CN116686147A - 覆盖制品、包含该覆盖制品的电池包以及该电池包的制备方法 - Google Patents
覆盖制品、包含该覆盖制品的电池包以及该电池包的制备方法 Download PDFInfo
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- CN116686147A CN116686147A CN202180087339.8A CN202180087339A CN116686147A CN 116686147 A CN116686147 A CN 116686147A CN 202180087339 A CN202180087339 A CN 202180087339A CN 116686147 A CN116686147 A CN 116686147A
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Abstract
本发明涉及一种3D形状的覆盖制品，其包含作为芯层的反应注射成型产品，以及位于芯层两侧的两个金属片，还涉及一种包含该覆盖制品的电池包，以及该电池包的制备方法。
Description
技术领域
本发明涉及一种新型覆盖制品、包含该覆盖制品的电池包以及该电池包的制备方法。所述电池包包括上盖和底部托盘，所述上盖为反应注射成型(reaction injectionmolded，RIM)产品；所述底部托盘包括作为芯层的反应注射成型产品和位于芯层两侧的两个金属片。
背景技术
随着电动车辆的发展，电池的轻量化设计和容量限制越来越受到关注。目前，人们主要使用冲压金属片作为电池包的上盖和底部托盘以保护其中的电池部件。尽管金属材料显示出良好的机械性能，但是它们的密度以及因此部件重量高。因此，迫切需要提供一种新的轻质部件来代替金属壳体。
夹层部件由面片、中间的芯层以及将芯层与面片粘合的粘合层组成。夹层部件因其高强度/重量比而广泛应用于航空航天领域。面片包括金属例如钢、铝合金以及由碳纤维、玻璃纤维、芳纶纤维或玄武岩纤维等增强的复合板等。芯层材料包括泡沫状或致密的聚合物、蜂窝状结构和微桁架结构。例如，US2019/0153185A1公开了一种以平面形式构造的夹层部件及其作为非承重壁元件、外壁包层和天花板元件的用途；然而，它没有公开或暗示这种夹层部件可以用作电池包的底部托盘。就电池包的底部托盘而言，需要满足诸如机械强度和阻燃性等特殊性能的要求，还需要弯曲的甚至有图样的部件形状以满足电池的复杂轮廓。
现有技术公开了基于聚丙烯或聚酰胺的注塑件作为电池包的上盖。然而，这种聚丙烯或聚酰胺材料注射成型解决方案难以实现诸如上盖等非常大尺寸的部件；注射成型需要高加工成本、高注射压力和温度。截至目前，没有出版物或专利公开或暗示反应注射成型(RIM)产品，如聚氨酯等，可以用作电池上盖。
因此，仍需要提供一种新型3D形状的覆盖制品，其重量轻，且同时具有良好的机械强度和阻燃性。
附图说明
图1示出了电池包的上盖和底部托盘，其中上盖是基于聚氨酯，底部托盘包括聚氨酯芯层和位于聚氨酯芯层两侧的两个金属片。
图2是制备3D形状夹层部件的单步工艺(single-step process)。
图3-4示出了具有肋条图样设计、优化的厚度分布以及推荐的肋条图样的上盖。
图5-6示出了底部托盘的结构、其中内板的细节以及弯曲/焊接工艺。
图7示出了法兰的密封设计。
发明内容
本发明的目的是克服上述现有技术的问题，并提供一种电池包的制造方法及其结构，该电池包的重量轻，且同时具有良好的机械强度和阻燃性。
令人惊讶的是，发明人已经发现，上述目的可以通过覆盖制品来实现，所述覆盖制品包含作为芯层的反应注射成型产品和位于芯层两侧的两个金属片，其中所述覆盖制品是3D形状制品。
在另一方面，本发明涉及一种电池包，其包括上盖；底部托盘，其中所述底部托盘是如上所述的覆盖制品。
在又一方面，本发明涉及用于制备本发明的电池包的方法，包括以下步骤：
-通过反应注射成型(RIM工艺)提供上盖，以及
-提供底部托盘，其包括以下步骤：
1)将平的金属片弯曲成目标3D形状的顶部和底部金属片，并在开口转角(opencorner)处焊接；
2)将所述顶部和底部金属片固定到RIM模具中，然后闭合所述模具；
3)将反应物注射到所述金属片之间的空腔中以通过所述反应注射成型(RIM工艺)形成模塑芯层；
4)脱模和任选地修整。
在本申请中已令人惊讶地发现，包含基于反应注射成型(RIM)产品的覆盖制品的电池包表现出重量减轻，同时也表现出良好的机械强度和阻燃性。
具体实施方式
除非另有定义，否则本文中使用的所有技术术语和科学术语均具有本发明所属领域的技术人员通常理解的含义。如本文中所用，除非另有说明，否则以下术语具有下文赋予它们的含义。
如本文中所用，冠词“一(a)”和“一个(an)”是指一个或多于一个(即，至少一个)冠词的语法对象。例如，“一个元件”是指一个元件或多于一个元件。
如本文中所用，表述“包含”还涵盖表述“由……组成”。
除非另有说明，否则所有百分比(％)均是指“重量百分比”。
除非另有说明，否则温度是指室温，压力是指环境压力。
覆盖制品
在一方面，本发明提供了一种覆盖制品，其包含作为芯层的反应注射成型产品和位于芯层两侧的两个金属片，其中所述覆盖制品是3D形状的制品。
反应注射成型(RIM)是一种工艺，其包括两种或多种反应性、低粘度液体的加压混合，然后将其注射到模腔中，在几分钟甚至几秒钟内聚合从而固化出零件的形状。RIM可以通过增加撞击流的速度来实现试剂的有效混合。RIM相对低的压力和温度要求转化为低的工具成本，RIM可以成功地成型含有厚壁和薄壁的高分辨率复杂零件。所述反应注射成型产品选自聚氨酯、聚酰胺、不饱和聚酯树脂、环氧树脂、酚醛树脂(phenol-formaldehyderesin)，优选聚氨酯。
在本发明中，覆盖制品通过以下步骤制备：1)将平的金属片弯曲成目标3D形状的顶部和底部金属片，并在开口转角处焊接；2)将顶部和底部金属片固定到RIM模具中；3)将反应物注射到所述金属片之间的空腔中以通过所述反应注射成型(RIM)形成模塑芯层；4)脱模和任选地修整。
金属片是从铝合金、铁、钢、铝中选择的相同或不同材料。金属片的厚度在0.08和0.6mm之间，优选在0.12和0.4mm之间，更优选在0.2和0.3mm之间。优选地，金属片的四边以一定角度弯曲，优选以80°至100°弯曲，更优选以90°弯曲，然后通过焊接连接开口转角，优选通过氩弧焊连接。弯曲角度的曲率半径在0至10mm的范围内，优选在2至5mm的范围内。芯层的厚度在0.8和5mm之间，优选在2和3mm之间；芯层的密度在600和2000kg/m3之间，优选在900和1300kg/m3之间，更优选在900和1100kg/m3之间。
本发明的覆盖制品可以用作电池包的底部托盘。
电池包
在一方面，本发明提供了一种电池包，其包括
上盖；
底部托盘，其中所述底部托盘为本发明的覆盖制品。
所述上盖是反应注射成型产品(RIM)，其选自聚氨酯、聚酰胺、不饱和聚酯树脂、环氧树脂、酚醛树脂，优选聚氨酯。反应注射成型(RIM)工艺可以容易地实现复杂(尤其是深的)的肋条图样设计。在本发明中，所述上盖设置有肋条图样以提高零件刚度。因此，可以在减轻上盖重量的同时保持其机械性能。
在本发明中，所述上盖可以设置有多个能够相互交叉的纵向加强肋和横向加强肋。在一个实施方式中，上盖设置有规则的肋条图样。在优选的实施方式中，上盖设置有不规则的肋条图样。在本发明中，肋条高度在3mm至30mm的范围内，优选为3mm至8mm的范围内。
例如，可以利用CAE(Computer Aided Engineering，计算机辅助工程)系统根据模具的CAE模型的形状参数设计肋条图样，所述形状参数包括但不限于肋条高度变化、肋条厚度变化、肋条方向变化、肋条位置变化等等。根据预设的规则，计算机辅助工程系统可以更有效地分析并允许调整模具的模型的各种特征。例如，可以加厚展示高应力的肋条。
众所周知，电池通常安装在车辆底盘上或附近，因此有必要保护电池免受外力影响。根据本发明，底部托盘的金属片具有波浪形表面，以防止外力穿透。正交偏转是将危险的Z轴输入能量转换为安全的相垂直的XY能量。损耗的能量是为使钢和PU变形所损耗的能量。
在本发明中，上盖的总厚度在1至5mm的范围内，优选1.5至4mm的范围内，更优选2至3mm的范围内；底部托盘的总厚度在1至5mm的范围内，优选1.5至4mm的范围内，更优选2至3mm的范围内。
平垫片和密封设计适用于金属壳体，不适用于塑料。根据本发明，上盖和底部托盘优选用法兰上的凹槽和位于凹槽中的竖直椭圆形垫片密封。应当理解，凹槽将被要求与垫片的形状相对应，以使垫片在使用时可以部分地被容纳在凹槽中。当拧紧螺丝将上盖和底部托盘固定在一起时，垫片被压缩在凹槽内，从而于其间形成密封。这种密封设计表现出更好的密封性能，对电池包的水密性至关重要。
使用椭圆的、长圆的或细长的垫片可以是特别有利的。垫片材料选自聚氨酯泡沫、乙烯丙烯酸酯弹性体(ethylene acrylic elastomer，AEM)、丙烯酸酯材料(acrylatematerial，ACM)、丁腈橡胶(nitrile butadiene rubber，NBR)、氟橡胶(fluorocarbonrubber，FPM)、三元乙丙橡胶(ethylene propylene diene rubber，EPDM)、氢化丁腈橡胶(hydrogenated acrylonitrile butadiene rubber，HNBR)、甲基乙烯基硅橡胶(methyl-vinyl silicone rubber，MVQ)、有机硅和氟硅橡胶，优选肖氏A硬度为45至60的AEM弹性体。优选地，微小凸缘(micro lips)位于垫片的顶侧和底侧，以进一步集中垫片表面压力并将对法兰的反作用力降至最低。
在本发明中，所述凹槽的深度在5mm至10mm的范围内，优选在6mm至7mm的范围内，所述凹槽的宽度在2mm至5mm的范围内，优选在3mm至4mm的范围内。
RIM最常用于通过使液体多元醇和多异氰酸酯反应形成氨基甲酸酯键，从而制备热固性聚氨酯(polyurethane，PU)网络。此外，RIM还可用于制备聚酰胺(polyamide，PA)、不饱和聚酯树脂(unsaturated polyester resin，UPR)、环氧树脂、酚醛树脂等，前提是其反应物的粘度范围适合RIM工艺。在本发明中，反应注射成型(RIM)产品选自聚氨酯(PU)、聚酰胺(PA)、不饱和聚酯树脂(UPR)、环氧树脂、酚醛树脂，优选聚氨酯。
聚氨酯
在制备聚氨酯上盖或底部托盘的聚氨酯芯层中，使用“异氰酸酯组分”和“树脂组分”，“树脂组分”是对异氰酸酯呈反应性的物质(b)、任选地扩链剂和/或交联剂(c)、阻燃剂(d)、填料(e)、发泡剂(f)、催化剂(g)和任选地助剂以及添加剂(h)的混合物，“异氰酸酯组分”是异氰酸酯类。多元醇组分与异氰酸酯反应形成氨基甲酸酯键。此类体系公开于例如美国专利第4,218,543号中。
将“异氰酸酯组分”和“树脂组分”在约2000psi的压力进行冲击混合，并在约大气压注入到模具中，随后闭合模具。将模具在40℃至65℃，优选50℃至55℃预热，模具表面上可以设置有诸如金属片等的插入物。通常将原材料进行中心注射，然后在通常一到四分钟后使零件脱模。
异氰酸酯组分(a)
用于制备本发明聚氨酯的异氰酸酯组分包括已知用于制备聚氨酯的所有异氰酸酯。这些包括脂族、脂环族、芳脂族和/或芳族异氰酸酯，如三-、四-、五-、六-、七-和/或八亚甲基二异氰酸酯、2-甲基五亚甲基1,5-二异氰酸酯、2-乙基亚丁基1,4-二异氰酸酯、五亚甲基1,5-二异氰酸酯、亚丁基1,4-二异氰酸酯、1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷(异佛尔酮二异氰酸酯，IPDI)、1,4-和/或1,3-双(异氰酸根合甲基)环己烷(HXDI)、环己烷1,4-二异氰酸酯、1-甲基环己烷2,4-和/或2,6-二异氰酸酯和/或二环己基甲烷4,4’-/2,4’-和2,2’-二异氰酸酯、二苯基甲烷2,2’-、2,4’-和/或4,4’-二异氰酸酯(MDI)、聚合MDI、亚萘基1,5-二异氰酸酯(NDI)、甲苯2,4-和/或2,6-二异氰酸酯(TDI)、3,3’-二甲基二苯基二异氰酸酯、1,2-二苯基乙烷二异氰酸酯和/或亚苯基二异氰酸酯。特别优选使用2,2’-、2,4’-和/或4,4’-二异氰酸酯和聚合MDI。
其他可能的异氰酸酯例如在"Kunststoffhandbuch,Band 7,Polyurethane"[Plastics handbook,第7卷,Polyurethanes],Carl Hanser Verlag,第3版,1993,第3.2和3.3.2章中给出。
组分(b)
对异氰酸酯呈反应性的物质(b)可以是本领域中可用于聚氨酯制备并且具有至少两个反应性氢原子的任何化合物。举例来说，可使用聚醚多胺和/或选自聚醚多元醇和聚酯多元醇的多元醇，或其混合物。
优选使用的多元醇是聚醚多元醇，其分子量在500和6000之间，优选在2000到5000之间，更优选在2500到3500之间，其OH值在20和200mg KOH/g之间，优选30到100mg KOH/g之间；和/或聚酯多元醇，其分子量在350和2000之间，优选在350到650之间，其OH值在60和650mg KOH/g之间，优选在120至310mg KOH/g之间。在本发明中优选以下多元醇：2095(BASF)、/>2090(BASF)、/>3905(BASF)、/>3907(BASF)、/>3909(BASF)、PS 3152、PS 2412、PS 1752、CF 6925(Stepan Company)。
可用于本发明的聚醚多元醇是通过已知方法制备的。例如，它们可以由一种或多种在亚烷基中具有2至4个碳原子的环氧烷烃通过阴离子聚合制备，使用碱金属氢氧化物如氢氧化钠或氢氧化钾，或使用碱金属醇化物如甲醇钠、乙醇钠、乙醇钾或丙醇钾作为催化剂，加入至少一种包含2至8个反应性氢原子的起始剂分子；或通过阳离子聚合，使用路易斯酸如五氯化锑、氟化硼醚合物等，或漂白土作为催化剂。
合适的环氧烷烃的实例是四氢呋喃、1,2-环氧丙烷、1,2-环氧丁烷或2,3-环氧丁烷、氧化苯乙烯，并且优选环氧乙烷和1,2-环氧丙烷。环氧烷烃可以单独使用、交替连续使用或作为混合物使用。
可以使用的起始剂分子的实例是：水，有机二羧酸如琥珀酸、己二酸、邻苯二甲酸和对苯二甲酸，脂族和芳族的、在烷基中具有1至4个碳原子的任选N-单-、N,N-和N,N'-二烷基取代的二胺，例如任选地单-和二烷基取代的乙二胺、二亚乙基三胺、三亚乙基四胺、1,3-丙二胺、1,3-或1,4-丁二胺、1,2-、1,3-、1,4-、1,5-和1,6-六亚甲基二胺、苯二胺、2,3-、2,4-和2,6-亚甲苯基二胺和4,4'-、2,4'-和2,2'-二氨基二苯基甲烷。
聚酯多元醇可以例如由具有2至12个碳原子、优选4至6个碳原子的二羧酸和多元醇制备。可以使用的二羧酸的实例是：脂族二羧酸如琥珀酸、戊二酸、己二酸、辛二酸、壬二酸和癸二酸，以及芳族二羧酸如邻苯二甲酸、间苯二甲酸和对苯二甲酸。二羧酸可以单独使用或以混合物的形式使用，例如以琥珀酸、戊二酸和己二酸的混合物的形式使用。多元醇的实例是具有2至10个、优选2至6个碳原子的二醇，例如乙二醇、二乙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,10-癸二醇、2,2-二甲基-1,3-丙二醇、1,3-丙二醇和二丙二醇，具有3至6个碳原子的三醇，例如丙三醇和三羟甲基丙烷，以及作为高级官能度醇的季戊四醇。根据所需的性能，多元醇可以单独使用或任选地彼此混合使用。
聚醚多元醇和/或聚酯多元醇的量优选为0至40重量％、特别优选15至35重量％，基于树脂组分的总重量计。
扩链剂和/或交联剂(c)
可以使用的扩链剂和/或交联剂(c)是摩尔质量优选小于500g/mol、特别优选为60至400g/mol的物质，其中扩链剂具有2个对异氰酸酯呈反应性的氢原子，交联剂具有3个对异氰酸酯呈反应性的氢原子。这些物质可以单独使用或优选以混合物的形式使用。优选使用分子量小于500、特别是60至400、特别是60至350的二醇和/或三醇。可以使用的那些物质的实例是具有2至14个、优选2至10个碳原子的脂族、脂环族和/或芳脂族二醇，例如乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、1,10-癸二醇、1,2-、1,3-和1,4-二羟基环己烷、二乙二醇、二丙二醇、三丙二醇、二乙醇胺或三醇，例如1,2,4-或1,3,5-三羟基环己烷、丙三醇和三羟甲基丙烷。
扩链剂和/或交联剂c)(如果存在)的量优选为0至50重量％、特别优选10至40重量％，基于树脂组分的总重量计。
阻燃剂(d)
可以使用的阻燃剂(d)是固体阻燃剂、液体阻燃剂或其组合，例如三聚氰胺、可膨胀石墨(expandable graphite，EG)、红磷、多磷酸铵、磷酸三(1-氯-2-丙基)酯(tris(1-chloro-2-propyl)phosphate，TCPP)、磷酸三乙酯(triethyl phosphate，TEP)。
出于阻燃的目的，阻燃剂的总量优选为5至30重量％、更优选10至25重量％，基于树脂组分的总重量计。
填料(e)
可以使用的填料是本身已知的常用有机或无机填料。可以提及的单个实例是：无机填料如硅酸盐矿物；金属氧化物如氧化铝、氧化钛和氧化铁；以及聚酰胺纤维、聚丙烯腈纤维、聚氨酯纤维和聚酯纤维。优选使用矿物粉末或玻璃/碳纤维。
填料的量为5至30重量％，优选10至25重量％，基于树脂组分的总重量计。阻燃剂(d)和填料(e)的重量比在0.1至10的范围内，优选在0.5至2的范围内。
填料可用于降低聚氨酯泡沫的热膨胀系数(该热膨胀系数大于例如金属的热膨胀系数)，并且因此使该系数与金属的热膨胀系数匹配。这对于金属片和聚氨酯芯层之间的持久强结合是特别有利的，因为当它们经受热负荷时，这导致层之间的较低应力。
发泡剂(f)
根据本发明使用的发泡剂(f)优选包含水。所用的发泡剂(f)除了水之外还可以包含本领域中的其它化学和/或物理发泡剂。化学发泡剂是通过与异氰酸酯反应形成气态产物的化合物，实例是水或甲酸。物理发泡剂是已经溶解或乳化在用于聚氨酯制备的起始材料中并且在聚氨酯形成的条件下蒸发的化合物。举例来说，这些物质是烃、卤代烃和其他化合物，如全氟烷烃，例如全氟己烷、氟氯烃，和醚、酯、酮和/或缩醛。在一个优选的实施方式中，水用作唯一的发泡剂(f)。在这种情况下，根据本发明的聚氨酯泡沫是水发泡聚氨酯喷涂泡沫。关于水，没有特别限制。可以使用矿泉水、去离子水或自来水。
发泡剂的量为0至5重量％，优选0.1至3重量％，基于树脂组分的总重量计。
催化剂(g)
作为催化剂(g)，可以使用加速异氰酸酯-多元醇反应的所有化合物。这样的化合物是已知的，并且记载于例如"Kunststoffhandbuch,第7卷,Polyurethane",Carl HanserVerlag,第3版,1993,第3.4.1章中。这些物质包括胺基催化剂和基于有机金属化合物的催化剂。
作为基于有机金属化合物的催化剂，可以使用例如有机锡化合物如有机羧酸的锡(II)盐，例如乙酸锡(II)、辛酸锡(II)、乙基己酸锡(II)和月桂酸锡(II)，和有机羧酸的二烷基锡(IV)盐，例如二乙酸二丁基锡、二月桂酸二丁基锡、马来酸二丁基锡和二乙酸二辛基锡，以及羧酸铋，例如新癸酸铋(III)、2-乙基己酸铋和辛酸铋，或羧酸的碱金属盐，例如乙酸钾或甲酸钾。
优选使用基于胺的催化剂作为催化剂(g)，如N,N,N',N'-四甲基二亚丙基三胺、2-[2-(二甲基氨基)乙基-甲基氨基]乙醇、N,N,N'-三甲基-N'-2-羟乙基-双-(氨基乙基)醚、双(2-二甲基氨基乙基)醚、N,N,N,N,N-五甲基二亚乙基三胺、N,N,N-三乙基氨基乙氧基乙醇、二甲基环己胺、三甲基羟乙基乙二胺、二甲基苄胺、三乙胺、三亚乙基二胺、五甲基二亚丙基三胺、二甲基乙醇胺、N-甲基咪唑、N-乙基咪唑、四甲基六亚甲基二胺、三(二甲基氨基丙基)六氢三嗪、二甲基氨基丙胺、N-乙基吗啉、二氮杂双环十一碳烯和二氮杂双环壬烯。这里，可提及的实例是Jeffcat ZF10(CAS号83016-70-0)、Jeffcat DMEA(CAS号108-01-0)和Dabco T(CAS号2212-32-0)。这种反应性催化剂具有降低VOC值的效果。
催化剂(g)的量优选为0.1至5重量％，特别优选0.1至3.5重量％，基于树脂组分的总重量计。
添加剂和/或助剂(h)
可使用的添加剂和/或助剂(h)包括表面活性剂、防腐剂、着色剂、抗氧化剂、增强剂、稳定剂和吸水剂。在制备聚氨酯泡沫时，通常高度优选使用少量表面活性剂以稳定发泡反应混合物直至其固化。这种表面活性剂有利地包括液体或固体有机硅氧烷表面活性剂，其用量足以稳定发泡反应混合物。通常，助剂、尤其是表面活性剂的量优选为0至15重量％，更优选0.5至6重量％，基于树脂组分的总重量计。
关于上述助剂和添加剂的使用和作用方式的进一步信息以及另外的实例例如在"Kunststoffhandbuch,Band 7,Polyurethane"[“Plastics handbook,第7卷,Polyurethanes”],Carl Hanser Verlag,第3版,1993,第3.4章中给出。
树脂组分和异氰酸酯组分的重量比在1:0.6至1:1.2的范围内，优选在1:0.7至1:1的范围内。
聚酰胺尼龙
在另一实施方式中，本发明还包括通过内酰胺的反应注射成型制备的聚酰胺尼龙。在制备聚酰胺尼龙中，将“含有碱催化剂的熔融内酰胺”与“含有助催化剂的熔融内酰胺”混合并注入模具中。
作为要进行聚合的内酰胺，可以提及的有，例如，γ-丁内酰胺、δ-戊内酰胺、ε-己内酰胺、ω-庚内酰胺、ω-辛内酰胺、ω-十一烷基内酰胺和ω-十二烷基内酰胺。这些内酰胺可以单独使用或以其两种或多种的混合物的形式使用。
就碱催化剂而言，可以使用内酰胺的碱聚合的已知方法中使用的所有化合物。例如，可以提及碱金属和碱土金属、它们的氢化物、氧化物、氢氧化物、碳酸盐、烷基化产物、醇盐和格利雅化合物、萘基钠。优选碱催化剂以0.05至10摩尔％的量使用，更优选以0.2至5摩尔％的量使用，基于内酰胺计。
在已知的碱聚合方法中使用的所有助催化剂都可以用于本发明。例如，可以提及N-酰基内酰胺、有机异氰酸酯、酰氯、酸酐、酯类、脲类衍生物、碳化二亚胺和烯酮类。助催化剂以0.01至5摩尔％的量使用，基于内酰胺计。
在本发明中，内酰胺的聚合可以在基本上不抑制聚合反应的增塑剂、填料、纤维、发泡剂、染料、颜料或诸如抗氧化剂等稳定剂的存在下进行。优选N-烷基吡咯烷酮或二烷基咪唑烷酮作为增塑剂，并且增塑剂以2至25重量％的量使用，基于内酰胺计。就填料而言，可以提及碳酸钙、硅灰石、高岭土、石墨、石膏、长石、云母、石棉、炭黑和二硫化钼。就纤维而言，可以提及诸如磨碎玻璃(粉碎玻璃)等玻璃纤维、石墨纤维、矿物纤维和钢纤维。填料可以以2至50重量％的量使用，基于内酰胺计。就发泡剂而言，优选使用苯、甲苯和二甲苯，其量为1至15重量％，基于内酰胺计。
不饱和聚酯树脂
在另一实施方式中，本发明还包括由反应注射成型制备的不饱和聚酯树脂。在制备聚酯树脂中，将组分A“流体形式的聚酯树脂的主要基体、至少一种包含有机氢过氧化物的聚酯固化促进剂，以及对异氰酸酯呈高度放热反应性的添加剂”与组分B“有机异氰酸酯和表面活性剂”混合并注入模具中。添加剂的高度放热反应产生的热量几乎立即触发并加速异氰酸酯与有机氢过氧化物的气体析出反应。析出的气体使树脂块体在压力下膨胀从而填充模具空腔，同时，持续的热量产生导致聚酯固化促进剂反应从而使聚酯在完全膨胀的状态下固化。
构成组分A的大部分的不饱和聚酯树脂可以通过不饱和二羧酸，如马来酸或富马酸，与二醇或二醇的混合物，如乙二醇、丙二醇、1,4-丁二醇、1,6-己二醇或二乙二醇的缩合来制备。
有机氢过氧化物是叔丁基过氧化氢，其与有机异氰酸酯反应从而生成二氧化碳，并在升高的温度反应从而固化聚酯树脂。这种特定的有机氢过氧化物在室温基本上不与树脂反应，通常具有20小时的保质期，其可以用抑制剂例如氢醌来延长保质期，因此将这种特定的有机氢过氧化物在组分A中与树脂和添加剂一起引入系统中。在RRIM(ReinforcedReaction Injection Molding，增强反应注射成型)工艺中，增强纤维也被引入含该组分的混合物中。
对异氰酸酯呈高度放热反应性的添加剂可以是叔胺。
用于膨胀不饱和聚酯树脂的组分B优选由反应性有机异氰酸酯和表面活性剂的混合物组成。
有机异氰酸酯与组分A的成分一混合就反应从而在树脂块体内析出二氧化碳气体。合适的异氰酸酯的实例是芳族异氰酸酯或脂族异氰酸酯，例如正丁基异氰酸酯、苯基异氰酸酯、二苯甲烷二异氰酸酯、萘二异氰酸酯、三苯甲烷三异氰酸酯和聚合多异氰酸酯。
表面活性剂——其用于控制泡孔形成的气泡的尺寸分布——可以是当有机氢过氧化物与异氰酸酯反应时调节表面张力从而促进所需泡孔形成的任何合适的试剂(优选非离子表面活性剂)。优选使用硅酮，例如聚氧化烯-聚硅氧烷聚合物。
环氧树脂
在另一实施方式中，本发明还包括通过反应注射成型制备的环氧树脂，其中将组分A“环氧树脂、甲基丙烯酸缩水甘油酯和乙烯基酯”和组分B“固化剂、固化促进剂和自由基聚合引发剂”混合并注入模具中。
环氧树脂是那些具有两个或更多个环氧基团的树脂。优选使用在室温下为液体的环氧树脂。
甲基丙烯酸缩水甘油酯具有以下作用。首先，它降低了整个组合物的粘度。其次，由于它同时具有环氧基团和甲基丙烯酸酯基团，因此它起到环氧树脂和乙烯基酯的聚合网络之间的交联剂的作用，由此可以使所得固化产物的结构更均一。优选将甲基丙烯酸缩水甘油酯与环氧树脂预混合。
乙烯基酯用于促进固化反应。环氧树脂的缺点在于在反应注射成型中的固化时间长。然而，当允许同时进行乙烯基酯的自由基聚合时，似乎促进了环氧树脂的固化反应。从反应速率来考虑，优选具有丙烯酸酯结构的乙烯基酯。
环氧树脂的固化剂——在本发明中使用的——主要与环氧树脂和甲基丙烯酸缩水甘油酯反应，从而促进环氧树脂聚合网络的形成。固化剂可以从常规固化剂中选择，例如多胺、聚酰胺、二元酸和二元酸酐，这取决于固化产物的预期用途、反应速率和所需物理性质。
固化促进剂具有促进引发和进行固化反应的作用。固化促进剂可以选自叔胺、咪唑、酚、有机金属化合物和/或无机金属化合物。
本发明中使用的自由基聚合引发剂通过加热产生自由基，并起到甲基丙烯酸缩水甘油酯和乙烯基酯的聚合引发剂的作用。优选通常用作引发剂的有机过氧化物。有机过氧化物的实例包括叔丁基过氧化氢、异丙苯过氧化氢、二叔丁基过氧化物、过氧化二异丙苯、过氧化月桂酰、过氧化苯甲酰和过氧化苯甲酸叔丁酯。
酚醛树脂
在另一实施方式中，本发明还包括通过反应注射成型制备的酚醛树脂，其中将“酚醛组合物和表面活性剂”和“发泡剂和引发剂”混合并注入模具中。
酚醛组合物可以是本领域已知的液体酚醛组合物，其具有足够低的粘度用于反应注射成型工艺。
表面活性剂选自聚氯乙烯/聚环氧乙烷、乙氧基化蓖麻油、环氧乙烷/环氧丙烷的嵌段共聚物。
发泡剂选自CFCS系列、HCFC系列和烷烃发泡剂。
引发剂选自诸如硫酸、盐酸、硝酸、磷酸等无机酸；诸如苯磺酸、甲苯磺酸、苯酚磺酸、二甲苯磺酸、萘磺酸等有机酸。
电池包的制备方法
在另一方面，本发明还提供了一种制备本发明的电池包的方法，其包括以下步骤：
-通过反应注射成型(RIM)提供上盖，以及
-提供底部托盘，其包括以下步骤：
1)将平的金属片弯曲成目标3D形状的顶部和底部金属片，并在开口转角处焊接；
2)将所述顶部和底部金属片固定到RIM模具中，然后闭合所述模具；
3)将反应物注射到所述金属片之间的空腔中以通过所述反应注射成型形成模塑芯层；
4)脱模和任选地修整。
就薄钢片(<0.3mm)而言，发现冲压具有小曲率半径(例如≤10mm)的钢片会导致拐角处一定程度的裂纹缺陷。为避免这种裂纹缺陷，冲压曲率半径必须大于50mm。但在这样的设计中，它将极大地影响电池包的内部空间效率，从而对电池包的能量密度造成负面影响。为克服这个问题，使用弯曲/焊接工艺来取代传统的冲压工艺。
根据本发明，在步骤1)中，首先将平的金属片切割成预定形状，然后弯曲成目标3D形状，最后在开口转角处焊接。如图5-6所示，1m×1m的平的金属片从其四个角切割出0.1m×0.1m的正方形，然后将切割后的金属片沿着弯曲线(即虚线)以80°至100°的角度弯曲，优选90°，从而获得开口盒形状。可以首先借助激光束机器将平的金属片切割成预定形状。弯曲金属片通常通过使用手动工具或包括压力机和箱式制动器在内的折弯机来完成。最终对所获得的3D形状进行焊接，例如氩弧焊。氩弧焊是一种使用氩气作为保护气体的焊接技术，也称为氩气保护焊。在电弧焊的周围通过氩气，将空气与焊接区域隔离，防止焊接区域氧化。
通过使用弯曲/焊接工艺，钢片具有完好的四个尖锐转角，其曲率半径非常小，该钢片便于后续的RIM工艺加工。
优选地，步骤2)包括将3D形状的顶部和底部金属片放入RIM模具中，通过在金属片下方真空吸气或磁吸将金属片紧密地吸到RIM模具上，然后在金属片之间放置间隔件，闭合模具。对闭合的模具抽真空以帮助芯层的反应物填满模具的细长空腔。
在步骤2)中，金属片优选通过蚀刻、底漆、等离子体、激光或粘合剂在面向芯层的一侧上进行预处理，从而增强对芯层的附着力。
步骤3)是通过模具的入口将反应物注入RIM模具空腔中直至反应物填满模具，然后通过保持温度使反应物反应固化从而形成芯层的步骤。为反应固化所保持的温度为45℃至80℃，反应固化的时间为1至10分钟。反应物的粘度为100-1000mPa·s。
优选地，模具设有加热装置，并且在步骤3)之前，将模具预热至45℃-80℃。
芯层可以是通常完全填充中空空间的刚性泡沫或致密物质。本发明方法以短的循环时间经济地生产用于电池包的覆盖零件。
实施例
现在将参考实施例和对比例描述本发明，这些实施例和对比例不旨在限制本发明。
使用了以下起始材料：
A组分(多元醇组分)
·聚醚多元醇：
含有伯羟基的高反应性三官能聚醚多元醇，其可在市场上以商品名2095自BASF购得，OH值：28～35mg KOH/g；分子量：3000～6000。
·聚酯多元醇：
芳族聚酯多元醇，其可在市场上以商品名LUPRAPHEN 3905自BASF购得，OH值：175～310mg KOH/g；分子量：350～650。
·吸水剂：
分子筛，4A。
·表面活性剂：
有机硅表面活性剂，其可在市场上作为ORTEGOL 501自Evonik购得。
·固体阻燃剂：
来自Sigma-Aldrich的可膨胀石墨(EG)，80目。
·液体阻燃剂：
磷酸三(1-氯-2-丙基)酯(tris(1-chloro-2-propyl)phosphate，TCPP)，CAS编号：13674-84-5，其可在市场上自Albright和Wilson Ltd购得。
·填料
玻璃纤维粉末，单纤维直径：9-20μm，纤维长度：<1000μm。
·催化剂
胺催化剂，CAS编号：83016-70-0，其可在市场上以商品名JEFFCAT ZF10自Huntsman购得。
·发泡剂：去离子水。
·扩链剂：二丙二醇(Dipropylene glycol，DPG)。
B组分(异氰酸酯组分)
·异氰酸酯：
PMDI，其可在市场上以商品名ISOCYANATE B1001自BASF购得。
使用以下方法来测定性质：
密度(kg/m3)： GB/T 6343-2008
可燃性： G 8410-2006
弯曲刚度(KN/mm2)： ASTM D7250-20
外部火烧测试：GB 38031-2020
■试验方法：(8.2.7.1)
■在距离目标≥3米处点燃燃料盘
■预热火焰60秒
■将燃料盘移动到电池包下方
■电池包直接暴露至火焰70秒
■在燃料盘上加一个盖子，继续测试60秒
■移开燃料盘
■观察电池包2小时。
■要求：(5.2.7)
■电池包应不爆炸
■未使用镍氢电池
实施例1-预混树脂组分和异氰酸酯组分
根据表1配制树脂组分和异氰酸酯组分，然后将其放入多元醇罐和异氰酸酯罐中用于后续的反应注射成型。在本文记载的反应条件下，用于聚氨酯成型产品的双组分反应体系的粘度为100-1000mPa·s。
表1
实施例2-制备夹层底部托盘
本发明的底部托盘是通过包括以下步骤的方法制备：
S101：将厚度为约0.3mm的金属片SUS304以约90°的角度弯曲成目标3D形状的顶部和底部金属片，并在开口转角处通过氩弧焊进行焊接；
S102：将顶部和底部钢片放入RIM模具中；
S103：通过在钢片下方真空吸气将钢片紧密地吸到模具上，然后在钢片之间放置间隔件，闭合模具；
S104：将模具预热至50℃的温度；
S105：通过模具的注入口将用于形成聚氨酯芯层的聚氨酯合成材料注入模具中，直到聚氨酯合成材料充满模具，其中聚氨酯合成材料的温度为50℃，然后通过将温度保持在80℃5分钟来反应固化聚氨酯合成材料(RIM工艺)；
S106：冷却7分钟后，打开模具并取出成型的底部托盘，其中成型托盘的芯层是厚度约2mm、密度约1000kg/m3的聚氨酯层，聚氨酯芯层的两侧为钢片。
所获得的底部托盘表现出减少了约40％的重量，为约200,000KN/mm2的弯曲刚度，其高于厚度等于或大于2.5mm的纯钢冲压片的弯曲刚度。
实施例3-制备上盖
以类似的方式，同样通过反应注射成型工艺生产本发明的具有肋条图样的上盖。
最后，用法兰将上盖、电池模组和底部托盘密封，其成功通过了火烧测试。
a.底部托盘的夹层结构可减轻重量。
发明人测试了钢片、铝片和几个夹层底部托盘的重量和弯曲刚度。根据上述实施例2的步骤制备本发明的底部托盘，不同之处在于如下表2所示改变芯和面层的厚度。
表2
从表2中可以看出，通过使用包含聚氨酯芯层的夹层底部托盘，可以减轻底部托盘约40％的重量，并可以显著地提高特定部件厚度下的最大刚度。
b.托盘底部3D金属片的新设计(用弯曲/焊接代替冲压)
发明人发现，在冲压底部托盘的具有小曲率半径(例如≤10mm)的钢片的过程中，在薄钢片(<0.3mm)的转角处会形成裂纹。为避免这种裂纹缺陷，冲压曲率半径必须大于50mm。但在这样的设计中，它将极大地影响电池包的内部空间效率，从而对电池包的能量密度造成负面影响。考虑到这种情况，本发明人使用弯曲/焊接工艺来代替传统的冲压工艺。
首先通过激光束机器将尺寸约1m×1m×0.3mm的SUS 304平金属片切割成如图6所示的预定形状，然后沿着弯曲线以约90°的角度弯曲，从而获得目标开口盒形状，最后在开口转角处通过氩弧焊焊接。已发现该3D形状钢片具有完好的四个尖锐转角，其曲率半径非常小，该钢片便于后续的RIM工艺加工。
底部托盘的金属片还具有波浪形表面，以防止外力穿透。
c.上盖的肋条可实现提高零件刚度/减轻重量。
本发明人进行了另一实验以获得具有各种肋条图样设计的上盖。根据实施例3重复所有步骤，不同之处在于如下表3所示改变肋条高度。
表3
令人惊讶的是，RIM工艺可以容易地实现复杂(特别是深)的肋条图样设计，而对于其他一些工艺例如热成型和冷成型(冲压)而言则很难实现。从表3可以看出，随着聚氨酯上盖的肋条高度从3mm增加到8mm，Z方向上的最大位移减少了60％～70％，这意味着零件的刚度显著提高。
因此，即使RIM零件由于填料含量有限(最高达20％)而具有固有的低刚度，肋条图样设计也能够有效地增加零件刚度。图3-4示出了上盖的推荐肋条图样。
d.浸水安全性
根据新的浸水安全标准GB 38031-2020，IPX7，所要求的浸水安全性比以前高得多。到目前为止，平垫片和密封设计适用于金属壳体，不适用于塑料。
发明人发现，凹槽密封设计可以满足浸水安全性的要求。
用法兰密封根据实施例2制备的底部托盘和根据实施例3制备的上盖，塑料法兰上具有深7mm、宽3.5mm的垫片槽，高9mm、宽2.5mm的垂直椭圆形AEM垫片(肖氏A硬度为50)部分位于凹槽中。AEM垫片的顶部和底部都有微小凸缘。在拧紧螺丝将上盖和底部托盘固定在一起后，垫片被压缩在凹槽内，从而于其间形成密封。这种密封设计表现出更好的密封性能，对电池包的水密性至关重要。
根据上述步骤重复凹槽密封设计，不同之处在于凹槽的深度和宽度分别为8mm和4mm，AEM垫片的高度和宽度分别为10mm和3mm。结果表明，密封性能仍然良好。
本文所述的结构、材料、组合物和方法旨在作为本发明的代表性示例，并且应当理解，本发明的范围不受实施例的范围的限制。本领域技术人员将认识到，本发明可以通过对所公开的结构、材料、组合物和方法的变化来实践，并且这些变化被认为在本发明的范围内。因此，本发明旨在覆盖落入所附权利要求及其等同物的范围内的这些修饰和变化。
Claims (33)
1.一种覆盖制品，其包含作为芯层的反应注射成型产品和位于芯层两侧的两个金属片，其中所述覆盖制品是3D形状的制品。
2.根据权利要求1所述的覆盖制品，其中所述反应注射成型产品选自聚氨酯、聚酰胺、不饱和聚酯树脂、环氧树脂、酚醛树脂，优选聚氨酯。
3.根据权利要求1所述的覆盖制品，其中所述金属片是从铝合金、铁、钢、铝中选择的相同或不同材料。
4.根据权利要求1所述的覆盖制品，其中所述金属片的四边以80°至100°弯曲，优选以90°弯曲，然后通过焊接连接开口转角。
5.根据权利要求4所述的覆盖制品，其中弯曲角度的曲率半径在0至10mm的范围内，优选在2至5mm的范围内。
6.根据权利要求1所述的覆盖制品，其中所述金属片的厚度在0.08和0.6mm之间，优选在0.12和0.4mm之间，更优选在0.2和0.3mm之间。
7.根据权利要求1所述的覆盖制品，其中所述芯层的厚度在0.8和5mm之间，优选在2和3mm之间；所述芯层的密度在600和2000kg/m3之间，优选在900和1300kg/m3之间，更优选在900和1100kg/m3之间。
8.根据权利要求1至7中任一项所述的覆盖制品，其中所述覆盖制品通过以下步骤制备：
1)将平的金属片弯曲成目标3D形状的顶部和底部金属片，并在开口转角处焊接；
2)将所述顶部和底部金属片固定到模具中；
3)将反应物注射到金属片之间的空腔中以通过反应注射成型形成模塑芯层；
4)脱模和任选地修整。
9.根据权利要求1-8中任一项所述的覆盖制品作为电池包的底部托盘的用途。
10.一种电池包，其包括：
上盖；
底部托盘，其中所述底部托盘是根据权利要求1-8中任一项所述的覆盖制品。
11.根据权利要求10所述的电池包，其中所述上盖是选自聚氨酯、聚酰胺、不饱和聚酯树脂、环氧树脂、酚醛树脂的反应注射成型产品，优选所述上盖是选自聚氨酯的反应注射成型产品。
12.根据权利要求10或11所述的电池包，其中所述上盖设置有肋条图样，例如规则的肋条图样或不规则的肋条图样。
13.根据权利要求12所述的电池包，其中所述肋条的高度在3mm至30mm的范围内，优选为3mm至8mm的范围内。
14.根据权利要求10所述的电池包，其中所述上盖的总厚度在1至5mm的范围内，优选1.5至4mm的范围内，更优选2至3mm的范围内；所述底部托盘的总厚度在1至5mm的范围内，优选1.5至4mm的范围内，更优选2至3mm的范围内。
15.根据权利要求10所述的电池包，其中所述底部托盘的金属片具有波浪状表面。
16.根据权利要求10所述的电池包，其中所述上盖和所述底部托盘用法兰上的凹槽和凹槽中的竖直椭圆形垫片密封。
17.根据权利要求16所述的电池包，其中所述垫片的顶部和底部都有微小凸缘。
18.根据权利要求16所述的电池包，其中所述凹槽的深度在5mm至10mm的范围内，优选在6mm至7mm的范围内，所述凹槽的宽度在2mm至5mm的范围内，优选在3mm至4mm的范围内。
19.根据权利要求16至17中任一项所述的电池包，其中所述垫片材料选自聚氨酯泡沫、乙烯丙烯酸酯橡胶(AEM)、丙烯酸酯材料(ACM)、丁腈橡胶(NBR)、氟橡胶(FPM)、三元乙丙橡胶(EPDM)、氢化丁腈橡胶(HNBR)、甲基乙烯基硅橡胶(MVQ)、有机硅和氟硅橡胶。
20.根据权利要求11所述的电池包，其中用于聚氨酯成型产品的双组分反应体系包括：
异氰酸酯组分，其由以下组成：
a)至少一种异氰酸酯，以及
树脂组分，其由以下物质组成：
b)至少一种对异氰酸酯呈反应性的物质，
c)任选地扩链剂和/或交联剂，
d)阻燃剂，
e)填料，
f)发泡剂，
g)催化剂，以及任选地
h)添加剂和/或助剂，
其中所述阻燃剂(d)选自可膨胀石墨、红磷、多磷酸铵、三聚氰胺、磷酸三乙酯和磷酸三(2-氯丙基)酯，所述填料(e)选自矿物粉末、玻璃纤维粉末和碳纤维粉末。
21.根据权利要求20所述的电池包，其中所述树脂组分和所述异氰酸酯组分的重量比在1:0.6至1:1.2的范围内，优选在1:0.7至1:1的范围内。
22.根据权利要求20所述的电池包，其中所述阻燃剂(d)和所述填料(e)的重量比在5至30的范围内，优选在10至20的范围内。
23.根据权利要求20所述的电池包，其包括以下组分，各组分基于树脂组分(b)-(h)的总重量计：
b)0-40重量％，优选15-35重量％的至少一种对异氰酸酯呈反应性的物质，
c)0-50重量％，优选10-40重量％的任选地扩链剂和/或交联剂，
d)5-30重量％，优选10-25重量％的阻燃剂，
e)5-30重量％，优选10-25重量％的填料，
f)0-5重量％，优选0.1-3重量％的发泡剂，
g)0.1-5重量％，优选0.1-3.5重量％的催化剂，以及任选地
h)0-15重量％，优选0.5-6重量％的其它添加剂和/或助剂。
24.根据权利要求10所述的电池包，其还包括电池单体模组、用于感测和平衡的电池单体控制器、高压连接器、母线和电池控制器。
25.根据权利要求10所述的电池包，其包括在所述电池包内部作为结构加强件的PU拉挤梁，或在所述电池包外部作为防侵入加强件的PU拉挤梁。
26.一种用于制备根据权利要求10至25中任一项所述的电池包的方法，其包括以下步骤：
-通过反应注射成型提供上盖，以及
-提供底部托盘，其包括以下步骤：
1)将平的金属片弯曲成目标3D形状的顶部和底部金属片，并在开口转角处焊接；
2)将所述顶部和底部金属片固定到RIM模具中；
3)将反应物注射到所述金属片之间的空腔中以通过反应注射成型形成模塑芯层；
4)脱模和任选地修整。
27.根据权利要求26所述的方法，其中所述步骤2)包括：
-将所述顶部和底部金属片放置到RIM模具中；
-通过在所述金属片下方真空吸气或磁吸将所述金属片紧密地吸到所述模具上，然后在所述金属片之间放置间隔件，闭合所述模具。
28.根据权利要求26所述的方法，其中在步骤2)中，所述金属片在面向所述芯层的一侧上通过蚀刻、底漆、等离子体、激光或粘合剂进行预处理。
29.根据权利要求27所述的方法，其中在步骤2)中，对闭合的模具抽真空以帮助芯层的反应物填满所述模具的细长空腔。
30.根据权利要求26所述的方法，其中步骤3)是通过所述模具的入口将反应物注入模具中直至所述反应物填满所述模具，然后通过保持温度使所述反应物反应固化从而形成所述芯层的步骤。
31.根据权利要求30所述的方法，其中为反应固化所保持的温度为45℃至80℃，反应固化的时间为1至10分钟。
32.根据权利要求30所述的方法，其中所述反应物的粘度为100-1000mPa·s。
33.根据权利要求26所述的方法，其中所述模具设有加热装置，并且在所述步骤3)之前，将所述模具预热至45℃-80℃。
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