WO2023286940A1 - 신규한 화합물, 이를 포함하는 이차 전지용 전해액 및 이를 포함하는 이차 전지 - Google Patents
신규한 화합물, 이를 포함하는 이차 전지용 전해액 및 이를 포함하는 이차 전지 Download PDFInfo
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- WO2023286940A1 WO2023286940A1 PCT/KR2021/017825 KR2021017825W WO2023286940A1 WO 2023286940 A1 WO2023286940 A1 WO 2023286940A1 KR 2021017825 W KR2021017825 W KR 2021017825W WO 2023286940 A1 WO2023286940 A1 WO 2023286940A1
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- WIPO (PCT)
- Prior art keywords
- unsubstituted
- substituted
- formula
- secondary battery
- lithium secondary
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 109
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 42
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 92
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000000126 substance Substances 0.000 claims abstract description 14
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 27
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 26
- 229910052736 halogen Inorganic materials 0.000 claims description 19
- 150000002367 halogens Chemical class 0.000 claims description 19
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 239000003660 carbonate based solvent Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 15
- 125000004122 cyclic group Chemical group 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 13
- 239000011737 fluorine Substances 0.000 claims description 13
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000003759 ester based solvent Substances 0.000 claims description 9
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 8
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000002596 lactones Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 7
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 6
- 150000008053 sultones Chemical class 0.000 claims description 6
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 6
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 5
- 125000005463 sulfonylimide group Chemical group 0.000 claims description 5
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 239000005456 alcohol based solvent Substances 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 239000000010 aprotic solvent Substances 0.000 claims description 4
- 239000004210 ether based solvent Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000005453 ketone based solvent Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 230000000052 comparative effect Effects 0.000 description 51
- 238000002360 preparation method Methods 0.000 description 25
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 16
- -1 alkali metal salt Chemical class 0.000 description 14
- 230000014759 maintenance of location Effects 0.000 description 13
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000004020 conductor Substances 0.000 description 9
- 239000011883 electrode binding agent Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000011267 electrode slurry Substances 0.000 description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 5
- OQYOVYWFXHQYOP-UHFFFAOYSA-N 1,3,2-dioxathiane 2,2-dioxide Chemical compound O=S1(=O)OCCCO1 OQYOVYWFXHQYOP-UHFFFAOYSA-N 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000006182 cathode active material Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 3
- YHTPVDJKWQQLPM-UHFFFAOYSA-N 2,4,8,10-tetraoxa-3$l^{6},9$l^{6}-dithiaspiro[5.5]undecane 3,3,9,9-tetraoxide Chemical compound C1OS(=O)(=O)OCC21COS(=O)(=O)OC2 YHTPVDJKWQQLPM-UHFFFAOYSA-N 0.000 description 3
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
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- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 3
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- PZHDBRGFHRWRBN-UHFFFAOYSA-N n,n-diethylethanamine;ethenesulfonic acid Chemical compound OS(=O)(=O)C=C.CCN(CC)CC PZHDBRGFHRWRBN-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
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- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
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- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
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- MRDKYAYDMCRFIT-UHFFFAOYSA-N oxalic acid;phosphoric acid Chemical compound OP(O)(O)=O.OC(=O)C(O)=O MRDKYAYDMCRFIT-UHFFFAOYSA-N 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
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- 229920002239 polyacrylonitrile Polymers 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- H01M10/0567—Liquid materials characterised by the additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/02—Lithium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/46—Phosphinous acids R2=P—OH; Thiophosphinous acids; Aminophosphines R2-P-NH2 including R2P(=O)H; derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
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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
- 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
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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
- H01M10/056—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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/03—Monoamines
- C07C211/05—Mono-, di- or tri-ethylamine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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 invention relates to a novel compound, an electrolyte solution for a secondary battery including the same, and a secondary battery including the same.
- a secondary battery is a battery that can be repeatedly charged and discharged and is applied as a power source for small electronic devices such as mobile phones and notebook PCs.
- lithium secondary batteries have high operating voltage, high energy density and high charging speed, and are advantageous in light weight. Accordingly, the lithium secondary battery is applied as a power source for electric vehicles as well as small electronic devices.
- a lithium secondary battery includes a negative electrode including a negative electrode active material (eg, graphite); a positive electrode including a positive electrode active material (eg, lithium metal oxide particles); and a non-aqueous electrolyte containing a lithium salt and an organic solvent.
- a negative electrode including a negative electrode active material (eg, graphite); a positive electrode including a positive electrode active material (eg, lithium metal oxide particles); and a non-aqueous electrolyte containing a lithium salt and an organic solvent.
- a lithium secondary battery may be charged and discharged by repeating a process of intercalating and deintercalating lithium ions from lithium metal oxide particles and graphite.
- the output characteristics and lifespan characteristics of the lithium secondary battery may be improved by changing the composition of the electrolyte solution.
- the output characteristics of the lithium secondary battery may be improved by improving the conductivity of lithium ions.
- SEI solid electrolyte interface
- Korean Patent Registration No. 10-1999615 discloses an electrolyte solution for a lithium secondary battery capable of improving lifespan characteristics of a lithium secondary battery.
- One object of the present invention is to provide novel compounds.
- An object of the present invention is to provide an electrolyte solution for a lithium secondary battery capable of improving lifespan characteristics (eg, repetition charge/discharge capacity retention rate) and output characteristics of the lithium secondary battery.
- One object of the present invention is to provide a lithium secondary battery with improved lifespan characteristics, output characteristics, and the like.
- a novel compound according to the present invention may be represented by Formula 1 below.
- R 1 is a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, or a substituted or unsubstituted C3-C7 A cycloalkyl group, a substituted or unsubstituted C3-C7 cycloalkenyl group, or -OR 1 ; R 2 to R 5 are each independently a halogen or a substituted or unsubstituted C1-C6 alkyl group; M is an alkali metal; Y + may be a cationic material.
- R 1 is a substituted or unsubstituted C1-C6 alkyl group or a substituted or unsubstituted C2-C6 alkenyl group; at least one of R 2 to R 5 is halogen; M is Li, Na or K; Y + is N + RaRbRcRd, and at least one of Ra to Rd may be hydrogen.
- R 1 is a substituted or unsubstituted C2-C6 alkenyl group; R 2 to R 5 are all halogen; M is Li; Y + is N + RaRbRcRd, Ra is hydrogen, and Rb to Rd may be each independently a C1-C3 alkyl group.
- the method for preparing the compound represented by Formula 1 may include reacting the compound represented by Formula 2 and the compound represented by Formula 3.
- R 1 is a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, or a substituted or unsubstituted C3-C7 A cycloalkyl group, a substituted or unsubstituted C3-C7 cycloalkenyl group, or -OR 1 ; Y + may be a cationic material.
- R 2 and R 3 are each independently a halogen or a substituted or unsubstituted C1-C6 alkyl group; M + may be an alkali metal ion.
- An electrolyte solution for a lithium secondary battery may include a lithium salt; organic solvents; And it may include the compound represented by Formula 1 above.
- the content of the compound represented by Formula 1 may be 0.01 to 10% by weight of the total weight of the electrolyte solution.
- the organic solvent is at least one of a linear carbonate-based solvent, a cyclic carbonate-based solvent, a linear ester-based solvent, a cyclic ester-based solvent, an ether-based solvent, a ketone-based solvent, an alcohol-based solvent, and an aprotic solvent.
- a linear carbonate-based solvent e.g., a linear carbonate-based solvent, a cyclic carbonate-based solvent, a linear ester-based solvent, a cyclic ester-based solvent, an ether-based solvent, a ketone-based solvent, an alcohol-based solvent, and an aprotic solvent.
- the electrolyte solution is a fluorine-containing cyclic carbonate-based compound, a vinyl group-containing cyclic carbonate-based compound, a vinylene carbonate-based compound, a cyclic sulfate-based compound, a sultone-based compound, a fluorine-containing lithium phosphate-based compound, a lithium borate-based compound , It may further include an auxiliary additive including at least one of a lactone-based compound and a sulfonyl imide-based compound.
- the content of the auxiliary additive may be 0.01 to 10% by weight of the total weight of the electrolyte solution.
- the ratio of the content of the auxiliary additive to the content of the compound represented by Formula 1 in the electrolyte solution may be 0.1 to 10.
- a lithium secondary battery includes a cathode; a cathode facing the anode; a separator interposed between the anode and the cathode; And it may include the electrolyte solution for the lithium secondary battery.
- the compound represented by Chemical Formula 1 may be included in an electrolyte solution for a rechargeable lithium battery.
- An electrolyte solution for a lithium secondary battery includes the compound represented by Chemical Formula 1, thereby improving lifespan characteristics (eg, cyclic charge/discharge capacity retention rate) and output characteristics of the lithium secondary battery.
- Figure 1 shows the three-dimensional structure of the compound of Preparation Example 1 analyzed by SC-XRD (single crystal X-ray diffraction).
- FIGS. 2 and 3 are planar perspective views and cross-sectional views schematically illustrating a lithium secondary battery according to exemplary embodiments, respectively.
- Example 5 is a graph showing AC-impedance measured for lithium secondary batteries of Example 2 and Comparative Example 1;
- a novel compound represented by Chemical Formula 1 an electrolyte solution for a lithium secondary battery including the same, and a lithium secondary battery including the same are provided.
- X-based compound may refer to a compound containing an X unit as a parent, a side group or a substituent.
- Ca-Cb may mean “the number of carbon atoms from a to b”. Also, “5-7 membered ring” may mean “the number of atoms in the ring is 5 to 7".
- a novel compound according to the present invention may be represented by Formula 1 below.
- R 1 is a substituted or unsubstituted C1-C6 alkyl group; A substituted or unsubstituted C2-C6 alkenyl group; A substituted or unsubstituted C2-C6 alkynyl group; A substituted or unsubstituted C3-C7 cycloalkyl group; A substituted or unsubstituted C3-C7 cycloalkenyl group; or -OR 1 .
- R 2 to R 5 are each independently halogen; Or it may be a substituted or unsubstituted C1-C6 alkyl group.
- M is an alkali metal, and Y + may be a cationic material.
- substituted may mean that a hydrogen atom is substituted with an arbitrary substituent, and an arbitrary substituent is further bonded to the substituent.
- the optional substituent may be a halogen, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxy group, a nitro group, a cyano group, and the like.
- the optional substituent may be a halogen or a C1-C6 alkyl group.
- R 1 is a substituted or unsubstituted C1-C6 alkyl group; Or it may be a substituted or unsubstituted C2-C6 alkenyl group.
- R 1 may be a substituted or unsubstituted C2-C6 alkenyl group. In some embodiments, R 1 can be an unsubstituted C2-C6 alkenyl group.
- At least one of R 2 to R 5 is halogen (eg, F, Cl, Br or I). In some embodiments, at least one of R 2 to R 5 can be F.
- R 2 to R 5 may be halogen. In some embodiments, R 2 to R 5 can all be F.
- M may be Li, Na or K.
- Y + is an alkali metal ion; ammonium ion; Or it may be a primary to quaternary ammonium ion.
- Ra to Rd are each independently hydrogen; A substituted or unsubstituted C1-C6 alkyl group; It may be a substituted or unsubstituted C2-C6 alkenyl group. In addition, at least two of Ra to Rd may be bonded to each other to form a 5-7 membered heterocyclic ring.
- Re to Rh independently of each other, hydrogen; A substituted or unsubstituted C1-C6 alkyl group; It may be a substituted or unsubstituted C2-C6 alkenyl group.
- at least two of Re to Rh may be bonded to each other to form a 5-7 membered heterocyclic ring.
- Y + is N + RaRbRcRd, and at least one of Ra to Rd can be hydrogen.
- Y + is N + RaRbRcRd
- Ra is hydrogen
- Rb to Rd may each independently be a C1-C3 alkyl group.
- the compound of Formula 1 may be prepared by reacting a sulfonate-based salt or a sulfate-based salt with a phosphate-based alkali metal salt.
- the sulfonate-based salt or sulfate-based salt may be represented by Formula 2 below.
- R 1 is a substituted or unsubstituted C1-C6 alkyl group; A substituted or unsubstituted C2-C6 alkenyl group; A substituted or unsubstituted C2-C6 alkynyl group; A substituted or unsubstituted C3-C7 cycloalkyl group; A substituted or unsubstituted C3-C7 cycloalkenyl group; or -OR 1 .
- Y + may be a cationic material.
- R 1 is a substituted or unsubstituted C1-C6 alkyl group; Or it may be a substituted or unsubstituted C2-C6 alkenyl group.
- R 1 may be a substituted or unsubstituted C2-C6 alkenyl group. In some embodiments, R 1 can be an unsubstituted C2-C6 alkenyl group.
- Y + is an alkali metal ion; ammonium ion; Or it may be a primary to quaternary ammonium ion.
- Ra to Rd are each independently hydrogen; A substituted or unsubstituted C1-C6 alkyl group; It may be a substituted or unsubstituted C2-C6 alkenyl group. In addition, at least two of Ra to Rd may be bonded to each other to form a 5-7 membered heterocyclic ring.
- Re to Rh independently of each other, hydrogen; A substituted or unsubstituted C1-C6 alkyl group; It may be a substituted or unsubstituted C2-C6 alkenyl group.
- at least two of Re to Rh may be bonded to each other to form a 5-7 membered heterocyclic ring.
- Y + is N + RaRbRcRd, and at least one of Ra to Rd can be hydrogen.
- Y + is N + RaRbRcRd
- Ra is hydrogen
- Rb to Rd may each independently be a C1-C3 alkyl group.
- Ra is a substituted or unsubstituted C1-C6 alkyl group; Or it may be a substituted or unsubstituted C2-C6 alkenyl group.
- Ra may be a substituted or unsubstituted C2-C6 alkenyl group. In some embodiments, Ra may be an unsubstituted C2-C6 alkenyl group.
- the phosphate-based alkali metal salt may be represented by Formula 3 below.
- R 2 and R 3 are each independently halogen (eg, F, Cl, Br or I); Or it may be a substituted or unsubstituted C1-C6 alkyl group.
- At least one of R 2 and R 3 may be halogen. In some embodiments, at least one of R 2 and R 3 can be F.
- both R 2 and R 3 may be halogen. In some embodiments, R 2 and R 3 can both be F.
- the sulfonate-based salt or sulfate-based salt; And the compound represented by Formula 1 can be obtained by filtering and drying the crystal product produced by reacting the phosphate-based alkali metal salt.
- the reaction temperature may be 10 to 50 °C.
- the sulfonate-based salt or sulfate-based salt; And the mixing molar ratio of the phosphate-based alkali metal salt may be 1:0.9 to 1:1.1.
- an electrolyte solution for a rechargeable lithium battery including the compound represented by Chemical Formula 1 is provided.
- the compound represented by Chemical Formula 1 may be provided as an additive for an electrolyte solution for a rechargeable lithium battery.
- a lithium secondary battery according to exemplary embodiments includes the lithium secondary battery electrolyte, and life characteristics (eg, repeated charge/discharge capacity retention rate), output characteristics, and the like may be improved.
- the compound represented by Chemical Formula 1 may be reduced and decomposed at a voltage of about 2.1V to form a solid electrolyte interface (SEI) film on the surface of the negative electrode.
- SEI solid electrolyte interface
- the SEI film can suppress decomposition of an organic solvent (eg, ethylene carbonate) generated at a voltage of 2.9V. Accordingly, lifespan characteristics of the lithium secondary battery may be improved.
- the compound represented by Chemical Formula 1 may reduce the anode interface resistance. Accordingly, the output characteristics of the lithium secondary battery can be improved.
- An electrolyte solution for a lithium secondary battery may include a lithium salt (except for the lithium salt form of the compound represented by Chemical Formula 1); organic solvents; And it may include the compound represented by Formula 1 above.
- the content of the compound represented by Formula 1 may be 0.01 to 10% by weight, preferably 0.1 to 7.5% by weight, more preferably 0.3 to 5% by weight, based on the total weight of the electrolyte. Within the above range, lifespan characteristics and output characteristics of the lithium secondary battery may be further improved.
- the compound represented by Formula 1 may exist as a single entity in the electrolyte solution, or may exist in the form of a dimer (for example, see Formula 4 below, description of substituents is omitted), a trimer, a tetramer, or a multimer. may be
- the electrolyte solution for a lithium secondary battery may further include an auxiliary additive to further improve lifespan characteristics and output characteristics of the lithium secondary battery, or to improve high-temperature storage characteristics, etc.
- the auxiliary additive may include a fluorine-containing cyclic carbonate-based compound, a vinyl group-containing cyclic carbonate-based compound, a vinylene carbonate-based compound, a cyclic sulfate-based compound, a sultone-based compound, a fluorine-containing lithium phosphate-based compound, a lithium borate-based compound, A lactone-based compound, a sulfonyl imide-based compound, and the like may be included.
- the content of the auxiliary additive may be 0.01 to 10% by weight, 0.1 to 7.5% by weight, or 0.3 to 5% by weight of the total weight of the electrolyte solution. Within this range, lifespan characteristics, output characteristics, and high-temperature storage characteristics of the lithium secondary battery may be further improved.
- the ratio of the content of the auxiliary additive to the content of the compound represented by Formula 1 in the total weight of the electrolyte solution is 0.1 to 10, preferably 0.1 to 7, more preferably 0.5 to 5 days.
- the fluorine-containing cyclic carbonate-based compound may have a 5- to 7-membered cyclic structure.
- the fluorine-containing cyclic carbonate-based compound may have a fluorine atom directly bonded to a carbon atom or a fluorine-substituted alkyl group (eg, -CF 3 ) bonded thereto.
- the fluorine-containing cyclic carbonate-based compound may include fluoro ethylene carbonate (FEC) or the like.
- the content of the fluorine-containing cyclic carbonate-based compound may be 0.01 to 2% by weight or 0.1 to 1% by weight of the total weight of the electrolyte solution.
- the vinyl group-containing cyclic carbonate-based compound may include vinyl ethylene carbonate (VEC) and the like.
- VEC vinyl ethylene carbonate
- VC vinylene carbonate
- the content of the vinyl group-containing cyclic carbonate-based compound may be 0.01 to 2% by weight or 0.1 to 1% by weight of the total weight of the electrolyte solution.
- the content of the vinylene carbonate-based compound may be 0.01 to 2% by weight or 0.1 to 1% by weight of the total weight of the electrolyte.
- the cyclic sulfate-based compound may have a 5- to 7-membered cyclic structure.
- the cyclic sulfate-based compound may include ethylene sulfate (ESA), trimethylene sulfate (TMS), methyltrimethylene sulfate (MTMS), 1,3-propanediolcyclic sulfate, and the like.
- the cyclic sulfate-based compound may include a bicyclic sulfate-based compound.
- the bicyclic sulfate-based compound is 2,4,8,10-tetraoxa-3,9-dithiaspiro[5.5]undecane 3,3,9,9-tetraoxide, 4,4 '-bi(1,3,2-dioxathiolane)] 2,2,2',2'-tetraoxide and the like.
- the content of the cyclic sulfate-based compound may be 0.01 to 2% by weight or 0.1 to 1% by weight of the total weight of the electrolyte solution.
- the sultone-based compound may have a 5- to 7-membered cyclic structure.
- the sultone-based compound may include at least one of an alkyl sultone-based compound and an alkenyl sultone-based compound.
- the alkyl sultone-based compound may have only a saturated bond in a ring, and the alkenyl sultone-based compound may include a double bond in a ring.
- the alkyl sultone-based compound may include 1,3-propane sultone (PS), 1,4-butane sultone, and the like.
- the alkenyl sultone-based compound may include ethene sultone, 1,3-propene sultone (PRS), 1,4-butene sultone, 1-methyl-1,3-propene sultone, and the like.
- the content of the sultone-based compound may be 0.01 to 2% by weight or 0.1 to 1% by weight with respect to the total weight of the electrolyte solution.
- a fluorine atom may be directly bonded to a phosphorus atom, or a fluorine-substituted alkyl group (eg, -CF 3 ) may be bonded.
- the fluorine-containing lithium phosphate-based compound may include lithium difluorophosphate, lithium tetrafluoro oxalate phosphate, lithium difluorobis(oxalato)phosphate, and the like.
- the content of the fluorine-containing lithium phosphate-based compound may be 0.01 to 2% by weight or 0.1 to 1% by weight of the total weight of the electrolyte solution.
- the lithium borate-based compound may include lithium tetraphenylborate, lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiFOB), and the like.
- the content of the lithium borate-based compound may be 0.01 to 2% by weight or 0.1 to 1% by weight of the total weight of the electrolyte solution.
- the lactone-based compound may include at least one of a bicyclo lactone-based compound and a lactone-based compound including a double bond in a ring.
- the lactone-based compound may include muconic lactone and the like.
- the content of the lactone-based compound may be 0.01 to 2% by weight or 0.1 to 1% by weight of the total weight of the electrolyte solution.
- the sulfonyl imide-based compound may include lithium bis(fluorosulfonyl)imide or the like.
- the content of the sulfonyl imide-based compound may be 0.01 to 2% by weight or 0.1 to 1% by weight of the total weight of the electrolyte solution.
- the organic solvent may have sufficient solubility for the lithium salt, the compound represented by Chemical Formula 1, and the auxiliary additive.
- the organic solvent may be a non-aqueous organic solvent.
- the organic solvent may include a carbonate-based solvent, an ester-based (carboxylate-based) solvent, an ether-based solvent, a ketone-based solvent, an alcohol-based solvent, an aprotic solvent, and the like.
- the carbonate-based solvent may include a linear carbonate-based solvent and a cyclic carbonate-based solvent.
- the linear carbonate-based solvent is dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl propyl carbonate, ethyl It may include ethyl propyl carbonate, dipropyl carbonate, and the like.
- the cyclic carbonate-based solvent may include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, and the like.
- the organic solvent may include more of the linear carbonate-based solvent than the cyclic carbonate-based solvent based on volume.
- the volume ratio of the cyclic carbonate-based solvent to the linear carbonate-based solvent may be 1:1 to 9:1, preferably 1.5:1 to 4:1.
- the ester-based solvent may include a linear ester-based solvent and a cyclic ester-based solvent.
- the linear ester-based solvent may include methyl propionate, ethyl propionate, propyl acetate, butyl acetate, ethyl acetate, and the like.
- the cyclic ester-based solvent may include butyrolactone, caprolactone, valerolactone, and the like.
- the ether-based solvent is dibutyl ether, tetraethylene glycol dimethyl ether (TEGDME), diethylene glycol dimethyl ether (DEGDME), dimethoxyethane ), tetrahydrofuran (THF), and 2-methyltetrahydrofuran (2-methyltetrahydrofuran).
- the ketone-based solvent may include cyclohexanone and the like.
- the alcohol-based solvent may include at least one of ethyl alcohol and isopropyl alcohol.
- the aprotic solvent is a nitrile-based solvent, an amide-based solvent (eg, dimethylformamide) and a dioxolane-based solvent (eg, 1,3-dioxolane), a sulfolane-based solvent It may contain at least one of the solvents.
- the organic solvent may include the carbonate-based solvent
- the carbonate-based solvent may include ethylene carbonate (EC), ethylmethyl carbonate (EMC), dimethyl carbonate (DMC), and diethyl carbonate (DEC). may include at least one of them.
- the lithium salt may be expressed as Li + X - .
- the anion (X - ) of the lithium salt is F - , Cl - , Br - , I - , NO 3 - , N(CN) 2 - , BF 4 - , ClO 4 - , PF 6 - , (CF 3 ) 2 PF 4 - , (CF 3 ) 3 PF 3 - , (CF 3 ) 4 PF 2 - , (CF 3 ) 5 PF - , (CF 3 ) 6 P - , CF 3 SO 3 - , CF 3 CF 2 SO 3 - , (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , (SF 5 ) 3 C - , (CF 3 SO 2 ) 3 C - , CF 3 (CF 2 ) 7 SO 3 - , CF 3 CO
- the lithium salt is LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiN(C 2 F 5 SO 2 ) 2 , LiN(CF 3 SO 2 ) 2 , CF 3 SO 3 Li , LiC(CF 3 SO 2 ) 3 , and the like.
- the lithium salt may be included in a concentration of 0.01 to 5 M, preferably 0.01 to 2 M with respect to the organic solvent. Within the above concentration range, lithium ions and/or electrons may move smoothly during charging and discharging of the battery.
- a lithium secondary battery including the electrolyte solution for a lithium secondary battery is provided.
- FIGS. 2 and 3 are schematic plan perspective views and cross-sectional views respectively illustrating a rechargeable lithium battery according to exemplary embodiments.
- the lithium secondary battery may include a positive electrode 100 and a negative electrode 130 facing the positive electrode 100 .
- the cathode 100 may include a cathode current collector 105 and a cathode active material layer 110 on the cathode current collector 105 .
- the cathode active material layer 110 may include a cathode active material, a cathode binder, and a conductive material, if necessary.
- a positive electrode slurry is prepared by mixing and stirring a positive electrode active material, a positive electrode binder, a conductive material, a dispersion medium, and the like, and then the positive electrode slurry is coated on the positive electrode current collector 105, dried, and rolled. can be manufactured.
- the cathode current collector 105 may include stainless steel, nickel, aluminum, titanium, copper, or an alloy thereof.
- the cathode active material may include lithium metal oxide particles capable of reversibly intercalating and deintercalating lithium ions.
- the lithium metal oxide particles may be nickel, cobalt, manganese, aluminum or the like.
- the lithium metal oxide particle may contain nickel, and the content of nickel in the lithium metal oxide particle may be 80 mol% or more of all elements excluding lithium and oxygen.
- the lithium metal oxide particle may be represented by LiNiO 2 , LiCoO 2 , LiMnO 2 , LiMn 2 O 4 , or Chemical Formula 5 below.
- M is at least one of Al, Zr, Ti, Cr, B, Mg, Mn, Ba, Si, Y, W and Sr, and 0.9 ⁇ x ⁇ 1.2, 1.9 ⁇ y ⁇ 2.1, 0 ⁇ a+ b ⁇ 0.5.
- a and b may satisfy 0 ⁇ a+b ⁇ 0.4, 0 ⁇ a+b ⁇ 0.3, 0 ⁇ a+b ⁇ 0.2, or 0 ⁇ a+b ⁇ 0.1.
- the positive electrode binder may be polyvinylidenefluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyacrylonitrile, or polymethyl methacrylate.
- organic binders such as (polymethylmethacrylate), water-based binders such as styrene-butadiene rubber (SBR), etc.
- the positive electrode binder may be used together with a thickener such as carboxymethyl cellulose (CMC).
- the conductive material may include carbon-based conductive materials such as graphite, carbon black, graphene, and carbon nanotubes;
- a metal-based conductive material such as perovskite materials such as tin, tin oxide, titanium oxide, LaSrCoO3, and LaSrMnO3 may be included.
- the anode 130 may include a cathode current collector 125 and an anode active material layer 120 on the anode current collector 125 .
- the anode active material layer 120 may include an anode active material, an anode binder, and a conductive material, if necessary.
- a negative electrode slurry is prepared by mixing and stirring a negative electrode active material, a negative electrode binder, a conductive material, a solvent, etc., and then the negative electrode slurry is coated on the negative electrode current collector 125, dried, and rolled. can be manufactured.
- the anode current collector 125 may include gold, stainless steel, nickel, aluminum, titanium, copper, or an alloy thereof, preferably, copper or a copper alloy.
- the anode active material may be a material capable of intercalating and deintercalating lithium ions.
- the negative electrode active material may include a lithium alloy, a carbon-based active material, a silicon-based active material, and the like.
- the lithium alloy may include aluminum, zinc, bismuth, cadmium, antimony, silicon, lead, tin, gallium, indium, and the like.
- the carbon-based active material may include crystalline carbon, amorphous carbon, carbon composites, carbon fibers, and the like.
- the amorphous carbon may include hard carbon, coke, mesocarbon microbeads (MCMB) calcined at 1500° C. or less, mesophase pitch-based carbon fiber (MPCF), and the like.
- the crystalline carbon may include natural graphite, artificial graphite, graphitized coke, graphitized MCMB, graphitized MPCF, and the like.
- the negative electrode active material may include a silicon-based active material.
- the silicon-based active material may include Si, SiO x (0 ⁇ x ⁇ 2), Si/C, SiO/C, Si-Metal, and the like.
- the negative electrode binder and conductive material may be materials substantially the same as or similar to the above-described positive electrode binder and conductive material.
- the negative electrode binder may be an aqueous binder such as styrene-butadiene rubber (SBR).
- SBR styrene-butadiene rubber
- the negative electrode binder may be used together with a thickener such as carboxymethyl cellulose (CMC).
- a separator 140 may be interposed between the anode 100 and the cathode 130 .
- the area of the negative electrode 130 may be greater than the area of the positive electrode 100 . In this case, lithium ions generated from the positive electrode 100 can be smoothly transferred to the negative electrode 130 without being precipitated in the middle.
- the separator 140 includes a porous polymer film made of polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer. can do.
- the separator 140 may include a nonwoven fabric formed of high melting point glass fiber, polyethylene terephthalate fiber, or the like.
- an electrode cell may be formed including an anode 100 , a cathode 130 and a separator 140 .
- the electrode assembly 150 may be formed by stacking a plurality of electrode cells (however, one electrode cell is shown in FIG. 3 for convenience).
- the electrode assembly 150 may be formed by winding, lamination, or z-folding of the separator 140 .
- a lithium secondary battery includes a cathode lead 107 connected to the cathode 100 and protruding out of the case 160; and a cathode lead 127 connected to the cathode 130 and protruding out of the case 160 .
- the anode 100 and the cathode lead 107 may be electrically connected.
- the cathode 130 and the cathode lead 127 may be electrically connected.
- the positive lead 107 may be electrically connected to the positive current collector 105 .
- the anode lead 130 may be electrically connected to the anode current collector 125 .
- the cathode current collector 105 may include a protrusion (anode tab) 106 on one side.
- the positive electrode active material layer 110 may not be formed on the positive electrode tab 106 .
- the positive electrode tab 106 may be integral with the positive electrode current collector 105 or may be connected by welding or the like.
- the positive current collector 105 and the positive electrode lead 107 may be electrically connected through the positive electrode tab 106 .
- the negative current collector 125 may include a protrusion (negative electrode tab) 126 on one side.
- the negative electrode active material layer 120 may not be formed on the negative electrode tab.
- the negative electrode tab 126 may be integral with the negative electrode current collector 125 or may be connected by welding or the like.
- the negative current collector 125 and the negative electrode lead 127 may be electrically connected through the negative electrode tab 126 .
- the electrode assembly 150 may include a plurality of positive electrodes and a plurality of negative electrodes.
- a plurality of positive electrodes and a plurality of negative electrodes may be alternately disposed, and a separator may be interposed between the positive electrode and the negative electrode.
- the lithium secondary battery according to an embodiment of the present invention may include a plurality of positive electrode tabs and a plurality of negative electrode tabs protruding from each of the plurality of positive electrodes and the plurality of negative electrodes.
- the positive electrode tabs may be stacked, compressed, and welded to form a positive electrode tab stack (or negative electrode tab stack).
- the positive electrode tab stack may be electrically connected to the positive electrode lead 107 .
- the negative electrode tab laminate may be electrically connected to the negative electrode lead 127 .
- the electrode assembly 150 and the above-described electrolyte may be accommodated together in the case 160 to form a lithium secondary battery.
- the lithium secondary battery may be manufactured in a cylindrical shape, a prismatic shape, a pouch shape, or a coin shape, for example.
- EC ethylene carbonate
- DMC dimethyl carbonate
- LiPO 2 F 2 lithium difluorophosphate
- SC-XRD analysis data are listed in Table 1 below.
- a 1.0 M LiPF 6 solution was prepared using a mixed solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed in a ratio of 3:7 (v/v).
- EC ethylene carbonate
- EMC ethyl methyl carbonate
- Electrolytes of Examples and Comparative Examples were prepared by adding additives to the LiPF 6 solution, based on the total weight (100 wt%) of the electrolyte, according to Table 2 below.
- Li(Ni 0.6 Co 0.2 Mn 0.2 )O 2 , polyvinylidene fluoride (PVdF), and carbon black were dispersed in N-methyl-2-pyrrolidone (NMP) at a weight ratio of 92:4:4 to form a cathode slurry. manufactured.
- the positive electrode slurry was coated on an aluminum foil (thickness: 20 ⁇ m) having a protrusion (hereinafter, a positive electrode tab) on one side (excluding the protrusion portion), dried, and rolled to prepare a positive electrode.
- a protrusion hereinafter, a positive electrode tab
- An anode slurry was prepared by dispersing crystalline artificial graphite, acetylene black, and PVDF in NMP at a weight ratio of 92:1:7.
- the negative electrode slurry was coated on a copper foil (thickness: 15 ⁇ m) having a protrusion (hereinafter, a negative electrode tab) on one side (excluding the protrusion portion), dried, and rolled to prepare a negative electrode.
- a protrusion hereinafter, a negative electrode tab
- a cell was formed with a polyethylene separator (thickness: 20 ⁇ m) interposed between the anode and the cathode.
- a positive lead and a negative lead were connected to the positive electrode tab and the negative electrode tab by welding, respectively.
- the cell was accommodated in a pouch so that portions of the positive lead and the negative lead were exposed to the outside.
- An electrolyte solution was injected into the pouch, and the pouch was sealed and sealed to prepare a lithium secondary battery.
- Example 1 Preparation example compound 0.5wt%
- Example 2 Preparation example compound 1.0wt%
- Example 3 Preparation Example compound 1.0wt% + A-1 1wt%
- Example 4 Preparation Example compound 1.0wt% + A-2 1wt%
- Example 5 Preparation Example compound 1.0wt% + A-3 1wt%
- Example 6 Preparation Example Compound 1.0wt% + A-4 1wt%
- Example 7 Preparation Example Compound 1.0wt% + B-1 1wt%
- Example 8 Preparation Example Compound 1.0wt% + B-2 1wt%
- Example 9 Preparation Example Compound 1.0wt% + B-3 1wt%
- Example 10 Preparation Example Compound 1.0wt% + B-4 1wt%
- Example 11 Preparation Example compound 1.0wt% + B-5 1wt%
- Example 12 Preparation Example Compound 1.0wt% + C-1 1wt%
- Example 13 Preparation Example Compound 1.0
- Lithium secondary batteries of Examples and Comparative Examples were 1C CC/CV charged (4.2V CUT-OFF) and 1C CC discharged (3V CUT-OFF) to measure initial discharge capacity C1.
- the charging and discharging process was repeatedly performed 500 times for the lithium secondary batteries of Examples and Comparative Examples, and the discharge capacity C2 was measured at the 500th time.
- the capacity retention rate was calculated as a percentage of C1 versus C2 as follows.
- Capacity retention rate (%) C2/C1 ⁇ 100 (%)
- Example 2 and Comparative Example 1 were charged at 0.2 C CC/CV (4.2 V CUT-OFF), then discharged at 0.2 C CC (2.75 V CUT-OFF), and the charge/discharge capacities were differentiated by voltage. The relationship between capacity curve and voltage was derived.
- the plotted differential capacity curve is shown in FIG. 4 .
- the AC impedance graph is shown in FIG. 5 .
- the lithium secondary batteries of Examples and Comparative Examples were 1C CC/CV charged (4.2V CUT-OFF) and then 2C CC discharged to 440 mA. Thereafter, DCIR was measured by discharging and replenishing charge for 10 seconds, respectively, while changing the C-rate to 0.5C, 1C, 2C, and 4C.
- the lithium secondary batteries of Examples 1 and 2 exhibited improved lifespan characteristics and output characteristics compared to the lithium secondary batteries of Comparative Examples 1 and 17.
- the lithium secondary batteries of Examples 1 and 2 exhibited capacity retention rates improved by 3.9% to 6.4% compared to the capacity retention rates of the lithium secondary batteries of Comparative Examples 1 and 17.
- the lithium secondary batteries of Examples 1 and 2 showed output values improved by 7.5% to 13.4% compared to the output values of the lithium secondary batteries of Comparative Examples 1 and 17.
- the compound of Preparation Example improves the performance of the lithium secondary battery by reducing the resistance of the anode side in the low frequency region.
- the lithium secondary batteries of Examples 3 to 11 exhibited 4.2% to 5.8% improved capacity retention rate values compared to the lithium secondary batteries of Comparative Examples 2 to 10.
- the lithium secondary batteries of Examples 12 to 17 showed output values improved by 4.7% to 7.0% compared to the lithium secondary batteries of Comparative Examples 11 to 16.
- the compound of Preparation Example 1 can modify the structure of the SEI film on the negative electrode formed by the additives C-1 to C-6. Accordingly, lifespan characteristics and output characteristics of the lithium secondary battery may be further improved.
Abstract
Description
실험식 | C8H19F4Li2NO7P2S |
화학식량 | 425.12 |
온도 | 223(2) K |
파장 | 0.71073 Å |
결정계 | Monoclinic |
공간군 | P21/c |
단위 격자 치수 | a = 13.4915(13) Åb = 12.5771(13) Å c = 11.0764(11) Å α = 90° β = 96.338(3)° γ = 90° |
부피 | 1868.0(3) Å3 |
Z | 4 |
밀도(이론값) | 1.512 mg/m3 |
흡수 계수 | 0.410 mm-1 |
F(000) | 872 |
결정 사이즈 | 0.413 × 0.207 × 0.144 mm3 |
데이터 수집 세타 범위 | 2.220 to 28.389° |
지수 범위 | -18<=h<=15, -16<=k<=16, -14<=l<=14 |
수집된 반사 | 25372 |
독립적 반사 | 4581[R(int) = 0.0655] |
세타 = 25.242°까지의 완성도 | 98.10% |
흡수 보정 | Semi-empirical from equivalents |
최대 및 최소 투과 | 0.7457 및 0.5236 |
세분화 방법 | F2에 대한 전-행렬 최소-제곱 |
데이터/억제/변수 | 4581/0/233 |
F2에 대한 적합도 | 1.078 |
최종 R 지수[I>2sigma(I)] | R1 = 0.0587, wR2 = 0.1633 |
R 지수(all data) | R1 = 0.0762, wR2 = 0.1797 |
흡장 계수 | n/a |
최대 회절 피크 및 홀 | 1.097 및 -0.660 e.Å-3 |
첨가제 조성 및 함량 | |
실시예 1 | 제조예 화합물 0.5wt% |
실시예 2 | 제조예 화합물 1.0wt% |
실시예 3 | 제조예 화합물 1.0wt% + A-1 1wt% |
실시예 4 | 제조예 화합물 1.0wt% + A-2 1wt% |
실시예 5 | 제조예 화합물 1.0wt% + A-3 1wt% |
실시예 6 | 제조예 화합물 1.0wt% + A-4 1wt% |
실시예 7 | 제조예 화합물 1.0wt% + B-1 1wt% |
실시예 8 | 제조예 화합물 1.0wt% + B-2 1wt% |
실시예 9 | 제조예 화합물 1.0wt% + B-3 1wt% |
실시예 10 | 제조예 화합물 1.0wt% + B-4 1wt% |
실시예 11 | 제조예 화합물 1.0wt% + B-5 1wt% |
실시예 12 | 제조예 화합물 1.0wt% + C-1 1wt% |
실시예 13 | 제조예 화합물 1.0wt% + C-2 1wt% |
실시예 14 | 제조예 화합물 1.0wt% + C-3 1wt% |
실시예 15 | 제조예 화합물 1.0wt% + C-4 1wt% |
실시예 16 | 제조예 화합물 1.0wt% + C-5 1wt% |
실시예 17 | 제조예 화합물 1.0wt% + C-6 1wt% |
비교예 1 | - |
비교예 2 | A-1 1wt% |
비교예 3 | A-2 1wt% |
비교예 4 | A-3 1wt% |
비교예 5 | A-4 1wt% |
비교예 6 | B-1 1wt% |
비교예 7 | B-2 1wt% |
비교예 8 | B-3 1wt% |
비교예 9 | B-4 1wt% |
비교예 10 | B-5 1wt% |
비교예 11 | C-1 1wt% |
비교예 12 | C-2 1wt% |
비교예 13 | C-3 1wt% |
비교예 14 | C-4 1wt% |
비교예 15 | C-5 1wt% |
비교예 16 | C-6 1wt% |
비교예 17 | D-1 0.7wt% + C-1 0.3wt% |
A-1: 비닐렌 카보네이트(vinylene carbonate) A-2: 비닐 에틸렌 카보네이트(vinyl ethylene carbonate) A-3: 플로오로에틸렌 카보네이트(fluoroethylene carbonate) A-4: 뮤코닉 디락톤(muconic dilactone) B-1: 1,3-프로판 설톤(1,3-proane-sultone) B-2: 1,3-프로펜-1,3-설톤(1,3-propene-1,3-sultone) B-3: 에틸렌 설페이트(ethylene sulfate) B-4: 1,3-프로판디올 시클릭 설페이트(1,3-propanediolcyclic sulfate) B-5: 2,4,8,10-테트라옥사-3,9-디티아스피로[5,5]운데칸 3,3,9,9-테트라 옥사이드(2,4,8,10-Tetraoxa-3,9-dithiaspiro[5.5]undecane 3,3,9,9-tetra oxide) C-1: 리튬 디플루오로포스페이트(lithium difluorophosphate) C-2: 리튬 테트라플루오로옥살레이트포스페이트(lithium tetrafluoro oxalate phosphate) C-3: 리튬 디플루오로비스(옥살라토)포스페이트(lithium difluoro bis(oxalato) phosphate) C-4: 리튬 디플루오로(옥살라토)보레이트(lithium difluoro(oxalato)borate) C-5: 리튬 비스(옥살라토)보레이트(lithiumbis(oxalato)borate) C-6: 리튬 비스(플루오로설포닐)이미드(lithium bis(fluorosulfonyl)imide) D-1: 트리에틸암모늄 에텐설포네이트(Triethylammonium ethenesulfonate) |
25℃ 수명 특성 | 25℃ 출력 특성 | |||
초기 용량 (mAh) |
500회 용량 (mAh) |
용량 유지율 (%) |
출력 (W) |
|
실시예 1 | 879.4 | 830.2 | 94.4 | 62.1 |
실시예 2 | 878.2 | 831.7 | 94.7 | 61.5 |
비교예 1 | 873.9 | 769.0 | 88.0 | 54.2 |
비교예 17 | 876.1 | 792.9 | 90.5 | 57.2 |
25℃ 수명 특성 | |||
초기 용량 (mAh) |
500회 용량 (mAh) |
용량 유지율 (%) |
|
실시예 3 | 884.8 | 856.5 | 96.8 |
실시예 4 | 882.2 | 840.7 | 95.3 |
실시예 5 | 883.4 | 843.6 | 95.5 |
실시예 6 | 880.4 | 845.2 | 96 |
실시예 7 | 879.4 | 835.4 | 95 |
실시예 8 | 879.8 | 827.9 | 94.1 |
실시예 9 | 884.3 | 853.3 | 96.5 |
실시예 10 | 881.4 | 833.8 | 94.6 |
실시예 11 | 881.5 | 848 | 96.2 |
비교예 2 | 879.4 | 800.3 | 91 |
비교예 3 | 878.5 | 790.7 | 90 |
비교예 4 | 878.7 | 792.6 | 90.2 |
비교예 5 | 877.7 | 792.6 | 90.3 |
비교예 6 | 876.4 | 790.5 | 90.2 |
비교예 7 | 875.9 | 787.4 | 89.9 |
비교예 8 | 879 | 799 | 90.9 |
비교예 9 | 877.5 | 793.3 | 90.4 |
비교예 10 | 877.2 | 796.5 | 90.8 |
25℃ 출력 특성 출력(W) |
|
실시예 12 | 64.3 |
실시예 13 | 58.5 |
실시예 14 | 62 |
실시예 15 | 62.4 |
실시예 16 | 55.2 |
실시예 17 | 60 |
비교예 11 | 60.3 |
비교예 12 | 55.9 |
비교예 13 | 58.2 |
비교예 14 | 58.3 |
비교예 15 | 51.8 |
비교예 16 | 56.8 |
Claims (13)
- 청구항 1에 있어서,R1은 치환 또는 비치환된 C1-C6의 알킬기; 또는 치환 또는 비치환된 C2-C6의 알케닐기이고,R2 내지 R5 중 적어도 하나는 할로겐이며,M은 Li, Na 또는 K이고,Y+는 N+RaRbRcRd이고, Ra 내지 Rd 중 적어도 하나는 수소인, 화합물.
- 청구항 1에 있어서,R1는 치환 또는 비치환된 C2-C6의 알케닐기이고,R2 내지 R5는 전부 할로겐이며,M은 Li이고,Y+는 N+RaRbRcRd이며, Ra는 수소이고, Rb 내지 Rd는 서로 독립적으로 C1-C3의 알킬기인, 화합물.
- 화학식 2로 표시되는 화합물 및 화학식 3으로 표시되는 화합물을 반응시키는 단계를 포함하는, 청구항 1에 따른 화합물의 제조 방법:[화학식 2](화학식 2에서,R1은 치환 또는 비치환된 C1-C6의 알킬기; 치환 또는 비치환된 C2-C6의 알케닐기; 치환 또는 비치환된 C2-C6의 알키닐기; 치환 또는 비치환된 C3-C7의 시클로알킬기; 치환 또는 비치환된 C3-C7의 시클로알케닐기; 또는 -OR1이고, Y+은 양이온성 물질임),[화학식 3](화학식 3에서,R2 및 R3는 서로 독립적으로, 할로겐; 또는 치환 또는 비치환된 C1-C6의 알킬기이고, M+은 알칼리 금속 이온임).
- 청구항 5에 있어서,R1은 치환 또는 비치환된 C1-C6의 알킬기; 또는 치환 또는 비치환된 C2-C6의 알케닐기이고,R2 내지 R5 중 적어도 하나는 할로겐이며,M은 Li, Na 또는 K이고,Y+는 N+RaRbRcRd이고, Ra 내지 Rd 중 적어도 하나는 수소인, 리튬 이차 전지용 전해액.
- 청구항 5에 있어서,R1는 치환 또는 비치환된 C2-C6의 알케닐기이고,R2 내지 R5는 전부 할로겐이며,M은 Li이고,Y+는 N+RaRbRcRd이며, Ra는 수소이고, Rb 내지 Rd는 서로 독립적으로 C1-C3의 알킬기인, 리튬 이차 전지용 전해액.
- 청구항 5에 있어서, 상기 화학식 1로 표시되는 화합물의 함량은 상기 전해액 총 중량 중 0.01 내지 10중량%인, 리튬 이차 전지용 전해액.
- 청구항 5에 있어서, 상기 유기 용매는 선형 카보네이트계 용매, 환형 카보네이트계 용매, 선형 에스테르계 용매, 환형 에스테르계 용매, 에테르계 용매, 케톤계 용매, 알코올계 용매 및 비양성자성 용매 중 적어도 하나를 포함하는, 리튬 이차 전지용 전해액.
- 청구항 5에 있어서, 불소 함유 환형 카보네이트계 화합물, 비닐기 함유 환형 카보네이트계 화합물, 비닐렌 카보네이트계 화합물, 환형 설페이트계 화합물, 설톤계 화합물, 불소 함유 리튬 포스페이트계 화합물, 리튬 보레이트계 화합물, 락톤계 화합물 및 설포닐 이미드계 화합물 중 적어도 하나를 포함하는 보조 첨가제를 더 포함하는, 리튬 이차 전지용 전해액.
- 청구항 10에 있어서, 상기 보조 첨가제의 함량은 상기 전해액 총 중량 중 0.01 내지 10중량%인, 리튬 이차 전지용 전해액.
- 청구항 11에 있어서, 상기 전해액 중, 상기 화학식 1로 표시되는 화합물의 함량에 대한 상기 보조 첨가제의 함량의 비는 0.1 내지 10인, 리튬 이차 전지용 전해액.
- 양극;상기 양극과 대향하는 음극;상기 양극 및 상기 음극 사이에 개재되는 분리막; 및청구항 5에 따른 리튬 이차 전지용 전해액을 포함하는, 리튬 이차 전지.
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