CN104779377A - 一种改善三元电池安全性能的方法 - Google Patents
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Abstract
本发明公开了改善三元电池安全性能的方法,包括如下步骤,1)将常见的正极材料与三元正极材料以及磷酸铁锂或磷酸锰铁锂混合,得到正极材料;2)将正极材料按照常规的锂离子电池正极极片制造工艺制备成三元电池的正极;3)将石墨和钛酸锂材料混合后按照常规的锂离子电池负极极片制造工艺制备成三元电池的负极;4)按常规的锂离子电池组装工艺、化成工艺制备成三元电池。相对比现有技术,有益效果是:由于磷酸铁锂和磷酸锰铁锂都为橄榄石结构,其结构非常稳定,混入适量比例的磷酸铁锂或磷酸锰铁锂并不影响电池容量,有助于改善正极材料整体的安全性。同时,负极掺杂的钛酸锂也是一种化学性质非常稳定的化合物,有效的改善三元电池针刺安全性。
Description
技术领域
本发明涉及电化学技术领域,更具体地说,涉及一种改善三元电池安全性能的方法。
背景技术
众所周知,目前锂离子电池存在一定的安全问题,如果制备工业或条件控制不严,就会产生安全事故。2006年最引人关注的就是日本索尼公司制造的笔记本用锂离子电池发生起火现象而大规模召回,造成很大的损失,其中召回的成本就高达30亿美金。为了提高锂离子电池的安全性能,目前的主要方法是:在电解液中加入阻燃的添加剂(参见吴宇平等,《锂离子电池-应用与实践》第9章,非水液体电解质,2004年,北京,化学工业出版社出版)。前述方法尽管可以适当地提高了电池的安全性能,但是,由于阻燃剂的加入,导致电解液电导率的下降,制备的电池其倍率性能、循环性能均出现了明显的下降。
于是,有人在电池的隔膜上进行改善,即在原PE/PP膜基础上单面或双面涂覆Al2 O3涂层。该种改进的隔膜相对于传统隔膜在高温100-160℃下的收缩明显减少,可预防正负极片接触短路,显著改善电池在过充、短路测试时的安全性能,但在针刺时,电池内部短路,电池瞬间温升较大,依然存在起火的现象。
近年来,以特斯拉为代表的车型在汽车行业刮起的纯电动之风,吸引了业界对该三元电池正极所使用的三元材料广泛关注。然而,在实际的实验中,以三元材料制成的三元电池尽管其在能量密度、循环上达到要求,但在安全性能测试上特别是针刺测试上容易存在起火***的现象,不能通过安全性能检测,限制了其在动力电池的大规模应用。
有签于此,确有必要提供一种改善三元电池安全性能的方法以克服上述缺陷。
发明内容
为解决上述技术问题,本发明的目的在于提供既能保持原有三元电池优良特性,又能使其通过安全性能测试的一种改善三元电池安全性能的方法。
为解决上述技术问题,本发明提供一种改善三元电池安全性能的方法,其包括如下步骤,
1)将常见的正极材料与三元正极材料以及磷酸铁锂或磷酸锰铁锂混合,得到正极材料;
2)将上述混合好的正极材料按照常规的锂离子电池正极极片制造工艺制备成三元电池的正极;
3)将石墨和钛酸锂材料混合后按照常规的锂离子电池负极极片制造工艺制备成三元电池的负极;
4)按常规的锂离子电池组装工艺、化成工艺制备成三元电池;
其中,所述常见的正极材料为LiCoO2、LiMn2O4或它们的掺杂物,或者它们任意比例的混合物;所述的三元正极材料为LiNi1-x-yCoxMnyO2﹙0<X,Y<1﹚,或其掺杂物;所述磷酸铁锂或磷酸锰铁锂占正极材料的质量比例为10%~30%,负极钛酸锂占负极材料的质量比例为10%~30%。
优选的是,所述LiNi1-x-yCoxMnyO2﹙0<X,Y<1﹚为111型或523型或其混合物;所述石墨为人造石墨、天然石墨或中间相碳微球的一种或几种混合而成。
优选的是,所述步骤3中负极制浆采用油系。
优选的是,所述步骤4中,所采用的导电剂为SP/VGCF/CNT的一种或几种组合。
优选的是,所述步骤4中所采用的隔膜厚度为16~24μm,材质为PP、PE或PP-PE-PP。
相对比现有技术,本发明的有益效果是:由于磷酸铁锂和磷酸锰铁锂都为橄榄石结构,其结构非常稳定,安全性高,混入适量比例的磷酸铁锂或磷酸锰铁锂并不影响电池容量,有助于改善正极材料整体的安全性。同时,负极掺杂的钛酸锂也是一种化学性质非常稳定的化合物,其嵌锂后形成的Li7Ti5O12也非常稳定,在针刺的情况下不与电解液和空气发生化学反应,混入后能降低负极材料活性,有效的改善三元电池针刺安全性。
具体实施方式
本发明下面将通过具体的实施例进行更详细的描述,但本发明的保护范围并不受限于这些实施例。
对比例1:采用LiNi1/3Co1/3Mn1/3O2为正极材料,人造石墨为负极材料,制备成能量密度为165Wh/kg的26650圆柱型电池。然后,做针刺测试,结果显示于表1中,发现,针刺时,发生起火现象。
对比例2:采用LiNi0.5Co0.2Mn0.3O2为正极材料,改性天然石墨为负极材料,制备成能量密度为172Wh/kg的26650圆柱型电池。然后,做针刺测试,结果显示于表1中,发现,针刺时,发生起火现象。
实施例1:正极由LiNi1/3Co1/3Mn1/3O2、LiFePO4按质量比90:10混合成为正极材料,负极材料由人造石墨、钛酸锂按质量比为90:10混合而成,制备成能量密度为165Wh/kg的26650圆柱型电池。然后,做针刺测试,结果显示于表1中,发现,针刺时,无起火、***现象。
实施例2:正极由LiNi1/3Co1/3Mn1/3O2、LiFePO4按质量比80:20混合成为正极材料,负极材料由人造石墨、钛酸锂按质量比为80:20混合而成,制备成能量密度为165Wh/kg的26650圆柱型电池。然后,做针刺测试,结果显示于表1中,发现,针刺时,无起火、***现象。
实施例3:正极由LiNi0.5Co0.2Mn0.3O2、LiMn0.8Fe0.2PO4按质量比70:30混合成为正极材料,负极材料由改性天然石墨,钛酸锂按质量比为70:30混合而成,制备成能量密度为172Wh/kg的26650圆柱型电池。然后,做针刺测试,结果显示于表1中,发现,针刺时,无起火、***现象。
编号 | 结果 |
对比例1 | 起火 |
对比例2 | 起火 |
实施例1 | 不起火、不*** |
实施例2 | 不起火、不*** |
实施例3 | 不起火、不*** |
通过上述对比例与实施例之间的对比,可以明显看出,本发明制备方法工艺简单,制备的三元电池具有良好的安全性能。
Claims (5)
1.一种改善三元电池安全性能的方法,其特征在于:包括如下步骤,
1)将常见的正极材料与三元正极材料以及磷酸铁锂或磷酸锰铁锂混合,得到正极材料;
2)将上述混合好的正极材料按照常规的锂离子电池正极极片制造工艺制备成三元电池的正极;
3)将石墨和钛酸锂材料混合后按照常规的锂离子电池负极极片制造工艺制备成三元电池的负极;
4)按常规的锂离子电池组装工艺、化成工艺制备成三元电池;
其中,所述常见的正极材料为LiCoO2、LiMn2O4或它们的掺杂物,或者它们任意比例的混合物;所述的三元正极材料为LiNi1-x-yCoxMnyO2﹙0<X,Y<1﹚,或其掺杂物;所述磷酸铁锂或磷酸锰铁锂占正极材料的质量比例为10%~30%,负极钛酸锂占负极材料的质量比例为10%~30%。
2.如权利要求1所述的改善三元电池安全性能的方法,其特征在于:所述LiNi1-x-yCoxMnyO2﹙0<X,Y<1﹚为111型或523型或其混合物;所述石墨为人造石墨、天然石墨或中间相碳微球的一种或几种混合而成。
3.如权利要求1所述的改善三元电池安全性能的方法,其特征在于:所述步骤3中负极制浆采用油系。
4.如权利要求1所述的改善三元电池安全性能的方法,其特征在于:所述步骤4中,所采用的导电剂为SP/VGCF/CNT的一种或几种组合。
5.如权利要求1所述的改善三元电池安全性能的方法,其特征在于:所述步骤4中所采用的隔膜厚度为16~24μm,材质为PP、PE或PP-PE-PP。
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CN106252587A (zh) * | 2016-08-31 | 2016-12-21 | 天津市捷威动力工业有限公司 | 一种高安全、高性能的锂离子电池负极及其电池 |
CN109075323A (zh) * | 2016-06-08 | 2018-12-21 | 昭和电工株式会社 | 锂离子二次电池用负极及锂离子二次电池 |
CN111883742A (zh) * | 2019-05-03 | 2020-11-03 | 三星Sdi株式会社 | 用于可再充电锂电池的负极和包括其的可再充电锂电池 |
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