CN114142086A - Low-temperature-resistant lithium ion battery electrolyte and lithium ion battery - Google Patents
Low-temperature-resistant lithium ion battery electrolyte and lithium ion battery Download PDFInfo
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- CN114142086A CN114142086A CN202111355689.6A CN202111355689A CN114142086A CN 114142086 A CN114142086 A CN 114142086A CN 202111355689 A CN202111355689 A CN 202111355689A CN 114142086 A CN114142086 A CN 114142086A
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- lithium
- ion battery
- lithium ion
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 56
- 239000003792 electrolyte Substances 0.000 title claims abstract description 49
- -1 silane potassium salt compound Chemical class 0.000 claims abstract description 29
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 26
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 16
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 9
- 239000011149 active material Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 3
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005463 sulfonylimide group Chemical group 0.000 claims 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 2
- 229910000077 silane Inorganic materials 0.000 abstract description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 12
- 238000007600 charging Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 4
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229940125782 compound 2 Drugs 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000009517 secondary packaging Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a low-temperature-resistant lithium ion battery electrolyte and a lithium ion battery, which relate to the technical field of lithium ion batteries and comprise the following components: lithium salt, organic solvent, film forming additive and low temperature resistant additive; the low-temperature resistant additive is a silane potassium salt compound containing sulfonic acid, which has the structure shown in the specification:
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to low-temperature-resistant lithium ion battery electrolyte and a lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, no memory effect and the like, and is widely researched and applied. At present, the anode materials of commercial high-capacity lithium ion batteries mainly comprise lithium cobaltate, lithium manganate, lithium nickel manganese, ternary materials and the like, and in order to meet the requirements of sustainable work of portable electronic products and electric automobiles, the lithium ion batteries are required to have the advantages of high energy density, high specific energy density, wide working temperature range and long cycle life, so that the lithium ion batteries occupy the mainstream status in the market for a long time.
The electrolyte serves as an important component of the lithium ion battery, and has a significant influence on the performance of the lithium ion battery. All high-voltage cathode materials face a common problem, namely the decomposition problem of the electrolyte under high voltage, and how to solve the oxidative decomposition reaction of the electrolyte on the surface of the high-voltage cathode material is one of the core problems faced by the current high-voltage electrolyte research. On the other hand, more and more battery cell products pay attention to low-temperature charge and discharge performance, but such conditions worsen the risk of lithium precipitation of the lithium ion battery, so in order to meet the high-performance use requirement of the battery, it is necessary to develop a novel lithium ion battery electrolyte to improve the performance of the lithium ion battery under the low-temperature condition and further reduce the impedance of the lithium ion battery under the low temperature condition.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a low-temperature-resistant lithium ion battery electrolyte and a lithium ion battery.
The invention provides a low-temperature-resistant lithium ion battery electrolyte, which comprises the following components: lithium salt, organic solvent, film forming additive and low temperature resistant additive; the low-temperature resistant additive is a potassium silane sulfonate compound with a structure shown in a formula (I):
wherein R is1、R2Each independently selected from hydrogen, C1-C5 alkyl, C1-C5 haloalkyl or K, and R1、R2At least one of which is K.
Preferably, the low temperature resistant additive is selected from one or more of the following compounds:
preferably, the mass of the low-temperature resistant additive accounts for 0.05-12% of the total mass of the electrolyte; preferably 1 to 6%.
In the invention, the addition amount of the low-temperature resistant additive is too low, so that the improvement effect on the electrolyte is not obvious; when the amount of the additive is too high, the film formation is thick, the resistance increases, and the cycle of the battery is adversely affected to some extent.
Preferably, the film forming additive is one or more of vinylene carbonate, 1, 3-propane sultone, fluoroethylene carbonate, ethylene carbonate, lithium difluorophosphate, ethylene sulfate, ethylene sulfite, methylene methanedisulfonate, adiponitrile, succinonitrile, succinic anhydride, phthalic anhydride and pyridine.
Preferably, the lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorooxalato borate, lithium bis (oxalato) borate, lithium perchlorate, lithium nitrate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethyl) sulfonyl imide.
Preferably, the organic solvent is one or a combination of more than one of a carbonate solvent, a carboxylate solvent, an ether solvent, a nitrile solvent and an ionic liquid; preferably, the organic solvent is one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, fluoroethylene carbonate, ethyl acetate, methyl acetate, propyl acetate and propyl propionate.
Preferably, the electrolyte comprises the following components in percentage by mass: based on the total mass of the electrolyte, the mass percentage concentration of the following components is as follows: 1-10 wt% of film forming additive, 0.05-12 wt% of low temperature resistant additive and 65-85 wt% of organic solvent; the molar concentration of the lithium salt is 0.5-1.5 mol/L.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and the low-temperature-resistant lithium ion battery electrolyte as claimed in any one of claims 1 to 7.
Preferably, the active material of the positive electrode is selected from one of lithium cobaltate, lithium manganate, nickel cobalt manganese ternary material, nickel cobalt aluminum ternary material and spinel nickel lithium manganate material.
Preferably, the mass percentage of the graphitized carbon-based material in the active material of the negative electrode is 30-100%.
In the active material of the negative electrode, the graphitized carbon-based material refers to a carbon-based material having a graphite sheet structure, such as artificial graphite, natural graphite, mesocarbon microbeads, hard carbon, and the like, and may be a mixture of one or more of them in any proportion; the active material of the negative electrode may include, but is not limited to, silicon-based materials such as nano silicon and silicon oxide.
Has the advantages that: according to the invention, the silane sylvite compound containing sulfonic acid is added into the electrolyte, so that the crystal form stability of the anode material can be protected, the compound contains silane group and sulfoxy, the compound is subjected to redox reaction in preference to a solvent during battery charging, an oxidation product is deposited on the surface of the anode, a formed CEI film is compact and thin, and the side reaction of the anode and the electrolyte under high voltage is prevented; meanwhile, the film can be formed on the negative electrode to form an organic polymer film with high conductivity, and the increase of the resistance of the battery cell in the circulating process is improved, so that the low-temperature resistance and the circulating stability of the lithium battery under high voltage are improved.
Detailed Description
The invention provides a low-temperature-resistant lithium ion battery electrolyte, which comprises the following components: lithium salt, organic solvent, film forming additive and low temperature resistant additive; the low-temperature resistant additive is a potassium silane sulfonate compound with a structure shown in a formula (I):
wherein R is1、R2Each independently selected from hydrogen, C1-C5 alkyl, C1-C5 haloalkyl or K, and R1、R2At least one of which is K.
Wherein, the low temperature resistant additive is preferably selected from one or more than one of the following compounds:
the synthesis method of the compound comprises the following steps: oxidizing sulfonic acid silane by using dilute nitric acid, and uniformly stirring in a saturated ammonia gas atmosphere due to the release of nitrogen dioxide under the condition that the alkaline pH is 9-10, adding a saturated potassium chloride solution, and slowly adding potassium chloride dropwise at the addition rate to separate out a target product.
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The low-temperature-resistant lithium ion battery electrolyte comprises the following raw materials in percentage by weight: 8.5 percent of lithium hexafluorophosphate, 5 percent of silane potassium salt compound 1 containing sulfonic acid, 0.2 percent of lithium difluorophosphate, 5 percent of fluoroethylene carbonate, 3 percent of vinyl sulfate and the balance of organic solvent;
wherein the organic solvent is ethylene carbonate, propylene carbonate, ethyl methyl carbonate and diethyl carbonate, and the mass ratio of the ethylene carbonate to the propylene carbonate to the ethyl methyl carbonate to the diethyl carbonate is 20: 5: 50: 20, or a mixed solvent thereof.
The preparation method of the lithium ion battery electrolyte comprises the following steps: in a glove box filled with argon (moisture is less than 10ppm, oxygen content is less than 1ppm), taking an organic solvent, uniformly mixing, then adding fluoroethylene carbonate, ethylene sulfate and lithium difluorophosphate, slowly adding lithium hexafluorophosphate, and stirring until the lithium hexafluorophosphate is completely dissolved.
Example 2
The low-temperature-resistant lithium ion battery electrolyte comprises the following raw materials in percentage by weight: 8.5 percent of lithium hexafluorophosphate, 5 percent of silane potassium salt compound 2 containing sulfonic acid, 0.2 percent of lithium difluorophosphate, 5 percent of fluoroethylene carbonate, 3 percent of vinyl sulfate and the balance of organic solvent; the rest is the same as example 1.
Example 3
The low-temperature-resistant lithium ion battery electrolyte comprises the following raw materials in percentage by weight: 8.5 percent of lithium hexafluorophosphate, 5 percent of silane potassium salt compound containing sulfonic acid 3, 0.2 percent of lithium difluorophosphate, 5 percent of fluoroethylene carbonate, 3 percent of vinyl sulfate and the balance of organic solvent; the rest is the same as example 1.
Example 4
The low-temperature-resistant lithium ion battery electrolyte comprises the following raw materials in percentage by weight: 8.5 percent of lithium hexafluorophosphate, 5 percent of silane potassium salt compound containing sulfonic acid 4, 0.2 percent of lithium difluorophosphate, 5 percent of fluoroethylene carbonate, 3 percent of vinyl sulfate and the balance of organic solvent; the rest is the same as example 1.
Example 5
The low-temperature-resistant lithium ion battery electrolyte comprises the following raw materials in percentage by weight: 5% of lithium hexafluorophosphate, 8.5% of silane potassium salt compound 2 containing sulfonic acid, 0.2% of lithium difluorophosphate, 5% of fluoroethylene carbonate, 3% of vinyl sulfate and the balance of organic solvent; the rest is the same as example 2.
Example 6
The low-temperature-resistant lithium ion battery electrolyte comprises the following raw materials in percentage by weight: 5% of lithium hexafluorophosphate, 12% of silane potassium sulfonate compound 2, 0.2% of lithium difluorophosphate, 5% of fluoroethylene carbonate, 3% of vinyl sulfate and the balance of organic solvent; the rest is the same as example 2.
Example 7
The low-temperature-resistant lithium ion battery electrolyte comprises the following raw materials in percentage by weight: 10.5% of lithium hexafluorophosphate, 3% of silane potassium salt compound 2 containing sulfonic acid, 0.2% of lithium difluorophosphate, 5% of fluoroethylene carbonate, 3% of vinyl sulfate and the balance of organic solvent; the rest is the same as example 2.
Example 8
The low-temperature-resistant lithium ion battery electrolyte comprises the following raw materials in percentage by weight: 12% of lithium hexafluorophosphate, 1.5% of silane potassium salt compound 2 containing sulfonic acid, 0.2% of lithium difluorophosphate, 5% of fluoroethylene carbonate, 3% of vinyl sulfate and the balance of organic solvent; the rest is the same as example 2.
Example 9
The low-temperature-resistant lithium ion battery electrolyte comprises the following raw materials in percentage by weight: 13% of lithium hexafluorophosphate, 12% of silane potassium sulfonate compound 2, 0.2% of lithium difluorophosphate, 5% of fluoroethylene carbonate, 3% of vinyl sulfate and the balance of organic solvent; the rest is the same as example 2.
Comparative example 1
The lithium ion battery electrolyte comprises the following raw materials in percentage by weight: 8.5% of lithium hexafluorophosphate, 0.2% of lithium difluorophosphate, 5% of fluoroethylene carbonate, 3% of vinyl sulfate and the balance of an organic solvent; the rest is the same as example 1.
Comparative example 2
The lithium ion battery electrolyte comprises the following raw materials in percentage by weight: 8.5% of lithium hexafluorophosphate, 5% of potassium hexafluorophosphate, 0.2% of lithium difluorophosphate, 5% of fluoroethylene carbonate, 3% of vinyl sulfate, and the balance of an organic solvent; the rest is the same as example 1.
The performance of the electrolytes prepared in the examples and comparative examples of the present invention was tested, and the specific operations were as follows:
and taking the electrolytes of comparative examples 1-2 and examples 1-9, respectively injecting the electrolytes into a soft package lithium ion battery with a positive electrode active substance of nickel cobalt lithium manganate and a negative electrode active substance of artificial graphite, and respectively obtaining the corresponding ternary lithium ion battery after the batteries after injection are subjected to processes of packaging, laying aside, formation, aging, secondary packaging, capacity grading and the like.
The detection method for the ternary lithium ion battery assembled by the materials comprises the following steps:
low temperature 0.33C/0.5C cycling experiment: the lithium ion battery assembled by the materials is charged to a limit voltage of 4.4V at 0.2C and then is charged at a constant voltage, the lithium ion battery is kept stand for 30min until the charging current is less than or equal to a cut-off current, then the lithium ion battery is discharged to the cut-off voltage of 2.8V at 1.0C and kept stand for 30min, a charge-discharge experiment is carried out according to the procedures, the cycle is carried out for more than 100 weeks, and after the cycle is finished, the battery core is taken out, and the impedance is immediately tested. The capacity retention rate and the impedance value of the battery cell at low temperature were calculated, and the results are shown in table 1.
Low-temperature discharge experiment: the batteries obtained in comparative examples 1-2 and examples 1-9 were charged to a limit voltage of 4.4V at 0.5C, then changed to constant voltage charging until the charging current was less than or equal to the cutoff current, left to stand for 5min, and then discharged at 0.5C, where the current discharge capacity was the initial capacity; the charging is changed into constant voltage charging after the voltage is limited to 4.4V by 0.5C until the charging current is less than or equal to the cut-off current. The cell was then placed in a cold box at-30 ℃ and the discharge capacity was tested. The discharge capacity retention rate at low temperature of the battery cell was calculated, and the results are shown in table 1.
TABLE 1 data on-10 ℃ cycle and-30 ℃ low temperature discharge performance of the batteries prepared in examples 1-9 and comparative examples 1-2
From the data in table 1, it can be seen that after the sulfonic acid silane potassium salt-containing compound is added into the electrolyte as the low temperature resistant additive of the lithium ion battery, the oxidative decomposition reaction of the electrolyte and the active material under high voltage is inhibited through the film forming action of the sulfonic acid silane potassium salt-containing compound on the positive electrode and the negative electrode, and the internal resistance of the battery is reduced; meanwhile, the ionic conductivity of the interface film at low temperature is improved, and the low-temperature cycle performance of the battery is obviously improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The low-temperature-resistant lithium ion battery electrolyte is characterized by comprising the following components: lithium salt, organic solvent, film forming additive and low temperature resistant additive; the low-temperature resistant additive is a potassium silane sulfonate compound with a structure shown in a formula (I):
wherein R is1、R2Each independently selected from hydrogen, C1-C5 alkyl, C1-C5 haloalkyl or-K, and R1、R2At least one of which is-K.
2. The low temperature resistant lithium ion battery electrolyte of claim 1, wherein the low temperature resistant additive is selected from one or more of the following compounds:
3. the electrolyte for the low-temperature-resistant lithium ion battery of claim 1 or 2, wherein the mass of the low-temperature-resistant additive accounts for 0.05-12% of the total mass of the electrolyte; preferably 1 to 6%.
4. The low temperature resistant lithium ion battery electrolyte of claim 1, wherein the film forming additive is one or a combination of more than one of vinylene carbonate, 1, 3-propane sultone, fluoroethylene carbonate, ethylene carbonate, lithium difluorophosphate, ethylene sulfate, ethylene sulfite, methylene methanedisulfonate, adiponitrile, succinonitrile, succinic anhydride, phthalic anhydride, and pyridine.
5. The low temperature resistant lithium ion battery electrolyte of claim 1, wherein the lithium salt is one or a combination of more than one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorooxalato borate, lithium bis-oxalato borate, lithium perchlorate, lithium nitrate, lithium bis (trifluoromethyl) sulfonylimide and lithium bis (trifluoromethyl) sulfonylimide.
6. The low temperature resistant lithium ion battery electrolyte of claim 1, wherein the organic solvent is one or a combination of more than one of a carbonate solvent, a carboxylate solvent, an ether solvent, a nitrile solvent, and an ionic liquid; preferably, the organic solvent is one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, fluoroethylene carbonate, ethyl acetate, methyl acetate, propyl acetate and propyl propionate.
7. The electrolyte for the low-temperature-resistant lithium ion battery according to any one of claims 1 to 6, wherein the following components are present in percentage by mass based on the total mass of the electrolyte: 1-10 wt% of film forming additive, 0.05-12 wt% of low temperature resistant additive and 65-85 wt% of organic solvent; the molar concentration of the lithium salt is 0.5-1.5 mol/L.
8. A lithium ion battery, characterized by comprising a positive electrode, a negative electrode, a separator and the low temperature resistant lithium ion battery electrolyte of any one of claims 1 to 7.
9. The lithium ion battery of claim 8, wherein the active material of the positive electrode is selected from one of lithium cobaltate, lithium manganate, nickel cobalt manganese ternary material, nickel cobalt aluminum ternary material, and spinel nickel lithium manganate material.
10. The lithium ion battery according to claim 8, wherein the mass percentage of the graphitized carbon-based material in the active material of the negative electrode is 30-100%.
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