CN110077043B - 一种新能源汽车锂电池用软包装材料及其制备方法 - Google Patents

一种新能源汽车锂电池用软包装材料及其制备方法 Download PDF

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CN110077043B
CN110077043B CN201910382223.1A CN201910382223A CN110077043B CN 110077043 B CN110077043 B CN 110077043B CN 201910382223 A CN201910382223 A CN 201910382223A CN 110077043 B CN110077043 B CN 110077043B
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Abstract

本发明公开了一种新能源汽车锂电池用软包装材料及其制备方法，所述的锂电池用软包装材料具有层状结构，中间层为铝基层，所述铝基层外侧分为上下两侧，下侧依次由内到外分布为粘合树脂层、PET层、粘合树脂层和共聚丙烯层，上侧依次由内到外分布为粘合树脂层、PET层、粘合树脂层和均聚丙烯层；所述粘合树脂层为网格状结构的粘合树脂，网格中分布有α‑Al2O3纳米粉，所述的粘合树脂包括均聚丙烯、苯乙烯‑马来酸酐的共聚物、过氧化二异丙苯、醋酐、羟基硅油。本发明通过采用特定的结构以及添加了醋酐、羟基硅油，综合提高了新能源汽车锂电池用软包装材料的热封强度、阻燃性能和散热性能。

Description

一种新能源汽车锂电池用软包装材料及其制备方法
技术领域
本发明属于锂电池包装技术领域，具体涉及一种新能源汽车锂电池用软包装材料及其制备方法。
背景技术
目前，市场上锂电池包装的铝塑膜被日本两家公司垄断，国内虽然后很多厂家在研制，但都没能成功，市场上还没有批量生产的国产锂电池软包装用铝塑膜。软包装锂电池由于其可以做的很薄、面积大、形状可以异形、不燃烧、爆炸威力极小等优点广泛应用于锂电池的包装。
目前市场的上的锂电池软包装铝塑膜大都采用干式复合工艺生产，干式复合工艺主要是把各种功能膜和基材铝箔通过溶剂粘结层复合而成，由于锂电池软包装铝塑膜材料使用的特殊性，就是要经过电解液侵泡很长时间，我们知道电解液有很强的腐蚀性，电解液会产生腐蚀性极强的氢氟酸(HF)，还含有溶解能力极强的碳酸乙烯酯(EC)、碳酸二甲酯(DMC)，一旦电解液透过CPP层，与粘结剂和铝箔接触，会使溶剂粘结层分解，使CPP与AL之间分层，AL遇到HF，也会被腐蚀，使电池漏液、鼓胀。所以干式复合的锂电池软包装铝塑膜对溶剂粘结层要求很高，很难保证质量。
中国专利文献“一种锂电池铝塑膜及制备方法(专利号：CN103647029B)”公开了铝塑膜具有耐热性聚酰亚胺(PI)层、胶黏层、铝箔层、耐腐蚀涂层、胶黏层、热封层，其特征在于，所述热封层的表面设有凹凸网格结构。相对于现有技术，该发明热封层的凹凸网格大幅度增加热封比表面积，且热封时形成有力的机械钳锁，可达到更高的热封强度，对锂电池使用安全性提供了可靠的保障。
中国专利文献“一种锂电池用软包装铝塑膜材料(专利号：CN104241556B)”公开了锂电池软用包装铝塑膜材料。它具有层状结构，它由中间的铝基层(AL)内外两侧,内侧依次由内到外分布为新型功能粘合树脂层(AD)、聚脂层(PET)、新型功能粘合树脂层(AD)、共聚丙烯层(CPP)，外侧依次由内到外分布为聚脂层(PET)、新型功能粘合树脂层(AD)、均聚丙烯层(PP)。
发明内容
本发明的目的是提供一种新能源汽车锂电池用软包装材料及其制备方法，优化新能源汽车锂电池用软包装材料的组分、用量、方法等，提高新能源汽车锂电池用软包装材料的热封强度、散热性能和阻燃性能。
为了解决以上技术问题，本发明采用以下技术方案：
一种新能源汽车锂电池用软包装材料，所述的锂电池用软包装材料具有层状结构，中间层为铝基层，所述铝基层外侧分为上下两侧，下侧依次由内到外分布为粘合树脂层、PET层、粘合树脂层和共聚丙烯层，上侧依次由内到外分布为粘合树脂层、PET层、粘合树脂层和均聚丙烯层；所述粘合树脂层为网格状结构的粘合树脂，网格中分布有α-Al2O3纳米粉，所述的粘合树脂包括均聚丙烯、苯乙烯-马来酸酐的共聚物、过氧化二异丙苯、醋酐、羟基硅油；所述PET层、共聚丙烯层、均聚丙烯层在热处理140-160℃下施加一定压力复合到粘合树脂层上。
进一步地，所述粘合树脂按质量份计包括：85-95份的均聚丙烯，5-15份的苯乙烯-马来酸酐的共聚物，0.1-0.3份的过氧化二异丙苯，3-5份的羟基硅油，0.2-0.4份的醋酐。
进一步地，所述粘合树脂按质量份计包括：90份的均聚丙烯，10份的苯乙烯-马来酸酐的共聚物，0.2份的过氧化二异丙苯，4份的羟基硅油，0.3份的醋酐。
进一步地，所述网格结构密度为6-10格/mm2，所述网格结构的深度为4-8μm。
进一步地，所述的铝基层为经过退火处理的软态高成性型铝箔，该铝基层的厚度为30-40μm。
进一步地，所述的聚对苯二甲酸乙二醇酯层的厚度为5-20μm，所述均聚丙烯层的厚度为8-10μm，共聚丙烯层的厚度为8-10μm。
进一步地，所述的PET层、共聚丙烯层、均聚丙烯层在热处理下施加的压力为2-3Kgf。
一种上述的新能源汽车锂电池用软包装材料的制备方法，包括以下步骤：(1)将均聚丙烯、苯乙烯-马来酸酐的共聚物、过氧化二异丙苯、醋酐、羟基硅油混合后作为粘合树脂原料；(2)将铝基层与粘合树脂通过挤出流延工艺，经具有精密凹凸结构的钢辊压延粘合树脂形成网格状结构；(3)在粘合树脂形成网格状结构的网格中填充50体积％的α-Al2O3纳米粉形成粘合树脂层，将PET层热处理140-160℃下施加一定压力复合到粘合树脂层上；(4)重复步骤2和3的流程，在PET层的另一面上复合上粘合树脂层和共聚丙烯层、均聚丙烯层。
本发明具有以下有益效果：
本发明的铝基层，具有良好延展性有良好的力学性能；聚脂层(PET)作为包装功能保护材料，有很好的耐电解液性能，耐冲击强度强，耐折性好，且耐油、耐脂肪、耐烯酸、稀碱，耐大多数溶剂，气体和水蒸气渗透率低；外层采用PP材料，拉伸和压缩强度及硬度性能好，且刚性好，热封强度高，同时具有较好的耐热性，耐腐蚀性，稳定高，几乎不吸水。
本发明中通过将粘合树脂层设置为网格状结构，同时在其中填充部分纳米氧化铝，大幅增大接触面积，可以起到良好的散热性能和阻燃性能，在内层丙烯层发生破碎的情况下，纳米氧化铝作为阻燃剂能够分散到电解液中，起到阻燃效果，同时由于粘合树脂层总共有4层，可以起到多重保护，在电池外部发生燃烧的情况下，当明火接触到包装材料，整个包装材料发生软化熔融时，多层粘合树脂网格中的纳米氧化铝层能够分散到整个包装材料体系中，起到良好的阻燃效果。在制备过程中，对PET层和丙烯层进行热处理后施加压力，使部分PET层和丙烯层材料软化后进入网格状的空腔中，能够增强复合强度，提高热封强度。
所述的新型功能粘合树脂层,主要采用质量百分比85-95％的均聚丙烯作为基材、以苯乙烯-马来酸酐的共聚物为活性单体、过氧化二异丙苯作为添加剂。本发明的苯乙烯-马来酸酐的共聚物(SMA)，克服了市面上的PP接枝马来酸酐的接枝率不高，导致粘合树脂与铝材的粘接力有限的缺点。使用SMA作为马来酸酐源，由于SMA自身的马来酸酐含量高且具有更高的活性，可大大提高PP接枝物中马来酸酐的含量，上述配方马来酸酐含量可达8％，远高于其它接枝物；较好的与铝箔、PET、CPP、PP等材料低温热合性能，流延工艺使其粘结牢度更强。本发明中还添加羟基硅油和醋酐，从而协同促进热封强度。羟基硅油的活性羟基团可以与未反应的活性单体的活性基团进一步反应，提高粘合强度，同时增强成型后的稳定性，醋酐可以脱水，去除粘合树脂中的微量水分，同时由于其脱水性可以作为催化剂吸收羟基硅油与苯乙烯-马来酸酐反应产生的一分子水，从而使反应平衡向右侧进行，从而促进羟基硅油的反应，从而增强粘合强度，并可以作为马来酸酐的补充酐源，同时可以改善马来酸酐大量接枝后，分子量增大带来的流动性下降，增加粘性和操作简易度。羟基硅油与醋酐的添加量在特定比例范围内时，制得的新能源汽车锂电池用软包装材料的热封性能效果更优，这是由于当醋酐过量时，整体的粘度下降过大，并且与羟基硅油络合团聚，降低热封强度，过小时，不能实现同时促进羟基硅油的反应和补充酐源的技术效果，而当羟基硅油过量时，导致粘度更高，加工成型困难，过小时，不能与未反应的活性单体的活性基团充分反应，改性效果下降。
具体实施方式
为便于更好地理解本发明，通过以下实例加以说明，这些实例属于本发明的保护范围，但不限制本发明的保护范围。
实施例1
一种新能源汽车锂电池用软包装材料，所述的锂电池用软包装材料具有层状结构，中间层为铝基层，所述铝基层外侧分为上下两侧，下侧依次由内到外分布为粘合树脂层、PET层、粘合树脂层和共聚丙烯层，上侧依次由内到外分布为粘合树脂层、PET层、粘合树脂层和均聚丙烯层；所述粘合树脂层为网格状结构的粘合树脂，网格中分布有α-Al2O3纳米粉，所述粘合树脂按质量份计包括：90份的均聚丙烯，10份的苯乙烯-马来酸酐的共聚物，0.2份的过氧化二异丙苯，4份的羟基硅油，0.3份的醋酐；所述PET层、共聚丙烯层、均聚丙烯层在热处理150℃下施加一定压力复合到粘合树脂层上。
所述网格结构密度为8格/mm2，所述网格结构的深度为6μm。所述的铝基层为经过退火处理的软态高成性型铝箔，该铝基层的厚度为35μm。所述的聚对苯二甲酸乙二醇酯层的厚度为12.5μm，所述均聚丙烯层的厚度为9μm，共聚丙烯层的厚度为9μm。
一种上述的新能源汽车锂电池用软包装材料的制备方法，包括以下步骤：(1)将均聚丙烯、苯乙烯-马来酸酐的共聚物、过氧化二异丙苯、醋酐、羟基硅油混合后作为粘合树脂原料；(2)将铝基层与粘合树脂通过挤出流延工艺，经具有精密凹凸结构的钢辊压延粘合树脂形成网格状结构；(3)在粘合树脂形成网格状结构的网格中填充50体积％的α-Al2O3纳米粉形成粘合树脂层，将PET层热处理150℃下施加一定压力复合到粘合树脂层上；(4)重复步骤2和3的流程，在PET层的另一面上复合上粘合树脂层和共聚丙烯层、均聚丙烯层。
实施例2
与实施例1基本相同，除了所述粘合树脂按质量份计包括：85份的均聚丙烯，15份的苯乙烯-马来酸酐的共聚物，0.1份的过氧化二异丙苯，5份的羟基硅油，0.2份的醋酐。
实施例3
与实施例1基本相同，除了所述粘合树脂按质量份计包括：95份的均聚丙烯，5份的苯乙烯-马来酸酐的共聚物，0.3份的过氧化二异丙苯，3份的羟基硅油，0.4份的醋酐。
对比例1
与实施例1的生产工艺基本相同，唯有不同的是制备新能源汽车锂电池用软包装材料的原料中缺少羟基硅油，醋酐。
对比例2
与实施例1的生产工艺基本相同，唯有不同的是制备新能源汽车锂电池用软包装材料的原料中缺少羟基硅油。
对比例3
与实施例1的生产工艺基本相同，唯有不同的是制备新能源汽车锂电池用软包装材料的原料中缺少醋酐。
对比例4
采用中国专利文献“一种锂电池铝塑膜及制备方法(专利号：CN103647029B)”中具体实施例1所述的方法生产。
对比例5
与实施例1的制备工艺基本相同，唯有不同的是制备新能源汽车锂电池用软包装材料的原料中包括7份的羟基硅油，0.1份的醋酐。
对比例6
与实施例1的制备工艺基本相同，唯有不同的是制备新能源汽车锂电池用软包装材料的原料中2份的羟基硅油，0.6份的醋酐。
对比例7
与实施例1的制备工艺基本相同，唯有不同的是制备新能源汽车锂电池用软包装材料不填充α-Al2O3纳米粉。
对比例8
与实施例1的制备工艺基本相同，唯有不同的是制备新能源汽车锂电池用软包装材料中填充100％体积的α-Al2O3纳米粉。
对比例9
与实施例1的制备工艺基本相同，唯有不同的是制备新能源汽车锂电池用软包装材料中粘合树脂层为平层状结构(厚度一致)，且不填充α-Al2O3纳米粉。
对比例10
与实施例1的制备工艺基本相同，唯有不同的是制备新能源汽车锂电池用软包装材料中粘合树脂层为平层状结构(厚度一致)，且α-Al2O3纳米粉分散到粘合树脂中。
根据实施例1-3和对比例1-10的工艺生产新能源汽车锂电池用软包装材料，测试热封强度，阻燃性能，散热性能(导热系数W/m.k)，结果如下表所示。所述阻燃性能采用明火灼烧包装材料30s，观察阻燃情况，5级为熔融发黑未燃烧
Figure BDA0002052401920000061
Figure BDA0002052401920000071
由上表可知：由实施例1-3和对比例4的数据可见，实施例1-3制得的新能源汽车锂电池用软包装材料的热封强度效果显著高于对比例4制得的新能源汽车锂电池用软包装材料的热封强度效果。由实施例1和对比例1-3的数据可见，羟基硅油，醋酐在生产新能源汽车锂电池用软包装材料中起到了协同作用，协同提高了新能源汽车锂电池用软包装材料的热封强度，由对比例5-6的数据可见，羟基硅油，醋酐的重量比不在特定范围内时，制得的新能源汽车锂电池用软包装材料的热封强度效果与实施例1-3的数值相差甚大。由实施例1和对比例8-10相比较可知，本发明的网格结构和网格空隙填充纳米氧化铝可以综合提高阻燃性能和散热能力。
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 (4)

1.一种新能源汽车锂电池用软包装材料，其特征在于，所述的锂电池用软包装材料具有层状结构，中间层为铝基层，所述铝基层外侧分为上下两侧，下侧依次由内到外分布为粘合树脂层、PET层、粘合树脂层和共聚丙烯层，上侧依次由内到外分布为粘合树脂层、PET层、粘合树脂层和均聚丙烯层；所述粘合树脂层为网格状结构的粘合树脂，网格中分布有50体积%的α-Al2O3纳米粉，所述网格结构密度为6-10格/mm2，所述网格结构的深度为4-8μm，所述粘合树脂按质量份计包括：85-95份的均聚丙烯， 5-15份的苯乙烯-马来酸酐的共聚物，0.1-0.3份的过氧化二异丙苯，3-5份的羟基硅油，0.2-0.4份的醋酐，所述PET层、共聚丙烯层、均聚丙烯层在热处理140-160℃下施加一定压力复合到粘合树脂层上；
所述的铝基层为经过退火处理的软态高成性型铝箔，该铝基层的厚度为30-40μm；
所述的聚对苯二甲酸乙二醇酯层的厚度为5-20μm，所述均聚丙烯层的厚度为8-10μm，共聚丙烯层的厚度为8-10μm。
2.根据权利要求1所述的新能源汽车锂电池用软包装材料，其特征在于，所述粘合树脂按质量份计包括：90份的均聚丙烯，10份的苯乙烯-马来酸酐的共聚物， 0.2份的过氧化二异丙苯，4份的羟基硅油，0.3份的醋酐。
3.根据权利要求1所述的新能源汽车锂电池用软包装材料，其特征在于，所述的所述PET层、共聚丙烯层、均聚丙烯层在热处理下施加的压力为2-3Kgf。
4.一种根据权利要求1-3任一项所述的新能源汽车锂电池用软包装材料的制备方法，其特征在于，包括以下步骤：（1）将均聚丙烯、苯乙烯-马来酸酐的共聚物、过氧化二异丙苯、醋酐、羟基硅油混合后作为粘合树脂原料；（2）将铝基层与粘合树脂通过挤出流延工艺，经具有精密凹凸结构的钢辊压延粘合树脂形成网格状结构；（3）在粘合树脂形成网格状结构的网格中填充50体积%的α-Al2O3纳米粉形成粘合树脂层，将PET层热处理140-160℃下施加一定压力复合到粘合树脂层上；（4）重复步骤2和3的流程，在PET层的另一面上复合上粘合树脂层和共聚丙烯层、均聚丙烯层。
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