CN109337153A - 一种汽车电池壳体包胶材料及其制备方法 - Google Patents

一种汽车电池壳体包胶材料及其制备方法 Download PDF

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CN109337153A
CN109337153A CN201810900001.XA CN201810900001A CN109337153A CN 109337153 A CN109337153 A CN 109337153A CN 201810900001 A CN201810900001 A CN 201810900001A CN 109337153 A CN109337153 A CN 109337153A
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parts
shell cover
automobile batteries
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foaming agent
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王滨
刘曙阳
蒋顶军
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NANJING JULONG TECHNOLOGY Co Ltd
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Abstract

本发明涉及一种汽车电池壳体包胶材料及其制备方法。本发明材料包括以下重量份数的组分：热塑性弹性体60‑90份，熔喷型聚合物5‑25份，阻燃剂5‑30份，填充剂0‑20份，界面改性剂1‑20份，发泡剂0.5‑12份，发泡协效剂1‑10份，润滑剂0.5‑2份，抗氧剂0.2‑1份，并公开了其制备方法。本发明通过具有高流动性，优良的加工成型性，保证了其对复杂电池壳体结构的精确复制和有效贴合以及产品壁厚的优化减薄，实现了产品便携性，同时具有与金属或工程塑料壳体良好粘接性，有效改善了目前市场产品易脱落等问题，对电池起到更好的缓冲保护作用，具有优良的耐低温性、优良的缓冲性、阻燃特性等性能，解决了产品低温落球冲击性能差以及抗震性能差等问题。

Description

一种汽车电池壳体包胶材料及其制备方法
技术领域
本发明涉及一种汽车电池壳体包胶材料及其制备方法，属于材料领域
背景技术
汽车电池壳体作为电池模块的承载体，对电池模块的安全工作和防护起着关键作用。要求(1)具有维护的方便性；(2)在车辆发生碰撞或电池发生自燃等意外情况下，起到防护措施作用。目前材料主要以热固性SMC复合材料、PC/ABS合金材料等为主，这些材料机械强度足够，但无法满足电池壳体跌落试验，尤其是-30℃低温跌落实验；因此，通常会在外部包一层包胶材料提高壳体抗摔性，但目前市场上的包胶材料存在以下问题：1、包胶后的电池壳体低温跌落实验仍然无法完全通过；2、包胶材料因属于超高分子量的橡胶材料，其流动性较差，对电池壳体这种复杂结构制件的结构复制性差，造成二者贴合不牢固，易脱落；3、目前包胶材料普遍超过4mm以上，太厚，重量过重，携带不方便，且表观缩痕严重，产品凹凸不平，同时，加工成型周期太长，产率低。
发明内容
为解决以上问题，本发明提供一种汽车电池壳体包胶材料及其制备方法。本发明具有高流动性，优良的加工成型性，保证了其对复杂电池壳体结构的精确复制和有效贴合以及产品壁厚的优化减薄，实现了产品便携性，同时具有与金属或工程塑料壳体良好粘接性，有效改善了目前市场产品易脱落等问题，对电池起到更好的缓冲保护作用。另外，本发明采用微发泡技术改善了产品缩水严重等质量外观，还具有优良的耐低温性、优良的缓冲性、阻燃特性等性能，解决了产品低温冲击性能差以及抗震性能差等问题。在车辆发生碰撞或电池发生自燃等意外情况下，能够保护电池壳体和电池，防止烟火、液体、气体等进入车厢等其他危机乘客人身安全的舱室。为实现上述目的，本发明采用如下技术方案：
一种汽车电池壳体包胶材料，包括以下重量份数的组分：
热塑性弹性体60-90份，
熔喷型聚烯烃5-25份，
阻燃剂5-30份，
填充剂0-20份，
界面改性剂1-20份，
发泡剂0.5-12份，
发泡协效剂1-10份，
润滑剂0.5-2份，
抗氧剂0.2-1份，
进一步技术方案，所述弹性体为烯烃类弹性体(例如弹性体TPV、TPE等)、芳烃类弹性体(例如弹性体SEBS、SBS等)、聚酯类弹性体(例如弹性体TPEE等)、双烯类弹性体(例如弹性体TPB等)、乙丙橡胶、酰胺类弹性体中的一种，优选弹性体TPETPE(ThermoplasticElastomer)；
进一步，所述汽车电池壳体包胶材料，其特征在于：所述熔喷型聚合物为熔融指数大于等于800g/10min的聚合物，例如熔喷型聚乙烯、熔喷型聚丙烯、熔喷型聚对苯二甲酸乙二醇酯等，优选熔融指数1800g/10min的聚乙烯。
进一步，所述阻燃剂为环三磷腈类阻燃剂(例如六氯环三磷腈等)、烷基磷系阻燃剂(如异丁基次磷酸铝等)、三嗪类膨胀型阻燃剂(如三聚氰胺氰尿酸盐等)、无机纳米阻燃剂(例如石墨、纳米氢氧化镁、纳米三氧化二锑、纳米氢氧化铝、纳米层状双氢氧化物等)中的一种，优选纳米层状双氢氧化物；所述填充剂为滑石粉、碳酸钙、云母中的一种，优选碳酸钙；所述界面改性剂为马来酸酐接枝改性聚苯乙烯类、甲基丙烯酸脱水甘油酯接枝烯烃弹性体，、马来酸酐接枝乙丙橡胶中的一种，所述的甲基丙烯酸脱水甘油酯接枝烯烃弹性体包含了甲基丙烯酸脱水甘油酯接枝聚丙烯烃弹性体以及甲基丙烯酸脱水甘油酯接枝聚乙烯烃弹性体等)优选甲基丙烯酸脱水甘油酯接枝聚丙烯烃弹性体。
进一步，所述发泡剂为有机无机复配型发泡剂：有机类包括酰肼类发泡剂、偶氮类发泡剂、二亚硝基类发泡剂；无机发泡剂主要是碳酸盐类发泡剂、碳酸氢盐类发泡剂；二者比例为1：9-1：1，优选酰肼类发泡剂和碳酸氢盐类发泡剂，比例为1：2；
进一步，所述发泡协效剂包括成核剂和分散剂；其中，所述成核剂为石墨烯、碳纳米管、纳米羟基磷灰石、纳米玻璃微珠、纳米氧化锌中的一种，优选纳米羟基磷灰石；分散剂为聚乙烯蜡、硬脂酸盐(例如硬脂酸锌、硬脂酸钙等)、十二烷基苯磺酸盐(例如十二烷基苯磺酸钠等)中的一种，优选硬脂酸锌；
进一步，所述润滑剂为硅酮粉、油酸酰胺、不饱和脂肪酸中的一种，优选硅酮粉；所述抗氧剂为抗氧剂1010、抗氧剂168，抗氧剂1076中的一种，优选抗氧剂1010；
进一步，所述的汽车电池壳体包胶材料的制备方法，其特征在于：包括以下步骤：
步骤一：将热塑性弹性体60-90份，熔喷型聚烯烃5-25份，阻燃剂5-30份，填充剂0-20份，界面改性剂1-20份，发泡协效剂1-10份，润滑剂0.5-2份，抗氧剂0.2-1份按照一定重量份数在混合机中混合1-5min，通过料斗加入到双螺杆挤出机中，在140-190℃温度下造粒，螺杆转速200-600r/min，得到用于电池壳体包胶复合材料；
步骤二：将发泡剂和步骤一得到的包胶复合材料按照重量份数加入到注塑机料筒；在150-230℃温度下，进行包胶注塑，获得具有包胶电池壳体。
有益效果
与现有产品相比，本发明具有如下显著优点：
1、本发明采用超低分子量高流动聚烯烃对高分子量热塑弹性体流变行为进行调控，实现了热塑性弹性体高流动性，从而保证了其对复杂电池壳体结构的精确复制和有效贴合，同时，实现了产品壁厚优化减薄，提高了产品便携性，而且，也在一定程度上改善了微发泡泡孔生长稳定性和均匀性，提升了制品表观质量；另外，本发明还具有优良的耐低温性、优良的缓冲性、优良的阻燃特性等性能，解决了产品的表观缩痕、低温落球冲击性能以及抗震性能差等问题。在车辆发生碰撞等意外情况下，高缓冲性保护了电池壳体不受破坏，进而保护电池不发生电池液体泄露等情况，良好的阻燃性能够防止燃烧产生大量烟雾，进而达到防止烟火、液体、气体等进入车厢等其他危机乘客人身安全舱室的目的。
2、本发明具有优异的加工流动性以及与金属或工程塑料壳体优良的粘接性，有效改善了目前市场产品易脱落等问题，对电池起到更好的缓冲保护作用，延长使用年限，确保使用时的安全性。
3、本发明提供该材料的制备方法，工艺可控，成型周期更短，制造成本低，效率高，易于实现工业化。
具体实施方式
实施例1
一种汽车电池壳体包胶材料的制备方法，包括以下步骤：
步骤一：将热塑性弹性体烯烃类弹性体TPE90份，熔喷型聚丙烯25份，石墨5份，甲基丙烯酸脱水甘油酯接枝聚丙烯1份，，纳米羟基磷灰石0.5份，硬脂酸锌0.5份，硅酮粉0.2份，抗氧剂1010重量份数1份在混合机中混合1min，通过料斗加入到双螺杆挤出机中，在140-190℃温度下造粒，螺杆转速200r/min，得到用于电池壳体包胶复合材料；
步骤二：将发泡剂(碳酸铵0.4份，偶氮二甲酰胺0.1份)和步骤一得到的包胶复合材料按照重量份数加入到注塑机料筒；在150-230℃温度下，进行包胶注塑，获得具有包胶电池壳体。
所述的熔喷型聚丙烯熔融指数为800g/10min。
实施例2
一种汽车电池壳体包胶材料的制备方法，包括以下步骤：
步骤一：将热塑性弹性体烯烃类弹性体TPV60份，熔喷型聚乙烯5份，碳酸钙20份，纳米层状双氢氧化物20份，马来酸酐接枝改性聚苯乙烯20份，纳米氧化锌7份，十二烷基苯磺酸钠3份，油酸酰胺2份，抗氧剂1010重量份数0.2份在混合机中混合5min，通过料斗加入到双螺杆挤出机中，在140-190℃温度下造粒，螺杆转速600r/min，得到用于电池壳体包胶复合材料；
步骤二：将发泡剂(碳酸镁10.8份，N，N-二亚硝基五亚甲基四胺1.2份)和步骤一得到的包胶复合材料按照重量份数加入到注塑机料筒；在150-230℃温度下，进行包胶注塑，获得具有包胶电池壳体。
所述的熔喷型聚丙烯熔融指数为1000g/10min。
实施例3
一种汽车电池壳体包胶材料的制备方法，包括以下步骤：
步骤一：将热塑性弹性体烯烃类弹性体SEBS70份，熔喷型聚丙烯10份，滑石粉10份，异丁基次磷酸铝30份，甲基丙烯酸脱水甘油酯接枝聚丙烯10份，纳米羟基磷灰石5份，硬脂酸锌1份，硅酮粉1份，抗氧剂1010重量份数0.5份在混合机中混合2min，通过料斗加入到双螺杆挤出机中，在140-190℃温度下造粒，螺杆转速500r/min，得到用于电池壳体包胶复合材料；
步骤二：将发泡剂(碳酸氢钙2.5份，偶氮二甲酰胺2.5份)和步骤一得到的包胶复合材料按照重量份数加入到注塑机料筒；在150-230℃温度下，进行包胶注塑，获得具有包胶电池壳体。
所述的熔喷型聚丙烯熔融指数为1500g/10min。
实施例4
一种汽车电池壳体包胶材料的制备方法，包括以下步骤：
步骤一：将热塑性弹性体烯烃类弹性体TPB70份，熔喷型聚乙烯15份，碳酸钙8份，纳米羟基磷灰石15份，马来酸酐接枝改性聚苯乙烯12份，纳米氧化锌1份，十二烷基苯磺酸钠1份，油酸酰胺0.8份，抗氧剂1010重量份数0.3份在混合机中混合3min，通过料斗加入到双螺杆挤出机中，在140-190℃温度下造粒，螺杆转速600r/min，得到用于电池壳体包胶复合材料；
步骤二：将发泡剂(碳酸铵2份，N，N-二亚硝基五亚甲基四胺1份)和步骤一得到的包胶复合材料按照重量份数加入到注塑机料筒；在150-230℃温度下，进行包胶注塑，获得具有包胶电池壳体。
所述的熔喷型聚丙烯熔融指数为1200g/10min。
根据上述制备方法，对比例1、实施例1、实施例2、实施例3、实施例4，具体配方如下表所示：
对上表中的实施例进行检测，性能结果如下表所示：
本发明产品实施例性能表
从以上结果可以看出，与现有技术对比例1相比，本发明实施例1、实施例2、实施例3、实施例4技术方案在阻燃等级、悬臂梁缺口冲击强度和断裂伸长率上明显优于对比例1，具有更高流动性，因此具有优异的成型性，从而保证了其对复杂电池壳体模具结构的精确复制和有效贴合，有利于产品壁厚优化减薄。另外，还可以看出，本发明还具有更加优良的耐低温性、阻燃特性等性能，解决了产品的低温落球冲击性能以及抗震性能差等问题，保护了电池壳体，在车辆发生碰撞或电池发生自燃等意外情况下，能够防止烟火、液体、气体等进入车厢等其他危机乘客人身安全的舱室。
以上所述仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本领域的技术人员根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (12)

1.一种汽车电池壳体包胶材料，其特征在于，涉及材料包括以下物质重量份数的组分：
热塑性弹性体60-90份，
熔喷型聚合物5-25份，
阻燃剂5-30份，
填充剂0-20份，
界面改性剂1-20份，
发泡剂0.5-12份，
发泡协效剂1-10份，
润滑剂0.5-2份，
抗氧剂0.2-1份。
2.根据权利要求1所述汽车电池壳体包胶材料，其特征在于：所述热塑性弹性体为烯烃类弹性体、芳烃类弹性体、乙丙橡胶、聚酯类弹性体、酰胺类弹性体、双烯类弹性体中的一种。
3.根据权利要求2所述汽车电池壳体包胶材料，其特征在于：所述热塑性弹性体为烯烃类弹性体。
4.根据权利要求1所述汽车电池壳体包胶材料，其特征在于：所述熔喷型聚合物为熔融指数大于等于800g/10min的聚合物，所述的熔喷型聚合物为熔喷型聚乙烯、熔喷型聚丙烯、熔喷型聚对苯二甲酸乙二醇酯。
5.根据权利要求4所述汽车电池壳体包胶材料，其特征在于：所述熔喷型聚合物为熔融指数大于等于1800g/10min的聚乙烯。
6.根据权利要求1所述汽车电池壳体包胶材料，其特征在于： 所述阻燃剂为环三磷腈类阻燃剂、烷基磷系阻燃剂、三嗪类膨胀型阻燃剂、无机纳米阻燃剂中的一种；所述填充剂为滑石粉、碳酸钙、云母中的一种；所述界面改性剂为马来酸酐接枝改性聚苯乙烯类、甲基丙烯酸脱水甘油酯接枝聚烯烃弹性体、马来酸酐接枝乙丙橡胶中的一种；所述润滑剂为硅酮粉、油酸酰胺、不饱和脂肪酸中的一种；所述抗氧剂为抗氧剂1010、抗氧剂168，抗氧剂1076中的一种。
7.根据权利要求6所述汽车电池壳体包胶材料，其特征在于： 所述阻燃剂纳米层状双氢氧化物；所述填充剂为碳酸钙；所述界面改性剂为甲基丙烯酸脱水甘油酯接枝聚烯烃弹性体；所述润滑剂为硅酮粉、；所述抗氧剂为抗氧剂1010。
8.根据权利要求1所述汽车电池壳体包胶材料，其特征在于： 所述发泡协效剂包括成核剂和分散剂；其中，所述成核剂为石墨烯、碳纳米管、纳米羟基磷灰石、纳米玻璃微珠、纳米氧化锌中的一种；分散剂为聚乙烯蜡、硬脂酸盐、十二烷基苯磺酸盐中的一种。
9.根据权利要求8所述汽车电池壳体包胶材料，其特征在于：所述发泡协效剂中成核剂为纳米羟基磷灰石，所述的分散剂为硬脂酸盐。
10.根据权利要求1所述汽车电池壳体包胶材料，其特征在于：所述发泡剂为有机无机复配型发泡剂：有机类包括酰肼类发泡剂、偶氮类发泡剂、二亚硝基类发泡剂；无机发泡剂主要是碳酸盐类发泡剂、碳酸氢盐类发泡剂；二者比例为1：9-1：1。
11.根据权利要求10所述汽车电池壳体包胶材料，其特征在于：所述发泡剂为酰肼类发泡剂和碳酸氢盐类发泡剂组合，二者比例为1：2。
12.根据权利要求1-11任一项所述的汽车电池壳体包胶材料的制备方法，其特征在于：包括以下步骤：
步骤一：将热塑性弹性体60-90份，熔喷型聚烯烃5-25份，阻燃剂5-30份，填充剂0-20份，界面改性剂1-20份，发泡协效剂1-10份，润滑剂0.5-2份，抗氧剂0.2-1份按照一定重量份数在混合机中混合1-5min，通过料斗加入到双螺杆挤出机中，在140-190℃温度下造粒，螺杆转速200-600r/min，得到用于电池壳体包胶复合材料；
步骤二：将发泡剂和步骤一得到的包胶复合材料按照重量份数加入到注塑机料筒；在150-230℃温度下，进行包胶注塑，获得具有包胶电池壳体。
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