CN112143017B - 一种用于动力电池铝塑膜的尼龙层及其制备工艺 - Google Patents

一种用于动力电池铝塑膜的尼龙层及其制备工艺 Download PDF

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CN112143017B
CN112143017B CN202010886741.XA CN202010886741A CN112143017B CN 112143017 B CN112143017 B CN 112143017B CN 202010886741 A CN202010886741 A CN 202010886741A CN 112143017 B CN112143017 B CN 112143017B
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吴安理
王桂彬
陈汉城
熊泽民
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Guangdong Dexing Polymer Film Material Research Co ltd
Guangdong Andeli New Materials Co ltd
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Abstract

本发明公开了一种用于动力电池铝塑膜的尼龙层，由尼龙膜以及涂覆于所述尼龙膜表面的防护层组成，所述防护层包括1‑5％的水溶性酚醛环氧树脂、70‑85％的乳液胶粘剂和余量乙醇，并具体公开了尼龙层的制备工艺为基材放卷‑预涂‑热风干燥‑冷却‑主涂‑干燥‑冷却‑收卷‑固化‑分切‑包装。本发明制备得到的用于动力电池铝塑膜的尼龙层能够有效的阻隔氧气、水蒸气，并且提高了尼龙层各方面的机械性能及耐电解液的腐蚀能力。

Description

一种用于动力电池铝塑膜的尼龙层及其制备工艺
技术领域
本发明涉及动力电池技术领域，更具体的说是涉及一种用于动力电池铝塑膜的尼龙层及其制备工艺。
背景技术
铝塑膜是软包装锂电池电芯封装的关键材料，是由多种塑料、铝箔和粘合剂组成的高强度、高阻隔的多层复合材料，单片电池组装后用铝塑膜密封，形成一个电池，铝塑膜起保护内容物的作用。典型铝塑膜的结构主要为：ON(表层)/Al(铝箔层)/CPP(树脂层)。其中，最外层通常为尼龙层或PET与尼龙的复合层，主要起防污染、耐腐蚀及防止外力损伤的保护功能；中间铝箔层为基体材料，起防水、阻隔作用及用于产品形态成型；聚丙烯为热封层，主要作用是封口粘接，并起到将铝层与电芯隔开，防止包装的电解质泄露而腐蚀铝箔的作用；粘合剂或粘合树脂复合层主要起到层间强联接作用。
目前市场上的PA6或PA66等尼龙薄膜材料具有良好的阻隔氧气的性能，但存在易吸湿和不耐锂电池用电解液的缺点，外购尼龙材料在锂电池电解液浸泡下易发生溶胀、溶解，失去锂离子电池的保护作用。
因此，如何提供一种耐电解液腐蚀能力性能优异的用于动力电池铝塑膜的尼龙层是本领域技术人员亟需解决的问题。
发明内容
有鉴于此，本发明提供了一种用于动力电池铝塑膜的尼龙层及其制备方法，通过对尼龙膜表面涂覆保护材料，提高了尼龙材料的耐电解液腐蚀能力，进一步增强了尼龙层对锂离子动力电池的保护作用。
为了实现上述目的，本发明采用如下技术方案：
一种用于动力电池铝塑膜的尼龙层，由尼龙膜、以及涂覆于所述尼龙膜表面的防护层组成，所述防护层包括1-5wt％的水溶性酚醛环氧树脂、70-85wt％的乳液胶粘剂和余量乙醇。
优选的，在上述一种用于动力电池铝塑膜的尼龙层中，所述乳液胶粘剂为聚偏氯乙烯树脂乳液、聚醋酸乙烯酯乳液或者聚丙烯酸酯乳液中的任意一种。
优选的，在上述一种用于动力电池铝塑膜的尼龙层中，所述乳液胶粘剂为聚偏氯乙烯树脂乳液，并且所述聚偏氯乙烯树脂乳液的固含量为60％，其中偏二氯乙烯含量为90-95％。
上述技术方案的有益效果是：所述乳液胶粘剂的添加，尤其是当乳液胶粘剂为聚偏氯乙烯树脂乳液时，可以有效增强尼龙膜的耐腐蚀性，并且在很大程度上阻隔水分及外部气体，提高动力电池铝塑膜的耐电解液腐蚀能力。
优选的，在上述一种用于动力电池铝塑膜的尼龙层中，所述防护层涂覆于所述尼龙膜表面的涂布量为1-10g/m3，优选为2-6g/m3，可根据实际情况进行涂布量的选择。
优选的，在上述一种用于动力电池铝塑膜的尼龙层中，所述水溶性酚醛环氧树脂为苯酚型酚醛环氧树脂、邻甲酚型酚醛环氧树脂、双酚A型酚醛环氧树脂中的任意一种或者几种的混合物。
上述技术方案的有益效果是：所述水溶性酚醛环氧树脂不仅能提高尼龙膜的耐温性能，使其能承受210℃以上的高温，并且与乳液胶黏剂协同作用，能够使得尼龙层在电解液中浸泡48h而不被腐蚀，有效提高了尼龙层的耐腐蚀能力。
优选的，在上述一种用于动力电池铝塑膜的尼龙层中，所述尼龙膜为尼龙6或尼龙66材料。
本发明还公开了一种用于动力电池铝塑膜的尼龙层的制备方法，包括以下步骤：
(1)涂覆液配制：向配料桶中加入水溶性酚醛环氧树脂、乳液胶粘剂和乙醇，以100-150r/min的转速搅拌5-10min，然后调至500-800r/min的转速搅拌10-20min至完全溶解，得涂覆液；
(2)涂覆液预涂：将尼龙膜基材卷安放在连续性的放卷机上放卷，将基材卷尼龙膜张开，在尼龙膜表面流延涂覆所述涂覆液，热风干燥至所述涂覆液固化，冷却至室温，得到表面包覆有预涂膜的尼龙膜；
(3)涂覆液主涂：采用凹版涂布工艺，在所述预涂膜表面涂覆所述涂覆液，经过涂布机烘道加热和红外光照结合的方式烘干后固化、冷却、收卷、二次固化、分切、包装，得到包覆有防护层的尼龙层。
优选的，在上述一种用于动力电池铝塑膜的尼龙层的制备方法中，步骤(2)中所述热风干燥的温度为55-80℃。
优选的，在上述一种用于动力电池铝塑膜的尼龙层的制备方法中，步骤(3)中所述涂布机烘道加热的温度为80-125℃，时间为40-45s，所述红外光照的温度为90-100℃，时间为所述涂布机烘道加热结束前的5-6s。
优选的，在上述一种用于动力电池铝塑膜的尼龙层的制备方法中，步骤(3)中所述二次固化的温度为40-45℃，固化时间为48-76h。
上述技术方案的有益效果是：本发明经过对收卷后尼龙层的二次固化，可以有效提高尼龙层的拉伸强度、断裂伸长率等机械性能，并且对尼龙层的耐腐蚀性能有一定程度的提升。
经由上述的技术方案可知，与现有技术相比，本发明公开提供了一种用于动力电池铝塑膜的尼龙层及其制备方法，通过对尼龙膜表面涂覆保护材料，提高了尼龙材料的耐电解液腐蚀能力，进一步增强了尼龙层对锂离子动力电池的保护作用；并且通过乳液胶黏剂与水性酚醛环氧树脂的协同作用，不仅提高了尼龙层的耐电解液腐蚀能力和耐高温能力，而且对于尼龙层的拉伸强度、断裂伸长率、耐撕裂力、热收缩率、阻水、阻水蒸气等机械性能的提升均有较大程度的改善。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明实施例提供了一种用于动力电池铝塑膜的尼龙层及其制备方法，对于涂覆于尼龙膜表面的防护层的原材料组成，本发明是通过大量的测试实验得出的，具体参见实施例1-5及对比例1-4。
实施例1
一种用于动力电池铝塑膜的尼龙层的制备方法，包括以下步骤：
(1)涂覆液配制：向配料桶中加入1％的苯酚型酚醛环氧树脂、78％的聚偏氯乙烯树脂乳液和21％的乙醇，以100-150r/min的转速搅拌5-10min，然后调至500-800r/min的转速搅拌10-20min至完全溶解，得涂覆液；
(2)涂覆液预涂：将尼龙膜基材卷安放在连续性的放卷机上放卷，将基材卷尼龙膜张开，在尼龙膜表面流延涂覆所述涂覆液，在75℃热风干燥至所述涂覆液固化，冷却至室温，得到表面包覆有预涂膜的尼龙膜；
(3)涂覆液主涂：采用凹版涂布工艺，在所述预涂膜表面涂覆所述涂覆液，经过100℃的涂布机烘道加热45s，同时在涂布机烘道加热结束前5s结合95℃的红外光照进行烘干，固化、冷却、收卷、在45℃的温度下二次固化48h、分切、包装，得到包覆有防护层的尼龙层。
实施例2
实施例2用于动力电池铝塑膜的尼龙层的制备方法中，步骤(2)与步骤(3)与实施例1相同，其区别仅在于：
涂覆液配制：向配料桶中加入3％的邻甲酚型酚醛环氧树脂、85％的聚偏氯乙烯树脂乳液和12％的乙醇，以100-150r/min的转速搅拌5-10min，然后调至500-800r/min的转速搅拌10-20min至完全溶解，得涂覆液。
实施例3
实施例3用于动力电池铝塑膜的尼龙层的制备方法中，步骤(2)与步骤(3)与实施例1相同，其区别仅在于：
涂覆液配制：向配料桶中加入5％的双酚A型酚醛环氧树脂、70％的聚偏氯乙烯树脂乳液和25％的乙醇，以100-150r/min的转速搅拌5-10min，然后调至500-800r/min的转速搅拌10-20min至完全溶解，得涂覆液。
实施例4
实施例4用于动力电池铝塑膜的尼龙层的制备方法中，步骤(2)与步骤(3)与实施例1相同，其区别仅在于：
涂覆液配制：向配料桶中加入3％的邻甲酚型酚醛环氧树脂、85％的聚醋酸乙烯酯乳液和12％的乙醇，以100-150r/min的转速搅拌5-10min，然后调至500-800r/min的转速搅拌10-20min至完全溶解，得涂覆液。
实施例5
实施例5用于动力电池铝塑膜的尼龙层的制备方法中，步骤(2)与步骤(3)与实施例1相同，其区别仅在于：
涂覆液配制：向配料桶中加入5％的双酚A型酚醛环氧树脂、70％的聚丙烯酸酯乳液和25％的乙醇，以100-150r/min的转速搅拌5-10min，然后调至500-800r/min的转速搅拌10-20min至完全溶解，得涂覆液。
对比例1
对比例1用于动力电池铝塑膜的尼龙层的制备方法中，步骤(2)与步骤(3)与实施例1相同，其区别仅在于：
涂覆液配制：向配料桶中加入1％的苯酚型酚醛环氧树脂、78％的聚氨酯乳液和21％的乙醇，以100-150r/min的转速搅拌5-10min，然后调至500-800r/min的转速搅拌10-20min至完全溶解，得涂覆液。
对比例2
对比例2用于动力电池铝塑膜的尼龙层的制备方法中，步骤(2)与步骤(3)与实施例1相同，其区别仅在于：
涂覆液配制：向配料桶中加入3％的聚硅氧烷树脂、85％的聚偏氯乙烯树脂乳液和12％的乙醇，以100-150r/min的转速搅拌5-10min，然后调至500-800r/min的转速搅拌10-20min至完全溶解，得涂覆液。
对比例3
对比例3用于动力电池铝塑膜的尼龙层的制备方法中，步骤(2)与步骤(3)与实施例1相同，其区别仅在于：
涂覆液配制：向配料桶中加入3％的聚酰胺树脂、85％的聚偏氯乙烯树脂乳液和12％的乙醇，以100-150r/min的转速搅拌5-10min，然后调至500-800r/min的转速搅拌10-20min至完全溶解，得涂覆液。
对比例4
对比例4用于动力电池铝塑膜的尼龙层的制备方法中，步骤(2)与步骤(3)与实施例1相同，其区别仅在于：
涂覆液配制：向配料桶中加入85％的聚偏氯乙烯树脂乳液和15％的乙醇，以100-150r/min的转速搅拌5-10min，然后调至500-800r/min的转速搅拌10-20min至完全溶解，得涂覆液。
对比例5
对比例5用于动力电池铝塑膜的尼龙层的制备方法中，步骤(1)与步骤(2)与实施例1相同，其区别仅在于：
(3)涂覆液主涂：采用凹版涂布工艺，在所述预涂膜表面涂覆所述涂覆液，经过100℃的涂布机烘道加热45s，固化、冷却、收卷、在45℃的温度下二次固化48h、分切、包装，得到包覆有防护层的尼龙层。
对比例6
对比例6用于动力电池铝塑膜的尼龙层的制备方法中，步骤(1)与步骤(2)与实施例1相同，其区别仅在于：
(3)涂覆液主涂：采用凹版涂布工艺，在所述预涂膜表面涂覆所述涂覆液，经过100℃的涂布机烘道加热45s，同时在涂布机烘道加热结束前5s结合95℃的红外光照进行烘干，固化、冷却、收卷、分切、包装，得到包覆有防护层的尼龙层。
对实施例1-5及对比例1-6得到的用于动力电池铝塑膜的尼龙层进行性能测试，结果参见表1。
表1性能测试结果
Figure BDA0002655788060000071
Figure BDA0002655788060000081
另外，本发明还对尼龙膜、实施例1-5及对比例1-6得到的尼龙层进行了耐电解液性能测试，按照常规热法制备铝塑膜，以本发明制备得到的尼龙层作为最外层，将铝塑膜裁条浸泡于电解液中，经过48h后，用沾有酒精的无尘布擦去尼龙层表面的电解液，并用肉眼观察铝塑膜表面的腐蚀情况，实施例1-5铝塑膜最外的尼龙层没有被腐蚀，并且尼龙层与铝箔层不脱层，对比例1-6均出现部分腐蚀现象，尼龙层的腐蚀面积由强到弱依次为对比例4＞对比例1＞对比例2≈对比例3＞对比例5≈对比例6，尤其以单独尼龙膜制备的铝塑膜腐蚀面积最大。
本说明书中各个实施例采用递进的方式描述，每个实施例重点说明的都是与其他实施例的不同之处，各个实施例之间相同相似部分互相参见即可。对于实施例公开的方案而言，由于其与实施例公开的方法相对应，所以描述的比较简单，相关之处参见方法部分说明即可。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (5)

1.一种用于动力电池铝塑膜的尼龙层，其特征在于，由尼龙膜、以及涂覆于所述尼龙膜表面的防护层组成，所述防护层包括1-5wt％的水溶性酚醛环氧树脂、70-85wt％的乳液胶粘剂和余量乙醇；
所述防护层涂覆于所述尼龙膜表面的涂布量为1-10g/m3；
所述用于动力电池铝塑膜的尼龙层的制备方法，包括以下步骤：
(1)涂覆液配制：向配料桶中加入水溶性酚醛环氧树脂、乳液胶粘剂和乙醇，搅拌至完全溶解，得涂覆液；
(2)涂覆液预涂：将尼龙膜基材卷安放在连续性的放卷机上放卷，将基材卷尼龙膜张开，在尼龙膜表面流延涂覆所述涂覆液，热风干燥至所述涂覆液固化，冷却至室温，得到表面包覆有预涂膜的尼龙膜；
(3)涂覆液主涂：采用凹版涂布工艺，在所述预涂膜表面涂覆所述涂覆液，经过涂布机烘道加热和红外光照结合的方式烘干后固化、冷却、收卷、二次固化、分切、包装，得到包覆有防护层的尼龙层；
步骤(2)中所述热风干燥的温度为55-80℃；
步骤(3)中所述涂布机烘道加热的温度为80-125℃，时间为40-45s，所述红外光照的温度为90-100℃，时间为所述涂布机烘道加热结束前的5-6s；
步骤(3)中所述二次固化的温度为40-45℃，固化时间为48-76h。
2.根据权利要求1所述的一种用于动力电池铝塑膜的尼龙层，其特征在于，所述乳液胶粘剂为聚偏氯乙烯树脂乳液、聚醋酸乙烯酯乳液或者聚丙烯酸酯乳液中的任意一种。
3.根据权利要求2所述的一种用于动力电池铝塑膜的尼龙层，其特征在于，所述乳液胶粘剂为聚偏氯乙烯树脂乳液，并且所述聚偏氯乙烯树脂乳液的固含量为60％，其中偏二氯乙烯含量为90-95％。
4.根据权利要求1所述的一种用于动力电池铝塑膜的尼龙层，其特征在于，所述水溶性酚醛环氧树脂为苯酚型酚醛环氧树脂、邻甲酚型酚醛环氧树脂、双酚A型酚醛环氧树脂中的任意一种。
5.根据权利要求1所述的一种用于动力电池铝塑膜的尼龙层，其特征在于，所述尼龙膜为尼龙6或尼龙66材料。
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