CN114045121A - 一种锂电池用单面热熔终止胶带及其制备方法 - Google Patents
一种锂电池用单面热熔终止胶带及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种锂电池用单面热熔终止胶带及其制备方法,包括自上而下依次排列的第一压敏胶层、第二胶黏剂层;所述第一压敏胶层在常温下有粘性,用于粘结锂电池电芯的外表面,所述第二胶黏剂层在常温下低粘性,用于连接第一层压敏胶和基材;所述锂电池用单面热熔胶带总厚为8‑25μm;本发明胶带中使用的材料不与电解液起反应,在电解液中能够保持良好的稳定性,主要靠加热和加压对锂电池电芯和外包装铝塑膜进行粘结,耐电解液老化后粘结强度高;同时该设计使胶带厚度减薄到25μm以下,极大提高电池的能量密度。
Description
技术领域
本发明属于胶黏剂技术领域,尤其涉及一种锂电池用单面热熔终止胶带及其制备方法。
背景技术
锂离子电池是一种可充电电池,由于其工作电压高、体积小、质量轻、能量高、无记忆效应、自放电小、循环寿命长等优点,广泛应用于手机、笔记本等便携式领域。另由于锂离子电池中不含有重金属铬,与镍铬电池相比,大大减少了对环境的污染。
随着科学技术的发展,各个应用领域对锂电池的要求越来越高,特别是高能量密度、轻量化的趋势,而锂电池的抗跌落性能决定着锂电池的稳定性和安全性。现有的解决办法是用热熔胶黏带固定锂电池电芯和外包装铝塑膜的内表面,中国发明专利CN104610883公开了以聚对苯二甲酸乙酯为基材,涂覆合成橡胶苯乙烯-异戊二烯-苯乙烯共聚物(SIS)、低分子量聚烯烃橡胶、石油树脂的橡胶型压敏胶,采用引发剂交联,制成的胶带存在以下几个缺点:(1)胶带总体较厚,一定程度上影响锂电池的能量密度;(2)使用聚对苯二甲酸乙二酯(PET)作为胶带基材,在一定的温度和压力下粘接后,耐电解液后粘接性能差,对电池性能和安全性有潜在的影响。
针对锂电池市场对单面热熔胶带越来越薄的需求,需要提供一款更薄,使用时应力更小的胶带产品,同时能够保证其耐电解液老化后粘接性能,并且不影响锂电池的电性能。
发明内容
本发明针对现有锂电池用单面热熔胶带存在的不足,提供一种锂电池用单面热熔终止胶带及其制备方法。
本发明涉及一种锂电池用单面热熔终止胶带,包括自上而下依次排列的第一压敏胶层、第二胶黏剂层和基材;所述第一压敏胶层在常温下有粘性,用于粘结锂电池电芯的外表面,具有良好的耐电解液性能和初粘性;所述第二胶黏剂层在常温下低粘性,用于连接第一层压敏胶和基材;所述锂电池用单面热熔胶带总厚为8~25μm,本发明胶带中使用的材料不与电解液起反应,在电解液中能够保持良好的稳定性,主要靠加热和加压对锂电池电芯和外包装铝塑膜进行粘结,耐电解液老化后粘结强度高;同时该设计使胶带厚度减薄到25μm以下,极大提高电池的能量密度。
本发明的技术方案如下:
本发明涉及一种锂电池用单面热熔终止胶带,包括自上而下依次排列的第一压敏胶层、第二胶黏剂层和第三层基材。
所述第一压敏胶层的厚度为2~10μm,按重量份计,包括如下组分:
所述第二胶黏剂层的厚度为2~6μm,按重量份计,包括如下组分:
所述第三层为基材层,其厚度为6-12μm;
其中,所述氢化石油树脂I是指软化点为70~125℃的氢化石油树脂,所述氢化石油树脂Ⅱ是指软化点为105~150℃的氢化石油树脂。氢化石油树脂I的软化点较低,作为第一压敏胶层,能够很好地增加胶水体系的柔软度,增加胶水体系的初粘力。氢化石油树脂Ⅱ的软化点较较高,作为第二压敏胶层,不需要初粘力,因此提升软化点,降低胶水体系的柔韧度。
所述氢化苯乙烯嵌段共聚物为氢化苯乙烯-聚异戊二烯-苯乙烯嵌段共聚物(SEPS)、氢化苯乙烯-聚丁二烯-苯乙烯嵌段共聚物(SEBS)的一种或二者的复配。SEPS和SEBS分子量都控制在10000到30000;使胶水体系能够具有很好的耐电解液效果。
所述非晶态α-烯烃共聚物的软化点为70~150℃,160℃熔融粘度为2000~5000mPas,能够有效地提供耐电解液效果。
所述抗氧剂为四(3,5-二叔丁基-4-羟基)苯丙酸季戊四醇酯。
所述氧化聚乙烯蜡,与聚烯烃树脂等有良好的相容性,在常温下的抗湿性能好,耐化学性能优良,厂家为江苏省海安石油化工厂,型号OPE蜡。
所述改性帖烯树脂,为自制改性合成,能够提供较好的耐电解液后粘接性能。作为第一压敏胶层的成分,主要为增加胶水体系的耐电解液后粘接强度。
首先取89g的萜烯树脂,该萜烯树脂软化点温度为90-100℃,放入到三口烧瓶中,加入100g甲苯溶剂,120℃油浴搅拌1h,之后缓慢滴加2g的N,N,N′,N′-四缩水甘油基-4,4′-二氨基二苯甲烷,滴加时间10min,120℃油浴搅拌0.5h后,再加入一滴发烟盐酸,120℃油浴搅拌1.5h后出料,即为改性萜烯树脂,其中后续加入,按照该混合树脂的固体成分比添加。
锂电池用单面热熔终止胶带的制备方法,包括如下步骤:
1)按重量份数称取第一压敏胶层和第二胶黏剂层的原料,分别用溶剂溶解,配制成固含量为20~30wt%的第一压敏胶层和第二胶黏剂层的溶液;
2)将第二胶黏剂层的溶液加入到转移式涂布机中,同时将双面离型膜放置于转移式涂布机的放卷单元,在双面离型膜的一侧涂布第二胶黏剂层,后经过烘道烘干,烘道的温度设置为80~110℃,烘干3~5min后收卷得半成品;
3)将第一压敏胶层的溶液加入到转移式涂布机中,同时将过程膜放入转移式涂布机的第一放卷单元,在过程膜的一侧涂布第一压敏胶层,后经过烘道烘干,烘道的温度设置为80~110℃,烘干3~5min;
4)最后将步骤2)收卷的半成品放入第二放卷单元,与步骤3)所得的涂布在过程膜上的第一压敏胶层于温度为80~100℃、压力0.5~0.6MPa下复合,收卷得成品。制备过程中,所述溶剂为甲苯溶剂。
本发明有益效果:通过制备双层结构的单面热熔终止胶带,自上而下依次排列为第一压敏胶层、第二胶黏剂层和基材,第一层敏胶层通过引入改性萜烯树脂,能够具有较好的初粘性,以及耐电解液老化后粘接性能,第二胶黏剂层能够具有较高的软化点和粘接性能,能够一定程度上屏蔽电解液的渗透,基材则是提供胶水附着地点,三层体系相互支持,最终使得胶带具有优异的耐电解液老化性能。
附图说明
图1为单面热熔终止胶带的图例,1为压敏胶层,2为胶黏剂层,3为基材层。
具体实施方式
以下结合实例对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。
实施例1
一种锂电池用单面热熔终止胶带,总厚25um,包括自上而下依次排列的第一压敏胶层、第二胶黏剂层和第三层基材层;
所述第一压敏胶层的涂布厚度为10μm,按重量份计,包括如下组分:
氢化苯乙烯嵌段共聚物SEBS G1654(Kraton)45份,非晶态α-烯烃共聚物Vestoplast 408(Evonik)5份,氢化石油树脂ARKON P90(Arakawa)40份,改性萜烯树脂5份,抗氧剂Irganox 1010 1份;
所述第二胶黏剂层的涂布厚度为5μm,按重量份计,包括如下组分:
氢化苯乙烯嵌段共聚物SEBS G1654(Kraton)40份,非晶态α-烯烃共聚物Vestoplast 408(Evonik)35份,氢化石油树脂ARKON P125(Arakawa)15份,氧化聚乙烯蜡(江苏省海安石油化工厂,型号OPE蜡)10份,抗氧剂Irganox 1010 1份;
所述第三双面离型膜为厚度10μm的PET膜。
实施例2
一种锂电池用单面热熔终止胶带,总厚20um,包括自上而下依次排列的第一压敏胶层、第二胶黏剂层和第三层基材层;
所述第一压敏胶层的涂布厚度为5μm,按重量份计,包括如下组分:
氢化苯乙烯嵌段共聚物SEBS G1650(Kraton)47份,非晶态α-烯烃共聚物Vestoplast 308(Evonik)5份,氢化石油树脂ARKON P100(Arakawa)40份,改性萜烯树脂5份,抗氧剂Irganox 1010 1份;
所述第二胶黏剂层的涂布厚度为5μm,按重量份计,包括如下组分:
氢化苯乙烯嵌段共聚物SEBS G1650(Kraton)42份,非晶态α-烯烃共聚物Vestoplast 308(Evonik)35份,氢化石油树脂ARKON P125(Arakawa)15份,氧化聚乙烯蜡(江苏省海安石油化工厂,型号OPE蜡)10份,抗氧剂Irganox 1010 1份;
所述第三双面离型膜为厚度10μm的PET膜。
实施例3
一种锂电池用单面热熔终止胶带,总厚16um,包括自上而下依次排列的第一压敏胶层、第二胶黏剂层和第三层基材层;
所述第一压敏胶层的涂布厚度为3μm,按重量份计,包括如下组分:
氢化苯乙烯嵌段共聚物SEPS G1657(Kraton)45份,非晶态α-烯烃共聚物Vestoplast 508(Evonik)10份,氢化石油树脂ARKON P115(Arakawa)39份,改性萜烯树脂5份,抗氧剂Irganox 1076 1份;
所述第二胶黏剂层的涂布厚度为3μm,按重量份计,包括如下组分:
氢化苯乙烯嵌段共聚物SEPS G1657(Kraton)42份,非晶态α-烯烃共聚物Vestoplast 508(Evonik)35份,氢化石油树脂ARKON P140(Arakawa)15份,氧化聚乙烯蜡(江苏省海安石油化工厂,型号OPE蜡)10份,抗氧剂Irganox 1076 1份;
所述第三双面离型膜为厚度10μm的PET膜。
对比例1:
一种锂电池用单面热熔终止胶带,总厚20um,包括自上而下依次排列的第一压敏胶层、第二胶黏剂层和第三层基材层;
所述第一压敏胶层的涂布厚度为5μm,按重量份计,包括如下组分:
氢化苯乙烯嵌段共聚物SEPS G1657(Kraton)45份,非晶态α-烯烃共聚物Vestoplast 508(Evonik)15份,氢化石油树脂ARKON P115(Arakawa)39份,抗氧剂Irganox1076 1份;
所述第二胶黏剂层的涂布厚度为5μm,按重量份计,包括如下组分:
氢化苯乙烯嵌段共聚物SEPS G1657(Kraton)42份,非晶态α-烯烃共聚物Vestoplast 508(Evonik)42份,氢化石油树脂ARKON P140(Arakawa)15份,氧化聚乙烯蜡(江苏省海安石油化工厂,型号OPE蜡)10份,抗氧剂Irganox 1076 1份;
所述第三双面离型膜为厚度10μm的PET膜。
对比例2:
一种锂电池用单面热熔终止胶带,总厚16um,包括自上而下依次排列的第一压敏胶层、第二胶黏剂层和第三层基材层;
所述第一压敏胶层的涂布厚度为3μm,按重量份计,包括如下组分:
氢化苯乙烯嵌段共聚物SEPS G1657(Kraton)45份,非晶态α-烯烃共聚物Vestoplast 508(Evonik)15份,氢化石油树脂ARKON P115(Arakawa)39份,抗氧剂Irganox1076 1份;
所述第二胶黏剂层的涂布厚度为3μm,按重量份计,包括如下组分:
氢化苯乙烯嵌段共聚物SEPS G1657(Kraton)42份,非晶态α-烯烃共聚物Vestoplast 508(Evonik)42份,氢化石油树脂ARKON P140(Arakawa)15份,氧化聚乙烯蜡(江苏省海安石油化工厂,型号OPE蜡)10份,抗氧剂Irganox 1076 1份;
所述第三双面离型膜为厚度10μm的PET膜。
实施例1~3和对比实施例1~2所述单面热熔胶带的制备方法如下:
1)按重量份数称取第一压敏胶层和第二胶黏剂层的原料,分别用甲苯溶解,配制成固含量为20~30wt%的第一压敏胶层和第二胶黏剂层的溶液;
2)将第二胶黏剂层的溶液加入到转移式涂布机中,同时将双面离型膜放置于转移式涂布机的放卷单元,在双面离型膜的一侧涂布第二胶黏剂层,后经过烘道烘干,烘道的温度设置为80~110℃,烘干3~5min后收卷得半成品;
3)将第一压敏胶层的溶液加入到转移式涂布机中,同时将过程膜放入转移式涂布机的第一放卷单元,在过程膜的一侧涂布第一压敏胶层,后经过烘道烘干,烘道的温度设置为80~110℃,烘干3~5min;
4)最后将步骤2)收卷的半成品放入第二放卷单元,与步骤3)所得的涂布在过程膜上的第一压敏胶层于温度为80~100℃、压力0.5~0.6MPa下复合,收卷得成品。
我们对实施例1~3所得胶带以及对比实施例的产品进行了各项性能的测试,测试方法如下:
1)按照国家标准GB/T 2792-2014所述方法进行压敏胶黏带的剥离强度测试;
2)热压后剥离强度测试:第一压敏胶层粘接铝箔、第二胶黏剂层粘接铝塑膜中流延聚丙烯(cast polypropylene),简称cpp层,用大于10kg压力,80~90℃热压60min以上,冷却到常温后按照国家标准GB/T 2792-2014所述方法进行剥离强度测试;
3)热压后浸泡电解液剥离强度测试:按照2)做好测试样件浸泡于锂电池电解液,电解液质量配比如下:EC/PC/DEC/EP=30/10/30/30,1M LiPF6锂盐质量比按12.5%计算。80~90℃6h以上,冷却到常温后按照国家标准GB/T2792-2014所述方法进行剥离强度测试;
4)电解液浸泡颜色测试:浸泡电解液80~90℃6h以上,(胶带和电解液质量比例为1:20~100)观察电解液颜色变化。结果如表1所示:
表1:实施例1~3所得胶带和对比例产品的性能测试数据
从表1所示的结果可以看出,本发明提供的锂电池单面热熔胶带对铝和CPP粘接性能较好,耐电解液老化后粘接强度高,且不与电解液起化学反应。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (6)
2.根据权利要求1所述的锂电池用单面热熔终止胶带,其特征在于,所述改性帖烯树脂制备过程包括:取89g萜烯树脂,该萜烯树脂软化点温度为90-100℃,加入100g甲苯溶剂,120℃油浴搅拌1h,之后缓慢滴加2g N,N,N′,N′-四缩水甘油基-4,4′-二氨基二苯甲烷,滴加时间10min,120℃搅拌0.5h后,再加入一滴发烟盐酸,120℃油浴搅拌1.5h后出料,即为改性帖烯树脂。
3.根据权利要求1所述的锂电池用单面热熔终止胶带,其特征在于,所述氢化石油树脂I是软化点70~125℃的氢化石油树脂,所述氢化石油树脂Ⅱ是软化点105~150℃的氢化石油树脂。
4.根据权利要求1所述的锂电池用单面热熔终止胶带,其特征在于,所述氢化苯乙烯嵌段共聚物为氢化苯乙烯-聚异戊二烯-苯乙烯嵌段共聚物、氢化苯乙烯-聚丁二烯-苯乙烯嵌段共聚物的一种或二者。
5.根据权利要求1所述的锂电池用单面热熔终止胶带,其特征在于,所述抗氧剂为四(3,5-二叔丁基-4-羟基)苯丙酸季戊四醇酯。
6.一种如权利要求1~5任一项所述的锂电池用单面热熔终止胶带的制备方法,其特征在于,包括如下步骤:
1)按重量份数称取第一压敏胶层和第二胶黏剂层的原料,分别用溶剂溶解,配制成固含量为20~30wt%的第一压敏胶层和第二胶黏剂层的溶液;
2)将第二胶黏剂层的溶液加入到转移式涂布机中,同时将双面离型膜放置于转移式涂布机的放卷单元,在双面离型膜的一侧涂布第二胶黏剂层,后经过烘道烘干,烘道的温度设置为80~110℃,烘干3~5min后收卷得半成品;
3)将第一压敏胶层的溶液加入到转移式涂布机中,同时将过程膜放入转移式涂布机的第一放卷单元,在过程膜的一侧涂布第一压敏胶层,后经过烘道烘干,烘道的温度设置为80~110℃,烘干3~5min;
4)最后将步骤2)收卷的半成品放入第二放卷单元,与步骤3)所得的涂布在过程膜上的第一压敏胶层于温度为80~100℃、压力0.5~0.6MPa下复合,收卷得成品。
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