CN111363498B - 一种锂电池用密封胶黏剂及其制备方法 - Google Patents
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Abstract
本发明提供了锂电池用密封胶黏剂及其制备方法,其包括:聚苯乙烯、聚丁二烯、苯乙烯‑丁二烯共聚物、氢化萜烯树脂、溶剂、乙二醇、引发剂、聚乙烯吡咯烷酮、纤维素接枝壳聚糖和纳米碳酸钙;所述氢化萜烯树脂具有50℃以下的玻璃化转变温度,所述聚乙烯吡咯烷酮的K值为20‑40之间,所述纳米碳酸钙的粒径为20‑50nm;聚乙烯吡咯烷酮、纤维素接枝壳聚糖、纳米碳酸钙的质量比为1:2‑5:0.2‑0.5,所述溶剂与乙二醇的质量比为2:1。本发明的胶黏剂用于锂电池的制备,具有增强的耐电解液性能和粘结力,并且大幅提高生产效率,降低了生产成本。
Description
技术领域
本发明涉及一种胶黏剂,特别涉及一种锂电池用密封胶黏剂及其制备方法。
背景技术
锂电池用密封胶黏剂用于将卷芯与电池外包装材料进行粘结固定。因为铝塑膜化学稳定性好,拉伸强度高,所以常被锂电池用作外包装材料;铝塑膜由聚丙烯、铝、尼龙构成,聚丙烯和尼龙分别在铝两面。作为锂电池外包装材料,聚丙烯面要能够耐锂电池用电解液的浸泡和腐蚀,同时还要跟卷芯要有较好的粘结力,因此要使用一款密封胶黏剂进行粘结,该密封胶黏剂要求跟卷芯及铝塑膜聚丙烯面要粘结牢固;锂电池工艺中要求在整形前期,铝塑膜和卷芯要能够移动,从而调整卷芯位置,所以要求胶黏剂在整形前期不能跟聚丙烯面发生粘结作用,在后续工序中如高温高压工序中发挥粘结性,从而将聚丙烯面粘结。锂电池内部充满电解液,在充放电过程中还伴随电化学反应,在其内部使用的胶粘剂要求化学稳定性好,不参加电化学反应,不能被电解液溶解;现有的密封胶黏剂不能满足上述性能要求。
CN104559846A公开了一种锂电池用常温无粘性密封胶黏剂及其制备方法,该密封胶黏剂在室温下不胶黏,在高温下能实现胶黏,但是其存在胶黏剂的黏胶强度不够,抗电解质能力不强的问题,其制备方法过于复杂将造成大规模化生产的成本过高的问题。
发明内容
针对上述问题,本发明提供了一种锂电池用密封胶黏剂,该密封胶黏剂在室温下胶黏速度慢,在高温下能实现快速胶黏,且黏胶强度大,抗电解质能力强,且制备流程简单,成本低,适合工业化生产。
本发明提供了一种锂电池用密封胶黏剂,其包括:聚苯乙烯、聚丁二烯、苯乙烯-丁二烯共聚物、氢化萜烯树脂、溶剂、乙二醇、引发剂、聚乙烯吡咯烷酮、纤维素接枝壳聚糖和纳米碳酸钙;所述氢化萜烯树脂具有50℃以下的玻璃化转变温度,所述聚乙烯吡咯烷酮的K值为20-40之间,所述纳米碳酸钙的粒径为20-50nm;聚乙烯吡咯烷酮、纤维素接枝壳聚糖、纳米碳酸钙的质量比为1:2-5:0.2-0.5,所述溶剂与乙二醇的质量比为2:1。
进一步地,聚乙烯吡咯烷酮、纤维素接枝壳聚糖、纳米碳酸钙的质量比为1:3:0.3。
进一步地,按质量份,聚苯乙烯10~25质量份、聚丁二烯10~25质量份、苯乙烯-丁二烯共聚物5~15质量份、氢化萜烯树脂5~15质量份、溶剂20~40质量份、乙二醇10-20质量份、引发剂0.5~1质量份、聚乙烯吡咯烷酮1-2质量份、纤维素接枝壳聚糖2-10质量份和纳米碳酸钙0.2-1质量份。
进一步地,溶剂为甲苯、异丙醇、二甲苯、异构十二烷和乙酸丁酯中的一种或一种以上的混合物。
进一步地,所述引发剂为过氧化苯甲酰、过硫酸钾、偶氮二异丁腈和N,N-二乙基苯胺的一种或一种以上的混合物。
本发明还提供了一种锂电池用密封胶黏剂的制备方法,其特征在于:包括以下加工步骤:
步骤A、按照配方准确称取配方量的物料,分别放置到不同的容器中;
步骤B、将聚苯乙烯、聚丁二烯、苯乙烯-丁二烯共聚物、氢化萜烯树脂、溶剂加入第一反应釜中,升温至95~105℃;
步骤C、将乙二醇、聚乙烯吡咯烷酮、引发剂混合均匀形成混合液,将混合液缓慢滴加到反应釜中,滴加时间为1~2小时,恒温1~2小时,;
步骤D、降温至室温后,纤维素接枝壳聚糖和纳米碳酸钙加入,搅拌均匀,即得成品。
胶黏剂中加入具有50℃以下的玻璃化转变温度的氢化萜烯树脂,可以有效的增强初始粘结力和抗电解液能力。具有50℃以下Tg的萜烯系树脂,可以防止由于高玻璃化转变温度而导致在高温胶黏时产生裂缝,从而导致粘结力强度下降,同时可以保持胶黏剂的柔软性,从而进一步提高强度。氢化萜烯系树脂降低其溶解度参数(SP)值,这提高与其他聚合物组分相容性,使胶黏更充分均匀。
加入乙二醇作为溶剂一部分可以起到一定增强作用。乙二醇作为常见的醇类抗冻剂,可以有效起到降低室温条件下胶黏速度,从而使室温条件下,胶黏速度较慢,便于锂电池的生产过程中进行调节。而在高温下,乙二醇具有更好的挥发性,从而促进胶黏快速形成。
K值通常用粘数来表示聚合物分子量大小,划分聚合物型号。在国际上还有用K值或聚合度来划分聚合物型号。国标GB/T5761-2006中规定粘数、K值和平均聚合度的测定方法可任选其一,若有争议,以GB/T3401为仲裁方法。K值测定也按GB/T3401进行,并通过公式计算得到K值。聚乙烯吡咯烷酮按其平均分子量大小分为四级,***均分子量范围。K值实际上是与聚乙烯吡咯烷酮水溶液的相对粘度有关的特征值,而粘度又是与高聚物分子量有关的物理量,因此可以用K值来表征聚乙烯吡咯烷酮的平均分子量。通常K值越大,其粘度越大,粘接性越强。
加入K值为20-40之间的聚乙烯吡咯烷酮,可以有效的增强初始粘结力和抗电解液能力。K值与分子量密切相关,通过调节K值,从而控制加入的聚乙烯吡咯烷酮的分子量,K也有粘度密切相关,K值越大粘度越高。通过控制K值,从而使聚乙烯吡咯烷酮作为添加剂调控粘度,从而使室温条件下降低胶黏剂的粘度,使其较慢的胶黏。同时其成膜性,在发生胶黏时,能有效促进胶黏层的均匀形成。
加入纤维素接枝壳聚糖或纳米碳酸钙,可以有效的增强抗电解液的能力。纤维素接枝壳聚糖通过表面改性,使壳聚糖表面具有丰富的极性基团,不容易团聚,并且可以有效防止极性电解液对胶黏剂的腐蚀作用。纳米碳酸钙作为一种无机填料添加,可以有效分散在胶黏剂中,进一步提高其耐腐蚀作用。同时加入聚乙烯吡咯烷酮,纤维素接枝壳聚糖,纳米碳酸钙,比单独加入任一种物质,效果都要优异,这是因为这3者之间具有促进的协同作用。聚乙烯吡咯烷酮作为一种高分子表面活性剂,与纤维素接枝壳聚糖和纳米碳酸钙,都具有良好的亲和性,可以促进这两者在胶黏中过程的分散,从而使胶黏层更加均匀,抗电解液效果更好。纳米碳酸钙作为纤维素接枝壳聚糖为主体的填料的一种补充,可以填充在壳聚糖与其它组分的空隙之间,使胶黏剂抗电解液能力进一步提高。
本发明的胶黏剂制备工艺与传统的工艺如CN104559846A公开的方法相比,流程简单,设备少,成本低,适合工业化生产。
本发明提供了一种锂电池用密封胶黏剂,该密封胶黏剂在室温下胶黏速度慢,在高温下能实现快速胶黏,且黏胶强度大,抗电解质能力强,且制备流程简单,成本低,适合工业化生产。
具体实施方式
下面结合具体实施例解释本发明。
聚苯乙烯10~25质量份、聚丁二烯10~25质量份、苯乙烯-丁二烯共聚物(SBS)5~15质量份、氢化萜烯树脂5~15质量份、甲苯20~40质量份、乙二醇10-20质量份、过氧化苯甲酰0.5~1质量份、聚乙烯吡咯烷酮1-2质量份、纤维素接枝壳聚糖2-10质量份和纳米碳酸钙0.2-1质量份。所述氢化萜烯树脂具有50℃以下的玻璃化转变温度,所述聚乙烯吡咯烷酮的K值为20-40之间,所述纳米碳酸钙的粒径为20-50nm;聚乙烯吡咯烷酮、纤维素接枝壳聚糖、纳米碳酸钙的质量比为1:2-5:0.2-0.5,所述溶剂与乙二醇的质量比为2:1。
氢化萜烯树脂1:由Yasuhara Chemical Co.,Ltd.制造的P85(Tg:43)
氢化萜烯树脂2:由Yasuhara Chemical Co.,Ltd.制造的P150(Tg:90)
聚乙烯吡咯烷酮1:BASF Luvikol K30(K=27-33)
聚乙烯吡咯烷酮2:BASF Luvikol K80(K=74-82)
纤维素接枝壳聚糖的制备:将纤维素加入到蒸馏水中,搅拌分散,通30min氮气除氧,然后在氮气保护下加入过硫酸钾溶液,在55℃下预处理2h,然后加入溶有交联剂的壳聚糖的1wt%乙酸溶液,在50℃反应4h,反应结束后,水洗除去水溶性杂质,然后将产物放入1wt%乙酸溶液中萃取24h继续除去均聚物,然后再水洗,抽滤,干燥,得纤维素接枝壳聚糖;纤维素与壳聚糖的质量比为2:1,过硫酸钾在混合液中的浓度为1.5mmol/L,交联剂在混合液中的浓度为0.12ml/100ml,壳聚糖在混合液中的浓度为0.5g/100ml。
按表1的配方,如下制备锂电池用密封胶黏剂,包括以下加工步骤:
步骤A、按照配方准确称取配方量的物料,分别放置到不同的容器中;
步骤B、将聚苯乙烯、聚丁二烯、苯乙烯-丁二烯共聚物、氢化萜烯树脂、溶剂加入第一反应釜中,升温至95~105℃;
步骤C、将乙二醇、聚乙烯吡咯烷酮、引发剂混合均匀形成混合液,将混合液缓慢滴加到反应釜中,滴加时间为1~2小时,恒温1~2小时,;
步骤D、降温至室温后,纤维素接枝壳聚糖和纳米碳酸钙加入,搅拌均匀,即得成品。
表1实施例与对比例的配方
对比例9按照CN104559846A的实施例1制备的胶黏剂。
根据表1的配方,按以下测试。
用凹版或辊式涂布,将上述制备得到的胶黏剂涂布在铝箔的聚丙烯表面,加压贴合在卷芯表面。卷芯采用螺旋绕制结构,在正、负极间间隔的是聚乙烯薄膜。烘箱温度控制在90-130℃,干胶涂布量2-5克/平米。
性能测试:
经过测试,发现在温度低于40℃,实施例制备的胶黏剂凝固缓慢,便于调节。高温条件下,快速凝固,并进行如下粘结力测试。
根据GB/T 2792-2014,对实施例与对比例进行粘结力测试,结果如下:(单位:MPa)。
锂电池电解液采购自国泰华荣化工新材料有限公司的商业化电解液。
表2实施例与对比例的性能测试结果
对比实施例与对比例2,3,可知胶黏剂中加入具有50℃以下的玻璃化转变温度的氢化萜烯树脂,可以有效的增强初始粘结力和抗电解液能力。对比实施例与对比例4,可知加入乙二醇作为溶剂一部分可以起到一定增强作用。对比实施例与对比例5,6,可知加入K值为20-40之间的聚乙烯吡咯烷酮,可以有效的增强初始粘结力和抗电解液能力。对比实施例与对比例7,8,可知加入纤维素接枝壳聚糖或纳米碳酸钙,可以有效的增强抗电解液的能力。综合对比实施例1与对比例1,5,7,8,可知同时加入聚乙烯吡咯烷酮,纤维素接枝壳聚糖,纳米碳酸钙,比单独加入任一种物质,效果都要优异,这是因为这3者之间具有促进的协同作用。对比实施例1与对比例9,可知本发明采用的配方制备出来的产品性能更好,并且制备流程简化,成本降低。
以上内容不能认定本发明具体实施只局限于这些说明,对于本发明所属技术领域的普通技术人员来说,在不脱离本发明构思前提下,还可以做出若干简单推演或替换,都应当视为属于本发明由所提交的权利要求书确定的专利保护范围。
Claims (6)
1.一种锂电池用密封胶黏剂,其包括:聚苯乙烯、聚丁二烯、苯乙烯-丁二烯共聚物、氢化萜烯树脂、溶剂、乙二醇、引发剂、聚乙烯吡咯烷酮、纤维素接枝壳聚糖和纳米碳酸钙;所述氢化萜烯树脂具有50℃以下的玻璃化转变温度,所述聚乙烯吡咯烷酮的K值为20-40之间,所述纳米碳酸钙的粒径为20-50nm;聚乙烯吡咯烷酮、纤维素接枝壳聚糖、纳米碳酸钙的质量比为1:2-5:0.2-0.5,所述溶剂与乙二醇的质量比为2:1。
2.根据权利要求1所述的锂电池用密封胶黏剂,其中,聚乙烯吡咯烷酮、纤维素接枝壳聚糖、纳米碳酸钙的质量比为1:3:0.3。
3.根据权利要求1所述的锂电池用密封胶黏剂,其中,按质量份,聚苯乙烯10~25质量份、聚丁二烯10~25质量份、苯乙烯-丁二烯共聚物5~15质量份、氢化萜烯树脂5~15质量份、溶剂20~40质量份、乙二醇10-20质量份、引发剂0.5~1质量份、聚乙烯吡咯烷酮1-2质量份、纤维素接枝壳聚糖2-10质量份和纳米碳酸钙0.2-1质量份。
4.根据权利要求1所述的锂电池用密封胶黏剂,其中,溶剂为甲苯、异丙醇、二甲苯、异构十二烷和乙酸丁酯中的一种或一种以上的混合物。
5.根据权利要求1所述的锂电池用密封胶黏剂,其中,所述引发剂为过氧化苯甲酰、过硫酸钾、偶氮二异丁腈和N,N-二乙基苯胺的一种或一种以上的混合物。
6.如权利要求1-5任意一项所述的锂电池用密封胶黏剂的制备方法,其特征在于:包括以下加工步骤:
步骤A、按照配方准确称取配方量的物料,分别放置到不同的容器中;
步骤B、将聚苯乙烯、聚丁二烯、苯乙烯-丁二烯共聚物、氢化萜烯树脂、溶剂加入第一反应釜中,升温至95~105℃;
步骤C、将乙二醇、聚乙烯吡咯烷酮、引发剂混合均匀形成混合液,将混合液缓慢滴加到反应釜中,滴加时间为1~2小时,恒温1~2小时,;
步骤D、降温至室温后,纤维素接枝壳聚糖和纳米碳酸钙加入,搅拌均匀,即得成品。
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