CN116813655A - Preparation process of lithium difluoro oxalate borate - Google Patents
Preparation process of lithium difluoro oxalate borate Download PDFInfo
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- CN116813655A CN116813655A CN202311082416.8A CN202311082416A CN116813655A CN 116813655 A CN116813655 A CN 116813655A CN 202311082416 A CN202311082416 A CN 202311082416A CN 116813655 A CN116813655 A CN 116813655A
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- lithium
- boron trifluoride
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- difluoroborate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 title abstract description 8
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 32
- -1 chlorosilane compound Chemical class 0.000 claims abstract description 25
- 239000000047 product Substances 0.000 claims abstract description 25
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 9
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 5
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000000706 filtrate Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- WXNUAYPPBQAQLR-UHFFFAOYSA-N B([O-])(F)F.[Li+] Chemical compound B([O-])(F)F.[Li+] WXNUAYPPBQAQLR-UHFFFAOYSA-N 0.000 claims description 14
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-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
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical group [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- MEMUCXUKCBNISQ-UHFFFAOYSA-N acetonitrile;trifluoroborane Chemical compound CC#N.FB(F)F MEMUCXUKCBNISQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- SLCLABDXYGNNOO-UHFFFAOYSA-N dimethyl carbonate;trifluoroborane Chemical compound FB(F)F.COC(=O)OC SLCLABDXYGNNOO-UHFFFAOYSA-N 0.000 claims description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 3
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000005049 silicon tetrachloride Substances 0.000 claims description 3
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical class [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- VHSLGFZDYCMVHY-UHFFFAOYSA-N boric acid;oxalyl difluoride Chemical compound OB(O)O.FC(=O)C(F)=O VHSLGFZDYCMVHY-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (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)
Abstract
The invention discloses a preparation process of lithium difluoro oxalate borate, which comprises the following steps: adding anhydrous oxalic acid and boron trifluoride complex into aprotic polar organic solvent, and dropwise adding chlorosilane compounds at 10-40 ℃ under stirring; after the chlorosilane compound is completely dripped, the temperature is raised to 40-100 ℃, and the reaction is stirred for 1-8 hours; adding lithium salt compound and continuing to react for 1-8 hours at the temperature; and after the reaction is finished, cooling to room temperature, filtering, concentrating and crystallizing filtrate, washing with a nonpolar solvent, filtering and drying to obtain a lithium difluorooxalate borate product. The method has the advantages of moderate raw material price, full reaction, high conversion rate and yield, easy purification of products, high quality, short process flow, less three wastes and low production cost, is suitable for industrial production, and can fully meet the use requirements of lithium ion battery industry.
Description
Technical Field
The invention belongs to the technical field of preparation of battery additives, and particularly relates to a preparation process of lithium difluoro oxalate borate.
Background
The lithium difluoroborate is a novel material for replacing the existing electrolyte lithium salt, and the unique chemical structure of the lithium difluoroborate combines the advantages of the lithium difluoroborate and the lithium tetrafluoroborate, so that the lithium difluoroborate has better high-low temperature performance, higher conductivity and good thermal stability, and simultaneously the abuse resistance of the lithium ion battery can be improved. In the prior art, the preparation method of the lithium difluorooxalato borate mainly comprises the following two steps:
(1) Boron trifluoride preparation method: the boron trifluoride complex and lithium oxalate react in an organic solvent to generate lithium difluorooxalate borate and lithium tetrafluoroborate, and then the lithium difluorooxalate borate product is obtained through repeated recrystallization and purification treatment. The method has the defects that the reaction time is longer, the structure of the difluoro oxalic acid lithium borate and the tetrafluoroboric acid lithium product is similar, the solubility difference in the solvent is smaller, the thorough separation and the purification are difficult, and the purity of the product is low; the lithium difluorooxalate borate product yield is lower and the industrial manufacturing cost is higher by repeated recrystallization and purification.
(2) Preparation method of lithium tetrafluoroborate: lithium tetrafluoroborate and oxalic acid are used as reaction raw materials, and a lithium difluorooxalate borate product is generated under the action of a catalyst such as aluminum trichloride or silicon tetrachloride in an organic solvent. Although the product of the method is only lithium difluoro oxalate borate, new impurities are introduced in the process, chlorine and acid residues are easy to cause, the product quality is low, and the use requirement of the lithium ion battery industry is difficult to meet; a large amount of strong acid gas is generated in the reaction process, and the tail gas treatment is complicated; lithium tetrafluoroborate as a reaction raw material is expensive and has high production cost.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide the preparation process of the lithium difluorooxalate borate, which has the advantages of moderate raw material price, sufficient reaction, high conversion rate and yield, easy purification and high quality of products, short process flow, less three wastes and low production cost, is suitable for industrial production, and can fully meet the use requirements of lithium ion battery industry.
In order to achieve the above purpose and achieve the above technical effects, the present invention adopts the following technical scheme:
the preparation process of the lithium difluoro oxalate borate is characterized by comprising the following steps: adding anhydrous oxalic acid and boron trifluoride complex into aprotic polar organic solvent, and dropwise adding chlorosilane compounds at 10-40 ℃ under stirring; after the chlorosilane compound is completely dripped, the temperature is raised to 40-100 ℃, and the reaction is stirred for 1-8 hours; adding lithium salt compound and continuing to react for 1-8 hours at the temperature; and after the reaction is finished, cooling to room temperature, filtering, concentrating and crystallizing filtrate, washing with a nonpolar solvent, filtering and drying to obtain a lithium difluorooxalate borate product.
Further, the chlorosilane compound is selected from one or more than two of methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane and silicon tetrachloride.
Further, the addition amount of the chlorosilane compound is 1-2 times of the molar multiple of the anhydrous oxalic acid calculated by chlorine element; preferably 1 to 1.5 times; more preferably 1 to 1.2 times by mol.
Further, the lithium salt compound is anhydrous halogenated lithium salt, lithium hydride or lithium nitride; the anhydrous lithium halide salt is selected from lithium fluoride or lithium chloride.
Further, the boron trifluoride complex is selected from one of boron trifluoride diethyl etherate, boron trifluoride dimethyl carbonate or boron trifluoride acetonitrile.
Further, the addition amount of the lithium salt compound is 1 to 1.1 times by mole of the boron element in the boron trifluoride complex.
Further, the molar ratio of the anhydrous oxalic acid to the boron trifluoride complex is (1-1.2) to 1.
Further, the aprotic polar organic solvent is selected from one or more than two of acetonitrile, propionitrile, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl ethyl ketone, 1, 4-dioxane, 1, 4-butyrolactone and tetrahydrofuran.
Further, the nonpolar solvent is selected from one of cyclohexane, petroleum ether, methylene dichloride, dichloroethane, toluene and xylene.
Further, the water content of the aprotic polar organic solvent is less than or equal to 500ppm; preferably 300ppm or less, more preferably 200ppm or less.
Further, the addition amount of the aprotic polar organic solvent is 1 to 6 times of the total mass of the anhydrous oxalic acid and the boron trifluoride complex; preferably 2 to 4 times.
Further, tail gas generated in the preparation process of the lithium difluorooxalato borate is absorbed by alkali liquor.
The reaction principle of the invention: first, an anhydrous complex of oxalic acid and boron trifluoride (BF) 3 ) Under the action of a co-reactant chlorosilane compound, strong organic acid difluoro oxalic acid boric acid is generated first and then reacts with anhydrous lithium chloride (LiCl) to obtain a target product difluoro oxalic acid lithium borate, which belongs to the reaction of preparing weak acid by strong acid. The reaction process can refer to the first reaction formula and the second reaction formula.
Reaction formula one:
reaction formula II:
compared with the prior art, the invention has the beneficial effects that: the raw materials have moderate price, the raw materials can fully react in the reaction system, the conversion rate and the yield are high, no new impurity is introduced in the reaction process, the target product lithium difluorooxalato borate is easy to purify and has high quality, the process flow is short, the three wastes are few, the production cost is low, the method is suitable for industrial production, and the use requirements of the lithium ion battery industry can be fully met.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is an IC spectrum of lithium difluorooxalato borate of example 1.
FIG. 2 is an IC spectrum of lithium difluorooxalato borate of example 2.
FIG. 3 is an IC spectrum of lithium difluorooxalato borate of example 3.
Detailed Description
The invention will be further illustrated with reference to specific examples.
The following example used an ion chromatograph as an instrument for measuring the purity of lithium difluorooxalato borate product, which was ion chromatograph manufactured by Metrohm. The specific working principle is as follows: and (3) dissolving the lithium difluoro oxalate borate product by using ultrapure water, then diluting to a constant volume, injecting sample, and leaching the solution by using aqueous solution of sodium carbonate and sodium bicarbonate. The lithium difluorooxalato borate product is completely hydrolyzed during formulation to form cationic Li + The anion being F - And oxalate ions. The ion chromatograph detects anions, the front peak in the chromatograph is F ion, and the rear peak in the chromatograph is oxalate ion, and the anions are calibrated by using a standard sample.
Calculating the purity of the lithium difluoro oxalate borate product by adopting an area normalization method, and F - Adding the content of oxalic acid radical ion to obtain the relative content of the sample. Or the impurity content except F ions and oxalate ions is deducted, namely the relative content of the difluoro oxalic acid lithium borate product.
Example 1
To a dry three-necked flask, 90g (1 mol) of anhydrous oxalic acid, 110g of boron trifluoride acetonitrile complex (boron trifluoride BF3 content: 62%) and 400g of acetonitrile having a water content of 182ppm were charged under nitrogen atmosphere and stirred uniformly. The temperature is controlled to be 30-40 ℃, 109g (1 mol) of trimethylchlorosilane is slowly added dropwise into the mixture through a constant pressure dropping funnel, and tail gas is absorbed by adopting 30% potassium hydroxide aqueous solution. After the dripping is finished, slowly heating to 60-70 ℃ and preserving heat for 3 hours. Then 28.6g (1.1 mol) of anhydrous lithium fluoride was added to the flask, the reaction was continued at this temperature for 8 hours with the flask contents being substantially clear, and the reaction was stopped.
The reaction solution was cooled to room temperature, and filtered through a 0.1 μm PTFE filter membrane under nitrogen protection to remove solid impurities. Concentrating, evaporating, crystallizing, adding dichloromethane, washing, filtering, and vacuum drying to obtain lithium difluoroborate product 121g, with yield of 84%, detecting by ion chromatograph to obtain IC spectrum shown in figure 1, and analyzing data shown in table 1, and calculating to obtain lithium difluoroborate product with purity of 99.86%.
And (3) standing the tail gas absorption liquid to separate 70g of upper organic phase hexamethyldisiloxane, wherein the reaction process can refer to a reaction formula III.
Reaction III:
example 2
To a dry three-necked flask, 108g (1.2 mol) of anhydrous oxalic acid, 142g of boron trifluoride diethyl etherate (boron trifluoride content: 47.2%) and 1000g of 1, 4-dioxane having a water content of 86ppm were charged under nitrogen atmosphere and stirred uniformly. 60g (0.4 mol) of methyltrichlorosilane is slowly added dropwise into the mixture through a constant pressure dropping funnel at the temperature of 10-20 ℃, and tail gas is absorbed by 30% potassium hydroxide aqueous solution. After the dripping is finished, slowly heating, extracting diethyl ether with a low boiling point solvent, and reacting for 1 hour at the temperature of 90-100 ℃. Next, 8g (1.1 mol) of lithium hydride was added to the flask, and the reaction was continued at this temperature for 1 hour with keeping the flask contents clear, and the reaction was stopped.
The reaction solution was cooled to room temperature, and filtered through a 0.45 μm PTFE filter membrane under nitrogen protection to remove solid impurities. Concentrating, evaporating, crystallizing, adding petroleum ether, washing, filtering, and drying under vacuum to obtain lithium difluorooxalate borate product 126g with a yield of 87.5%, detecting by ion chromatograph to obtain IC spectrum shown in figure 2 and analytical data shown in table 2, and calculating to obtain lithium difluorooxalate borate product with a purity of 99.73%.
Example 3
To a dry three-necked flask, 99g (1.1 mol) of anhydrous oxalic acid, 158g of boron trifluoride-dimethyl carbonate complex (boron trifluoride content: 43%) and 550g of dimethyl carbonate having a water content of 132ppm were charged under nitrogen atmosphere and stirred uniformly. The temperature is controlled to be 30-40 ℃, 60g (0.4 mol) of dimethyl dichlorosilane is slowly added into the mixture through a constant pressure dropping funnel, and tail gas is absorbed by 30% potassium hydroxide aqueous solution. After the dripping is finished, slowly heating to 80-90 ℃ and preserving heat for reaction for 3 hours. 45g (1.06 mol) of anhydrous lithium chloride was then added to the flask, the reaction was continued at this temperature for 5 hours with the flask contents being substantially clear and stopped.
The reaction solution was cooled to room temperature, and filtered through a 0.45 μm PTFE filter membrane under nitrogen protection to remove solid impurities. Concentrating, evaporating, crystallizing, adding toluene, washing, filtering, and drying under vacuum to obtain 132g of lithium difluorooxalato borate product, wherein the yield is 91.7%, the IC spectrum shown in FIG. 3 and the analytical data shown in Table 3 are obtained through detection by an ion chromatograph, and the purity of the lithium difluorooxalato borate product is 99.88% through calculation.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation process of lithium difluorooxalato borate is characterized in that: adding anhydrous oxalic acid and boron trifluoride complex into aprotic polar organic solvent, and dropwise adding chlorosilane compounds at 10-40 ℃ under stirring; after the chlorosilane compound is completely dripped, the temperature is raised to 40-100 ℃, and the reaction is stirred for 1-8 hours; adding lithium salt compound and continuing to react for 1-8 hours at the temperature; and after the reaction is finished, cooling to room temperature, filtering, concentrating and crystallizing filtrate, washing with a nonpolar solvent, filtering and drying to obtain a lithium difluorooxalate borate product.
2. The process for preparing the lithium difluoroborate as claimed in claim 1, wherein: the chlorosilane compound is selected from one or more than two of methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane and silicon tetrachloride.
3. The process for preparing the lithium difluoroborate as claimed in claim 2, wherein: the addition amount of the chlorosilane compound is 1-2 times of the molar multiple of the anhydrous oxalic acid calculated by chlorine element.
4. The process for preparing the lithium difluoroborate as claimed in claim 1, wherein: the lithium salt compound is anhydrous halogenated lithium salt, lithium hydride or lithium nitride; the anhydrous lithium halide salt is selected from lithium fluoride or lithium chloride.
5. The process for preparing lithium difluoroborate according to claim 1 or 4, wherein: the boron trifluoride complex is selected from one of boron trifluoride diethyl etherate, boron trifluoride dimethyl carbonate or boron trifluoride acetonitrile.
6. The process for preparing the lithium difluoroborate as claimed in claim 5, wherein: the addition amount of the lithium salt compound is 1 to 1.1 molar times of boron element in the boron trifluoride complex.
7. The process for preparing the lithium difluoroborate as claimed in claim 5, wherein: the molar ratio of the anhydrous oxalic acid to the boron trifluoride complex is (1-1.2) to 1.
8. The process for preparing lithium difluorooxalato borate as claimed in claim 7, wherein: the aprotic polar organic solvent is selected from one or more than two of acetonitrile, propionitrile, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl ethyl ketone, 1, 4-dioxane, 1, 4-butyrolactone and tetrahydrofuran; the water content of the aprotic polar organic solvent is less than or equal to 500ppm; the nonpolar solvent is selected from one of cyclohexane, petroleum ether, dichloromethane, dichloroethane, toluene and xylene.
9. The process for preparing the lithium difluoroborate as claimed in claim 8, wherein: the addition amount of the aprotic polar organic solvent is 1 to 6 times of the total mass of the anhydrous oxalic acid and the boron trifluoride complex.
10. The process for preparing the lithium difluoroborate as claimed in claim 1, wherein: the tail gas generated in the preparation process of the lithium difluorooxalato borate is absorbed by alkali liquor.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007077046A (en) * | 2005-09-12 | 2007-03-29 | Tomiyama Pure Chemical Industries Ltd | Method for producing spiro compound |
| CN101139352A (en) * | 2007-09-29 | 2008-03-12 | 张家港市国泰华荣化工新材料有限公司 | Method for preparing difluorine oxalic acid boracic acid lithium |
| CN104387411A (en) * | 2014-11-07 | 2015-03-04 | 周阳 | Series one-pot synthesis method of lithium oxalyldifluroborate |
| CN106946921A (en) * | 2017-04-07 | 2017-07-14 | 上海如鲲新材料有限公司 | The method that ethanedioic acid fluorine boron ester prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate |
| CN107698611A (en) * | 2017-09-06 | 2018-02-16 | 浙江圣持新材料科技有限公司 | A kind of synthetic method of electrolyte lithium salt difluorine oxalic acid boracic acid lithium |
| CN109438488A (en) * | 2018-11-13 | 2019-03-08 | 九江天赐高新材料有限公司 | A kind of preparation method of liquid Lithium bis (oxalate) borate salt |
| CN111057083A (en) * | 2019-12-27 | 2020-04-24 | 合肥利夫生物科技有限公司 | Preparation method of lithium difluoroborate |
| CN111978341A (en) * | 2020-09-03 | 2020-11-24 | 江苏华盛锂电材料股份有限公司 | Preparation method of lithium difluoroborate |
| CN113512052A (en) * | 2021-07-13 | 2021-10-19 | 河北津宏化工有限公司 | Preparation process of lithium difluoroborate |
-
2023
- 2023-08-28 CN CN202311082416.8A patent/CN116813655A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007077046A (en) * | 2005-09-12 | 2007-03-29 | Tomiyama Pure Chemical Industries Ltd | Method for producing spiro compound |
| CN101139352A (en) * | 2007-09-29 | 2008-03-12 | 张家港市国泰华荣化工新材料有限公司 | Method for preparing difluorine oxalic acid boracic acid lithium |
| CN104387411A (en) * | 2014-11-07 | 2015-03-04 | 周阳 | Series one-pot synthesis method of lithium oxalyldifluroborate |
| CN106946921A (en) * | 2017-04-07 | 2017-07-14 | 上海如鲲新材料有限公司 | The method that ethanedioic acid fluorine boron ester prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate |
| CN107698611A (en) * | 2017-09-06 | 2018-02-16 | 浙江圣持新材料科技有限公司 | A kind of synthetic method of electrolyte lithium salt difluorine oxalic acid boracic acid lithium |
| CN109438488A (en) * | 2018-11-13 | 2019-03-08 | 九江天赐高新材料有限公司 | A kind of preparation method of liquid Lithium bis (oxalate) borate salt |
| CN111057083A (en) * | 2019-12-27 | 2020-04-24 | 合肥利夫生物科技有限公司 | Preparation method of lithium difluoroborate |
| CN111978341A (en) * | 2020-09-03 | 2020-11-24 | 江苏华盛锂电材料股份有限公司 | Preparation method of lithium difluoroborate |
| CN113512052A (en) * | 2021-07-13 | 2021-10-19 | 河北津宏化工有限公司 | Preparation process of lithium difluoroborate |
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