CN112467209A - High-voltage lithium ion battery with high and low temperature performance - Google Patents
High-voltage lithium ion battery with high and low temperature performance Download PDFInfo
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- CN112467209A CN112467209A CN201910849388.5A CN201910849388A CN112467209A CN 112467209 A CN112467209 A CN 112467209A CN 201910849388 A CN201910849388 A CN 201910849388A CN 112467209 A CN112467209 A CN 112467209A
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- Prior art keywords
- ion battery
- lithium ion
- lithium
- additive
- positive
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 53
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 19
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims abstract description 19
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 9
- LNLFLMCWDHZINJ-UHFFFAOYSA-N hexane-1,3,6-tricarbonitrile Chemical compound N#CCCCC(C#N)CCC#N LNLFLMCWDHZINJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007774 positive electrode material Substances 0.000 claims abstract description 9
- 239000010954 inorganic particle Substances 0.000 claims abstract description 8
- 239000007773 negative electrode material Substances 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 7
- 239000010439 graphite Substances 0.000 claims abstract description 7
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 21
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 16
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- -1 lithium hexafluorophosphate Chemical group 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920000131 polyvinylidene Polymers 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- 239000002000 Electrolyte additive Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 150000002596 lactones Chemical class 0.000 description 10
- 238000007600 charging Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 2
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910001928 zirconium oxide 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
- H01M10/056—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
- H01M10/052—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
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
A high voltage lithium ion battery with high and low temperature performance has excellent cycle, high temperature storage and low temperature performance under high voltage. The positive active material is lithium cobaltate which is subjected to doping and coating treatment by one or more elements of Al, Mg, Ti and Zr; the negative active material is graphite or a graphite composite material containing 1-10 wt.% SiOx/C or Si/C; the separator comprises a substrate and a composite layer of inorganic particles and polymer coated on the substrate; the non-aqueous electrolyte comprises a non-aqueous organic solvent, lithium salt and an additive, wherein the additive is a positive electrode protection additive 1,3, 6-hexanetricarbonitrile, a negative electrode film-forming additive fluoroethylene carbonate, a low-impedance additive ethylene sulfate and/or lithium difluorophosphate. The lithium ion battery prepared by the electrolyte additive synergistic effect and the combination of the positive and negative electrode materials can effectively improve the high-temperature circulation, storage performance and low-temperature discharge performance of the high-voltage lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-voltage lithium ion battery with high and low temperature performances.
Background
In recent years, with the rapid development of electronic products such as smart phones, tablet computers, smart wearing and the like, in consideration of the difference between the service life and the working environment of the electronic products, consumers have higher and higher requirements on the energy density of lithium ion batteries, and meanwhile, the lithium ion batteries are required to have excellent high-temperature cycle, storage and low-temperature charge and discharge performances.
Disclosure of Invention
At present, the energy density of the lithium ion battery is mainly improved by adopting a lithium cobaltate positive electrode material with high voltage of 4.4V or more and a high-capacity and high-compaction graphite negative electrode material. However, as the voltage of the lithium ion battery increases, a series of safety problems such as deterioration of cycle performance of the high voltage lithium ion battery, and high temperature storage and air blowing are generated. The main factors responsible for these problems are: (1) elution of metal ions in the positive electrode material. With the increase of voltage, the structural stability of the lithium cobaltate of the positive electrode is deteriorated, metal ions are dissolved out from the positive electrode and reduced and deposited on the surface of the negative electrode, so that the structure of an SEI (solid electrolyte interphase) film of the negative electrode is damaged, the impedance of the negative electrode and the thickness of the battery are continuously increased, and the capacity loss and the cycle performance of the battery are deteriorated; (2) decomposition of the electrolyte at high voltage. Under high temperature and high voltage, the electrolyte is easy to be oxidized and decomposed on the surface of the anode to generate a large amount of gas, so that the battery bulges and the electrode interface is damaged, and the storage and cycle performance of the battery is poor; meanwhile, the oxidation activity of the anode lithium cobalt oxide is high under high voltage, so that the side reaction between the anode and the electrolyte is further aggravated, and decomposition products of the electrolyte are continuously deposited on the surface of the anode, so that the internal resistance of the battery is increased, and the circulation capacity retention rate and the low-temperature discharge capacity are reduced.
In view of the above, it is imperative to develop a high voltage lithium ion battery with both high and low temperature performance, so that the lithium ion battery has excellent high temperature cycle, storage and low temperature discharge performance to meet the needs of consumers.
The invention aims to solve the problems of high-temperature storage gas generation, quick cycle performance attenuation, battery internal resistance increase and the like of the conventional high-voltage lithium ion battery so as to meet the requirement of high-temperature and low-temperature performance, and provides a high-voltage lithium ion battery with high and low-temperature performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-voltage lithium ion battery with high and low temperature performance, which comprises a positive plate, a negative plate, a diaphragm arranged between the positive plate and the negative plate, and non-aqueous electrolyte used; the positive plate comprises a positive current collector and a mixed layer of a positive active material, a conductive agent and a binder coated on the positive current collector; the negative plate comprises a positive current collector and a mixed layer of a negative active material, a conductive agent and a binder coated on the positive current collector;
the positive active material is lithium cobaltate which is subjected to doping and coating treatment by one or more elements of Al, Mg, Ti and Zr;
the negative active material is graphite or a graphite composite material containing 1-10 wt.% SiOx/C or Si/C;
the separator includes a substrate and a composite layer of inorganic particles and a polymer coated on the substrate.
As an improvement of the high-voltage lithium ion battery with the high and low temperature performance, the lithium cobaltate subjected to doping and coating treatment by one or more elements of Al, Mg, Ti and Zr has a median particle diameter D5010-26 μm, and a specific surface area BET of 0.15-0.4m2/g。
As an improvement of the high-voltage lithium ion battery with the high and low temperature performance, the thickness of the composite layer of the inorganic particles and the polymer is 1-6 mu m.
As an improvement of the high-voltage lithium ion battery with both high and low temperature performance, the inorganic particles are one or a mixture of more than two of alumina, titanium oxide, magnesium oxide, zirconium oxide and barium titanate.
As an improvement of the high-voltage lithium ion battery with both high and low temperature performance, the polymer is one or two of polyvinylidene fluoride, polyvinylidene fluoride-co-hexafluoropropylene, polyacrylonitrile, polyimide and polymethyl methacrylate.
As an improvement of the high voltage lithium ion battery compatible with the high and low temperature performance of the present invention, the mass ratio of the inorganic particles to the polymer is known in the art.
As an improvement of the high-voltage lithium ion battery with the high and low temperature performance, the non-aqueous electrolyte comprises a non-aqueous organic solvent, lithium salt and an additive, wherein the additive is a positive electrode protection additive 1,3, 6-hexanetricarbonitrile, a negative electrode film forming additive fluoroethylene carbonate, a low-impedance additive ethylene sulfate and/or lithium difluorophosphate.
In the improvement of the high-voltage lithium ion battery with both high and low temperature performance, the non-aqueous organic solvent is a mixture of at least one of cyclic carbonates and at least one of linear carbonates and linear carboxylates in any proportion, the cyclic carbonates are ethylene carbonate and propylene carbonate, and the linear carbonates and the carboxylic carbonates are compounds such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethyl propionate, propyl propionate and propyl acetate.
As an improvement of the high-voltage lithium ion battery with the high and low temperature performance compatible with the present invention, the content of the 1,3, 6-hexanetricarbonitrile is 2 to 6 wt.%, for example, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, and 6 wt.% of the total mass of the nonaqueous electrolytic solution.
As an improvement of the high-voltage lithium ion battery with both high and low temperature performance, the fluoroethylene carbonate is contained in an amount of 5 to 15 wt.%, for example, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.% based on the total mass of the nonaqueous electrolyte.
As an improvement of the high-voltage lithium ion battery with the high and low temperature performance compatible with the present invention, the content of lithium difluorophosphate and/or ethylene sulfate is 0.2 to 3 wt.%, for example, 0.2 wt.%, 0.5 wt.%, 0.8 wt.%, 1 wt.%, 1.2 wt.%, 1.5 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.% of the total mass of the nonaqueous electrolyte.
As an improvement of the high-voltage lithium ion battery with both high and low temperature performance, the lithium salt of the nonaqueous electrolyte is lithium hexafluorophosphate, which accounts for 13-18 wt.%, for example, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, and 18 wt.% of the total mass of the electrolyte;
as an improvement of the high-voltage lithium ion battery with both high and low temperature performance, the non-aqueous electrolyte further comprises one or more than two of 1, 3-propane sultone, succinonitrile, adiponitrile, ethylene glycol bis (propionitrile) ether, lithium bis (fluorosulfonyl) imide, lithium bis (oxalato) borate and lithium difluoro (oxalato) borate; it accounts for 0-10 wt.%, e.g., 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.% of the total mass of the electrolyte.
As an improvement of the high-voltage lithium ion battery with high and low temperature performance, the charge cut-off voltage of the lithium ion battery is more than 4.4V.
Compared with the prior art, the invention has the advantages that:
1. the lithium ion battery prepared by combining the electrolyte additive and the anode and cathode materials can effectively improve the high-temperature cycle and storage performance of the high-voltage lithium ion battery.
2. According to the invention, the additive is added into the electrolyte, so that the interface impedance of the battery can be obviously reduced, and the low-temperature discharge performance of the lithium ion battery can be improved.
Detailed Description
The preparation method of 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 technologies 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.
Example 1
Preparing a positive plate: dispersing a positive electrode active material lithium cobaltate, conductive carbon black and a binder polyvinylidene fluoride in a proper amount of N-methylpyrrolidone (NMP) solvent according to a mass ratio of 97:1.5:1.5, and fully stirring and mixing to form uniform positive electrode slurry; and uniformly coating the positive slurry on a positive current collector aluminum foil, and drying, rolling and slitting to obtain the positive plate.
Preparing a negative plate: dispersing a negative active material artificial graphite, conductive carbon black, a binder Styrene Butadiene Rubber (SBR) and a thickener carboxymethyl cellulose sodium (CMC) in a proper amount of deionized water solvent according to a mass ratio of 96.5:0.5:1.5:1.5, and fully stirring and mixing to form uniform negative slurry; and uniformly coating the negative electrode slurry on a copper foil of a negative current collector, and drying, rolling and slitting to obtain a negative plate.
Preparing a diaphragm: a polyethylene separator having a thickness of 7 μm was coated with a 2 μm thick composite layer of a mixture of titanium oxide and polyvinylidene fluoride.
Preparation of nonaqueous electrolyte: ethylene Carbonate (EC), Propylene Carbonate (PC), diethyl carbonate (DEC) and Propyl Propionate (PP) were mixed uniformly in a mass ratio of 20:10:20:50 in an argon-filled glove box (moisture < 10ppm, oxygen < 1ppm), and 14 wt.% of LiPF based on the total mass of the nonaqueous electrolyte was slowly added to the mixed solution6Stirring until the mixture is completely dissolved, and then adding 5 wt.% of fluoroethylene carbonate, 4 wt.% of 1, 3-propanesulfonic acid lactone, 1 wt.% of adiponitrile, 2 wt.% of 1,3, 6-hexanetrinitrile and 0.2 wt.% of lithium difluorophosphate in this order based on the total mass of the nonaqueous electrolytic solution to obtain the solution of example 1A lithium ion battery electrolyte.
Preparing a high-voltage lithium ion battery: and winding the prepared positive plate, the diaphragm and the prepared negative plate to obtain a naked battery cell, and packaging the battery cell into an aluminum plastic film bag formed in a stamping manner in advance. And (3) after the packaged battery is dried at 85 ℃, injecting the prepared nonaqueous electrolytic solution into the dried battery, and finishing the preparation of the lithium ion battery after the battery is laid aside, formed and sealed for the second time.
Example 2
Unlike example 1, the active material used in the preparation of the positive electrode sheet was lithium cobaltate doped with Ti element in an amount of 500 ppm. The rest is the same as in example 1.
Example 3
Unlike example 2, 5 wt.% fluoroethylene carbonate, 4 wt.% 1, 3-propanesulfonic lactone, 1 wt.% adiponitrile, 3 wt.% 1,3, 6-hexanetrinitrile, and 0.2 wt.% lithium difluorophosphate were added to the electrolyte preparation, based on the total mass of the nonaqueous electrolyte. The rest is the same as in example 2.
Example 4
Unlike example 2, 5 wt.% fluoroethylene carbonate, 4 wt.% 1, 3-propanesulfonic lactone, 1 wt.% adiponitrile, 4 wt.% 1,3, 6-hexanetrinitrile, and 0.2 wt.% lithium difluorophosphate were added to the electrolyte preparation, based on the total mass of the nonaqueous electrolyte. The rest is the same as in example 2.
Example 5
Unlike example 2, the electrolyte was prepared by adding 6 wt.% fluoroethylene carbonate, 4 wt.% 1, 3-propanesulfonic lactone, 1 wt.% adiponitrile, 2 wt.% 1,3, 6-hexanetrinitrile, and 0.2 wt.% lithium difluorophosphate, based on the total mass of the nonaqueous electrolyte. The rest is the same as in example 2.
Example 6
Unlike example 2, 7 wt.% fluoroethylene carbonate, 4 wt.% 1, 3-propanesulfonic lactone, 1 wt.% adiponitrile, 2 wt.% 1,3, 6-hexanetrinitrile, and 0.2 wt.% lithium difluorophosphate were added to the electrolyte preparation, based on the total mass of the nonaqueous electrolyte. The rest is the same as in example 2.
Example 7
Unlike example 2, the electrolyte was prepared by adding 6 wt.% fluoroethylene carbonate, 4 wt.% 1, 3-propanesulfonic lactone, 1 wt.% adiponitrile, 2 wt.% 1,3, 6-hexanetrinitrile, and 0.5 wt.% lithium difluorophosphate, based on the total mass of the nonaqueous electrolyte. The rest is the same as in example 2.
Example 8
Different from the embodiment 2, the electrolyte is prepared by adding 6 wt.% fluoroethylene carbonate, 4 wt.% 1, 3-propanesulfonic lactone, 1 wt.% adiponitrile, 2 wt.% 1,3, 6-hexanetrinitrile and 1 wt.% lithium difluorophosphate based on the total mass of the nonaqueous electrolyte. The rest is the same as in example 2.
Example 9
Unlike example 2, 7 wt.% fluoroethylene carbonate, 4 wt.% 1, 3-propanesulfonic lactone, 1 wt.% adiponitrile, 3 wt.% 1,3, 6-hexanetrinitrile, and 0.5 wt.% lithium difluorophosphate were added to the electrolyte preparation, based on the total mass of the nonaqueous electrolyte. The rest is the same as in example 2.
Example 10
Unlike example 2, 7 wt.% fluoroethylene carbonate, 4 wt.% 1, 3-propanesulfonic acid lactone, 1 wt.% adiponitrile, 3 wt.% 1,3, 6-hexanetrinitrile, 0.5 wt.% ethylene sulfate, and 0.5 wt.% lithium difluorophosphate were added to the electrolyte preparation, based on the total mass of the nonaqueous electrolyte. The rest is the same as in example 2.
Comparative example 1
Unlike example 2, 4 wt.% of 1, 3-propanesulfonic lactone and 1 wt.% of adiponitrile, based on the total mass of the nonaqueous electrolytic solution, were added to the preparation of the electrolytic solution. The rest is the same as in example 2.
Comparative example 2
Unlike example 2, 5 wt.% fluoroethylene carbonate, 4 wt.% 1, 3-propanesulfonic lactone, and 1 wt.% adiponitrile, based on the total mass of the nonaqueous electrolyte, were added to the electrolyte preparation. The rest is the same as in example 2.
Comparative example 3
Unlike example 2, 4 wt.% of 1, 3-propanesulfonic lactone, 1 wt.% of adiponitrile, and 1 wt.% of 1,3, 6-hexanetricarbonitrile based on the total mass of the nonaqueous electrolyte were added to the electrolyte preparation. The rest is the same as in example 2.
Comparative example 4
Unlike example 2, the electrolyte was prepared by adding 4 wt.% of 1, 3-propanesulfonic acid lactone, 1 wt.% of adiponitrile, and 0.2 wt.% of lithium difluorophosphate based on the total mass of the nonaqueous electrolyte, and the rest was the same as example 2.
The lithium ion batteries obtained in the above comparative examples and examples were subjected to electrochemical performance tests, and the following descriptions were made:
high temperature cycling experiment at 45 ℃: the batteries obtained in the examples 1 to 10 and the comparative examples 1 to 4 are placed in an environment of (45 +/-2) DEG C and are kept stand for 2 to 3 hours, when the battery body reaches (45 +/-2) DEG C, the cut-off current of the battery is 0.025C according to 1C constant current charging, the battery is kept stand for 5 minutes after being fully charged, the battery is discharged to the cut-off voltage of 3.0V at a constant current of 0.7C, the highest discharge capacity of the previous 3 cycles is recorded as an initial capacity Q, and when the cycles reach the required times, the last discharge capacity Q of the battery is recorded1The results are reported in Table 1.
The calculation formula used therein is as follows:
capacity retention (%) ═ Q1/Q×100％
High temperature storage experiment: the batteries obtained in examples 1 to 10 and comparative examples 1 to 4 were subjected to a charge-discharge cycle test at room temperature for 3 times at a charge-discharge rate of 0.5C, and then charged to a full charge state at a rate of 0.5C, and the maximum discharge capacity Q and the battery thickness T of the previous 3 times at 0.5C cycles were recorded, respectively. The fully charged cells were stored at 85 ℃ for 6 hours and the cell thickness T after 6 hours was recorded0And 0.5C discharge capacity Q1Then, the cell was charged and discharged 3 times at a rate of 0.5C at room temperature, and the maximum discharge capacity Q was recorded for 3 cycles2And calculating to obtain experimental data such as the thickness change rate, the capacity retention rate, the capacity recovery rate and the like of the battery stored at high temperature, and recording the results as shown in table 1.
The calculation formula used therein is as follows:
thickness ofRate of change (%) - (T)0-T)/T×100％
Capacity retention (%) ═ Q1/Q×100％
Capacity recovery rate (%) ═ Q2/Q×100％
Low-temperature discharge experiment: the batteries obtained in examples 1-10 and comparative examples 1-4 were discharged to 3.0V at 0.2C at an ambient temperature of 25 + -3 deg.C, and left for 5 min; charging at 0.7C, changing to constant voltage charging when the voltage at the cell terminal reaches the charging limit voltage, stopping charging until the charging current is less than or equal to the cut-off current, standing for 5 minutes, discharging to 3.0V at 0.2C, and recording the discharge capacity as the normal temperature capacity Q0. Then the battery cell is charged at 0.7C, when the voltage of the battery cell terminal reaches the charging limiting voltage, constant voltage charging is changed, and charging is stopped until the charging current is less than or equal to the cut-off current; standing the fully charged battery at-20 +/-2 ℃ for 4h, discharging to cut-off voltage of 3.0V at 0.2C, and recording discharge capacity Q3The low-temperature discharge capacity retention rate was calculated and reported in table 1.
The low-temperature discharge capacity retention rate is calculated by the following formula:
low-temperature discharge capacity retention (%) ═ Q3/Q0×100％
TABLE 1 results of the charge-discharge cycles, high-temperature storage, and low-temperature discharge tests of examples 1 to 10 and comparative examples 1 to 4
As can be seen from the results of table 1:
as can be seen from comparative examples 1 and 2, the addition of lithium difluorophosphate can significantly improve the low-temperature discharge performance of the battery. As can be seen from comparison of example 2 with comparative examples 1 to 4, the battery of example 1, which contains fluoroethylene carbonate, 1,3, 6-hexanetricarbonitrile and lithium difluorophosphate together, has better high-temperature cycle properties, storage and low-temperature discharge properties. Further, by comparing the examples with comparative examples 1 to 4, it can be found that the optimized combination of the additives fluoroethylene carbonate, 1,3, 6-hexanetricarbonitrile and lithium difluorophosphate can significantly improve the high-temperature cycle and storage properties of the high-voltage lithium ion battery, while having good low-temperature discharge properties.
In summary, the non-aqueous electrolyte for the high-voltage lithium ion battery provided by the invention contains the additives of fluoroethylene carbonate, 1,3, 6-hexanetricarbonitrile and lithium difluorophosphate, and further can be optimally combined by adding various additives such as 1, 3-propane sultone, succinonitrile, adiponitrile, ethylene glycol bis (propionitrile) ether, lithium bis (fluorosulfonyl) imide, lithium bis (oxalato) borate and lithium difluoro (oxalato) borate, and the high-voltage lithium ion battery can have excellent high-temperature cycle, storage and low-temperature discharge performances through the synergistic effect of the additives.
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, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A high-voltage lithium ion battery with high and low temperature performance, wherein the high-voltage lithium ion battery with high and low temperature performance comprises a positive plate, a negative plate, a diaphragm arranged between the positive plate and the negative plate, and used non-aqueous electrolyte; the positive plate comprises a positive current collector and a mixed layer of a positive active material, a conductive agent and a binder coated on the positive current collector; the negative plate comprises a positive current collector and a mixed layer of a negative active material, a conductive agent and a binder coated on the positive current collector;
the positive active material is lithium cobaltate which is subjected to doping and coating treatment by one or more elements of Al, Mg, Ti and Zr;
the negative active material is graphite or a graphite composite material containing 1-10 wt.% SiOx/C or Si/C;
the separator includes a substrate and a composite layer of inorganic particles and a polymer coated on the substrate.
2. The lithium ion battery of claim 1, wherein the coating is doped with one or more of Al, Mg, Ti, ZrMedian particle diameter D of the treated lithium cobaltate5010-26 μm, and a specific surface area BET of 0.15-0.4m2/g。
3. The lithium ion battery of claim 1 or 2, wherein the composite layer of inorganic particles and polymer has a thickness of 1-6 μm.
4. The lithium ion battery according to any one of claims 1 to 3, wherein the inorganic particles are one or a mixture of two or more of alumina, titania, magnesia, zirconia, and barium titanate.
5. The lithium ion battery of any of claims 1-4, wherein the polymer is one or a blend of two of polyvinylidene fluoride, polyvinylidene fluoride-co-hexafluoropropylene, polyacrylonitrile, polyimide, polymethyl methacrylate.
6. The lithium ion battery of any of claims 1-5, wherein the nonaqueous electrolyte comprises a nonaqueous organic solvent, a lithium salt, and an additive that is a positive electrode protection additive 1,3, 6-hexanetricarbonitrile, a negative electrode film forming additive fluoroethylene carbonate, a low impedance additive ethylene sulfate, and/or lithium difluorophosphate.
7. The lithium ion battery according to any one of claims 1 to 6, wherein the non-aqueous organic solvent is a mixture of at least one of cyclic carbonates, ethylene carbonate and propylene carbonate, and at least one of linear carbonates, propyl propionate and propyl acetate, mixed in any ratio.
8. The lithium ion battery according to any one of claims 1 to 7, wherein the 1,3, 6-hexanetricarbonitrile is present in an amount of 2 to 6 wt.% of the total mass of the nonaqueous electrolytic solution;
the content of the fluoroethylene carbonate is 5 to 15 wt.% of the total mass of the nonaqueous electrolyte;
the content of the lithium difluorophosphate and/or the ethylene sulfate is 0.2 to 3 wt.% of the total mass of the nonaqueous electrolyte;
the lithium salt of the non-aqueous electrolyte is lithium hexafluorophosphate, and accounts for 13-18 wt% of the total mass of the electrolyte.
9. The lithium ion battery according to any one of claims 1 to 8, wherein the nonaqueous electrolytic solution further comprises one or more of 1, 3-propane sultone, succinonitrile, adiponitrile, ethylene glycol bis (propionitrile) ether, lithium bis fluorosulfonylimide, lithium bis (oxalato) borate, and lithium difluoro (oxalato) borate; which accounts for 0-10 wt.% of the total mass of the electrolyte.
10. The lithium ion battery of any of claims 1-9, wherein the lithium ion battery has a charge cut-off voltage of 4.4V or greater.
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