CN110740863A - 用于防火的材料 - Google Patents

用于防火的材料 Download PDF

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Publication number
CN110740863A
CN110740863A CN201880039410.3A CN201880039410A CN110740863A CN 110740863 A CN110740863 A CN 110740863A CN 201880039410 A CN201880039410 A CN 201880039410A CN 110740863 A CN110740863 A CN 110740863A
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China
Prior art keywords
fiber core
composite material
inorganic fiber
phyllosilicate
insulator
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CN110740863B (zh
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S·K·郑
J·M·申
J·S·李
D·默里
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Morgan Korea Ltd
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Morgan Korea Ltd
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    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)
  • Inorganic Insulating Materials (AREA)
  • Paper (AREA)

Abstract

一种用于防火的复合材料，所述用于防火的复合材料包含：‑a)无机纤维芯，所述无机纤维芯包括无机纤维，所述无机纤维经互锁或缠结以形成抗分离的粘结体，所述无机纤维芯层压在b)至少两层页硅酸盐绝缘体之间，所述材料还包含阻挡层，所述阻挡层是所述材料不可或缺的，用以阻止湿气进入所述无机纤维芯的边缘。

Description

用于防火的材料
技术领域
本发明涉及用于防火的材料。本发明的材料尤其可用于提供被动防火以防止电存储装置中的热失控，例如电动车辆动力总成中的热失控，然而本发明不限于在此类组件中使用。
背景技术
电存储装置可以例如包括多个电池单元或电池(例如，锂离子电池单元)。锂离子电池单元可能在运行中发生故障，这可能导致存储能量从故障电池不受控制地释放，这可导致局部极高温区域。例如，各种类型的电池单元已显示为在所谓的“热失控”条件下产生在600-900℃范围内的温度。
如此高的温度可能会点燃附近的可燃物，从而引起火灾。高温还可能导致一些材料开始分解并产生气体。在此类事件期间产生的气体可能是有毒和/或易燃的，从而进一步增加了与热失控事件相关的危害。
锂离子电池单元可能使用具有高挥发性和易燃性的有机电解质。此类电解质往往在150℃至200℃范围内的温度下开始分解，并且无论如何甚至在分解开始之前就具有很大的蒸气压。一旦分解开始，产生的气体混合物(通常为CO2、CH4、C2H4、C2H5F等的混合物)就能够燃烧。由于电解质分解而产生此类气体会导致压力升高，并且所述气体通常排放到大气中；然而，这种排气过程是危险的，因为用空气稀释所述气体可导致形成爆炸性的燃料-空气混合物，该爆炸性的燃料-空气混合物如果被点燃，就可使火焰燃烧回到所讨论的电池单元中，从而点燃整个布置。
热失控的问题在包括多个电池单元的装置中变得复杂化，因为与故障电池单元相邻的电池单元可能从故障电池吸收足够的能量而升温到高于所设计的其工作温度，由此被触发而进入热失控。这可导致连锁反应，在所述连锁反应中当一个电池单元点燃相邻的电池单元时，各电池单元进入一系列级联的热失控。
包括层压在云母纸片材之间的陶瓷纤维纸的绝缘材料已知用于炉子的绝缘，但是未已知被用于防火。
然而，对为电动汽车动力总成提供防火的具体要求可能包括以下中的一项或多项：-
·用于防止短路的低电导率(例如，优选小于1.0×10-13S/cm，更优选小于1.0×10-14S/cm)。
·耐湿性
·用于满足电动汽车动力总成的特定设计的适当压缩特性
·不含硅胶以允许在使用寿命结束后进行回收。
发明内容
在本发明的第一方面，提供了一种复合材料，所述复合材料包括：-
a)无机纤维芯，所述无机纤维芯包含无机纤维，所述无机纤维经互锁或缠结以形成抗分离的粘结体所述无机纤维芯层压在
b)至少两层页硅酸盐绝缘体之间所述材料还包括
c)阻挡层，所述阻挡层是所述材料不可或缺的，用以阻止湿气进入所述无机纤维芯的边缘。
密封的无机纤维芯层的水分吸收(当样品暴露于40℃、95％相对湿度的环境23小时时)优选小于5重量％，更优选小于4重量％，甚至更优选小于3重量％，最优选小于2.5重量％。
除了无机纤维芯层的密封边缘阻止水分进入之外，所述密封边缘还阻止无机芯层内形成的灰尘被排放到环境中。
如在所附权利要求中所提出的，本发明提供了一种复合材料以及所述复合材料的用途。在权利要求书中，术语“页硅酸盐绝缘体”是指一种或多种包含一种或多种页硅酸盐矿物的材料，所述一种或多种页硅酸盐矿物的量按所材料的重量计大于5％(以及任选地按所述绝缘材料的重量计>10％、>20％、>30％、>40％、>50％、>60％、>70％，或>80％)。页硅酸盐绝缘体可包含其他组分，作为非限制性示例包括填充剂和/或粘合剂和/或纤维。
附图说明
通过参照附图进行的以下描述说明了本发明，但本发明不受所述描述的限制，在附图中：
图1示意性地示出了常规已知的纸/云母片材。
图2示意性地示出了本发明的第一实施方案中的纸/云母片材。
图3示意性地示出了本发明的第二实施方案中的纸/云母片材。
图4示意性地示出了本发明的第三实施方案中的纸/云母片材。
图5示出了可用于第一实施方案、第二实施方案和第三实施方案中的材料的耐热性测试的结果。
图6示出了可用于第一实施方案、第二实施方案和第三实施方案中的材料的耐热性测试的结果。
具体实施方式
图1的传统云母片材是包括夹在云母纸片材2、2'之间的无机纤维芯1的层压体，所述云母纸片材2、2'任选地包括稀松布层3、3'，从而为云母纸片材提供机械完整性。所述层压体的各层粘合地固定。此类层压体提供了无机纤维芯的自由边缘4，所述自由边缘4可以用作湿气或液体进入层压体的路径。湿气和液体可导致对纸的损坏，并导致降低纸的电阻率。云母纸片材的厚度优选为至少0.06mm，最小面密度为100g/m2，以使该片材能够提供足够的阻挡层来阻止水分进入，从而使密封剂能够局限于自由边缘4。提供了减少密封剂所需程度的优点，从而降低了复合材料的重量和大小。
在图2中示出的第一实施方案中，对于与图1相同的事物使用相同的附图标记，将密封剂5浸渍到无机纤维芯1的边缘中，以减少或消除湿气或液体的进入。
在图3所示的第二实施方案中，对于与图1相同的事物使用相同的附图标记，保护层6粘附到层压体的表面并且至少围绕无机纤维芯1与云母纸片材2、2'的层压体的边缘7。可以任选地从层压体表面的区域8中省略掉保护涂层6。
在图4中示出的第三实施方案中，对于与图1相同的事物使用相同的附图标记，将密封剂5浸渍到无机纤维芯1的边缘中，以减少或消除湿气或液体的进入；并且保护层6围绕无机纤维芯1与云母纸片材2、2'的层压体。
更详细地(但不限于)：-
无机纤维芯1包括无机纤维，所述无机纤维经互锁或缠结以形成抗分离的粘结体，但是在各纤维之间具有足够的空间以提供隔热效应和一定程度的压缩性。所述无机纤维可以通过任何已知手段来互锁或缠结，例如通过沉积为非织造材料，或者通过将来自羊毛的纤维针织或以其他方式缠结以形成毯状物。然而，特别有用的形式是作为纸，所述纸是通过造纸技术而由无机纤维形成的。
无机纤维可以是足以提供所需的绝缘和耐火性质的任何类型，并且通常是熔点高于1000℃的纤维。合适的纤维包括(但不限于)铝硅酸盐纤维、碱土硅酸盐纤维、碱金属铝硅酸盐纤维。
无机纤维芯1具有厚度大于0.5mm的陶瓷，以提供用于变形的一定范围的压缩性和弹性。这有助于使用复合材料进行产品组装，以及为由所述复合材料所保护的产品提供一定程度的缓冲。无机纤维芯1的最大厚度取决于复合材料的应用和保持完整性，但是通常小于10cm，小于5cm，或小于1cm。优选地，所述芯的密度在200kg/m3至280kg/m3的范围内，更优选地在220kg/m3至250kg/m3的范围内。
可使用的示例性材料是
Figure BDA0002316273600000051
PLUS碱土硅酸盐纸，该材料以包括2mm、3mm和6mm在内的厚度可用。该材料的烧失量为约8重量％，并且本发明考虑这样的无机纤维芯，在所述无机纤维芯中所述无机纤维占所述无机纤维芯的低至50重量％，但是优选地，所述无机纤维的量是所述无机纤维芯的>60％、>70％、>80％、>90％，或者甚至>95％。除了纤维之外，无机纤维芯还可以包含其他材料作为填充剂、粘合剂或其他。
云母纸片材2、2'和任选的稀松布层3、3'可以是适用于提供防火阻挡层和机械完整性的任何材料。合适的材料是带有玻璃布背衬的0.1mm厚云母纸。此类纸/稀松布材料中通常存在树脂粘合剂。树脂粘合剂可以准备好固化的(ready cured)(在这种情况下，需要将纸/稀松布材料粘合固定到无机纤维芯1)，或者纸/稀松布材料可以是未固化的预浸料(用于在将所述纸或稀松布材料与无机纤维芯1直接层压的过程中固化树脂)。
优选地，云母纸的面密度在100g/m2至150g/m2的范围内。合适的材料由SWECO Inc.[http://www.swecomica.net/eng/]供应。云母纸片材的密度通常高达约1300kg.m-3，但是该密度随纸和背衬的相对比例而变化。本发明不限于任何特定的密度。
对于一些应用优选的是，云母纸片材2、2'和任选的稀松布层3、3'具有低硅胶(即，优选小于5重量％，更优选小于1重量％，最优选基本上不含硅胶)含量，并且环氧粘合剂可用于该应用中，但是也可以考虑任何合适的粘合剂体系。
在云母纸片材2、2'和任选的稀松布层3、3'被粘结到无机纤维芯1的情况下，可以使用任何合适的粘合剂。使用包含丙烯酸酯共聚物、盐化的烷基醚磺基琥珀酸酯和聚氧乙烯烷基醚的粘合剂获得了良好的结果。
密封剂5可以是能够执行密封无机纤维芯1的边缘的功能的任何材料。典型的材料包括聚合物材料，但也包括无机材料(例如胶态无机材料，包括(例如)硅溶胶、氧化铝溶胶)。
保护涂层6至少围绕无机纤维芯1与云母纸片材2、2'的层压体的边缘，并且可以(如图所示)覆盖所述层压体整体。合适的材料包括在适当位置施加并固化的聚合物涂层(例如合成橡胶)，或者可包括聚合物片材，所述聚合物片材热层压到无机纤维芯1与云母纸片材2、2'的层压体上。真空封装(例如用高密度聚乙烯[HDPE])是一种方便的方法。
本发明的材料可以原样使用，或者与诸如金属等材料组合使用，以提供散热效应来限制“热点”。出于相同的目的，可以提供导热层(诸如金属箔或网)作为复合材料的一部分。
对于用作锂离子电池总成中抗热失控的绝缘体的适用性的典型要求包括：能够承受600℃的温度10分钟；以及在一侧暴露于600℃时，在10分钟后且优选在20分钟后，其相对侧上的温度不超过120℃。
这是通过以下方式测试的：使用热风枪将多个样品的一侧置于600℃下，以及使用位于热侧的热电偶和位于冷侧的两个隔开的热电偶(一个与样品相邻，另一个与所述样品间隔30mm)来测量温度。
实施例
实施例1包括为6mm厚的
Figure BDA0002316273600000071
PLUS碱土硅酸盐纸的无机纤维芯，所述无机纤维芯粘合地层压在为来自SWECO Inc.的0.1mm厚云母/玻璃布纸的片材之间。图5示出了温度时间曲线，其中实线表示热表面温度，其他线条表示与样品相邻处的温度Δ和与样品隔开处的温度□。如可以看出的，该材料满足在10分钟暴露后冷面上的温度不达到120℃的要求。适当地浸渍边缘和/或涂覆无机纤维芯可为材料提供不可或缺的阻挡层，以阻止湿气进入无机纤维芯的边缘，并且将产生这样的材料，所述材料不仅满足热要求，而且还可防护抵抗湿气侵袭。
通过以下方式来测试密封的无机芯的水分吸收：首先使样品经受根据ASTM B117(操作盐喷雾(雾)设备的标准实践(Standard Practice for Operating Salt Spray(Fog)Apparatus))的盐喷雾条件；盐溶液：5重量％的NaCl；温度35℃；1小时持续时间，使用恒温恒湿箱(JEIO TECH co./TH-ME-065)。然后将样品在室温下干燥24小时，之后将样品放入40℃、相对湿度95％的恒温恒湿箱中23小时。在室温下干燥24小时后，计算出样品的水分吸收为2.23重量％(三个样品的平均值)。
实施例2包括3mm厚的
Figure BDA0002316273600000072
PLUS碱土硅酸盐纸，所述
Figure BDA0002316273600000073
PLUS碱土硅酸盐纸粘合地层压在为来自SWECO Inc.的0.1mm厚云母/玻璃布纸的片材之间。将碱土金属硅酸盐纸与云母/玻璃布的层压体固定至3mm厚的铝板。图6示出了温度时间曲线，其中实线表示热表面温度，其他线条表示与样品相邻处的温度Δ和与样品隔开处的温度□。如可以看出的，该材料满足在10分钟暴露后冷面上的温度不达到120℃的要求并且确实显示出的温度低于实施例1的温度。然而，这种材料的压缩性低于实施例1的压缩性；并且金属的包含添加了传导层，因此不一定是优选的。然而，铝板的提供提供了更大的刚度和散热，这在某些应用中可为有用的。
用途
本发明提供了一系列复合材料，所述复合材料可以是可压缩的和有回弹力的，或者相对刚性的，具有低的透材料电导率，耐湿；并且任选地具有低硅胶含量。
所述复合材料可用于电力总成中以保护电池单元免受热失控，或用于需要防火的其他应用中。
变型
以上实施例使用云母纸。云母类矿物是包括许多矿物(例如黑云母、白云母、金云母、锂云母、珍珠云母、海绿石(Glauconite))的片状硅酸盐(页硅酸盐)。其他片状硅酸盐显示出类似的绝缘效应(例如蛭石)。本发明不限于云母绝缘体，而是还扩展到包含其他片状硅酸盐的绝缘体。
另外，以上实施例使用纸形式的页硅酸盐绝缘体，但是所述绝缘体不是必需为纸形式，而是可以包含通过涂漆、喷涂或以其他方式施加包含(任选地具有其他成分)一种或多种页硅酸盐矿物的悬浮液到无机纤维芯的表面而产生的涂层。此类涂层还可以构成阻止湿气进入无机纤维芯的边缘的阻挡层或构成该阻挡层的一部分。
上面的实施例使用碱土硅酸盐纤维纸形式的无机纤维芯。无机纤维芯不是必需包含此类纤维，而是可以使用任何合适的纤维。

Claims (19)

1.一种复合材料，所述复合材料包括：-
a)无机纤维芯，所述无机纤维芯包括无机纤维，所述无机纤维经互锁或缠结以形成抗分离的粘结体，
所述无机纤维芯层压在
b)至少两层页硅酸盐绝缘体之间
所述材料还包括
c)阻挡层，所述阻挡层是所述材料不可或缺的，用以阻止湿气进入所述无机纤维芯的边缘。
2.如权利要求1所述的复合材料，其中用以阻止湿气进入的所述阻挡层包含密封剂，所述密封剂浸渗到所述无机纤维芯的边缘中。
3.如权利要求1或权利要求2所述的复合材料，其中用以阻止湿气进入的所述阻挡层包括保护涂层，所述保护涂层粘附到至少无机纤维芯与页硅酸盐绝缘体的层压体的边缘。
4.如权利要求1至3中任一项所述的复合材料，其中所述保护涂层包围并封装无机纤维芯与页硅酸盐绝缘体的层压体整体。
5.如权利要求1至4中任一项所述的复合材料，其中所述无机纤维芯包括纸，所述纸包含至少90重量％的无机纤维。
6.如权利要求1至5中任一项所述的复合材料，其中所述无机纤维芯包括由碱土硅酸盐纤维形成的纸。
7.如权利要求1至6中任一项所述的复合材料，其中所述无机纤维芯的厚度大于0.5mm。
8.如权利要求1至7中任一项所述的复合材料，其中所述无机纤维芯的厚度小于10cm，小于5cm，或小于1cm。
9.如权利要求1至8中任一项所述的复合材料，其中所述页硅酸盐绝缘体包括固定至背衬的云母纸。
10.如权利要求1至9中任一项所述的复合材料，其中所述背衬是稀松布或玻璃布。
11.如权利要求1至10中任一项所述的复合材料，其中所述页硅酸盐绝缘体的厚度在0.06mm与0.25mm之间。
12.如权利要求11所述的复合材料，其中所述页硅酸盐绝缘体的厚度在0.08mm至0.15mm的范围内。
13.如权利要求2或从属于权利要求2的权利要求3至12中任一项所述的复合材料，其中所述密封剂包括选自由聚合物材料、无机材料和它们的混合物组成的组的材料。
14.如权利要求13所述的复合材料，其中所述无机材料包括胶体无机材料。
15.如权利要求3或从属于权利要求3的权利要求4至12中任一项所述的复合材料，其中所述保护涂层包括聚合物涂层。
16.如权利要求15所述的复合材料，其中所述聚合物涂层包括聚合物片材，所述聚合物片材热层压至所述无机纤维芯与页硅酸盐绝缘体的层压体。
17.如前述权利要求中任一项所述的复合材料，其中在所述页硅酸盐绝缘体层中的一个层的外表面上暴露于600℃达10分钟时，相对的页硅酸盐绝缘体层上的外表面的温度不超过120℃。
18.如权利要求17所述的组合物材料，其中在所述页硅酸盐绝缘体层中的一个层的外表面上暴露于600℃达20分钟时，相对的页硅酸盐绝缘体层上的外表面的温度不超过120℃。
19.一种电存储装置，所述电存储装置包括多个电池或蓄电池，所述多个电池或蓄电池中的至少一些由如权利要求1至18中任一项所述的复合材料分隔开。
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