在剥离衬上得到1.5密耳(0.0015英寸)厚的胶粘剂层。将2密耳(0.002英寸)的第二有机硅剥离衬层合至暴露的胶粘剂表面上。
将样品切割成2.54cm×15.24cm(1英寸×6英寸)试条。除去第一衬,并将样品使用4.5lb辊层合至15.24cm×15.24cm(6英寸×6英寸)316不锈钢板。除去第二衬,并将0.23mm厚的锡涂覆的铜(Sn-Cu)条带(3.05cm×30.48cm(1.2英寸×12英寸))用4.5lb辊层合至暴露的胶粘剂。然后将样品在MTS剥离粘合测试机上测试,以测量剥离力。与工业剥离测试标准一致,将样品从所述板以30.48cm/min(12英寸/分钟)的速率以90度牵拉。
在未固化状态和在固化后测量样品的剥离力;为确保完全固化,将样品在160°C固化14分钟。预固化剥离力测量值为5.7N/cm至7.3N/cm。后固化剥离测量值为22.0N/cm至22.7N/cm。
实施例7
通过使用加速测试,将实施例3中描述的可固化导电PSA与典型的非可固化导电PSA进行对比,所述加速测试通过以下方法进行:使用与用于太阳能电池板测试的UL1703规程一致的方法,从-40°C至85°C循环测试("T-循环")包封的搭接样品。
在显微镜载玻片上使用与根据实施例3形成的胶带的0.5"宽试条重叠的0.5"宽的底部Sn涂覆的Cu箔形成搭接,重叠面积为0.25平方英寸。将搭接区域用1"×1"盖玻片和15密耳快速固化EVA包封,使用以20psi在150°C进行15分钟的固化特征,其类似于在包封光伏电池中使用的特征。搭接样品电阻使用四点探针几何(four-point probe geometry)测量。外接触在箔片的非重叠端施加,并用于驱使1安培电流通过样品。将内电极置于包封的搭接区域的任一侧上,并用于测量跨越搭接的电压降,使用欧姆定律将所述电压降转化成搭接电阻。使用常规的非反应性电荷收集胶带进行类似的实验。
在图2中示出了通过一周热循环的搭接电阻测量值。如图2示意性示出,与常规非反应性导电PSA相比,根据实施例3制造的胶带呈现较好的稳定性和可靠性,如热循环1周得到的电阻的较小增加所证实。
尽管参照具体实施方式描述了本发明,但是本领域技术人员应理解的是,可作出各种变化并且可使用等同物替代本发明的要素,而不脱离本发明范围。另外,可进行许多修饰,以使特定情况或者材料适应于本发明教导,而不脱离其基本范围。因此,本发明意图不限于作为实施本发明的最佳模式披露的特定实施方式,本发明包括落在所附权利要求范围内的所有实施方式。
Claims (28)
1.反应性导电胶带,其包含:
反应性胶粘剂层,所述反应性胶粘剂层包含:
可固化压敏胶粘剂,和
导电填料;和
导电基底,其中所述胶粘剂层层合在所述导电基底上并与所述导电基底接触,
其中预先选择所述胶粘剂层的固化特征,以对应于光伏电池制造过程的固化特征。
2.权利要求1的反应性导电胶带,其中所述可固化压敏胶粘剂包含反应性聚合物。
3.权利要求2的反应性导电胶带,其中所述可固化压敏胶粘剂还包含交联组分。
4.权利要求2的反应性导电胶带,其中所述反应性聚合物包括丙烯酸类共聚物,所述丙烯酸类共聚物结合一个或者多个选自以下的官能团:环氧基团、羧酸基团、胺基团、硫醇基团、酰胺基团、异氰酸酯基团、氰酸酯基团、烯丙基、马来酰亚胺基团、丙烯酸酯基团、环氧丙烷基团、氢化有机硅基团、烷氧基硅烷基团,及其组合,所述官能团悬垂于聚合物主链或者在聚合物主链中。
5.权利要求1的反应性导电胶带,其中所述可固化压敏胶粘剂包含非反应性基础聚合物和交联组分。
6.权利要求5的反应性导电胶带,其中所述非反应性聚合物包括丙烯酸类聚合物。
7.权利要求1的反应性导电胶带,其中所述可固化压敏胶粘剂包含酚醛树脂、脂族聚酯、芳族聚酯、聚醚多元醇、聚酯多元醇、胺官能的丙烯腈丁二烯共聚物、羧酸官能的丙烯腈丁二烯共聚物、聚氨酯、聚酰胺、橡胶化的环氧预聚物,或者羟基官能的丙烯腈丁二烯聚合物。
8.权利要求1的反应性导电胶带,其还包含以所述胶粘剂的有机固体含量的约0.1重量%至约70重量%存在的交联组分。
9.权利要求8的反应性导电胶带,其中所述交联组分以所述胶粘剂的有机固体含量的约0.5重量%至约20重量%存在。
10.权利要求8的反应性导电胶带,其中所述交联组分具有环氧基团、丙烯酸酯基团、环氧丙烷基团、马来酰亚胺基团、醇基团、硫醇基团、异氰酸酯基团、氰酸酯基团、烷氧基硅烷基团、氢化有机硅基团、烯丙基,或者苯并噁嗪官能团。
11.权利要求8的反应性导电胶带,其中所述交联组分包含氨基甲酸酯丙烯酸酯、环氧树脂或者封端的异氰酸酯。
12.权利要求1的反应性导电胶带,其中当所述胶粘剂为未固化状态时,所述胶带的剥离强度为至少2.7N/cm。
13.权利要求12的反应性导电胶带,其中当所述胶粘剂为未固化状态时,所述胶带的剥离强度为至少4.3N/cm。
14.权利要求1的反应性导电胶带,其中所述导电填料存在的量以所述反应性胶粘剂层固体计为约0.1重量%至约90重量%。
15.权利要求14的反应性导电胶带,其中所述导电填料选自银、金、镍、铜、炭黑、碳纤维、金属化碳纤维、金属包覆的玻璃珠粒、金属包覆的玻璃片/纤维、金属包覆的镍粒子及其组合。
16.权利要求1的反应性导电胶带,其中所述导电基底为锡涂覆的铜箔、铝箔、铜箔、金属化塑料,或者导电斯克林布。
17.构建光伏电池的方法,其包括:
将权利要求1的反应性导电胶带作为电互连物施用于光伏电池;和
在所述光伏电池的制造期间固化所述反应性导电胶带的胶粘剂层。
18.权利要求17的方法,其中所述固化胶粘剂层的步骤与光伏电池固化同时发生。
19.权利要求18的方法,其中所述固化步骤在约150°C至约170°C的温度进行约10分钟至约15分钟。
20.权利要求17的方法,其中所述反应性导电胶带的可固化压敏胶粘剂包含环氧和羧酸官能化的丙烯酸类聚合物、疏水性脂族氨基甲酸酯丙烯酸酯低聚物,和氨基甲酸酯丙烯酸酯低聚物。
21.权利要求17的方法,其中所述反应性导电胶带的可固化压敏胶粘剂包含羟基官能的丙烯酸类聚合物和封端的异氰酸酯。
22.权利要求17的方法,其中所述光伏电池为结晶Si光伏电池、多晶Si光伏电池、无机薄膜光伏电池或者有机光伏电池。
23.包含可固化压敏胶粘剂和导电填料的反应性导电压敏胶粘剂组合物,其中所述胶粘剂组合物具有在未固化状态至少约2.7N/cm的剥离强度和在未固化状态约-50°C至约-10°C的玻璃化转变温度。
24.权利要求23的反应性导电压敏胶粘剂组合物,其中所述组合物具有在固化状态低于约0°C的玻璃化转变温度。
25.权利要求23的反应性导电压敏胶粘剂组合物,其中将所述胶粘剂组合物配制成是通过自由基固化机制、羟基-封端的异氰酸酯固化机制、环氧-潜在的胺固化机制或者不溶性环氧-胺固化机制可固化的。
26.权利要求23的反应性导电压敏胶粘剂组合物,其中所述胶粘剂包含反应性聚合物。
27.权利要求23的反应性导电压敏胶粘剂组合物,其中所述胶粘剂包含非反应性聚合物和交联组分。
28.权利要求23的反应性导电压敏胶粘剂组合物,其具有以下固化特征:在约150°C至约170°C固化约10分钟至约15分钟。
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Also Published As
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JP2014500360A (ja) | 2014-01-09 |
US20130233485A1 (en) | 2013-09-12 |
KR20130129222A (ko) | 2013-11-27 |
WO2012071484A2 (en) | 2012-05-31 |
MY169514A (en) | 2019-04-19 |
US9735299B2 (en) | 2017-08-15 |
EP2643418A2 (en) | 2013-10-02 |
WO2012071484A3 (en) | 2013-04-18 |
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