CN102548750A - 用于电力驱动的机动车辆中的电源电池的外壳 - Google Patents

用于电力驱动的机动车辆中的电源电池的外壳 Download PDF

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Publication number
CN102548750A
CN102548750A CN2010800373401A CN201080037340A CN102548750A CN 102548750 A CN102548750 A CN 102548750A CN 2010800373401 A CN2010800373401 A CN 2010800373401A CN 201080037340 A CN201080037340 A CN 201080037340A CN 102548750 A CN102548750 A CN 102548750A
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shell
thermoplastic polymer
supporting layer
layer
preferred
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CN102548750B (zh
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B·赫克
K·米勒
I·施瓦茨
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Basell Polyolefine GmbH
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Basell Polyolefine GmbH
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Abstract

适于在电力驱动的机动车辆中包含多个电源电池的外壳，其包含至少一个下部容纳部件和一个上部覆盖部件。两个部件装配在一起并在内部产生中空空间。两个部件由多层材料制备，该多层材料包含彼此粘附的至少一个热塑性聚合物的支撑层和至少一个金属的覆盖层。这种外壳极佳地适于保护内部电池免受机械破坏和免受火和/或电磁辐射的影响。

Description

用于电力驱动的机动车辆中的电源电池的外壳
本发明涉及一种适于在电力驱动的机动车辆中包含多个电源电池的新型外壳。
本发明还涉及一种用于生产所述外壳的方法。
在机动车辆中包含多个电源电池的外壳通常需要保护内部排列的电源电池免受外部影响。反之亦然，外壳同样适于保护坐在汽车中的任何人免受由外壳内部的电源电池产生的任何影响，所述电池可能过热或经受泄漏。这种外壳主要由塑性材料(比如聚乙烯或聚丙烯)通过注塑为不同的尺寸并且至多1000升的体积来制造。一方面，这种外壳的优点在于，它们电绝缘并且重量轻。然而，另一方面，它们的缺点在于，它们的机械强度差，并且在高温或在有火的情况下易燃。
因此，本发明的目的是提供一种用于机动车辆中的多个电源电池的新的外壳，其重量轻，然而同时结合了较高的机械强度，因此对其中所包含的电池提供保护以免受机械破坏，和易燃，并为其中所包含的电池提供至少部分保护以免受电磁辐射的影响。
通过如前所述的外壳实现所述目的，所述外壳包含至少一个下部容纳部件和一个上部覆盖部件，它们装配在一起，并且可闭合以在内部产生中空空间，并且它们由多层材料制备，该多层材料包含彼此粘附的至少一个热塑性聚合物的支撑层和至少一个金属的覆盖层。
出于本发明的目的，所述金属的覆盖层可在所述外壳的外侧或者在所述外壳的内侧排列。然而，还可在所述外壳的外侧和所述外壳的内侧中任一侧排列金属的覆盖层。
意外地，包含至少一个热塑性聚合物的支撑层和至少一个金属的覆盖层的多层材料能制备一种完美地适于在其中并入多个电源电池的外壳，其中这些电池用于电力驱动的机动车辆。这种外壳仍然具有足够的强度，特别是在外壳的大面积局部(比如底部)处也如此，而且还提供足够的保护以免受从内部到外部或从外部到内部的火的快速穿透。
意外地，已发现，经由将支撑层与金属的覆盖层层压，可显著地改善外壳的劲度。例如，可实现对于外壳应用迄今为止经由纯的塑性-部件方案无法获得的劲度水平。良好的实例为以其高劲度著称的由丙烯腈-丁二烯-苯乙烯共聚物(ABS)组成的外壳。这特别地用于在机动车辆中外壳暴露于相对高温的区域。本发明的外壳导致明显的优点。如果在支撑层的两侧上排列金属的覆盖层，则可进一步改进外壳的机械强度。
通过热塑性聚合物的支撑层的受控改性(所述改性可为抗冲-改性，由矿物填料提供或玻璃纤维-增强的)，外壳的机械性质可进一步在特别宽的范围内变化，机械性质可因此与对外壳的要求匹配，而对外壳部件的表面性质和表面品质没有任何影响，无论是下部容纳部件还是上部覆盖部件。
在所有情况下，基于所述支撑层的重量，由热塑性聚合物组成的支撑层可包含1-60％重量，优选5-50％重量，特别优选10-40％重量的增强填料。这些增强填料的实例为硫酸钡、氢氧化镁、根据DIN 66115测量平均颗粒尺寸在0.1-10μm范围内的滑石、木材、亚麻、白垩、玻璃珠、涂布的玻璃纤维、短的、长的或其他玻璃纤维，或这些物质的混合物。下部背衬层此外还可包含分别为有利量的其他添加剂，例如光稳定剂、UV稳定剂、热稳定剂、颜料、炭黑、润滑剂、加工助剂、阻燃剂、起泡剂等。根据本发明，下部背衬层本身由热塑性聚合物组成。
根据本发明，有利地用于支撑层的热塑性聚合物包括聚合物，比如聚丙烯(PP)、聚乙烯(PE)、聚氯乙烯(PVC)、聚砜、聚醚酮、聚酯比如聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯或聚萘二甲酸亚烷基酯、聚环烯烃、聚丙烯酸酯、聚甲基丙烯酸酯、聚酰胺比如聚ε-己内酰胺或聚己二酰己二胺或聚癸二酰己二胺、聚碳酸酯、聚氨酯、聚缩醛比如聚甲醛(POM)或聚苯乙烯(PS)。此处主要合适的热塑性聚合物为均聚物和共聚物。关于这一点，特别值得提及由丙烯和乙烯组成的共聚物或由乙烯或丙烯和由具有4-10个碳原子的其他烯烃组成的共聚物，如由苯乙烯和由相对小比例的丁二烯、α-甲基苯乙烯、丙烯腈、乙烯基咔唑，或丙烯酸、甲基丙烯酸或衣康酸的酯组成的共聚物或三元共聚物。
为了在本发明的外壳生产中改进成本效率，基于上部覆盖部件的总重量，外壳的上部覆盖部件还可包含至多60％重量的量的由提及的聚合物再循环的回收材料。
根据本发明，术语聚甲醛(POM)是指醛(比如甲醛或乙醛，但优选环状缩醛)的均聚物和共聚物。POM的特征在于存在形成分子链的独特特性的不断重复出现的碳-氧键。在230℃温度和2.16kg负载下，根据ISO 1133测量，POM的熔体流动指数(MI)通常在5-50g/10分钟范围内，优选5-30g/10分钟。
如果本发明使用聚酯用于外壳的支撑层，用于该目的的材料明显优选聚对苯二甲酸乙二酯(PET)或聚对苯二甲酸丁二酯(PBT)。二者为对苯二甲酸分别与乙二醇和丁二醇的高分子量酯化产物。在230℃温度和2.16kg负载下，根据DIN 1133测量，根据本发明特别合适的聚酯的MI在5-50g/10分钟范围内，优选5-30g/10分钟。
可用于外壳的支撑层的苯乙烯的共聚物特别是在聚合物内具有至多45％重量，优选具有至多20％重量的丙烯腈的共聚物。在230℃温度和2.16kg负载下，根据DIN 1133测量，这些共聚物的MI通常在1-25g/10分钟范围内，优选4-20g/10分钟。
其他苯乙烯的三元共聚物在聚合物内包含至多35％重量，特别是至多20％重量的丙烯腈和至多35％重量，优选至多30％重量的丁二烯。缩写术语ABS也用于这些三元共聚物，在230℃温度和2.16kg负载下，根据DIN 1133测量，其MI通常在1-40g/10分钟范围内，优选2-30g/10分钟。
用于外壳的支撑层的其他热塑性材料特别是聚烯烃，比如聚乙烯(PE)和聚丙烯(PP)，其中特别优选使用PP。根据本发明，PP是指丙烯的均聚物和共聚物。共聚物包含附属量的可与丙烯共聚的单体，例如具有2-8或4-8个碳原子的1-烯烃。如果需要，还可使用两种或更多种共聚单体。
作为特别适合外壳的支撑层可提及的热塑性材料为丙烯的均聚物或由丙烯与至多50％重量的具有至多8个碳原子的其他1-烯烃组成的共聚物。这些共聚物通常为无规共聚物，但是也可为嵌段共聚物。
用于生产PP的聚合反应通常可在1-100巴(0.1-10MPa)范围内的压力下，在悬浮液中或在气相中以及在齐格勒-纳塔催化剂系统存在下进行。优选不仅包含含钛的固体组分，而且还包含有机铝化合物形式的助催化剂和电子-供体化合物的催化剂系统。
齐格勒-纳塔催化剂系统通常包含含钛的固体组分(特别是三价或四价钛的卤化物或醇化物)，和此外的含有卤素的镁化合物、无机氧化物比如硅胶作为载体材料，以及电子-供体化合物。可提及的具体的电子-供体化合物为羧酸衍生物或酮、醚、醇或有机硅化合物。
含钛的固体组分可通过已知的方法制备。优选通过在DE 19529240中详述的方法来制备。
适用于齐格勒-纳塔催化剂系统的助催化剂不仅为三烷基铝化合物，而且还为其中烷基被烷氧基或卤素原子(比如氯或溴)代替的化合物。各烷基可相同或不同。还可使用线性或支化的烷基。根据本发明，优选使用其中烷基包含1-8个碳原子的三烷基铝化合物，其实例为三乙基铝、三异丁基铝、三辛基铝或甲基二乙基铝，或它们的混合物。
然而，PP还可在金属茂作为催化剂存在下来生产。金属茂为具有层状结构的络合化合物，并且包含来自元素周期表的过渡族的金属加上有机(优选芳族)配体。为了能用于生产PP，将金属茂络合物有利地施用于载体材料。已证实有利的载体材料为也用于制备齐格勒-纳塔催化剂中的含钛的固体组分的无机氧化物。
通常所用的金属茂包含钛、锆或铪作为中心原子，其中优选锆。中心原子具有对至少一个π系统的π键合，π系统由环戊二烯基具体化。在大多数情况下，环戊二烯基具有另外的取代基，这些另外的取代基可用于控制催化剂的活性。优选的金属茂包含通过两个类似的或不同的π键与两个π系统键合的中心原子，并且这些还可同时为适当的杂芳族系统的组成。
用于金属茂的合适的助催化剂在原则上为能将中性金属茂转化为阳离子并且可稳定金属茂的任何化合物。此外，如EP 427 697中所发现的，助催化剂或由其形成的阴离子不应进入与所形成的金属茂阳离子的任何其他反应。所用的助催化剂优选为铝化合物和/或硼化合物。
硼化合物的化学式优选为R18 xNH4-xBR19 4、R18 xPH4-xBR19 4、R18 3CBR19 4或BR19 3，其中x为1-4的数，优选3，基团R18相同或不同，优选相同，并且为C1-C10-烷基或C6-C18-芳基，或者两个基团R18与它们连接的原子一起形成环，基团R19相同或不同，优选相同，并且为C6-C18-芳基，其可为烷基、卤代烷基或氟取代的。具体地，R18为乙基、丙基、丁基或苯基，并且R19为苯基、五氟苯基、3，5-双三氟甲基苯基、均三甲苯基、二甲苯基或甲苯基。EP 426 638描述了硼化合物作为金属茂的助催化剂。
优选所用的助催化剂为铝化合物，比如铝氧烷和/或烷基铝化合物。
特别优选所用的助催化剂为铝氧烷，特别是线性类型或环状类型，并且这里的两类化合物中还可存在有机基团，这些有机基团是相同或不同的，并且可为氢或C1-C20-烃基团，比如C1-C18-烷基、C6-C18-芳基或苄基。
外壳的支撑层与金属的覆盖层共同可采用具有不同厚度和尺寸的注塑的、挤出的或压塑的片材形式。支撑层的优选的层厚度在1-20mm范围内，特别优选2-15mm。
对于金属的覆盖层，可使用不同的金属。因此，铝非常合适，而且铁也是可用的，或者可使用贵金属如银或铬，其中优选铝、铁或铬。金属的覆盖层的厚度在50-1000μm范围内，优选在70-500μm范围内。
在本发明的优选的实施方式中，在热塑性聚合物的支撑层和金属的覆盖层之间可排列另外的中间层，以改进两层的粘附强度。可用于中间层的特别的材料为热塑性聚合物，优选与用于支撑层的相同的热塑性聚合物。该组合在支撑层和金属的覆盖层之间可产生特别坚固的粘附结合。根据本发明，中间层为薄网或别的形式，优选薄的非织造材料形式，厚度在0.001-1mm范围内，优选0.005-0.5mm。
优选用于中间层的一种热塑性材料为在金属茂作为催化剂存在下生产的PP，并且在230℃温度和2.16kg负载下，根据DIN 1133测量，其MI在10-60g/10分钟范围内。
由热塑性聚合物组成的中间层还可高度有利地为树脂-饱和的非织造材料。此处可特别使用丙烯酸酯树脂、酚醛树脂、尿素树脂或三聚氰胺树脂作为饱和树脂。此处由树脂饱和的程度可至多达300％，这意味着实际上中间层的整个表面由树脂浓密饱和，则该树脂达到不含树脂的中间层重量的300％。由树脂饱和的程度优选为15-150％，特别优选80-120％。根据本发明，中间层的重量在15-150g/m2范围内，优选30-70g/m2
本发明还提供了一种由通过注塑方法的反向涂布(reverse coating)技术生产外壳的方法。为了将支撑层和中间层和金属的覆盖层结合以得到坚固粘附多层复合材料，在通过注塑方法的反向涂布技术中的初始进料将用于一侧上的中间层和金属的覆盖层的材料置入注塑模具的一半，而且，如果期望，将用于另一侧上的中间层和另一个金属的覆盖层的材料置入注塑模具的另一半。一旦将模具闭合，将热塑性聚合物在150-330℃范围内的温度下和在5-2500巴(＝0.5-250MPa)的高压下注塑进入存在于每一侧上的中间层之间的隔室内。在每一侧，模具温度通常为8-160℃。一旦热塑性材料已在所述条件下注入，将模具冷却至环境温度。对此的冷却时间在0.01-5.0分钟范围内。
在该方法的另一种形式中，将包含中间层和层厚度在0.02-20mm范围内的金属箔的预制的层压材料，或者作为其备选，将单个的箔(覆盖物、金属、树脂)首先与非织造材料(约30g/m2；金属茂聚合物，
Figure BPA00001514919600071
)层压。随后预制具有期望的厚度和形状的用于另一预制的层压材料的材料。随后将两种变体放置在注塑隔室的各自的相对的两半模具中，将模具闭合，随后在至少170℃的温度和至少50巴(5MPa)压力下，在变体之间，将热塑性材料注入至隔室内。
在压塑中发生的程序在原则上是相同的。唯一的差别在于，将用于支撑层的热塑性聚合物以粒料形式引入按层序列插入的单个的箔之间，并且在每一侧上暴露于至少5巴的压力和至少100℃的挤压温度，历时至少30秒的挤压时间段。
相同的程序已显著地证明在注入-挤压模塑和转移模塑的实践中是成功的。
根据本发明，用于电源电池的外壳在内部包含从至少1升到最大至多约1000升的体积，优选1.5升-约800升。外壳的下部容纳部件和上部覆盖部件像榫槽接合一样装配在一起，并且通过将两个部件拧紧在一起或将它们夹紧在一起而彼此连接。然而，对于许多应用，还适合通过热密封或焊接或通过某一类型的热熔融将两个部件密封在一起，使得该连接气密和液密。
为了对本领域技术人员提供本发明的更清楚的说明，附图详细说明在电力驱动的机动车辆中用于电源电池的各种外壳的外壳结构中的原理以及在其生产期间的原理。
图1说明外壳的一部分的垂直切割(cut through)，其侧视具有在外壳的外侧排列的金属的覆盖层。
附图标记指出，可见包含铝箔的金属的覆盖层1，并且可见滑石增强的PP的支撑层2。
图2说明侧视为夹心结构的另一种形式的外壳的另一垂直切割。该形式使用在两侧上具有排列的覆盖层的支撑层。
图3中的附图标记指出，包含PP并且在两侧被含有铝箔的覆盖层1覆盖的支撑层2。

Claims (14)

1.适于在电力驱动的机动车辆中包含多个电源电池的外壳，其中所述外壳包含至少一个下部容纳部件和一个上部覆盖部件，所述部件装配在一起并在内部产生中空空间，并且所述部件由多层材料制备，所述多层材料包含彼此粘附的至少一个热塑性聚合物的支撑层和至少一个金属的覆盖层。
2.权利要求1的外壳，其中所述金属的覆盖层排列在所述外壳的外侧和/或所述外壳的内侧。
3.权利要求1或2的外壳，所述外壳包含以下物质作为用于支撑层的热塑性聚合物：聚丙烯(PP)、聚乙烯(PE)、聚氯乙烯(PVC)、聚砜、聚醚酮、聚酯比如聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯或聚萘二甲酸亚烷基酯、聚环烯烃、聚丙烯酸酯、聚甲基丙烯酸酯、聚酰胺比如聚ε-己内酰胺或聚己二酰己二胺或聚癸二酰己二胺、聚碳酸酯、聚氨酯、聚缩醛比如聚甲醛(POM)或聚苯乙烯(PS)，或这些物质的混合物。
4.权利要求1-3中任一项的外壳，其中在所有情况下，基于所述支撑层的重量，所述支撑层的热塑性聚合物另外包含1-60％重量，优选5-50％重量，特别优选10-40％重量的量的增强填料。
5.权利要求1-4中任一项的外壳，其中所述支撑层的热塑性聚合物包含以下物质作为增强填料：硫酸钡、氢氧化镁、根据DIN 66115测量平均颗粒尺寸在0.1-10μm范围内的滑石、木材、亚麻、白垩、玻璃珠、涂布的玻璃纤维，或短的、长的或其他玻璃纤维，或这些物质的混合物。
6.权利要求1-5中任一项的外壳，其中所述支撑层为注塑的或挤出的或压塑的片材，其层厚度在1-20mm范围内，优选2-15mm。
7.权利要求1-6中任一项的外壳，其中所述覆盖层包含金属，比如铝、铁、贵金属如银或铬。
8.权利要求1-7中任一项的外壳，所述外壳包含在热塑性聚合物的支撑层和金属的覆盖层之间排列的另外的中间层，所述中间层包含热塑性聚合物，该热塑性聚合物优选为与用于所述支撑层的相同的热塑性聚合物。
9.权利要求1-8中任一项的外壳，其中所述中间层为薄网或别的形式，优选薄的非织造材料，其中厚度在0.001-1mm范围内，优选0.005-0.5mm。
10.权利要求1-9中任一项的外壳，其中所述中间层包含树脂-饱和的热塑性聚合物的非织造材料，并且其中使用丙烯酸酯树脂、酚醛树脂、尿素树脂或三聚氰胺树脂作为饱和树脂。
11.权利要求1-10中任一项的外壳，其中所述中间层的重量在15-150g/m2范围内，优选30-70g/m2
12.权利要求1-11中任一项的外壳，其中所述下部容纳部件和所述上部覆盖部件像榫槽接合一样装配在一起，并且通过将两个部件拧紧或夹紧或密封在一起而彼此连接。
13.一种用于生产权利要求1-12中任一项的外壳的方法，其中所用的技术包括通过注塑方法反向-涂布，并且初始进料包含用于中间层和金属的覆盖层的材料，在所有情况下为片状结构形式，并且随后通过注塑方法经由反向-涂布将用于支撑层的热塑性聚合物与之结合。
14.权利要求1-9中的一项或多项的外壳的用途，用于包含用于电力驱动的电动汽车或电动自行车的电源电池。
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