CN113497272A - 非水电解液以及包含其的锂二次电池 - Google Patents
非水电解液以及包含其的锂二次电池 Download PDFInfo
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- CN113497272A CN113497272A CN202110340195.4A CN202110340195A CN113497272A CN 113497272 A CN113497272 A CN 113497272A CN 202110340195 A CN202110340195 A CN 202110340195A CN 113497272 A CN113497272 A CN 113497272A
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Images
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Abstract
根据本发明实施方案的非水电解液包括非水有机溶剂、锂盐和具有预定化学结构的膦酸酯基添加剂。可以通过膦酸酯基添加剂抑制正极活性物质的表面损伤和副反应。根据本发明的实施方案,提供了一种包括非水电解液的锂二次电池。
Description
相关申请的交叉引用和优先权要求
本申请要求于2020年4月3日向韩国知识产权局(KIPO)提交的第10-2020-0040766号韩国专利申请的优先权,其全部内容通过引用并入本文。
技术领域
本发明涉及一种非水电解液以及包含其的锂二次电池。更具体地,本发明涉及包含非水溶剂和添加剂的非水电解液以及包含其的锂二次电池。
背景技术
随着信息技术和显示技术的发展,可重复充电和放电的二次电池已被广泛用作便携式电子设备(例如便携式摄像机、移动电话、笔记本电脑等)的电源。近来,包括二次电池的电池组正在被开发并被用作诸如混合动力车辆的电动汽车的环保电源。
在各种二次电池中,锂二次电池由于高的工作电压和高的每单位重量的能量密度、高的充电速率、紧凑的尺寸等而受到关注。
例如,锂二次电池可包括电极组件,该电极组件包括正极、负极、隔膜层(隔膜)和浸没该电极组件的电解液。锂二次电池可以进一步包括具有例如软包的外壳。
锂金属氧化物可以用作锂二次电池的正极活性物质。锂金属氧化物可以包括例如镍基锂金属氧化物。
随着锂二次电池的应用范围的扩大,需要具有更长的寿命、更高的容量和操作稳定性的锂二次电池。因此,在重复的充电和放电操作期间提供均匀的功率和容量的锂二次电池可能是有利的。
然而,在重复的充电和放电操作期间,用作正极活性物质的镍基锂金属氧化物的表面可能会被损坏,从而导致功率和容量的降低。此外,可能引起电解液与镍基锂金属氧化物之间的副反应。
例如,如韩国公开专利申请第10-2019-0119615号中所公开的,可以在用于锂二次电池的非水电解液中包含添加剂以增强电池性能。
发明内容
根据本发明的一个方面,提供了一种能够提供改善的机械和化学稳定性的非水电解液。
根据本发明的一个方面,提供了一种锂二次电池,其包括非水电解液并且具有改善的操作稳定性和电性能。
根据本发明的示例性实施方案,非水电解液包括非水有机溶剂、锂盐和由化学式1表示的膦酸酯基添加剂。
[化学式1]
在化学式1中,R1和R2各自独立地为具有3-10个碳原子并且包括末端炔基的取代或未取代的烃。
在一些实施方案中,膦酸酯基添加剂可以由化学式1-1表示。
[化学式1-1]
在化学式1-1中,R3和R4各自独立地为取代或未取代的C1-C8亚烷基。
在一些实施方案中,取代基可以与亚烷基的至少一个碳原子键合,并且该取代基可以包括C1-C7烷基、C2-C7烯基、C2-C7炔基、C1-C7烷氧基、卤素、氰基(-CN)、羟基(-OH)或硝基(-NO2)。
在一些实施方案中,基于非水电解液的总重量,膦酸酯基添加剂的量可以为0.1重量%至5重量%。
在一些实施方案中,非水有机溶剂可包括选自碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二甲酯(DMC)和碳酸二乙酯(DEC)中的至少一种。
根据本发明的示例性实施方案,锂二次电池包括:正极,其包含作为正极活性物质的锂-过渡金属氧化物;负极;插入于负极和正极之间的隔膜层;和根据上述实施方案的非水电解液。
在一些实施方案中,锂-过渡金属氧化物可以由以下化学式2表示。
[化学式2]
Li1+aNi1-(x+y)CoxMyO2
在化学式2中,-0.05≤a≤0.15、0.01≤x≤0.3、0.01≤y≤0.3,并且M包括选自Mn、Mg、Sr、Ba、B、Al、Si、Ti、Zr或W中的至少一种元素。
在一些实施方案中,在化学式2中,0.01≤x≤0.2、0.01≤y≤0.2。
根据本发明的实施方案的非水电解液可以包括具有特定结构的膦酸酯基添加剂。例如,在膦酸酯基添加剂中,磷(P)原子可以通过例如互变异构化与正极活性物质的金属元素结合。此外,可以通过膦酸酯基添加剂中包含的三键基团促进与金属元素的结合。
因此,即使在高温环境下操作时,也可以抑制对正极活性物质的表面的损害以及正极活性物质与非水电解液的副反应,从而改善锂二次电池的电学和化学稳定性。
附图说明
图1和图2分别为示出根据示例性实施方案的锂二次电池的示意性俯视平面图和示意性截面图。
具体实施方式
根据本发明的示例性实施方案,提供了包含膦酸酯基添加剂的非水电解液。还提供了一种锂二次电池,其包括非水电解液并且具有改善的电学、机械和化学稳定性。
非水电解液
根据本发明的示例性实施方案的非水电解液可以包括非水有机溶剂、电解质(例如,锂盐)和膦酸酯基添加剂。
非水有机溶剂可以包括为锂盐和膦酸酯基添加剂提供足够的溶解性并且与锂二次电池不具有反应性的有机化合物。在示例性实施方案中,有机溶剂可包括碳酸酯基溶剂、酯基溶剂、醚基溶剂、酮基溶剂、醇基溶剂、非质子溶剂等。这些溶剂可以单独使用或组合使用。
碳酸酯基溶剂的实例可包括碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、碳酸甲丙酯、碳酸乙丙酯、碳酸二乙酯(DEC)、碳酸二丙酯、碳酸丙烯酯(PC)、碳酸乙烯酯(EC)、氟代碳酸乙烯酯(FEC)、碳酸丁烯酯等。
酯基溶剂的实例可包括乙酸甲酯(MA)、乙酸乙酯(EA)、乙酸正丙酯(n-PA)、乙酸1,1-二甲基乙酯(DMEA)、丙酸甲酯(MP)、丙酸乙酯(EP)、γ-丁内酯(GBL)、癸内酯(decanolide)、戊内酯、甲瓦龙酸内酯(mevalonolactone)、己内酯等。
醚基有机溶剂的实例可以包括二丁醚、四甘醇二甲醚(TEGDME)、二甘醇二甲醚(DEGDME)、二甲氧基乙烷、2-甲基四氢呋喃、四氢呋喃等。
环己酮可用作酮基溶剂。醇基溶剂的实例可以包括乙醇、异丙醇等。
非质子溶剂可包括腈基溶剂、酰胺基溶剂(例如二甲基甲酰胺(DMF))、二氧戊环基溶剂(例如1,3-二氧戊环)、环丁砜基溶剂等。
在优选的实施方案中,可以使用碳酸酯基溶剂作为有机溶剂。例如,有机溶剂可以包括碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)或它们的组合。
电解质可以包括例如锂盐。锂盐可以包括例如由Li+X-表示的化合物。锂盐的阴离子(X-)的非限制性实例可包括F-、Cl-、Br-、I-、NO3 -、N(CN)2 -、BF4 -、ClO4 -、PF6 -、(CF3)2PF4 -、(CF3)3PF3 -、(CF3)4PF2 -、(CF3)5PF-、(CF3)6P-、CF3SO3 -、CF3CF2SO3 -、(CF3SO2)2N-、(FSO2)2N-、CF3CF2(CF3)2CO-、(CF3SO2)2CH-、(SF5)3C-、(CF3SO2)3C-、CF3(CF2)7SO3 -、CF3CO2 -、CH3CO2 -、SCN-、(CF3CF2SO2)2N-等。这些阴离子可以单独使用或组合使用。
在一个实施方案中,基于有机溶剂,可以以约0.01M至约5M,优选约0.01M至2M的浓度包含锂盐。在上述范围内,可以在锂二次电池的充电和放电期间促进锂离子和/或电子的转移,从而提供改善的容量。
在示例性实施方案中,膦酸酯基添加剂可包括由以下化学式1表示的化合物。
[化学式1]
在以上化学式1中,R1和R2可各自独立地为具有3-10个碳原子并且包括末端炔基的取代或未取代的烃。
在本申请中使用的术语“烃”可以包括环状脂族基团、直链脂族基团、芳族基团或它们的组合。所述烃基可包括其中在至少一个碳-碳键之间插入有包括杂原子的官能团的结构。
在示例性实施方案中,膦酸酯基添加剂可以由以下化学式1-1表示。
[化学式1-1]
在以上化学式1-1中,R3和R4可各自独立地为具有1-8个碳原子的取代或未取代的烃。例如,R3和R4可各自独立地为取代或未取代的C1-C8亚烷基。
亚烷基可包括键合至至少一个碳原子的取代基。取代基的实例可包括C1-C7烷基、C2-C7烯基、C2-C7炔基、C1-C7烷氧基、卤素、氰基(-CN)、羟基(-OH)、硝基(-NO2)等。
根据上述示例性实施方案的膦酸酯基添加剂可以包括与磷(P)原子键合的氢原子。例如,膦酸酯基添加剂可以通过互变异构化在非水电解液中形成H-P=O相和:P-OH相的平衡。因此,磷(P)原子的未共享电子对可以与例如随后所述的正极活性物质的金属原子形成配位键。
因此,可以基本上在正极活性物质的表面上实现钝化效果,并且可以减少正极活性物质与非水电解液之间的副反应。
另外,膦酸酯基添加剂可以包括两个具有末端三键的烷氧基。相对富电子的三键单元可以暴露于添加剂的末端,从而可以产生与正极活性物质的金属原子的额外的相互作用或键。
因此,可以增强正极活性物质的钝化和表面稳定化作用,从而可以显著提高锂二次电池的高温稳定性和寿命稳定性。
在一些实施方案中,基于非水电解液的总重量,膦酸酯基添加剂的量可以小于约10重量%,优选地为约0.1重量%至5重量%。在上述范围内,在充分发挥正极活性物质的上述钝化和表面稳定效果的同时,锂离子的迁移率和正极活性材料的活性不会过度降低。
在一些实施方案中,非水电解液可以进一步包括辅助添加剂。
辅助添加剂可包括例如碳酸酯基化合物,例如碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯等;酸酐基化合物,例如琥珀酸酐和马来酸酐;腈基化合物,例如戊二腈、丁二腈(succinonitrile)、己二腈等;砜基化合物(sulfone-based compound),例如1,3-丙烷磺酸内酯、1,3-丙烯磺酸内酯、硫酸乙烯酯等。这些化合物可以单独使用或组合使用。
辅助添加剂可以在不抑制上述膦酸酯基添加剂的钝化效果和非水电解液中的锂离子的迁移率的范围内以适当量包含。
例如,基于非水电解液的总重量,可以以约0.1重量%至5重量%,优选0.1重量%至3重量%的量包含辅助添加剂。
锂二次电池
根据本发明的示例性实施方案,提供了一种包含非水电解液的锂二次电池。
图1和图2分别为示出根据示例性实施方案的锂二次电池的示意性俯视平面图和示意性截面图。例如,图2为沿图1的线I-I’截取的截面图。
参照图1和图2,锂二次电池可以包括电极组件,该电极组件包括正极100、负极130和插入于正极和负极之间的隔膜层140。电极组件可以与要浸渍在其中的电解液一起容纳在壳体160中。
正极100可以包括通过将正极活性物质涂覆到正极集流体105而形成的正极活性物质层110。正极活性物质可以包括能够使锂离子可逆地嵌入和脱嵌的化合物。
在示例性实施方案中,正极活性物质可以包括锂-过渡金属氧化物。例如,锂-过渡金属氧化物可包括镍(Ni),并且可以进一步包括钴(Co)和锰(Mn)中的至少一种。
例如,锂-过渡金属氧化物可以由以下化学式2表示。
[化学式2]
Li1+aNi1-(x+y)CoxMyO2
在以上化学式2中,-0.05≤a≤0.15、0.01≤x≤0.3、0.01≤y≤0.3,并且M可以包括选自Mn、Mg、Sr、Ba、B、Al、Si、Ti、Zr或W中的至少一种元素。
如化学式1所示,锂-过渡金属氧化物可以以Ni、Co和Mn中的最大量或摩尔比包含Ni。Ni可以基本上用作与锂二次电池的功率和/或容量有关的金属,并且可以通过在过渡金属中包含最大量的Ni来实现高容量和高功率的锂二次电池。
在一个实施方案中,在化学式2中,0.01≤x≤0.2且0.01≤y≤0.2。
如果正极活性物质或锂-过渡金属氧化物中的Ni量增加,则二次电池在高温下的化学稳定性和储存稳定性可能会下降。此外,在重复的充电/放电操作期间可能引起对正极活性物质的表面的损坏或与非水电解液的副反应,并且可能无法实现由高Ni含量引起的足够的高功率/高容量特性。
然而,如上所述,根据化学式1的膦酸酯基添加剂可以通过配位或化学相互作用在正极活性物质或锂-过渡金属氧化物的表面上与Ni结合以使正极活性物质钝化。因此,即使在高温环境下,也可以长期基本均匀地保持由高Ni含量引起的高功率/容量特性。
可以通过在溶剂中将正极活性物质与粘合剂、导电剂和/或分散剂混合并搅拌来制备浆料。可以将浆料涂覆在正极集流体105上,然后干燥并压制以形成正极100。
正极集流体105可以包括不锈钢、镍、铝、钛、铜或它们的合金。优选地,可以使用铝或其合金。
粘合剂可包括有机基粘合剂,例如聚偏二氟乙烯-六氟丙烯共聚物(PVDF-co-HFP)、聚偏二氟乙烯(PVDF)、聚丙烯腈、聚甲基丙烯酸甲酯等,或水基粘合剂,例如丁苯橡胶(SBR),其可以与诸如羧甲基纤维素(CMC)的增稠剂一起使用。
例如,PVDF基粘合剂可以用作正极粘合剂。在这种情况下,可以减少用于形成正极活性物质层的粘合剂的量,并且可以相对增加正极活性物质的量。因此,可以进一步提高锂二次电池的容量和功率。
可以添加导电剂以促进活性物质颗粒之间的电子迁移。例如,导电剂可以包括碳基材料,例如石墨、炭黑、石墨烯、碳纳米管等,和/或金属基材料,例如锡、氧化锡、氧化钛、钙钛矿材料(例如LaSrCoO3或LaSrMnO3)等。
负极130可包括负极集流体125和通过将负极活性物质涂覆于负极集流体125而形成的负极活性物质层120。
负极活性物质可以包括在相关技术中通常使用的能够吸附和解吸锂离子的材料。例如,可以使用诸如结晶碳、无定形碳、碳络合物(carbon complex)或碳纤维的碳基材料;锂合金;硅(Si)基化合物;锡等。无定形碳可以包括硬碳、焦炭、中间相碳微球(MCMB)、中间相沥青基碳纤维(MPCF)等。
结晶碳可包括石墨基材料,例如天然石墨、石墨化焦炭、石墨化MCMB、石墨化MPCF等。锂合金还可包括铝、锌、铋、镉、锑、硅、铅、锡、镓、铟等。
硅基化合物可以包括例如氧化硅或诸如碳化硅(SiC)的硅-碳复合化合物。
例如,可以在溶剂中将负极活性物质与上述粘合剂、导电剂、增稠剂等一起混合并搅拌以形成浆料。可以将浆料涂覆在负极集流体125的至少一个表面上,干燥并压制以形成负极130。
隔膜层140可以插入在正极100和负极130之间。隔膜层140可以包括由诸如乙烯均聚物、丙烯均聚物、乙烯/丁烯共聚物、乙烯/己烯共聚物、乙烯/甲基丙烯酸酯共聚物的聚烯烃基聚合物制得的多孔聚合物膜。隔膜层140还可包括由具有高熔点的玻璃纤维、聚对苯二甲酸乙二醇酯纤维等形成的无纺布。
在一些实施方案中,负极130的面积和/或体积(例如,与隔膜层140的接触面积)可以大于正极100的面积和/或体积。因此,从正极100产生的锂离子可以容易地转移至负极130而不会因例如析出或沉淀而损失。
在示例性实施方案中,电极单元可以由正极100、负极130和隔膜层140限定,并且多个电极单元可以被堆叠以形成可具有例如果冻卷(jelly roll)形状的电极组件150。例如,电极组件150可以通过缠绕、层叠或折叠隔膜层140来形成。
电极组件150可以与根据如上所述的示例性实施方案的非水电解液一起容纳在壳体160中,以获得锂二次电池。
如图1所示,电极极耳(正极极耳和负极极耳)可以从每个电极单元中包括的正极集流体105和负极集流体125伸出到壳体160的一侧。电极极耳可以与壳体160的一侧焊接在一起,以形成延伸至或暴露于壳体160外部的电极引线(正极引线107和负极引线127)。
锂二次电池可以以例如圆柱形(使用罐)、棱柱形、软包或硬币形制造。
在下文中,提出优选实施方案以更具体地描述本发明。然而,以下实施例仅用于说明本发明,并且相关领域的技术人员将清楚地理解,在本发明的范围和精神内可以进行各种改变和修改。这样的改变和修改应当包括在所附权利要求内。
实施例和比较例
实施例1
通过以92:5:3的重量比混合作为正极活性物质的Li[Ni0.6Co0.2Mn0.2]O2、作为导电材料的炭黑和作为粘合剂的聚偏二氟乙烯(PVDF)来制备浆料。将浆料均匀地施加至厚度为15μm的铝箔上,并在130℃下真空干燥并压制以制备用于锂二次电池的正极。
制备浆料,其包含95重量%的作为负极活性物质的天然石墨、1重量%的作为导电剂的Super-P、2重量%的作为粘合剂的丁苯橡胶(SBR)以及2重量%的作为增稠剂的羧甲基制备纤维素(CMC)。将负极浆料在15μm厚的铜箔上均匀地涂布、干燥并压制以制备负极。
将如上所述获得的正极和负极以适当尺寸切割(notched)并堆叠,并且在正极和负极之间插入隔膜(聚乙烯,厚度:20μm)以形成电极单元。焊接正极和负极的每个极耳部分。将焊接的正极/隔膜/负极组件插入软包中,并且密封该软包的除了注入电解液的一侧以外的三个侧面。极耳部分也包括在密封部分中。通过电解液注入侧注入非水电解液,然后也将电解液注入侧密封。随后,将上述结构浸渍12小时以上以制备锂二次电池样品。
在EC/EMC/DEC(25/45/30;体积比)的混合溶剂中溶解1.0M LiPF6之后,添加0.5重量%的由以下化学式3表示的化合物作为膦酸酯基添加剂以制备非水电解液。
[化学式3]
实施例2
通过与实施例1中相同的方法制备锂二次电池样品,不同之处在于,将非水电解液中的膦酸酯基添加剂的量更改为0.1重量%。
实施例3
通过与实施例1中相同的方法制备锂二次电池样品,不同之处在于,将非水电解液中的膦酸酯基添加剂的量更改为5重量%。
实施例4
通过与实施例1中相同的方法制备锂二次电池样品,不同之处在于,将非水电解液中的膦酸酯基添加剂的量改变为10重量%。
比较例1
通过与实施例1中相同的方法制备锂二次电池样品,不同之处在于,不使用膦酸酯基添加剂。
比较例2
通过与实施例1中相同的方法制备锂二次电池样品,不同之处在于,使用以下化学式4表示的化合物作为膦酸酯基添加剂。
[化学式4]
比较例3
通过与实施例1中相同的方法制备锂二次电池样品,不同之处在于,使用以下化学式5表示的化合物作为膦酸酯基添加剂。
[化学式5]
实验例
(1)室温下的寿命特性的评价
将实施例和比较例中制备的每个锂二次电池样品重复充电(CC-CV 1.0C 4.2V0.05C截止)和放电(CC 1.0C 3.0V截止)1000次。计算第1000次循环的放电容量相对于第1次循环的放电容量的比率(%),以评价室温下的寿命特性。
(2)高温特性评价
将实施例和比较例中制备的每个锂二次电池样品在CC-CV 1C 4.2V 0.1C截止的条件下充电,然后在60℃的烘箱中储存8周。将样品在CC 0.5C 2.75V截止的条件下放电,然后在CC-CV 0.5C 4.2V 0.05C截止的条件下充电。之后,在CC 0.5C 2.75V截止的条件下再次测量放电量。通过将放电量与进行标准充电和放电时的放电量进行比较来测量容量恢复率。另外,在如上所述的高温储存/充电和放电后,测量二次电池的厚度的增加率。
评价结果示于下表1中。
[表1]
参考表1,与比较例相比,当根据示例性实施方案在非水电解液中包含化学式1所示的膦酸酯基添加剂时,即使在高温储存之后,也实现了改善的容量保持性和机械稳定性。然而,在实施例4的情况下,由于膦酸酯基添加剂的量略微增加,室温下的寿命特性略微降低。
当使用其中甲基键合到磷(P)原子上的添加剂(比较例2)和具有一个末端炔基的添加剂(比较例3)时,由于与正极的相互作用的减少,基本上没有实现高温稳定性的提高。
Claims (8)
3.根据权利要求2所述的非水电解液,其中,取代基与所述亚烷基的至少一个碳原子键合,并且所述取代基包括C1-C7烷基、C2-C7烯基、C2-C7炔基、C1-C7烷氧基、卤素、氰基(-CN)、羟基(-OH)或硝基(-NO2)。
4.根据权利要求1所述的非水电解液,其中,基于所述非水电解液的总重量,所述膦酸酯基添加剂的量为0.1重量%至5重量%。
5.根据权利要求1所述的非水电解液,其中,所述非水有机溶剂包括选自碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二甲酯(DMC)和碳酸二乙酯(DEC)中的至少一种。
6.一种锂二次电池,其包括:
正极,所述正极包含作为正极活性物质的锂-过渡金属氧化物;
负极;
插入于所述正极和所述负极之间的隔膜层;和
根据权利要求1所述的非水电解液。
7.根据权利要求6所述的锂二次电池,其中,所述锂-过渡金属氧化物由以下化学式2表示:
[化学式2]
Li1+aNi1-(x+y)CoxMyO2
其中,在化学式2中,-0.05≤a≤0.15、0.01≤x≤0.3、0.01≤y≤0.3,并且M包括选自Mn、Mg、Sr、Ba、B、Al、Si、Ti、Zr或W中的至少一种元素。
8.根据权利要求7所述的锂二次电池,其中,在化学式2中,0.01≤x≤0.2,0.01≤y≤0.2。
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