CN113782880A - 一种耐腐蚀的锂电池铝塑膜及其制备方法 - Google Patents
一种耐腐蚀的锂电池铝塑膜及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种耐腐蚀的锂电池铝塑膜及其制备方法,涉及锂电池铝塑膜技术领域;包括内层、铝箔芯层、外层;内层包括耐腐蚀涂层、热塑性树脂膜和内粘结剂层,外层包括外粘结剂层和耐热性树脂膜;制备方法:A、铝箔芯层上涂布外粘结剂层并干燥;B、外粘结剂层与铝箔芯层贴合;C、铝箔芯层另一面涂布内粘结剂层并干燥;D、内粘结剂层与热塑性树脂膜热贴合;E、热塑性树脂膜涂布耐腐蚀涂层并干燥;F、最后熟化即得耐腐蚀的锂电池铝塑膜。本申请引入特定的耐腐蚀涂层,交联结构与电解液直接接触但不会被破坏,还能保护外层的铝塑膜不被腐蚀刺穿,避免漏液等事故;还大大提高了铝塑膜的冷压冲深性能、二次封装性能,提高生产的效率。
Description
技术领域
本发明涉及锂电池铝塑膜技术领域,具体涉及一种耐腐蚀的锂电池铝塑膜及其制备方法,尤其涉及一种耐腐蚀耐摩擦便于再利用的锂电池铝塑膜及其制备方法。
背景技术
锂离子电池是一种具有能量密度高、更小型化、超薄化、轻量化,高安全性等多种明显优势的一种新型电池;软包装铝塑膜作为一种聚合物电池外包装膜,在聚合物锂离子电池中起着保护电池不受损伤及防止电池中液体泄漏等重要功能。
在电池生产过程及使用过程中,铝塑膜内层需要直接接触具有强腐蚀性的电解液,并完全封装好防止漏液。公告号为CN204189833U的中国实用新型专利公开了一种高性能锂电池铝塑膜,所述铝塑膜包括从上到下依次设置的耐热层、铝箔层、耐腐蚀涂层、粘结层和热封层,耐热层采用聚酰亚胺层,通过将液态耐热性聚酰亚胺直接涂覆在基材铝箔烘干的复合方式,可以达到较高的外层剥离力,保护铝塑膜不被外界破坏,并具有一定的耐腐蚀作用。
目前市面上的铝塑膜内层塑料膜多为聚丙烯薄膜,不耐电解液腐蚀,电解液会逐渐渗透到聚丙烯薄膜内部并有几率腐蚀铝箔芯层,耐腐蚀涂层内部都有其他铝塑膜结构,电解液会直接腐蚀其他铝塑膜结构,导致铝塑膜容易被击穿,无法保护电池结构;并且持液时间增长后二次封装时电解液也会残留在膜上影响封装,增加生产的次品率,从而导致漏液短路等事故。
发明内容
为了克服现有技术中存在的缺点和不足,本发明的目的在于提供一种耐腐蚀的锂电池铝塑膜及其制备方法。
本发明的目的是通过以下技术方案实现的:一种耐腐蚀的锂电池铝塑膜,包括依次设置的内层、铝箔芯层、外层,所述内层位于铝箔芯层内侧,所述内层包括耐腐蚀涂层、热塑性树脂膜和内粘结剂层,所述外层位于铝箔芯层的外侧,所述外层包括外粘结剂层和耐热性树脂膜。
优选地,所述外粘结剂层位于铝箔芯层和耐热性树脂膜之间,将铝箔芯层和耐热性树脂膜粘合在一起;所述耐腐蚀涂层、热塑性树脂膜和内粘结剂层与铝箔芯层的距离由远及近依次设置。
优选地,所述耐热性树脂膜包括尼龙膜;所述外粘结剂层的材质为丙烯酸树脂、聚酯及其衍生物中的至少一种;所述铝箔芯层为经双面钝化处理的O态软质铝箔;所述内粘结剂层的材质为马来酸酐接枝聚丙烯树脂及其衍生物中的一种或多种;所述热塑性树脂膜为聚丙烯薄膜。
优选地,所述耐腐蚀涂层包括交联聚合物,交联的聚合物网络稳定性强且较为致密可以有效耐腐蚀。
优选地,所述交联聚合物包括聚丙烯酸酯、马来酸酐接枝改性的聚烯烃树脂中的一种或多种。
优选地,所述耐腐蚀涂层中还添加有芥酸酰胺,所述芥酸酰胺的添加量为耐腐蚀涂层质量的10%-80%,余量为交联聚合物,芥酸酰胺的添加量超过其下限加工性不好影响冲深,超过上限耐腐蚀性能不好。
优选地,所述耐热性树脂膜的厚度为15-30um;所述外粘结剂层的涂布量为4-5g/m2;所述铝箔芯层厚度为20um-50um;所述内粘结剂层的涂布量为2-3g/m2;所述热塑性树脂膜厚度20um-80um;所述耐腐蚀的涂布量0.1-1g/m2,涂布量不足则耐腐蚀性达不到要求,超过上限成本压力和冲深会受影响。
一种根据权利要求1-7所述的耐腐蚀的锂电池铝塑膜的制备方法,包括如下步骤:
A、在铝箔芯层的外侧涂布外粘结剂层,在100℃下干燥0.5-2min,所述外粘结剂层的涂布方法包括浸涂、喷涂、凹版涂布、静电吸附、三辊逆转涂布方式中的一种;
B、将外粘结剂层远离铝箔芯层的一面与耐热性树脂膜在80-100℃下贴合;
C、在铝箔芯层远离外粘结剂层的另一面采用凹版涂布机涂布内粘结剂层,在100℃下干燥0.5-2min;
D、然后在内粘结剂层远离铝箔芯层的一面与热塑性树脂膜在80-100℃下进行热贴合;
E、然后在热塑性树脂膜的远离铝箔芯层的一面涂布耐腐蚀涂层,在80℃下干燥1min,所述耐腐蚀涂层的涂布方法包括喷涂、凹版涂布、静电吸附、三辊逆转涂布中的一种;
F、最后在60℃下熟化时间5天,即得所述耐腐蚀的锂电池铝塑膜。
综上所述,与现有技术相比,本发明具有如下的有益效果:
(1)在锂电池铝塑膜中引入了耐腐蚀涂层之后,交联结构与电解液直接接触但不会被破坏,进而保护外层的铝塑膜被腐蚀刺穿,从而避免漏液等事故;
(2)引入耐腐蚀涂层后,因为电解液无法腐蚀热塑性铝塑膜,大大提高了铝塑膜的二次封装性能,提高生产的效率;
(3)耐腐蚀涂层中添加的芥酸酰胺可以提高铝塑膜的耐摩擦性能,从而提升铝塑膜的冷压冲深性能。
附图说明
图1是本发明实施例1-5一种耐腐蚀的锂电池铝塑膜的结构示意图。
具体实施方式
以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变化和改进,这些都属于本发明的保护范围。在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开,下面结合具体实施例对本发明进行详细说明:
实施例1
一种耐腐蚀的锂电池铝塑膜,如图1所示,由六层不同功能的膜层组成,由内至外依次为耐腐蚀涂层、热塑性塑料膜、内粘结剂层、铝箔芯层、外粘结剂层和耐热性树脂膜。
制备方法具体为:选用日本东洋铝业的45um厚的合金型号为8079的O态软质铝箔(铝箔芯层),在铝箔的外侧采用凹版涂布方式涂布聚酯粘结剂(外粘结剂层K55,日本东洋莫顿公司产品,涂布量5g/m2),在100℃下干燥2min,再将铝箔层涂布有外粘结剂层的一面与厦门长塑实业有限公司的25um厚的双向拉伸聚酰胺薄膜(耐热性树脂膜BOPA)在100℃下贴合;再在铝箔层的另一面采用凹版涂布机涂布酸改性聚烯烃粘结剂(内粘结剂层VP118,上海维凯光电有限公司产品,涂布量3g/m2),在100℃下干燥2min,而后在铝箔层涂布有内胶层的一面与日本冈本株式会社的40um厚的拉伸聚丙烯膜在80℃下进行热贴合;然后在热塑性树脂膜的外侧采用凹版涂布方法涂布0.1g/m2的耐腐蚀涂层(其中聚丙烯酸酯:芥酸酰胺=20%:80%,聚丙烯酸酯举例可由甲基丙烯酸酯加1%的过氧化苯甲酰值得),在80℃下干燥1min,最后在60℃下熟化时间5天,制得软包锂离子电池用铝塑复合膜。
实施例2
一种耐腐蚀的锂电池铝塑膜,其主要结构和使用的材料与实施例1相同,不同点在于,聚酯粘结剂涂布量为4g/m2,贴合温度为80℃,酸改性聚烯烃粘结剂涂布量为2g/m2,贴合温度为100℃。耐腐蚀涂层配方中芥酸酰胺的质量百分含量为10%。
实施例3
一种耐腐蚀的锂电池铝塑膜,其主要结构和使用的材料与实施例1相同,不同点仅在于,耐腐蚀涂层涂布量为1g/m2。
实施例4:
一种耐腐蚀的锂电池铝塑膜,与实施例1的不同之处在于,耐腐蚀涂层配方中芥酸酰胺的质量百分含量为45%。
实施例5:
一种耐腐蚀的锂电池铝塑膜,与实施例1的不同之处在于,耐腐蚀涂层配方中交联聚合物为马来酸酐接枝改性的聚丙烯,马来酸酐接枝改性的聚丙烯举例可由马来酸酐改性聚丙烯XP11B(日本三井化学株式会社)加入10%异氰酸酯类固化剂N-3300(日本三井化学株式会社)制得。
对比例1:
一种耐腐蚀的锂电池铝塑膜,其主要结构和使用的材料与实施例1相同,不同点仅在于,耐腐蚀涂层涂布量为0g/m2。
对比例2
一种耐腐蚀的锂电池铝塑膜,与实施例1的不同之处在于,耐腐蚀涂层里不加入过氧化苯甲酰得到非交联涂层。
对比例3
一种耐腐蚀的锂电池铝塑膜,与实施例1的不同之处在于,芥酸酰胺的加入量为85%。
实施例1-5和对比例1-3的性能测试
封装剥离强度测试:划取16*10mm的长方形样条对折后用190℃封刀将两边封住。灌入5g电解液(LiPF6,EC/DEC=1:1),在85℃烘箱内放置2天后,用拉力机测试封装剥离强度,剥离速度为300mm/min。
极限成型深度测试:采用冲壳机进行,分别测试3.0mm,3.5mm,4.0mm,4.5mm,5.0mm,5.5mm深度下,铝塑膜的成型后是否出现针孔或破损,由小到大每个深度分别测试20个样品,全部完好判定达到该深度的成型要求,有一个或一个以上出现针孔或破损,判定达不到该深度的成型要求。取达到的最大的深度为极限成型深度。
测试结果如表1所示。
表1实施例1-5、对比例1-3性能测试结果
二次封装强度 | 极限成型深度 | |
实施例1 | 59N | 5.5mm |
实施例2 | 55N | 5mm |
实施例3 | 65N | 5.5mm |
实施例4 | 62N | 5mm |
实施例5 | 60N | 5.5mm |
对比例1 | 10N | 3mm |
对比例2 | 14N | 3mm |
对比例3 | 19N | 5mm |
以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变化或修改,这并不影响本发明的实质内容。在不冲突的情况下,本申请的实施例和实施例中的特征可以任意相互组合。
Claims (10)
1.一种耐腐蚀的锂电池铝塑膜,其特征在于,包括依次设置的内层、铝箔芯层、外层,所述内层位于铝箔芯层内侧,所述内层包括耐腐蚀涂层、热塑性树脂膜和内粘结剂层,所述外层位于铝箔芯层的外侧,所述外层包括外粘结剂层和耐热性树脂膜。
2.根据权利要求1所述的耐腐蚀的锂电池铝塑膜,其特征在于,所述外粘结剂层位于铝箔芯层和耐热性树脂膜之间,所述耐腐蚀涂层、热塑性树脂膜和内粘结剂层与铝箔芯层的距离由远及近依次设置。
3.根据权利要求1所述的耐腐蚀的锂电池铝塑膜,其特征在于,所述耐热性树脂膜包括尼龙膜;所述外粘结剂层的材质为丙烯酸树脂、聚酯及其衍生物中的至少一种。
4.根据权利要求1所述的耐腐蚀的锂电池铝塑膜,其特征在于,所述铝箔芯层为经双面钝化处理的O态软质铝箔;所述内粘结剂层的材质为马来酸酐接枝聚丙烯树脂及其衍生物中的一种或多种;所述热塑性树脂膜为聚丙烯薄膜。
5.根据权利要求1所述的耐腐蚀的锂电池铝塑膜,其特征在于,所述耐腐蚀涂层包括交联聚合物。
6.根据权利要求5所述的耐腐蚀的锂电池铝塑膜,其特征在于,所述交联聚合物包括聚丙烯酸酯、马来酸酐接枝改性的聚烯烃树脂中的一种或多种。
7.根据权利要求5所述的耐腐蚀的锂电池铝塑膜,其特征在于,所述耐腐蚀涂层中还添加有芥酸酰胺,余量为交联聚合物。
8.根据权利要求5所述的耐腐蚀的锂电池铝塑膜,其特征在于,所述芥酸酰胺的添加量为耐腐蚀涂层质量的10%-80%。
9.根据权利要求1所述的耐腐蚀的锂电池铝塑膜,其特征在于,所述耐热性树脂膜的厚度为15-30um;所述外粘结剂层的涂布量为4-5g/m2;所述铝箔芯层厚度为20um-50um;所述内粘结剂层的涂布量为2-3g/m2;所述热塑性树脂膜厚度20um-80um;所述耐腐蚀的涂布量0.1-1g/m2。
10.一种根据权利要求1-9所述的任一耐腐蚀的锂电池铝塑膜的制备方法,其特征在于,包括如下步骤:
A、在铝箔芯层的外侧涂布外粘结剂层,在100℃下干燥0.5-2min,所述外粘结剂层的涂布方法包括浸涂、喷涂、凹版涂布、静电吸附、三辊逆转涂布方式中的一种;
B、将外粘结剂层远离铝箔芯层的一面与耐热性树脂膜在80-100℃下贴合;
C、在铝箔芯层远离外粘结剂层的另一面采用凹版涂布机涂布内粘结剂层,在100℃下干燥0.5-2min;
D、然后在内粘结剂层远离铝箔芯层的一面与热塑性树脂膜在80-100℃下进行热贴合;
E、然后在热塑性树脂膜的远离铝箔芯层的一面涂布耐腐蚀涂层,在80℃下干燥1min,所述耐腐蚀涂层的涂布方法包括喷涂、凹版涂布、静电吸附、三辊逆转涂布中的一种;
F、最后在60℃下熟化时间5天,即得所述耐腐蚀的锂电池铝塑膜。
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Application publication date: 20211210 |