EP3665737A1 - Lithium salt mixture and uses thereof as a battery electrolyte - Google Patents
Lithium salt mixture and uses thereof as a battery electrolyteInfo
- Publication number
- EP3665737A1 EP3665737A1 EP18758933.8A EP18758933A EP3665737A1 EP 3665737 A1 EP3665737 A1 EP 3665737A1 EP 18758933 A EP18758933 A EP 18758933A EP 3665737 A1 EP3665737 A1 EP 3665737A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mol
- lithium
- carbonate
- molar
- imide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 55
- 229910003002 lithium salt Inorganic materials 0.000 title claims description 10
- 159000000002 lithium salts Chemical class 0.000 title claims description 10
- 239000011833 salt mixture Substances 0.000 title description 5
- 239000000203 mixture Substances 0.000 claims abstract description 158
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 83
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 50
- 239000002904 solvent Substances 0.000 claims description 37
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 33
- CVVIFWCYVZRQIY-UHFFFAOYSA-N lithium;2-(trifluoromethyl)imidazol-3-ide-4,5-dicarbonitrile Chemical compound [Li+].FC(F)(F)C1=NC(C#N)=C(C#N)[N-]1 CVVIFWCYVZRQIY-UHFFFAOYSA-N 0.000 claims description 25
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 22
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 19
- 239000000654 additive Substances 0.000 claims description 19
- 230000000996 additive effect Effects 0.000 claims description 17
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 14
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 13
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002000 Electrolyte additive Substances 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- FWZHZWOOUOCBME-UHFFFAOYSA-N 1,3,4,6-tetrafluoro-2,5-dimethoxy-5-methylcyclohexa-1,3-diene Chemical compound COC1(C)C(C(=C(C(=C1F)F)OC)F)F FWZHZWOOUOCBME-UHFFFAOYSA-N 0.000 claims description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical class CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- MMZYCBHLNZVROM-UHFFFAOYSA-N 1-fluoro-2-methylbenzene Chemical compound CC1=CC=CC=C1F MMZYCBHLNZVROM-UHFFFAOYSA-N 0.000 claims description 2
- XUGNJOCQALIQFG-UHFFFAOYSA-N 2-ethenylquinoline Chemical compound C1=CC=CC2=NC(C=C)=CC=C21 XUGNJOCQALIQFG-UHFFFAOYSA-N 0.000 claims description 2
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- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical class C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 claims description 2
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- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical class 0.000 claims description 2
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical class COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 claims description 2
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- 150000002923 oximes Chemical class 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims 3
- 229910013872 LiPF Inorganic materials 0.000 claims 1
- 101150058243 Lipf gene Proteins 0.000 claims 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 36
- 238000000034 method Methods 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 239000011262 electrochemically active material Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 5
- 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 5
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
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- 150000001875 compounds Chemical class 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
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- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
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- 239000002905 metal composite material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 150000005217 methyl ethers Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
- GWWNCLHJCFNTJA-UHFFFAOYSA-N nicandrenone-2 Natural products C12OC2C2(O)CC=CC(=O)C2(C)C(CCC23C)C1C3CCC2(O)C(C)C1OC(O)C2(C)OC2(C)C1 GWWNCLHJCFNTJA-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- JAMNHZBIQDNHMM-UHFFFAOYSA-N pivalonitrile Chemical compound CC(C)(C)C#N JAMNHZBIQDNHMM-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
Classifications
-
- 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
- H01M10/052—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
- H01M10/0569—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
- 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
-
- 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
Definitions
- the present application relates to a mixture of lithium salts, as well as its use as a battery electrolyte.
- a lithium-ion battery or a Li-Suffre battery comprises at least one negative electrode (anode), a positive electrode (cathode), a separator and an electrolyte.
- the electrolyte generally consists of a lithium salt dissolved in a solvent which is generally a mixture of organic carbonates, in order to have a good compromise between the viscosity and the dielectric constant. Additives can then be added to improve the stability of the electrolyte salts.
- LiPF6 lithium hexafluorophosphate
- HF hydrofluoric acid
- the reaction of LiPF6 with the residual water thus affects the longevity of the battery and can cause safety problems, particularly in the context of the use of lithium-ion batteries in private vehicles.
- Other salts have been developed, such as LiTFSI
- lithium bis (trifluoromethanesulfonyl) imide lithium bis (trifluoromethanesulfonyl) imide
- LiFSI lithium bis (fluorosulfonyl) imide
- the present application relates to a mixture comprising (preferably consisting essentially of, and preferably consisting of):
- LiFSI lithium bis (fluorosulfonyl) imide
- LiTDI lithium 2-trifluoromethyl-4,5-dicyanoimidazolate
- LiPFe lithium hexafluorophosphate
- the mixture comprises (preferably consisting essentially of, and preferably consisting of):
- LiFSI lithium bis (fluorosulfonyl) imide
- LiPFe lithium hexafluorophosphate
- the molar percentages are based on the total number of moles of the compounds present in the mixture.
- lithium salt of bis (fluorosulfonyl) imide lithium bis (sulfonyl) imide
- LiFSI lithium bis (fluorosulfonyl) imide
- total number of moles of the compounds of the mixture corresponds to the sum of the number of moles of each compound present in the mixture.
- LiTDI Lithium 2-trifluoromethyl-4,5-dicyanoimidazolate, known under the name LiTDI, has the following structure:
- Impurities may be present in the mixtures, for example less than 3000 ppm, preferably less than 1000 ppm, in particular less than 500 ppm relative to the total weight of said mixture.
- ppm or "part per million” means ppm by weight. Impurities may be present in each LiFSI, LiTDI or LiPF 6 salt, for example less than 3000 ppm, preferably less than 1000 ppm, in particular less than 500 ppm, for example less than 300 ppm by weight. relative to the total weight of each salt.
- LiFSI can be obtained by any known method, for example by the method described in WO2015 / 158979, WO201 1/065502 or WO201 1/149095.
- LiTDI can be obtained by any known method, for example by the method described in WO2013 / 072591 or WO2010 / 023413.
- LiPF6 can be obtained by any known method, for example by the method described in US 3,607,020, US 3,907,977 or in JP60251 109.
- the mixture according to the invention comprises:
- LiFSI LiFSI
- the content of LiFSI in the mixture according to the invention is chosen from one of the following molar percentages: from 1% to 99%, from 1% to 95%, from 5% to 90%, from 5% to 85%, 5% to 80%, 5% to 75%, 5% to 70%, 5% to 65%, 5% to 50%, 5% to 45%, 5% to % to 99%, 10% to 95%, 10% to 90%, 10% to 85%, 10% to 80%, 10% to 75%, 10% to 70%, 10% at 65%, from 10% to 60%, from 10% to 55%, from 10% to 50%, from 10% to 45%, from 15% to 99%, from 15% to 95%, from 15% to 90%, 15% to 85%, 15% to 80%, 15% to 75%, 15% to 70%, 15% to 65%, 15% to 60%, 15% to 55% %, 15% to 50%, 15% to 45%, 20% to 99%, 20% to 95%, 20% to 90%, 20% to 85%, 20% to 80% , from 20% to 75%, from 20% to 70%, from 20% to 99%,
- the content of LiTDI in the mixture according to the invention is chosen from one of the following molar percentages: from 1% to 99%, from 1% to 95%, from 5% to 90%, from 5% to 85%, 5% to 80%, 5% to 75%, 5% to 70%, 5% to 65%, 5% to 50%, 5% to 45%, 5% to % to 99%, 10% to 95%, 10% to 90%, 10% to 85%, 10% to 80%, 10% to 75%, 10% to 70%, 10% at 65%, from 10% to 60%, from 10% to 55%, from 10% to 50%, from 10% to 45%, from 15% to 99%, from 15% to 95%, from 15% to 90%, 15% to 85%, 15% to 80%, 15% to 75%, 15% to 70%, 15% to 65%, 15% to 60%, 15% to 55% %, 15% to 50%, 15% to 45%, 20% to 99%, 20% to 95%, 20% to 90%, 20% to 85%, 20% to 80% , from 20% to 75%, from 20% to 70%, from 20% to 99%,
- the content of LiPF 6 in the mixture according to the invention is chosen from one of the following molar percentages: from 1% to 99%, from 1% to 95%, from 5% to 90%, from 5% to 85%, 5% to 80%, 5% to 75%, 5% to 70%, 5% to 65%, 5% to 50%, 5% to 45%, 5% to % to 99%, 10% to 95%, 10% to 90%, 10% to 85%, 10% to 80%, 10% to 75%, 10% to 70%, 10% at 65%, from 10% to 60%, from 10% to 55%, from 10% to 50%, from 10% to 45%, from 15% to 99%, from 15% to 95%, from 15% to 90%, 15% to 85%, 15% to 80%, 15% to 75%, 15% to 70%, 15% to 65%, 15% to 60%, 15% to 55% %, 15% to 50%, 15% to 45%, 20% to 99%, 20% to 95%, 20% to 90%, 20% to 85%, 20% to 80% , from 20% to 75%, from 20% to 70%, from 20% to 99%,
- the aforementioned mixture comprises (preferably consists essentially of, and preferably consists of):
- the aforementioned mixture comprises (preferably consists essentially of, and preferably consists of):
- the aforementioned mixture comprises (preferably consists essentially of, and preferably consists of):
- the aforementioned mixture comprises (preferably consists essentially of, and preferably consists of):
- the aforementioned mixture comprises (preferably consists essentially of, and preferably consists of):
- the aforementioned mixture comprises (preferably consists essentially of, and preferably consists of):
- the aforementioned mixture comprises (preferably consisting essentially of, and preferably consists of):
- the aforementioned mixture comprises (preferably consists essentially of, and preferably consists of):
- the LiFSI content is greater than or equal to the LiTDI content, and / or the LiPF6 content is greater than or equal to LiTDI.
- the molar ratio LiFSI / LiTDI / LiPF6 is included:
- the molar ratio LiFSI / LiTDI / LiPF 6 is 4/3/3; between 1/1/1 and 1/10/1, preferably between 1/1/1 and 1/5/1, preferably between 1/1/1 and 1/2/1;
- LiFSI / LiTDI / LiPF 6 is 5/2/3.
- the LiFSI / LiPF6 molar ratio in the aforementioned mixture is between 1 and 10, preferably between 1 and 5, preferably between 1 and 2.
- the molar ratio LiFSI / LiPF6 in the mixture is 4 / 3 or 5/3.
- the present application also relates to the use of a mixture as defined above, in a battery, for example a Li-ion battery, in particular in a temperature range of between -30 ° C. and 65 ° C., preferentially between -25 ° C and 60 ° C, preferably at a temperature greater than or equal to 25 ° C, preferably between 25 ° C and 65 ° C, preferably between 40 ° C and 60 ° C.
- the use is done in mobile devices, such as mobile phones, cameras, tablets or laptops, in electric vehicles, or in renewable energy storage.
- the present invention also relates to an electrolyte composition, in particular for a Li-ion battery, comprising the mixture of lithium salts as defined above, at least one solvent, and optionally at least one electrolytic additive.
- the electrolyte composition does not comprise any other alkali or alkaline earth salt than those of the aforementioned mixture.
- the electrolyte composition does not comprise any other lithium salt than LiFSI, LiPF6 and LiTDI.
- the electrolyte composition does not include LiTFSI.
- the LiFSI, LiPF6 and LiTDI salts represent 100% of all the salts present in the composition.
- electrospray composition In the context of the invention, “electrolyte composition”, “electrolyte” and “electrolyte composition” are used interchangeably.
- the electrolyte composition comprises from 1% to 99% by weight of the aforementioned mixture, preferably from 5% to 99%, and advantageously from 20% to 95%, relative to the total mass of the composition.
- the electrolyte composition comprises from 1% to 99% by weight of solvent, preferably from 5% to 99%, and advantageously from 20% to 95%, relative to the total mass of the composition.
- the molar concentration of the aforementioned mixture in the electrolyte composition is less than or equal to 5 mol / L, advantageously less than or equal to 4 mol / L, preferably less than or equal to 2 mol / L, preferentially less than or equal to 1, 5 mol / L, and in particular less than or equal to 1, 1 mol / L, for example less than or equal to 1 mol / L.
- the molar concentrations of LiFSI, LiTDI and LiPF6 in the electrolyte composition are such that:
- the aforementioned electrolyte composition comprises:
- the electrolyte composition according to the invention comprises: at least 0.05 mol / L, preferably at least 0.1 mol / L, preferably at least 0.15, even more preferably at least 0 2 mol / L, advantageously at least 0.25 mol / L, and still more advantageously at least 0.3 mol / L of LiFSI; and or
- At least 0.05 mol / L preferably at least 0.1 mol / L, preferably at least 0.15, still more preferably at least 0.2 mol / L, advantageously at least 0.25 mol / L, and still more preferably at least 0.3 mol / L of LiTDI; and or
- At least 0.05 mol / l preferably at least 0.1 mol / l, preferably at least 0.15, even more preferably at least 0.2 mol / l, advantageously at least 0.25 mol / l, and still more preferably at least 0.3 mol / L of LiPF6.
- the molar concentration of LiFSI in the electrolyte composition is chosen from one of the following concentrations: from 0.01 to 0.99 mol / L, from 0.01 to 0.95 mol / L , from 0.05 to 0.90 mol / L, from 0.05 to 0.85 mol / L, from 0.05 to 0.80 mol / L, from 0.05 to 0.75 mol / L, from 0.05 to 0.70 mol / L, 0.05 to 0.65 mol / L, 0.05 to 0.50 mol / L, 0.05 to 0.45 mol / L, 0.1 at 0.99 mol / L, from 0.1 to 0.95 mol / L, from 0.1 to 0.90 mol / L, from 0.1 to 0.85 mol / L, from 0.1 to 0 , 80 mol / L, 0.1 to 0.75 mol / L, 0.1 to 0.70 mol / L, 0.1 to 0.65 mol / L, 0.1 to 0.50 mol / L, 0.1 to 0.
- the molar concentration of LiTDI in the electrolyte composition is chosen from one of the following concentrations: from 0.01 to 0.99 mol / L, from 0.01 to 0.95 mol / L , from 0.05 to 0.90 mol / L, from 0.05 to 0.85 mol / L, from 0.05 to 0.80 mol / L, from 0.05 to 0.75 mol / L, from 0.05 to 0.70 mol / L, 0.05 to 0.65 mol / L, 0.05 to 0.50 mol / L, 0.05 to 0.45 mol / L, 0.1 at 0.99 mol / L, from 0.1 to 0.95 mol / L, from 0.1 to 0.90 mol / L, from 0.1 to 0.85 mol / L, from 0.1 to 0 , 80 mol / L, 0.1 to 0.75 mol / L, 0.1 to 0.70 mol / L, 0.1 to 0.65 mol / L, 0.1 to 0.50 mol / L, 0.1 to 0.
- the molar concentration of LiPF6 in the electrolyte composition is chosen from one of the following concentrations: from 0.01 to 0.99 mol / L, from 0.01 to 0.95 mol / L , from 0.05 to 0.90 mol / L, from 0.05 to 0.85 mol / L, from 0.05 to 0.80 mol / L, from 0.05 to 0.75 mol / L, from 0.05 to 0.70 mol / L, 0.05 to 0.65 mol / L, 0.05 to 0.50 mol / L, 0.05 to 0.45 mol / L, 0.1 at 0.99 mol / L, from 0.1 to 0.95 mol / L, from 0.1 to 0.90 mol / L, from 0.1 to 0.85 mol / L, from 0.1 to 0 , 80 mol / L, 0.1 to 0.75 mol / L, 0.1 to 0.70 mol / L, 0.1 to 0.65 mol / L, 0.1 to 0.50 mol / L, 0.1 to 0.
- the electrolyte composition comprises:
- the electrolyte composition comprises:
- the electrolyte composition comprises:
- the electrolyte composition comprises:
- the electrolyte composition comprises:
- the electrolyte composition comprises
- the electrolyte composition comprises:
- the electrolyte composition comprises:
- the above-mentioned electrolyte composition is such that:
- the molar concentration of LiFSI is greater than or equal to 0.30 mol / L, and / or
- the molar concentration of LiTDI is less than or equal to 0.40 mol / L;
- the molar concentration of LiPF 6 is less than or equal to 0.50 mol / l.
- the aforementioned electrolyte composition is such that the molar concentration of LiFSI is greater than or equal to the molar concentration of LiTDI, and / or the molar concentration of LiPF6 is greater than or equal to that of LiTDI.
- the aforementioned electrolyte composition is such that the molar ratio LiFSI / LiPF 6 in said composition is between 1/1 and 10/1, preferably between 1/1 and 5/1, preferably between 1 / 1 and 2/1.
- the molar ratio LiFSI / LiPFe in the mixture is 4/3 or 5/3.
- the electrolyte composition may comprise a solvent or a mixture of solvents, such as for example two, three or four different solvents.
- the solvent of the electrolyte composition may be a liquid solvent, optionally gelled with a polymer, or a polar polymer solvent optionally plasticized with a liquid.
- the solvent is an organic solvent, preferably aprotic.
- the solvent is a polar organic solvent.
- the solvent is selected from the group consisting of ethers, carbonates, esters, ketones, partially hydrogenated hydrocarbons, nitriles, amides, alcohols, sulfoxides, sulfolane, nitromethane, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 3-methyl-2-oxazolidinone, and their mixtures.
- ethers such as, for example, dimethoxyethane (DME), methyl ethers of oligoethylene glycols of 2 to 5 oxyethylene units, dioxolane, dioxane, dibutyl ether, tetrahydrofuran, and their mixtures.
- DME dimethoxyethane
- esters mention may be made of phosphoric acid esters or sulphite esters.
- Mention may be made, for example, of methyl formate, methyl acetate, methyl propionate, ethyl acetate, butyl acetate, gamma butyrolactone or their mixtures.
- ketones there may be mentioned cyclohexanone.
- nitriles there may be mentioned for example acetonitrile, pyruvonitrile, propionitrile, methoxypropionitrile, dimethylaminopropionitrile, butyronitrile, isobutyronitrile, valeronitrile, pivalonitrile, isovaleronitrile, glutaronitrile, methoxyglutaronitrile, 2 methylglutaronitrile, 3-methylglutaronitrile, adiponitrile, malononitrile, and mixtures thereof.
- cyclic carbonates such as, for example, ethylene carbonate (EC) (CAS: 96-49-1), propylene carbonate (PC) (CAS: 108-32-7) , butylene carbonate (BC) (CAS: 4437-85-8), dimethyl carbonate (DMC) (CAS: 616-38-6), diethyl carbonate (DEC) (CAS: 105-58-8 ), methyl carbonate ethyl (EMC) (CAS: 623-53-0), diphenyl carbonate (CAS 102-09-0), methyl carbonate phenyl (CAS: 13509-27-8), carbonate of dipropyl (DPC) (CAS: 623-96-1), methyl carbonate and propyl (MPC) (CAS: 1333-41-1), ethyl carbonate and propyl carbonate (EPC), carbonate of vinylene (VC) (CAS: 872-36-6), fluoroethylene carbonate (FEC) (CAS: cyclic carbonates such as, for example, ethylene
- the particularly preferred solvent is selected from carbonates and mixtures thereof.
- the following mixtures may notably be mentioned: ethylene carbonate (EC) / propylene carbonate (PC) / dimethyl carbonate (DMC) in a weight ratio 1/1/1; ethylene carbonate (EC) / propylene carbonate (PC) / diethyl carbonate (DEC) in a weight ratio 1/1/1;
- EC ethylene carbonate
- EMC methyl ethyl carbonate
- the solvent of the electrolyte composition is ethylene carbonate (EC) / methyl ethyl carbonate (EMC) in a volume ratio of 3/7.
- the electrolyte composition comprises at least one electrolytic additive.
- the electrolyte additive is selected from the group consisting of fluoroethylene carbonate (FEC), vinylene carbonate, 4-vinyl-1,3-dioxolan-2-one, pyridazine, vinyl pyridazine, quinoline, vinyl quinoline, butadiene, sebaconitrile, LiB (C20 4 ) 2, lithium nitrate, alkyldisulfide, fluorotoluene, 1,4-dimethoxytetrafluorotoluene, t-butylphenol, di-t -butylphenol, tris (pentafluorophenyl) borane, oximes, aliphatic epoxides, halogenated biphenyls, methacrylic acids, ethyl allyl carbonate, vinyl acetate, divinyl adipate, acrylonitrile , 2-vinylpyridine, maleic anhydride, methyl c
- the content of electrolyte additive in the electrolyte composition is between 0.01% and 10%, preferably between 0.1% and 4% by weight relative to the total mass of the electrolyte composition.
- the content of electrolytic additive in the electrolyte composition is less than or equal to 2% by weight relative to the total mass of the composition.
- the content of electrolyte additive in the electrolyte composition may for example be between 0.01% and 10%, preferably between 0.1% and 4% by weight, relative to the total weight of the solvent of said composition.
- the electrolyte composition according to the invention is chosen from one of the following compositions:
- the electrolyte composition according to the invention is chosen from one of the following compositions:
- the electrolyte composition may be prepared by any means known to those skilled in the art, for example by dissolving, preferably with stirring, salts in appropriate proportions of solvent (s) and / or additive (s). .
- the present application also relates to the use of an electrolyte composition as defined above, in a Li-ion battery, in particular in a temperature range of between -30 ° C. and 65 ° C., preferably between -30 ° C. and 65 ° C. 25 ° C and 60 ° C, preferably at a temperature greater than or equal to 25 ° C, preferably between 25 ° C and 65 ° C, preferably between 40 ° C and 60 ° C.
- the use is in mobile devices, for example mobile phones, cameras, tablets or laptops, in electric vehicles, or in the storage of renewable energy.
- the present application also relates to an electrochemical cell comprising a negative electrode, a positive electrode, and a mixture of lithium salts as described above.
- the present application also relates to an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte composition as defined above, interposed between the negative electrode and the positive electrode.
- the electrochemical cell may also comprise a separator, in which the electrolyte composition as defined above is impregnated.
- the present invention also relates to a battery comprising at least one electrochemical cell as described above. When the battery comprises several electrochemical cells according to the invention, said cells can be assembled in series and / or in parallel.
- the term "negative electrode" means the electrode which acts as anode, when the battery delivers current (that is to say when it is in the process of discharge) and which makes cathode office when the battery is charging process.
- the negative electrode typically comprises an electrochemically active material, optionally an electronically conductive material, and optionally a binder.
- electrochemically active material means a material capable of reversibly inserting ions.
- the term "electronically conductive material” means a material capable of driving the electrons.
- the negative electrode of the electrochemical cell comprises as electrochemically active material, graphite, lithium, a lithium alloy, a type lithium titanate LÎ4Ti 5 0 i2 or ⁇ 2, silicon or an alloy of lithium and silicon, a tin oxide, a lithium intermetallic compound, or a mixture thereof.
- the negative electrode may comprise lithium, which may then consist of a metal lithium film or an alloy comprising lithium.
- An example of a negative electrode may comprise a bright lithium film prepared by rolling between rolls of a lithium strip.
- positive electrode means the electrode which acts as cathode, when the battery delivers current (that is to say when it is in the process of discharge) and which serves anode when the battery is charging.
- the positive electrode typically comprises an electrochemically active material, optionally an electronically conductive material, and optionally a binder.
- the material of the positive electrode may also include, in addition to the electrochemically active material, an electronically conductive material such as a carbon source, including, for example, carbon black, Ketjen ® carbon, Shawinigan carbon, graphite, graphene, carbon nanotubes, carbon fibers (such as gas-phase carbon fibers (VGCF), non-powdery carbon obtained by carbonization of an organic precursor, or a combination of two or more thereof
- an electronically conductive material such as a carbon source, including, for example, carbon black, Ketjen ® carbon, Shawinigan carbon, graphite, graphene, carbon nanotubes, carbon fibers (such as gas-phase carbon fibers (VGCF), non-powdery carbon obtained by carbonization of an organic precursor, or a combination of two or more thereof
- Other additives may also be present in the material of the positive electrode, such as lithium salts or inorganic particles of ceramic or glass type, or other compatible active materials (for example, sulfur).
- the material of the positive electrode may also comprise a binder
- binders include linear, branched and / or cross-linked polymeric polyether binders (e.g. s based on poly (ethylene oxide) (PEO), or poly (propylene oxide) (PPO) or a mixture of both (or a co-polymer EO / PO), and optionally comprising crosslinkable units ), water-soluble binders (such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber)) or fluoropolymer-type binders (such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and combinations thereof.
- PEO poly (ethylene oxide)
- PPO poly (propylene oxide)
- crosslinkable units e.g. s based on poly (
- Some binders such as those soluble in water, may also include an additive such as CMC (carboxymethylcellulose).
- CMC carboxymethylcellulose
- the salt mixture according to the invention advantageously has good ionic conductivity in solution.
- the salt mixture according to the invention advantageously makes it possible to improve the power performances of the battery, which makes it possible, for example, to recharge the battery more quickly, or to provide the necessary power in the event of a peak of energy.
- the salt mixture according to the invention also advantageously allows to have good performance, especially in terms of power over a wide temperature range, for example cold, or over a temperature range of about -25 ° C. at about 60 ° C.
- the salt mixture according to the invention advantageously allows a good compromise between good ionic conductivity in solution, a good lifetime, electrochemical stability, and power performance over a wide range of temperatures, such as for example - About 25 ° C to about 60 ° C.
- "between x and y" or “between x and y” means an interval in which the terminals x and y are included.
- the range “between 1% and 98%” or “ranging from 1% to 98%” includes in particular the values 1 and 98%.
- EMC methyl carbonate ethyl (CAS 623-53-0)
- FEC fluoroethylene carbonate
- LiFF 6 BASF Corporation
- the LiFSI used is obtained in particular by the process described in application WO2015 / 158979, while LiTDI is derived from the process described in patent application WO2013 / 072591.
- composition 1 (according to the invention): 0.40M LiFSI, 0.30M LiTDI and 0.30M LiPF 6 , solvent mixture EC / EMC 3/7 (volume ratio), 2% by weight in FEC (relative to the total weight of the EC / EMC solvent mixture);
- composition 2 (comparative): 0.40M LiTFSI, 0.30M LiTDI and 0.30M LiPF 6 , solvent mixture EC / EMC 3/7 (volume ratio), 2% by weight FEC (relative to the total weight) EC / EMC solvent mixture).
- the compositions were prepared according to the following procedure: Composition 1:
- the composition 1 comprises LiFSI, LiTDI, LiPF 6 , EC / EMC (3/7 ratio by volume), FEC (2% by weight relative to the weight of the solvent EC / EMC 3/7 volume), the total content of LiFSI in composition 1 being 0.40 mol / L, the total content of LiTDI in composition 1 being 0.30 mol / L, the total content of LiPF6 in the composition being 0.30 mol / L.
- Composition 2 is a composition of Composition 2:
- R is equal to the opposite of the ordinate at the origin divided by the directing coefficient of the equation of the linear regression.
- composition 1 advantageously has a better ionic conductivity than the composition 2.
- Example 2 Power test
- the method involves increasing the discharge rate of a battery to observe the ability of the electrolyte to respond to the stress imposed by the electrical circuit.
- Cathode LiNo.33 Mno.33Coo.33O2 (89%), VGCF carbon fiber (2.5%), carbon black (2.5%) and 6% Pvdf binder.
- the current was varied between 2.7 and 4.2 V, with discharges operated in the following order: C / 20, C / 10, C / 5, C / 2, C and 2C.
- composition 1 advantageously allows to work at higher power regimes than the composition 2.
- These high speeds are particularly sought after in commercial batteries as part of nomadic devices that demand more power, and electric vehicles because of their low autonomy require fast recharges and therefore electrolytes to work at high speeds.
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Abstract
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Application Number | Priority Date | Filing Date | Title |
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FR1757559A FR3069959B1 (en) | 2017-08-07 | 2017-08-07 | MIXTURE OF LITHIUM SALTS AND USES THEREOF AS BATTERY ELECTROLYTE |
PCT/FR2018/051912 WO2019030440A1 (en) | 2017-08-07 | 2018-07-26 | Lithium salt mixture and uses thereof as a battery electrolyte |
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EP3665737A1 true EP3665737A1 (en) | 2020-06-17 |
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US (1) | US11757133B2 (en) |
EP (1) | EP3665737A1 (en) |
JP (1) | JP2020529425A (en) |
KR (1) | KR102645232B1 (en) |
CN (1) | CN110998950A (en) |
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WO (1) | WO2019030440A1 (en) |
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FR3096512B1 (en) * | 2019-05-22 | 2021-11-05 | Arkema France | ELECTROLYTE BASED ON LITHIUM SALTS |
FR3102010B1 (en) * | 2019-10-15 | 2022-06-03 | Arkema France | Method for regulating the temperature of a battery comprising a lithium salt |
CN111477957B (en) * | 2020-04-22 | 2021-04-16 | 浙江大学 | Lithium metal battery electrolyte containing composite additive and preparation method thereof |
KR102632922B1 (en) * | 2023-03-22 | 2024-02-05 | 주식회사 천보 | Solution of lithium bis(fluorosulfonyl)imide and electrolyte thereof |
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US3907977A (en) | 1969-05-29 | 1975-09-23 | United States Steel Corp | Method for the preparation of high purity, highly surface active LiAsF{HD 6 |
US3607020A (en) | 1970-03-19 | 1971-09-21 | Foote Mineral Co | Preparation of lithium hexafluorophosphate |
JPS60251109A (en) | 1984-05-28 | 1985-12-11 | Daikin Ind Ltd | Manufacture of lithium hexafluorophosphate |
US7285356B2 (en) * | 2004-07-23 | 2007-10-23 | The Gillette Company | Non-aqueous electrochemical cells |
WO2006077763A1 (en) * | 2005-01-20 | 2006-07-27 | Ube Industries, Ltd. | Nonaqueous electrolyte solution and lithium secondary battery using same |
FR2935382B1 (en) | 2008-08-29 | 2010-10-08 | Centre Nat Rech Scient | SALT OF PENTACYLIC ANION AND ITS USE AS ELECTROLYTE |
CN102405189B (en) | 2009-11-27 | 2014-07-09 | 株式会社日本触媒 | Fluorosulfonyl imide salt and method for producing fluorosulfonyl imide salt |
US9079780B2 (en) | 2010-05-28 | 2015-07-14 | Nippon Shokubai Co., Ltd. | Alkali metal salt of fluorosulfonyl imide, and production method therefor |
FR2982610B1 (en) | 2011-11-14 | 2016-01-08 | Arkema France | PROCESS FOR PREPARING SALT OF PENTACYLIC ANION |
FR2983466B1 (en) * | 2011-12-06 | 2014-08-08 | Arkema France | USE OF MIXTURES OF LITHIUM SALTS AS ELECTROLYTES OF LI-ION BATTERIES |
CN104798245B (en) * | 2012-11-20 | 2017-06-23 | 日本电气株式会社 | Lithium rechargeable battery |
PL232931B1 (en) * | 2013-01-11 | 2019-08-30 | Marek Marcinek | Mixtures of organic solvents, in particular for primary cells and primary cells electrolytes |
CA2820468A1 (en) * | 2013-06-21 | 2014-12-21 | Hydro-Quebec | Anode including a lithium alloy for high energy batteries |
FR3018635A1 (en) * | 2014-03-14 | 2015-09-18 | Arkema France | IMPROVING IONIC ELECTROLYTE CONDUCTIVITY BASED ON IMIDAZOLATE LITHIUM SALTS |
FR3018634B1 (en) * | 2014-03-14 | 2021-10-01 | Arkema France | LONG-LIFE LITHIUM-ION BATTERIES |
FR3020060B1 (en) | 2014-04-18 | 2016-04-01 | Arkema France | PREPARATION OF IMIDES CONTAINING FLUOROSULFONYL GROUP |
US9722277B2 (en) * | 2014-10-31 | 2017-08-01 | Battelle Memorial Institute | Electrolyte for batteries with regenerative solid electrolyte interface |
FR3033945B1 (en) * | 2015-03-16 | 2017-03-03 | Arkema France | ELECTROLYTE FORMULATION FOR LITHIUM-ION BATTERIES |
US20190181494A1 (en) * | 2016-08-03 | 2019-06-13 | Nec Corporation | Nonaqueous electrolytic solution and lithium ion secondary battery |
CN106532120B (en) * | 2016-12-19 | 2019-02-01 | 广州天赐高新材料股份有限公司 | A kind of nonaqueous electrolytic solution and the lithium secondary battery using the electrolyte |
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- 2018-07-26 US US16/630,223 patent/US11757133B2/en active Active
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- 2018-07-26 EP EP18758933.8A patent/EP3665737A1/en active Pending
- 2018-07-26 WO PCT/FR2018/051912 patent/WO2019030440A1/en unknown
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US20210151798A1 (en) | 2021-05-20 |
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KR20200038927A (en) | 2020-04-14 |
US11757133B2 (en) | 2023-09-12 |
FR3069959A1 (en) | 2019-02-08 |
KR102645232B1 (en) | 2024-03-07 |
CN110998950A (en) | 2020-04-10 |
FR3069959B1 (en) | 2019-08-23 |
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