CN111052484A - 用于锂二次电池的液体电解质添加剂、包含该添加剂的非水液体电解质和锂二次电池 - Google Patents
用于锂二次电池的液体电解质添加剂、包含该添加剂的非水液体电解质和锂二次电池 Download PDFInfo
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- CN111052484A CN111052484A CN201580053570.XA CN201580053570A CN111052484A CN 111052484 A CN111052484 A CN 111052484A CN 201580053570 A CN201580053570 A CN 201580053570A CN 111052484 A CN111052484 A CN 111052484A
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- liquid electrolyte
- aqueous liquid
- carbonate
- carbon
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Abstract
本发明提供一种非水液体电解质,包括非水有机溶剂、锂盐和含碳‑碳三键的异氰酸酯类化合物添加剂。通过在非水液体电解质中包括含碳‑碳三键的异氰酸酯类化合物添加剂,寿命性能和高温耐久性能够得到增强,并且电池的内部电阻能够得以降低。
Description
技术领域
[相关申请的交叉引用]
本申请要求于2014年10月2日向韩国知识产权局提交的韩国专利申请No.10-2014-0133432以及于2015年10月1日向韩国知识产权局提交的韩国专利申请No.10-2015-0138640的优先权和权益,其全部内容通过引用并入本文。
[技术领域]
本发明涉及一种二次电池,其通过在二次电池中包括含异氰酸酯类化合物的非水液体电解质而具有提高的寿命性能和高温耐久性。
背景技术
随着技术进步和对移动装置需求的增加,对于的二次电池作为能源的需求急剧地增加。在这些二次电池中,具有高能量密度和高电压的锂二次电池已经商业化并广为使用。
锂金属氧化物被用作锂二次电池的正极活性材料,锂金属、锂合金、结晶碳或无定形碳、或碳复合物被用作负极活性材料。通过将活性材料以适当的厚度和长度涂布到集电器上,或者以膜的形式涂布活性材料本身,并且将所得物与作为绝缘体的隔膜一同进行卷绕或堆叠,以形成电极组,然后,将所得物放入罐或类似的容器中,然后通过注入液体电解质而制备二次电池。
这种锂二次电池经历充电和放电,同时重复锂离子从正极的锂金属氧化物至负极的石墨电极的嵌入(intercalation)和脱嵌(deintercalation)。在此,由于高反应性锂与碳电极发生反应,并通过产生Li2CO3、LiO、LiOH等而在负极表面形成膜。这种膜称为固体电解质界面(SEI)膜,且在充电伊始形成的SEI膜防止了在充电和放电期间锂离子与碳负极或其他材料的反应。另外,SEI膜起到离子通道(Ion Tunnel)的作用,且仅传递锂离子。这种离子通道溶剂化(solvation)锂离子,并通过液体电解质的高分子量有机溶剂一并迁移并共嵌入至碳负极而起到防止碳负极结构崩塌的作用。
因此,为了提高锂二次电池的高温循环特性及低温输出特性,需要在锂二次电池的负极上形成牢固的SEI膜。一旦在初始充电时形成SEI膜,在随后电池使用而重复充电和放电时,该膜防止锂离子与负极或其他材料的反应,并且起到在液体电解质与负极之间仅传递锂离子的离子通道(Ion Tunnel)的作用。
在现有技术中,在不含液体电解质添加剂、或含具有性质不佳的液体电解质添加剂的液体电解质中,由于会形成不均匀的SEI膜而难以指望电池寿命增强。而且,甚至在含有液体电解质添加剂但所加入的添加剂的量未调节到所需量时,存在着正极表面由于液体电解质添加剂而在高温反应中分解、或者液体电解质导致氧化反应并且最终导致二次电池的不可逆容量增加且电池的耐久性下降的问题。
发明内容
技术问题
鉴于上述,做出本发明。
本申请的发明人已经确定,当在非水液体电解质中包括含碳-碳三键的异氰酸酯类化合物添加剂时,功率输出性能和稳定性得到提高,并且本申请的发明人已完成本发明。
技术方案
本发明的一个实施方案提供一种非水液体电解质,包括:非水有机溶剂、锂盐和添加剂,其中所述添加剂是含碳-碳三键的异氰酸酯类化合物。
含碳-碳三键的异氰酸酯类化合物可包括选自以下化学式1至3表示的化合物中的一种或多种化合物。
[化学式1]
[化学式2]
[化学式3]
在化学式3中,R可以是直链或环状烷基、或芳基烷基化合物。
含碳-碳三键的异氰酸酯类化合物可以包括为基于非水液体电解质的总重量的0.05重量%至2重量%。
锂盐可以包括选自LiPF6、LiAsF6、LiCF3SO3、LiN(FSO2)2、LiN(CF3SO2)2、LiBF6、LiSbF6、LiN(C2F5SO2)2、LiAlO4、LiAlCl4、LiSO3CF3和LiClO4中的任一种、或两种以上这些物质的混合物,并且非水有机溶剂可包括腈基溶剂、直链碳酸酯、环状碳酸酯、酯、醚、酮或其组合。
有益效果
根据本发明的锂二次电池在非水液体电解质中包括含碳-碳三键的异氰酸酯类化合物,因此能够改善所制得的二次电池的功率输出性能和稳定性。
附图说明
图1是示出测量实施例1至4以及比较例1中所制成的二次电池于高温储存之后厚度增加的程度的结果的图。
具体实施方式
在下文中,将参照实施方式详细描述本发明。然而,根据本发明的实施方式可以修改为各种其他形式,并且本发明的范围不应被解释为限于下述实施方式。提供本发明的这些实施方式是为了向本领域普通技术人员更完整地描述本发明。
根据本发明的一个实施方式的非水液体电解质可包括非水有机溶剂、锂盐和添加剂,所述添加剂是含碳-碳三键的异氰酸酯类化合物。
异氰酸酯类化合物容易与薄膜态的电极表面反应,并且是一种具有在结构上易于配位Li离子的结构的化合物,具体地,异氰酸酯类化合物可包括选自以下化学式1至3表示的化合物中的一种或多种化合物。
[化学式1]
[化学式2]
[化学式3]
在化学式3中,R可以是直链或环状烷基、或芳基烷基化合物。
更具体地,R可以是在选自由以下化学式4至7表示的化合物中的化合物上除去两个异氰酸酯基团之外的烃基团。
[化学式4]
[化学式5]
[化学式6]
[化学式7]
根据本发明的一个实施方式的添加剂在液体电解质中具有对正电极或负电极表面上的-OH基团的亲和性(philic),并能够形成均匀的膜。更具体地,在异氰酸酯化合物的异氰酸酯基团中的氮(N)部分的+电荷与在正电极或负电极表面上的-OH基团反应。因此,根据本发明的一个实施方式的异氰酸酯类的化合物的添加剂能够在电极表面上形成稳定的SEI膜。
特别地,在异氰酸酯类化合物中的官能团之一的碳-碳三键能够通过还原反应形成稳定的膜,并且几乎没有还原反应的部分能够通过异氰酸酯基团与电极表面上的-OH基团反应形成稳定的SEI膜。换句话说,根据本发明的一个实施方式的同时包含碳-碳三键和异氰酸酯基团的化合物能够通过互补作用在电极表面上更有效地形成膜。
在此,异氰酸酯类化合物添加剂可包括为基于非水液体电解质的总重量的0.05重量%至2重量%。当异氰酸酯类化合物的含量小于0.05重量%时,根据本发明的一实施方式,寿命性能提高和高温耐久性提高的效果比较低,而当该含量大于2重量%时,在高温下气体产生的可能性会增加。
此外,根据本发明的一个实施方式的非水液体电解质还可以包括不同类型的添加剂。特别地,取决于目的,非水液体电解质可进一步包括用于形成固体电解质界面(SEI,Solid Electrolyte Interface)的通常公知的添加剂。例如,为了延长使用寿命,可进一步包括添加剂,例如碳酸亚乙烯酯、碳酸乙烯亚乙酯、1,3-丙烯磺内酯、1,3-丙烷磺酸内酯、琥珀酰酐、内酰胺类或己内酰胺类,这些均为寿命增强添加剂。此外,为了增强过充电,可进一步包括环己基苯、联苯、对氯苯等。添加剂不限于上述实例,为了提高电池性能,用于形成负极和正极膜的各种类型的添加剂可进一步添加到电解质中。
锂盐的实例可包括选自LiPF6、LiAsF6、LiCF3SO3、LiN(FSO2)2、LiN(CF3SO2)2、LiBF6、LiSbF6、LiN(C2F5SO2)2、LiAlO4、LiAlCl4、LiSO3CF3和LiClO4中的任意一种、或两种以上这些物质的混合物。
可包括在非水液体电解质中的非水有机溶剂没有限制,只要其在电池的充电和放电工艺期间将通过氧化反应等的分解减至最少,并且与添加剂一起显示出目标性能即可,非水有机溶剂的实例可包括腈基溶剂、环状碳酸酯、直链碳酸酯、酯、醚、酮等。这些溶剂可以单独使用或作为两种以上类型的组合使用。
在这些有机溶剂中,碳酸酯类有机溶剂会是有用的,并且环状碳酸酯可以是选自碳酸乙烯酯(EC)、碳酸丙烯酯(PC)和碳酸丁烯酯(BC)中的任一种、或两种以上的混合物,直链碳酸酯可以是选自碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯(DPC)、碳酸甲乙酯(EMC)、碳酸甲丙酯(MPC)和碳酸乙丙酯(EPC)中的任意一种、或两种以上的混合物。
腈基溶剂可以是选自乙腈、丙腈、丁腈、戊腈、辛腈、庚腈、环戊腈、环己腈、邻氟苯腈、对氟苯腈、二氟苯腈、三氟苯腈、苯乙腈、2-氟苯基乙腈和4-氟苯基乙腈中的一种或多种,根据本发明的一个实施方式的非水溶剂可以使用乙腈。
本发明的另一个实施方式可以是包含负极、正极、隔膜和含异氰酸酯类化合物的非水液体电解质的锂二次电池,其中SEI膜形成于负极或正极中至少一个的表面上。
当在液体电解质中所包含的具有碳-碳三键的异氰酸酯类化合物经历初始充电和放电工艺、或者注入到二次电池的液体电解质中时,SEI膜可以通过氨基甲酸酯键、或者负极或正极表面上的羟基(R’-OH)与非水液体电解质的异氰酸酯类化合物的氮(N)的静电作用而形成,或者通过异氰酸酯类化合物的官能团碳-碳三键的还原反应而形成。
通过在正极集电器上涂布正极混合物,然后干燥该所得物,可形成正极;通过在负极集电器上涂布负极混合物,然后干燥该所得物,可形成负极。
具体地,正极集电器没有特别限制,只要其具有高导电性且不会在相应的电池中引发化学变化即可。例如,不锈钢、铝、镍、钛、烧结碳、或表面用碳、镍、钛、银等处理过的铝或不锈钢均可使用。在此,正极集电器可以使用各种形式,例如在表面上形成有微小凹凸的膜、片、箔、网、多孔体、发泡体和无纺布,以便提高与正极活性材料的粘合强度。
此外,负极集电器没有特别限制,只要其具有导电性且不会在相应的电池中引发化学变化即可,例如,铜、不锈钢、铝、镍、钛、烧结碳、或表面用碳、镍、钛、银等处理过的铜或不锈钢、铝-镉合金等均可使用。与正极集电器一样,负极集电器可以使用各种形式,例如在表面上形成有微小凹凸的膜、片、箔、网、多孔体、发泡体和无纺布。
此外,在本发明的正极或负极中,正极混合物或负极混合物可包括含有至少一个羟基(-OH)的氧化物,其能够用于制备二次电池常用的正极或负极。
具体地,在正极混合物中,所述氧化物可包括选自锂钴基氧化物、锂锰基氧化物、锂铜氧化物、钒氧化物、锂镍基氧化物、锂锰复合氧化物和锂-镍-锰-钴基氧化物中的任一种锂过渡金属氧化物,且更具体地,可包括锂锰氧化物,例如Li1+xMn2-xO4(在此,x为0-0.33)、LiMnO3、LiMn2O3和LiMnO2;锂铜氧化物(Li2CuO2);钒氧化物例如LiV3O8、LiFe3O4、V2O5和Cu2V2O7;由LiNi1-xMxO2(在此,M=Co、Mn、Al、Cu、Fe、Mg、B或Ga,以及x=0.01-0.3)表示的锂镍氧化物;由LiMn2-xMxO2(在此,M=Co、Ni、Fe、Cr、Zn或Ta,以及x=0.01-0.1)或Li2Mn3MO8(在此,M=Fe、Co、Ni、Cu或Zn)表示的锂锰复合氧化物;由Li(NiaCobMnc)O2(在此,0<a<1,0<b<1,0<c<1,a+b+c=1)表示的锂-镍-锰-钴基氧化物;以及诸如此类,但不限于此。
在负极混合物中,所述氧化物可包括促进锂离子吸收和释放的含锂的钛复合氧化物(LTO),选自Si、Sn、Li、Zn、Mg、Cd、Ce、Ni和Fe等中的任一种金属(Me)的氧化物(MeOx),且具体地,可包括金属复合氧化物,例如LixFe2O3(0=x=1)、LixWO2(0<x=1)、SnxMe1-xMe’yOz(Me:Mn、Fe、Pb、Ge;Me’:Al、B、P、Si、周期表中第1、2和3族的元素,卤素;0<x=1;1=y=3;1=z=8);或氧化物,例如SnO、SnO2、PbO、PbO2、Pb2O3、Pb3O4、Sb2O3、Sb2O4、Sb2O5、GeO、GeO2、Bi2O3、Bi2O4和Bi2O5等,以及诸如结晶碳、无定形碳或碳复合物之类的碳基负极活性材料可单独使用或作为两种以上的混合物使用,并且碳粉可用于本发明的一个实施方式中。
在此,正极混合物或负极混合物还可包括粘合剂树脂、导体、填料和其它添加剂。
粘合剂树脂是对电极活性材料和导体的粘合以及用于集电器的粘合起到帮助的一种组分,且通常是以基于电极混合物的总重量的1重量%-50重量%进行添加。这种粘合剂的实例可包括聚偏二氟乙烯(PVDF)、聚乙烯醇、羧甲基纤维素(CMC)、淀粉、羟丙基纤维素、再生纤维素、聚乙烯吡咯烷酮、四氟乙烯、聚乙烯、聚丙烯、乙烯-丙烯-二烯单体(EPDM)、磺化的EPDM、丁苯橡胶(SBR)、氟橡胶和各种共聚物等。
导体是用于进一步提高电极活性材料的导电性的一种组分,且可以基于电极混合物的总重量的1重量%-20重量%进行添加。这种导体没有特别限制,只要其具有导电性且不会在相应的电池中引发化学变化即可,并且导体的实例可包括石墨,例如天然石墨或人工石墨;炭黑,例如炭黑、乙炔黑、Ketjen黑、槽法炭黑、炉法炭黑、灯黑或热炭黑;导电纤维,例如碳纤维或金属纤维;金属粉末,例如氟化碳粉、铝粉或镍粉;导电晶须,例如氧化锌或钛酸钾;导电金属氧化物,例如氧化钛;聚苯撑的衍生物等。
填料是抑制电极膨胀的一种组分,可以根据需要使用,并且没有特别限制,只要其是不会在相应的电池中引发化学变化的纤维材料即可,并且填料的实例可包括烯烃类的聚合物,例如聚乙烯或聚丙烯;或纤维材料,例如玻璃纤维或碳纤维。
隔膜可使用本领域中用作隔膜的常规的多孔聚合物膜,例如,利用聚烯烃类聚合物制备的多孔聚合物膜,例如乙烯均聚物、丙烯均聚物、乙烯/丁烯共聚物、乙烯/己烯共聚物和乙烯/甲基丙烯酸酯共聚物,可单独使用或作为其叠层使用,或者常规的多孔无纺布,例如由高熔点玻璃纤维、聚对苯二甲酸乙二醇酯纤维等制成的无纺布可以使用,但是,隔膜并不局限于此。
实施例
实施例1
(非水液体电解质的制备)
通过加入具有碳酸乙烯酯(EC):碳酸甲乙酯(EMC):碳酸二甲酯(DMC)=3:3:4(重量比)组成的非水有机溶剂、基于非水液体电解质总量的1.0mol/L作为锂盐的LiPF6、和基于非水液体电解质总量的0.5重量%作为添加剂的化学式1表示的化合物来制备非水液体电解质。
(正极的制备)
通过将94重量%作为正极活性材料的Li(Ni0.6Co0.2Mn0.2)O2、3重量%作为导体的炭黑、以及3重量%作为粘合剂的PVdF加入到溶剂N-甲基-2-吡咯烷酮(NMP)中来制备正极混合物浆料。将该正极混合浆料涂覆在具有20μm厚度的铝(Al)薄膜(正极集电器)上,并将所得物干燥,以制备含孔洞的正极。
(负极的制备)
通过将95.5重量%作为负极活性材料的碳粉、1.5重量%的超-P(导体)和3重量%的SBR/CMC(粘合剂)加入到H2O中来制备负极混合物浆料。将该浆料涂覆在铜箔的两个表面上,并将所得物干燥并压制,以制备负极。
(电池组装)
将以上制备的负极和正极、以及由聚丙烯/聚乙烯/聚丙烯(PP/PE/PP)的三层所形成的隔膜以堆叠方式进行组装,然后将上面制备的液体电解质注入其中,以最终完成电池。
实施例2
除了使用由化学式2形成的异氰酸酯类化合物作为非水液体电解质添加剂代替由化学式1表示的化合物以外,以与实施例1相同的方式完成二次电池。
实施例3
除了使用在化学式3化合物中的R由化学式4形成的异氰酸酯类化合物代替由化学式1表示的化合物作为非水液体电解质添加剂以外,以与实施例1相同的方式完成二次电池。
实施例4
除了化学式1表示的化合物以0.3重量%使用且碳酸亚乙烯酯以1重量%使用作为非水液体电解质添加剂以外,以与实施例1相同的方式完成二次电池。
比较例1
除了在非水液体电解质中不包括添加剂以外,以与实施例1相同的方式完成二次电池。
测试例1
<容量特性评价>
将实施例1至4和比较例1中制造的二次电池在恒流/恒压(CC/CV)条件下用1C充电至4.15V/38mA,然后在恒流(CC)条件下用1C放电至2.5V,并测量放电容量。结果示于下表1中。
测试例2
<使用HPPC的放电电阻测定>
使用混合脉冲功率表征(HPPC)试验来测量实施例1至4和比较例1中制造的二次电池的电阻。用1C(30mA)将电池完全充电(SOC=100)至4.15V,然后从SOC100放电至10,并将每个电池稳定1小时。在每个SOC阶段使用HPPC测试方法来测量每个锂二次电池的放电电阻。结果示于下表1中。
测试例3
<电池厚度增加率的测量>
测量在实施例1至4和比较例1中制造的二次电池的厚度,并且于60℃存储电池一周和两周后再次测量厚度。电池厚度的程度示于图1中。
【表1】
初始容量(mAh) | 放电电阻(mΩ) | |
实施例1 | 748 | 48 |
实施例2 | 745 | 49 |
实施例3 | 744 | 52 |
实施例4 | 746 | 50 |
比较例1 | 745 | 54 |
参见表1,可以确定,与不包含添加剂的比较例1的锂二次电池相比,包括本发明的含碳-碳三键的异氰酸酯类化合物作为添加剂的非水液体电解质的实施例1至4的锂二次电池表现出较低的放电电阻。
另外,如图1所示,包括本发明的含碳-碳三键的异氰酸酯类化合物作为添加剂的非水液体电解质的实施例1至4的锂二次电池在高温下储存时经历小的厚度增加,并且特别地,电池在高温下储存两周后,厚度增加的差异更加明显,并且可以确定,当包括含碳-碳三键的异氰酸酯类化合物作为添加剂时,锂二次电池能够具有提高的高温存储性,并因此在高温储存后降低了厚度的增加。
Claims (10)
1.一种非水液体电解质,包括:非水有机溶剂,锂盐和添加剂,
其中所述添加剂是含碳-碳三键的异氰酸酯类合物。
4.根据权利要求1所述的非水液体电解质,其中所述锂盐包括选自LiPF6、LiAsF6、LiCF3SO3、LiN(FSO2)2、LiN(CF3SO2)2、LiBF6、LiSbF6、LiN(C2F5SO2)2、LiAlO4、LiAlCl4、LiSO3CF3和LiClO4中的任意一种、或两种以上这些物质的混合物。
5.根据权利要求1所述的非水液体电解质,其中所述非水有机溶剂包括腈基溶剂、直链碳酸酯、环状碳酸酯、酯、醚、酮或其组合。
6.根据权利要求5所述的非水液体电解质,其中,所述环状碳酸酯是选自碳酸乙烯酯(EC)、碳酸丙烯酯(PC)和碳酸丁烯酯(BC)组成的组中的任意一种、或两种以上的混合物,所述直链碳酸酯是选自由碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯(DPC)、碳酸甲乙酯(EMC)、碳酸甲丙酯(MPC)和碳酸乙丙酯(EPC)中的任意一种、或两种以上的混合物。
7.根据权利要求5所述的非水液体电解质,其中,所述腈基溶剂为选自乙腈、丙腈、丁腈、戊腈、辛腈、庚腈、环戊腈、环己腈、邻氟苯腈、对氟苯腈、二氟苯腈、三氟苯腈,苯乙腈、2-氟苯基乙腈和4-氟苯乙腈中的一种或多种。
8.根据权利要求1所述的非水液体电解质,其中,所述含碳-碳三键的异氰酸酯类化合物包括为基于所述非水液体电解质的总重量的0.05重量%-2重量%。
9.一种锂二次电池,包括:负极、正极、隔膜和非水液体电解质,
其中所述非水液体电解质是权利要求1至8中的任一项所述的非水液体电解质,并且SEI膜形成于负极或正极中至少一个的表面上。
10.根据权利要求9所述的锂二次电池,其中,所述SEI膜是通过氨基甲酸酯键、或者负极或正极的表面上的羟基(R’-OH)与非水液体电解质的含碳-碳三键的异氰酸酯类化合物的氮(N)的静电作用而形成,或者是通过异氰酸酯类化合物的官能团碳-碳三键的还原反应而形成。
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