CN108598552B - 一种阻水阻燃的锂电池封装用复合膜及其制备方法 - Google Patents

一种阻水阻燃的锂电池封装用复合膜及其制备方法 Download PDF

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CN108598552B
CN108598552B CN201810301171.6A CN201810301171A CN108598552B CN 108598552 B CN108598552 B CN 108598552B CN 201810301171 A CN201810301171 A CN 201810301171A CN 108598552 B CN108598552 B CN 108598552B
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徐雄剑
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Anhui Greentech Technology Co ltd
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Abstract

本发明提高了一种阻水阻燃的锂电池封装用复合膜，包括改性铝箔基础层和设于改性铝箔基础层上、下两表面的设有阻燃层，所述阻燃层的外侧设有热塑性树脂层，所述阻燃层是由阻燃剂均匀分散在接着剂中形成；所述改性铝箔基础层先表面经过钝化处理进行，然后使用有机硅油防水剂进行表面改性两次；所述热塑性树脂层通过所述阻燃层粘结在铝箔基础层上，再经压合成铝塑膜。本发明提供一种阻水阻燃的锂电池封装用复合膜和制备方法，制备得到的复合膜具有高阻水阻燃性，并且工艺制备流程简单，成本低。

Description

一种阻水阻燃的锂电池封装用复合膜及其制备方法
技术领域
本发明涉及封装材料领域，具体涉及一种阻水阻燃的锂电池封装用复合膜及其制备方法。
背景技术
由于铝塑膜制作成本低，且构成液态软包装锂离子电池的一个不可缺少的重要组成部分，目前铝塑复合膜作为电池的外壳，取代了一般锂离子电池的钢制或铝制外壳，铝塑复合膜大致可以分为三层：内层为粘结层，多采用聚乙烯或聚丙烯材料，起封口粘结作用；中间层为铝箔，能够防止电池外部水汽的渗入，同时防止内部电解液的渗出；外层为保护层，多采用高熔点的聚酯或尼龙材料，有很强的机械性能，防止外力对电池的损伤，起保护电池的作用。
目前商业化的软包锂离子电池的铝塑膜没有阻燃效果，用在超过200Ah的大容量电池时无法保证安全性。如充电电压高，而且电解质多为有机易燃物，若使用不当，电池会发生危险甚至爆炸。为了提高铝塑膜的阻燃性，目前是通过在电解液中添加一些高沸点、高闪点和不易燃的溶剂来改善电解液的稳定性，该溶剂主要分有机磷化物、有机氟代化合物和卤代烷基磷酸酯。但这些溶剂使电解液的粘度增大、阻抗增大，影响电池的使用性能。另外，也在直接在电解液里面添加阻燃剂，从而导致电池内阻增大，恒流比、电压平台变差，而且还无法保证所有安全测试通过。铝塑膜一般由三层膜材料复合而成，从外到内依次是保护层、铝箔层、耐腐蚀热封层，通常保护层是双向拉伸的尼龙膜（BOPA膜）、铝箔层采用单面或双面钝化处理、耐腐蚀层是流延聚丙烯膜（CPP膜）。外层的尼龙膜，由于本身易吸水，且阻水性较差，对使用环境要求较高，保存期短，用于尼龙膜和中间层铝箔粘结胶黏剂也易因水解造成粘结力降低等问题，尼龙膜本身阻燃性也不佳，在电池短路、受挤压等引发起火的情况下，不能有效的保证安全。
发明内容
本发明提供一种阻水阻燃的锂电池封装用复合膜和制备方法，制备得到的复合膜具有高阻水阻燃性，并且工艺制备流程简单，成本低。
一种阻水阻燃的锂电池封装用复合膜，包括改性铝箔基础层和设于改性铝箔基础层上、下两表面的设有阻燃层，所述阻燃层的外侧设有热塑性树脂层，所述阻燃层是由阻燃剂均匀分散在接着剂中形成；所述改性铝箔基础层先表面经过钝化处理进行，然后使用有机硅油防水剂进行表面改性两次；所述热塑性树脂层通过所述阻燃层粘结在铝箔基础层上，再经压合成铝塑膜。
进一步地，其中铝箔经腐蚀和清洗处理工艺后，将铝箔在磷酸的水溶液中浸渍，再经纯水清洗和热处理。进一步地，其中磷酸的水溶液的浓度为2-5%，浸渍时间为60-90s，热处理温度为250-300℃。
进一步地，其中有机硅油防水剂进行表面改性步骤为将铝箔基础层浸渍入油性有机硅防水剂中30-90s，在140-160℃进行热处理30-60s，重复一次。
进一步地，其中接着剂为环氧树脂、丙烯酸树脂、有机硅树脂、或有机氟树脂之一。
进一步地，其中所述阻燃剂为三聚氰胺、三聚氰胺磷酸盐中至少一种。
进一步地，其中所述阻燃层中接着剂和阻燃剂的质量比为1：（0.4-0.8）。
进一步地，其中热塑性树脂层按质量份包括均聚聚丙烯50-60质量份、聚偏氟乙烯10-20质量份、苯乙烯10-20质量份、抗氧剂1-2质量份。
进一步地，其中所述热塑性树脂层的厚度为20-30μm、阻燃层的厚度为2-4μm、铝箔基础层的厚度为40μm。
进一步地，其中所述有机硅油防水剂为低分子聚硅氧烷防水剂。
一种上述的锂电池封装用复合膜的生产工艺，包括：
（1）基层铝箔层采用厚度为40μm的退火软铝，对铝箔双面进行表面钝化处理，然后进行有机硅油防水剂进行表面改性，然后在基层铝箔层涂布阻燃层；
（2）将热塑性树脂熔融挤出成预定厚度的热塑性树脂层；
（3）将步骤2的热塑性树脂层通过阻燃层粘结在铝箔基础层上，再经压合成铝塑膜。
本发明通过对铝箔双面进行进行表面钝化处理，在铝箔表面形成致密的氧化物保护层，提高了阻水性，然后在氧化物表面上进行有机硅油防水剂进行处理，当聚硅乳加热到140℃以上时，聚硅氧烷在织物上定向排列，疏水基-CH3朝外，聚硅油乳液的硅原子、氧原子与纤维上的某些原子形成配价键和氢键，因而水蒸汽、空气能通过织物，水珠却不能透过。有机硅油防水剂有渗透性和成膜性两种，成膜性一般为含端氢硅油的大分子聚硅油，渗透性为小分子量的聚硅油，本发明中优选为小分子量的聚硅油，因为大分子的硅油成的膜，会影响粘合的强度。并且通过两次重复处理，可以更加均匀形成防水层。阻燃层加入三聚氰胺阻燃剂，可有有效阻燃，并且三聚氰胺具有很好的相容性。在热塑性树脂层加入聚偏氟乙烯形成的高分子组合物，具有较强的密封性和防水性，并且能提高热封效果。
本发明的有益技术效果：
本发明通过对铝箔双面进行进行表面钝化处理，进行有机硅油防水剂表面防水处理，防水剂优选为低分子的有机聚硅氧烷，并在阻燃层加入三聚氰胺阻燃剂，同时热塑性树脂层加入一定量的聚偏氟乙烯，实现了铝塑膜的高阻水和阻燃性，并且产品的其他性能达标，适合锂电池的软包装。
具体实施方式
下面结合具体实施例对本发明做进一步说明。
有机硅防水剂购自杭州瑞江新材料技术有限公司的大分子有机聚硅氧烷RJ-202，低分子聚硅氧烷防水剂RJ-WP03E。
实施例1
一种上述的锂电池封装用复合膜的生产工艺，包括：
（1）基层铝箔层采用厚度为40μm的退火软铝，铝箔经腐蚀和清洗处理工艺后，将铝箔在3%磷酸的水溶液中浸渍，浸渍时间为75s，再经纯水清洗和热处理，热处理温度为280℃对铝箔双面进行表面钝化处理，将铝箔基础层浸渍入低分子聚硅氧烷防水剂RJ-WP03E中60s，在150℃进行热处理40s，重复一次，然后在基层铝箔层涂布阻燃层，其中所述阻燃层包括接着剂环氧树脂和阻燃剂三聚氰胺的质量比为1：0.6；
（2）热塑性树脂层按质量份包括均聚聚丙烯55质量份、聚偏氟乙烯15质量份、苯乙烯15质量份、抗氧剂B215 1.5质量份，将热塑性树脂熔融挤出成预定厚度的热塑性树脂层；
（3）将步骤2的热塑性树脂层通过阻燃层粘结在铝箔基础层上，再经压合成铝塑膜。
调节参数，控制热塑性树脂层的厚度为25μm、阻燃层的厚度为3μm、铝箔基础层的厚度为40μm。
实施例2
一种上述的锂电池封装用复合膜的生产工艺，包括：
（1）基层铝箔层采用厚度为40μm的退火软铝，铝箔经腐蚀和清洗处理工艺后，将铝箔在5%磷酸的水溶液中浸渍，浸渍时间为60s，再经纯水清洗和热处理，热处理温度为300℃对铝箔双面进行表面钝化处理，将铝箔基础层浸渍入低分子聚硅氧烷防水剂RJ-WP03E中30s，在140-160℃进行热处理60s，重复一次，然后在基层铝箔层涂布阻燃层，其中所述阻燃层包括接着剂环氧树脂和阻燃剂三聚氰胺的质量比为1：0.4；
（2）热塑性树脂层按质量份包括均聚聚丙烯60质量份、聚偏氟乙烯10质量份、苯乙烯20质量份、抗氧剂B215 1质量份，将热塑性树脂熔融挤出成预定厚度的热塑性树脂层；
（3）将步骤2的热塑性树脂层通过阻燃层粘结在铝箔基础层上，再经压合成铝塑膜。
调节参数，控制热塑性树脂层的厚度为30μm、阻燃层的厚度为2μm、铝箔基础层的厚度为40μm。
实施例3
一种上述的锂电池封装用复合膜的生产工艺，包括：
（1）基层铝箔层采用厚度为40μm的退火软铝，铝箔经腐蚀和清洗处理工艺后，将铝箔在2%磷酸的水溶液中浸渍，浸渍时间为90s，再经纯水清洗和热处理，热处理温度为250℃对铝箔双面进行表面钝化处理，将铝箔基础层浸渍入低分子聚硅氧烷防水剂RJ-WP03E中90s，在140℃进行热处理60s，重复一次，然后在基层铝箔层涂布阻燃层，其中所述阻燃层包括接着剂环氧树脂和阻燃剂三聚氰胺的质量比为1：0.8；
（2）热塑性树脂层按质量份包括均聚聚丙烯50质量份、聚偏氟乙烯20质量份、苯乙烯10质量份、抗氧剂B215 2质量份，将热塑性树脂熔融挤出成预定厚度的热塑性树脂层；
（3）将步骤2的热塑性树脂层通过阻燃层粘结在铝箔基础层上，再经压合成铝塑膜。
调节参数，控制热塑性树脂层的厚度为20μm、阻燃层的厚度为4μm、铝箔基础层的厚度为40μm。
对比例1
与实施例1相同，除了铝箔双面不进行进行表面钝化处理。
对比例2
与实施例1相同，除了铝箔双面不进行有机硅油防水剂表面处理。
对比例3
与实施例1相同，除了铝箔双面的有机硅油防水剂为大分子有机聚硅氧烷RJ-202。
对比例4
与实施例1相同，除了阻燃层不加入三聚氰胺阻燃剂。
对比例5
与实施例1相同，除了热塑性树脂层不加入聚偏氟乙烯。
将上述实施例与对比例制备的铝塑膜分别做成200Ah锂离子电池，然后按照本行业的标准GB/T18287-2013检测锂离子电池的安全性。结果如表1所示。根据GB 1037标准，使用透水性测试仪测试24h内透过制备的铝塑膜的透水量。结果如表1所示。
表1 实施例与对比例的性能测试结果
对比实施例与对比例发现，本发明通过对铝箔双面进行进行表面钝化处理，进行有机硅油防水剂表面防水处理，防水剂优选为低分子的有机聚硅氧烷，并在阻燃层加入三聚氰胺阻燃剂，同时热塑性树脂层加入一定量的聚偏氟乙烯，实现了铝塑膜的高阻水和阻燃性，并且产品的其他性能达标，适合锂电池的软包装。

Claims (7)

1.一种阻水阻燃的锂电池封装用复合膜，包括改性铝箔基础层和设于改性铝箔基础层上、下两表面的阻燃层，所述阻燃层的外侧设有热塑性树脂层，所述阻燃层是由阻燃剂均匀分散在接着剂中形成；所述改性铝箔基础层先表面经过钝化处理进行，然后使用有机硅油防水剂进行表面改性两次；所述热塑性树脂层通过所述阻燃层粘结在铝箔基础层上，再经压合成铝塑膜；所述钝化处理为铝箔经腐蚀和清洗处理工艺后，将铝箔在磷酸的水溶液中浸渍，再经纯水清洗和热处理；所述有机硅油防水剂进行表面改性步骤为将铝箔基础层浸渍入油性有机硅防水剂中30-90s，在140-160℃进行热处理30-60s，重复一次；所述有机硅油防水剂为低分子聚硅氧烷防水剂RJ-WP03E；所述热塑性树脂层按质量份包括均聚聚丙烯50-60质量份、聚偏氟乙烯10-20质量份、苯乙烯10-20质量份、抗氧剂1-2质量份。
2.根据权利要求1所述的锂电池封装用复合膜，其中磷酸的水溶液的浓度为2-5％，浸渍时间为60-90s，热处理温度为250-300℃。
3.根据权利要求1所述的锂电池封装用复合膜，其中接着剂为环氧树脂、丙烯酸树脂、有机硅树脂、或有机氟树脂之一。
4.根据权利要求1所述的锂电池封装用复合膜，其中所述阻燃剂为三聚氰胺、三聚氰胺磷酸盐中至少一种。
5.根据权利要求1所述的锂电池封装用复合膜，其中所述阻燃层中接着剂和阻燃剂的质量比为1：(0.4-0.8)。
6.根据权利要求1所述的锂电池封装用复合膜，其中所述热塑性树脂层的厚度为20-30μm、阻燃层的厚度为2-4μm、铝箔基础层的厚度为40μm。
7.一种根据权利要求1-6所述的锂电池封装用复合膜的生产工艺，包括：(1)基层铝箔层采用厚度为40μm的退火软铝，对铝箔双面进行表面钝化处理，然后进行有机硅油防水剂进行表面改性，然后在基层铝箔层涂布阻燃层；
(2)将热塑性树脂熔融挤出成预定厚度的热塑性树脂层；
(3)将步骤2的热塑性树脂层通过阻燃层粘结在铝箔基础层上，再经压合成铝塑膜。
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