CN116574488B - 一种高导热半固态相变隔热复合材料及其制备方法和应用 - Google Patents
一种高导热半固态相变隔热复合材料及其制备方法和应用 Download PDFInfo
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- 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
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/659—Means for temperature control structurally associated with the cells by heat storage or buffering, e.g. heat capacity or liquid-solid phase changes or transition
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
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Abstract
本发明涉及电池安全技术领域,特别是涉及一种电池模组用热蔓延防护用高导热相变隔热复合材料及其制备方法。本发明一种高导热半固态相变隔热复合材料,包括骨架支撑材料、相变材料、导热材料和绝缘封装材料;且相变材料和导热材料固定于骨架支撑材料中形成复合材料封装于绝缘封装材料,导热材料通过原位复合法或掺杂复合法加入到复合材料中。本发明提供了一种高导热半固态相变隔热复合材料,该材料在电池模组内对热失控电芯产生的热蔓延具有很好的抑制和延缓作用。
Description
技术领域
本发明涉及电池安全技术领域,特别是涉及一种电池模组用热蔓延防护用高导热相变隔热复合材料及其制备方法。
背景技术
随着电动汽车的快速发展,电动汽车动力电池***的安全问题受到越来越多的重视。在整个电动汽车安全事故中,一般最初是由单一电芯热失控引起。电芯热失控后短时间内释放出大量热量,传递到相邻电芯上引起温度上升而发生热失控,最终热蔓延到整个模组内电芯甚至于整个电池包,从而造成灾难性事故。因此,在任一电芯发生热失控时,抑制或者延缓其产生的热量蔓延到相邻电芯上对保证乘客生命财产安全具有重要意义。
目前,对于动力电池模组内热蔓延抑制的隔热材料非常多,各种陶瓷纤维、陶瓷化硅胶材料、气凝胶等等,已经被广泛运用于模组内电芯热失控热蔓延抑制或延缓作用。上述材料在电池热失控时,将失控电池释放的热量依靠自身优异的隔热性能起到延缓热传递作用,从而给乘客逃生提供宝贵的时间。但是,从热守恒原理来看,热失控电芯产生的能量只是被限制在电池模组内,通过隔热材料延缓其传递时间,最终随着时间的延长还是会引起其他电芯的热失控而造成电池包的热蔓延。为了在现有传统隔热材料的基础上,进一步延缓热蔓延时间或者抑制热蔓延,有研究学者将相变材料引入到隔热材料中,在热失控时,通过隔热材料的隔热和相变材料相变消耗能量。
SK新技术株式会社的金泰日等在专利CN114006105A中设计了一种吸热防火壁隔热材料,该材料包括由相变材料组成的吸热层和纤维组成的隔热层构成。在电池热失控中,起到较好的效果。但是该设计采用三明治结构,采用两层纤维层和一层相变材料层,且由于电池模组内空间的限制,给防火墙留的空间很小,相变材料量引入受到限制,对热失控热量的消耗量还有待进一步提高。
为了解决该问题,清华大学冯旭宁等在专利CN113506935A中提出一种新的用于电池模组防止热蔓延的隔热材料,其采用硅溶胶、阻燃剂和相变材料与纤维基材复合,然后用绝缘膜进行包覆制备复合材料。该复合材料具有很高的相变焓值,解决了相变材料量的问题,在电池模组内热蔓延上起到较好的结果。但是该设计中,相变材料与基材之间浸泡在一起,流动的相变材料在封装中带来很大的麻烦,同时在电池模组组装的过程中,流动液态相变材料受压后,容易挤破绝缘膜而流到模组内,引起电芯短路而造成更大的事故。因此,如此在不影响电池模组内比能量和安全的情况下,开发的抑制电池模组热蔓延的复合材料。
发明内容
本发明希望提供一种高导热半固态相变隔热复合材料,该材料在电池模组内对热失控电芯产生的热蔓延具有很好的抑制和延缓作用,具体方案如下:
一种高导热半固态相变隔热复合材料,包括骨架支撑材料、相变材料、导热材料和绝缘封装材料;且相变材料和导热材料固定于骨架支撑材料中形成复合材料封装于绝缘封装材料,导热材料通过原位复合法或掺杂复合法加入到复合材料中。
所述的骨架支撑材料为厚度为1mm-5mm的纤维材料,包括氧化锆纤维、莫来石纤维、氧化硅纤维、氧化铝纤维、岩棉、硅酸铝纤维或预氧丝纤维,纤维孔隙率为80%-90%。
所述的相变材料包括硅油、硅溶胶、铝溶胶、锆溶胶、硅铝溶胶、硅锆溶胶、铝锆溶胶、硅铝锆溶胶、石蜡、六水氯化钙、十水硫酸钠、十水磷酸氢钠、八水氢氧化钡或六水氯化镁中的一种或多种。优选采用溶胶与无机相变材料的复合杂化形式,硅溶胶是为了后续形成半固态凝胶所用原料前驱体,杂化多种相变材料,是为了保证更高的相变焓值。
所述绝缘封装材料为铝塑膜、尼龙膜、聚酰亚胺膜、聚丙烯膜、聚乙烯膜或聚氯乙烯膜中的一种或多种,且厚度为0.05-0.25mm。
原位复合法所用导热材料为铜粉、银粉、炭黑、石墨烯、氮化铝、氮化硼、氮化硅、氧化镁中的一种或多种,导热材料粒径为50-100μm;掺杂复合法所用导热材料为铁网、铝网、铜网、碳纤维、碳纳米管中的一种或多种,目数为100-200目,厚度为0.1-0.5mm。
导热材料通过原位复合法加入到复合材料时,具体步骤如下:将相变材料、红外遮蔽剂、阻燃剂和导热材料,搅拌均匀得到溶液,并调控pH至4.2-5.8,然后将骨架支撑材料浸渍于溶液中,20~70℃下保温,取出复合材料,用封装用绝缘膜封装。
导热材料通过掺杂复合法加入到复合材料时,具体步骤如下:将相变材料、红外遮蔽剂和阻燃剂搅拌均匀,并调控pH至4.2-5.8,得到溶液,将复合导热材料的骨架支撑材料浸渍于溶液中,20~70℃下保温,取出复合材料,用封装用绝缘膜封装。
所述红外遮蔽剂为二氧化钛、碳化硅、碳粉和六钛酸钾晶须中的一种或多种。
所述阻燃剂为磷酸二氢铵、三(2,3-二溴丙基)磷酸酯、硫代磷酸三异氰酸酯、尿素、五硼酸铵、碳酸氢铵或氰尿酸三聚氰胺中的一种或多种。
所述的高导热半固态相变隔热复合材料应用于电池模组。
本发明与现有技术不同之处在于,本发明为高导热半固态相变隔热复合材料,便于封装和解决破包风险。同时为了提高相变材料之间的热传导,本发明引入导热物质保证复合材料在热失控时能将热量迅速扩散到相变材料上,在短时间内通过相变材料相变过程将热量转移出电池模组内。同时,本发明在相变材料作用消耗后,多孔隔热材料还能起到较好的隔热效果。通过相变热转移和热量传递的抑制,本发明的相变隔热材料在电池模组内对热失控电芯产生的热蔓延具有很好的抑制和延缓作用。
本发明一种半固态相变隔热复合材料,相变材料以凝胶的形式固定于骨架支撑材料中形成复合材料封装于绝缘封装材料中。与之前技术不同之处在于,本发明中将相变材料通过喷淋或浸涂的方式使基体材料(骨架支撑材料)浸满相变材料,通过调节PH值形成凝胶,凝胶中含有连续的纳米或微米孔洞,把相变材料束缚在孔洞中,便于加工封装和解决破包风险。同时,该设计的相变隔热材料在相变材料作用消耗后,基体材料和凝胶之间形成的多孔隔热材料还能起到较好的隔热效果。在热失控过程中,通过相变材料快速将失控电芯产生的热量转移出模组内,同时基体材料和凝胶高温干燥后形成的多孔隔热材料能有效阻隔失控电芯产生的热量传递到相邻电芯电芯。本发明涉及的半固态相变隔热材料,在散热和隔热双重作用下,能有效抑制和延缓电池模组内热失控电芯产生的热蔓延。
附图说明
图1为本发明一种高导热半固态相变隔热复合材料封装实物图。
图2为实施例与对比例气凝胶热烧蚀曲线图。
具体实施方式
实施例1
本实施例以硅酸铝纤维为基体,将50g硅溶胶分散于100g水中,然后依次加入5g二氧化钛粉、3g磷酸二氢铵、2g碳酸氢铵和2g碳粉,搅拌均匀,并用稀硫酸调控pH至4.5,得到溶液。然后将硅酸铝纤维浸渍于溶液中,60℃下保温30min,取出复合材料,用0.15mm厚铝塑膜封装,得到相变复合材料成品,密度为1.2g/cm3。
该实施例采用磷酸二氢铵,氮磷协效阻燃机理能够凝聚相阻燃和气相阻燃的综合作用,具体表现为阻燃剂受热分解吸热,分解生成磷酸,聚磷酸等无机酸,可在被阻燃基材表面形成一层不挥发性的保护膜,隔绝了空气,同时受热后易放出氨气,氮气,水蒸气和深度氮氧化物等不燃性气体,这些气体阻断了氧的供应,并与阻燃剂分解吸热一起带走大部分热量,极大降低了被阻燃基材表面温度;大部分磷的氧化物与氮的化合物形成P-N-P,P-O-P,通过P-C等化学键形成一种焦化碳结构的糊状物留在剩碳中,产生覆盖作用,中断燃烧的连锁反应,从而有力的抑制基材的燃烧,另外基材燃烧时有PO形成,它可与火焰区域中的H,HO自由基结合,起到抑制火焰的作用。
实施例2
本实施例以玻璃纤维为基体,将50g硅-铝复合溶胶分散于100g水中,然后依次加入10g碳化硅粉、8g五硼酸铵和0.5g铜粉,搅拌均匀,并用稀硫酸调控pH至5.0,得到溶液。然后将玻璃纤维浸渍于溶液中,60℃下保温30min,取出复合材料,用0.15mm厚聚酰亚胺封装,得到相变复合材料成品,密度为1.1g/cm3。
实施例3
本实施例以硅酸铝纤维为基体,预先复合0.15mm铁网。将50g硅-锆复合溶胶分散于100g水中,然后依次加入5g六钛酸钾晶须和5g氰尿酸三聚氰胺,搅拌均匀,并用稀硫酸调控pH至4.5,得到溶液。然后将复合铁网的硅酸铝纤维浸渍于溶液中,60℃下保温30min,取出复合材料,用0.15mm厚聚丙烯膜封装,得到相变复合材料成品,密度为1.15g/cm3。
对比例1
采用市面上相同厚度陶瓷纤维气凝胶、玻璃纤维气凝胶和预氧丝气凝胶作为对比样品,进行热烧蚀实验。
表1实施例和对比例热烧蚀实验数据一览表
从表1可以看出,相同厚度的玻纤气凝胶和预氧丝气凝胶,在1100℃左右热烧蚀过程中,样品直接烧穿。本发明的相变隔热材料和陶纤气凝胶未烧穿,对比两者温差发现,本发明的相变隔热材料隔热效果要优于同等厚度的气凝胶隔热材料。
实施例4-6(以下实施例用于研究pH对于本申请的影响)
实施例4-6其他均与实施例1相同,除了pH不同,具体情况如下表:
表2实施例和不同pH对比例热烧蚀实验数据一览表
实施例7-10(以下实施例用于研究温度对于本申请的影响)
表3实施例和不同温度对比例热烧蚀实验数据一览表
上述实施例仅仅是为清楚地说明所作的工作,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其他不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (4)
1.一种高导热半固态相变隔热复合材料的制备方法,其特征在于:
导热材料通过原位复合法加入到复合材料时,具体步骤如下:将相变材料、红外遮蔽剂、阻燃剂和导热材料,搅拌均匀得到溶液,并调控pH至4.2-5.8,然后将骨架支撑材料浸渍于溶液中,20~70℃下保温,取出复合材料,用封装用绝缘膜封装;
所述一种高导热半固态相变隔热复合材料,包括骨架支撑材料、相变材料、导热材料和绝缘封装材料;且相变材料和导热材料固定于骨架支撑材料中形成复合材料封装于绝缘封装材料,导热材料通过原位复合法加入到复合材料中;所述的骨架支撑材料为厚度为1mm-5mm的硅酸铝纤维,纤维孔隙率为80%-90%;所述的相变材料为硅溶胶或硅铝溶胶;所述绝缘封装材料为铝塑膜、尼龙膜、聚酰亚胺膜、聚丙烯膜、聚乙烯膜或聚氯乙烯膜中的一种或多种,且厚度为0.05-0.25mm;原位复合法所用导热材料为铜粉,粒径为50-100μm。
2.如权利要求1所述的高导热半固态相变隔热复合材料的制备方法,其特征在于:所述红外遮蔽剂为二氧化钛、碳化硅、碳粉和六钛酸钾晶须中的一种或多种。
3.如权利要求1所述的高导热半固态相变隔热复合材料的制备方法,其特征在于:所述阻燃剂为磷酸二氢铵、三(2,3-二溴丙基)磷酸酯、硫代磷酸三异氰酸酯、尿素、五硼酸铵、碳酸氢铵或氰尿酸三聚氰胺中的一种或多种。
4.一种如权利要求1所述的高导热半固态相变隔热复合材料的制备方法制备得到的高导热半固态相变隔热复合材料应用于电池模组的用途。
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CN113998983A (zh) * | 2021-10-28 | 2022-02-01 | 中国电子科技集团公司第十八研究所 | 一种与电池壳体一体成型的复合保温材料及其制备工艺 |
CN115000590A (zh) * | 2022-06-29 | 2022-09-02 | 巩义市泛锐熠辉复合材料有限公司 | 一种具备散热功能的气凝胶产品、制备方法及应用 |
CN115353865A (zh) * | 2022-08-12 | 2022-11-18 | 广东工业大学 | 一种具有高导热和高强度的相变材料、制备方法及其制备的电池支架和电池热管理装置 |
CN115851240A (zh) * | 2022-12-21 | 2023-03-28 | 杭州英诺克新材料有限公司 | 一种基于碳骨架的绝缘高焓值高导热材料的制备方法 |
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