CN113793975B - Preparation method of fluorine-containing electrolyte - Google Patents
Preparation method of fluorine-containing electrolyte Download PDFInfo
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- CN113793975B CN113793975B CN202111013856.9A CN202111013856A CN113793975B CN 113793975 B CN113793975 B CN 113793975B CN 202111013856 A CN202111013856 A CN 202111013856A CN 113793975 B CN113793975 B CN 113793975B
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 112
- 239000011737 fluorine Substances 0.000 title claims abstract description 112
- 239000003792 electrolyte Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims description 58
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- 229940017219 methyl propionate Drugs 0.000 claims description 14
- 229960004063 propylene glycol Drugs 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- MSDKIQILHSEFNE-UHFFFAOYSA-N methyl acetate;oxolane Chemical compound COC(C)=O.C1CCOC1 MSDKIQILHSEFNE-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 7
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- OEMGCAOEZNBNAE-UHFFFAOYSA-N [P].[Li] Chemical compound [P].[Li] OEMGCAOEZNBNAE-UHFFFAOYSA-N 0.000 description 12
- QQIRAVWVGBTHMJ-UHFFFAOYSA-N [dimethyl-(trimethylsilylamino)silyl]methane;lithium Chemical compound [Li].C[Si](C)(C)N[Si](C)(C)C QQIRAVWVGBTHMJ-UHFFFAOYSA-N 0.000 description 7
- UYAYJKQIJSLENS-UHFFFAOYSA-N 2-fluoro-2-trimethylsilylpropanedioic acid Chemical compound C[Si](C)(C)C(C(O)=O)(C(O)=O)F UYAYJKQIJSLENS-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- MXJGZAMERDEUKM-UHFFFAOYSA-N N[Li].C[Si](N[Si](C)(C)C)(C)C Chemical compound N[Li].C[Si](N[Si](C)(C)C)(C)C MXJGZAMERDEUKM-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- GTGWNUMFICCHDX-UHFFFAOYSA-N fluoromethyl hydrogen carbonate Chemical group OC(=O)OCF GTGWNUMFICCHDX-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
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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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
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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
- H01M10/0568—Liquid materials characterised by the solutes
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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
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
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- 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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Abstract
The invention discloses a preparation method of fluorine-containing electrolyte, which mainly comprises two fluorine-containing compounds, wherein the first fluorine-containing compound contains a fluoro-methyl alkenyl carbonate structure, and the compound with the structure can improve the flash point of the electrolyte and is beneficial to improving the safety performance of the electrolyte. The carbon-oxygen bond of the annular structure in the structural formula of the second fluorine-containing compound can be automatically broken at high temperature, and participates in the formation of an SEI film on the positive electrode and the negative electrode, so that the high-temperature performance of the lithium battery can be improved.
Description
Technical Field
The invention belongs to the technical field of electrolyte, and particularly relates to a preparation method of fluorine-containing electrolyte.
Background
In the overheat state of the battery, there is a risk of the electrolyte burning or even explosion due to the excessively high temperature. Meanwhile, in a long-term heating environment, the stability of the electrical property is difficult to ensure.
It is very necessary to improve the high-temperature storage capacity of the electrolyte and to ensure the stability of the electrolyte at high temperature.
Disclosure of Invention
The technical problem to be solved by the invention is as follows:
provides a preparation method of fluorine-containing electrolyte.
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of fluorine-containing electrolyte comprises the following steps:
adding urea and a first solvent into 3, 3-trifluoro-1, 2-propylene glycol, and reacting for 3-6h under vacuum to obtain a first fluorine solution containing a first fluorine-containing compound;
adding a lithium source and a fluorine-containing phosphorus source into a second solvent, reacting for 4-8h at the temperature of-30-20 ℃, adding a fluorine-containing disilicate compound, and reacting for 3-6h at the temperature of 5-30 ℃ to obtain a second fluorine solution containing a second fluorine-containing compound;
mixing the first fluorine solution with the second fluorine solution to obtain the fluorine-containing electrolyte;
the molar ratio of the first fluorine solution to the second fluorine solution is 1-5:4-8.
According to one embodiment of the present invention, the reaction temperature of the 3, 3-trifluoro-1, 2-propanediol and the urea is 160 ℃ to 180 ℃.
According to one embodiment of the present invention, the reaction formula of the above 3, 3-trifluoro-1, 2-propanediol and urea is as follows:
according to one embodiment of the present invention, a metal oxide is further added as a catalyst in the reaction of the 3, 3-trifluoro-1, 2-propanediol with urea. The metal oxide may be at least one of MgO, cao and ZnO.
According to an embodiment of the present invention, the fluorine-containing phosphorus source includes at least one of lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorobis (oxalato) phosphate, lithium difluorooxalato phosphate, and lithium tetrafluorooxalato phosphate.
According to an embodiment of the present invention, the lithium source includes at least one of lithium hexamethyldisilazide and lithium bistrimethylsilylamide.
According to one embodiment of the present invention, the above fluorochemical disilicate compound is a compound containing the following formula:
according to one embodiment of the present invention, the molar ratio of the 3, 3-trifluoro-1, 2-propanediol to urea is 1-5:1-5.
According to an embodiment of the present invention, a molar ratio of the lithium source to the fluorine-containing phosphorus source is 1 to 2.5:1.5-3.
According to an embodiment of the present invention, the fluorine-containing compound in the second fluorine solution has the following structure:
in the reaction process of the lithium source, the fluorine-containing phosphorus source and the fluorine-containing disilicate compound, a nitrogen-silicon bond in the lithium source is broken and forms a nitrogen-phosphorus bond with the fluorine-containing phosphorus source, and an ester bond in the fluorine-containing disilicate compound is also broken and forms a nitrogen-phosphorus bond-COOP-structure with the fluorine-containing phosphorus source, so that the fluorine-containing compound in the second fluorine solution is synthesized.
According to an embodiment of the present invention, the solvent includes at least one of methyl propionate, methyl acetate tetrahydrofuran, propylene carbonate, ethyl acetate, diethyl carbonate, ethyl methyl carbonate, and acetonitrile.
According to one embodiment of the present invention, the ratio of the solvent to the fluorine-containing electrolyte solution in parts by mass is 80 to 99:100.
one of the above technical solutions has at least one of the following advantages or beneficial effects:
the fluorine-containing electrolyte mainly comprises two fluorine-containing compounds, wherein the first fluorine-containing compound contains a fluoromethyl carbonate structure, and the compound with the structure can improve the flash point of the electrolyte, so that the electrolyte can not burn at 80 ℃, and the safety performance of the electrolyte can be improved.
The second fluorine-containing compound is derived from the second fluorine solution, and carbon-oxygen bonds of a ring structure in the structural formula of the second fluorine-containing compound can be automatically broken at high temperature to generate condensation reaction, so that the condensation reaction participates in the formation of SEI films on the positive electrode and the negative electrode, and the high-temperature performance of the lithium battery can be improved. In addition, fluorine in the structural formula of the second fluorine-containing compound is beneficial to improving the flash point of the electrolyte and improving the transmission performance of lithium ions in the electrolyte; in addition, the phosphate group in the structural formula of the second fluorine-containing compound is beneficial to discharging the lithium battery at high temperature; the imide structure can be used for complexing metal ions dissolved out from the anode material together with carbonyl, so that the decomposition of the metal ions catalytic electrolyte is inhibited, and the generation of gas is inhibited.
The first fluorine-containing compound and the second fluorine-containing compound are used in combination, so that the high-temperature storage performance and the safety performance of the lithium ion battery can be improved.
Further, when the molar ratio of the first fluorine solution to the second fluorine solution is 1 to 5:4-8, the prepared fluorine-containing electrolyte has higher battery capacity retention rate.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
Example 1
A preparation method of fluorine-containing electrolyte comprises the following steps:
adding 0.2mol of urea into 0.8mol of 3, 3-trifluoro-1, 2-propylene glycol, adding 0.2mol of MgO and CaO in total, dissolving in 25ml of methyl propionate, and carrying out vacuum reaction for 3h at 180 ℃ to obtain a first fluorine solution;
1.5mol of hexamethyldisilazane lithium amide is added with 1.2mol of lithium hexafluorophosphate, dissolved in 25ml of methyl propionate, and reacted for 4h at the temperature of 10 ℃ to obtain a phosphorus lithium solution;
adding 3.3mol of trimethylsilyl fluoromalonic acid into the phosphorus-lithium solution, and reacting for 3 hours to obtain a second fluorine solution;
mixing the first fluorine solution with the second fluorine solution to obtain the fluorine-containing electrolyte;
the molar ratio of the first fluorine solution to the second fluorine solution is 1:6.
example 2
A preparation method of fluorine-containing electrolyte comprises the following steps:
adding 0.2mol of urea into 0.8mol of 3, 3-trifluoro-1, 2-propylene glycol, adding 0.2mol of MgO and CaO in total, dissolving in 25ml of methyl propionate, and carrying out vacuum reaction for 3h at 180 ℃ to obtain a first fluorine solution;
adding 2mol of lithium hexafluorophosphate into 0.5mol of hexamethyldisilazane lithium, dissolving in 25ml of methyl propionate, controlling the temperature to be 10 ℃, and reacting for 4h to obtain a phosphorus lithium solution;
adding 1.5mol of trimethylsilyl fluoromalonic acid into the phosphorus-lithium solution, and reacting for 3 hours to obtain a second fluorine solution;
mixing the first fluorine solution with the second fluorine solution to obtain the fluorine-containing electrolyte;
the molar ratio of the first fluorine solution to the second fluorine solution is 1:4.
example 3
A preparation method of fluorine-containing electrolyte comprises the following steps:
adding 2.5mol of urea into 2.5mol of 3, 3-trifluoro-1, 2-propylene glycol, adding 0.2mol of MgO and CaO in total, dissolving in 25ml of methyl propionate, and carrying out vacuum reaction for 3h at 180 ℃ to obtain a first fluorine solution;
2.5mol of lithium hexafluorophosphate is added into 2.5mol of hexamethyldisilazane lithium, and the mixture is dissolved in 25ml of methyl propionate, the temperature is controlled at 10 ℃, and the reaction is carried out for 4 hours to obtain a phosphorus lithium solution;
adding 3mol of trimethylsilyl fluoromalonic acid into the phosphorus-lithium solution, and reacting for 3 hours to obtain a second fluorine solution;
mixing the first fluorine solution with the second fluorine solution to obtain the fluorine-containing electrolyte;
the molar ratio of the first fluorine solution to the second fluorine solution is 5:8.
comparative example 1
A preparation method of fluorine-containing electrolyte comprises the following steps:
adding 0.5mol of urea into 0.5mol of 3, 3-trifluoro-1, 2-propylene glycol, adding 0.2mol of MgO and CaO in total, dissolving in 25ml of methyl propionate, and carrying out vacuum reaction for 3h at 180 ℃ to obtain a first fluorine solution;
adding 0.5mol of lithium hexafluorophosphate into 0.5mol of hexamethyldisilazane lithium, dissolving in 25ml of methyl propionate, controlling the temperature to be 10 ℃, and reacting for 4 hours to obtain a phosphorus lithium solution;
adding 2mol of trimethylsilyl fluoromalonic acid into the phosphorus-lithium solution, and reacting for 3 hours to obtain a second fluorine solution;
mixing the first fluorine solution with the second fluorine solution to obtain the fluorine-containing electrolyte;
the molar ratio of the first fluorine solution to the second fluorine solution is 1:3.
comparative example 2
A preparation method of fluorine-containing electrolyte comprises the following steps:
adding 0.5mol of urea into 0.5mol of 3, 3-trifluoro-1, 2-propylene glycol, adding 0.2mol of MgO and CaO in total, dissolving in 25ml of methyl propionate, and carrying out vacuum reaction for 3h at 180 ℃ to obtain a first fluorine solution;
adding 5mol of lithium hexafluorophosphate into 5mol of hexamethyldisilazane lithium, dissolving in 25ml of methyl propionate, controlling the temperature to be 10 ℃, and reacting for 4h to obtain a phosphorus lithium solution;
adding 5mol of trimethylsilyl fluoromalonic acid into the phosphorus-lithium solution, and reacting for 3 hours to obtain a second fluorine solution;
mixing the first fluorine solution with the second fluorine solution to obtain the fluorine-containing electrolyte;
the molar ratio of the first fluorine solution to the second fluorine solution is 5:15.
comparative example 3
A preparation method of fluorine-containing electrolyte comprises the following steps:
0.5mol of urea is added into 0.5mol of 3, 3-trifluoro-1, 2-propylene glycol, then 0.2mol of MgO and CaO in total are added, the mixture is dissolved in 25ml of methyl propionate, and the reaction is carried out for 3h under vacuum at 180 ℃ to obtain the fluorine-containing electrolyte.
Comparative example 4
A preparation method of fluorine-containing electrolyte comprises the following steps:
adding 5mol of hexamethyldisilazane lithium into 3mol of sulfuric acid for activation, adding 5mol of lithium hexafluorophosphate into the activated hexamethyldisilazane lithium, dissolving the activated hexamethyldisilazane lithium in 25ml of methyl propionate, controlling the temperature to be 10 ℃, and reacting for 4 hours to obtain a phosphorus lithium solution;
and adding 5mol of trimethylsilyl fluoromalonic acid into the phosphorus-lithium solution, and reacting for 3 hours to obtain the fluorine-containing electrolyte.
And (3) performance testing:
li 2 MnSiO 4 The battery comprises a positive electrode, a negative electrode, a PE diaphragm and the fluorine-containing electrolyte prepared according to the invention.
The experimental examples 1 to 3 and the comparative examples 1 to 4 were respectively tested for high-temperature cycle performance and high-temperature storage performance, and the test indexes and test methods were as follows:
high temperature cycle performance: the cell was charged with a 1C constant current and constant voltage to 4.2V, a cutoff current of 0.02C, and then discharged with a 1C constant current to 3.0V by leaving the cell at 45 ℃. After such charge/discharge cycles, the capacity retention rate after 200 weeks of cycling was calculated to evaluate the high-temperature cycle performance thereof.
High-temperature storage performance: the initial discharge capacity of the battery is measured by charging the battery to 4.2V at a constant current and constant voltage of 1C at normal temperature, then discharging to 3.0V at a constant current of 1C, measuring the initial thickness of the battery, then storing the battery at 60 ℃ for 7 days, measuring the thickness of the battery, then discharging to 3.0V at a constant current of 1C, measuring the retention capacity of the battery, then charging to 3.0V at a constant current and constant voltage of 1C, stopping to 0.02C, then discharging to 3.0V at a constant current of 1C, and measuring the recovery capacity.
TABLE 1 Performance test
Through testing the high-temperature cycle and high-temperature storage performance of the lithium battery prepared in the embodiment, the lithium battery prepared by applying the electrolyte disclosed by the invention is found to have the best electrolyte effect in the embodiment 1, the capacity retention rate after the lithium battery is cycled at 45 ℃ reaches 99.8%, the capacity retention rate after the lithium battery is stored at 60 ℃ for 7 days reaches 98.4%, the capacity recovery rate after the lithium battery is stored at 60 ℃ for 7 days reaches 97.2%, and in general, all indexes of the lithium batteries in the embodiments 1 to 3 are far better than those in a comparative example. Therefore, the electrolyte provided by the invention is applied to the lithium ion battery, and the high-temperature storage performance and the safety performance of the lithium ion battery can be improved.
The above description is only an example of the present invention and is not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or the related technical fields, which are directly or indirectly applied, are included in the scope of the present invention.
Claims (7)
1. A preparation method of fluorine-containing electrolyte is characterized by comprising the following steps: the method comprises the following steps:
adding urea and a first solvent into 3, 3-trifluoro-1, 2-propylene glycol, and reacting under vacuum to obtain a first fluorine solution containing a first fluorine-containing compound;
reacting a lithium source, a fluorine-containing phosphorus source and a fluorine-containing disilicate compound in the presence of a second solvent to obtain a second fluorine solution containing a second fluorine-containing compound;
mixing the first fluorine solution and the second fluorine solution to obtain the fluorine-containing electrolyte;
the molar ratio of the first fluorine-containing compound to the second fluorine-containing compound is 1-5:4-8.
2. The method according to claim 1, wherein the fluorine-containing electrolyte solution comprises:
the fluorine-containing phosphorus source comprises at least one of lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorobis-oxalato phosphate, lithium difluorooxalato phosphate and lithium tetrafluorooxalato phosphate.
3. The method of producing a fluorine-containing electrolyte according to claim 1, characterized in that:
the fluorine-containing disilicate compound is a compound containing the following formula:
4. the method according to claim 1, wherein the fluorine-containing electrolyte solution comprises:
the molar ratio of the 3, 3-trifluoro-1, 2-propanediol to the urea is 1-5:1-5.
5. The method of producing a fluorine-containing electrolyte according to claim 1, characterized in that:
the molar ratio of the lithium source to the fluorine-containing phosphorus source is 1-2.5:1.5-3.
6. The method according to claim 1, wherein the fluorine-containing electrolyte solution comprises:
the reaction temperature of the 3, 3-trifluoro-1, 2-propanediol and the urea is 160 ℃ to 180 ℃.
7. The method of producing a fluorine-containing electrolyte according to claim 1, characterized in that:
the first solvent and the second solvent independently comprise at least one of methyl propionate, methyl acetate tetrahydrofuran, propylene carbonate, ethyl acetate, diethyl carbonate, ethyl methyl carbonate and acetonitrile.
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| JP2009163999A (en) * | 2008-01-08 | 2009-07-23 | Sony Corp | Electrolyte and battery |
| CN102569891A (en) * | 2010-12-31 | 2012-07-11 | 张家港市国泰华荣化工新材料有限公司 | Energy storage battery of non-aqueous electrolyte solution of fluorine-containing lithium sulfonyl imide |
| CN103236561B (en) * | 2013-03-29 | 2015-04-15 | 东莞市杉杉电池材料有限公司 | Method for detecting alkylsilazane compounds in lithium hexafluorophosphate electrolyte |
| JP6285263B2 (en) * | 2014-04-17 | 2018-02-28 | トヨタ自動車株式会社 | Electrolyte for fluoride ion battery and fluoride ion battery |
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| JP6761178B2 (en) * | 2016-12-02 | 2020-09-23 | セントラル硝子株式会社 | Method for producing lithium difluorophosphate |
| CN108178752B (en) * | 2017-12-19 | 2021-02-23 | 西安近代化学研究所 | Method for preparing 3,3, 3-trifluoropropene carbonate and 3,3, 3-trifluoro-1, 2-propylene glycol in co-production mode |
| WO2020018731A1 (en) * | 2018-07-18 | 2020-01-23 | Nanotek Instruments, Inc. | Fast-chargeable lithium battery electrodes |
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