CN115141525A - 一种防火涂料层及其在软包电池铝塑膜中的应用 - Google Patents
一种防火涂料层及其在软包电池铝塑膜中的应用 Download PDFInfo
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- CN115141525A CN115141525A CN202210594045.0A CN202210594045A CN115141525A CN 115141525 A CN115141525 A CN 115141525A CN 202210594045 A CN202210594045 A CN 202210594045A CN 115141525 A CN115141525 A CN 115141525A
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- Prior art keywords
- aluminum
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- plastic film
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Abstract
本发明涉及锂电池领域,针对锂电池一旦失火能量瞬间释放的问题,提供一种防火涂料层及其在软包电池铝塑膜中的应用,防火涂料层的原料配方为:按质量份数计,30‑45份粘结剂、5‑15份分散剂、25‑35份水、5‑10份盐酸、5‑10份灭火增强剂和5‑10份耐火纤维。本发明将防火涂层与铝塑膜直接复合在一起,制备有阻燃性能的铝塑膜,让成品电池直接具备防火能力,可阻隔热量传播及防止外界氧气的进入,延缓电池热失控的发生,从而预留出足够的安全逃生时间。
Description
技术领域
本发明涉及锂电池领域,尤其是涉及一种防火涂料层及其在软包电池铝塑膜中的应用。
背景技术
随着锂电池技术的发展,在越来越多领域内开始应用锂电池。随着韩国储能电站、乘用车、低速车等起火事件的发生,锂电池的安全问题引发争议,如何解决及控制锂电池的着火,预留逃生的空间,成为当下锂电池技术发展的重中之重。且按照国家新出的热失控标准,要求当整车发生起火事件的时候,需预留5min的人员逃生时间,为达到此标准,各大电池厂家争相采取措施,以解决电池的安全问题。
现有技术通过调整电解液配方和改善电芯的封装工艺提高电池安全性,比如专利CN108336409A描述到电解液的成分里面加入防过充添加剂,如在电解液中添加2-氟-N,N-二甲氨苯和多氟联苯液晶化合物,让其在过充条件下过充添加剂发生电聚合,在电极表面形成保护膜,形成断路,从而阻止热失控的发生。但是此类方式会影响到电池性能发挥。专利CN108155307A通过在铝塑膜的粘结层中加入具有阻燃效果的微胶囊,使电池在热失控自燃时,通过释放粘结层中的阻燃微胶囊,来达到阻燃的效果。此种方法在铝塑膜粘结层中加入了10-60%体积分数的阻燃剂,一方面,阻燃剂加入份数较大,会严重降低粘结层自身的强度以及铝塑膜的机械性能(冲坑深度降低),另一方面,由于阻燃剂与粘结层物质不具有相容性,在电池长时间使用过程中,阻燃剂与粘结层会发生相分离导致阻燃剂从粘结层中析出,从而严重影响铝塑膜各层之间的层间结合强度,最终导致封装失效,存在极大安全隐患。据此需要一种理想的解决方法。
发明内容
本发明为了克服锂电池一旦失火,能量瞬间释放的问题,提供一种防火涂料层及其在软包电池铝塑膜中的应用,将防火涂层与铝塑膜直接复合在一起,制备有阻燃性能的铝塑膜,让成品电池直接具备防火能力,可阻隔热量传播及防止外界氧气的进入,延缓电池热失控的发生,从而预留出足够的安全逃生时间。
为了实现上述目的,本发明采用以下技术方案:
一种防火涂料层,其原料配方为:按质量份数计,30-45份粘结剂、5-15份分散剂、25-35份
水、5-10份盐酸、5-10份灭火增强剂和5-10份耐火纤维。
作为优选,所述粘结剂为聚丙烯酸,分散剂为分子量100-130万的聚乙烯吡咯烷酮,盐酸的质量浓度为36-38%,灭火增强剂包括质量份数为30-40份的氢氧化镁、40-50份的磷酸铝镁和10-30份的磷酸氢钙。聚乙烯吡咯烷酮可以有效地提高粘结剂的粘度,提高催化效果。
作为优选,所述耐火纤维的制备方法为:将硅酸铝纤维打浆分散10-20min,配置成硅酸铝纤维-水悬浮液;在悬浮液中加入硅溶胶和植酸铝盐,硅酸铝纤维、硅溶胶和植酸铝盐的质量比为100:(10-20):(10-15),60-80℃下搅拌20-24h,过滤、干燥得耐火纤维。植酸铝盐有6个磷酸基团,受热分解时会生成偏磷酸等酸性物质,燃烧时可以促进形成炭层,降低传热效率,抑制挥发性物质的生成,从而提高体系的阻燃性能。但是植酸铝盐和硅酸铝纤维的粘结性不好,为此加入硅溶胶。使用植酸铝盐代替植酸,不但阻燃效果比植酸好,而且与硅溶胶的粘结性也更好。硅溶胶粒径小、渗透性好,可以附着在硅酸铝纤维表面,水分蒸发后,SiO2.nH2O粒子间脱水,形成牢固的Si-O键交联的立体网络涂膜。但是Si-O键的刚性较强,无变形能力,涂料成膜脱水过程中容易出现裂缝、微孔等缺陷,植酸铝盐刚好可以随机均匀的分布在Si-O键涂膜间隙中,提高涂膜的韧性、抗冲击性和耐水性。所以植酸铝盐和硅溶胶的用量比例需要控制在合理范围,以达到相互配合、增益的效果。
作为进一步优选,所述干燥分段进行,先80-100℃干燥2-4h、然后100-110℃干燥2-4h、最后150-180℃干燥2-3h。分段干燥的好处是,起初含水量大,硅溶胶不稳定,所以先以较低的温度除水,可以让硅溶胶粒子逐渐聚集,增强粒子间的致密性,提高植酸铝盐和硅酸铝纤维之间的粘结强度。然后升温加快硅溶胶的凝胶化,最后升温除去化学吸附水。
作为优选,所述防火涂料层的制备方法包括以下步骤:
1)将粘结剂和水混合搅拌,加入分散剂和盐酸,进行酸催化,酸催化的温度为25-40℃、pH值2-4、催化时间为25-35min;
2)在步骤1)中加入灭火增强剂和耐火纤维,混合得均匀溶液;
3)将步骤2)的均匀溶液涂覆在薄膜上,形成防火涂料层。
防火涂料层在软包电池铝塑膜中的应用,铝塑膜从外到内依次为尼龙层、铝箔层和聚丙烯层,铝箔层的内侧或外侧设有所述防火涂料层,相邻层间通过粘结层连接。最外层的尼龙层保护中间层不被划伤和防止外界水汽进入;铝箔层用于铝塑膜冲坑成型,同时防止外界水分入侵;聚丙烯层耐电解液腐蚀,聚丙烯层可以由两层聚丙烯经过热封后粘结在一块形成;防火涂层与铝塑膜直接复合在一起,让成品电池直接具备防火能力,可阻隔热量传播及防止外界氧气的进入,延缓电池热失控的发生,从而预留出足够的安全逃生时间。按照新国标GB38031标准中要求,当电池包发生热失控时,需控制在5min内不发生热扩散。目前行业内的电池基本通不过此标准验证。通过采用本专利的铝塑膜,可以将电芯热扩散时间延缓至7-8min,保证电芯的安全性,预留足够多的逃生空间。
作为优选,尼龙层厚度为23-27μm,铝箔层厚度为38-42μm,聚丙烯层厚度为78-82μm,粘结层厚度为2-4μm,防火涂料层位于铝箔层内侧时厚度为20-25μm,防火涂料层位于铝箔层的外侧时厚度为28-32μm。若将防火涂料层涂覆在PP层与铝箔层之间,可以提前起到防火的作用。因防火涂层不具备拉伸能力,降低铝箔层的延展能力,想达到更好的铝塑膜冲坑效果,需将铝箔层厚度由28-32μm降至20-25μm。
作为优选,所述铝塑膜的制备方法为:将尼龙层、防火涂料层、铝箔层和聚丙烯层按顺序通过粘结层粘结,用辊压机压延紧密,其中复合层为复合膜粘结剂,由质量份数为6-10份的树脂、2-4份的聚偏氟乙烯和86-92份的丁二醇组成,辊压机的温度为60-90℃,压力为250-350N。
本发明还提供一种防火涂料层在软包电池铝塑膜中的另一种应用,在锂电池完成制造后,分别在电池铝塑膜两侧刷一层防火涂料。此时防火涂料层可以将两个电芯粘结在一起,还有安全涂层的作用。
因此,本发明的有益效果为:(1)将防火涂层与铝塑膜直接复合在一起,制备有阻燃性能的铝塑膜,让成品电池直接具备防火能力,可阻隔热量传播及防止外界氧气的进入,延缓电池热失控的发生,从而预留出足够的安全逃生时间;(2)在硅酸铝纤维中加入硅溶胶和植酸铝盐,提高铝塑膜的阻燃性能。
附图说明
图1是实施例1的铝塑膜的结构示意图;
图2是实施例2的铝塑膜的结构示意图;
图中,1、尼龙层,2、铝箔层,3、聚丙烯层,4、粘结层,5、防火涂料层。
具体实施方式
下面通过具体实施例,对本发明的技术方案做进一步说明。
本发明中,若非特指,所采用的原料和设备等均可从市场购得或是本领域常用的,实施例中的方法,如无特别说明,均为本领域的常规方法。
总实施例一
一种软包电池铝塑膜,从外到内依次为尼龙层、铝箔层和聚丙烯层,铝箔层的内侧或外侧设有防火涂料层,相邻层间通过粘结层连接。尼龙层厚度为23-27μm,铝箔层厚度为38-42μm,聚丙烯层厚度为78-82μm,粘结层厚度为2-4μm,防火涂料层位于铝箔层内侧时厚度为20-25μm、防火涂料层位于铝箔层的外侧时厚度为28-32μm。所述铝塑膜的制备方法为:将尼龙层、防火涂料层、铝箔层和聚丙烯层按顺序采用复合膜粘结剂粘结,用辊压机压延紧密,其中复合膜粘结剂由质量份数为6-10份的树脂、2-4份的聚偏氟乙烯和86-92份的丁二醇组成,辊压机的温度为60-90℃,压力为250-350N。
所述防火涂料层的原料配方为:按质量份数计,30-45份粘结剂、5-15份分散剂、25-35份水、5-10份盐酸、5-10份灭火增强剂和5-10份耐火纤维。所述粘结剂为聚丙烯酸,分散剂为分子量100-130万的聚乙烯吡咯烷酮,盐酸的质量浓度为36-38%,灭火增强剂包括质量份数为30-40份的氢氧化镁、40-50份的磷酸铝镁和10-30份的磷酸氢钙。所述防火涂料层的制备方法包括以下步骤:
1)将粘结剂和水混合搅拌,加入分散剂和盐酸,进行酸催化,酸催化的温度为25-40℃、pH值2-4、催化时间为25-35min;
2)在步骤1)中加入灭火增强剂和耐火纤维,混合得均匀溶液;
3)将步骤2)的均匀溶液涂覆在薄膜上,形成防火涂料层。
作为优选,所述耐火纤维的制备方法为:将硅酸铝纤维打浆分散10-20min,配置成硅酸铝纤维-水悬浮液;在悬浮液中加入硅溶胶和植酸铝盐,硅酸铝纤维、硅溶胶和植酸铝盐的质量比为100:(10-20):(10-15),60-80℃下搅拌20-24h,过滤、干燥得耐火纤维,所述干燥分段进行,先80-100℃干燥2-4h、然后100-110℃干燥2-4h、最后150-180℃干燥2-3h。
总实施例二
本发明还提供另一种防火涂料层在软包电池铝塑膜中的应用方式,在锂电池完成制造后,分别在电池铝塑膜两侧刷一层防火涂料,此时防火涂料层可以将两个电芯粘结在一起,还有安全涂层的作用。
实施例1
一种软包电池铝塑膜,如图1所示,从外到内依次为尼龙层1、防火涂料层5、铝箔层2和聚丙烯层3,相邻层间通过粘结层4连接。尼龙层1厚度为25μm,防火涂料层5厚度为30μm,铝箔层2厚度为40μm,聚丙烯层3厚度为80μm,粘结层4厚度为3μm。所述铝塑膜的制备方法为:将尼龙层1、防火涂料层5、铝箔层2和聚丙烯层3按顺序采用复合膜粘结剂粘结,用辊压机压延紧密,其中复合膜粘结剂由质量份数为8份的树脂、3份的聚偏氟乙烯和90份的丁二醇组成,辊压机的温度为80℃,压力为300N。
所述防火涂料层5的原料配方为:按质量份数计,40份粘结剂、10份分散剂、30份水、5份盐酸、5份灭火增强剂和5份耐火纤维。所述粘结剂为聚丙烯酸,分散剂为分子量100-130万的聚乙烯吡咯烷酮,盐酸的质量浓度为37%,灭火增强剂由质量份数为35份的氢氧化镁、45份的磷酸铝镁和15份的磷酸氢钙组成。所述防火涂料层5的制备方法包括以下步骤:
1)将粘结剂和水混合搅拌,加入分散剂和盐酸,进行酸催化,酸催化的温度为30℃、pH值3、催化时间为30min;
2)在步骤1)中加入灭火增强剂和耐火纤维(市购普通硅酸铝纤维),混合得均匀溶液;
3)将步骤2)的均匀溶液涂覆在薄膜上,形成防火涂料层5。
实施例2
一种软包电池铝塑膜,如图2所示,从外到内依次为尼龙层1、铝箔层2、防火涂料层5和聚丙烯层3,相邻层间通过粘结层4连接。尼龙层1厚度为23μm,铝箔层2厚度为38μm,防火涂料层5厚度为20μm,聚丙烯层3厚度为78μm,粘结层4厚度为2μm。所述铝塑膜的制备方法为:将尼龙层1、防火涂料层5、铝箔层2和聚丙烯层3按顺序采用复合膜粘结剂粘结,用辊压机压延紧密,其中复合膜粘结剂由质量份数为6份的树脂、2份的聚偏氟乙烯和86份的丁二醇组成,辊压机的温度为60℃,压力为350N。
所述防火涂料层5的原料配方为:按质量份数计,45份粘结剂、5份分散剂、25份水、10份盐酸、10份灭火增强剂和10份耐火纤维。所述粘结剂为聚丙烯酸,分散剂为分子量100-130万的聚乙烯吡咯烷酮,盐酸的质量浓度为36%,灭火增强剂包括质量份数为30份的氢氧化镁、40份的磷酸铝镁和10份的磷酸氢钙。所述防火涂料层5的制备方法包括以下步骤:
1)将粘结剂和水混合搅拌,加入分散剂和盐酸,进行酸催化,酸催化的温度为25℃、pH值2、催化时间为35min;
2)在步骤1)中加入灭火增强剂和耐火纤维(市购普通硅酸铝纤维),混合得均匀溶液;
3)将步骤2)的均匀溶液涂覆在薄膜上,形成防火涂料层5。
实施例3
一种防火涂料层在软包电池铝塑膜中的应用,铝塑膜为常规铝塑膜,从外到内依次为尼龙层、铝箔层和聚丙烯层,相邻层间通过粘结层连接。在锂电池完成制造后,分别在电池铝塑膜两侧刷一层防火涂料层,此时防火涂料层可以将两个电芯粘结在一起,还有安全涂层的作用。所述防火涂料层和实施例1相同。
实施例4
与实施例1的区别在于,所述耐火纤维经过改性处理,制备方法为:将硅酸铝纤维打浆分散15min,配置成硅酸铝纤维-水悬浮液;在悬浮液中加入硅溶胶和植酸铝盐,硅酸铝纤维、硅溶胶和植酸铝盐的质量比为100:10:13,70℃下搅拌22h,过滤、干燥得耐火纤维,所述干燥分段进行,先90℃干燥3h、然后100℃干燥3h、最后180℃干燥2h。
实施例5
与实施例1的区别在于,所述耐火纤维经过改性处理,制备方法为:将硅酸铝纤维打浆分散15min,配置成硅酸铝纤维-水悬浮液;在悬浮液中加入植酸铝盐,硅酸铝纤维和植酸铝盐的质量比为100:13,70℃下搅拌22h,过滤、干燥得耐火纤维,所述干燥分段进行,先90℃干燥3h、然后100℃干燥3h、最后180℃干燥2h。。
实施例6
与实施例1的区别在于,所述耐火纤维经过改性处理,制备方法为:将硅酸铝纤维打浆分散15min,配置成硅酸铝纤维-水悬浮液;在悬浮液中加入硅溶胶和植酸铝盐,硅酸铝纤维、硅溶胶和植酸铝盐的质量比为100:25:8,70℃下搅拌22h,过滤、干燥得耐火纤维,所述干燥分段进行,先90℃干燥3h、然后100℃干燥3h、最后180℃干燥2h。
实施例7
与实施例1的区别在于,所述耐火纤维经过改性处理,制备方法为:将硅酸铝纤维打浆分散15min,配置成硅酸铝纤维-水悬浮液;在悬浮液中加入硅溶胶和植酸铝盐,硅酸铝纤维、硅溶胶和植酸铝盐的质量比为100:25:8,70℃下搅拌22h,过滤、150℃干燥8h得耐火纤维。
对比例1
与实施例1的区别在于,软包电池铝塑膜未设置防火涂料层。
对比例2
与实施例1的区别在于,防火涂层的厚度为27μm。
对比例3
与实施例1的区别在于,防火涂层的厚度为33μm。
对比例4
与实施例2的区别在于,防火涂层的厚度为19μm。
性能测试
对各实施例和对比例的铝塑膜做阻燃测试,测试方法为:
1、正极采用镍锰钴酸锂,负极为常规的人造石墨,分别采用上述实施例及对比例的铝塑膜制备成软包电池,将电池充电至4.2V,即充满电;
2、将步骤1满电电池放在温箱内,温箱以5℃/min的速度升温至200℃,保持此温度30min后停止加热;
3、观察电池在200℃箱体内部30min的状态变化,记录电池在膨胀、冒烟、起火三个阶段的持续时间。
结果如下表所示:
案例 | 膨胀持续时间min | 冒烟持续时间min | 起火持续时间min |
实施例1 | 25.0 | 5.0 | 0 |
实施例2 | 25.2 | 4.8 | 0 |
实施例3 | 22.6 | 7.4 | 0 |
实施例4 | 27.6 | 3.2 | 0 |
实施例5 | 26.0 | 4.2 | 0 |
实施例6 | 26.5 | 4.0 | 0 |
实施例7 | 26.8 | 3.6 | 0 |
对比例1 | 10.0 | 3.0 | 1 |
对比例2 | 20.2 | 8.8 | 1 |
对比例3 | 25.6 | 5.4 | 0 |
对比例4 | 19.8 | 8.5 | 0.7 |
从上表可以看出,对比例1未采用阻燃型铝塑膜,电池在环境中达到200℃后,电池内部的电解液进行快速反应,产生气体和大量的热,导致气体冲开铝塑膜,接触到外界空气,从而快速引发电池热失控。与对比例1相比,本发明的实施例1和实施例2加了防火涂料层后,膨胀持续时间显著延长,可以预留出足够的安全逃生时间。实施例3在常规的电池铝塑膜两侧刷一层防火涂料,亦可以起到延缓起火的作用,电芯在冒烟阶段持续时间增加。
对比例2、对比例4分别相对于实施例1、2,将防火涂料层的厚度减薄至低于优选范围,防火涂料热传递加快且防火涂料发泡数量减少,导致热失控时间提前,阻燃效果下降。对比例3与实施例1相比,增加了防火涂层厚度,加长了电芯在膨胀阶段的时间,且在30min内电芯未着火,由于热失控要求30min内不发生起火、爆炸即为通过测试,在优选范围内已经可以起到保护作用,所以不再额外增加防火涂层厚度增加成本。
实施例4相对于实施例1对耐火纤维进行了改性,植酸铝盐燃烧时可以促进形成炭层,抑制挥发性物质的生成,体现在铝塑膜的膨胀持续时间延长、冒烟持续时间下降。与实施例4相比,实施例5耐火纤维改性时未使用硅溶胶,因为植酸铝盐和硅酸铝纤维的粘结性不好,对铝塑膜的阻燃性能也有影响;实施例6硅溶胶和植酸铝盐的比例不在优选范围内,硅溶胶过多、植酸铝盐过少,导致铝塑膜的阻燃性能下降,硅溶胶和植酸铝盐是相互配合的关系,硅溶胶提高植酸铝盐和硅酸铝纤维制剂浓度粘结性、植酸铝盐提高硅溶胶的;实施例7干燥时一步完成,未进行分段干燥,植酸铝盐和硅酸铝纤维之间的粘结不佳,影响铝塑膜的阻燃性能。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (9)
1.一种防火涂料层,其特征在于,其原料配方为:按质量份数计,30-45份粘结剂、5-15份分散剂、25-35份水、5-10份盐酸、5-10份灭火增强剂和5-10份耐火纤维。
2.根据权利要求1所述的一种防火涂料层,其特征在于,所述粘结剂为聚丙烯酸,分散剂为分子量100-130万的聚乙烯吡咯烷酮,盐酸的质量浓度为36-38%,灭火增强剂包括质量份数为30-40份的氢氧化镁、40-50份的磷酸铝镁和10-30份的磷酸氢钙。
3.根据权利要求1所述的一种防火涂料层,其特征在于,所述耐火纤维的制备方法为:将硅酸铝纤维打浆分散10-20 min,配置成硅酸铝纤维-水悬浮液;在悬浮液中加入硅溶胶和植酸铝盐,硅酸铝纤维、硅溶胶和植酸铝盐的质量比为100:(10-20):(10-15),60-80 ℃下搅拌20-24 h,过滤、干燥得耐火纤维。
4.根据权利要求3所述的一种防火涂料层,其特征在于,所述干燥分段进行,先80-100℃干燥2-4 h、然后100-110 ℃干燥2-4 h、最后150-180 ℃干燥2-3 h。
5.根据权利要求1-4任一所述的一种防火涂料层,其特征在于,其制备方法为:
1)将粘结剂和水混合搅拌,加入分散剂和盐酸,进行酸催化,酸催化的温度为25-40℃、pH值2-4、催化时间为25-35 min;
2)在步骤1)中加入灭火增强剂和耐火纤维,混合得均匀溶液;
3)将步骤2)的均匀溶液涂覆在薄膜上,形成防火涂料层。
6.权利要求1所述的防火涂料层在软包电池铝塑膜中的应用,其特征在于,铝塑膜从外到内依次为尼龙层、铝箔层和聚丙烯层,铝箔层的内侧或外侧设有所述防火涂料层,相邻层间通过粘结层连接。
7.根据权利要求6所述的防火涂料层在软包电池铝塑膜中的应用,其特征在于,尼龙层厚度为23-27 μm,铝箔层厚度为38-42 μm,聚丙烯层厚度为78-82 μm,粘结层厚度为2-4 μm,防火涂料层位于铝箔层内侧时厚度为20-25 μm,防火涂料层位于铝箔层的外侧时厚度为28-32 μm。
8.根据权利要求6或7所述的防火涂料层在软包电池铝塑膜中的应用,其特征在于,所述铝塑膜的制备方法为:将尼龙层、防火涂料层、铝箔层和聚丙烯层按顺序通过粘结层粘结,用辊压机压延紧密,其中粘结层由质量份数为6-10份的树脂、2-4份的聚偏氟乙烯和86-92份的丁二醇组成,辊压机的温度为60-90 ℃,压力为250-350 N。
9.权利要求1所述的防火涂料层在软包电池铝塑膜中的另一种应用,其特征在于,分别在电池铝塑膜两侧刷一层防火涂料。
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