JP2015522209A - リチウム二次電池用電解液添加剤、前記電解液添加剤を含む非水性電解液及びリチウム二次電池 - Google Patents
リチウム二次電池用電解液添加剤、前記電解液添加剤を含む非水性電解液及びリチウム二次電池 Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 73
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 42
- 239000000654 additive Substances 0.000 title claims abstract description 30
- 230000000996 additive effect Effects 0.000 title claims abstract description 29
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims abstract description 35
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 30
- -1 vinylidene carbonate compound Chemical class 0.000 claims abstract description 28
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 21
- 239000002000 Electrolyte additive Substances 0.000 claims description 20
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 10
- 150000008053 sultones Chemical class 0.000 claims description 10
- BUPLCMMXKFWTTA-UHFFFAOYSA-N 4-methylidene-1,3-dioxetan-2-one Chemical compound C=C1OC(=O)O1 BUPLCMMXKFWTTA-UHFFFAOYSA-N 0.000 claims description 8
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 4
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 4
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 claims description 2
- 229910010238 LiAlCl 4 Inorganic materials 0.000 claims description 2
- 229910010090 LiAlO 4 Inorganic materials 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910013075 LiBF Inorganic materials 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- 229910012424 LiSO 3 Inorganic materials 0.000 claims description 2
- 229910012513 LiSbF 6 Inorganic materials 0.000 claims description 2
- AVTOEKKTKXLWDL-UHFFFAOYSA-N acetylene;1,3-dioxolan-2-one Chemical compound C#C.O=C1OCCO1 AVTOEKKTKXLWDL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 claims description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims 2
- 230000008961 swelling Effects 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 40
- 239000010408 film Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910003543 Li(Ni0.33Co0.33Mn0.33)O2 Inorganic materials 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910015644 LiMn 2 - z Ni Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- VIEVWNYBKMKQIH-UHFFFAOYSA-N [Co]=O.[Mn].[Li] Chemical compound [Co]=O.[Mn].[Li] VIEVWNYBKMKQIH-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
Images
Classifications
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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
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/056—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
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M10/056—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
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- H01M10/056—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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte 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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
[電解液の製造]
エチレンカーボネート(EC):エチルメチルカーボネート(EMC):ジメチルカーボネート(DMC)=3:3:4(体積比)の組成を有する非水性有機溶媒及び1.0MのLiPF6を含む混合溶媒に、電解液総量を基準に、リチウムジフルオロホスフェート0.2重量%、ビニレンカーボネート(VC)3重量%及び1,3-プロパンスルトン(PS)0.5重量%を添加して非水性電解液を製造した。
正極活物質として、LiMn2O4及びLi(Ni0.33Co0.33Mn0.33)O2の混合物92重量%、導電剤としてカーボンブラック(carbon black)4重量%、バインダとしてポリビニリデンフルオライド(PVdF)4重量%を溶媒であるN-メチル-2-ピロリドン(NMP)に添加して正極混合物スラリーを製造した。前記正極混合物スラリーを厚さが20μm程度の正極集電体であるアルミニウム(Al)薄膜に塗布し、乾燥して正極を製造した後、ロールプレス(roll press)を行って正極を製造した。
添加剤として、リチウムジフルオロホスフェートを1重量%添加した電解液添加剤を用いたことを除いては、実施例1と同一にして非水性電解液及びリチウム二次電池を製造した。
添加剤として、ビニレンカーボネート(VC)を2.9重量%、1,3-プロパンスルトンを0.5重量%添加した電解液添加剤を用いたことを除いては、実施例2と同一にして非水性電解液及びリチウム二次電池を製造した。ここで前記ビニレンカーボネート(VC)と1, 3-プロパンスルトン(PS)の重量比は5.8:1であった。
添加剤として、リチウムジフルオロホスフェートを含まない電解液添加剤を用いたことを除いては、実施例1と同一にして非水性電解液及びリチウム二次電池を製造した。
添加剤として、ビニレンカーボネート(VC)及び1,3-プロパンスルトン(PS)を含まない電解液添加剤を用いたことを除いては、実施例1と同一にして非水性電解液及びリチウム二次電池を製造した。
添加剤として、リチウムジフルオロホスフェートを1.2重量%添加した電解液添加剤を用いたことを除いては、実施例1と同一にして非水性電解液及びリチウム二次電池を製造した。
添加剤として、ビニレンカーボネート(VC)を3.1重量%、1,3-プロパンスルトンを0.5重量%添加した電解液添加剤を用いたことを除いては、実施例2と同一にして非水性電解液及びリチウム二次電池を製造した。ここで、前記ビニレンカーボネート(VC)と1,3-プロパンスルトン(PS)の重量比は6.2:1であった。
<リチウム二次電池の低温出力特性の実験>
実施例1及び比較例1のリチウム二次電池を-30℃でSOC(充電深度)別に、0.5Cで10秒間放電して発生する電圧差で低温出力を計算した。その結果を図1に示す。
<リチウム二次電池の高温サイクル特性の実験>
実施例1、及び比較例1と2のリチウム二次電池を55℃で定電流/定電圧(CC/CV)条件で4.2V/38mAまで1Cで充電した後、定電流(CC)条件で3.03Vまで3Cで放電し、その放電容量を測定した。これを1から1000サイクルで繰り返して行って、測定した放電容量を図2に示した。
<リチウム二次電池の高温貯蔵後の出力特性の実験>
実施例1及び比較例1のリチウム二次電池を60℃で貯蔵した後、SOC 50%において5Cで10秒間放電して発生する電圧差で出力を計算した。その結果を図3に示す。
<リチウム二次電池の高温貯蔵後のスエリング(swelling)特性の実験>
実施例1及び比較例1のリチウム二次電池を60℃で貯蔵した後、SOC 95%で貯蔵した後の電池厚さを測定してその結果を図4に示す。
<リチウム二次電池の低温出力特性の実験>
実施例2及び比較例3のリチウム二次電池を-30℃でSOC(充電深度)別に、0.5Cで10秒間放電して発生する電圧差で低温出力を計算した。その結果を図5に示す。
<リチウム二次電池の高温サイクル特性実験>
実施例2、及び比較例3のリチウム二次電池を55℃で、定電流/定電圧(CC/CV)条件で4.2V/38mAまで1Cで充電した後、定電流(CC)条件で3.03Vまで3Cで放電し、その放電容量を測定した。これを1から800サイクルで繰り返して行って、測定した放電容量を図7に示した。
<リチウム二次電池の高温貯蔵後の出力特性の実験>
実施例2、及び比較例3のリチウム二次電池を60℃から12週間貯蔵した後、定電流/定電圧(CC/CV)条件で4.2V/38mAまで1Cで充電した後、定電流(CC)条件で3.0Vまで1Cで放電し、その放電容量を測定した。結果を図9に示した。
Claims (14)
- リチウムジフルオロホスフェート(LiDFP)、ビニリデンカーボネート系化合物及びスルトン系化合物を含む電解液添加剤。
- 前記リチウムジフルオロホスフェートの含量は、電解液総量を基準に0.05から5重量%である請求項1に記載の電解液添加剤。
- 前記リチウムジフルオロホスフェートの含量は、電解液総量を基準に0.05から1重量%である請求項2に記載の電解液添加剤。
- 前記ビニリデンカーボネート系化合物は、ビニレンカーボネート、ビニレンエチレンカーボネート、またはこれらの組合せである請求項1に記載の電解液添加剤。
- 前記ビニリデンカーボネート系化合物の含量は、電解液総量を基準に0.1から5重量%である請求項1に記載の電解液添加剤。
- 前記スルトン系化合物は、1,3-プロパンスルトン、1,4-ブタンスルトン、1,3-プロペンスルトンからなる群より選択されるいずれか一つ、またはこれらのうち2種以上の混合物である請求項1に記載の電解液添加剤。
- 前記スルトン系化合物の含量は、電解液総量を基準に0.01から5重量%である請求項1に記載の電解液添加剤。
- 前記ビニリデンカーボネート系化合物及び前記スルトン系化合物は、重量比が1:1〜6:1である請求項1に記載の電解液添加剤。
- リチウムジフルオロホスフェート(LiDFP)、ビニリデンカーボネート系化合物及びスルトン系化合物を含む電解液添加剤;
非水性有機溶媒;及び
リチウム塩を含む非水性電解液。 - 前記電解液添加剤の含量は、電解液総量を基準に1から10重量%であることを特徴とする請求項9に記載の非水性電解液。
- 前記リチウム塩は、LiPF6、LiAsF6、LiCF3SO3、LiN(CF3SO2)2、LiBF4、LiBF6、LiSbF6、LiN(C2F5SO2)2、LiAlO4、LiAlCl4、LiSO3CF3及びLiClO4からなる群より選択されるいずれか一つ、またはこれらのうち2種以上の混合物を含む請求項9に記載の非水性電解液。
- 前記非水性有機溶媒は、線形カーボネート、環状カーボネート、エステル、エーテル、ケトンまたはこれらの組合せを含むことを特徴とする請求項9に記載の非水性電解液。
- 前記環状カーボネートは、エチレンカーボネート(EC)、プロピレンカーボネート(PC)及びブチレンカーボネート(BC)からなる群より選択されるいずれか一つ、またはこれらのうち2種以上の混合物であり、線形カーボネートは、ジメチルカーボネート(DMC)、ジエチルカーボネート(DEC)、ジプロピルカーボネート(DPC)、エチルメチルカーボネート(EMC)、メチルプロピルカーボネート(MPC)及びエチルプロピルカーボネート(EPC)からなる群より選択されるいずれか一つ、またはこれらのうち2種以上の混合物であることを特徴とする請求項12に記載の非水性電解液。
- 正極、負極及び請求項9に記載の非水性電解液を含むリチウム二次電池。
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KR1020140019557A KR101639858B1 (ko) | 2013-02-20 | 2014-02-20 | 리튬 이차 전지용 전해액 첨가제, 상기 전해액 첨가제를 포함하는 비수성 전해액 및 리튬 이차 전지 |
PCT/KR2014/001386 WO2014129823A1 (ko) | 2013-02-20 | 2014-02-20 | 리튬 이차 전지용 전해액 첨가제, 상기 전해액 첨가제를 포함하는 비수성 전해액 및 리튬 이차 전지 |
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JP2020528639A (ja) * | 2017-11-13 | 2020-09-24 | エルジー・ケム・リミテッド | リチウム二次電池用非水電解液及びこれを含むリチウム二次電池 |
JP7045589B2 (ja) | 2017-11-13 | 2022-04-01 | エルジー エナジー ソリューション リミテッド | リチウム二次電池用非水電解液及びこれを含むリチウム二次電池 |
US11309583B2 (en) | 2017-11-13 | 2022-04-19 | Lg Energy Solution, Ltd. | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery including the same |
JP2021501450A (ja) * | 2018-01-30 | 2021-01-14 | エルジー・ケム・リミテッド | 高温貯蔵特性が向上されたリチウム二次電池 |
JP7038967B2 (ja) | 2018-01-30 | 2022-03-22 | エルジー エナジー ソリューション リミテッド | 高温貯蔵特性が向上されたリチウム二次電池 |
CN112448029A (zh) * | 2019-08-28 | 2021-03-05 | 珠海冠宇电池股份有限公司 | 一种锂二次电池用电解液和包括该电解液的锂二次电池 |
CN112448029B (zh) * | 2019-08-28 | 2022-06-14 | 珠海冠宇电池股份有限公司 | 一种锂二次电池用电解液和包括该电解液的锂二次电池 |
Also Published As
Publication number | Publication date |
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WO2014129823A1 (ko) | 2014-08-28 |
US9608290B2 (en) | 2017-03-28 |
EP2797156B1 (en) | 2017-06-21 |
EP2797156A4 (en) | 2015-02-25 |
TW201505231A (zh) | 2015-02-01 |
CN104781976A (zh) | 2015-07-15 |
KR20140104383A (ko) | 2014-08-28 |
KR101639858B1 (ko) | 2016-07-14 |
TWI636603B (zh) | 2018-09-21 |
EP2797156A1 (en) | 2014-10-29 |
CN104781976B (zh) | 2020-07-07 |
US20140272604A1 (en) | 2014-09-18 |
JP6067851B2 (ja) | 2017-01-25 |
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