CN114614096A - Fast-charging electrolyte and application thereof in lithium ion battery - Google Patents
Fast-charging electrolyte and application thereof in lithium ion battery Download PDFInfo
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- CN114614096A CN114614096A CN202210174011.6A CN202210174011A CN114614096A CN 114614096 A CN114614096 A CN 114614096A CN 202210174011 A CN202210174011 A CN 202210174011A CN 114614096 A CN114614096 A CN 114614096A
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- lithium ion
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- NRGKMKILWIVZJM-UHFFFAOYSA-N 3-fluoro-1,2-oxazole Chemical group FC=1C=CON=1 NRGKMKILWIVZJM-UHFFFAOYSA-N 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 11
- -1 litodfp Inorganic materials 0.000 claims description 9
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 8
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000009830 intercalation Methods 0.000 claims description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 claims description 3
- BOMPXIHODLVNMC-UHFFFAOYSA-N difluoro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](F)(F)C1=CC=CC=C1 BOMPXIHODLVNMC-UHFFFAOYSA-N 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 3
- KJWHEZXBZQXVSA-UHFFFAOYSA-N tris(prop-2-enyl) phosphite Chemical compound C=CCOP(OCC=C)OCC=C KJWHEZXBZQXVSA-UHFFFAOYSA-N 0.000 claims description 3
- DEIXAXKIKOHRED-UHFFFAOYSA-N 5-(4-chlorophenyl)-1,2-thiazole Chemical compound C1=CC(Cl)=CC=C1C1=CC=NS1 DEIXAXKIKOHRED-UHFFFAOYSA-N 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 229910012265 LiPO2F2 Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910006095 SO2F Inorganic materials 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
- 239000007770 graphite material Substances 0.000 claims description 2
- LNLFLMCWDHZINJ-UHFFFAOYSA-N hexane-1,3,6-tricarbonitrile Chemical compound N#CCCCC(C#N)CCC#N LNLFLMCWDHZINJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 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
- 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 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- MRDKYAYDMCRFIT-UHFFFAOYSA-N oxalic acid;phosphoric acid Chemical compound OP(O)(O)=O.OC(=O)C(O)=O MRDKYAYDMCRFIT-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 229910000319 transition metal phosphate Inorganic materials 0.000 claims description 2
- FUJPAQRDHMJPBB-UHFFFAOYSA-N tris(ethenyl)-phenylsilane Chemical compound C=C[Si](C=C)(C=C)C1=CC=CC=C1 FUJPAQRDHMJPBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims 1
- 238000009831 deintercalation Methods 0.000 claims 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims 1
- SYUQQUMHOZQROL-UHFFFAOYSA-N trimethylsilyl dihydrogen phosphite Chemical compound C[Si](C)(C)OP(O)O SYUQQUMHOZQROL-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 20
- 229910002804 graphite Inorganic materials 0.000 abstract description 19
- 239000010439 graphite Substances 0.000 abstract description 19
- 238000007614 solvation Methods 0.000 abstract description 9
- 150000002545 isoxazoles Chemical class 0.000 abstract description 5
- 239000011737 fluorine Substances 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000004807 desolvation Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VMZOBROUFBEGAR-UHFFFAOYSA-N tris(trimethylsilyl) phosphite Chemical compound C[Si](C)(C)OP(O[Si](C)(C)C)O[Si](C)(C)C VMZOBROUFBEGAR-UHFFFAOYSA-N 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910011279 LiCoPO4 Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000002946 graphitized mesocarbon microbead Substances 0.000 description 1
- 230000002687 intercalation Effects 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
- 238000000034 method Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention belongs to the technical field of electrochemistry, and particularly relates to a quick-charging electrolyte and application thereof in a graphite-based lithium ion battery. The electrolyte takes fluorine substituted isoxazole and derivatives thereof as main solvents, lithium salt as solute and contains film forming additives; the electrolyte has the characteristic of weak solvation binding energy, still has higher ionic conductivity at lower temperature, is applied to a lithium ion battery system taking graphite as a cathode, can quickly desolvate solvated lithium ions under large multiplying power and is embedded between graphite layers, and shows better quick-charging characteristic; meanwhile, the excellent low-temperature capacity retention rate of the graphite electrode is ensured by rapid ion transmission and desolvation at low temperature. The quick-charging electrolyte can effectively ensure that the lithium ion battery system has the characteristics of high power, long circulation and large capacity at wide temperature.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a quick-charging electrolyte and application thereof in a lithium ion battery.
Background
With the progress of energy storage technology, lithium ion batteries have been taken in various fieldsHave found widespread use, for example, as power sources for various consumer electronic devices and electric vehicles. However, in some extremely cold weather, electronic devices such as mobile phones and computers with lithium ion batteries have the defects of difficult charging, fast power consumption and the like in the using process. The power density and energy density of lithium ion batteries at low temperatures will be severely compromised; for example, at-40 ℃, the capacity retention of the lithium ion battery currently commercialized can only reach 12% of that at normal temperature, and polarization occurs to a great extent. In addition, in hot tropical regions, the lithium ion battery has a low capacity and a low efficiency due to volatilization of the lithium ion battery electrolyte caused by high temperature and various side reactions occurring inside the battery at high temperature. Therefore, it is urgent to develop an electrolyte that can normally operate in a wide temperature range. As a lithium ion battery cathode material, the graphite has the advantages of abundant reserves, wide sources, stable electrochemical performance and higher theoretical specific capacity (372 mAh/g), and is consistently considered as a more ideal cathode material at present. However, the high and low temperature performance of graphite negative electrodes is yet to be improved. Under the charging and discharging conditions of-20 ℃ and 0.1C, LiPF is used6The specific capacity of the graphite negative electrode lithium ion battery taking/EC-EMC (v: v =1:1) as electrolyte is only less than 50 mAh/g; when the temperature is increased to 50 ℃, the efficiency is less than 95%, and the capacity is reduced. Therefore, the application of the current graphite cathode lithium ion battery electrolyte in a wide temperature range is still to be studied more deeply.
The working temperature of the graphite cathode is mainly limited by the components of the electrolyte, but the key component of the current commercial electrolyte, namely Ethylene Carbonate (EC), has a melting point as high as 36.4 ℃, so that the viscosity of the electrolyte at low temperature is increased, the conductivity of lithium ion is reduced, and Li is difficult to supplement from the electrolyte in time+And severely hamper its use at lower temperatures. In addition, studies have shown that the charge transfer resistance (R) at low temperatures is lower than that of other resistance portionsct) The increase is particularly obvious, and the desolvation energy is the most main part of the charge transfer resistance, so that the selective use of a solvent with weak solvation energy is the main research direction of subsequent electrolytes. Specifically, in Li+During intercalation, the introduction of the solvent with weak solvation energy can enable solvated lithium ions on an SEI interface to be more easily extracted from a solvated structure to become naked lithium ions to be intercalated into graphite, so that solvent co-intercalation is inhibited. In addition, when the solvent and anion compete into Li+By using a solvent with a lower solvation energy when solvating the sheath, more anions can be made to react with Li+And (4) carrying out coordination. Even at lower salt concentrations, large numbers of ion pairs or aggregates can form due to the presence of weak solvent energy solvents, resulting in an anionically derived SEI. The SEI can obviously reduce the lithium ion transmission energy barrier, and is beneficial to improving the rate performance and realizing the fast charge and the cycling stability. Therefore, there is an urgent need to develop a novel electrolyte system with low solvation energy, low melting point, low viscosity and higher conductivity in a wide temperature range to improve the problem of energy density and power density attenuation of the graphite cathode lithium ion battery at a specific temperature.
The invention provides an electrolyte with weak solvent energy for a graphite cathode, which takes fluorine substituted isoxazole and derivatives thereof as main solvents. In the fluorine substituted isoxazole, due to the existence of atoms with large electronegativity of nitrogen and oxygen on five-membered rings and the conjugation effect on the rings, charges are dispersed, and Li is reacted with the five-membered rings+The binding capacity of the composite material is reduced, the composite material has weak solvation energy, and the electrochemical performance at wide temperature is better. Meanwhile, the fluorine-substituted isoxazole has the advantages of good film-forming property, high conductivity, small viscosity, low freezing point and the like, and the high-temperature stability of the fluorine-substituted isoxazole is combined, so that the electrolyte has good application prospect in a wide temperature range.
Disclosure of Invention
The invention aims to provide a quick-charging electrolyte with weak solvation energy and application thereof in a lithium ion battery.
The quick-charging electrolyte provided by the invention contains a solvent, lithium salt and a film-forming additive, wherein the solvent is substituted isoxazole and derivatives thereof; wherein the fluoroisoxazole has the following structural formula:
formula (I)
Wherein R is1，R2，R3= F or CHxF3-x(x =0, 1, 2), and at least includes R1，R2，R3One kind of (1).
The fluoroisoxazole and the derivatives thereof disclosed in the invention include but are not limited to one of the following structural formulas:
in the invention, the fluoroisoxazole or the derivative thereof accounts for 0.5-0.95 of the volume ratio of the electrolyte.
In the present invention, the film forming additive is selected from one or more of fluoroethylene carbonate (FEC), Vinylene Carbonate (VC), 1,3, 6-Hexanetricarbonitrile (HTCN), phenyltrivinylsilane (TESB), triallyl phosphite (TAPP), difluorodiphenylsilane (DFDPS), tris (trimethylsilyl) phosphite (TTMSP), ethylene glycol bis (propionitrile) ether (DPN) compounds.
In the present invention, the lithium salt is selected from lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide LiTFSI, lithium tris (trifluoromethanesulfonyl) methide, lithium bis (fluorosulfonyl) imide LiFSI, lithium bis (oxalato) borate, lithium difluorobis (oxalato) phosphate LiDODFP, LiN (SO)2RF)2、LiN(SO2F)(SO2RF) (wherein RF = -C)nF2n+1N = 1-10), lithium difluorophosphate LiPO2F2One or more compounds of lithium perchlorate, lithium tetrafluoro oxalate phosphate LiOTFP, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium hexafluoroarsenate (V) and the like.
In the invention, the concentration of the solute is 0.1-2.0 mol/L.
The quick-charging electrolyte provided by the invention can be applied to quick-charging and wide-temperature lithium ion batteries.
The quick-charging electrolyte provided by the invention can be used as a positive and negative electrode material capable of reversibly inserting/extracting lithium ions.
In the invention, the active material of the negative electrode is graphite material, including natural graphite, carbon black, graphene, graphitized mesocarbon microbeads and the like. The positive electrode is lithiated transition metal phosphate and transition metal oxide, such as LiFePO4、LiCoPO4、LiMn2O4、LiCoO2Ternary positive electrode materials, and the like.
The fast-charging electrolyte provided by the invention takes fluorine substituted isoxazole and derivatives thereof as main solvents. As the charges on the five-membered ring of the fluorine-substituted isoxazole are dispersed, when the fluorine-substituted isoxazole acts with metal cations, the solvent has weak solvation energy, and is beneficial to the de-intercalation of the metal cations between graphite layers. The electrolyte provided by the invention is applied to a quick-charging and wide-temperature lithium ion battery, and can show good rate performance and long cycle life.
The electrolyte has the characteristic of weak solvation binding energy, still has higher ionic conductivity at lower temperature, is applied to a lithium ion battery system taking graphite as a cathode, can quickly desolvate and embed lithium ions into graphite layers under large multiplying power, and shows better quick charge characteristic; meanwhile, the excellent low-temperature capacity retention rate of the graphite electrode is ensured by rapid ion transmission and desolvation at low temperature. The fast-charging electrolyte can effectively ensure that the lithium ion battery system has the characteristics of high power, long circulation and large capacity at wide temperature.
Drawings
Fig. 1 is the low temperature performance of graphite li half cells assembled with example 1.
Fig. 2 is the rate performance of graphite li half cells assembled with example 1.
Fig. 3 is the cycle performance of graphite li half cells assembled with example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described with reference to the following specific examples, but the present invention is not limited to these examples.
Example 1: under anhydrous and oxygen-free conditions, fluoroisoxazole (structural formula 1) is taken as a solvent, and fluoroethylene carbonate (FEC) with the volume fraction of 10 percent is added. Lithium difluorooxalato borate (LiDFOB) was dissolved therein at a molar concentration of 1 mol/L. Using artificial graphite as anode material and lithium metal (Li) as cathode material, assembling button type half cell, charging and discharging at 0.1C rate, and having capacity of 368 mAhg at 25 deg.C-1Low temperature-20 deg.C capacity of 230 mAhg-1(FIG. 1), a capacity of 370 mAhg at 60 ℃ C-1. Meanwhile, the rate performance (1C-10C, figure 2) and the cycle performance (1C, figure 3) are measured at the normal temperature of 25 ℃. See table 1.
Example 2: under the anhydrous and oxygen-free conditions, 30 volume percent of Vinylene Carbonate (VC) is added by taking fluoroisoxazole (structural formula 2) as a solvent. Lithium difluorooxalato borate (LiDFOB) was dissolved therein at a molar concentration of 1 mol/L. The button type half cell is assembled by taking artificial graphite as a negative electrode material and lithium metal (Li) as a negative electrode material, and is charged and discharged at a rate of 0.1C, and the capacity is 365 mAhg at the normal temperature of 25 DEG C-1The capacity is 210mAhg at the low temperature of-20 DEG C-1Capacity of 368 mAh g at 60 ℃ at high temperature-1. See table 1.
Example 3: under the anhydrous and oxygen-free conditions, 30 volume percent of Vinylene Carbonate (VC) is added by taking fluoroisoxazole (structural formula 3) as a solvent. Lithium difluorooxalato borate (LiDFOB) and lithium difluorophosphate (LiPO)2F2) Dissolved therein at molar concentrations of 0.7 mol/L and 0.3 mol/L, respectively. The button-type half cell is assembled by taking artificial graphite as a negative electrode material and lithium metal (Li) as a negative electrode material, is charged and discharged at a rate of 0.1C, and has a capacity of 370 mAhg at a normal temperature of 25 DEG C-1Low temperature-20 ℃ capacity of 250 mAhg-1371 mAh g capacity at 60 ℃ high temperature-1. See table 1.
Example 4: under anhydrous and oxygen-free conditions, fluoroisoxazole (structural formula 4) is taken as a solvent, and fluoroethylene carbonate (FEC) with the volume fraction of 10 percent is added. Lithium difluorooxalato borate (LiDFOB) was dissolved therein at a molar concentration of 1 mol/L. Using artificial graphite as anode material and lithium metal (Li) as cathode material, assembling button-type half cell, charging and discharging at 0.1C rateThe capacity is 366mAhg at 25 DEG C-1Capacity of 236mAhg at-20 ℃ at low temperature-1 High temperature 60 ℃ capacity of 368 mAhg-1. See table 1.
Example 5: under anhydrous and oxygen-free conditions, fluoroisoxazole (structural formula 5) is used as a solvent, and fluoroethylene carbonate (FEC) with the volume fraction of 10 percent is added. Lithium difluorooxalato borate (LiDFOB) was dissolved therein at a molar concentration of 1 mol/L. The button type lithium ion battery is assembled by taking artificial graphite as a negative electrode material and ternary nickel cobalt lithium manganate (NMC) as a positive electrode material, is charged and discharged at a rate of 0.1C, and has a capacity of 185 mAhg at a normal temperature of 25 DEG C-1Low temperature-20 ℃ capacity of 152mAhg-1High temperature of 60 ℃ and capacity of 186 mAhg-1. See table 1.
Example 6: under anhydrous and oxygen-free conditions, fluoroisoxazole (structural formula 5) is used as a solvent, and fluoroethylene carbonate (FEC) with the volume fraction of 10 percent is added. Lithium difluorooxalato borate (LiDFOB) was dissolved therein at a molar concentration of 1 mol/L. Artificial graphite as negative electrode material, lithium iron phosphate (LiFePO)4) As a positive electrode material, the button cell is assembled and charged and discharged at a rate of 0.1C, and the capacity is 168 mAh g at the normal temperature of 25 DEG C-1The capacity is 132 mAh g at the low temperature of-20 DEG C-1Capacity of 165 mAh g at 60 ℃ at high temperature-1. See table 1.
TABLE 1
Claims (9)
1. A fast-charging electrolyte is characterized by comprising a solvent, lithium salt and a film-forming additive; the solvent is fluoroisoxazole and derivatives thereof; wherein the fluoroisoxazole has the following structural formula:
formula (I)
Wherein R is1，R2，R3= F or CHxF3-xX =0, 1, 2, and includes at least R1，R2，R3One kind of (1).
2. The fast-charging electrolyte as claimed in claim 1, wherein the fluoroisoxazole or the derivative thereof has one of the following structures:
3. the fast-charging electrolyte as claimed in claim 1, wherein the fluoroisoxazole or the fluoroisoxazole accounts for 0.5-0.95 of the volume ratio of the electrolyte.
4. The fast-charging electrolyte as claimed in claim 1, wherein the film-forming additive is one or more selected from fluoroethylene carbonate, vinylene carbonate, 1,3, 6-hexanetricarbonitrile, phenyltrivinylsilane, triallyl phosphite, difluorodiphenylsilane, tris (trimethylsilylphosphite), ethyleneglycol bis (propionitrile) ether.
5. The fast-charging electrolyte according to claim 1, wherein the lithium salt is selected from the group consisting of lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, LiTFSI, lithium tris (trifluoromethanesulfonyl) methide, lithium bis (fluorosulfonyl) imide, LiFSI, lithium bis (oxalato) borate, lithium difluorobis (oxalato) phosphate, litodfp, LiN (SO)2RF)2、LiN(SO2F)(SO2RF), lithium difluorophosphate LiPO2F2One or more of lithium perchlorate, lithium tetrafluoro oxalate phosphate LiOTFP, lithium tetrafluoroborate, lithium hexafluorophosphate and lithium hexafluoroarsenate (V); wherein RF = -CnF2n+1，n=1~10。
6. The fast-charging electrolyte as claimed in claim 1, wherein the concentration of the solute is 0.1-2.0 mol/L.
7. Use of the fast-charging electrolyte according to claim 1 in fast-charging and wide-temperature lithium ion batteries.
8. A lithium ion battery comprising the fast-charging electrolyte according to claim 1, and a positive-negative electrode material capable of reversibly intercalating/deintercalating lithium ions.
9. The lithium ion battery according to claim 8, wherein a graphite material is used as an active material of the negative electrode, and the positive electrode is a lithiated transition metal phosphate or a transition metal oxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001143748A (en) * | 1999-11-15 | 2001-05-25 | Denso Corp | Electrolyte for cell and non-aqueous electrolyte secondary cell |
| CN1484337A (en) * | 2002-09-17 | 2004-03-24 | 三星Sdi株式会社 | Lithium cell |
| US20050095507A1 (en) * | 2003-10-29 | 2005-05-05 | Kwang-Chun Kim | Lithium battery having effective performance |
| WO2011037250A1 (en) * | 2009-09-28 | 2011-03-31 | 住友化学株式会社 | Sodium-ion-type power storage device |
| CN111446501A (en) * | 2020-04-08 | 2020-07-24 | 青岛滨海学院 | Electrolyte containing-F and-B two-group compound and electrochemical device thereof |
| CN112204009A (en) * | 2017-11-02 | 2021-01-08 | 卡里科生命科学有限责任公司 | Modulators of integrated stress pathways |
-
2022
- 2022-02-24 CN CN202210174011.6A patent/CN114614096B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001143748A (en) * | 1999-11-15 | 2001-05-25 | Denso Corp | Electrolyte for cell and non-aqueous electrolyte secondary cell |
| CN1484337A (en) * | 2002-09-17 | 2004-03-24 | 三星Sdi株式会社 | Lithium cell |
| US20040058250A1 (en) * | 2002-09-17 | 2004-03-25 | Kim Jin Sung | Lithium secondary battery |
| US20050095507A1 (en) * | 2003-10-29 | 2005-05-05 | Kwang-Chun Kim | Lithium battery having effective performance |
| WO2011037250A1 (en) * | 2009-09-28 | 2011-03-31 | 住友化学株式会社 | Sodium-ion-type power storage device |
| CN112204009A (en) * | 2017-11-02 | 2021-01-08 | 卡里科生命科学有限责任公司 | Modulators of integrated stress pathways |
| CN111446501A (en) * | 2020-04-08 | 2020-07-24 | 青岛滨海学院 | Electrolyte containing-F and-B two-group compound and electrochemical device thereof |
Non-Patent Citations (2)
| Title |
|---|
| NUWANTHI D. RODRIGO；ZULIPIYA SHADIKE: "Improved Low Temperature Performance of Graphite/Li Cells Using Isoxazole as a Novel Cosolvent in Electrolytes", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 168, no. 7 * |
| SHA TAN;UNDUGODAGE NUWANTHI DILHARI RODRIGO等: "Novel Low-Temperature Electrolyte Using Isoxazole as the Main Solvent for Lithium-Ion Batteries", ACS APPL. MATER. INTERFACES, vol. 13, no. 21, pages 24995 - 25001 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117239230A (en) * | 2022-10-12 | 2023-12-15 | 哈尔滨工业大学 | Lithium ion battery electrolyte additive, lithium ion battery electrolyte and preparation method of lithium ion battery electrolyte additive |
| CN117239230B (en) * | 2022-10-12 | 2024-06-04 | 哈尔滨工业大学 | Lithium ion battery electrolyte additive, lithium ion battery electrolyte and preparation method of lithium ion battery electrolyte additive |
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