CN106977894A - 一种复合阻燃塑料材料、复合阻燃塑料件、马甲结构的电池外壳及锂离子电池 - Google Patents
一种复合阻燃塑料材料、复合阻燃塑料件、马甲结构的电池外壳及锂离子电池 Download PDFInfo
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Abstract
本发明涉及一种复合阻燃塑料材料、复合阻燃塑料件、马甲结构的电池外壳及锂离子电池。该复合阻燃塑料材料,由以下重量份数的原料制成:丙烯腈‑苯乙烯‑丁二烯共聚树脂20~35份、聚碳酸酯60~80份、乙烯丙烯酸丁酯2~5份、相容改性剂1~5份、阻燃剂1~5份。复合阻燃塑料件包括塑料板,所述塑料板为由上述重量份数的原料经注塑成型制成的板材。各原料相互配合,协调作用,所得复合阻燃塑料材料具有高硬度、高强度、轻质阻燃的特性,作为电池外壳的塑料层材料使用,能兼顾机械保护与有效阻燃,防止电池膨胀及热失控;提升电池抗外力冲击的保护能力以及在发生鼓胀时外壳阻燃防变形能力,保证电池正常的循环等电化学性能。
Description
技术领域
本发明属于锂离子电池技术领域,具体涉及一种复合阻燃塑料材料、复合阻燃塑料件、马甲结构的电池外壳及锂离子电池。
背景技术
锂离子二次电池作为未来的新能源储能设备,具有绿色、环保、高效等优点,已经广泛应用在便携式电子消费类产品,诸如手机、笔记本、数码相机等,目前正朝着大容量,高能量密度,高功率密度的方向发展,作为电动交通工具的能量载体。
随着电动汽车续航里程要求的不断提高,对于锂离子动力电池能量密度要求越来越紧迫。目前市场上主要的高能量密度锂离子动力电池已经可以达到较高的能量密度,但是随之而来的是锂离子动力电池的安全性问题。
在塑料壳、金属壳、铝塑膜软包锂离子电池中,铝塑膜软包装电池具有质量轻,能量密度高的明显优势,但是铝塑膜包装机械硬度有限,难以抵抗外力,容易产生变形而造成短路问题等,也难以克服锂离子电池自身可能存在的鼓胀问题。这些问题容易导致电池系统的失效,从而引发更为严重的热失控问题等。
现有技术中,CN201072765Y公开了一种锂离子动力电池盒,包括一个塑料壳体,塑料壳体上至少一个侧面为复合层,复合层的里层为铝塑复合膜,外层为硬质保护板,复合层与塑料壳体密封贴紧;所述硬质保护板的周边与铝塑复合膜粘接成一体;所述硬质保护板为塑料板或金属板。CN203377273U公开了一种锂电池外壳,具有层状结构的壳壁,所述壳壁包括固连在一起的外层的塑料层和内层的阻隔层,所述阻隔层为阻隔性塑料板层或中间为铝箔、两侧为塑料膜层的铝塑复合膜层。
上述采用塑料层与铝塑膜复合层作为锂离子电池的外壳,虽然一定程度上增大了机械强度,但是普通塑料层材料的阻燃性能较差,还不能达到机械保护与有效阻燃兼顾,防止电池膨胀及热失控的目的。
发明内容
本发明的目的是提供一种复合阻燃塑料材料,作为电池外壳的塑料层材料使用,能兼顾机械保护与有效阻燃,防止电池膨胀及热失控。
本发明的第二个目的是提供一种电池外壳用复合阻燃塑料件。
本发明的第三个目的是提供一种马甲结构的电池外壳。
本发明的第四个目的是提供一种采用上述电池外壳的高安全型锂离子电池。
为了实现以上目的,本发明所采用的技术方案是:
一种复合阻燃塑料材料,由以下重量份数的原料制成:丙烯腈-苯乙烯-丁二烯共聚树脂20~35份、聚碳酸酯60~80份、乙烯丙烯酸丁酯2~5份、相容改性剂1~5份、阻燃剂1~5份。
所述相容改性剂为聚乙二醇、马来酸酐、乙烯醋酸乙烯与一氧化碳的共聚物、琥珀酸酐中的任意一种或几种。
所述阻燃剂为氢氧化镁、氢氧化铝、含DOPO的双氧己内磷酸酯阻燃剂、三氧化二锑、硼酸锌中的任意一种或几种。
该复合阻燃塑料材料可采用注塑成型或其他现有的塑料成型技术制备。材料的形状及尺寸可根据用途通过成型模具进行设置。
本发明的复合阻燃塑料材料,是以丙烯腈-苯乙烯-丁二烯共聚树脂、聚碳酸酯、乙烯丙烯酸丁酯和相容改性剂、阻燃剂复配为原料制成的,各原料相互配合,协调作用,所得复合阻燃塑料材料具有高硬度、高强度、轻质阻燃的特性,作为电池外壳的塑料层材料使用,能兼顾机械保护与有效阻燃,防止电池膨胀及热失控;提升电池抗外力冲击的保护能力、以及在发生鼓胀时外壳阻燃防变形能力,保证电池正常的循环等电化学性能。
一种复合阻燃塑料件,包括塑料板,所述塑料板为由以下重量份数的原料经注塑成型制成的板材:丙烯腈-苯乙烯-丁二烯共聚树脂20~35份、聚碳酸酯60~80份、乙烯丙烯酸丁酯2~5份、相容改性剂1~5份、阻燃剂1~5份。
所述相容改性剂为聚乙二醇、马来酸酐、乙烯醋酸乙烯与一氧化碳的共聚物、琥珀酸酐中的任意一种或几种。
所述阻燃剂为氢氧化镁、氢氧化铝、含DOPO的双氧己内磷酸酯阻燃剂、三氧化二锑、硼酸锌中的任意一种或几种。
所述塑料板的四周边缘设有用于粘接的凸缘。
所述塑料板上表面或下表面粘接有铝塑膜。所述铝塑膜为冲压成型件。
粘接铝塑膜所用的粘结剂为VAE、SBR、聚丙烯酸酯、苯甲酸甲酯、六氨基己酸、聚苯乙烯、二月桂酸二丁基锡中的任意一种或两种以上的混合物。粘接层的厚度为0.02~3mm。
本发明的复合阻燃塑料件,利用上述的复合阻燃材料制成的塑料板,与铝塑膜粘接形成复合材料层,作为电池外壳材料使用,可以达到机械保护、有效阻燃的目的,同时防止电池膨胀,保护电池内部正负极与隔膜之间的良好接触,避免电池发生热失控并获得高能量密度和优异循环性能。
一种马甲结构的电池外壳,包括两个上述的复合阻燃塑料件相对设置,分别为上板和下板;所述上板和下板均包括塑料板,所述塑料板的四周边缘设有凸缘,相对的内侧表面粘接有铝塑膜;上板与下板的四周凸缘用于粘接成一体,使上板与下板之间形成容纳电池电芯的腔体。
所述塑料板的厚度为0.3~20mm。
所述铝塑膜包括金属层和设置在金属层表面的塑料层,金属层为铝、铝合金或铁合金材料;塑料层为聚乙烯或聚丙烯材料。铝塑膜的金属层厚度为10~30μm,塑料层厚度为100~150μm。
所述铝塑膜上远离塑料板的一侧塑料层四周边缘凸出,用于与塑料板的凸缘粘接在一起。
所述塑料板的凸缘的宽度为1~30mm,厚度为0.1~10mm。粘接凸缘所用的粘结剂为VAE、SBR、聚丙烯酸酯、苯甲酸甲酯、六氨基己酸、聚苯乙烯、二月桂酸二丁基锡中的任意一种或两种以上的混合物。粘接层的厚度为0.02~3mm。
一种采用上述的马甲结构的电池外壳的锂离子电池。该锂离子电池包括上述的马甲结构的电池外壳,及密封于上板与下板之间的腔体内的电池电芯。所述电池电芯由正极片、负极片、隔膜叠片或卷绕而成。
本发明的马甲结构的电池外壳,由上述的塑料板和铝塑膜粘接形成复合阻燃塑料件,两个相对设置的复合阻燃塑料件作为上板和下板,四周凸缘粘接在一起,用于将电池电芯密封在上板、下板之间;该电池外壳具有高硬度、高强度、轻质阻燃的特性。
与现有软包装电池相比,采用马甲结构的电池外壳的锂离子电池具有以下明显优势:
1)显著改善软包锂离子电池反复充放电过程中存在的鼓胀问题,改善锂离子电池过充、挤压安全性能以及循环、使用寿命等电化学性能;
2)具有良好的机械防护能力,减少软包装电池在储存、使用过程中的破损程度,提高电池成组的安全性和便捷性。
附图说明
图1为实施例4的马甲结构的电池外壳的结构示意图;
图2为图1的正视图;
图3为图1的俯视图。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明。
实施例1
本实施例的复合阻燃塑料材料,由以下重量份数的原料制成:丙烯腈-苯乙烯-丁二烯共聚树脂20份、聚碳酸酯60份、乙烯丙烯酸丁酯2份、相容改性剂1份、阻燃剂1份;所述相容改性剂为聚乙二醇;所述阻燃剂为三氧化二锑。
本实施例的复合阻燃塑料件,包括塑料板,所述塑料板为由以下重量份数的原料经注塑成型制成的板材:丙烯腈-苯乙烯-丁二烯共聚树脂20份、聚碳酸酯60份、乙烯丙烯酸丁酯2份、相容改性剂1份、阻燃剂1份。所述相容改性剂为聚乙二醇;所述阻燃剂为三氧化二锑。
所述注塑成型的具体操作如下:将配方量的丙烯腈-苯乙烯-丁二烯共聚树脂、聚碳酸酯、乙烯丙烯酸丁酯混合后加热熔融成液态,后加入相容改性剂和阻燃剂混合均匀,通过模具注塑形成塑料板。
实施例2
本实施例的复合阻燃塑料材料,由以下重量份数的原料制成:丙烯腈-苯乙烯-丁二烯共聚树脂30份、聚碳酸酯70份、乙烯丙烯酸丁酯3份、相容改性剂3份、阻燃剂3份;所述相容改性剂为马来酸酐;所述阻燃剂为硼酸锌。
本实施例的复合阻燃塑料件,包括塑料板,所述塑料板为由以下重量份数的原料经注塑成型制成的板材:丙烯腈-苯乙烯-丁二烯共聚树脂30份、聚碳酸酯70份、乙烯丙烯酸丁酯3份、相容改性剂3份、阻燃剂3份;所述相容改性剂为马来酸酐;所述阻燃剂为硼酸锌。
所述注塑成型的具体操作步骤同实施例1。
实施例3
本实施例的复合阻燃塑料材料,由以下重量份数的原料制成:丙烯腈-苯乙烯-丁二烯共聚树脂35份、聚碳酸酯80份、乙烯丙烯酸丁酯5份、相容改性剂5份、阻燃剂5份;所述相容改性剂为琥珀酸酐;所述阻燃剂为氢氧化镁。
本实施例的复合阻燃塑料件,包括塑料板,所述塑料板为由以下重量份数的原料经注塑成型制成的板材:丙烯腈-苯乙烯-丁二烯共聚树脂35份、聚碳酸酯80份、乙烯丙烯酸丁酯5份、相容改性剂5份、阻燃剂5份;所述相容改性剂为琥珀酸酐;所述阻燃剂为氢氧化镁。
所述注塑成型的具体操作步骤同实施例1。
实施例4
本实施例的马甲结构的电池外壳,如图1-3所示,包括两个实施例1的复合阻燃塑料件相对设置,分别为上板和下板;所述上板包括塑料板1,所述塑料板1的四周边缘设有凸缘2,所述塑料板1与下板相对的内侧表面粘接有铝塑膜3;所述下板包括塑料板6,所述塑料板6的四周边缘设有凸缘9,所述塑料板6与上板相对的内侧表面粘接有铝塑膜5。
其中,所述塑料板1、6的厚度均为2mm;凸缘2、9的宽度均为5mm,厚度均为0.5mm。
所述铝塑膜包括金属层和设置在金属层表面的塑料层,金属层为铝合金材料;塑料层为聚乙烯材料;铝塑膜的金属层厚度为20μm,塑料层厚度为120μm。所述铝塑膜上远离塑料板的一侧塑料层四周边缘凸出,用于与塑料板的凸缘粘接在一起。
上板与下板的四周凸缘2、9粘接成一体,使上板与下板之间形成容纳电池电芯的腔体。
如图1-3所示,本实施例的锂离子电池的电池电芯包括电芯本体4和与电芯本体4连接的正极耳7、负极耳8;电池外壳的上板与下板的四周凸缘2、9粘接成一体,将电芯本体4密封在上板与下板之间的腔体内,正极耳7、负极耳8与上板、下板的凸缘2、9粘接在一起,并伸出电池外壳。
本实施例的锂离子电池的制备方法为:将塑料板和铝塑膜进行50℃预热,用粘结剂将塑料板和铝塑膜的接触面粘接分别形成上板、下板,将电池电芯置于上板、下板之间,上板、下板的四周凸缘(包括塑料板的凸缘和铝塑膜的凸出)用粘结剂粘接成一体,使电芯本体密封在上板与下板之间的腔体内,正极耳、负极耳与上板、下板的凸缘粘接在一起,并伸出电池外壳。
其中,所用的粘结剂为VAE、SBR的质量比为1:1的混合物;粘结剂形成的粘接层的厚度为0.05mm。
Claims (10)
1.一种复合阻燃塑料材料,其特征在于:由以下重量份数的原料制成:丙烯腈-苯乙烯-丁二烯共聚树脂20~35份、聚碳酸酯60~80份、乙烯丙烯酸丁酯2~5份、相容改性剂1~5份、阻燃剂1~5份。
2.根据权利要求1所述的复合阻燃塑料材料,其特征在于:所述相容改性剂为聚乙二醇、马来酸酐、乙烯醋酸乙烯与一氧化碳的共聚物、琥珀酸酐中的任意一种或几种。
3.根据权利要求1所述的复合阻燃塑料材料,其特征在于:所述阻燃剂为氢氧化镁、氢氧化铝、含DOPO的双氧己内磷酸酯阻燃剂、三氧化二锑、硼酸锌中的任意一种或几种。
4.一种复合阻燃塑料件,其特征在于:包括塑料板,所述塑料板为由以下重量份数的原料经注塑成型制成的板材:丙烯腈-苯乙烯-丁二烯共聚树脂20~35份、聚碳酸酯60~80份、乙烯丙烯酸丁酯2~5份、相容改性剂1~5份、阻燃剂1~5份。
5.根据权利要求4所述的复合阻燃塑料件,其特征在于:所述塑料板的四周边缘设有用于粘接的凸缘。
6.根据权利要求4或5所述的复合阻燃塑料件,其特征在于:所述塑料板上表面或下表面粘接有铝塑膜。
7.一种马甲结构的电池外壳,其特征在于:包括两个如权利要求4所述的复合阻燃塑料件相对设置,分别为上板和下板;所述上板和下板均包括塑料板,所述塑料板的四周边缘设有凸缘,相对的内侧表面粘接有铝塑膜;上板与下板的四周凸缘用于粘接成一体,使上板与下板之间形成容纳电池电芯的腔体。
8.根据权利要求7所述的马甲结构的电池外壳,其特征在于:所述塑料板的厚度为0.3~20mm。
9.根据权利要求7所述的马甲结构的电池外壳,其特征在于:所述塑料板的凸缘的宽度为1~30mm,厚度为0.1~10mm。
10.一种采用如权利要求7-9中任一项所述的马甲结构的电池外壳的锂离子电池。
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