CN111761907A - 一种耐腐蚀软包电池铝塑膜及其制备方法 - Google Patents

一种耐腐蚀软包电池铝塑膜及其制备方法 Download PDF

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CN111761907A
CN111761907A CN202010651912.0A CN202010651912A CN111761907A CN 111761907 A CN111761907 A CN 111761907A CN 202010651912 A CN202010651912 A CN 202010651912A CN 111761907 A CN111761907 A CN 111761907A
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aluminum
plastic film
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corrosion
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史纪峰
张敏
高秀玲
申津靖
黄伟
彭世语
李雪
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Tianjin EV Energies Co Ltd
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Abstract

本发明创造涉及一种耐腐蚀软包电池铝塑膜及其制备方法，即在铝塑膜的铝箔层镀一层致密碳层，该碳层的厚度很小，但可有效阻隔电解液与铝箔层的接触，大大降低铝箔层因受腐蚀而产生的层间分离现象。

Description

一种耐腐蚀软包电池铝塑膜及其制备方法
技术领域
本发明创造涉及锂离子电池技术领域，尤其是涉及一种耐腐蚀软包电池铝塑膜及其制备方法。
背景技术
锂离子电池包装由钢壳包装逐步改进为铝壳包装，目前广泛使用的是软包锂电池，其具有重量小、安全性高和可设计性佳等优点，已成为锂电池的主要发展方向。
软包装材料质量的好坏对电池的各项性能都有重要的影响，若电池中进入一定量的水分及氧气将严重影响电池的充放电性能和循环寿命，严重可导致电池失效甚至发生安全隐患，因此软包装材料需要良好的热封性能、阻隔性能和延展成型等特点。传统软包锂离子电池所用的铝塑膜是由外层尼龙保护层、中间铝箔层以及内层热封PP层复合而成，层与层之间通过粘接剂压合粘结，对电芯起到密封、绝缘和保护作用。但目前铝塑膜在使用过程中仍存在耐电解液腐蚀性能较差的安全隐患。
电池电解液是渗透性和极性很强的有机溶剂，易侵蚀铝塑膜内层的PP层，且电解液中含有微量水分，二者相互反应产生气体和氢氟酸，而一旦内层PP膜出现损坏，反应产生的氢氟酸便会腐蚀中间铝箔层，引起铝塑膜层间分离，造成严重的安全问题。
发明内容
为减少铝塑膜层间分离现象的发生几率，本发明提供了一种耐腐蚀软包电池铝塑膜及其制备方法，具体为在铝塑膜的铝箔层表面镀碳，将铝塑膜变为尼龙层/铝箔层/碳层/PP层的四层新结构，降低电解液中氢氟酸对铝箔层的腐蚀性，不仅可以有效防止铝塑膜分层现象的发生，还可在一定程度上提高防水性能，提高使用安全性。
为解决上述技术问题，本发明创造采用的技术方案是：
一种耐腐蚀软包电池铝塑膜，该铝塑膜中铝箔层的至少一面镀碳。
进一步，所述铝塑膜包括由上至下设置的尼龙层、铝箔层、碳层和PP层，所述尼龙层和铝箔层之间设有粘接剂层，所述碳层和PP层之间设有粘接剂层。
进一步，所述铝塑膜包括由上至下设置的尼龙层、碳层、铝箔层和PP层，所述尼龙层和碳层之间设有粘接剂层，所述铝箔层和PP层之间设有粘接剂层。
进一步，所述铝塑膜包括由上至下设置的尼龙层、碳层、铝箔层、碳层和PP层，所述尼龙层和相邻的碳层之间设有粘接剂层，所述PP层和相邻的铝箔层之间设有粘接剂层。
本发明还在于公开一种耐腐蚀软包电池铝塑膜的制备方法，主要包括如下步骤：应用物理气相沉积装置，在高能电子束激发状态下将固态石墨气化，气化石墨原子在触及铝箔层时受冷凝集，均匀的排布于铝箔层表面，即可形成碳层。
进一步，碳层厚度为80-120nm。
进一步，所述物理气相沉积装置为电子束蒸镀装置。
进一步，碳层形成的过程在真空环境下进行，真空度为10-5～10-6MPa。
本发明创造的有益效果：
目前铝塑膜在使用过程中仍存在PP层破损耐电解液腐蚀性能较差的安全隐患，电解液中微量的水分生成的氢氟酸以及电池电压异常升高会腐蚀中间铝箔层，引起铝塑膜层间分离，本发明在中间铝箔层镀一层致密碳层，其厚度可以忽略不计，但可有效阻隔电解液与铝箔层的接触，大大降低铝箔层因受腐蚀而产生的层间分离现象。此外，镀碳层也可镀在靠近尼龙层的铝箔层上，有效阻隔尼龙层所吸附的水分，提高电池安全性能。
附图说明
图1为实施例中耐腐蚀软包电池铝塑膜的层结构示意图。
具体实施方式
需要说明的是，在不冲突的情况下，本发明创造中的实施例及实施例中的特征可以相互组合。
下面将参考附图并结合实施例来详细说明本发明创造。
实施例1铝塑膜及电芯的制备
原材料准备：铝塑膜专用铝箔，普通石墨。
在真空度约10-5～10-6MPa条件下，将普通石墨置于坩埚中，使用物理气相沉积装置如电子束蒸镀装置，在高能电子束(功率约150KW左右)激发状态下将固态石墨气化，气化石墨原子在触及铝箔时受冷凝集，均匀的排布于铝箔层表面即可形成镀碳的铝箔层，镀碳层厚度大约在100nm左右。后续利用粘接剂将镀碳铝箔层的非镀碳面与尼龙层粘接，镀碳面与PP层粘接，最终尼龙层/铝箔层/碳层/PP层的四层结构的新铝塑膜结构构建完成。
使用制备好的新型铝塑膜应用于锂离子电芯包装外壳，为进行对比，在相同条件下使用普通铝塑膜(无镀碳层)用作同型号电芯包装外壳。锂离子电池叠片式或卷绕式均可。
根据电池生产工艺流程进行静置、擀压、高温静置、预充、排气以及充放电循环等流程包装成品电芯。
实施例2性能测试
铝塑膜耐腐蚀性能测试：分别取镀碳铝塑膜和普通铝塑膜10×10cm，并置于一定酸碱度(pH6.8～7.2)的盐雾环境中85℃保温480h进行盐雾测试，观察两种铝塑膜耐腐蚀情况。镀碳铝塑膜PP/碳/铝层粘接性良好，边缘无开胶卷边现象，而未经镀碳的铝塑膜铝箔层与PP层边缘则出现明显的开胶卷边现象，可见镀碳层具有提高铝塑膜耐盐雾腐蚀性能的作用。
铝塑膜镀碳层耐腐蚀性能测试：将镀碳铝塑膜内层PP层去除，露出镀碳层，将盐酸(pH 1)滴于碳层上，并开始计时，统计铝箔层被溶解穿透的时间与普通铝塑膜被穿透的差异。经盐酸腐蚀实验发现，镀碳铝箔层具有明显优于普通铝塑膜的耐腐蚀性能。在镀碳铝箔层裸露的情况下滴加盐酸，经10min左右镀碳铝箔层被腐蚀穿透，而未经镀碳的铝塑膜铝箔层在1min左右便被腐蚀穿透，可见碳层对铝箔层防酸腐蚀的优势所在。
剥离力性能测试：将两层镀碳铝塑膜沿MD(平行于条纹)和TD(垂直于条纹)方向在0.4MPa压力下热封，热封温度185℃，热封时间3s，然后剪成15mm×100mm的条状使用拉伸试验机进行热封强度测试，二者在MD和TD两个方向上的抗拉强度分别在122N/15mm和119N/15mm左右，测试结果证明镀碳铝塑膜热封强度比普通铝塑膜热封强度稍高。
另，镀碳铝塑膜镀碳铝箔层与PP层剥离力测试发现镀碳结构的铝塑膜表现出更佳的粘接性能，镀碳铝塑膜的剥离力(约25N/15mm)平均比普通铝塑膜强度高约3～7N/15mm，说明镀碳层不仅可以与铝箔层很好地结合在一起，还能提高与PP层的粘接力，减小层间分离的可能性。
密封性能测试：为进行镀碳铝塑膜和普通铝塑膜密封性能对比，将两种铝塑膜进行冲坑并通过正常电芯制作和充放电过程制成电池进行比较。表1为两种电池在85℃高温，湿度为65％±5％条件下密封性能测试的数据对比：
表1镀碳铝塑膜和普通铝塑膜密封性能对比
Figure BDA0002575298440000031
Figure BDA0002575298440000041
由上表可以看出，在相同环境条件下本发明镀碳铝塑膜具有更好的防水密封性能。
以上对本发明创造的一个实施例进行了详细说明，但所述内容仅为本发明创造的较佳实施例，不能被认为用于限定本发明创造的实施范围。凡依本发明创造申请范围所作的均等变化与改进等，均应仍归属于本发明创造的专利涵盖范围之内。

Claims (8)

1.一种耐腐蚀软包电池铝塑膜，其特征在于，该铝塑膜中铝箔层的至少一面镀碳。
2.根据权利要求1所述的一种耐腐蚀软包电池铝塑膜，其特征在于，所述铝塑膜包括由上至下设置的尼龙层、铝箔层、碳层和PP层，所述尼龙层和铝箔层之间设有粘接剂层，所述碳层和PP层之间设有粘接剂层。
3.根据权利要求1所述的一种耐腐蚀软包电池铝塑膜，其特征在于，所述铝塑膜包括由上至下设置的尼龙层、碳层、铝箔层和PP层，所述尼龙层和碳层之间设有粘接剂层，所述铝箔层和PP层之间设有粘接剂层。
4.根据权利要求1所述的一种耐腐蚀软包电池铝塑膜，其特征在于，所述铝塑膜包括由上至下设置的尼龙层、碳层、铝箔层、碳层和PP层，所述尼龙层和相邻的碳层之间设有粘接剂层，所述PP层和相邻的铝箔层之间设有粘接剂层。
5.根据权利要求1-4任一所述的一种耐腐蚀软包电池铝塑膜的制备方法，其特征在于，主要包括如下步骤：应用物理气相沉积装置，在高能电子束激发状态下将固态石墨气化，气化石墨原子在触及铝箔层时受冷凝集，均匀的排布于铝箔层表面，即可形成碳层。
6.根据权利要求5所述的一种耐腐蚀软包电池铝塑膜的制备方法，其特征在于，碳层厚度为80-120nm。
7.根据权利要求5所述的一种耐腐蚀软包电池铝塑膜的制备方法，其特征在于，所述物理气相沉积装置为电子束蒸镀装置。
8.根据权利要求5所述的一种耐腐蚀软包电池铝塑膜的制备方法，其特征在于，碳层形成的过程在真空环境下进行，真空度为10-5～10-6MPa。
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JP2008283152A (ja) * 2007-05-14 2008-11-20 Toyo Aluminium Kk 集電体材料とその製造方法
CN110893705A (zh) * 2019-10-14 2020-03-20 宁波瑞成包装材料有限公司 高阻隔、耐腐蚀锂电池包装膜及其制备方法

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CN110893705A (zh) * 2019-10-14 2020-03-20 宁波瑞成包装材料有限公司 高阻隔、耐腐蚀锂电池包装膜及其制备方法

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