CN111574566A - Preparation method of lithium tetrafluoro oxalate phosphate and lithium difluorobis oxalate phosphate - Google Patents
Preparation method of lithium tetrafluoro oxalate phosphate and lithium difluorobis oxalate phosphate Download PDFInfo
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- CN111574566A CN111574566A CN202010577849.0A CN202010577849A CN111574566A CN 111574566 A CN111574566 A CN 111574566A CN 202010577849 A CN202010577849 A CN 202010577849A CN 111574566 A CN111574566 A CN 111574566A
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- oxalate phosphate
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- oxalic acid
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 64
- MRDKYAYDMCRFIT-UHFFFAOYSA-N oxalic acid;phosphoric acid Chemical compound OP(O)(O)=O.OC(=O)C(O)=O MRDKYAYDMCRFIT-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 78
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 57
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 26
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 21
- 239000010452 phosphate Substances 0.000 claims abstract description 21
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 150000005678 chain carbonates Chemical class 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 8
- 239000000654 additive Substances 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract 2
- 230000000996 additive effect Effects 0.000 abstract 1
- 150000001805 chlorine compounds Chemical class 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000011255 nonaqueous electrolyte Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 48
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 239000012528 membrane Substances 0.000 description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910004014 SiF4 Inorganic materials 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 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 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
Classifications
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- 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
-
- 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
- C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
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Abstract
The invention discloses a preparation method of lithium tetrafluoro oxalate phosphate and lithium difluorobis oxalate phosphate. Adding lithium carbonate into an oxalic acid solution in a nitrogen atmosphere, uniformly stirring, and then dropwise adding a lithium hexafluorophosphate solution, wherein the molar ratio of the dropwise adding amount of lithium hexafluorophosphate to oxalic acid is 1: (0.8-1.2), and reacting to obtain lithium tetrafluoro oxalate phosphate; or adding lithium carbonate into the oxalic acid solution in the nitrogen atmosphere, uniformly stirring, and then dropwise adding a lithium hexafluorophosphate solution, wherein the molar ratio of the dropwise adding amount of lithium hexafluorophosphate to oxalic acid is 1: (1.8-2.4), and reacting to obtain the lithium difluorobis (oxalato) phosphate solution. The preparation method is simple and practical, and can be used for industrial production, the prepared product can be directly used as the nonaqueous electrolyte battery additive, and the prepared product contains less free acid and no chlorine compound, and the free acid is less than 100 mass ppm by the acid concentration converted by hydrofluoric acid.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of lithium tetrafluoro oxalate phosphate and lithium difluorobis oxalate phosphate.
Background
The lithium difluorobis (oxalato) phosphate and the lithium tetrafluoro (oxalato) phosphate can form stable SEI films on the surfaces of the positive electrode and the negative electrode of the lithium battery, improve the thermal stability and the hydrolytic stability of the lithium battery electrolyte, improve the low-temperature stability and the cycle performance of the lithium battery, and become excellent additives of the lithium battery electrolyte. The lithium difluorobis (oxalato) phosphate and the lithium tetrafluoro (oxalato) phosphate are used in the lithium battery electrolyte, so that the using amount of the lithium hexafluorophosphate can be reduced, the performance of the lithium battery is improved, and the cost is reduced.
The preparation method of the lithium difluorobis (oxalato) phosphate and the lithium tetrafluorooxalato phosphate mainly comprises the following steps: patent No. CN200980145463 proposes a method for preparing lithium difluorobis (oxalato) phosphate and lithium tetrafluorooxalato phosphate using oxalic acid, lithium hexafluorophosphate and silicon tetrachloride as raw materials. The process produces large amounts of HCl and SiF4Highly corrosive acid gases, high equipment requirements, and difficult separation from the product. The chloride ion content and acid value of the product are difficult to control. The method has hidden dangers and risks in safety and reliability. Patent No. CN109850926A proposes a method for producing lithium difluorobis (oxalato) phosphate and lithium tetrafluorooxalato phosphate using oxalic acid, lithium hexafluorophosphate and trimethylchlorosilane as raw materials. The method also generates a large amount of HCl high-corrosivity acid gas, has high requirements on equipment, and is difficult to control chloride ions and acid values. Therefore, the method also has potential safety and reliability risks.
Disclosure of Invention
The invention aims to provide a preparation method of lithium tetrafluoro oxalate phosphate and lithium difluorobis oxalate phosphate.
A preparation method of lithium tetrafluoro oxalate phosphate and lithium difluorobis oxalate phosphate comprises the following steps:
1) dissolving lithium hexafluorophosphate in an organic solvent to prepare a lithium hexafluorophosphate solution;
2) dissolving oxalic acid in an organic solvent to prepare an oxalic acid solution;
3) under the nitrogen atmosphere, adding lithium carbonate into an oxalic acid solution, fully stirring uniformly, then dropwise adding a lithium hexafluorophosphate solution at a constant speed, wherein the molar ratio of the dropwise adding amount of lithium hexafluorophosphate to oxalic acid is 1: (0.8-1.2), fully reacting, and filtering a reaction product to obtain lithium tetrafluoro oxalate phosphate;
or under the nitrogen atmosphere, adding lithium carbonate into the oxalic acid solution, fully stirring uniformly, and then dropwise adding the lithium hexafluorophosphate solution at a constant speed, wherein the molar ratio of the dropwise adding amount of the lithium hexafluorophosphate to the oxalic acid is 1: (1.8-2.4), fully reacting, and filtering a reaction product to obtain a lithium difluorobis (oxalato) phosphate solution.
The organic solvent is: one or more of carbonates, ketones, carboxylic esters, ethers, nitriles, dimethylformamide and dimethyl sulfoxide.
The carbonate is cyclic carbonate or chain carbonate; the esters are cyclic ethers and chain ethers.
The molar ratio of the oxalic acid to the lithium carbonate is 1: (2.5-6.0).
In the reaction process for preparing the lithium difluorobis (oxalato) phosphate, the reaction temperature is 60-95 ℃.
In the reaction process for preparing the lithium tetrafluoro oxalate phosphate, the reaction temperature is 50-80 ℃.
The dropping time of the lithium hexafluorophosphate is 3-5 h.
The reaction time is 2-10 h.
The reaction principle of the invention is as follows:
or
And after the reaction is finished, continuously stirring at the temperature of 50-95 ℃ for 2-4 h, and degassing to remove impurities.
The invention has the beneficial effects that: reaction scheme of the present invention andthe reaction conditions are safe, environment-friendly, economical and industrialized, the generated byproducts are lithium bicarbonate and lithium fluoride, the separation is simple, and corrosive gases (such as HCl, HF, (CH) are not generated3)3SiF and SiF4) The safety of the whole process is improved, the requirement on equipment is reduced, the reaction is kept at the temperature and stirred for a period of time after the reaction is finished, HF which is possibly generated can be effectively removed, the acid value of the product is effectively controlled, and lithium fluoride and lithium bicarbonate are filtered and removed to obtain a target product; the used solvent can be reused after being simply treated and qualified, so that the yield is further improved, and the cost is saved; the base solution and the titration solution are the same organic solvent, and a uniform and stable solution can be formed.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Example 1
Under the protection of nitrogen, 18.08g of oxalic acid and 125.0g of diethyl carbonate are added into a dry 1000mL three-neck flask, stirred, and then 46.3g of anhydrous lithium carbonate is added, and stirred for 30min to be uniformly mixed. Preparing a lithium hexafluorophosphate solution: under nitrogen protection, 38.0g of lithium hexafluorophosphate was added to 125.0g of diethyl carbonate in portions, and the mixture was stirred while being added to dissolve the lithium hexafluorophosphate sufficiently. Setting the temperature to 50 ℃, and slowly dripping the lithium hexafluorophosphate solution after the flask reaches the set temperature for 3 hours. After the dropwise addition, the reaction is continued for 2h under heat preservation, then the temperature is reduced to 30 ℃, the negative pressure is pumped by using an oil pump, the pressure in the flask is controlled to be 1000Pa, the reaction is kept for 2h, and then nitrogen is filled to prepare for filtration. And (4) filtering under positive pressure by using nitrogen, and selecting a polypropylene membrane with the thickness of 0.45um as a microporous filter membrane to obtain the lithium tetrafluoro oxalate phosphate solution. Finally, lithium tetrafluoro-oxalate phosphate with the purity of 99.80% and the yield of 93.63% (based on the content of lithium hexafluorophosphate) was obtained.
Example 2
Under the protection of nitrogen, 40.7g of oxalic acid and 125.0g of diethyl carbonate were added to a dry 1000mL three-neck flask, stirred, and then 185.1g of anhydrous lithium carbonate was added, and stirred for 30min to mix uniformly. Preparing a lithium hexafluorophosphate solution: under nitrogen protection, 38.0g of lithium hexafluorophosphate was added to 125.0g of diethyl carbonate in portions, and the mixture was stirred while being added to dissolve the lithium hexafluorophosphate sufficiently. Setting the temperature to be 60 ℃, slowly dripping the lithium hexafluorophosphate solution after the flask reaches the set temperature, wherein the dripping time is 3 hours. After the dropwise addition, the reaction is continued for 2h under heat preservation, then the temperature is reduced to 30 ℃, the negative pressure is pumped by using an oil pump, the pressure in the flask is controlled to be 1000Pa, the reaction is kept for 2h, and then nitrogen is filled to prepare for filtration. And (3) carrying out positive pressure filtration on nitrogen, and selecting a polypropylene membrane with the thickness of 0.45um as a microporous filter membrane to obtain the lithium difluorobis (oxalate) phosphate solution. Lithium difluorobis (oxalato) phosphate with a purity of 99.60% and a yield of 92.25% (based on the lithium hexafluorophosphate content) was finally obtained.
Example 3
Under the protection of nitrogen, 22.6g of oxalic acid and 125.0g of ethylene glycol dimethyl ether were added into a dry 1000mL three-neck flask, stirred, then 92.5g of anhydrous lithium carbonate was added, and stirred for 30min to mix uniformly. Preparing a lithium hexafluorophosphate solution: under nitrogen protection, 38.0g of lithium hexafluorophosphate was added to 125.0g of diethyl carbonate in portions, and the mixture was stirred while being added to dissolve the lithium hexafluorophosphate sufficiently. Setting the temperature to be 75 ℃, and slowly dropwise adding a lithium hexafluorophosphate solution after the flask reaches the set temperature, wherein the dropwise adding time is 4 hours. After the dropwise addition, the reaction is continued for 5h, then the temperature is reduced to 40 ℃, the negative pressure is pumped by using an oil pump, the pressure in the flask is controlled to be 1000Pa, the flask is kept for 2h, and then nitrogen is filled to prepare for filtration. And (4) filtering under positive pressure by using nitrogen, and selecting a polypropylene membrane with the thickness of 0.45um as a microporous filter membrane to obtain the lithium tetrafluoro oxalate phosphate solution. Finally, lithium tetrafluoro-oxalate phosphate with the purity of 99.58% and the yield of 95.23% (based on the content of lithium hexafluorophosphate) was obtained.
Example 4
Under the protection of nitrogen, 45.2g of oxalic acid and 125.0g of ethylene glycol dimethyl ether were added into a dry 1000mL three-neck flask, stirred, added with 55.6g of anhydrous lithium carbonate, and stirred for 30min to be uniformly mixed. Preparing a lithium hexafluorophosphate solution: under nitrogen protection, 38.0g of lithium hexafluorophosphate was added to 125.0g of diethyl carbonate in portions, and the mixture was stirred while being added to dissolve the lithium hexafluorophosphate sufficiently. The set temperature is 65 ℃, and after the flask reaches the set temperature, the lithium hexafluorophosphate solution is slowly dripped for 4 hours. After the dropwise addition, the reaction is continued for 5h, then the temperature is reduced to 40 ℃, the negative pressure is pumped by using an oil pump, the pressure in the flask is controlled to be 1000Pa, the flask is kept for 2h, and then nitrogen is filled to prepare for filtration. And (3) carrying out positive pressure filtration on nitrogen, and selecting a polypropylene membrane with the thickness of 0.45um as a microporous filter membrane to obtain the lithium difluorobis (oxalate) phosphate solution. Lithium difluorobis (oxalato) phosphate with a purity of 99.23% and a yield of 95.63% (based on the lithium hexafluorophosphate content) was finally obtained.
Example 5
Under the protection of nitrogen, 27.0g of oxalic acid and 125.0g of ethylene glycol dimethyl ether were added to a dry 1000mL three-neck flask, stirred, then 111.0g of anhydrous lithium carbonate was added, and stirred for 30min to mix uniformly. Preparing a lithium hexafluorophosphate solution: under nitrogen protection, 38.0g of lithium hexafluorophosphate was added to 125.0g of diethyl carbonate in portions, and the mixture was stirred while being added to dissolve the lithium hexafluorophosphate sufficiently. The set temperature is 95 ℃, and after the flask reaches the set temperature, the lithium hexafluorophosphate solution is slowly dripped for 5 hours. After the dropwise addition, the reaction is continued for 12h under heat preservation, then the temperature is reduced to 60 ℃, the negative pressure is pumped by using an oil pump, the pressure in the flask is controlled to be 1000Pa, the flask is kept for 2h, and then nitrogen is filled to prepare for filtration. And (3) carrying out positive pressure filtration on nitrogen, and selecting a polypropylene membrane with the thickness of 0.45um as a microporous filter membrane to obtain the lithium difluorobis (oxalate) phosphate solution. Finally, the lithium difluorobis (oxalato) phosphate with the purity of 99.72% and the yield of 90.13% (based on the content of lithium hexafluorophosphate) is obtained.
Example 6
Under the protection of nitrogen, 54.0g of oxalic acid and 125.0g of ethylene glycol dimethyl ether were added to a dry 1000mL three-neck flask, stirred, then 74.0g of anhydrous lithium carbonate was added, and stirred for 30min to mix uniformly. Preparing a lithium hexafluorophosphate solution: under nitrogen protection, 38.0g of lithium hexafluorophosphate was added to 125.0g of diethyl carbonate in portions, and the mixture was stirred while being added to dissolve the lithium hexafluorophosphate sufficiently. Setting the temperature to 80 ℃, and slowly dripping the lithium hexafluorophosphate solution after the flask reaches the set temperature for 5 hours. After the dropwise addition, the reaction is continued for 12h under heat preservation, then the temperature is reduced to 60 ℃, the negative pressure is pumped by using an oil pump, the pressure in the flask is controlled to be 1000Pa, the flask is kept for 2h, and then nitrogen is filled to prepare for filtration. And (4) filtering under positive pressure by using nitrogen, and selecting a polypropylene membrane with the thickness of 0.45um as a microporous filter membrane to obtain the lithium tetrafluoro oxalate phosphate solution. Finally, the lithium tetrafluoro-oxalate phosphate with the purity of 99.63 percent and the yield of 91.38 percent (based on the content of the lithium hexafluorophosphate) is obtained.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A preparation method of lithium tetrafluoro oxalate phosphate and lithium difluorobis oxalate phosphate is characterized by comprising the following steps:
1) dissolving lithium hexafluorophosphate in an organic solvent to prepare a lithium hexafluorophosphate solution;
2) dissolving oxalic acid in an organic solvent to prepare an oxalic acid solution;
3) under the nitrogen atmosphere, adding lithium carbonate into an oxalic acid solution, fully stirring uniformly, then dropwise adding a lithium hexafluorophosphate solution at a constant speed, wherein the molar ratio of the dropwise adding amount of lithium hexafluorophosphate to oxalic acid is 1: (0.8-1.2), fully reacting, and filtering a reaction product to obtain lithium tetrafluoro oxalate phosphate;
or under the nitrogen atmosphere, adding lithium carbonate into the oxalic acid solution, fully stirring uniformly, and then dropwise adding the lithium hexafluorophosphate solution at a constant speed, wherein the molar ratio of the dropwise adding amount of the lithium hexafluorophosphate to the oxalic acid is 1: (1.8-2.4), fully reacting, and filtering a reaction product to obtain a lithium difluorobis (oxalato) phosphate solution.
2. The method for preparing lithium tetrafluoro oxalate phosphate and lithium difluorobis oxalate phosphate according to claim 1, wherein the organic solvent is: one or more of carbonates, ketones, carboxylic esters, ethers, nitriles, dimethylformamide and dimethyl sulfoxide.
3. The method for producing lithium tetrafluorooxalate phosphate and lithium difluorobis-oxalate phosphate according to claim 1, wherein the carbonates are cyclic carbonates and chain carbonates; the esters are cyclic ethers and chain ethers.
4. The method for preparing lithium tetrafluoro oxalate phosphate and lithium difluorobis oxalate phosphate according to claim 1, wherein the molar ratio of oxalic acid to lithium carbonate is 1: (2.5-6.0).
5. The method for preparing lithium tetrafluoro oxalate phosphate and lithium difluorobis-oxalate phosphate according to claim 1, wherein the reaction temperature is 60-95 ℃ in the reaction process for preparing lithium difluorobis-oxalate phosphate.
6. The method for preparing lithium tetrafluoro oxalate phosphate and lithium difluorobis-oxalate phosphate according to claim 1, wherein the reaction temperature is 50-80 ℃ in the reaction process for preparing lithium tetrafluoro oxalate phosphate.
7. The method for preparing lithium tetrafluoro oxalate phosphate and lithium difluorobis oxalate phosphate according to claim 1, wherein the dropping time of lithium hexafluorophosphate is 3 to 5 hours.
8. The method for preparing lithium tetrafluoro oxalate phosphate and lithium difluorobis oxalate phosphate according to claim 1, wherein the reaction time is 2 to 10 hours.
9. The preparation method of lithium tetrafluoro oxalate phosphate and lithium difluorobis oxalate phosphate according to claim 1, characterized in that after the reaction is finished, stirring is continued at the temperature of 50-95 ℃ for 2-4 h, and degassing and impurity removal are carried out.
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| CN113527363A (en) * | 2021-05-18 | 2021-10-22 | 深圳市研一新材料有限责任公司 | Preparation method of lithium difluorobis (oxalato) phosphate or lithium tetrafluorooxalato phosphate |
| CN113725430A (en) * | 2020-05-26 | 2021-11-30 | 恒大新能源技术(深圳)有限公司 | Preparation method of lithium tetrafluoro oxalate phosphate and derivative thereof, electrolyte and secondary battery |
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