CN117616597A - 用于锂离子电池组的正极以及该正极的制备方法 - Google Patents
用于锂离子电池组的正极以及该正极的制备方法 Download PDFInfo
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- CN117616597A CN117616597A CN202280042997.XA CN202280042997A CN117616597A CN 117616597 A CN117616597 A CN 117616597A CN 202280042997 A CN202280042997 A CN 202280042997A CN 117616597 A CN117616597 A CN 117616597A
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Abstract
包含物质的正极,所述物质包括:(1)含锂正极活性材料,其具有相对于所述正极活性材料中所含的除锂以外的金属为50‑85mol%的锰摩尔含量,(2)颗粒形式的SiO2,(3)导电形式的碳,和(4)粘合剂聚合物。
Description
本发明涉及一种包含物质的正极,所述物质包括:
(1)含锂正极活性材料,其具有相对于所述正极活性材料中所含的除锂以外的金属为50-85mol%的锰摩尔含量,
(2)颗粒形式的SiO2,
(3)导电形式的碳,和
(4)粘合剂聚合物。
此外,本发明涉及含有特定正极的电化学电池。
锂化的过渡金属氧化物目前被用作用于锂离子电池组的电极活性材料。在过去的几年中已经进行了广泛的研究和开发工作,以改善性能如电荷密度、比能量,以及其他性能如循环寿命降低和容量损失(所述性能可能不利地影响锂离子电池组的寿命或适用性)。已经进行了额外的努力来改进制备方法。
许多现今所讨论的电极活性材料为锂代镍-钴-锰氧化物(“NCM材料”)或锂代镍-钴-铝氧化物(“NCA材料”)类型。
在制备锂离子电池组用正极材料的典型方法中,首先通过将过渡金属以碳酸盐、氧化物或优选(氧)氢氧化物的形式共沉淀来形成所谓的前体。然后,将前体与锂化合物(例如但不限于LiOH、Li2O或Li2CO3)混合,并在高温下煅烧(焙烧)。锂化合物可以以水合物或脱水形式使用。煅烧或焙烧—通常也称为前体的热处理—通常在600-1000℃的温度下进行。在使用氢氧化物或碳酸盐作为前体的情况下,首先移除水或二氧化碳,然后进行锂化反应。热处理在烘箱或窑的加热区中进行。
在改进正极活性材料的各种性能方面,例如能量密度、充放电性能(如容量衰减)等,已经进行了广泛的研究。然而,许多正极活性材料的循环寿命有限且电压衰减。这特别适用于许多富Mn正极活性材料,其中可以观察到所谓的锰浸出。然后,锰可能会毒化负极。此外,另一个观察结果是在循环过程中产气,这归因于富锰正极的循环寿命有限。
因此,本发明的目的是提供具有高能量密度保持率但降低的因锰浸出导致的容量衰减倾向的电化学电池。
因此,发现开头所定义的正极,下文也称为本发明的正极。本发明的正极包含物质,所述物质包括:
(1)含锂正极活性材料(下文也称为正极活性材料(1)),其具有相对于所述正极活性材料中所含的除锂以外的金属为50-85mol%的锰摩尔含量,
(2)颗粒形式的SiO2,下文也称为二氧化硅(2),
(3)导电形式的碳,下文也称为碳(3),和
(4)粘合剂聚合物,下文也称为粘合剂(4)。粘合剂(4)可以包括单一聚合物或至少两种聚合物的共混物。
然后通常将所述物质附着于集流体,例如金属箔,优选铝箔。所述物质在肉眼看来可能是均匀的。然而,在放大500-1000倍的情况下,可以区分不同的组分,例如正极活性材料(1)、二氧化硅(2)和碳(3)。粘合剂(4)起到将所述物质附着于集流体的胶粘剂的作用。
下文将更详细地描述正极活性材料(1)、二氧化硅(2)、碳(3)和粘合剂(4)。
在本发明的上下文中,相对于所述正极活性材料中除锂以外的金属具有50-85mol%锰摩尔含量的该正极活性材料包括组成为LiNi0.5Mn1.5O4的所谓高压尖晶石,掺杂有例如Co、Fe、Ti、Al或Cu的高压尖晶石,以及特别是具有层状结构的所谓富锂材料,通式Li1+xTM1-xO2,其中x为0.1-0.35,TM包括两种或更多种过渡金属,并且50-85mol%,优选60-70mol%的TM为Mn。
在本发明的优选实施方案中,所述正极活性材料具有组成Li1+xTM1-xO2,其中x为0.1-0.35,优选为0.12-0.2,并且TM是通式(I)的元素组合:
(NiaCobMnc)1-dM1 d (I)
其中:
a为0.20-0.40,优选为0.25-0.35,
b为0-0.20,优选为0.05-0.15,
c为0.50-0.85,优选为60-0.70,且
d为0-0.02,
M1选自Al、Ti、Zr、W、Mo、Mg和Nb以及上述至少两种的组合,且a+b+c=1。
正极活性材料(1)可以是涂覆的或未涂覆的。
本发明的上下文中所述的涂覆的正极活性材料是指一批颗粒状正极活性材料的至少50%颗粒被涂覆,且每个颗粒的表面的0.5-2.5%,例如0.75-1.25%被涂覆。涂层可包括非锂化氧化物或锂化氧化物,或非锂化和锂化氧化物的组合。非锂化氧化物的实例为Al2O3、B2O3、TiO2、Sb2O3、ZrO2、WO3、Nb2O5以及上述至少两种的组合。锂化氧化物的实例为Li2TiO3、Li4TiO4、Li2ZrO3、LiNbO3、LiSbO3、Li2WO4、LiBO2、Li3BO3、Li2B4O7以及上述至少两种的组合。
在本发明的一个实施方案中,正极活性材料(1)具有2-20μm,优选5-16μm的平均颗粒直径D50。平均颗粒直径可例如通过光散射或激光衍射或电声光谱法测定。所述颗粒通常包含初级颗粒的附聚物,并且上述颗粒直径是指次级颗粒直径。
在本发明的一个实施方案中,正极活性材料(1)具有0.7-6.0m2/g,优选1.7-3.8m2/g或者甚至3.0-5.5m2/g的比表面积(BET),根据DIN-ISO 9277:2003-05测定。
一些金属是普遍存在的,例如钠、钙或锌,并且它们的痕量几乎无处不在,但在本发明的描述中将不考虑这些痕量。就此而言,痕量意指相对于总金属含量TM为0.05mol%或更少的量。
M1可均匀地或不均匀地分散在正极活性材料(1)的颗粒中。优选地,M1不均匀地分布在正极活性材料(1)的颗粒中,甚至更优选地以梯度的形式分布在正极活性材料(1)的颗粒中,其中M1在外壳中的浓度高于颗粒中心中的浓度。
在本发明的一个实施方案中,正极活性材料(1)包含球形颗粒,所述球形颗粒是具有球形形状的颗粒。球形颗粒不仅应包括完全球形的颗粒,还应包括至少90%(数均值)的代表性样品的最大和最小直径相差不超过10%的那些颗粒。
在本发明的一个实施方案中,正极活性材料(1)包含作为初级颗粒附聚物的次级颗粒。优选地,本发明的正极活性材料包含球形次级颗粒,所述次级颗粒是初级颗粒的附聚物。甚至更优选地,本发明的正极活性材料包含球形次级颗粒,所述球形次级颗粒是片状初级颗粒的附聚物。
在本发明的一个实施方案中,正极活性材料(1)的所述初级颗粒具有1-2000nm,优选10-1000nm,特别优选50-500nm的平均直径。平均初级颗粒直径可例如通过SEM或TEM测定。SEM是扫描电子显微镜的缩写,TEM是透射电子显微镜的缩写。
在本发明的一个实施方案中,正极活性材料(1)具有单峰颗粒直径分布。在替代实施方案中,正极活性材料(1)具有双峰颗粒直径分布,例如具有位于3-6μm范围内的一个最大值和位于9-12μm范围内的另一个最大值。
在本发明的一个实施方案中,正极活性材料(1)的压制密度为2.75-3.1g/cm3,优选为2.85-3.10g/cm3,在250MPa的压力下测定。
本发明的正极进一步包含二氧化硅(2),优选平均颗粒直径(d50)为5-100nm,优选5-20nm。平均颗粒直径(d50)是指初级颗粒的平均颗粒直径。所述初级颗粒可附聚以形成附聚物,然而,可通过搅拌来实现解附聚,例如在正极制备期间。所述附聚物可具有100nm至100μm,优选100nm至1μm的平均直径(D50)。颗粒直径的测定可通过粒度分析来进行,例如使用Malvern Panalytical进行。
在本发明的一个实施方案中,二氧化硅(2)以沙子的形式使用。在本发明的优选实施方案中,二氧化硅(2)选自喷雾干燥的二氧化硅和热解法二氧化硅。喷雾干燥的二氧化硅可通过水玻璃水溶液的酸化,然后喷雾干燥而制备。热解法二氧化硅可由SiCl4的火焰热解或由石英二氧化硅在电弧中蒸发制备。
二氧化硅(2)呈颗粒形式。优选地,颗粒是准球形或球形的。
二氧化硅(2)可具有酸性表面,通过将二氧化硅与水混合并测定pH值来确定。在23℃下测定的10重量%溶液的pH值可为3.5-6.5。
本发明的正极进一步包含碳(3)。碳(3)可选自烟灰、活性炭、碳纳米管、石墨烯和石墨,以及上述至少两种的组合。
合适的粘合剂(4)优选选自有机(共)聚合物。合适的(共)聚合物,即均聚物或共聚物,可选自例如可通过阴离子、催化或自由基(共)聚合获得的(共)聚合物,尤其是选自聚乙烯、聚丙烯腈、聚丁二烯、聚苯乙烯,和至少两种选自乙烯、丙烯、苯乙烯、(甲基)丙烯腈和1,3-丁二烯的共聚单体的共聚物。聚丙烯也是合适的。此外,聚异戊二烯和聚丙烯酸酯也是合适的。特别优选聚丙烯腈。
在本发明的上下文中,聚丙烯腈应理解为不仅意指聚丙烯腈均聚物,而且意指丙烯腈与1,3-丁二烯或苯乙烯的共聚物。优选聚丙烯腈均聚物。
在本发明的上下文中,聚乙烯应理解为不仅意指均聚乙烯,而且意指乙烯的共聚物,所述共聚物包含至少50mol%的共聚乙烯和至多50mol%的至少一种其他共聚单体,例如α-烯烃如丙烯、丁烯(1-丁烯)、1-己烯、1-辛烯、1-癸烯、1-十二碳烯、1-戊烯,以及异丁烯,乙烯基芳族化合物如苯乙烯,以及(甲基)丙烯酸、乙酸乙烯酯、丙酸乙烯酯、(甲基)丙烯酸的C1-C10烷基酯,尤其是丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯、甲基丙烯酸正丁酯、甲基丙烯酸2-乙基己酯,以及马来酸、马来酸酐和衣康酸酐。聚乙烯可为HDPE或LDPE。
在本发明的上下文中,聚丙烯应理解为不仅意指均聚丙烯,而且意指丙烯的共聚物,所述共聚物包含至少50mol%的共聚丙烯和至多50mol%的至少一种其他共聚单体,例如乙烯和α-烯烃如丁烯、1-己烯、1-辛烯、1-癸烯、1-十二碳烯和1-戊烯。聚丙烯优选为全同立构或基本上全同立构的聚丙烯。
在本发明的上下文中,聚苯乙烯应理解为不仅意指苯乙烯的均聚物,而且意指与丙烯腈、1,3-丁二烯、(甲基)丙烯酸、(甲基)丙烯酸的C1-C10烷基酯、二乙烯基苯,尤其是1,3-二乙烯基苯、1,2-二苯基乙烯和α-甲基苯乙烯的共聚物。
另一优选的粘合剂(4)是聚丁二烯。
其他合适的粘合剂(4)选自聚氧化乙烯(PEO)、纤维素、羧甲基纤维素、聚酰亚胺和聚乙烯醇。
在本发明的一个实施方案中,粘合剂(4)选自平均分子量Mw在50,000至1,000,000g/mol,优选至500,000g/mol的范围内的那些(共)聚合物。
粘合剂(4)可选自交联或非交联的(共)聚合物。
在本发明的一个特别优选的实施方案中,粘合剂(4)选自卤化(共)聚合物,尤其选自氟化(共)聚合物。卤化或氟化(共)聚合物应理解为意指包含至少一种(共)聚合(共聚)单体的那些(共)聚合物,所述(共)聚合(共聚)单体每分子具有至少一个卤原子或至少一个氟原子,更优选每分子具有至少两个卤原子或至少两个氟原子。实例为聚氯乙烯、聚偏二氯乙烯、聚四氟乙烯、聚偏二氟乙烯(PVdF)、四氟乙烯-六氟丙烯共聚物、偏二氟乙烯-六氟丙烯共聚物(PVdF-HFP)、偏二氟乙烯-四氟乙烯共聚物、全氟烷基乙烯基醚共聚物、乙烯-四氟乙烯共聚物、偏二氟乙烯-氯三氟乙烯共聚物和乙烯-氯氟乙烯共聚物。
合适的粘合剂(4)尤其是聚乙烯醇和卤化(共)聚合物,例如聚氯乙烯或聚偏二氯乙烯,尤其是氟化(共)聚合物如聚氟乙烯,尤其是聚偏二氟乙烯和聚四氟乙烯。
在本发明的一个实施方案中,本发明的正极包含:
(1)80-95重量%,优选90-95重量%的正极活性材料,
(2)1-10重量%,优选1-5重量%的颗粒形式的SiO2,
(3)1-10重量%,优选1-3重量%的导电形式的碳,
(4)1-5重量%,优选2-4重量%的粘合剂聚合物,
百分比相对于(1)、(2)、(3)和(4)的总和。因此,忽略集流体的重量。
包含本发明的正极的电化学电池显示出优异的电化学性能,尤其是在Mn浸出方面。
本发明的另一方面是一种电化学电池,其包含:
(A)本发明的正极,其包含本发明的电极活性材料、碳和粘合剂,
(B)负极,
(C)隔膜,和
(D)电解质。
上文已经详细描述了本发明正极(1)的实施方案。
所述负极(B)可包含至少一种负极活性材料,例如碳(石墨)、TiO2、氧化钛锂、硅或锡或硅合金。所述负极可额外包含集流体,例如金属箔如铜箔。
在本发明的一个实施方案中,本发明的电池包括一个或多个隔膜(C),借此将电极机械隔离。合适的隔膜(C)是聚合物膜,特别是多孔聚合物膜,其对金属锂没有反应性。特别合适的隔膜材料是聚烯烃,特别是成膜性多孔聚乙烯和成膜性多孔聚丙烯。
由聚烯烃,特别是聚乙烯或聚丙烯组成的隔膜(C)可具有35-45%的孔隙率。合适的孔径例如为30-500nm。
在本发明的另一个实施方案中,隔膜(C)选自填充有无机颗粒的PET无纺布。该隔膜可具有40-55%的孔隙率。合适的孔径例如为80-750nm。
优选的隔膜(C)选自包含玻璃纤维的那些。
电解质(D)可包含至少一种非水溶剂、至少一种电解质盐和任选地添加剂。
用于电解质的非水溶剂在室温下可以是液体或固体,并且优选选自聚合物、环状或非环状醚、环状和非环状缩醛以及环状或非环状有机碳酸酯。
合适的聚合物的实例特别是聚亚烷基二醇,优选聚-C1-C4亚烷基二醇,特别是聚乙二醇。此处,聚乙二醇可包含至多20mol%的一种或多种C1-C4亚烷基二醇。聚亚烷基二醇优选具有2个甲基或乙基端基的聚亚烷基二醇。
合适的聚亚烷基二醇,特别是合适的聚乙二醇的分子量Mw可为至少400g/mol。
合适的聚亚烷基二醇,特别是合适的聚乙二醇的分子量Mw可至多5,000,000g/mol,优选至多2,000,000g/mol。
合适的非环状醚的实例为例如二异丙基醚、二正丁基醚、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷,优选1,2-二甲氧基乙烷。
合适的环状醚的实例为四氢呋喃和1,4-二烷。
合适的非环状缩醛的实例为例如二甲氧基甲烷、二乙氧基甲烷、1,1-二甲氧基乙烷和1,1-二乙氧基乙烷。
合适的环状缩醛的实例为1,3-二烷(dioxane),特别是1,3-二氧戊环(dioxolane)。
合适的非环状有机碳酸酯的实例为碳酸二甲酯、碳酸甲乙酯和碳酸二乙酯。
合适的环状有机碳酸酯的实例是根据通式(II)和(III)的化合物:
其中R1、R2和R3可相同或不同,并且选自氢和C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基,其中R2和R3优选不同时为叔丁基。
在特别优选的实施方案中,R1为甲基,R2和R3各自为氢,或者R1、R2和R3各自为氢。在替代实施方案中,R1为F,且R2和R3各自为氢。
另一种优选的环状有机碳酸酯是碳酸亚乙烯酯,式(IV):
所述一种或多种溶剂优选以无水状态使用,即水含量为1ppm至0.1重量%,这可例如通过卡尔·费歇尔滴定法测定。
电解质进一步包含至少一种电解质盐。合适的电解质盐特别是锂盐。合适的锂盐的实例是LiPF6,LiBF4,LiClO4,LiAsF6,LiCF3SO3,LiC(CnF2n+1SO2)3,亚氨基锂(lithiumimide)如LiN(CnF2n+1SO2)2,其中n为1-20的整数,LiN(SO2F)2、Li2SiF6、LiSbF6、LiAlCl4和通式(CnF2n+1SO2)tYLi的盐,其中m定义如下:
当Y选自氧和硫时,t=1,
当Y选自氮和磷时,t=2,且
当Y选自碳和硅时,t=3。
优选的电解质盐选自LiC(CF3SO2)3、LiN(CF3SO2)2、LiPF6、LiBF4、LiClO4,特别优选LiPF6和LiN(CF3SO2)2。
本发明的电池组进一步包括壳体,该壳体可具有任何形状,例如立方体或圆柱形盘或圆柱形罐的形状。在一种变型中,将设置为袋的金属箔用作壳体。
本发明的电池组显示出良好的放电行为、非常好的放电和循环行为以及显著降低的锰浸出倾向。
本发明的电池组可包括两个或更多个彼此组合的电化学电池,例如可以串联连接或并联连接。优选串联连接。在本发明的电池组中,至少一个电化学电池包含至少一个本发明的正极。优选地,在本发明的电化学电池中,大多数电化学电池包含本发明的正极。甚至更优选地,在本发明的电池组中,所有电化学电池都包含本发明的正极。
本发明进一步提供了本发明的电池组在设备中的用途,特别是在移动设备中。移动设备的实例是交通工具,例如汽车、自行车、飞机或水上交通工具,例如船或艇。移动设备的其他实例是手动移动的设备,例如计算机,尤其是笔记本电脑、电话或电动手持工具,例如在建筑行业中,尤其是钻头、电池组驱动的螺丝刀或电池组驱动的敲钉器。
本发明的另一方面涉及一种制备本发明的正极的方法,下文也称为本发明的方法或本发明的制备方法。本发明的方法包括以下步骤:
(a)在有机溶剂或水存在下将如下物质组合:
(1)含锂正极活性材料,其具有相对于所述正极活性材料中所含的除锂以外的金属为50-85mol%的锰摩尔含量,
(2)颗粒形式的SiO2,
(3)导电形式的碳,和
(4)粘合剂聚合物,
(b)将获自步骤(a)的混合物施加于集流体,
(c)从步骤(a)中除去水或有机溶剂。
正极活性材料(1)、二氧化硅(2)、碳(3)和粘合剂(4)已在上文更详细地描述。
步骤(a)在下文中也可简称为(a)。步骤(b)在下文中也可简称为(b)。步骤(c)在下文中也可简称为(c)。
在步骤(a)中,将正极活性材料(1)、二氧化硅(2)、碳(3)和粘合剂(4)在一个步骤中或在两个或更多个子步骤中组合。优选为一个步骤。正极活性材料(1)、二氧化硅(2)、碳(3)和粘合剂(4)的组合可由混合操作辅助,例如通过搅拌。优选快速搅拌,例如1000-15000转/分钟(“rpm”)。
步骤(a)在水或有机溶剂或水和有机溶剂的组合或至少两种有机溶剂的组合的存在下进行。在有机溶剂中,优选非氯化溶剂。在有机溶剂中,优选非质子溶剂。有机溶剂的更优选的实例是丙酮、四氢呋喃(THF)、N-乙基吡咯烷酮(NEP)、N-甲基吡咯烷酮和N,N-二甲基甲酰胺(DMF)。
步骤(a)可在5-60℃的温度下进行,优选为15-40℃,甚至更优选为环境温度。
由步骤(a)得到的混合物可具有浆料或糊状物的外观,并且可具有5-80%或80.5-95%的固含量。
由步骤(a)得到的混合物优选是无团块的,因此肉眼不能检测到团块。
在本发明的一个实施方案中,由步骤(a)得到的混合物具有在23℃下为200-5000mPa·s,优选100-800mPa·s的动态粘度,在10Hz的剪切速率下测定。动态粘度可例如通过旋转粘度计测定,例如通过Haake粘度计测定。
然后,在步骤(b)中,将由步骤(a)得到的混合物施加于集流体。取决于混合物的粘度,所述施加可通过狭缝喷嘴或通过喷雾或用刮刀进行。挤出也是可能的。
由步骤(a)得到的混合物可具有30-500μm,优选50-200μm的厚度,在步骤(c)之后测定以消除溶剂的影响。
由步骤(a)得到的混合物可在步骤(b)和(c)的一个或多个循环中施加于集流体的一侧或优选地施加于集流体的两侧。
步骤(c)包括从步骤(a)中移除水或有机溶剂。所述移除可通过冷冻干燥、真空干燥加热(例如加热至25-150℃,优选100-130℃的温度)或加热与真空干燥的组合或冷冻与真空干燥的组合进行。
在进行真空干燥的情况下,优选10-100毫巴(绝对)的压力。此外,优选在工作条件下,例如在100毫巴下,从溶剂中置换蒸气,并供入一些惰性气体,例如N2。
步骤(c)的持续时间可为1分钟至24小时,优选10分钟至24小时。
步骤(c)可例如在干燥通道中进行。在干燥通道中的停留时间可为5-30分钟,优选为10-20分钟。
由步骤(c)中获得坯料,该坯料可直接用作正极,或者可以定制(“精加工”),例如通过切割成所需的形状。在优选实施方案中,首先将坯料压实,步骤(d),热处理,步骤(e),然后精加工。实施步骤(d)的优选方式是在压延机或压机中。
在压延机中实施步骤(d)的优选条件是所述压延机的辊的线压力为100-500N/mm,优选110-150N/mm。合适的加工速度为0.1-1m/分钟。
在压机中实施步骤(d)的优选条件是100-1000MPa,优选100-500MPa的压力。合适的停留时间为5-10分钟。
步骤(d)的合适加工温度为15-95℃,优选25-35℃。
热处理步骤(e)包括将由步骤(d)获得的压实坯料加热至比粘合剂(4)的熔点或软化点低35-5℃的温度,参见例如US2015/0280206,或者甚至更高,例如高于粘合剂(4)的熔点或软化点,例如高50℃。然而,应避免粘合剂(4)的分解。
精加工步骤的实例是压印或切割或冲压,以获得所需的几何形状。
通过以下工作实施例进一步说明本发明。
平均颗粒直径(D50)通过动态光散射(“DLS”)测定。除非另有特别说明,否则百分比是重量%。
表面酸度在将500mg二氧化硅(2.1)在5ml蒸馏水中搅拌15分钟后测定。
百分比和ppm分别指重量百分比和重量ppm,除非另有特别说明。
起始材料:
正极活性材料(1.1)(“CAM(1.1)”:Li1.14(Ni0.26Co0.14Mn0.60)0.86O2)
CAM(1.1)的制备如下:
通过从含有摩尔比为26:14:60的硫酸镍/硫酸钴/硫酸锰的溶液中沉淀混合Ni-Co-Mn碳酸盐,然后在空气中在200℃下干燥,制备前体。沉淀剂是在氨水溶液中的碳酸钠水溶液。平均颗粒直径(D50):10.2μm。
在辊道窑中,用前体和Li2CO3的充分混合物填充匣钵,因此锂与过渡金属之和的摩尔比为1.42:1。将所述混合物在强制空气流中加热至800℃。当温度达到800℃时,在800℃下继续加热4小时的时间。观察到式0.33Li2MnO3·0.67Li(Ni0.4Co0.2Mn0.4)O2的金属氧化物的形成。这对应于式Li1.14TM0.86O2。
二氧化硅(2.1):(细节:热解法二氧化硅,颗粒直径5-15nm,酸度:23℃下pH值6.5,购自Sigma-Aldrich)。
碳(3.1):炭黑,作为SuperC65由瑞士Imerys商购获得。
粘合剂(4.1):聚偏二氟乙烯(PVDF,Solef5130,比利时Solvay)
步骤(a)的所有操作均在手套箱中进行(O2和H2O低于0.1ppm)。
I.正极制备
I.1本发明正极(A.1)的制备:
将CAM(1.1)、二氧化硅(2.1)、碳(3.1)和粘合剂(4.1)以87.5:5.0:4.0:3.5的重量比混合。
步骤(a.1):在溶解器(Dispermat LC30,德国VMA-Getzmann)中在5000rpm下加入碳(3.1)和粘合剂(4.1)5分钟。然后,分三批加入固含量为50%的NMP中的二氧化硅(2.1),并在每次加入NMP后以10000rpm将所得油墨状浆料混合5分钟。然后,加入CAM(1.1),且将所得浆料以10000rpm再混合5分钟。
步骤(b.1):然后使用四棱刮刀(RK PrintCoat Instruments,UK)将获自步骤(a.1)的混合物涂覆在铝箔(厚度18μm,MTI Corporation,USA)上。获得涂覆的铝箔。
步骤(c.1):将涂覆的铝箔在手套箱内在环境温度下干燥15小时,以蒸发NMP。
在定制之后实施步骤(d.1)和(e.1):
精加工:
冲压出直径为14mm的圆盘形粗正极。
步骤(d.1)和(e.1):用液压机在2.5吨(相当于≈160MPa)下压缩圆盘形粗正极,并在玻璃烘箱(585干燥烘箱,瑞士Büchi)中在120℃下在动态真空下干燥15小时。CAM负载量为8.5mg CAM(1.1)/cm2,相当于2.1mA·h/cm2(基于250mA·h/g CAM(1.1)的标称比容量)。获得了本发明的正极(a.1)。
I.2对比正极C-(A.2)的制备
将CAM(1.1)、二氧化硅(2.1)、碳(3.1)和粘合剂(4.1)以92.5:0:4.0:3.5的重量比混合。
步骤C-(a.2):在溶解器(Dispermat LC30,德国VMA-Getzmann)中在5000rpm下加入碳(3.1)和粘合剂(4.1)5分钟。然后,分三批加入固含量为50%的NMP中的二氧化硅(2.1),并在每次加入NMP后以10000rpm将所得墨状浆料混合5分钟。然后,加入CAM(1.1),且将所得浆料以10000rpm再混合5分钟。
步骤(b.2):然后使用四棱刮刀(RK PrintCoat Instruments,UK)将获自步骤C-(a.2)的混合物涂覆在铝箔(厚度18μm,MTI Corporation,USA)上。获得涂覆的铝箔。
步骤(c.2):将涂覆的铝箔在手套箱内在环境温度下干燥15小时,以蒸发NMP。
在定制之后实施步骤(d.2)和(e.2):
精加工:
冲压出直径为14mm的圆盘形粗正极。
步骤(d.2)和(e.2):用液压机在2.5吨(相当于≈160MPa)下压缩圆盘形粗正极,并在玻璃烘箱(585烘箱,瑞士Büchi)中在120℃下在动态真空下干燥15小时。CAM负载量为8.5mg CAM(1.1)/cm2,相当于2.1mAh/cm2(基于250mAh/g CAM(1.1)的标称比容量)。获得对比正极C-(A.2)。
II.电化学电池的制备和测试
II.1纽扣电池的制备
负极(B.1):铜箔上的石墨
II.2测试
在25℃下在温度受控的烘箱(德国Binder)中且使用电池组循环仪(Series 4000,Maccor,USA),在2032型纽扣电池(日本Hohsen Corp.)中进行恒电流循环。对于全电池实验,将直径为15mm的石墨负极和直径为14mm的正极与两个聚丙烯隔膜(CG,C2500,Celgard,USA)(C.1)或两个玻璃纤维隔膜(GF,玻璃微纤维,GF/A,VWR,德国)(C.2)组装,在每种情况下含有80μl在氟亚乙基碳酸酯/碳酸二乙酯(2:8,g:g)中的1MLiPF6电解质。在组装后,在充电/放电循环之前将所有电池放置2小时(以便完全润湿隔膜),并且C倍率相对于250mAh/g的标称容量。将具有LRM-NCM正极的全电池在第一个循环中用恒电流程序(CC)以C/15的C倍率激活至4.7V,然后在C/15下放电至2.0V(CC)。在随后的3个循环中,在充电和放电期间,将上截止电池电压降低至4.6V,并且C倍率达到C/10。随后是快速循环,其中电池各自在C/2(CCCV)/3C(CC)下充电/放电3个循环,其中在1小时后或当电流降至低于C/100时终止所有恒压(CV)步骤。随后以C/2(CCCV)的充电速率和1C(CC)的放电速率进行33次循环,其中CV步骤如上所定义。这种3个C/10、3个3C和33个1C放电循环的序列总共重复120个循环。
表1:电化学电池测试
Claims (10)
1.包含物质的正极,所述物质包括:
(1)含锂正极活性材料,其具有相对于所述正极活性材料中所含的除锂以外的金属为50-85mol%的锰摩尔含量,
(2)颗粒形式的SiO2,
(3)导电形式的碳,和
(4)粘合剂聚合物,
其中所述物质涂覆在集流体上。
2.根据权利要求1所述的正极,其中所述SiO2具有5-100nm的平均颗粒直径(D50)。
3.根据权利要求1或2所述的正极,其包含:
(1)80-95重量%的正极活性材料,
(2)1-10重量%的颗粒形式的SiO2,
(3)1-10重量%的导电形式的碳,
(4)1-5重量%的粘合剂聚合物,
百分比相对于(1)、(2)、(3)和(4)的总和。
4.根据前述权利要求中任一项所述的正极,其中所述SiO2选自喷雾干燥的二氧化硅和热解法二氧化硅。
5.根据前述权利要求中任一项所述的正极,其中所述正极活性材料具有组成LiNi0.5Mn1.5O4。
6.根据权利要求1-4中任一项所述的正极,其中所述正极活性材料具有组成Li1+xTM1- xO2,其中x为0.1-0.35,并且TM为通式(I)的元素组合:
(NiaCobMnc)1-dM1 d (I)
其中:
a为0.20-0.40,
b为0-0.20,
c为0.60-0.70,且
d为0-0.02,
M1选自Al、Ti、Zr、W、Mo、Mg和Nb,且
a+b+c=1。
7.根据权利要求6所述的正极,其中a>b。
8.电化学电池,其包含:
(A)根据权利要求1-7中任一项所述的正极。
9.根据权利要求8所述的电化学电池,其进一步包含:
(B)包含玻璃纤维的隔膜。
10.制备根据权利要求1-7中任一项所述的正极的方法,其中所述方法包括以下步骤:
(a)在有机溶剂或水存在下将如下物质组合:
(1)含锂正极活性材料,其具有相对于所述正极活性材料中所含的除锂以外的金属为50-85mol%的锰摩尔含量,
(2)颗粒形式的SiO2,
(3)导电形式的碳,和
(4)粘合剂聚合物,
(b)将获自步骤(a)的混合物施加于集流体,
(c)从步骤(a)中移除水或有机溶剂。
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