CN111303800A - 一种锂电池铝塑膜胶粘剂的固化体系设计方法 - Google Patents
一种锂电池铝塑膜胶粘剂的固化体系设计方法 Download PDFInfo
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Abstract
本发明提供一种锂电池铝塑膜胶粘剂的固化体系设计方法,所述的胶粘剂为烯烃类聚合物,所述固化剂(A)是环氧树脂体系中的一种或几种混合物,但不含有缩水甘油胺型环氧树脂;所述第三组分(B)为催化剂。所述三组分的固化体系提供了更优越的粘结性能和粘结效率。
Description
技术领域
本发明涉及锂电池软包装技术领域,特别是锂电池胶粘剂的固化体系设计方法。更具体说,设计烯烃聚合物为主剂,环氧类化合物(固化剂A)为固化剂组分,第三组分是催化剂组分。
背景技术
锂离子电池软包装已经在锂电领域应用越来越广泛,其通过复合而成,从外到内依次为尼龙、外层胶、铝箔、内层胶、cpp;其中内层胶对铝塑膜的耐腐蚀起到决定性的作用,一旦内层胶出现腐蚀,会造成cpp与铝箔层分离,造成锂电池胀气、漏液等问题。
目前粘结cpp和铝箔的胶水全部采用双组分固化方式,主剂一般为聚烯烃类聚合物,固化剂体系的设计为环氧固化剂或者异氰酸酯固化剂。
CN106459703A专利采用改性聚烯烃或者改性氯化聚烯烃树脂,固化剂采用缩水甘油胺型环氧树脂和缩水甘油醚型环氧树脂,采用的是环氧体系,在粘结效率上有一定的局限。
CN109476969A专利采用改性聚烯烃,固化剂采用缩水甘油胺型环氧树脂和缩水甘油醚型环氧树脂,两种环氧树脂都是必须使用的;本专利要求不使用缩水甘油胺型环氧树脂。同时CN109476969A的酸酐单体或含两个以上氮杂环化合物的添加,或者杂环化合物与其他化合物并用,有利于耐化学品的提升。而本专利则不采用具有两个氮及以上的杂环式化合物,效果更优。
采用目前市售方案,或者本文提到的另外2个专利的方法,在粘结效果和效率上存在一定的不足,粘结性和耐腐蚀性仍有提高空间,尤其在要求更高的动力电池铝塑膜领域,看似很小的性能提升,都能提供更优的使用效果。本固化体系促进剂的设计方法可以解决这一问题。
发明内容
发明所解决的问题
采用目前市售方案,或者本文提到的另外2个专利的方法,在粘结效果和效率上存在一定的不足,粘结性和耐腐蚀性仍有提高空间,尤其在要求更高的动力电池铝塑膜领域,看似很小的性能提升,都能提供更优的使用效果。本发明人进行深入研究,设计出本固化体系,可以有所提升。
用于解决问题的方法
为解决上述问题,本发明人进行以下的固化体系设计。
由烯烃类聚合物构成主剂,所述固化剂(A)是环氧树脂体系中的一种或几种混合物,但不含有缩水甘油胺型环氧树脂;所述第三组分(B)为催化剂。
胶粘剂主剂的特征在于所述主体聚合物由改性氯化聚丙烯、改性氯化聚乙烯、改性聚丙烯、改性聚乙烯、改性乙烯丙烯酸共聚物、改性苯乙烯、改性POE、改性EVA、改性环烯烃、改性聚丁烯、改性聚戊烯中的一种或多种。同时添加部分助剂购成,包括增粘剂、抗水解剂、消泡剂、流平剂、润湿剂、增溶剂等。
固化剂(A)是环氧体系,包括含有环氧基的小分子或高分子聚合物,但不含有缩水甘油胺型环氧树脂。
第三组分(B)是催化剂组分,包含含羟基化合物、芳基取代脲、氨化酰亚胺、超配位硅酸盐、金属羧酸盐、金属羧酸盐络合物、乙酰丙酮金属盐、季磷化合物、含有一个氮的化合物、三氟化硼-胺络合物、二茂铁基化合物、复合纳米二氧化钛等的一种或几种。可从市售产品中进行选择,亦可根据基团特点自己合成所得。
粘合剂为三组分设计,用于锂电池铝塑膜中金属与cpp之间的粘结。本固化体系设计方法可以有更高的粘结强度和粘结效率。
具体实施方法
下文中,对于本发明的实施方式进行详细说明。
主剂
本发明中使用的主剂的特征在于所述主体聚合物由改性氯化聚丙烯、改性氯化聚乙烯、改性聚丙烯、改性聚乙烯、改性乙烯丙烯酸共聚物、改性苯乙烯、改性POE、改性EVA、改性环烯烃、改性聚丁烯、改性聚戊烯中的一种或多种。同时添加部分助剂购成,包括增粘剂、抗水解剂、消泡剂、流平剂、润湿剂、增溶剂等。没有特别限制,可以采用公知的熔融法、溶液法、辐射法中的任何一种方法制得。主剂可以选择日本东洋纺、日本制纸、三井化学、成都科成精化科技有限公司的市售产品,但亦不限于此。
固化剂
本发明采用环氧体系,包括含有环氧基的小分子或高分子聚合物,但不含有缩水甘油胺型环氧树脂。分子量不做特别限定,可从市售产品中进行测试优选。
固化剂的加量,针对主剂的0.1%-10%之间。
催化剂
本发明采用的催化剂,包含含羟基化合物、芳基取代脲、氨化酰亚胺、超配位硅酸盐、金属羧酸盐、金属羧酸盐络合物、乙酰丙酮金属盐、季磷化合物、含有一个氮的化合物、三氟化硼-胺络合物、二茂铁基化合物、复合纳米二氧化钛等的一种或几种。可从市售产品中进行选择,亦可根据基团特点自己合成所得。
催化剂的加量,针对主剂的0.001%-0.1%之间。
制造例1
东洋纺的PMA-KE100份作为主剂,1份作为固化剂的环氧树脂E-51,1份催化剂复合纳米二氧化钛。使用前将主剂、固化剂、催化剂混合均匀,进行涂布复合,而后继续进行测试剥离强度。
制造例2
将东洋纺的PMA-KE换成成都科成精化科技有限公司的LN-1212,其他与制造例1相同。
制造例3
将催化剂换成二茂铁基催化剂,将二茂铁的同系物环己基二茂铁与等当量的氯醌反应,得到催化剂,其他与制造例2相同。
制造例4
将催化剂换成三氟化硼单乙胺,其他与制造例2相同。
制造例5
将催化剂换成四丁基乙酸鳞,其他与制造例2相同。
制造例6
将催化剂换成乙酰丙酮铬,其他与制造例2相同。
制造例7
将催化剂换成四乙基溴化铵,其他与制造例2相同。
制造例8
将催化剂换成苄基二甲胺双苯基硅酸盐,其他与制造例2相同。
制造例9
将催化剂换成氮化酰亚胺,其他与制造例2相同。
制造例10
将催化剂换成N-二缩水甘油对甲苯胺,其他与制造例2相同。
制造例11
对比例1
采用东洋纺市售主剂和市售环氧固化剂(含有缩水甘油胺型环氧树脂和缩水甘油醚型环氧树脂,而制造例中皆不含缩水甘油胺型环氧树脂),进行涂布复合,而后继续进行测试剥离强度。
对比例2
采用东洋纺市售主剂和市售环氧固化剂(含有缩水甘油胺型环氧树脂和缩水甘油醚型环氧树脂,而制造例中皆不含缩水甘油胺型环氧树脂),同时添加酸酐单体(新日本理化制的RIKACID)和1,2-二甲基咪唑进行涂布复合,而后继续进行测试剥离强度。
对比例3
采用三井化学市售主剂和市售异氰酸酯固化剂,进行涂布复合,而后继续进行测试剥离强度。
说明
剥离强度是指15mm,180度剥离强度数据,5支样条重复数据平均值。
耐电解液是指在85℃,加水0.1%,将样条放入电解液中测试。取出后用水冲干净,然后将水擦干进行测试。
以上制造例无法全部列举出所有种类,不限于以上一种催化剂,亦可多种催化剂共混使用。以上制造例按照锂电池铝塑膜干法工艺进行使用,结果满足锂电池铝塑膜的使用要求,同时部分在粘结效率和强度上优于目前市售主流粘结体系。
Claims (5)
1.一种锂电池铝塑膜胶粘剂的固化体系设计方法,其特征在于使用三组分固化体系;由烯烃类聚合物构成主剂,所述固化剂(A)是环氧树脂体系中的一种或几种混合物,但不含有缩水甘油胺型环氧树脂,所述第三组分(B)为催化剂。
2.根据权利要求1所述的固化体系设计方法,胶粘剂主剂的特征在于所述主体聚合物由改性氯化聚丙烯、改性氯化聚乙烯、改性聚丙烯、改性聚乙烯、改性乙烯丙烯酸共聚物、改性苯乙烯、改性POE、改性EVA、改性环烯烃、改性聚丁烯、改性聚戊烯中的一种或多种;同时添加部分助剂购成,包括增粘剂、抗水解剂、消泡剂、流平剂、润湿剂、增溶剂等。
3.根据权利要求1所述的固化体系设计方法,固化剂(A)是环氧体系,包括含有环氧基的小分子或高分子聚合物,但不含有缩水甘油胺型环氧树脂。
4.根据权利要求1所述的固化体系设计方法,第三组分(B)是催化剂,包含含羟基化合物、芳基取代脲、氨化酰亚胺、超配位硅酸盐、金属羧酸盐、金属羧酸盐络合物、乙酰丙酮金属盐、季磷化合物、含有一个氮的化合物、三氟化硼-胺络合物、二茂铁基化合物、复合纳米二氧化钛等的一种或几种;可从市售产品中进行选择,亦可根据基团特点自己合成所得。
5.根据权利要求1-4中的粘合剂为三组分设计,用于锂电池铝塑膜中金属与cpp之间的粘结。
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CN112538322A (zh) * | 2020-12-08 | 2021-03-23 | 成都科成精化科技有限公司 | 一种锂电池铝塑膜胶粘剂的固化体系设计方法 |
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CN108291125A (zh) * | 2015-12-01 | 2018-07-17 | 琳得科株式会社 | 粘接剂组合物、密封片和密封体 |
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