CN114270606B - 用于可再充电的电能存储系统的热屏障材料 - Google Patents
用于可再充电的电能存储系统的热屏障材料 Download PDFInfo
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- CN114270606B CN114270606B CN202080055510.2A CN202080055510A CN114270606B CN 114270606 B CN114270606 B CN 114270606B CN 202080055510 A CN202080055510 A CN 202080055510A CN 114270606 B CN114270606 B CN 114270606B
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/62—Heating or cooling; Temperature control specially adapted for specific applications
- H01M10/625—Vehicles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/02—Layered products comprising a layer of paper or cardboard next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/028—Net structure, e.g. spaced apart filaments bonded at the crossing points
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
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Abstract
提供了一种用于在可再充电的电能存储系统中用作隔热屏障和/或火焰屏障的多层材料。该多层材料包括至少一个无机织物层,该无机织物层通过无机粘合剂粘结到包括无机颗粒和无机纤维的非织造层,其中该无机粘合剂。该无机粘合剂可以是改性无机粘合剂,基于该无机粘合剂的总固体含量,该改性无机粘合剂包括至少99重量%的无机成分和至少0.01重量%且小于1重量%的有机添加剂。
Description
背景技术
本发明涉及多层材料在可再充电的电能存储系统中作为隔热屏障的用途,该可再充电的电能存储系统包括例如电池组中的多个单个的可再充电的电池单元或电池单元模块。特别地,本发明涉及电动车辆电池模块,并且尤其涉及用于管理电池模块热逸溃事故的防爆和耐热屏障制品。
包括多个单个的电池单元(诸如例如锂离子电池单元)的可再充电或可重复装载的电池或可再充电的电能存储系统是已知的,并且用于包括例如作为移动电话和便携式计算机或电动汽车或车辆或混合动力汽车的电力供应的若干技术领域中。
还已知的是,特别地,可再充电的电池单元(诸如锂离子电池单元)有时经历由诸如电池单元内的短路、电池单元使用不当、制造缺陷或暴露于极端外部温度的事件引起的内部过热。当由高温引起的电池单元内的反应速率增加到在电池单元内产生的热量超过可抽出的热量并且所产生的热量导致反应速率的进一步增加并继而导致所产生的热量的进一步增加的点时,这种内部过热可导致所谓的“热逸溃”。例如,在锂离子(Li-ion)电池中,这种缺陷电池单元内产生的热量可达到500℃至1000℃,在局部热点中甚至可达到更高温度。
特别地,在这种情况下,关键的是中断或至少减少从缺陷电池单元或电池单元组到存储系统的其它部分的热传递或存储系统周围的热传递,这是因为在缺陷电池单元或电池单元组中产生的热量可扩散到邻近的电池单元,这继而会引起过热,并且然后经历热逸溃。同样,重要的是将热传递限制在存储系统周围的部分,当遭遇上述温度时,这些部分可被破坏或损坏,从而导致电气短缺,这继而可由于其它电池单元进入热逸溃状态而导致不想要的影响。
因此,通常提供安全预防措施以保护过热的电池单元或组的环境免受所产生的热量的影响,尤其包括尚未受影响的电池单元或组以及包含电池单元的系统或装置或设备的周围构造元件。
为此,例如已经建议在存储系统的内部插入隔热屏障元件,以便防止或减少从过热电池单元或电池单元组到其它电池单元或电池单元组和/或存储系统环境的热传递。
这种情况例如在美国公开第2006/0164795号(Jones等人)或美国专利第8,541,126号(Hermann等人)中有所描述。根据这些先前技术文件,热屏障元件可例如由陶瓷材料组成,该陶瓷材料为诸如氧化铝、氧化镁、二氧化硅、硅酸钙、硅酸钙镁或铝硅酸盐,这些材料提供约500℃至约1500℃和更高的熔化温度,即远高于在电池中热逸溃事件期间通常甚至在短时间内实现的温度,同时兼具相对低的热导率,诸如小于50W/mK的热导率(在25℃下测量)。此类陶瓷元件可例如由通过将浸渍有合适的耐温性的树脂的所述陶瓷材料的多个层压物压缩而制备的板组成。
在EP 3 142 166 A1中公开了一种可压缩复合材料,该可压缩复合材料尤其用作用于电池的隔热屏障元件,该可压缩复合材料是具有基本上刚性板和可压缩层的层状组件,该基本上刚性板和可压缩层在垂直于其大表面的方向上交替堆叠。
根据2018年3月14日在全球注册中建立的联合国第20号全球技术法规(即“电动车辆安全技术法规(EVS)”),未来的车辆需要满足以下要求:
为了确保配备包含易燃电解液的可再充电的电能存储系统(REESS)的车辆的整体安全性,车辆乘员不应暴露于扩散(这由于内部短路而由单个的电池热逸溃触发)导致的危险环境。第一个目标是完全抑制热蔓延。如果不能完全抑制热蔓延,则要求不发生外部火灾或爆炸,并且在热事件警告后5分钟内没有烟雾进入客舱。
用于可再充电的能量存储系统的外壳例如可由铝或有机聚合物片状模制化合物制成。温度一达到600℃和以上,两者就都可能被损坏。甚至在某些情况下,诸如例如由于事故或电绝缘材料的故障而使壳体变形,钢壳体可处于危险之中。一旦存在外壳内达到高于600℃的温度的热逸溃事件,就存在热量和气体逸出外壳的风险。
为了能够进行测试,在产品满足上述要求的情况下,已经开发了若干种测试方法,其中一种方法是所谓的钉子穿刺测试。
特别是在汽车工业中,另一趋势是值得注意的:可再充电的电能存储系统变得越来越大,并且能量密度越来越高,以便能够承载更多的能量,这有助于扩展车辆可利用完全充电的存储系统来驱动的范围,而无需对存储系统进行再充电。如果此类较大的存储系统出现故障,以下反应也可会变得更强烈,这是因为这些系统中存储的能量更高。这可导致更高的温度。
在电动车辆中使用可再充电的电池,包括镍金属氢化物或锂离子(Li-Ion)来储存能量和提供电力。电流在再充电期间流入电池或从电池流出到车辆和其附件中,都会产生热量,这些热量需要管理/耗散,热量与电流的平方乘以电池单元和互连系统的内阻成比例。电流越高,加热效应越强。
锂离子电池在特定操作温度范围内性能最佳。如果在规定范围的界限之外发生操作,则会损坏电池内的电池单元或加速电池单元的劣化。因此,取决于环境条件,电池可能还需要冷却或加热。这继而推动了在使用和再充电之前和期间有效地管理电池的热方面的需求。
电动车辆电池模块包括数百个电池单元,这些电池单元可通过各种电连接(即母线)存储在以组的形式彼此连接的袋中。当电池模块中的一个电池单元因为其操作中的刺穿、损坏或故障而着火时,会发生称为热逸溃蔓延的灾难性现象。所产生的火扩散到邻近的电池单元,并且然后在整个电池中以链式反应扩散到电池单元。这些火灾可能非常严重,在诸如电动车辆的高功率设备中尤为如此,在高功率设备中常见的是电池组包含数十、数百或甚至数千个单独单元。此类火灾不限于电池,并且可以扩展到车辆的周围结构并且危及乘员或这些电池所在的其它结构。
当热逸溃发生在电池单元中时,如果电池单元突然爆炸,也期望热管理系统阻挡和/或容纳喷射的碎片。在电动车辆应用中,同样重要的是,保护乘员免受火灾所产生的热量影响,从而允许有足够的时间使车辆停止并且逃离车辆。
热逸溃蔓延造成的严重风险需要电池模块的设计,该电池模块具有爆炸和隔热屏障,以减轻这种热逸溃的影响,并且为车辆乘员提供在火灾时安全撤离的时间。
发明内容
鉴于上述内容,仍然需要提供有助于防止或延迟可再充电的电能存储系统内的热蔓延以及到可再充电的电能存储系统周围或外部的部分的热传递的合适的材料和合适的布置,该可再充电的电能存储系统周围或外部的这些部分在遭遇上述条件和温度时可能被破坏或损坏。还需要这样的合适的材料,这些材料易于在组装过程中使用并且为设计可再充电的电能存储系统提供灵活性。
本发明涉及电动车辆电池模块,并且尤其涉及用于管理电池模块热逸溃事故的防爆和耐热屏障制品。所提供的制品可特别适用于例如汽车或其它电气化运输应用和固定式储能应用。
在示例性实施方案中,本发明提供了多层材料在可再充电的电能存储系统中作为隔热屏障的用途,其中该多层材料包括至少一个无机织物以及包括无机颗粒或无机纤维或它们的组合的至少一层。
在第二实施方案中,提供了在可再充电的电能存储系统中用作隔热屏障和/或火焰屏障的多层材料。该多层材料包括至少一个无机织物层,该无机织物层通过无机粘合剂粘结到包括无机颗粒和无机纤维的非织造层,其中该无机粘合剂是改性无机粘合剂,基于该无机粘合剂的总固体含量,该改性无机粘合剂包括至少99重量%的无机成分和至少0.01重量%且小于1重量%的有机添加剂。
在第三实施方案中,提供了在可再充电的电能存储系统中用作火焰屏障的多层材料。该多层材料包括:无机纸,该无机纸由玻璃纤维和微纤维、无机颗粒或颗粒填料和有机粘结剂制成;和涂覆的玻璃纤维织物层,该涂覆的玻璃纤维织物层通过无机粘合剂粘结到该无机纸的主表面。
在第四实施方案中,提供了在可再充电的电能存储系统中用作火焰屏障的多层材料。该多层材料包括第一无机织物层,该第一无机织物层通过无机粘合剂粘结到包括无机颗粒和无机纤维的非织造层的第一主表面;以及第二无机织物层,该第二无机织物层通过该无机粘合剂粘结到该非织造层的第二主表面,其中该无机粘合剂是改性无机粘合剂,基于该无机粘合剂的总固体含量,该改性无机粘合剂包括至少99重量%的无机成分和至少0.01重量%且小于1重量%的有机添加剂。
在第五实施方案中,提供了在可再充电的电能存储系统中用作火焰屏障的多层材料。该多层材料包括:第一涂覆玻璃纤维织物层,该第一涂覆玻璃纤维织物层通过无机粘合剂粘结到由玻璃纤维和微纤维、无机颗粒填料和有机粘结剂制成的无机纸的第一主表面;以及第二涂覆玻璃纤维织物层,该第二涂覆玻璃纤维织物层粘结到该无机纸的第二主表面。
在另一方面,本发明提供了一种具有至少一个电池单元和/或模块和多层材料的可再充电的电能存储系统,其中该多层材料用作隔热屏障和/或火焰屏障。该多层材料包括至少一个无机织物以及包括无机颗粒或无机纤维或它们的组合的至少一层。
防止电动车辆电池中与突然的热逸溃事件相关联的危险是一个重大的技术挑战。设计通用解决方案的一个问题在于,在防止热逸溃的一个方面作用良好的材料在其它方面则存在不足。例如,聚合物纤维和泡沫的非织造幅材可显示出优异的隔热性能,但是常见的聚合物往往是易燃的,或纤维和泡沫涂覆有易燃的密封剂材料。由织造的非可燃纤维(例如,无机纤维)制成的热屏蔽材料可有效地防止火灾穿透,但往往太薄而不能充分地隔绝火灾的巨大热量或吸收/偏转当电池单元爆炸时发射的碎屑。使用较厚的热屏蔽材料层通常性价比不高。这些材料的组合可起到作用,但可能难以将这些材料彼此粘结,当对粘结材料的选择可能受到易燃性问题约束时尤为如此。
当使用传统热管理系统中所使用的纤维和泡沫时,出现了另一个技术难题。即使是耐火纤维和泡沫也容易在足够高的温度(例如,高于600℃(1112℉))下熔化。在这种热逸溃事件期间不会熔化的纤维和泡沫(例如,氧化聚丙烯腈)倾向于相对脆并且可能在产品制造、中间处理和使用期间引入与纤维脱落或松散材料相关联的新问题。这些纤维在纤维幅材内彼此不粘结,因此必须设计替代方式以固定这些纤维,使得它们不会漏出并污染其它电池部件和围绕电池的空间。
当前的测试方法未能充分确定材料单独或与其它材料的组合如何能有效地用作电动车辆隔室中的屏障以提供防爆和热阻保护。此外,当前的测试方法使用实际的电池部件,包括电池单元和模块,这是昂贵和耗时的。
附图说明
现在将参照以下举例说明本发明的特定实施方案的附图更详细地描述本发明:
图1是根据本发明的多层材料的剖视图;
图2是可再充电的电能存储系统(REESS)的示意图。
在说明书和附图中重复使用的参考符号旨在表示本公开的相同或类似的特征结构或元件。应当理解,本领域的技术人员可设计出落入本公开原理的范围和实质内的许多其他修改形式和实施方案。附图可不按比例绘制。
定义
如本文所用:
“热屏障材料”意指被设计用于限制热事件扩散或扩大的材料。本发明的热屏障材料可减少热或火焰的传递,以及任选地在热逸溃事件期间提供免受弹片伤害的保护。
“厚度”意指一层或多层屏障制品的相对侧之间的距离。
“织物”意指通过对无机纤维进行交织、织造、针织或钩编所制备的柔软材料或布料。
“完全水解”参考其在参考完全水解的聚乙烯醇(PVA)中的用途意指通过滴定测定的PVA聚合物中的水解度大于或等于98摩尔%。
具体实施方式
如本文所用,术语“优选的”和“优选地”是指在某些情况下可提供某些益处的本文所述的实施方案。然而,在相同的情况或其它情况下,其它实施方案也可以是优选的。此外,对一个或多个优选实施方案的表述并不暗示其它实施方案是不可用的,且并非旨在将其它实施方案排除在本发明范围之外。
如本文和所附权利要求中所用,除非上下文另外明确指出,否则单数形式“一个/一种(a/an)”和“该/所述”包括复数对象。因此,举例来说,提及“一个/一种”或“该/所述”部件可包括本领域技术人员已知的一个或多个部件或其等价物。另外,术语“和/或”意指所列元件中的一个或全部或者所列元件中的任何两个或更多个的组合。
值得注意的是,术语“包括”及其变型在出现在所附说明书中时不具有限制性含义。此外,“一个”、“一种”、“该”、“至少一个”及“一个或多个”在本文中可互换使用。本文可使用相对术语诸如左、右、向前、向后、顶部、底部、侧面、上部、下部、水平以及垂直等,并且如果是这样,则它们来自在具体附图中所观察的视角。然而,这些术语仅用于简化描述,而并非以任何方式限制本发明的范围。
贯穿本说明书的对“一个实施方案”、“某些实施方案”、“一个或多个实施方案”或“实施方案”的引用,意指结合实施方案描述的具体特征、结构、材料或特性被包括在本发明的至少一个实施方案中。因此,贯穿本说明书的多处出现的短语,诸如“在一个或多个实施方案中”、“在某些实施方案中”、“在一个实施方案中”或“在实施方案中”,不是必须指本发明的相同实施方案。
根据本发明的多层材料可以是火焰屏障材料,该火焰屏障材料可用于改善配备有可再充电的电能存储系统的车辆的总体安全性。在示例性实施方案中,示例性多层材料包括至少一个无机织物,该至少一个无机织物粘结到包括无机颗粒或无机纤维或它们的组合的至少一个层。虽然该多层材料可取决于应用而包括两个层,但该多层材料也可包括两层以上的上述材料。这些层可用有机粘合剂或无机粘合剂粘结在一起。在示例性方面,无机粘合剂用于将至少一个无机织物粘结到包括无机颗粒或无机纤维的至少一层,这是因为在有机材料可充当燃料源的热逸溃事件期间,将有机材料包括在多层材料中可能对材料的性能有害。
棱柱形锂离子电池单元的热逸溃基本上可以分为3个阶段:
1.爆裂板打开时的爆炸性排放(例如对于120Ah棱柱形电池单元来说为6巴至8巴),即时温度升高至约700℃;
2.在高温(通常600℃至700℃,持续约30秒至50秒)下高压喷射气体排出和颗粒吹出;
3.安静的气体排放/发光火焰。
因此,用作隔热屏障以防止热蔓延的合适材料需要承受高温和高压以及气体排放和颗粒吹送而不会过分受损。此外,即使在高温、高压和气体和/或颗粒冲击期间和之后,该材料也需要提供热和电绝缘特性。
根据本发明的多层材料可以是柔性的。多层材料的柔性使得能够更广泛地使用该材料和更有效地应用该材料,这是因为柔性允许材料弯曲,并且因此允许在可再充电的电能存储系统内以一种或另一种方式应用该材料的更多选项。根据本发明的多层材料也可以是可压缩的。压缩性可允许更广泛的使用和更有效的应用。例如,材料可以是可压缩的,使得与未压缩状态相比,在压缩状态下该多层材料的总厚度小1/3。如果多层材料例如在未压缩状态下的厚度为6mm,则在压缩状态下应该可压缩至4mm。
根据本发明的多层材料可包括无机织物,该无机织物由无机纤维制成,该无机纤维为诸如E-玻璃纤维、R-玻璃纤维、ECR-玻璃纤维、C-玻璃纤维、AR-玻璃纤维、玄武岩纤维、陶瓷纤维、硅酸盐纤维、钢丝或它们的组合。纤维可被化学处理。无机织物例如可以是织造织物、布料、针织织物、缝编织物、钩编织物、交织织物或它们的组合。无机织物可改善多层复合物的增加的拉伸强度、撕裂强度和伸长率,这有助于工业制造和转化工艺以及保护多层材料中的其它层在热逸溃事件期间免受热和机械冲击。
该无机织物例如可具有介于0.3mm至3mm(例如0.4mm至1.5mm或0.4mm至1mm)的范围内的厚度。该无机织物还可具有超过400g/m2(gsm)的基重。示例性无机织物可具有400gsm到6100gsm的基重。在一些实施方案中,示例性无机织物将具有介于400gsm至1000gsm之间的基重。
在一些实施方案中,表面光洁度或表面涂层可被施加到无机织物,尤其是玻璃纤维织物,以增强对高达700℃的高温的耐受性或对高达750℃的瞬时爆炸的耐受性。示例性表面涂层包括硅酸钙、蛭石或硅溶胶以增强耐高温性。示例性表面涂层还可增强无机纤维的耐磨性。
根据本发明的多层材料还可包括至少一个非织造层,该至少一个非织造层包括无机颗粒或无机纤维或它们的组合。包括无机颗粒或无机纤维的至少一层的无机纤维可选自以下群组:E-玻璃纤维、S-玻璃纤维、R-玻璃纤维、ECR-玻璃纤维、C-玻璃纤维、AR-玻璃纤维、玄武岩纤维、陶瓷纤维、多晶纤维、非生物持久性纤维、氧化铝纤维、二氧化硅纤维、碳纤维、碳化硅纤维、硼硅酸盐纤维或其它呈非织造垫的形式的组合。非生物持久性纤维例如可以是碱土硅酸盐纤维。更具体地,纤维材料可包括退火的熔化形成的陶瓷纤维、溶胶-凝胶形成的陶瓷纤维、多晶陶瓷纤维、氧化铝-二氧化硅纤维、玻璃纤维(包括退火的玻璃纤维或非生物持久性纤维)。如果其它纤维能够承受在锂离子电池的热事件中产生的高温,则这些纤维也是可能的。
在一些实施方案中,无机颗粒或无机颗粒填料可包括但不限于玻璃泡、高岭土、滑石、云母、碳酸钙、硅灰石、蒙脱土、蒙皂石、膨润土、伊利石、绿泥石、海泡石、绿坡缕石、埃洛石、黏土、累托石、珍珠岩和它们的组合,优选地,颗粒填料混合物包括玻璃泡、高岭土、滑石、云母和碳酸钙中的至少两种。合适类型的高岭土包括但不限于水洗高岭土;分层高岭土;煅烧高岭土;和经表面处理的高岭土。在优选的实施方案中,无机颗粒填料包括玻璃泡、高岭土、云母和它们的混合物,如在诸如公开的专利合作条约申请WO 2020/023357中所描述的无机纸和板材料和层压物中所描述,该申请通过全文引用并入本文。任选地,可添加吸热填料,诸如三水合氧化铝。
在一些实施方案中,示例性材料可包括至少一个非织造层,该至少一个非织造层是无机纸或无机板,该无机板包括玻璃纤维和微纤维、无机颗粒和有机粘结剂,诸如可从美国明尼苏达州圣保罗的3M公司(3MCompany,St.Paul,MN,USA)商购获得的3M CEQUIN I无机纸。根据UL 1446和IEC标准61857,3M CEQUIN I无机纸被批准用作通过等级220(R)的电气绝缘系统中的主要绝缘。等级220(R)指示系统的最高允许操作温度为220℃,在此温度下系统可在保持电气完整性的同时连续操作。令人惊讶的是,具有高达220℃的最高系统操作温度的材料的组合可与诸如玻璃织物的材料组合,该材料能够在涂覆的玻璃织物的情况下承受高达600℃至650℃或高达750℃的温度,以产生能够在热逸溃事件中可能经历的至少10分钟内承受高达1000℃或2000℃的温度的材料。
包括无机颗粒或无机纤维的至少一个非织造层还可包括膨胀型材料。用于根据本发明的多层材料的可用的膨胀型材料包括但不限于未膨胀的蛭石矿石、经处理的未膨胀的蛭石矿石、部分脱水的蛭石矿石、可膨胀的石墨、可膨胀的石墨与经处理的或未处理的未膨胀的蛭石矿石的混合物、经加工的可膨胀的硅酸钠(例如可从美国明尼苏达州圣保罗的3M公司商购获得的EXPANTROL不溶解的硅酸钠)和它们的混合物。
包括无机颗粒或无机纤维的至少一个非织造层可具有介于0.1mm至20mm的范围内的厚度。在使用较薄材料的一些应用中,包括无机颗粒或无机纤维的至少一层可具有介于0.2mm至4.0mm(优选0.2mm至2.0mm)的范围内的厚度。包括无机颗粒或无机纤维的至少一层可具有介于100g/m2至2500g/m2(例如100g/m2至2000g/m2)的范围内的重量。
根据本发明的多层材料可包括至少一个稀松布层。通过防止纤维和/或颗粒从多层材料中脱落,稀松布层可用于改善对多层材料的处理。稀松布层可包括PET、PE、三聚氰胺、无机材料,诸如例如E-玻璃。该稀松布层还可以或作为替代方案包括无机或有机涂层。该稀松布层还可包括任何其它合适的材料。该稀松布层可被布置在包括无机颗粒或纤维的至少一层的旁边。在一些实施方案中,稀松布层可封装根据本发明的整个多层材料。
多层材料的总厚度可介于0.5mm与23mm之间。在使用较薄材料的一些应用中,多层材料的总厚度介于0.7mm与5mm之间。在一些实施方案中,多层材料将具有小于3mm(优选小于2mm)的总厚度。可取决于使用材料的应用来调整材料的厚度。如上所述,该材料可以是柔性的,以提高在组装过程中应用该材料的容易性。该材料也可以是可压缩的,以便提高在组装过程中应用该材料的容易性。
多层材料可包括至少一个无机织物与包括无机颗粒或无机纤维的至少一层之间的有机或无机粘合剂层。粘合剂可为有机的或无机的。粘合剂既可包括在无机织物中,也可包括在包括无机颗粒或无机纤维的层中。如果在多层材料中使用稀松布,则多层材料还可包括多层材料与稀松布之间的粘合剂。粘合剂可为有机的或无机的。该粘合剂既可包括在稀松布本身中,也可包括在用于多层材料的任何材料中。
示例性有机粘合剂可以是基于丙烯酸的粘合剂、基于环氧树脂的粘合剂或基于硅酮的粘合剂。有机粘合剂可以是绝缘粘合剂、导热粘合剂、阻燃粘合剂、导电粘合剂或具有导电和阻燃特性的组合的粘合剂。在层压中使用的示例性有机粘合剂可以是接触粘合剂、压敏(PSA)粘合剂、B级粘合剂或结构粘合剂。在示例性方面中,丙烯酸PSA可用于将热屏障复合材料的功能层粘结在一起。
基于粘合剂的总固体含量,本公开的示例性无机粘合剂包括至少99重量%(优选至少99.9重量%)的无机成分。在一些实施方案中,基于粘合剂的总固体含量,无机粘合剂包括100重量%的无机成分。无机粘合剂中的示例性无机成分可选自硅酸钠、硅酸锂、硅酸钾或它们的组合。
安置在水溶液中的无机硅酸盐当作为薄层施加在其它材料的表面上或之间时可用于粘结应用。无机硅酸盐溶液干燥,以形成坚韧的紧密粘合的无机粘结剂或膜,该坚韧的紧密粘合的无机粘结剂或膜不易燃,耐3000℉(1650°)的温度,坚固且刚性。应当注意的是,硅酸盐膜可以是湿敏的,这会导致降解。
无机硅酸钠是由不同比例的砂(SiO2)和苏打灰(Na2CO3)熔融而成的玻璃溶液。这些比例通常由SiO2/Na2O重量比定义。在一些实施方案中,示例性无机粘合剂可具有2.8至3.3的SiO2/Na2O重量比。
在一些实施方案中,无机粘合剂可以是改性无机粘合剂,基于无机粘合剂的总固体含量,该改性无机粘合剂包括小于1重量%的有机添加剂,以改善无机粘合剂的柔性。令人惊讶的是,基于无机粘合剂的总固体含量,包括小于1.0重量%、优选小于0.5重量%及更优选小于或等于0.1重量%的有机添加剂的本发明的改性无机粘合剂在不降低材料的火焰屏障性能的情况下显著改善了多层材料的性能(即,柔性)。改善的柔性允许在制造期间卷绕示例性多层材料以用于更方便的加工和递送以及在轮廓或非平面应用中的改进的安装。利用改性无机粘合剂的多层层压材料的改善的柔性使得材料能够在电池模块/组盖上的轮廓特征/形状周围弯曲。此外,发现使用改性无机粘合剂在暴露于高湿度之后提高粘合剂粘结强度,同时仍保持期望水平的火炬火焰性能。
在改性无机粘合剂中添加即使非常低浓度的有机添加剂(例如,基于粘合剂的总固体含量,小于1重量%,优选小于0.1重量%的有机添加剂),相对于基于无机粘合剂中的总固体使用100重量%的无机粘合剂形成的多层材料,将采用改性粘合剂的多层层压物的格利硬度(Gurley stiffness)降低至少10%,优选至少15%。
示例性有机添加剂包括糖、糖醇(诸如山梨糖醇和木糖醇)、甘油、多元醇、聚乙烯醇、丙烯酸聚合物和橡胶胶乳。
在一些实施方案中,聚合物添加剂为聚乙烯醇。在示例性方面中,聚乙烯醇为完全水解的聚乙烯醇。令人惊讶的是,基于无机粘合剂的总固体含量,将小于0.1重量%的聚乙烯醇结合到本发明的改性无机粘合剂中,在不降低材料的火焰屏障性能的情况下,显示出多层材料的性能(即,柔性)的显著改善。添加较高浓度的聚乙烯醇会导致改性无机粘合剂的不稳定性。例如,无机粘合剂中的0.5重量%和1重量%的聚乙烯醇、在混合后立即在溶液中形成的沉淀物和50重量%的聚乙烯醇混合物立即反应,并从可流动的水溶液形成凝胶。
有机或无机粘合剂可被直接涂覆到功能层中的一个功能层上,并且可任选地干燥,或可预成形为独立的层压膜粘合剂,该层压膜粘合剂可在接触下一个功能层之前被施加到功能层中的一个功能层的表面。在另选的方面中,功能层中的一个或多个功能层可呈具有已经安置在功能材料上的粘合剂层(例如压敏粘合剂层)的带的形式。
在一些应用中,示例性多层材料应为电绝缘材料。特别地,多层材料提供具有2kV(更优选大于3kV)的最小介电击穿电压的电绝缘可为有利的。
本发明还涉及一种具有至少一个电池单元和多层材料的可再充电的电能存储系统,该多层材料用作包括至少一个无机织物层和包括无机颗粒、无机纤维或它们的组合的至少一层的隔热屏障。
根据本发明的多层材料可例如用于确保配备有可再充电的电能存储系统的车辆的总体安全性。
多层材料可被布置在可再充电的电能存储系统中,使得无机织物面向至少一个电池单元或电池单元组。选择无机织物使得该无机织物对温度和其它冲击具有高耐受性,这是由于该其它冲击可能会在热逸溃事件期间发生。高抗喷砂性和/或高抗拉强度可以是这种高总体阻力的指示器。如果无机织物面向至少一个电池单元或电池单元组,则该织物可承受如上所述的热逸溃事件的主要阶段(即,爆炸性排放、具有颗粒喷射的高压气体排放和安静气体排放/发光火焰)。
在这种情境下,无机织物的主要功能是保护其它层免受这些阶段的热和机械冲击。在这种情境下,其它层的主要功能是提供隔热屏障,使得高温保持在可再充电的电能存储系统内,优选在缺陷电池或模块内。如果在车辆中使用可再充电的电能存储系统,则根据本发明的多层材料的主要目的是确保配备有可再充电的电能存储系统的车辆的总体安全性。
根据本发明的可再充电的电能存储系统可提供位于至少一个电池单元或模块与存储系统的盖之间的多层材料。多层材料可例如通过粘合剂、机械紧固件或其它的组合固定到盖。用于将多层材料附接到盖的示例性粘合剂可包括转移粘合剂、双层涂覆粘合剂带、热熔粘合剂或结构粘合剂。在一些方面中,示例性粘合剂可以是转移粘合剂、双层涂覆粘合剂带、热熔粘合剂或结构粘合剂的阻燃版本。在一些方面中,示例性多层材料可被放置在电池单元或模块与盖之间。在这种位置中,多层材料可用作盖的隔热屏障、火焰屏障和/或爆炸屏障,或保护盖和与盖相邻布置的任何系统、部件。
多层材料还可用作相邻电池单元、模块或电池组的隔热屏障或火焰屏障。该多层材料还可用作电池单元或电池组周围的任何电气部件(诸如例如电缆或母线)的隔热屏障或火焰屏障。当多层材料另外提供电绝缘特性时,还可防止例如由于变形或其它伤害而短路,例如不同电池系统周围的加热电绝缘。另一种可能性是布置多层材料,使得该多层材料覆盖至少一个电池单元的爆裂板。当然,该材料也可如此定位在可再充电的电能存储系统中以满足所有上述要求。如上所述,将根据本发明的多层材料定位成使得无机织物面向至少一个电池单元或模块可为有利的。
此外,根据本发明的多层材料的使用不限于在特定种类的可再充电的电能存储系统中的使用。该多层材料可例如用于包括棱形电池单元、袋式电池单元或圆柱形电池单元的可再充电的电能存储系统中。
已出人意料地发现,上述多层材料的用途可有效地用于使得在可再充电的电能存储系统内不发生外部火灾,并且不发生包含对可再充电的电能存储系统周围或外部的部分的热传递。如将在下面的示例性部分中描述的,测试已经显示出,根据本发明的多层材料能够承受第20号全球技术法规:关于电动车辆安全(EVS)的全球技术法规(也称为GTR 20)。
本发明的各种实施方案在本文下面有所描述并在附图中示出,其中类似的元件具有相同的参考标号。
图1示出根据本发明的多层材料1的剖视图。图1的多层材料包括附接到纤维垫3的无机织物层2,该纤维垫附接到任选的稀松布层4。稀松布层4和无机织物层2被布置在纤维垫3的任一侧上。无机织物层2、纤维垫3、稀松布层4可例如通过粘合剂彼此附接。粘合剂可为有机的或无机的粘合剂。
图2是可再充电的电能存储系统(REESS)5的示意图。该系统包括棱形电池单元6。棱柱形电池单元6各自包括爆裂板7,以例如在热逸溃事件的情况下,通过通风孔释放可能产生的过大压力。电池单元6被布置在模块外壳8中(其被示出为具有两个敞开的壁——一个前壁和一个侧壁——这些壁实际上是封闭的)。外壳提供盖9。多个模块外壳可组装成电池组(未示出)。
如上文已经描述,法规要求以不发生外部火灾的方式构建可再充电的能量存储系统。需要保护的一个区域是爆裂板7上方的区域。被布置在爆裂板上方的系统部分需要热屏障,以便避免电池的烧穿和系统外部的明火。根据本发明,图1中所示的多层材料1可被放置在电池单元6的顶部、在盖9下方的电池单元的爆裂板7上方,其中无机织物层2面向电池单元(未示出)。附加的多层材料可被放置在模块外壳8与电池组之间。
多层材料1也可被放置在电池单元6之间(未示出)。或者,该多层材料可被放置在电池单元6与模块外壳8的侧壁或底壁之间(未示出)。
在一些实施方案中,本文中所描述的防爆和耐热屏障制品可有效地减轻锂离子电池中热逸溃蔓延的影响。这些制品还可在需要保护人员或周围结构免受飞散制品和/或热波动的影响的诸如汽车、住宅、工业和航空航天应用的其它商业和工业应用中具有潜在用途。例如,所提供的防爆和耐热屏障制品可结合到沿或运输或建筑隔间结构或围绕运输或建筑隔间结构延伸的主要结构中,以保护用户和乘员。此类应用可包括电池模块、燃料箱和任何其它壳体或隔室周围的保护。
所提供的屏障制品通常包括芯层,该芯层包含多根纤维或联接至补充层或与补充层联接的阻燃泡沫。任选地,屏障制品可包括阻燃粘合剂。这些层可使用合适的粘结剂而被粘结到隔室壁或彼此粘结。部件、其构造和测试方法在以下的小节中进行描述。
实施例
测试方法
钉子穿透测试:
用于测试根据本发明的多层材料的钉子穿透测试如下进行:使用高容量(120Ah)棱柱形锂离子电池单元进行钉子穿透测试。一个单个的锂离子电池单元在两侧上覆盖有隔热硬石膏FERMACEL(可商购的板),以便保持电池单元内部的热量。这种夹层构造(FERMACELL板-电池单元-FERMACELL板)固定在两块坚固钢板之间的大型工作台上。具有5mm的直径的钢钉(X15CrNiSi25-21钉)以25mm/分钟的速度穿过钢板中的孔进入100%带电电池单元。
将待研究的屏障材料固定在尺寸为200mm乘200mm乘1.5mm的铝板处。该板以限定的距离(12mm和20mm)定位在电池单元的顶部上方。通过用具有屏障材料的铝板下方和上方的K型温度传感器测量温度来量化屏障材料的效率。将由PERTINAX酚醛片材制成的热屏蔽定位在板的顶侧上方,以便减少来自背侧的辐射,并且避免火焰回转加热。
当钉子穿透电池单元内部的隔板时,内部捷径开始热逸溃,随后温度升高并且电解质分解。在电池单元内部的压力超过几巴的极限之后,爆裂板制动,并且约600℃至750℃的热气体和颗粒在高压下吹出约45s至60s。在另外4分钟至5分钟内,热气体在减压下释放。
喷砂测试:
对于喷砂测试,使用可商购的喷砂柜。将样品材料安装到尺寸为100mm乘50mm的金属片材。将尺寸为80mm乘45mm的样品用遮蔽带固定在金属片材的所有侧面上。机柜内部的固定装置将样品保持在喷嘴前面的限定位置中。使用压缩空气将喷砂介质加速到目标上,直到在直径为4mm+/-1mm的区域中损坏试样为止。抛沙时间(以秒为单位)是样品对装载颗粒的空气的阻力的测量。在测试前,样品材料不热处理或在实验室窑炉(德国百利腾纳博热有限公司(Nabertherm GmBH of Lilienthal,Germany)的L24/11/P330)中在700℃下热处理5分钟。喷砂测试条件如下:样品距喷嘴的距离为65mm,喷嘴直径为4mm,具有70微米至110微米的粒径的211型玻璃微珠用作介质,并且冲击角介于90°与100°之间。
粘结强度
材料样品在环境温度和湿度下调节或在测试前暴露在95%相对湿度和23℃下至少16小时。通过将样品材料放置在密封的高湿度容器中(该容器由水和高架平台组成)以保持测试样品高于水位来实现湿度暴露。在可购自威廉斯设备公司(Williams ApparatusCo)(美国纽约州沃特敦市(Watertown,NY,USA))的实验室干燥罐上,在180℉(82℃)下对湿度暴露的样品进行干燥约10分钟,使得测试带片能够充分地粘合到样品上,以执行粘合粘结测试。
测试试样通过切割示例性多层示例性材料的5英寸(12.7cm)×1.5英寸(3.8cm)条带来制备。在每一条带的一端处,用长约1英寸(2.54cm)的实用刀小心地将织物和纸层隔开。将可购自3M公司(美国明尼苏达州圣保罗)的高粘结/强度带(3M 2960多用途胶带)施加在条带的隔开的每一端上方,并且将带折叠在带本身上,以形成可由测试固定装置的夹爪/夹具夹住的突片区域。为了最大化测试带片对样品端的粘合,将该样品端通过化学磺化剂国际热轧层压机(Chemsultants International Hot Roll Laminator)夹持器以100℉/38℃和40psi的压力以五英尺/分钟的速度运行。
然后以5.08cm/分钟的十字头速度将测试试样的2个片插入特温艾伯特(ThwingAlbert)QC-3A拉伸测试机万能测试机的夹爪/夹具中。对每个试样记录分离2层的力,并且根据四次重复测量计算平均粘结强度。
粘结保留率是湿老化粘结强度除以无湿老化粘结强度的比率,以百分比表示。
硬度
使用ASTM D-6125的格利硬度测试方法。将测试样品在环境条件下预处理。
拉伸测试:
使用IS0 4606和ASTM D-828的拉伸测试方法。对未热处理的样品进行拉伸测量。
埃尔门多夫(Elmendorf)撕裂强度
使用ASTM D-689的测试方法来确定撕裂强度。将测试样品在环境条件下预处理。
介电击穿电压
使用ASTM D-149的测试方法来确定介质击穿电压。将测试样品在环境条件下预处理。
火焰测试:
UL94 HB易燃性测试方法如下。如果材料未被刺穿,则样品通过测试。
火炬火焰测试A使用配备有MAP Pro燃料气缸的贝恩佐马蒂奇火炬TS-4000触发器进行,该MAP Pro燃料气缸在空气中提供2054℃/3730℉的火焰温度。将测试样品安装在距火焰2.75"(7cm)的固定距离处,其中金属夹附接在样品底部处,以帮助在测试期间稳定样品,并且暴露在火焰中连续10分钟,而不刺穿测试样品。在距火焰2.75"(7cm)的固定距离处测得的温度约为1000℃。
通过在距2054℃/3730℉火焰1"(2.54cm)的固定距离处连续10分钟测试样品而不刺穿测试样品来进行额外的更高温火炬火焰测试B。
材料
改性无机粘合剂的制备
通过在实验室混合机中在室温下将硅酸钠和所选择的有机添加剂进行组合来制备改性无机粘合剂。在表4中提供改性粘合剂组合物数据。
比较例1(CE1)
比较例1通过使用具有1.8mm大小的雾化头的3M宾格普赖一号喷枪(3M AccusprayONE Spray Gun)系统用云母盾D338S涂覆。将样品在80℃下干燥30分钟。云母层具有约30gsm的干重。样品构造在表1中表示,并且测试性能数据在表2中提供。
比较例2(CE2)
通过使用#30迈耶(Mayer)棒将RHOPLEX E-358丙烯酸乳液下拉并施加在15密耳CEQUIN I无机绝缘纸材料上来制备多层层压物。然后将TG 430/9KK-CS硅酸钙涂覆的玻璃织物放置在顶部,然后用4.54kg(10磅)滚轮滚压。然后将多层层压物在82℃(180℉)下干燥五分钟。样品构造在表4中表示,并且测试性能数据在表5中提供。
比较例3(CE3)
对15密耳CEQUIN I无机绝缘纸的样品进行1000℃火焰测试(火焰测试A)。样品不合格,其中火焰在45秒内烧穿。
比较例4(CE4)
对20密耳CEQUIN I无机绝缘纸的样品进行1000℃火焰测试(火焰测试A)。样品不合格,其中火焰在189秒内烧穿。
对20密耳CEQUIN I无机绝缘纸的样品进行2000℃火焰测试(火焰测试B)。样品不合格,其中火焰在19秒内烧穿。
比较例5(CE5)
对TG 430/9KK-CS硅酸钙涂覆的玻璃织物的样品进行1000℃火焰测试(火焰测试A)。样品不合格,其中火焰在9秒内烧穿。
对TG 430/9KK-CS硅酸钙涂覆的玻璃织物的样品进行2000℃火焰测试(火焰测试B)。样品不合格,其中火焰在3秒内烧穿。
测量TG 430/9KK-CS硅酸钙涂覆的玻璃织物的样品的介电击穿强度为0.39kV。
比较例6(CE6)
TW-600-13-100玄武岩织物的样品通过了1000℃火焰测试(火焰测试A),但未通过2000℃火焰测试(火焰测试B),其中火焰在5秒内烧穿。
测量TW-600-13-100玄武岩织物的样品的介电击穿强度为0.18kV。
实施例1至实施例3(EX1至EX3)
实施例1至实施例3的多层层压物通过将3M显示器安装喷涂粘合剂喷涂到织物上来制备。将纤维垫放置在织物的顶部,然后用4.54kg(10磅)滚轮滚压。样品构造在表1中表示,并且测试性能数据在表2中提供。
实施例4至实施例6(EX4至EX6)
实施例4至实施例6的多层层压物通过使用#30迈耶棒将硅酸钠粘合剂下拉并施加到CEQUIN I无机绝缘纸材料上来制备。然后将无机织物层放置在无机粘合剂层的顶部,然后用4.54kg(10磅)滚轮滚压。然后将多层层压物在82℃(180℉)下干燥五分钟。例如,EX6,使用#30迈耶棒将/>硅酸钠粘合剂的第二层施加到CEQUIN I无机绝缘纸的另一侧。然后将第二无机织物层放置在第二无机粘合剂层的顶部,用4.54kg(10磅)滚轮滚压,并且在82℃(180℉)下干燥五分钟。样品构造在表1中表示,所选择的物理、机械和电气特性在表2中提供,并且热/火焰屏障测试性能数据在表3中提供。
表1:用于实施例1至实施例6和比较例的样品构造
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表2:示例性材料的物理、机械和电气特性
#数据获自产品数据表
表3:实施例1至实施例6和比较例CE1的方法和结果
NM—未测量
比较例CE3至比较例CE5显示出,单独的织物和纸层本身不能通过火炬火焰测试(火焰测试A/火焰测试B)。比较例CE6通过了火焰测试A,但未通过火焰测试B,其中在5秒内在织物上形成孔。如前所述,示例性屏障材料也需要为电绝缘的,并且玄武岩织物的低介电击穿强度使得其不适合单独用作用于规定应用的火焰屏障材料。将无机纸层与涂覆的玻璃织物层用丙烯酸粘合剂组合的比较例CE2也未能通过火炬火焰测试(火焰测试A/火焰测试B——参见表5)。相反,无机织物层用无机粘合剂附接到无机纸层的本发明的示例性多层材料提供了必要的特性平衡,从而允许准许材料被用作汽车或其它电气化运输应用和固定储能应用中的屏障材料。
对于实施例EX3和实施例EX5,在机器方向和横幅方向上测量了格利硬度数据。Ex3的格利硬度在机器方向上被测量为16,894mg,并且在横幅方向上被测量为12,812mg。EX5的格利硬度在机器方向上被测量为28,804mg,并且在横幅方向上被测量为18,669mg。将这些值与CE2的格利硬度数据(在机器方向上为11,516mg,并且在横幅方向上为7,023mg)进行比较,说明了使用无机粘合剂将示例性多层材料的层层压在一起的刚性效应。
虽然实施例5经受住了较低温度的火炬火焰测试A,但该实施例未能经受住较高温度的火炬火焰测试B。然而,意外的是,添加额外的织物层使得织物层位于无机基纸层(CEQUIN)的两侧上允许实施例6层压物通过更高温度的火炬火焰B测试。
实施例7至实施例13(EX7至EX13)
实施例7至实施例13的多层层压物通过使用#30迈耶棒将无机或改性无机粘合剂下拉并施加到20密耳CEQUIN I无机绝缘纸材料上来制备。然后,将一层TG 430玻璃布织物放置在顶部,并且用4.54kg(10磅)滚轮滚压。将多层层压物在180℉(82℃)下干燥5分钟。实施例14按照与实施例EX7至实施例EX13相同的程序制备,不同之处在于用KSS无机粘合剂代替TG430玻璃布织物将SC2025硅酸钙涂覆的纤维玻璃织物粘结到20密耳CEQUIN I无机绝缘纸材料。样品构造在表4中表示,并且测试性能数据在表5中提供。
表4:用于实施例7至实施例14和比较例的样品构造
*重量百分比值是基于无机粘合剂的总固体含量
实施例15至实施例16(EX15至EX16)
实施例15通过使用#30迈耶棒将第一100重量%KSS无机粘合剂层下拉并施加到20密耳CeQUIN I无机绝缘纸上来制备。然后将第一层TG 430玻璃布织物放置在第一无机粘合剂层顶部,并且用4.54kg(10磅)滚轮滚压。将多层层压物在180℉(82℃)下干燥5分钟。接下来,KSS粘合剂的第二层使用#30迈耶棒施加到CEQUIN I无机绝缘纸的另一侧。然后将第二无机TG 430玻璃布织物层放置在第二无机粘合剂层的顶部,用4.54kg(10磅)滚轮滚压,并且在82℃(180℉)下干燥五分钟。所得多层层压物的基重为1415.9gsm,并且总样品厚度为1.48mm。测试性能数据在表5中提供。
实施例16通过使用#30迈耶棒将包括99.96重量%KSS和0.04重量%SELVOL 9-325的第一改性无机粘合剂层下拉并施加到20密耳CeQUIN I无机绝缘纸的第一侧上来制备。然后将第一层TG 430玻璃布织物放置在无机粘合剂层顶部,并且用4.54kg(10磅)滚轮滚压。将多层层压物在180℉(82℃)下干燥5分钟。接下来,第二改性无机粘合剂层使用#30迈耶棒施加到CEQUIN I无机绝缘纸的另一侧。然后将第二无机TG 430玻璃布织物层放置在第二无机粘合剂层的顶部,用4.54kg(10磅)滚轮滚压,并且在82℃(180℉)下干燥五分钟。所得多层层压物的基重为1345.4gsm,并且总样品厚度为1.43mm。测试性能数据在表5中提供。
表5:实施例EX7至实施例EX16的测试方法和结果
1通过与实施例EX7的多层材料的硬度进行比较得出的相对硬度
2通过与实施例EX14的多层材料的硬度进行比较得出的相对硬度
甘油是已知的硅酸盐粘合剂的增塑剂,基于无机粘合剂的总固体含量,该甘油的浓度范围为1重量%至5重量%。然而,与利用具有0.04重量%聚乙烯醇的改性无机粘合剂的EX8的多层材料相比,利用具有5重量%甘油的改性无机粘合剂的EX9的多层材料在更高的装载下显示出小得多的硬度降低(2.7%与17.1%)。添加5重量%甘油还降低高湿度暴露后的粘结强度恢复保留率。
在EX10中评价了对无机粘合剂的丙烯酸改性。丙烯酸粘合剂通常用作多层层压构造中的层压粘合剂。与利用具有0.04重量%聚乙烯醇的改性无机粘合剂的EX8的多层材料相比,对无机粘合剂进行的10重量%丙烯酸粘结剂改性产生了相当的层压物硬度降低。然而,在高湿度暴露后,在暴露于火焰的约七分钟时,10重量%丙烯酸改性K硅酸钠层压物未通过1000℃火炬火焰测试(火炬测试A)。
用实施例EX15和实施例EX16进行了简单的心轴弯曲测试。当缠绕在6英寸心轴上时,视觉上和触觉上观察到Ex15多层材料扣合,而EX16多层材料平滑地缠绕在6英寸心轴周围。
由于各种电池单元、电池模块和电池单元组设计,因此取决于该电池单元、电池模块和电池单元组设计如何结合到设计中,具有各种性能特性的材料可以适用。
以上获得专利证书的申请中所有引用的参考文献、专利和专利申请以一致的方式全文以引用方式并入本文中。在并入的参考文献部分与本申请之间存在不一致或矛盾的情况下,应以前述说明中的信息为准。为了使本领域的普通技术人员能够实践受权利要求书保护的本公开而给出的前述说明不应理解为是对本公开范围的限制,本公开的范围由权利要求书及其所有等同形式限定。
Claims (18)
1.一种用于在可再充电的电能存储系统中用作隔热屏障的多层材料,多层材料包括:
至少一个无机织物层;
包括无机颗粒和无机纤维的非织造层;以及
无机粘合剂层,所述无机粘合剂层位于所述至少一个无机织物层与所述非织造层之间,
所述无机粘合剂层包括:
以至少99重量%的量存在的无机成分,和
以至少0.01重量%且小于0.1重量%的量存在的有机添加剂,其中所述无机成分选自硅酸钠、硅酸锂、硅酸钾或它们的组合,所述有机添加剂是聚乙烯醇,
其中重量%基于所述无机粘合剂层的总固体含量,以及
其中所述至少一个无机织物层与所述非织造层经由所述无机粘合剂层粘结。
2.根据权利要求1所述的多层材料,其中所述无机织物包括E-玻璃纤维、R-玻璃纤维、ECR-玻璃纤维、玄武岩纤维、陶瓷纤维、硅酸盐纤维、钢丝或它们的组合。
3.根据权利要求1所述的多层材料,其中所述无机织物是玻璃纤维织物。
4.根据权利要求3所述的多层材料,其中所述玻璃纤维织物涂覆有硅酸钙涂层。
5.根据权利要求1所述的多层材料,其中所述非织造层包括E-玻璃纤维、S-玻璃纤维、R-玻璃纤维、ECR-玻璃纤维、玄武岩纤维、陶瓷纤维、多晶纤维或它们的组合。
6.根据权利要求5所述的多层材料,其中所述陶瓷纤维包括氧化铝纤维、二氧化硅纤维或它们的组合。
7.根据权利要求1所述的多层材料,其中所述非织造层包括无机纸或无机板。
8.根据权利要求1所述的多层材料,其中所述非织造层是包括玻璃纤维和微纤维、无机颗粒和有机粘合剂的无机绝缘纸。
9.一种用于在可再充电的电能存储系统中用作隔热屏障的多层材料,所述多层材料包括:
无机纸,所述无机纸包括:
玻璃纤维和微纤维、
无机颗粒、和
有机粘结剂,
经过表面涂覆的玻璃纤维织物层,和
无机粘合剂层,所述无机粘合剂层位于所述无机纸与所述经过表面涂覆的玻璃纤维织物层之间,所述无机粘合剂层包括:
以至少99重量%的量存在的无机成分,和
以至少0.01重量%且小于0.1重量%的量存在的有机添加剂,
所述无机成分选自硅酸钠、硅酸锂、硅酸钾或它们的组合,所述有机添加剂是聚乙烯醇,
其中重量%基于所述无机粘合剂层的总固体含量,以及
其中所述经过表面涂覆的玻璃纤维织物层经由所述无机粘合剂层粘结至所述无机纸的主表面。
10.根据权利要求9所述的多层材料,其中所述玻璃纤维织物涂覆有硅酸钙涂层。
11.根据权利要求9所述的多层材料,其中所述经过表面涂覆的玻璃纤维织物层具有介于0.3mm至3mm的范围内的厚度和超过400g/m2的基重。
12.根据权利要求9所述的多层材料,其中所述多层材料具有0.7mm至5mm的总厚度。
13.根据权利要求9所述的多层材料,还包括通过所述无机粘合剂粘结到所述无机纸的暴露的表面的第二织物层。
14.一种用于在可再充电的电能存储系统中用作隔热屏障的多层材料,所述多层材料包括:
第一无机织物层;
包括无机颗粒和无机纤维的非织造层;和
第二无机织物层;以及
第一无机粘合剂层和第二无机粘合剂层,所述第一无机粘合剂层所述第二无机粘合剂层包括:
以至少99重量%的量存在的无机成分,和
以至少0.01重量%且小于0.1重量%的量存在的有机添加剂,
所述无机成分选自硅酸钠、硅酸锂、硅酸钾或它们的组合,所述有机添加剂是聚乙烯醇,
其中重量%基于所述无机粘合剂层的总固体含量,
其中所述第一无机粘合剂层位于所述第一无机织物层与所述非织造层之间,以及所述第一无机粘合剂层将所述第一无机织物层粘结至所述非织造层的第一主表面处,以及
其中所述第二无机粘合剂层位于所述第二无机织物层与所述非织造层之间,以及所述第二无机粘合剂层将所述第二无机织物层粘结至所述非织造层的第二主表面处。
15.一种可再充电的电能存储系统,包括:
至少一个电池单元,和
根据权利要求1所述的多层材料,其中所述多层材料在热逸溃事件期间提供火焰屏障。
16.根据权利要求15所述的可再充电的电能存储系统,其中所述多层材料被布置有使所述无机织物层面向所述至少一个电池单元。
17.根据权利要求15或16所述的可再充电的电能存储系统,其中所述多层材料定位在所述至少一个电池单元与所述存储系统的盖之间。
18.根据权利要求17所述的可再充电的电能存储系统,其中所述多层材料用粘合剂附接到所述盖。
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