CN113707940A - 具有多机理阻燃功能的固态电池阻燃防爆电解质 - Google Patents
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Abstract
本发明涉及具有多机理阻燃功能的固态电池阻燃防爆电解质,把功能更强而且多机理的阻燃材料,用微胶囊包覆的办法,把多机理阻燃材料,包裹到锂电池工作温度下稳定微胶囊阻复合阻燃材料中,微胶囊囊心材料采用红磷材料。微胶囊本身具有良好的电解液兼容性和流动性,添加组分较多时,也不会影响电解液的性能。当出现满电针刺等热失控情况时,微胶囊破裂,把包裹在其中的复合阻燃材料释放到电解液中,快速阻燃。
Description
技术领域
本发明涉及具有多机理阻燃功能的固态电池阻燃防爆电解质,属于锂电池技术领域。
背景技术
目前,锂电池的阻燃防爆问题一直是一个焦点问题。阻燃防爆的一个关健是对现有的锂电池电解液改成固态电池电解质。但液态电解液改成固态电池质后,并不能彻底解决阻燃问题。一个重要的原因是,现有的固态电解质材料,都有界面问题,现在解决方案是将聚合物和无机固态电解质做一定的复合,或者保持一定比例的液体电解液解决界面问题,目前固态电解质的含液量或含有机噶分子溶剂及电解液添加剂含量都大大超过10%,这些高分子聚合物和有机溶剂分子,都会在满电针刺或热失控时出现火花,而按汽车车规电池的检测标准GB16949 -38031的满电针刺试验的要求,锂电池针刺时,要一个火星都没有,才算通过,根据中车北检中心北京205所检测实验室的统计数据,目前三元单体电芯,在不加外部防火的情况下,还没有能通过满电针刺检测的。传统的提高电解液阻燃性的方法是添加阻燃剂,但这些阻燃剂的添加量都很小,否则严重劣化锂电池的电性能。以常用的电解液阻燃添加剂TPP为例,添加量必须小于3%,否则影响锂电池电性能,而现有电池的电解液总量是有限的,添加的TPP阻燃剂的总量就很低,达不到策较好的灭火效果。以国际标准圆柱型锂离子电池特别是18650圆柱型锂离子电池为例,一般是由正极片、负极片、隔膜、电解液(或固态电解质)、外壳组成。 外壳由圆柱型的壳体、壳体顶端的盖帽构成。电池组装好后,注入电解液,电解液的注液量一般为5-6克,如果添加TPP阻燃剂,添加量3%仅为0.18克,而三元锂电池满电针刺的能量相当于7.9克TNT炸药,所以现有的通过电解液中添加阻燃剂的方法,不能通过满电针刺。中国专利CN200610170590.8,也有添加三氧化二铝粉末等来阻燃的研究。但三氧化二铝粉末的添加量也有问题,如果添加过多,锂电池本身阻抗会变大,导致电池不能工作,添加量不足,又不能达到车规电池16949 38031的满电针刺的要求。
发明内容
本发明发明了一种多机理阻燃功能的固态电池阻燃防爆电解质,对锂电池的阻燃和防爆问题,本发明解决的技术问题和方法克服现有的缺陷的方法是,把功能更强而且多机理的阻燃材料,用微胶囊包覆的办法,把多机理阻燃材料,包裹到锂电池工作温度下稳定微胶囊阻复合阻燃材料中。微胶囊本身具有良好的电解液兼容性和流动性,添加组分较多时,也不会影响电解液的性能。当出现满电针刺等热失控情况时,微胶囊破裂,把包裹在其中的复合阻燃材料释放到电解液中,快速阻燃。
本发明的微胶囊包裹的用于电解液的复合阻燃剂,不同于塑料工业中有一定应用的微胶囊阻燃剂。一个明显不同之处是,本发明的用于锂电池电解液的微胶囊复合阻燃剂,微胶囊的包裹层,选用了和锂电池电解液兼容的包覆层。用于高分子领域的微胶囊包覆阻燃剂,还没有用于锂电池电解液的报道。另一个明显的不同之处是,本发明的用于锂电池电解液的微胶囊复合阻燃剂,复合阻燃剂的选择上,不只是考虑阻止燃烧的效果,而且特别考虑阻燃剂如果破坏电解液的功能,使得电池的储存能量丧失,这样能比单纯用于高分子的微胶囊阻燃剂有更好的效果。
具体实施方式
本发明方法的一个实施例是,对复合阻燃材料采用和锂电池电解液兼容的包裹层,该包裹层在锂电池工作温度下稳定,在发生满电针刺等热失控高温时,包覆层打开,把包裹中的复合阻燃剂释放到电解液中。
本发明方法的一个实施例是包覆层采用和电解液兼容的聚合物材料。
一个实施例是,导离子的聚合物为聚偏氯乙烯(PVDF)、聚偏氯乙烯-六氟丙烯(PVDF- HFP)、聚四氟乙烯(PTFE)、聚氧化乙烯、聚酯、聚酰胺、聚酰胺酰亚胺、聚甲基丙烯酸甲酯、聚 碳酸酯、羧甲基纤维素、苯乙烯-丁二烯共聚物、聚丙烯酸、聚丙烯酸锂、聚丙烯腈、羧甲基纤 维素钠、丁苯橡胶或它们的任意组合。优选的,导离子的聚合物是密胺树脂材料、氢氧化镁和聚乙烯(PE)材料为囊材。
本发明的一个实施例是,囊心材料,由阻燃剂及阻燃剂的组合构成,按照分子结构的差异,包含的阻燃剂分为有机阻燃剂和无机阻燃剂两大类。 其中,有机阻燃剂多为卤系阻燃剂、有机磷、有机硅和有机硼等。虽然有机阻燃剂的阻燃效果较好,但其热分解产物往往具有一定的毒性,对人体和环境的危害较大。 相比之下,无机阻燃剂具有低毒、环 保、价格 低 廉 等 优 点 ,在近些年的研究中广受关注。 大多数无机阻燃剂属添加型,主要包括氢氧化物、无机磷系化合物、硼酸盐、氧化锑、钼化合物及状硅酸盐。优选的,本发明的一个实施例是,微胶囊囊心材料采用红磷材料。优选的,红磷材料及其外包的微胶囊的粒径为2500目。微胶囊的添加量根据锂电池的能量可以调节。
本发明的微胶囊包裹的阻燃剂的添加量在电解液中的占比为1%-30%。优选的,微胶囊包覆的阻燃剂的占比为7%-15%。更优选的,占比为7%。 本发明的微胶囊的囊材可以被本领域的工程师从盖得化工网上采购。红磷材料,可以从广东省清远市日光东成化工有限公司购买。购买的牌号市FRP系列的2500目红磷阻燃剂。该系列产品已经有一定厚度的包覆层,可以用本领域化工技术人员采用共沉淀法制备。包覆红磷制备的最优工艺条件:反应温度80℃,搅拌速度300r/min,氢氧化钠溶液浓度1mol/L,微胶囊红磷中氢氧化镁的比例30%。注意共沉淀的搅拌过程中,搅拌速度不能过快,在未包裹好前,如果搅拌摩擦过快,红磷材料可能爆炸。本发明的微胶囊包裹的阻燃材料,在遇到到高温时,有多种机理的阻燃协同作用,高温时,包裹层的微胶囊破裂,包裹的材料氢氧化镁,分解成氧化镁和水,该反应是吸热反应,能吸收热失控的能量。分解产物,氧化镁,可以和微胶囊的囊心材料红磷共同发生阻燃协同作用,和电解液中的有机物一起形成致密的碳层,起到隔绝空气和阻燃的作用。氧化镁本身是绝热材料,也起到阻燃的作用。氢氧化镁吸热分接的产物水分子,可以和电解液中的锂盐反用,破坏了锂电池电解液的锂离子穿梭桥梁作用,降低了锂电池的能量。这样进一步提高了锂电池的阻燃强度。本发明的方法,除了对液体电解液锂电池可以应用,对固态电解质的锂电池也可以应用。一个实施例是,对原位聚合的聚合物固态电解质,可以把本发明的微胶囊包裹阻燃剂的产品,先提前和聚合物固态电解质混合,再原位聚合。也可以把微胶囊阻燃剂的共沉淀工艺和聚合物电解质的制备二合一。一个实施例是,先用80度的温度完成共沉淀形成胶囊,然后再用聚合物固态电解质的热聚合温度聚合,或用引发剂引发聚合。这样的微胶囊包裹阻燃剂的固态电解质,在目前固态锂电池都有微量液态电解液的情况下,电池正常工作温度先不会影响电解液的性能,而在满电针刺或高温热失控时,可以大大改进阻燃防爆性能。
其他类的电池,比如钠电池,也可以用本发明同样的方案应用,实现阻燃防爆应用。
除了上述的电池外,对其他电化学体系的电池或超级电容的阻燃防爆,也可以应用本发明的方法。
以上发明和实施例是本发明的较佳实施方式,所属领域的技术人员还能够对上述实施方式进行变更和修改,因此,本发明并不局限于上述的具体实施方式,凡是本领域技术人员在本发明或实施例基础上所作的任何显而易见的改进、替换或变型均属于本发明的保护范围。
Claims (6)
1.具有多机理阻燃功能的固态电池阻燃防爆电解质,其特征在于,把功能更强而且多机理的阻燃材料,用微胶囊包覆的办法,把多机理阻燃材料,包裹到锂电池工作温度下稳定微胶囊阻复合阻燃材料中。
2.根据权利要求1所述的具有多机理阻燃功能的固态电池阻燃防爆电解质,其特征在于,微胶囊囊心材料采用红磷材料。
3.根据权利要求1所述的具有多机理阻燃功能的固态电池阻燃防爆电解质,其特征在于,对原位聚合的聚合物固态电解质,可以把微胶囊包裹阻燃剂的产品,先提前和聚合物固态电解质混合,再原位聚合。
4.根据权利要求1所述的具有多机理阻燃功能的固态电池阻燃防爆电解质,其特征在于,把微胶囊阻燃剂的共沉淀工艺和聚合物电解质的制备二合一。
5.根据权利要求1所述的具有多机理阻燃功能的固态电池阻燃防爆电解质,其特征在于,导离子的聚合物是密胺树脂材料、氢氧化镁和聚乙烯(PE)材料为囊材。
6.根据权利要求1所述的具有多机理阻燃功能的固态电池阻燃防爆电解质, 其特征在于,对液体电解液锂电池可以应用,对固态电解质的锂电池也可以应用。
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