CN102104172B - 改进电池安全性的电解质溶剂和包含其的锂二次电池 - Google Patents
改进电池安全性的电解质溶剂和包含其的锂二次电池 Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 66
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000002904 solvent Substances 0.000 title abstract description 53
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 40
- 239000011737 fluorine Substances 0.000 claims abstract description 39
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 37
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000011244 liquid electrolyte Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 description 22
- -1 trifluoropropylidenyl Chemical group 0.000 description 14
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
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- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
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- 239000000463 material Substances 0.000 description 4
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 238000002347 injection Methods 0.000 description 2
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- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 1
- CRJXZTRTJWAKMU-UHFFFAOYSA-N 4,4,5-trifluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1(F)F CRJXZTRTJWAKMU-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
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- 244000025254 Cannabis sativa Species 0.000 description 1
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- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910011279 LiCoPO4 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910014054 LiNi1-xCoxMyO2 Inorganic materials 0.000 description 1
- 229910014849 LiNi1−XCoXMYO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 description 1
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 239000005030 aluminium foil Substances 0.000 description 1
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- 239000010406 cathode material Substances 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
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- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
本发明提供电池的电解质溶剂,其包括氟亚乙基碳酸酯和线型酯溶剂。此外,本发明还提供包括正极、负极和电解质的锂二次电池,其中电解质包括氟亚乙基碳酸酯和线型酯溶剂。本发明的电解质溶剂可以提高电池的安全性而不破坏电池性能。
Description
本申请为国际申请日2004年9月6日、国际申请号PCT/KR2004/002252于2006年3月3日进入中国国家阶段、申请号200480025357.X、发明名称“改进电池安全性的电解质溶剂和包含其的锂二次电池”的分案申请。
技术领域
本发明涉及用于改进电池安全性的电解质溶剂和包含该溶剂的锂二次电池。
背景技术
随着移动装置,例如高性能笔记本电脑和移动电话在全世界变得越来越普遍,对于具有高能量密度的高性能二次电池的需求正急剧提高。具体的,尽管它的历史较短,锂离子二次电池正越来越多应用于大多数移动电子产品中,并因此正积极地进行通过提高锂二次电池的容量而延长移动装置的运行时间的研究。然而,由于电池容量的提高导致电池安全性的恶化,对于提高锂二次电池的安全性有着多种尝试。
综合到目前为止对锂二次电池安全性进行的研究结果,活性物质和电解液在充电状态的热稳定性对电池安全性具有最大的影响。因此,提高锂二次电池安全性的研究主要由尝试开发具有优良的热稳定性的正极活性物质和研究提高电解液热稳定性组成。
目前,用于锂二次电池电解液的溶剂主要是环状的和线状的碳酸酯。这样的溶剂是易燃的,因此在电池内由于局部短路或环境温度增加而导致温度升高的情况下,溶剂将容易与活性物质,特别是正极活性物质的结构降解产生的氧反应,产生氧化和爆炸。出于这一原因,赋予电解液阻燃性将大大有助于改善电池安全性。
对可用于锂二次电池的阻燃电解液的许多研究已经围绕含有在碳酸酯中具有置换氢的氟的化合物的溶剂或含有磷的溶剂而进行。这样的溶剂比早先的碳酸盐或酯溶剂具有更低的可燃性和易燃性,但是为了使电解液具有足够的阻燃性需要以很大的量使用。此外,这样的阻燃溶剂比现有的环状碳酸酯显示出更低的锂盐溶解性,且包含原子量比氢更高的氟或磷,使得电解液粘性大大增加。因而,如果电解液溶剂中该阻燃溶剂的体积比增加,由于锂离子电导率的大大降低,电池性能将要显著劣化。
日本专利公开出版号Hei 10-199567公开了如果以相对于电解质溶剂总体积60-90%的量使用以下通式1的三氟亚丙基碳酸酯,则可以改进电池的安全性:
[通式1]
然而,三氟亚丙基碳酸酯的粘性比通常使用溶剂亚乙基碳酸酯或亚丙基碳酸酯的粘性高大约两倍。因此,如果以日本专利公开中描述的量使用,将导致电离质的离子电导率的显著降低,从而不可避免产生电池性能的破坏。此外,因为三氟亚丙基碳酸酯是氟取代的亚丙基碳酸酯,其具有亚丙基碳酸酯的一些缺点。因此,如果其用于电解质溶剂中,在石墨负极和电解质之间的界面形成的涂层稳定性将不足,且将在电池的充电/放电寿命周期发生问题,如Electrochimica Acta Vol.45,p.99,1999所述。
US专利6,506,524描述了由氟亚乙基碳酸酯和亚丙基碳酸酯组成的溶剂用作电解质溶剂,且能够在石墨负极材料表面上形成得到的电解质稳定的保护层。然而,如果这个组合物的溶剂用作电解质溶剂,电解质的离子电导率将降低为小于7mS/cm,从而恶化电池的性能,这是因为氟亚乙基碳酸酯和亚丙基碳酸酯具有高介电常数但是具有不符合需要的高粘度。
附图说明
图1示例了现有的圆柱电池的结构。
图2和3是显示在满充电状态(4.2V)分别对比较实例3和实例2中制造的电池进行热箱试验的结果的图表。
图4和5是显示在过充状态(4.35V)分别对比较实例3和实例2中制造的电池进行热箱试验的结果的图表。
发明内容
本发明的发明人发现如果三氟亚乙基碳酸酯连同线状酯溶剂用作电池的电解质溶剂,电池的安全性将得到改进而与现有技术不同,电池性能没有恶化。
因此本发明的目的是提供电池的电解质溶剂,其包括氟亚乙基碳酸酯和线型酯溶剂,以及包含上述电解质溶剂的锂二次电池。
在一个方面,本发明提供包含氟亚乙基碳酸酯和线型酯溶剂的电池电解质溶剂。
在另一个方面,本发明提供包括正极、负极和电解质的锂二次电池,其中电解质包括氟亚乙基碳酸酯和线型酯溶剂。
下文中,将详细地描述本发明。
本发明提供用于电池的电解质溶剂,其包括氟亚乙基碳酸酯和线型酯溶剂。
可被用于本发明的氟亚乙基碳酸酯选自由以下通式2表示的单氟亚乙基碳酸酯的(F1EC),通式3或4表示的二氟乙烯碳酸酯,和其混合物:
[通式2]
[F1EC]
[通式3]
[反-二-FEC]
[通式4]
[顺-二-FEC]
在电池初始充电的情况下,氟亚乙基碳酸酯在负极形成具有高热稳定性的涂层,在电池暴露于高温的情况下,其在电极活性物质表面形成涂层,使得其抑制快速发热反应,从而显著改善电池安全性。具体地说,不同于无氟的碳酸酯,其在负极形成稳定的涂层。因此,在锂二次电池中,氟亚乙基碳酸酯阻止锂和电解质之间反应导致的锂损失,并因为其仅仅在高压表现氧化分解而阻止电解质分解。这使得电池储存特性改善。
此外,与日本专利公开号Hei 10-199567所述的含有至少三个氟原子的三氟亚丙基碳酸酯不同,氟亚乙基碳酸酯的仅仅包含一个或两个氟原子。因此,它可以防止在使用含有至少三个氟原子的化合物的情况下出现的粘性过度增加的问题,从而防止电池性能的恶化。此外,本领域公知的是,如果使用日本专利公开中描述的三氟亚丙基碳酸酯,由三氟亚丙基碳酸酯形成的涂层的稳定性不足,并将由于亚丙基碳酸酯本身的缺点出现电池充电/放电寿命周期的问题。反之,用在本发明中的氟亚乙基碳酸酯不引起这样的问题。
通过连同氟亚乙基碳酸酯一起使用线型酯化合物,本发明不仅能提高电池安全性而且防止电池性能的恶化,这是与现有技术不同的。具体的描述如下。
下面的表1显示下列物质的物理性质:氟亚乙基碳酸酯(F 1EC,F2EC),三氟亚丙基碳酸酯(TFPC),碳酸亚乙酯(EC),亚丙基碳酸酯(PC),碳酸二甲酯(DMC),乙基碳酸甲酯(EMC),碳酸二乙酯(DEC),乙二醇二乙酸酯(EA)和丙酸甲酯(MP),这些是现有技术已知的电解质溶剂。
表1:电解质溶剂的物理性质
溶剂 | 粘性(室温) | 介电常数 | 分子量 |
F1EC | 4.1 | 78.4 | 106.1 |
顺-F2EC | 2.5 | 37.1 | 124.0 |
TFPC | 5.0 | 62.0 | 156.0 |
EC | 2.5 | 89 | 88.1 |
PC | 2.53 | 65 | 102.1 |
DMC | 0.59 | 3.1 | 90.1 |
EMC | 0.65 | 3.0 | 104.1 |
DEC | 0.75 | 2.8 | 118.1 |
EA | 0.44 | 6.0 | 88.11 |
MP | 0.43 | 6.2 | 88.11 |
如表1所示,氟亚乙基碳酸酯(F1EC或F2EC)具有很高的粘性。因此,如果其单独使用将导致电池性能的恶化。
此外,环状碳酸酯(EC和PC)具有比线状碳酸酯(DMC,EMC,DEC,EA和MP)更高的粘性。因此,即使当氟亚乙基碳酸酯连同环状碳酸酯一起用作电解质溶剂,其也将破坏电池性能。例如,US专利6,506,524公开了氟亚乙基碳酸酯连同环状亚丙基碳酸酯的使用,在这样情况下电池性能将由于离子电导率的降低而恶化。
用于日本专利公开号Hei 10-199567的三氟亚丙基碳酸酯(TFPC)具有比氟亚乙基碳酸酯(F1EC或F2EC)高得多的粘性。因此,如果其与线状碳酸酯的溶剂组合使用,难以防止电池性能的恶化。
因此,在本发明中,氟亚乙基碳酸酯连同线型酯溶剂一起用作电池的电解质溶剂。这可以提高电池安全性而不破坏电池性能。
同时,日本专利公开号Hei 8-115742示出了使用氯亚乙基碳酸酯和线状碳酸酯作为电解质溶剂的例子。然而,如Journal of Power Source,81-82(1999),p.20所述的,如果氯亚乙基碳酸酯(C1EC)连同线状碳酸酯一起用作电解质溶剂,则在负极通过氯亚乙基碳酸酯(C1EC)的还原分解形成氯化锂(LiCl)。形成的氯化锂(LiCl)移动到正极形成氯气(Cl2),其随后移动到负极成为氯负离子(Cl-)。因为这个反应是重复的,连同线状碳酸酯一起使用氯亚乙基碳酸酯作为电解质溶剂对电池性能产生负面影响。
另一方面,用作发明电解质溶剂一个组分的由氟亚乙基碳酸酯(F1EC)形成氟化锂(LiF)具有比氯化锂低的溶解性,指示如上所述重复反应的降低。因此,所述发明的电解质溶剂与其中氯亚乙基碳酸酯连同线状碳酸酯一起用作电解质溶剂的情况相比,表现出电池性能恶化的减少。
简单地说,在本发明中,氟亚乙基碳酸酯结合线型酯溶剂用作不同于上述US专利和日本专利公开的电解质溶剂,从而改善电池安全性而不破坏电池性能。
可被用于本发明的线型酯溶剂包括酯(R-COO-R’)溶剂和碳酸酯(R-OCOO-R’)溶剂。其具体的例子包括但是不限于,乙基碳酸甲酯,二甲基碳酸酯,碳酸二乙酯,乙酸乙酯,丙酸甲酯,和上述两种或多种物质的混合物。
用于电池的本发明的电解质溶剂优选包含基于电解质溶剂总体积,按体积计算20-60%量的氟亚乙基碳酸酯。如果包含体积低于20%量的氟亚乙基碳酸酯,其不能提供电池足够的安全性和存储特性,如果其包含的体积量超过60%,对电池性能产生负面影响。同时,线型酯溶剂优选基于电解质溶剂的总体积包含体积量40-80%。
在另一个方面,本发明提供包括正极、负极和电解质的锂二次电池,其中电解质包括创造性的电解质溶剂和锂盐。
除使用本发明的电解质溶剂之外,可以使用本领域已知的相同材料和方法制造本发明的锂二次电池。例如,可以通过在正极和负极之间通过常规方法插入多孔隔离物以产生电极结构,将电极结构放入电池盒内并向产生的电池盒注入本发明的非水相电解质而制造本发明的锂二次电池。
可被用于本发明的锂盐的例子包括但是不限于锂六氟磷酸盐(LiPF6),锂四氟硼酸盐(LiBF4),锂三氟甲烷磺酰亚胺(LiN(CF3SO2)2),锂双(全氟乙基磺酰)亚胺(LiN(C2F5SO2)2),三氟甲烷磺酰甲基化锂(LiC(CF3SO2)3),lithium triflate(LiCF3SO3),锂二草酸基硼酸酯演(LiC4BO8)和其两种或多种的混合物。
本发明的电解质优选在室温具有大于7毫秒/厘米,和更优选8毫秒/厘米的离子电导率。在离子电导率小于7毫秒/厘米时,离子在电解质中的移动缓慢,从而破坏电池性能。
在本发明中,用于正极的活性物质包括锂过渡金属复合物氧化物。其非限制的例子包括LiCoO2,LiNiO2,LiMn2O4,LiMnO2和LiNi1-XCoXMYO2(M=Al、Ti、Mg或Zr,0<X≤1,0≤Y≤0.2),LiNiXCoYMn1-X-YO2(0<X≤0.5,0<Y≤0.5),LiMxM’yMn(2-x-y)O4(M,M’=V、Cr、Fe、Co、Ni或Cu,0<X≤1,0<Y≤1),LiCoPO4等。
在本发明中,用于负极的材料包括能够吸收、存储和释放锂的材料,其非限制性的例子包括可以吸收、存储和释放锂的碳、硅和锡化合物。
通过包含氟亚乙基碳酸酯和线型酯溶剂的电解质溶剂,本发明的锂二次电池具有改进的安全性而不破坏电池性能。
具体实施方式
以下通过实施例更加详细地描述本发明。但是,应该理解,本发明不局限于实例。
实例:制备电解质和测量离子电导率。
实例1到7和比较实例1和2
单氟亚乙基碳酸酯(F1EC)和乙基碳酸甲酯按以下表2给定的体积比互相混合以便制备溶剂。六氟磷酸锂(LiPF)盐溶解在制备的每个溶剂中,浓度为0.8-1.2M以便制备电离质。在室温使用Metrohm 712电导计测量电解质的离子电导率。
实例8到12
用和1-7同样的方法制备电解质和测量离子电导率,除了使用表2给定的体积比的二甲基碳酸酯(DMC)代替乙基碳酸甲酯。
比较实例3和4
用和1-7同样的方法制备电解质和测量离子电导率,除了使用表2给定的体积比的碳酸亚乙酯和乙基碳酸甲酯或二甲基碳酸酯,而不使用氟亚乙基碳酸酯。
比较实例5和6
用和1-7同样的方法制备电解质和测量离子电导率,除了使用表2给定的体积比的氟亚乙基碳酸酯,碳酸亚乙酯和乙基碳酸甲酯。
比较实例7
用和实施例1-7同样的方法制备电解质和测量离子电导率,除了使用表2给定的体积比的氟亚乙基碳酸酯和亚丙基碳酸酯。
制造电池
为了评估电池的性能和安全性,使用实例1-12和比较实例1-7制备的电解质制造具有图1显示的结构的锂二次电池。具体地,涂有作为负极活性物质的碳的负极集电器(铜箔)形成的负极,涂有作为正极活性物质的LiCoO2的正极集电极(铝箔)形成的正极,和多孔聚烯烃隔离物,环绕圆柱状胶体质卷状物几次。然后,在绝缘体被放置到圆柱状胶体质卷状物的上端和下端后,得到的圆柱状胶体质卷状物被放置在直径18mm和高度65mm的圆柱状电池盒中。之后,将制备的电解质注入得到的电池盒内,从而制造电池。
性能评估
通过电流1C放电容量和0.2C放电容量的比率评估电池的放电特性。结果显示于下面表3。
安全性评估
直径18mm和高度65mm的电池被满充电到4.2V或过充电到4.3V,然后放置在热空气烘箱中以5℃/分钟的速度被加热到150℃。当电池在烘箱中保持在该温度,测量电池热爆炸的时间。结果显示于表3和图2到5。
表2.电解质溶剂的组成
表3:电池性能和安全性的测试结果
从上述表3可以看出,包含氟亚乙基碳酸酯连同线型酯溶剂一起作为电解质溶剂的实例的电池在离子电导率和安全性都是优良的。
然而,比较实例3和4的电池,其不包含氟亚乙基碳酸酯,表现出比实例1-12制造的电池低得多的安全性。此外,比较实例5和6的电池,其包含相对少量的氟亚乙基碳酸酯而含有环状碳酸酯,显示出安全性比实例1-12的电池差。此外,比较实例7的电池,其包含氟亚乙基碳酸酯和亚丙基碳酸酯(环状碳酸酯)而不使用线型酯溶剂,该电池的放电特性和安全性不能测量,这是因为由于电解质的高粘度电极没有被浸渍。
同时,图4和5显示在过充电到4.35V的电池的安全试验结果。如图4和5所示,比较实例3制造的电池甚至不能在150℃的烘箱中保持40分钟(图4),而实例2中制造的电池在150℃的烘箱保持其安全性超过2小时。
工业实用性
从上文可以看出,根据本发明提供氟亚乙基碳酸酯结合线型酯用作电池的电解质溶剂。这可以提高电池安全性而防止电池性能的恶化。
Claims (2)
1.一种电池的液体电解质,其组成为0.8-1.2M LiPF6,33vol%的单氟亚乙基碳酸酯,以及67vol%的乙基碳酸甲酯。
2.一种锂二次电池,其包括正极、负极和电解质,其中该电解质为权利要求1所述的液体电解质。
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US20050031963A1 (en) | 2005-02-10 |
EP1661200A4 (en) | 2009-09-30 |
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CN102104172A (zh) | 2011-06-22 |
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BRPI0413390B1 (pt) | 2017-09-12 |
CN1846326A (zh) | 2006-10-11 |
EP1661200A1 (en) | 2006-05-31 |
TW200520276A (en) | 2005-06-16 |
BRPI0413390A (pt) | 2006-10-17 |
US8372549B2 (en) | 2013-02-12 |
KR20050024270A (ko) | 2005-03-10 |
EP2605323A1 (en) | 2013-06-19 |
TWI255060B (en) | 2006-05-11 |
KR100657225B1 (ko) | 2006-12-14 |
KR100751205B1 (ko) | 2007-08-22 |
US20120177956A1 (en) | 2012-07-12 |
WO2005024991A1 (en) | 2005-03-17 |
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