CN115763973A - Electrolyte and battery comprising same - Google Patents
Electrolyte and battery comprising same Download PDFInfo
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- CN115763973A CN115763973A CN202211393638.7A CN202211393638A CN115763973A CN 115763973 A CN115763973 A CN 115763973A CN 202211393638 A CN202211393638 A CN 202211393638A CN 115763973 A CN115763973 A CN 115763973A
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- Prior art keywords
- electrolyte
- additive
- battery
- alkyl
- fluorine
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 47
- -1 cyclic silane compound Chemical class 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims description 46
- 230000000996 additive effect Effects 0.000 claims description 44
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000011737 fluorine Substances 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 239000013538 functional additive Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 claims 1
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 230000001681 protective effect Effects 0.000 abstract description 10
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 5
- 238000006864 oxidative decomposition reaction Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- 239000007773 negative electrode material Substances 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical group 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 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 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- QVXQYMZVJNYDNG-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)methylsulfonyl-trifluoromethane Chemical compound [Li+].FC(F)(F)S(=O)(=O)[C-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F QVXQYMZVJNYDNG-UHFFFAOYSA-N 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- H01M10/052—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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides an electrolyte and a battery comprising the electrolyte, wherein a cyclic silane compound containing unsaturated bonds in the electrolyte has higher stability, silicon-carbon bonds formed by cyclic silicon atoms and branched chain molecules are broken under high voltage due to oxidative decomposition, the broken silicon-oxygen bonds are further oxidized, partial oxidation products can be subjected to polymerization reaction with an organic solvent (such as EC) in the electrolyte, and the generated polymer can not only form a protective film on the surface of a positive electrode, but also form a protective film on the surface of a negative electrode; the use of the electrolyte can improve the high-temperature cycle performance and the high-temperature storage performance of the battery, and simultaneously can also give consideration to the quick charge performance and the high-temperature cycle stability of the battery.
Description
Technical Field
The invention relates to an electrolyte and a battery comprising the same, and belongs to the technical field of lithium ion batteries.
Background
Lithium ion batteries have advantages such as high specific energy density and long cycle life, and thus are widely used in various electronic products, and in recent years, in electric vehicles, various electric tools, and energy storage devices in large quantities. Along with the improvement of living standard and the trend of more beautiful life, the upgrading of battery application scenes puts forward higher requirements on the performance of the battery, and especially puts forward higher requirements on the consideration of the high-temperature performance and the quick charging performance of the battery.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides the electrolyte and the battery comprising the electrolyte, wherein the electrolyte has higher oxidation resistance, partial oxidation products can generate polymerization reaction with a solvent to form protection on a positive electrode and a negative electrode, and the use of the electrolyte can improve the high-temperature cycle performance and the high-temperature storage performance of the battery and simultaneously can also give consideration to the quick charge performance of the battery.
The purpose of the invention is realized by the following technical scheme:
the electrolyte comprises an organic solvent, a lithium salt and a functional additive, wherein the functional additive comprises a first additive, and the first additive is a cyclic silane compound containing an unsaturated bond.
According to an embodiment of the present invention, the unsaturated bond-containing cyclic silane compound includes an unsaturated double bond and a cyclic siloxy group (-Si-O-).
According to an embodiment of the invention, the first additive is selected from at least one of the compounds of formula I:
in the formula I, R 1 Selected from alkyl groups; m is an integer of 2 to 12; n is an integer of 0 to 10And (4) counting.
According to an embodiment of the present invention, R 1 Is selected from C 1-12 Alkyl, preferably R 1 Is selected from C 1-6 Alkyl, e.g. R 1 Is selected from C 1-3 Alkyl, illustratively, R 1 Selected from methyl.
According to an embodiment of the present invention, m is an integer between 2 and 6, exemplarily, m is 2, 3, 4, 5 or 6. And when m is an integer between 2 and 6, the stability of the ring structure in the first additive is better, the oxidation resistance is strong, and the polymerization degree of the first additive can be enhanced, so that the protection formed on the surface of the negative electrode is more excellent.
According to an embodiment of the present invention, n is an integer between 0 and 5, and exemplarily, n is 0, 1, 2, 3, 4 or 5.n is different, and the stability of the unsaturated bond in the first additive is different, and the oxidation resistance is also different, and when n is an integer between 0 and 5, the stability of the unsaturated bond in the first additive is good, and the oxidation resistance is strong.
According to an embodiment of the present invention, the first additive is at least one selected from the group consisting of compounds represented by formula I-1 to formula I-3:
in this case, the first additive has high stability, high oxidation resistance and high degree of polymerization, and is more favorable for participating in film formation on the surface of the negative electrode.
According to an embodiment of the present invention, the functional additive further comprises a second additive selected from at least one of fluorinated cyclic carbonate-based compounds.
According to an embodiment of the present invention, the fluorocyclic carbonate compound has at least one of the structural formulas shown in formula II:
in the formula II, R 2 Is absent or-CH 2 -；R 3 、R 4 、R 5 、R 6 Identical or different, independently of one another, from the group consisting of hydrogen, fluorine, alkyl, fluorine-substituted alkyl, and R 3 、R 4 、R 5 、R 6 At least one group of (a) is selected from fluorine or fluorine substituted alkyl.
According to an embodiment of the invention, R 3 、R 4 、R 5 、R 6 Identical or different, independently of one another, from hydrogen, fluorine, C 1-12 Alkyl, fluoro substituted C 1-12 Alkyl, and R 3 、R 4 、R 5 、R 6 At least one group of (A) is selected from fluorine or fluorine substituted C 1-12 An alkyl group.
According to an embodiment of the invention, R 3 、R 4 、R 5 、R 6 Identical or different, independently of one another, from hydrogen, fluorine, C 1-6 Alkyl, fluoro substituted C 1-6 Alkyl, and R 3 、R 4 、R 5 、R 6 At least one group of (A) is selected from fluorine or fluorine substituted C 1-6 An alkyl group.
According to an embodiment of the invention, R 3 、R 4 、R 5 、R 6 Identical or different, independently of one another, from hydrogen, fluorine, C 1-3 Alkyl, fluoro substituted C 1-3 Alkyl, and R 3 、R 4 、R 5 、R 6 At least one group of (A) is selected from fluorine or fluorine substituted C 1-3 An alkyl group.
According to an embodiment of the present invention, the second additive is at least one selected from the group consisting of compounds represented by formulas II-1 to II-8:
according to the embodiment of the present invention, when the second additive is selected from compounds containing a large amount of F substitution, it is possible to form more LiF on the surface of the negative electrode, resulting in a battery with low resistance.
According to an embodiment of the present invention, the first additive is added in an amount of 0.1wt% to 5.0wt%, for example, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.2wt%, 1.3wt%, 1.5wt%, 1.6wt%, 1.8wt%, 2wt%, 2.2wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.8wt%, 3wt%, 3.3wt%, 3.5wt%, 3.8wt%, 4wt%, 4.2wt%, 4.5wt%, 4.8wt%, or 5wt% based on the total weight of the electrolyte.
According to an embodiment of the present invention, the second additive is added in an amount of 5wt% to 15wt%, for example, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, or 15wt% based on the total weight of the electrolyte.
According to embodiments of the present invention, the first additive may be prepared by methods known in the art or may be commercially available.
According to an embodiment of the present invention, the second additive may be prepared by a method known in the art, or may be commercially available.
According to an embodiment of the present invention, the functional additive further comprises a third additive selected from at least one of 1, 3-propylene sultone, lithium difluorooxalato borate, lithium difluorophosphate, lithium difluorodioxaoxalato phosphate.
According to an embodiment of the present invention, the third additive is added in an amount of 2wt% to 8.0wt%, for example, 2wt%, 2.2wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.8wt%, 3wt%, 3.3wt%, 3.5wt%, 3.8wt%, 4wt%, 4.2wt%, 4.5wt%, 4.8wt%, 5wt%, 6wt%, 7wt%, or 8wt%, based on the total weight of the electrolyte. The third additive can participate in the generation of the SEI film in the initial formation stage to play a role in protecting the negative electrode, and can also continuously repair the damaged SEI film in the later cycle stage, so that the electrochemical performance of the battery is improved.
According to an embodiment of the present invention, the lithium saltSelected from lithium hexafluorophosphate (LiPF) 6 ) Lithium difluorophosphate (LiPO) 2 F 2 ) One or more of lithium difluorooxalato borate (LiDFOB), lithium bistrifluoromethylsulfonyl imide, lithium difluorobis-oxalato phosphate, lithium tetrafluoroborate, lithium bisoxalato borate, lithium hexafluoroantimonate, lithium hexafluoroarsenate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (pentafluoroethylsulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methide or lithium bis (trifluoromethylsulfonyl) imide.
According to an embodiment of the present invention, the organic solvent is selected from carbonates and/or carboxylic esters, the carbonates being selected from one or several of the following fluorinated or unsubstituted solvents: ethylene Carbonate (EC), propylene Carbonate (PC), dimethyl carbonate, diethyl carbonate (DEC), ethyl methyl carbonate; the carboxylic ester is selected from one or more of the following fluorinated or unsubstituted solvents: propyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, propyl Propionate (PP), ethyl Propionate (EP), methyl butyrate, ethyl n-butyrate.
According to an embodiment of the invention, the electrolyte is used in a lithium ion battery.
The invention also provides a battery, which comprises the electrolyte.
According to an embodiment of the present invention, the battery further includes a positive electrode sheet containing a positive electrode active material, a negative electrode sheet containing a negative electrode active material, and a separator.
According to an embodiment of the present invention, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer coated on one or both surfaces of the positive electrode current collector, and the positive electrode active material layer includes a positive electrode active material, a conductive agent, and a binder.
According to an embodiment of the present invention, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer coated on one or both surfaces of the negative electrode current collector, the negative electrode active material layer including a negative electrode active material, a conductive agent, and a binder.
According to the embodiment of the invention, the positive electrode active material layer comprises the following components in percentage by mass: 80-99.8 wt% of positive active material, 0.1-10 wt% of conductive agent and 0.1-10 wt% of binder.
Preferably, the positive electrode active material layer comprises the following components in percentage by mass: 90-99.6 wt% of positive active material, 0.2-5 wt% of conductive agent and 0.2-5 wt% of binder.
According to the embodiment of the invention, the anode active material layer comprises the following components in percentage by mass: 80-99.8 wt% of negative active material, 0.1-10 wt% of conductive agent and 0.1-10 wt% of binder.
Preferably, the negative electrode active material layer comprises the following components in percentage by mass: 90-99.6 wt% of negative active material, 0.2-5 wt% of conductive agent and 0.2-5 wt% of binder.
According to an embodiment of the present invention, the negative active material is selected from at least one of artificial graphite, natural graphite, mesocarbon microbeads, hard carbon, soft carbon, and a silicon-based negative electrode material.
According to the embodiment of the invention, the positive active material is selected from one or more of transition metal lithium oxide, lithium iron phosphate, lithium manganate, lithium iron manganese phosphate and lithium vanadium phosphate; the chemical formula of the transition metal lithium oxide is Li 1+ x Ni y Co z M (1 -y-z)O 2 Wherein-0.1 is less than or equal to x is less than or equal to 1; y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and y + z is more than or equal to 0 and less than or equal to 1; wherein M is one or more of Mg, zn, ga, ba, al, fe, cr, sn, V, mn, sc, ti, nb, mo and Zr.
According to the embodiment of the invention, the capacity retention rate of the battery after being stored at 85 ℃ for 6 hours is greater than or equal to 69%, and the thickness expansion rate is reduced by less than or equal to 8%.
According to an embodiment of the present invention, the capacity retention rate of the battery is 80% or more at 45 ℃ after 300 cycles.
According to the embodiment of the invention, the discharge capacity retention rate of the battery at the 3C rate is greater than or equal to 76%.
According to an embodiment of the present invention, the capacity retention rate of the battery is 64% or more at 45 ℃ and 800 cycles.
Has the beneficial effects that:
the invention provides an electrolyte and a battery comprising the electrolyte, wherein a cyclic silane compound containing an unsaturated bond in the electrolyte has higher stability compared with a chain silane compound containing an unsaturated bond due to the ring-forming structural characteristic, and a silicon-carbon bond formed by a cyclic silicon atom and a branched chain molecule is broken under high voltage due to oxidative decomposition, the broken silicon-oxygen bond is further oxidized, wherein partial oxidation products can perform polymerization reaction with an organic solvent (such as EC) in the electrolyte, and the generated polymer can not only form a protective film on the surface of a positive electrode, but also form a protective film on the surface of a negative electrode; the cyclic silane compound containing the unsaturated bond can also generate a compound containing a-Si-O-F-bond after continuous oxidation, and the compound containing the-Si-O-F-bond can participate in film formation on the surfaces of the positive electrode and the negative electrode. The SEI film under the full power at high temperature has poor thermal stability, deformation and pore enlargement easily occur, the solvent is further reduced at the negative electrode, unsaturated double bonds on the branched chain of the cyclic silane compound containing the unsaturated bonds can also generate polymerization reaction on the surface of the negative electrode to form a reticular protective film, the formed reticular protective film has certain toughness, the firmness of the SEI film can be enhanced, the deformation of the SEI film is inhibited simultaneously, the high-temperature storage performance and the high-temperature cycle performance of the battery are obviously improved, and the multiplying power performance of the battery can be considered simultaneously. On the basis, the second additive is introduced, can act on the surface of the negative electrode together with the first additive to form a compact and repairable SEI structure layer without increasing impedance, and protects the positive electrode and the negative electrode together under the synergistic action to prevent the electrolyte from being further decomposed and improve the quick charging stability of the electrolyte.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
In the description of the present invention, it should be noted that the terms "first", "second", etc. are used for descriptive purposes only and do not indicate or imply relative importance.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is understood that the lithium ion battery of the present invention includes a negative electrode tab, an electrolyte, a positive electrode tab, a separator, and an outer package. The lithium ion battery can be obtained by stacking the positive plate, the isolating membrane and the negative plate to obtain a battery cell or stacking the positive plate, the isolating membrane and the negative plate, and/or winding to obtain the battery cell, placing the battery cell in an outer package, and injecting electrolyte into the outer package.
Examples 1 to 7 and comparative examples 1 to 5
The lithium ion batteries of examples 1 to 7 and comparative examples 1 to 5 were prepared by the following steps:
1) Preparation of positive plate
The positive electrode active material lithium cobaltate (LiCoO) 2 ) Mixing polyvinylidene fluoride (PVDF), SP (super P) and Carbon Nano Tubes (CNT) according to a mass ratio of 96; uniformly coating the positive active slurry on two surfaces of the aluminum foil; and drying the coated aluminum foil, and then rolling and slitting to obtain the required positive plate.
2) Preparation of negative plate
Mixing artificial graphite serving as a negative electrode active material, sodium carboxymethylcellulose (CMC-Na), styrene butadiene rubber, conductive carbon black (SP) and single-walled carbon nanotubes (SWCNTs) according to a mass ratio of 94.5; uniformly coating the negative active slurry on two surfaces of a copper foil; and (3) airing the coated copper foil at room temperature, then transferring the copper foil to an oven at 80 ℃ for drying for 10h, and then carrying out cold pressing and slitting to obtain the negative plate.
3) Preparation of the electrolyte
In a glove box filled with argon (H) 2 O<0.1ppm，O 2 <0.1 ppm), EC/PC/DEC/PP were uniformly mixed in a mass ratio of 10/10/20/60, and then 13wt% of fully dried lithium hexafluorophosphate (LiPF) based on the total mass of the electrolyte was rapidly added thereto 6 ) After dissolution, 4wt% of 1, 3-propane sultone based on the total mass of the electrolyte was added, and after adding the first additive and the second additive according to the additives shown in table 1, the electrolytes of examples 1 to 7 and comparative examples 1 to 5 were prepared after uniform mixing.
4) Preparation of lithium ion battery
Stacking the positive plate in the step 1), the negative plate in the step 2) and the isolation film in the order of the positive plate, the isolation film and the negative plate, and then winding to obtain a battery cell; and (3) placing the battery cell in an outer package aluminum foil, injecting the electrolyte in the step 3) into an outer package, and performing vacuum packaging, standing, formation, shaping, sorting and other processes to obtain the lithium ion battery. The battery has a charge-discharge range of 3.0-4.5V.
TABLE 1 compositions of electrolyte additives in lithium ion batteries of examples and comparative examples
| First additive and content | Second additive and content | |
| Example 1 | 1/1wt% of formula I | / |
| Example 2 | Formula I-2/1wt% | / |
| Example 3 | Formula I-3/1wt% | / |
| Comparative example 1 | / | / |
| Comparative example 2 | / | Formula II-1/8wt% |
| Comparative example 3 | / | Formula II-1/10wt% |
| Comparative example 4 | / | Formula II-1/13wt% |
The lithium ion batteries obtained in the examples and comparative examples were subjected to the following performance tests, respectively, and the test results are shown in table 2.
1) 45 ℃ cycle performance test
Carrying out charge-discharge circulation on the divided battery cell within a charge-discharge cut-off voltage range for 1000 weeks at 45 ℃ according to the multiplying power of 1C, wherein the discharge capacity in the 1 st week is measured to be x1mAh, and the discharge capacity in the Nth circle is measured to be y1mAh; the volume at week N was divided by the volume at week 1 to give the cycle volume retention at week N, R1= y1/x1.
2) High-temperature storage test at 85 ℃:
and (3) charging the partial-capacity battery core to 4.5V at normal temperature by using 0.5C current, placing the fully-charged battery in an environment of 85 ℃ for 6 hours, measuring the thickness expansion rate by heat, discharging to 3.0V by using 0.5C current after the room temperature is recovered, and recording the discharge capacity.
3) 3C rate discharge performance test:
and (3) charging the divided battery cell at 0.5 ℃ to the upper limit, cutting to voltage, keeping the voltage constant to 0.05 ℃, discharging the fully charged sample at the ambient temperature of 25 +/-5 ℃ according to the current magnitude of 3 ℃, and then calculating the discharge capacity retention rate.
Table 2 results of performance test of lithium ion batteries of examples and comparative examples
As can be seen from the test results of examples 1 to 3 and comparative examples 1 to 4 of table 2, examples 1 to 3 in which the first additive was added alone and comparative examples 2 to 4 in which the second additive was added alone both improved the high temperature performance and rate performance of the battery. The first additive and the second additive can be arranged on the surface of the negative electrode, so that the high-temperature storage performance and the high-temperature cycle performance of the battery can be improved, and the rate performance and the high-temperature cycle stability of the battery can be simultaneously considered.
TABLE 3 composition of electrolyte additive in lithium ion batteries of examples and comparative examples
| First additive and content | Second additive and content | |
| Example 4 | Formula I-2/0.5wt% | Formula II-1/13wt% |
| Example 5 | Formula I-2/1wt% | Formula II-1/13wt% |
| Example 6 | Formula I-2/2wt% | Formula II-1/13wt% |
| Example 7 | Formula I-2/3wt% | Formula II-1/13wt% |
| Comparative example 5 | Vinyltrimethoxysilane/1 wt.% | Formula II-1/13wt% |
The results of the battery performance tests performed on the batteries according to the above test methods are summarized in table 4 below.
Table 4 results of performance test of lithium ion batteries of examples and comparative examples
As can be seen from the test results of examples 1 to 7 and comparative examples 1 to 5 of tables 2 and 4, examples 4 to 7, in which the first additive and the second additive are simultaneously added, can significantly improve the high-temperature performance and rate performance of the battery, compared to other examples and comparative examples.
Specifically, the cyclic silane compound containing an unsaturated bond as the first additive has high stability due to the ring-forming structural characteristic, and a silicon-carbon bond formed by a cyclic silicon atom and a branched chain molecule is broken due to oxidative decomposition under high voltage, the broken silicon-oxygen bond is further oxidized, a part of oxidation products can be subjected to polymerization reaction with an organic solvent (such as EC) in an electrolyte, and the generated polymer can not only form a protective film on the surface of a positive electrode, but also form a protective film on the surface of a negative electrode; the cyclic silane compound containing the unsaturated bond can also generate a compound containing a-Si-O-F-bond after continuous oxidation, and the compound containing the-Si-O-F-bond can participate in film formation on the surfaces of the positive electrode and the negative electrode. The SEI film under high temperature and full power has poor thermal stability, is easy to deform and increase pores, so that the solvent is further reduced at the negative electrode, unsaturated double bonds on the branched chains of the cyclic silane compounds containing the unsaturated bonds can also perform polymerization reaction on the surface of the negative electrode to form a reticular protective film, and the formed reticular protective film has certain toughness, can strengthen the firmness of the SEI film and simultaneously inhibits the deformation of the SEI film. The introduced second additive and the first additive can act on the surface of the negative electrode together to form a compact and repairable SEI structure layer without increasing impedance, and the cooperation of the two additives protects the positive electrode and the negative electrode together to prevent the electrolyte from being further decomposed and improve the quick charging stability of the electrolyte.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement and the like made on the basis of the technical scheme of the invention shall be included in the protection scope of the invention.
Claims (10)
1. The electrolyte is characterized by comprising an organic solvent, a lithium salt and a functional additive, wherein the functional additive comprises a first additive, and the first additive is a cyclic silane compound containing an unsaturated bond.
2. The electrolyte of claim 1, wherein the first additive is selected from at least one of the compounds of formula I:
in the formula I, R 1 Selected from alkyl; m is an integer of 2 to 12; n is an integer of 0 to 10.
3. The electrolyte of claim 2, wherein R is 1 Is selected from C 1-12 Alkyl, m is an integer between 2 and 6, and/or; n is an integer of 0 to 5.
4. The electrolyte of claim 1, wherein the functional additive further comprises a second additive selected from at least one of fluorinated cyclic carbonate compounds.
5. The electrolyte of claim 4, wherein the fluorocyclic carbonate compound has at least one of the structural formulas shown in formula II:
in the formula II, R 2 Is absent or-CH 2 -；R 3 、R 4 、R 5 、R 6 Identical or different, independently of one another, from hydrogen, fluorine, alkyl, fluorine-substituted alkyl, and R 3 、R 4 、R 5 、R 6 At least one group of (a) is selected from fluorine or fluorine-substituted alkyl.
6. The electrolyte of claim 5,R 3 、R 4 、R 5 、R 6 identical or different, independently of one another, from hydrogen, fluorine, C 1-12 Alkyl, fluoro substituted C 1-12 Alkyl, and R 3 、R 4 、R 5 、R 6 At least one group of (A) is selected from fluorine or fluorine substituted C 1-12 An alkyl group.
7. The electrolyte according to claim 1, wherein the first additive is added in an amount of 0.1 to 5.0wt% based on the total weight of the electrolyte.
8. The electrolyte according to claim 1, wherein the second additive is added in an amount of 5 to 15wt% based on the total weight of the electrolyte.
9. The electrolyte of claim 1, wherein the functional additive further comprises a third additive selected from at least one of 1, 3-propene sultone, lithium difluorooxalate borate, lithium difluorophosphate, lithium difluorodioxalate phosphate;
preferably, the third additive is added in an amount of 2wt% to 8.0wt% based on the total weight of the electrolyte.
10. A battery comprising an electrolyte as claimed in any one of claims 1 to 9.
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| CN111640982B (en) * | 2020-05-18 | 2021-10-26 | 珠海冠宇电池股份有限公司 | Electrolyte for lithium ion battery and lithium ion battery comprising same |
| CN114464884A (en) * | 2022-01-21 | 2022-05-10 | 珠海冠宇电池股份有限公司 | Electrolyte and battery containing silicon-based negative electrode and comprising electrolyte |
| CN115036572A (en) * | 2022-06-21 | 2022-09-09 | 深圳新宙邦科技股份有限公司 | Lithium secondary battery |
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