CN114614096B - Quick-charging electrolyte and application thereof in lithium ion battery - Google Patents
Quick-charging electrolyte and application thereof in lithium ion battery Download PDFInfo
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- CN114614096B CN114614096B CN202210174011.6A CN202210174011A CN114614096B CN 114614096 B CN114614096 B CN 114614096B CN 202210174011 A CN202210174011 A CN 202210174011A CN 114614096 B CN114614096 B CN 114614096B
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- NRGKMKILWIVZJM-UHFFFAOYSA-N 3-fluoro-1,2-oxazole Chemical group FC=1C=CON=1 NRGKMKILWIVZJM-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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 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
- -1 lithium tetrafluoroborate Chemical compound 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 238000009830 intercalation Methods 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
- 238000009831 deintercalation Methods 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
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 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
- 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 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
- AUBNQVSSTJZVMY-UHFFFAOYSA-M P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] AUBNQVSSTJZVMY-UHFFFAOYSA-M 0.000 claims description 2
- 229910019142 PO4 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
- 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
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 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
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims 2
- 229910010941 LiFSI Inorganic materials 0.000 claims 1
- 229910012258 LiPO Inorganic materials 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 21
- 229910002804 graphite Inorganic materials 0.000 abstract description 19
- 239000010439 graphite Substances 0.000 abstract description 19
- 238000007614 solvation Methods 0.000 abstract description 10
- 239000011737 fluorine Substances 0.000 abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- 150000002545 isoxazoles Chemical class 0.000 abstract description 5
- 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
- 239000010406 cathode material Substances 0.000 description 7
- 229910021383 artificial graphite Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 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
- 150000001768 cations Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000002349 favourable effect Effects 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
- 238000000034 method Methods 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 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
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007547 defect 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
- 150000003949 imides Chemical class 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011835 investigation Methods 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
- 239000004005 microsphere Substances 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
- 239000013589 supplement Substances 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
- H01M10/0569—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention 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 of the invention takes fluorine substituted isoxazole and derivatives thereof as main solvents, lithium salt as solute and contains film forming additive; the electrolyte provided by the invention has the characteristics of weak solvation binding energy, and also has higher ionic conductivity at a lower temperature, and can be applied to a lithium ion battery system taking graphite as a negative electrode, solvated lithium ions can be rapidly desolvated and intercalated between graphite layers under a high multiplying power, so that good rapid charging characteristics are shown; meanwhile, the rapid ion transmission and desolvation at low temperature ensure the excellent low-temperature capacity retention rate of the graphite electrode. 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 widely used in various fields, such as power supplies for various consumer electronic devices and electric automobiles. However, in some extremely cold days, electronic devices such as mobile phones and computers with lithium ion batteries have 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; the capacity retention rate of the lithium ion battery commercialized at present can only reach 12% at normal temperature, and polarization can occur to a great extent at-40 ℃. In addition, in hot conditionsIn the area, the lithium ion battery electrolyte volatilizes due to high temperature and various side reactions occurring inside the battery at high temperature can cause the capacity of the lithium ion battery to be lowered and the efficiency to be lowered. Therefore, it is urgent to develop an electrolyte that can normally operate in a wide temperature range. Graphite is used as a cathode material of a lithium ion battery, has rich reserves and wide sources, has stable electrochemical performance and higher theoretical specific capacity (372 mAh/g), and is currently and consistently considered as an ideal cathode material. However, the high and low temperature performance of the graphite anode has yet to be improved. Under the charging and discharging conditions of-20 ℃ and 0.1C, liPF is adopted 6 The specific capacity of the graphite negative electrode lithium ion battery taking the EC-EMC (v: v=1:1) as the electrolyte is only less than 50 mAh/g; and when the temperature is increased to 50 ℃, the efficiency is less than 95%, and the capacity is attenuated. It can be seen that the application of the current graphite cathode lithium ion battery electrolyte in a wide temperature range needs to be further studied.
The working temperature of the graphite cathode is mainly limited by the components of the electrolyte, while the key component of the currently commercial electrolyte, namely Ethylene Carbonate (EC), has a melting point of up to 36.4 ℃, so that the viscosity of the electrolyte at low temperature is increased, the lithium ion conductivity is reduced, and the lithium ion electrolyte is difficult to timely supplement Li from the electrolyte + Severely hampering its application at lower temperatures. In addition, studies have shown that charge transfer resistance at low temperature (R ct ) The increase is particularly pronounced, and desolvation energy is the most dominant part of charge transfer resistance, so the selective use of solvents with weak solvation energy is the main direction of investigation of subsequent electrolytes. Specifically, in Li + In the intercalation process, the introduction of the solvent with weak solvation energy can enable solvated lithium ions on the SEI interface to be more easily separated from the solvated structure to become bare lithium ions to be intercalated into graphite, so that solvent co-intercalation is inhibited. In addition, when the solvent and the anion strive for phase to enter Li + In solvating the sheath, more anions can be made to react with Li by using solvents with lower solvation energy + Coordination is performed. Even at lower salt concentrations, due to the presence of weak solvating energy solventsTo form a large number of ion pairs or aggregates, thereby producing 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 quick charge and cycle stability. Therefore, there is an urgent need to develop a novel electrolyte system having low solvation energy, low melting point, low viscosity and higher conductivity in a wide temperature range to improve the problems of energy density and power density decay faced by graphite negative electrode lithium ion batteries at a specific temperature.
The invention provides an electrolyte with weak solvation energy for a graphite negative electrode, which uses fluorine substituted isoxazole and derivatives thereof as main solvents. In the fluorine-substituted isoxazole, the charges are dispersed and are matched with Li due to the existence of atoms with great nitrogen and oxygen electronegativity on the five-membered ring and the conjugation on the ring + The binding capacity of the polymer is reduced, and the polymer has weak solvation energy, so that the polymer is favorable for realizing better electrochemical performance at wide temperature. Meanwhile, the fluorine substituted isoxazole has the advantages of good film forming performance, high conductivity, small viscosity, low freezing point and the like, and the electrolyte has good application prospect in a wide temperature range by combining the high-temperature stability property.
Disclosure of Invention
The invention aims to provide a fast-charging electrolyte with weak solvation energy and application thereof in a lithium ion battery.
The quick-filling 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:
(I)
Wherein R is 1 ，R 2 ，R 3 =f or CH x F 3-x (x=0, 1, 2) and at least includes R 1 ，R 2 ，R 3 One of them.
The fluoroisoxazoles and derivatives thereof described in the present 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-Hexanetrinitrile (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 the group consisting of lithium trifluoromethane sulfonate, lithium bis (trifluoromethane sulfonyl) imide LiTFSI, lithium tris (trifluoromethane sulfonyl) methyl, lithium bis (fluorine sulfonyl) imide LiSSI, lithium bis (oxalato) borate, lithium difluorobis (oxalato) phosphate LiDODFP, liN (SO) 2 RF) 2 、LiN(SO 2 F)(SO 2 RF) (wherein rf= -C n F 2n+1 N=1 to 10), lithium difluorophosphate LiPO 2 F 2 One or more of lithium perchlorate, lithium tetrafluorooxalate phosphate LiOTFP, lithium tetrafluoroborate, lithium hexafluorophosphate, and lithium hexafluoroarsenate (V).
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 type lithium ion batteries.
The fast-charging electrolyte provided by the invention can be used as a positive and negative electrode material capable of reversibly intercalating/deintercalating lithium ions.
In the invention, the active material of the negative electrode adopts graphite materials, including natural graphite, carbon black, graphene, graphitized mesophase carbon microspheres and the like. The positive electrode is lithiated transition metal phosphate and transition metal oxide such as LiFePO 4 、LiCoPO 4 、LiMn 2 O 4 、LiCoO 2 And ternary positive electrode materials.
The quick-filling electrolyte provided by the invention uses fluorine substituted isoxazole and derivatives thereof as main solvents. Because the charges on the fluorine-substituted isoxazole five-membered ring are dispersed, when the fluorine-substituted isoxazole five-membered ring acts with metal cations, the solvent has weak solvation energy, and is favorable for the deintercalation of the metal cations between graphite layers. The electrolyte provided by the invention can be applied to fast-charge and wide-temperature type lithium ion batteries, and can show good rate capability and long cycle life.
The electrolyte provided by the invention has the characteristics of weak solvation binding energy, and also has higher ionic conductivity at a lower temperature, and can be applied to a lithium ion battery system taking graphite as a negative electrode, solvated lithium ions can be rapidly desolvated and intercalated between graphite layers under a high multiplying power, so that good rapid charging characteristics are shown; meanwhile, the rapid ion transmission and desolvation at low temperature ensure the excellent low-temperature capacity retention rate of the graphite electrode. 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.
Drawings
Fig. 1 is the low temperature performance of a graphite lithium half-cell assembled with example 1.
Fig. 2 is the rate performance of the graphite lithium half-cell assembled with example 1.
Fig. 3 is the cycle performance of the graphite lithium half-cell assembled with example 1.
Detailed Description
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
Example 1: fluoroisoxazole (formula 1) was used as a solvent under anhydrous and anaerobic conditions, and fluoroethylene carbonate (FEC) was added in a volume fraction of 10%. Lithium difluorooxalato borate (LiDFOB) was dissolved therein at a molar concentration of 1 mol/L. The artificial graphite is used as a positive electrode material, lithium metal (Li) is used as a negative electrode material, the button-type half cell is assembled, and the button-type half cell is charged and discharged at 0.1C multiplying power, and has a capacity of 368 mAhg at normal temperature of 25 DEG C -1 The capacity at low temperature of 20 ℃ below zero is 230 mAhg -1 (FIG. 1), high temperature 60 ℃ CIn an amount of 370 mAhg -1 . And the rate performance (1C-10C, figure 2) and the cycle performance (1C, figure 3) of the composite material are measured at the normal temperature of 25 ℃. See table 1.
Example 2: under the anhydrous and anaerobic condition, fluoroisoxazole (structural formula 2) is taken as a solvent, and Vinylene Carbonate (VC) with the volume fraction of 30% is added. Lithium difluorooxalato borate (LiDFOB) was dissolved therein at a molar concentration of 1 mol/L. The artificial graphite is used as a cathode material, lithium metal (Li) is used as a cathode material, the assembled button half-cell is charged and discharged at 0.1C multiplying power, and the capacity of the assembled button half-cell is 365 mAhg at the normal temperature of 25 DEG C -1 The capacity at low temperature of 20 ℃ below zero is 210mAhg -1 The capacity of the high-temperature 60 ℃ is 368 mAh g -1 . See table 1.
Example 3: under the anhydrous and anaerobic condition, fluoroisoxazole (structural formula 3) is taken as a solvent, and Vinylene Carbonate (VC) with the volume fraction of 30% is added. Lithium difluorooxalato borate (LiDFOB) and lithium difluorophosphate (LiPO) 2 F 2 ) Dissolved therein at a molar concentration of 0.7 mol/L and 0.3 mol/L, respectively. The artificial graphite is used as a cathode material, lithium metal (Li) is used as a cathode material, the assembled button half-cell is charged and discharged at 0.1C multiplying power, and the capacity of the assembled button half-cell is 370 mAhg at the normal temperature of 25 DEG C -1 The capacity at low temperature of 20 ℃ below zero is 250 mAhg -1 High-temperature 60 ℃ capacity of 371 mAh g -1 . See table 1.
Example 4: fluoroisoxazole (formula 4) was used as a solvent under anhydrous and anaerobic conditions, and fluoroethylene carbonate (FEC) was added in a volume fraction of 10%. Lithium difluorooxalato borate (LiDFOB) was dissolved therein at a molar concentration of 1 mol/L. The artificial graphite is used as a positive electrode material, lithium metal (Li) is used as a negative electrode material, the button-type half cell is assembled, the button-type half cell is charged and discharged at 0.1C multiplying power, and the capacity at the normal temperature of 25 ℃ is 366mAhg -1 The capacity at the low temperature of minus 20 ℃ is 236mAhg -1 The capacity of the high-temperature 60 ℃ is 368 mAhg -1 . See table 1.
Example 5: fluoroisoxazole (formula 5) was used as a solvent under anhydrous and anaerobic conditions, and fluoroethylene carbonate (FEC) was added in a volume fraction of 10%. Lithium difluorooxalato borate (LiDFOB) was dissolved therein at a molar concentration of 1 mol/L. Takes artificial graphite as a negative electrode material and ternary nickel cobalt lithium manganate (NMC) as a positive electrodeMaterial, assembled button lithium ion battery, charging and discharging with 0.1C multiplying power, capacity of 185 mAhg at normal temperature 25 DEG C -1 The capacity of the low-temperature-20 ℃ is 152mAhg -1 The capacity of the high-temperature 60 ℃ is 186 mAhg -1 . See table 1.
Example 6: fluoroisoxazole (formula 5) was used as a solvent under anhydrous and anaerobic conditions, and fluoroethylene carbonate (FEC) was added in a volume fraction of 10%. Lithium difluorooxalato borate (LiDFOB) was dissolved therein at a molar concentration of 1 mol/L. Artificial graphite is used as a cathode material, and lithium iron phosphate (LiFePO) 4 ) As positive electrode material, the assembled button cell charges and discharges at 0.1C multiplying power, and the capacity of the assembled button cell is 168 mAh g at the normal temperature of 25 DEG C -1 The capacity of the low temperature-20 ℃ is 132 mAh g -1 The capacity of the high-temperature 60 ℃ is 165 mAh g -1 . See table 1.
TABLE 1
。
Claims (8)
1. The quick-filling electrolyte is characterized by comprising a solvent, lithium salt and a film-forming additive; the solvent is fluoroisoxazole and derivatives thereof; wherein the fluoroisoxazole derivative has the following structural formula:
；
(I)
Wherein R is 1 ，R 2 ，R 3 =f or CH x F 3-x X=0, 1,2, and includes at least R 1 ，R 2 ，R 3 One of the following; the fluoroisoxazole or the derivative thereof accounts for 0.5-0.95 of the volume of the electrolyte.
2. The quick charge electrolyte as claimed in claim 1, wherein the fluoroisoxazole or derivative thereof is one of the following structures:
。
3. the quick-fill electrolyte of claim 1, wherein the film forming additive is selected from one or more of fluoroethylene carbonate, vinylene carbonate, 1,3, 6-hexanetrinitrile, phenyltrivinylsilane, triallyl phosphite, difluorodiphenylsilane, tris (trimethylsilyl) phosphite, ethylene glycol bis (propionitrile) ether.
4. The quick-fill electrolyte according to claim 1, wherein the lithium salt is selected from the group consisting of lithium triflate, lithium bis (trifluoromethylsulfonyl) imide LiTFSI, lithium tris (trifluoromethylsulfonyl) methyl, lithium bis (fluorosulfonyl) imide LiFSI, lithium bis (oxalato) borate, lithium difluorodioxaato phosphate litodfp, liN (SO) 2 RF) 2 、LiN(SO 2 F)(SO 2 RF), lithium difluorophosphate LiPO 2 F 2 One or more of lithium perchlorate, lithium tetrafluorooxalate phosphate LiOTFP, lithium tetrafluoroborate, lithium hexafluorophosphate and lithium hexafluoroarsenate (V); wherein rf= -C n F 2n+1 ，n=1~10。
5. The quick-charging electrolyte according to claim 1, wherein the concentration of the lithium salt is 0.1-2.0 mol/L.
6. The use of the fast-charging electrolyte according to claim 1 in fast-charging and wide-temperature lithium ion batteries.
7. A lithium ion battery comprising the fast-charging electrolyte of claim 1, a positive electrode material and a negative electrode material capable of reversibly intercalating/deintercalating lithium ions.
8. The lithium ion battery according to claim 7, wherein the active material of the negative electrode is graphite material, and the positive electrode is lithiated transition metal phosphate or transition metal oxide.
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