CN114843664A - 一种动力电池铝塑膜 - Google Patents
一种动力电池铝塑膜 Download PDFInfo
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- 239000002985 plastic film Substances 0.000 title claims abstract description 33
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Abstract
本发明公开了一种动力电池铝塑膜,由外向内依次包括外层、铝箔和内层,所述铝箔具有正面和背面,所述外层通过粘接层复合在所述铝箔的正面,所述内层通过多层共挤的方式复合在所述铝箔的背面,所述内层由改性聚丙烯制成。本发明的铝塑膜耐冲深,不易分层,可靠性高。
Description
技术领域
本申请涉及锂电池技术领域,尤其涉及一种动力电池铝塑膜。
背景技术
集流体是锂电池中不可或缺的组成部件之一,它不仅能承载活性物质,而且还可以将电极活性物质产生的电流汇集并输出,有利于降低锂电池的内阻,提高电池的库伦效率、循环稳定性和倍率性能。
现有的软包装铝塑膜一般由三层不同功能的薄膜复合而成,外层是由PA层作为保护层,中间是由铝箔作为绝缘层,内层是由CPP作为热封层,由此组成的铝塑膜由于金属铝箔与高分子材料CPP层的不相容性,粘接程度均有较大差异。当铝塑膜冲深形成用于容纳锂电池凹槽时,凹槽折边处容易出现分层,继而会产生鼓包、漏液、甚至短路等危险发生,降低锂离子电池的使用寿命,影响了锂离子电池的稳定性及使用广泛性。
发明内容
本申请所要解决的技术问题在于,提供一种耐冲深,不易分层,可靠性高的动力电池铝塑膜及其制备方法。
本申请所要解决的技术问题在于,提供一种动力电池铝塑膜,由外向内依次包括外层、铝箔和内层,所述铝箔具有正面和背面,所述外层通过粘接层复合在所述铝箔的正面,所述内层通过多层共挤的方式复合在所述铝箔的背面,所述内层由改性聚丙烯制成。
作为上述方案的改进,所述内层由5层或5层以上的改性聚丙烯制成,所述改性聚丙烯包括聚丙烯和高分子碳化二亚胺交联剂。
作为上述方案的改进,所述聚丙烯和所述高分子碳化二亚胺交联剂的质量比为100:(3~8)。
作为上述方案的改进,所述高分子碳化二亚胺交联剂的pH值为10.5~12.5,粘度为25~500mPas。
作为上述方案的改进,所述铝箔的正面和背面均具有粗化结构,所述铝箔的粗化结构由以下方法制得:
提供铝箔基材;
对所述铝箔基材进行清洗处理,其中,所述铝箔基材依次进过酸洗槽、碱洗槽和清洗槽,所述酸洗槽内的酸洗液包括HF和H2SO4,所述碱洗槽内的碱洗液包括氢氧化钙和氢氧化钠,所述清洗槽内含有去离子水;
将清洗处理后的铝箔基材进行烘干处理;
将烘干后的铝箔基材置于刻蚀槽内进行刻蚀处理,所述刻蚀槽内的刻蚀液包括HCl和Al2(SO4)3。
作为上述方案的改进,所述HF和H2SO4的总质量为酸洗液总质量的5%~8%,所述氢氧化钙和氢氧化钠的总质量为碱洗液总质量的5%~8%,所述刻蚀液包括4~6mol/L的HCl和1~1.3mol/L的Al2(SO4)3。
作为上述方案的改进,所述外层由尼龙、PA、PET中的一种或者几种制成,所述粘接层由耐冲压胶制成。
作为上述方案的改进,所述内层和外层之间设有环氧层,所述环氧层由环氧树脂制成。
作为上述方案的改进,所述外层的厚度为40~50μm,所述铝箔的厚度为40~50μm,所述内层的厚度为60~70μm。
作为上述方案的改进,所述动力电池铝塑膜的总厚度≤150μm。
实施本申请,具有如下有益效果:
本申请由改性聚丙烯制成的内层,阻隔性强,复合强度高,热封性好,同时,本申请的改性聚丙烯通过多层共挤的方式复合在铝箔的背面,使得本申请的内层与铝箔之间的复合强度比一般的PPC层与铝箔的复合强度要高。
附图说明
图1是本申请集流体的结构示意图;
图2是本申请铝箔的结构示意图;
图3是本申请内层的结构示意图。
具体实施方式
为使本申请的目的、技术方案和优点更加清楚,下面将结合附图对本申请作进一步地详细描述。
参见图1,本申请提供的一种动力电池铝塑膜,由外向内依次包括外层2、铝箔1和内层3。
参见图2,本申请的铝箔1具有正面11和背面12,厚度优选为30~60μm。若铝箔1的厚度过后,不仅成本增加,且硬度过大,影响冲深和包装效果;若铝箔1的厚度过薄,则容易破裂,影响电池的性能。更优的,铝箔1的厚度为40~50μm,示例性为40μm、42μm、45μm、47μm、50μm。
本申请的铝箔1可以为光面铝箔,但为了提高铝箔1与内层3和外层2的结合力,减少层与层之间的分离,本申请的铝箔1优选为刻蚀铝箔。具体的,本申请铝箔1的正面11和背面12均具有粗化结构,本申请铝箔1的比表面积大、表面湿润张力大。
本申请铝箔1的粗化结构由以下方法制得:
提供铝箔基材;
对铝箔基材进行清洗处理,其中,铝箔基材依次进过酸洗槽、碱洗槽和清洗槽,酸洗槽内的酸洗液包括HF和H2SO4,碱洗槽内的碱洗液包括氢氧化钙和氢氧化钠,清洗槽内含有去离子水;
将清洗处理后的铝箔基材进行烘干处理;
将烘干后的铝箔基材置于刻蚀槽内进行刻蚀处理,刻蚀槽内的刻蚀液包括HCl和Al2(SO4)3。
优先地,HF和H2SO4的总质量为酸洗液总质量的4%~6%,氢氧化钙和氢氧化钠的总质量为碱洗液总质量的4%~6%,刻蚀液包括3~5mol/L的HCl和0.5~0.8mol/L的Al2(SO4)3。
与现有的刻蚀方法相比,本申请先对铝箔基材进行清洗处理(酸性、碱洗、水洗),不仅可以去除铝箔基材表面的油污、杂质等,更重要的是提高了铝箔基材的表面润湿张力,以及有利于有助于后续的刻蚀液刻蚀铝箔,获得大孔径的凹孔。
具体的,对铝箔基材进行清洗处理的方法包括:采用放卷机将成卷铝箔基材放出至张力辊,铝箔基材经过张力辊依次输送至酸洗槽、碱洗槽和清洗槽其中,铝箔基材依次进过酸洗槽、碱洗槽和清洗槽。
对铝箔基材进行刻蚀处理的方法包括:采用放卷机将烘干后的铝箔基材放出至张力辊,铝箔基材经过张力辊输送至刻蚀槽。本申请的刻蚀液还可以是现有的其他刻蚀液。或者,本申请还可以采用电化学的方法来对铝箔基材进行刻蚀。
本申请的铝箔基材先进行酸洗后进行碱洗,且酸洗槽内的酸洗液、碱洗槽内的碱洗液是由特定的组分组成,不仅有效去除铝箔基材表面的杂质和油污,提高铝箔的表面润湿张力,还不影响铝箔的拉伸强度。
本申请的铝箔基材经过碱洗再采用一定温度的去离子水来进行清洗,以去除铝箔基材上残留的碱洗液以及碱洗过程中产生的分解物,有效提高铝箔基材的清洁度和表面润湿张力。
本申请采用放卷机将成卷铝箔基材放出至张力辊,其中铝箔基材经过张力辊依次输送至酸洗槽、碱洗槽和清洗槽,本申请可以通过调整输送辊的速度来调整铝箔基材在酸洗槽、碱洗槽和清洗槽中的停留时间,操作简单,清洗效果佳,适应大批量的生产。
本申请铝箔1的合金材质主要为8021材、8079材或8006材,但不限于此。
具体的,本申请外层2通过粘接层4复合在铝箔1的正面11。本申请的外层2由尼龙、PA、PET中的一种或者几种制成,粘接层4由耐冲压胶制成。
优选地,外层2的厚度为40~50μm。
优选地,耐冲压胶为聚氨酯、聚异氰酸酯、聚酰亚胺树脂、聚丙烯酸酯、有机氟树脂中的一种或者几种组成。
具体的,本申请内层3通过多层共挤的方式复合在铝箔1的背面,其中,内层3由改性聚丙烯制成。优先地,参见图3,内层3由5层或5层以上的改性聚丙烯制成。
内层3是铝塑膜最重要的结构,现有铝塑膜内层一般采用食品包装用的CPP膜,然而,食品包装用CPP膜作为铝塑膜内层材料,存在阻隔性能差、复合强度低、热封强度低、冲深白化等问题。
本申请由改性聚丙烯制成的内层3,阻隔性强,复合强度高,热封性好。具体的,本申请的改性聚丙烯包括聚丙烯和高分子碳化二亚胺交联剂,聚丙烯和高分子碳化二亚胺交联剂的质量比为100:(3~8)。其中,高分子碳化二亚胺交联剂的pH值为10.5~12.5,粘度为25~500mPas。
优选地,聚丙烯和高分子碳化二亚胺交联剂的质量比为100:(4~6)。
本申请的高分子碳化二亚胺交联剂与聚丙烯生产三维聚合物交联网络,提高聚丙烯的耐化学性,以及增加聚丙烯的拉伸强度和附着力。本申请的改性聚丙烯与金属Ni、Al及极耳胶块有良好的热封粘贴性,并具有良好的耐电解液和抗HF性能,以及极佳的绝缘性和良好的耐戳穿性能,能防止电极与锂离子电池软包装材料之间的短路。更重要的是,本申请的改性聚丙烯通过多层共挤的方式复合在铝箔的背面,使得本申请的内层与铝箔之间的复合强度比一般的PPC层与铝箔的复合强度要高。
具体的,本申请高分子碳化二亚胺交联剂的型号为CD-132。根据申请人的研究发现,高分子碳化二亚胺交联剂的pH值和年度对聚丙烯的改性效果起着重要的作用。优选地,高分子碳化二亚胺交联剂的pH值为10.5~12.5,粘度为25~500mPas。
由于本申请的内层3是通过多层共挤的方式复合在铝箔1的背面12上,因此本申请内层3与铝箔1的结合力比现有干法复合的铝塑膜的强。此外,由于本申请采用多层共挤的方式形成内层3,因此与一般的CPP膜组成的内层相比,本申请内层3的厚度可以做到60~70μm,阻隔性强且冲深性能好。
为了进一步提高内层3和铝箔1的结合力,优选地,内层3和铝箔1之间设有环氧层5,其中环氧层5由环氧树脂制成。经过申请人的研究发现,与其他粘结剂相比,环氧树脂与本申请改性聚丙烯的结合力更强。
为了降低电池的整体体积,本申请动力电池铝塑膜的总厚度≤150μm。
下面将以具体实施例来进一步阐述本申请
制备例1
一种刻蚀铝箔的制备方法,包括以下步骤:
S1、提供厚度为40μm的铝箔基材;
S2、采用放卷机将成卷的铝箔基材放出至张力辊,该铝箔基材经过张力辊按130m/min的速度依次输送至长度均为1m的酸洗槽、碱洗槽和清洗槽;其中,酸洗槽内的酸洗液包括1.8wt%HF和3.2wt%H2SO4,碱洗槽内的碱洗液包括1.2wt%氢氧化钙和3.8wt%氢氧化钠,清洗槽内含有温度为50℃的去离子水;
S3、将步骤S2清洗处理后的按130m/min的速度铝箔基材进行130℃的烘干处理;
S4、将步骤S3烘干后的铝箔基材输送至长度为1m的刻蚀槽,刻蚀槽内的刻蚀液包括4mol/L的HCl和1mol/L的Al2(SO4)3;
S5、将步骤S4刻蚀处理后的铝箔基材进行130℃的烘干处理,得到刻蚀铝箔。
制备例2
一种刻蚀铝箔的制备方法,包括以下步骤:
S1、提供厚度为45μm的铝箔基材;
S2、采用放卷机将成卷的铝箔基材放出至张力辊,该铝箔基材经过张力辊按130m/min的速度依次输送至长度均为1m的酸洗槽、碱洗槽和清洗槽;其中,酸洗槽内的酸洗液包括2wt%HF和4wt%H2SO4,碱洗槽内的碱洗液包括1.6wt%氢氧化钙和4.4wt%氢氧化钠,清洗槽内含有温度为50℃的去离子水;
S3、将步骤S2清洗处理后的按150m/min的速度铝箔基材进行140℃的烘干处理;
S4、将步骤S3烘干后的铝箔基材输送至长度为1m的刻蚀槽,刻蚀槽内的刻蚀液包括5mol/L的HCl和1.2mol/L的Al2(SO4)3;
S5、将步骤S4刻蚀处理后的铝箔基材进行140℃的烘干处理,得到刻蚀铝箔。
制备例3
一种刻蚀铝箔的制备方法,包括以下步骤:
S1、提供厚度为50μm的铝箔基材;
S2、采用放卷机将成卷的铝箔基材放出至张力辊,该铝箔基材经过张力辊按150m/min的速度依次输送至长度均为1m的酸洗槽、碱洗槽和清洗槽;其中,酸洗槽内的酸洗液包括3wt%HF和5wt%H2SO4,碱洗槽内的碱洗液包括2.5wt%氢氧化钙和5.5wt%氢氧化钠,清洗槽内含有温度为50℃的去离子水;
S3、将步骤S2清洗处理后的按170m/min的速度铝箔基材进行150℃的烘干处理;
S4、将步骤S3烘干后的铝箔基材输送至长度为1m的刻蚀槽,刻蚀槽内的刻蚀液包括6mol/L的HCl和1.3mol/L的Al2(SO4)3;
S5、将步骤S4刻蚀处理后的铝箔基材进行150℃的烘干处理,得到刻蚀铝箔。
制备例4
一种刻蚀铝箔的制备方法,包括以下步骤:
S1、提供厚度为45μm的铝箔基材;
S2、采用放卷机将成卷的铝箔基材放出至张力辊,该铝箔基材经过张力辊输送至长度均为1m的刻蚀槽,刻蚀槽内的刻蚀液为硫酸溶液,pH为1,温度为23℃,刻蚀时间为30s;
S3、将步骤S2刻蚀处理后的铝箔基材进行140℃的烘干处理,得到刻蚀铝箔。
实施例1
一种动力电池铝塑膜,由外向内依次包括外层、粘接层、铝箔、环氧层和内层,铝箔为制备例1的铝箔,外层由尼龙制成,厚度为40μm,粘接层由聚异氰酸酯制成,环氧层由环氧树脂制成,外层和粘接层通过干法复合的方法复合在铝箔的正面,内层和环氧层通过多层共挤的方式复合在铝箔的背面上,内层由8层改性聚丙烯制成,总厚度为70μm;其中,改性聚丙烯由100质量份聚丙烯和8质量份的高分子碳化二亚胺交联剂组成。
实施例2
一种动力电池铝塑膜,由外向内依次包括外层、粘接层、铝箔、环氧层和内层,该铝箔为制备例2的铝箔,外层由尼龙制成,厚度为45μm,粘接层由聚酰亚胺树脂制成,环氧层由环氧树脂制成,外层和粘接层通过干法复合的方法复合在铝箔的正面,内层和环氧层通过多层共挤的方式复合在铝箔的背面上,内层由5层改性聚丙烯制成,总厚度为60μm;其中,改性聚丙烯由100质量份聚丙烯和5质量份的高分子碳化二亚胺交联剂组成。
实施例3
一种动力电池铝塑膜,由外向内依次包括外层、粘接层、铝箔、环氧层和内层,该铝箔为制备例3的铝箔,外层由尼龙制成,厚度为50μm,粘接层由聚酰亚胺树脂制成,环氧层由环氧树脂制成,外层和粘接层通过干法复合的方法复合在铝箔的正面,内层和环氧层通过多层共挤的方式复合在铝箔的背面上,内层由4层改性聚丙烯制成,总厚度为50μm;其中,改性聚丙烯由100质量份聚丙烯和3质量份的高分子碳化二亚胺交联剂组成。
实施例4
与实施例2不同的是,实施例4的铝箔为制备例4的铝箔。
实施例5
与实施例2不同的是,实施例5的铝箔为光面铝箔,即未经过刻蚀处理的铝箔。
对比例1
与实施例2不同的是,对比例1的内层由聚丙烯制成。
对比例2
与实施例2不同的是,对比例2的内层先通过延压的方法形成厚度为45μm的薄膜,然后再与环氧层通过干法复合的方法复合在铝箔的背面。
对比例3
与实施例2不同的是,对比例3的内层为CPP膜制成,CPP膜通过环氧层和干法复合的方法复合在铝箔的背面。
对比例4
与实施例2不同的是,对比例4的铝箔为制备例4的铝箔,内层的材料为CPP,其中,内层与环氧层通过多层共挤的方法复合在铝箔的背面。
对上述实施例1~5及对比例1~4的铝塑膜进行检测,其中,检测项目包括:
冲深性能测试:采用双坑冲深模具,坑深5mm,两坑间距1mm。冲深后内层膜边角处是否有分层、泛白等异常现象;
结合力测试:利用T型剥离试验铝箔和内层的结合力;
耐电解液性能:将铝塑膜样品裁成100mm×15mm大小,于85℃电解液[碳酸乙烯酯/碳酸二乙酯/碳酸二甲酯=1/1/1(容积比)100g中添加六氟磷酸锂13g]中浸泡24h、7天后,取出铝塑膜样条并以去离子水洗涤,用擦拭纸擦掉水,使水分充分干燥,利用T型剥离试验进行铝箔和内层的结合力,测试数据表1所示:
表1
项目 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 对比例1 | 对比例2 | 对比例3 | 对比例4 |
冲深性能(7mm) | 无分层 | 无分层 | 无分层 | 无分层 | 分层 | 分层 | 分层 | 分层 | 分层 |
结合力(N/15mm) | 20.6 | 23.2 | 22.1 | 15.7 | 13.4 | 10.5 | 8.4 | 9.3 | 13.2 |
电解液浸泡24h后结合力(N/15mm) | 19.5 | 22.4 | 21.4 | 13.5 | 10.8 | 6.4 | 3.2 | 4.5 | 9.4 |
电解液浸泡7d后结合力(N/15mm) | 17.9 | 21.7 | 19.8 | 12.4 | 7.8 | 分层 | 分层 | 分层 | 6.1 |
从表1可知,本申请的铝塑膜具有良好的冲深性能和耐电解液性能,主要地,本申请的铝塑膜的内层与铝箔具有良好的结合力。
以上所揭露的仅为本申请一种较佳实施例而已,当然不能以此来限定本申请之权利范围,因此依本申请权利要求所作的等同变化,仍属本申请所涵盖的范围。
Claims (10)
1.一种动力电池铝塑膜,其特征在于,由外向内依次包括外层、铝箔和内层,所述铝箔具有正面和背面,所述外层通过粘接层复合在所述铝箔的正面,所述内层通过多层共挤的方式复合在所述铝箔的背面,所述内层由改性聚丙烯制成。
2.如权利要求1所述的动力电池铝塑膜,其特征在于,所述内层由5层或5层以上的改性聚丙烯制成,所述改性聚丙烯包括聚丙烯和高分子碳化二亚胺交联剂。
3.如权利要求2所述的动力电池铝塑膜,其特征在于,所述聚丙烯和所述高分子碳化二亚胺交联剂的质量比为100:(3~8)。
4.如权利要求2或3所述的动力电池铝塑膜,其特征在于,所述高分子碳化二亚胺交联剂的pH值为10.5~12.5,粘度为25~500mPas。
5.如权利要求1所述的动力电池铝塑膜,其特征在于,所述铝箔的正面和背面均具有粗化结构,所述铝箔的粗化结构由以下方法制得:
提供铝箔基材;
对所述铝箔基材进行清洗处理,其中,所述铝箔基材依次进过酸洗槽、碱洗槽和清洗槽,所述酸洗槽内的酸洗液包括HF和H2SO4,所述碱洗槽内的碱洗液包括氢氧化钙和氢氧化钠,所述清洗槽内含有去离子水;
将清洗处理后的铝箔基材进行烘干处理;
将烘干后的铝箔基材置于刻蚀槽内进行刻蚀处理,所述刻蚀槽内的刻蚀液包括HCl和Al2(SO4)3。
6.如权利要求5所述的动力电池铝塑膜,其特征在于,所述HF和H2SO4的总质量为酸洗液总质量的5%~8%,所述氢氧化钙和氢氧化钠的总质量为碱洗液总质量的5%~8%,所述刻蚀液包括4~6mol/L的HCl和1~1.3mol/L的Al2(SO4)3。
7.如权利要求1所述的动力电池铝塑膜,其特征在于,所述外层由尼龙、PA、PET中的一种或者几种制成,所述粘接层由耐冲压胶制成。
8.如权利要求1所述的动力电池铝塑膜,其特征在于,所述内层和外层之间设有环氧层,所述环氧层由环氧树脂制成。
9.如权利要求1所述的动力电池铝塑膜,其特征在于,所述外层的厚度为40~50μm,所述铝箔的厚度为40~50μm,所述内层的厚度为60~70μm。
10.如权利要求1或9所述的动力电池铝塑膜,其特征在于,所述动力电池铝塑膜的总厚度≤150μm。
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