CN112739652B - Preparation method of lithium fluorosulfonate - Google Patents
Preparation method of lithium fluorosulfonate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
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- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
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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
- H01M10/05—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
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- H01M10/0568—Liquid materials characterised by the solutes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of lithium fluorosulfonate, which comprises the following steps: (1) with a purity of not less than 98.5% of Metal Fluorosulfonate (MFSO)3) The raw materials are subjected to double decomposition exchange reaction with organic lithium salt in ester, alcohol, nitrile or amide solvents. (2) Precipitation of insoluble organometallic salts; vacuum drying, extracting with organic metal salt poor solvent, filtering, separating, vacuum concentrating, adding low-polarity aprotic solvent into the concentrated solution, standing for crystallization, and vacuum drying to obtain the product of high-purity lithium fluorosulfonate. The preparation method of the high-purity lithium fluorosulfonate has the advantages of simple post-reaction treatment method, high product yield and high purity, and can effectively reduce the content of impurities such as potassium ions, sodium ions, calcium ions, chloride ions, moisture and the like in the product. The preparation method provided by the invention has the characteristics of simple operation steps, reasonable production cost, high safety, wide substrate selection, low cost and high product purity.
Description
Technical Field
The invention relates to a preparation method of lithium fluorosulfonate, belonging to the technical field of chemical synthesis.
Background
1. Lithium fluorosulfonate abbreviated LiFSO3And the molecular weight is 106.1. Pure lithium fluorosulfonate is a white solid. The lithium fluorosulfonate is a chemical substance which can be widely applied to the field of electronic batteries, is widely applied, and has high purity, and is suitable for being used as a non-aqueous electrolyte additive of a secondary lithium ion battery. The electrolyte has the characteristics of electrochemical stability and thermal stability in the electrolyte, can improve the cycle performance and high-temperature storage performance of a secondary lithium ion battery, can inhibit the gas generation of the electrolyte in the using process, thereby improving the overall performance of the secondary lithium ion battery, and shows that the electrolyte can replace electrolyte additives (such as lithium difluorophosphate, lithium perchlorate, lithium hexafluoroarsenate and the like) which seriously pollute the environment in some fields.
2. The following is a technical introduction to the prior art regarding lithium p-fluorosulfonate.
3. The article (j.chem.soc. (a),1967, (3),355-358) reported the preparation of potassium fluorosulfonate by reacting fluorosulfonic acid with organic potassium acetate in an acetic acid solvent.
4. The electrical properties of lithium fluorosulfonate in EP2698350(a1) and CN 103492319B are studied intensively, and it is found that the characteristics can improve the high-temperature capacity of the secondary lithium ion battery, and the gas generation of the electrolyte can be inhibited during the use process, so as to improve the overall performance of the battery, and therefore, the synthesis of high-purity lithium fluorosulfonate will be helpful to improve the lithium ion battery technology. However, the patent proposes that fluorosulfonic acid reacts with various lithium salts to generate lithium fluorosulfonate, and then the lithium fluorosulfonate is purified through post-treatment to obtain a lithium fluorosulfonate finished product, so that the product purity is high. Although the fluorosulfonic acid can react with various lithium salts to prepare lithium fluorosulfonate, the raw material fluorosulfonic acid is a high-risk chemical and has strong irritation and corrosivity, white smoke is emitted in the exposed air, and hydrogen fluoride gas is released by the reaction of the raw material fluorosulfonic acid with water vapor in the air, so that the harm is great. If organic lithium salt is used as a raw material in the reaction, organic matters produced in the reaction can be immediately fluorinated by fluorosulfonic acid to generate side reaction, a large amount of impurities are generated, and the purification of the subsequent step of post-treatment is not facilitated, so that the method is only limited to the adoption of inorganic lithium as the raw material. There are therefore certain material limitations to this process.
Disclosure of Invention
1. The technical problem to be solved by the invention is to provide a preparation method of high-purity lithium fluorosulfonate, which has high safety, high yield, high purity and low impurity content.
2. In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
3. a method for preparing a lithium fluorosulfonate salt, comprising the steps of:
(1) with a purity of not less than 98.5% of Metal Fluorosulfonate (MFSO)3) The raw materials are subjected to double decomposition exchange reaction with organic lithium salt in an ester, alcohol, nitrile or amide organic solvent.
(2) Precipitation of insoluble organometallic salts; vacuum drying, extracting with organic metal salt poor solvent, filtering, separating, vacuum concentrating, adding low-polarity aprotic solvent into the concentrated solution, standing for crystallization, and vacuum drying to obtain the product of high-purity lithium fluorosulfonate.
4. Metal Fluorosulfonate (MFSO) in step (1)3) M of (b) is one of monovalent metal ions of potassium, sodium and cesium.
5. The esters in the step (1) are selected from one or more combinations of methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate or vinyl acetate, the alcohols are selected from one or more combinations of methanol, ethanol, propanol, butanol or isopropanol, the ethers are selected from one or more combinations of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, the nitriles are selected from one or more combinations of acetonitrile, propionitrile or isopropionitrile, and the amides are selected from N, N-dimethylformamide.
6. The organic lithium salt in the step (1) is one or a combination of more of lithium hexafluorophosphate, lithium methylsulfonate, lithium tetrafluoroborate, lithium paratoluenesulfonate, lithium perfluorobutylsulfonate, lithium saccharin, lithium sulfacetamide, lithium acetylacetonate, lithium diethylmalonate, lithium phthalimide, lithium maleimide, lithium succinimide and lithium trifluoromethanesulfonate.
7. The molar ratio of the double decomposition exchange reaction of the metal fluorosulfonate and the organic lithium salt in the step (1) is 1.0-4.0: 1.0.
The optimal ratio is 1.0-2.0: 1.0
8. The temperature of the double decomposition exchange reaction in the step (1) is 20-60 ℃, and the preferable temperature is 30-45 ℃. The reaction time is 1-24 hours, and the preferable time is 8-12 hours.
9. And (3) performing vacuum pumping in the step (2) until the vacuum degree is 3-4 torr and the temperature is 0-40 ℃. The preferred temperature is 20-40 ℃.
10. The poor solvent of the organic metal salt in the step (2) is one or more selected from dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate and fluoroethylene carbonate.
11. The vacuum degree during the reduced pressure concentration in the step (2) is 8-10 torr, and the temperature is 10-60 ℃. The temperature is preferably 30-45 ℃. Concentrating to 1/8-1/5 of the original volume.
12. The low-polarity aprotic solvent in the step (2) is selected from one or more of n-hexane, cyclohexane, cyclopentane, dichloromethane, chloroform, dichloroethane, bromoethane, dibromoethane, toluene, o-xylene and p-xylene.
13. The crystallization time in the step (2) is 12-48 hours. The preferable time is 16 to 24 hours. The crystallization temperature was-20 ℃.
14. The vacuum drying degree in the step (2) is 3-4 torr, and the temperature is 10-60 ℃. The temperature is preferably 20-40 ℃.
15. The invention achieves the following beneficial effects: the present invention utilizes organic lithium salts as a platform for metathesis exchange reactions to produce MFSO in a wide range3Replacement by LiFeSO3Thereby synthesizing LiFSO3The reaction(s) expands from the fluorosulfonic acid route, increasing the selectivity of the synthetic route. The high-purity lithium fluorosulfonate can be obtained more safely and easily.
17.(2) the organic metal salt obtained by the double decomposition exchange reaction is insoluble in carbonate solvents, can be directly filtered and removed, and is safe and simple to operate.
18.(3) the purity of the lithium fluorosulfonate prepared by the method is more than or equal to 99.5%, the purity of sodium ions is less than or equal to 50ppm, the purity of potassium ions is less than or equal to 50ppm, the purity of calcium ions is less than or equal to 10ppm, the purity of fluorine ions is less than or equal to 50ppm, and the purity of chloride ions is less than or equal to 50ppm, so that the lithium fluorosulfonate can be applied to preparation of secondary lithium ion battery electrolyte.
19. The method uses the great difference of the solubility of the organic lithium salt and the organic metal salt in the organic solvent to carry out double decomposition exchange reaction with the metal fluorosulfonate, improves the yield through the homogeneous reaction of the organic lithium salt and the metal fluorosulfonate, and is different from the characteristic that the weak acid and the lithium fluorosulfonate are prepared by using the reaction of strong acid fluorosulfonate and inorganic lithium salt proposed by CN 103492319B.
20. The lithium fluorosulfonate is prepared by carrying out double decomposition exchange reaction on metal fluorosulfonate and organic lithium salt, the treatment method after the reaction is simple, the product yield is high, the purity is high, and the content of impurities such as potassium ions, sodium ions, calcium ions, chloride ions, moisture and the like in the product can be effectively reduced.
Detailed Description
1. The present invention is further described below, and the following examples are only used to more clearly illustrate the technical solutions of the present invention, but not to limit the scope of the present invention.
2. Example 1
(1) Purification of potassium fluorosulfonate:
under the protection of inert gas, 100g (0.724mol) of potassium fluorosulfonate KFSO3(M is 138.16) (CAS:13455-22-6) purchased from the market is added into a 1000mL bottle, 400mL of ethylene glycol monomethyl ether is added as a solvent to be stirred and completely dissolved, then 400mL of ethyl acetate is added to be stirred continuously to generate a part of insoluble substances, the insoluble substances are filtered, the filtrate is concentrated at a reduced pressure rate until a small amount of solid appears, the filtrate is recovered to the normal pressure, then 500mL of dichloromethane is added, the solution is cooled to-15 ℃, the solution is kept stand for 24 hours to obtain crystals, the crystals are washed by dichloromethane after separation, and finally the solids are dried in vacuum, so that white powder of the potassium fluorosulfonate with the purity of more than or equal to 98.5 percent can be obtained.
(2) And (3) purifying sodium fluorosulfonate:
100g (0.819mol) of sodium fluorosulfonate NaFSO, which is commercially available, are introduced into a 1000mL flask under inert gas3(M is 122.05) (CAS:14483-63-7), firstly adding 400mL of methanol as a solvent, stirring to dissolve completely, then adding 500mL of ethyl acetate, continuing stirring to generate a part of insoluble matter, filtering out the insoluble matter, concentrating the filtrate at a reduced pressure rate until a small amount of solid appears, returning to normal pressure, then adding 400mL of dichloromethane, cooling the solution to-15 ℃, standing for 24 hours to obtain crystals, washing the crystals with dichloromethane after separation, and finally, vacuumizing and drying the solids to obtain sodium fluorosulfonate white powder with the purity of more than or equal to 98.5%.
3. Example 2
In a 500mL reaction flask, 30.38g (0.2mol) of lithium hexafluorophosphate (M ═ 151.91) was placed and dissolved in 150mL of methanol under protection of an inert gas, the temperature was controlled to 40 ℃, and 30.40g (0.22mol) of potassium fluorosulfonate (KFSO) dissolved in 200mL of methanol was added dropwise with stirring3) Potassium hexafluorophosphate precipitate is generated in the dropping process, stirring is continued for 8 hours after the dropping is finished, and then the reaction solvent is dried by vacuum pumping under reduced pressure. After obtaining a solid, 250mL of dimethyl carbonate is added to dissolve the solid, potassium hexafluorophosphate is removed by filtration, the obtained filtrate is concentrated to be slurry, 300mL of dichloromethane is added to be statically crystallized, a white solid product is separated out, and 18.59g of lithium fluorosulfonate with the yield of 87.6 percent is obtained after filtration and vacuum drying. (the detection result is ICP-OES (ppm): Na)+＝21.2ppm，K+＝44.8ppm，Fe2+＝1.5ppm，Ca2+＝9.1ppm；IC：F－＝31.5ppm，Cl－＝11.4ppm。KF：H2O＝21.9ppm。19FNMR(400MHz,DMSO-d6):40.22ppm
4. Example 3
Under the protection of inert gas, 37.80g (0.2mol) of saccharin lithium dissolved in 100mL of acetonitrile was placed in a 500mL reaction flask, the temperature was controlled to 30 ℃, and 26.85g (0.22mol) of fluorosulfonic acid sodium salt (NaFSO) dissolved in 250mL of acetonitrile was added dropwise with stirring3) And (3) generating saccharin sodium precipitate in the dropping process, continuously stirring for 16 hours after the dropping is finished, and then, drying the reaction solvent by adopting reduced pressure vacuum. After a solid had been obtained, 250mL of dimethyl carbonate were added and dissolved and filteredAfter the saccharin sodium is removed, the obtained filtrate is concentrated to be slurry, 300mL of dichloroethane is added for static crystallization, a white solid product is separated out, and 18.95g of lithium fluorosulfonate is obtained after filtration and vacuum drying, wherein the yield is 89.3%. (the detection result is ICP-OES (ppm): Na)+＝48.6ppm，K+＝8.9ppm，Fe2 +＝2.1ppm，Ca2+＝15.8ppm；IC：F－＝43.2ppm，Cl－＝18.6ppm。KF：H2O＝25.6ppm。19FNMR(400MHz,DMSO-d6):40.22ppm
5. Example 4
In a 500mL reaction flask, 17.82g (0.1mol) of lithium p-toluenesulfonate (M178.2) was dissolved in 150mL of ethanol under inert gas protection, the temperature was controlled to 45 ℃, and 16.58g (0.12mol) of potassium fluorosulfonate (KFSO) dissolved in 80mL of ethanol was added dropwise with stirring3) And (3) generating a potassium paratoluenesulfonate precipitate in the dripping process, continuing stirring for 8 hours after the dripping is finished, and then, vacuumizing and drying the reaction solvent under reduced pressure. After the solid is obtained, adding 100mL of diethyl carbonate to dissolve the diethyl carbonate, filtering the solution to remove potassium p-toluenesulfonate, concentrating the obtained filtrate into slurry, adding 150mL of toluene to perform static crystallization, separating out a white solid product, filtering the white solid product, and drying the white solid product in vacuum to obtain 9.41g of lithium fluorosulfonate LiFSO3Yield 88.7%. (the detection result is ICP-OES (ppm): Na)+＝14.9ppm，K+＝40.4ppm，Fe2+＝1.8ppm，Ca2+＝5.2ppm；IC：F－＝39.1ppm，Cl－＝14.2ppm。KF：H2O＝28.1ppm。19FNMR(400MHz,DMSO-d6):40.23ppm
6. Example 5
Under the protection of inert gas, 9.38g (0.1mol) of lithium tetrafluoroborate (M93.75) dissolved in 100mL of ethylene glycol monomethyl ether was placed in a 250mL reaction flask, the temperature was controlled to 45 ℃, and 16.58g (0.12mol) of potassium fluorosulfonate (KFSO) dissolved in 80mL of ethylene glycol monomethyl ether was added dropwise with stirring3) And (3) generating potassium tetrafluoroborate precipitate in the dripping process, continuously stirring for 8 hours after the dripping is finished, and then, drying the reaction solvent by adopting reduced pressure vacuum pumping. After obtaining a solid, 100mL of ethyl methyl carbonate was added to dissolve and filter the potassium tetrafluoroborate, the resulting filtrate was concentrated to a slurry, and then addedAdding 150mL of chloroform for standing crystallization, precipitating a white solid product, filtering, and drying in vacuum to obtain 9.83g of lithium fluorosulfonate with the yield of 92.6%. (the detection result is ICP-OES (ppm): Na)+＝14.9ppm，K+＝39.1ppm，Fe2+＝1.2ppm，Ca2+＝8.3ppm；IC：F－＝45.8ppm，Cl－＝21.2ppm。KF：H2O＝24.3ppm。19FNMR(400MHz,DMSO-d6):40.23ppm
7. Example 6
In a 250mL reaction flask, under the protection of an inert gas, 15.3g (0.05mol) of lithium perfluorobutylsulfonate (M. RTM. 306.03) was dissolved in 100mL of ethylene glycol dimethyl ether, the temperature was controlled to 45 ℃, and 8.98g (0.065mol) of potassium fluorosulfonate (KFSO) dissolved in 80mL of ethylene glycol dimethyl ether was added dropwise with stirring3) And generating potassium perfluorobutylsulfonate precipitate in the dropping process, continuing stirring for 18 hours after the dropping is finished, and then, vacuumizing the reaction solvent under reduced pressure. And after a solid is obtained, adding 100mL of dimethyl carbonate to dissolve, filtering to remove potassium perfluorobutyl sulfonate, concentrating the obtained filtrate into slurry, adding 200mL of dichloromethane to stand for crystallization, precipitating a white solid product, filtering, and drying in vacuum to obtain 4.61g of lithium fluorosulfonate with the yield of 86.9%. (the detection result is ICP-OES (ppm): Na)+＝18.7ppm，K+＝46.6ppm，Fe2+＝1.3ppm，Ca2+＝7.4ppm；IC：F－＝47.2ppm，Cl－＝25.7ppm。KF：H2O＝22.7ppm。19FNMR(400MHz,DMSO-d6):40.22ppm
8. Example 7
In a 500mL reaction flask, 15.6g (0.1mol) of lithium trifluoromethanesulfonate (M156.01) was dissolved in 150mL of ethyl acetate under the protection of an inert gas, the temperature was controlled to 45 ℃, and 14.65g (0.12mol) of sodium fluorosulfonate (NaFSO) dissolved in 150mL of acetonitrile was added dropwise with stirring3) Sodium trifluoromethanesulfonate precipitate is generated in the dropping process, stirring is continued for 18 hours after the dropping is finished, and then the reaction solvent is pumped out by adopting reduced pressure vacuum. After obtaining the solid, adding 200mL of dimethyl carbonate to dissolve the solid, filtering the solution to remove sodium trifluoromethanesulfonate, concentrating the obtained filtrate into slurry, adding 250mL of dibromoethane to the slurry for static crystallization, and separating out a white solid productAfter filtration and vacuum drying, 9.64g of lithium fluorosulfonate was obtained, the yield was 90.9%. (the detection result is ICP-OES (ppm): Na)+＝42.5ppm，K+＝17.6ppm，Fe2+＝1.8ppm，Ca2+＝6.9ppm；IC：F－＝41.5ppm，Cl－＝31.3ppm。KF：H2O＝18.8ppm。19FNMR(400MHz,DMSO-d6):40.23ppm
9. The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (17)
1. A preparation method of lithium fluorosulfonate is characterized by comprising the following steps:
(1) the purity is more than or equal to 98.5 percent and the chemical formula is MFSO3The metal fluorosulfonate is used as a raw material and is subjected to double decomposition exchange reaction with organic lithium salt in an ester, alcohol, ether, nitrile or amide organic solvent;
(2) precipitation of insoluble organometallic salts; vacuum drying, extracting with organic metal salt poor solvent, filtering, separating, vacuum concentrating, adding low-polarity aprotic solvent into the concentrated solution, standing for crystallization, and vacuum drying to obtain the product of high-purity lithium fluorosulfonate.
2. The method for producing a lithium fluorosulfonate salt according to claim 1, wherein said MFSO in step (1)3M of (b) is one of monovalent metal potassium, sodium and cesium ions.
3. The method of claim 1, wherein the ester in step (1) is selected from one or more of methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, and vinyl acetate, the alcohol is selected from one or more of methanol, ethanol, propanol, butanol, and isopropanol, the ether is selected from one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether, the nitrile is selected from one or more of acetonitrile, propionitrile, and isopropionitrile, and the amide is selected from N, N-dimethylformamide.
4. The method of claim 1, wherein the organic lithium salt in step (1) is one or more of lithium hexafluorophosphate, lithium methylsulfonate, lithium tetrafluoroborate, lithium p-toluenesulfonate, lithium perfluorobutanesulfonate, lithium saccharin, lithium sulfacetamide, lithium acetylacetonate, lithium diethylmalonate, lithium phthalimide, lithium maleimide, lithium succinimide, and lithium trifluoromethanesulfonate.
5. The method of claim 1, wherein the molar ratio of the metal fluorosulfonate in step (1) to the organic lithium salt in the metathesis exchange reaction is 1.0-4.0: 1.0.
6. The method of claim 1, wherein the metathesis-exchange reaction in step (1) is carried out at a temperature of 20 to 60 ℃ for 1 to 24 hours.
7. The method of claim 6, wherein the metathesis-exchange reaction in step (1) is carried out at a temperature of 30 to 45 ℃ for a period of 8 to 12 hours.
8. The method of claim 1, wherein the vacuum degree of the vacuum pumping in step (2) is 3 to 4torr and the temperature is 0to 40 ℃.
9. The method according to claim 8, wherein the vacuum drying temperature in step (2) is 20 to 40 ℃.
10. The method of claim 1, wherein the poor solvent of the organic metal salt in step (2) is one or more selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, and fluoroethylene carbonate.
11. The method of claim 1, wherein the concentration under reduced pressure in step (2) is carried out under a vacuum of 8 to 10torr and at a temperature of 10to 60 ℃ until the concentration reaches 1/8 to 1/5 of the original volume.
12. The method according to claim 11, wherein the concentration under reduced pressure in step (2) is carried out at a temperature of 30 to 45 ℃.
13. The method according to claim 1, wherein the low-polarity aprotic solvent used in step (2) is selected from the group consisting of n-hexane, cyclohexane, cyclopentane, dichloromethane, chloroform, dichloroethane, bromoethane, dibromoethane, toluene, o-xylene, and p-xylene.
14. The method according to claim 1, wherein the crystallization time in the step (2) is 12 to 48 hours, and the crystallization temperature is-20 ℃.
15. The method of claim 14, wherein the crystallization time in step (2) is 16 to 24 hours.
16. The method of claim 1, wherein the vacuum drying degree in step (2) is 3 to 4torr and the temperature is 10to 60 ℃.
17. The method of claim 16, wherein the vacuum drying temperature in step (2) is 20-40 ℃.
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| CN113363583B (en) * | 2021-06-25 | 2022-05-10 | 珠海市赛纬电子材料股份有限公司 | Electrolyte additive, non-aqueous electrolyte and lithium ion battery thereof |
| CN113562746B (en) * | 2021-07-14 | 2023-09-01 | 珠海理文新材料有限公司 | Preparation method of potassium fluorosulfonate |
| CN113562748A (en) * | 2021-07-23 | 2021-10-29 | 广州理文科技有限公司 | Method and device for preparing lithium fluorosulfonate crystal with assistance of ultrasonic waves |
| CN113979454B (en) * | 2021-11-23 | 2023-09-26 | 山东永浩新材料科技有限公司 | Preparation method of alkali metal fluorosulfonate |
| CN114933320B (en) * | 2022-04-29 | 2024-03-29 | 广东马车动力科技有限公司 | Lithium chloride refining method |
| CN115072745B (en) * | 2022-08-18 | 2022-12-02 | 如鲲(江苏)新材料科技有限公司 | Method for preparing fluorosulfonate from fluorosulfonic anhydride |
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| CN106241757B (en) * | 2016-07-27 | 2018-09-18 | 上海康鹏科技有限公司 | A kind of preparation method of imidodisulfuryl fluoride lithium salt |
| JP7439361B2 (en) * | 2017-03-31 | 2024-02-28 | 三井化学株式会社 | Lithium salt complex compound, additive for lithium secondary batteries, and method for producing lithium salt complex compound |
| WO2019073755A1 (en) * | 2017-10-11 | 2019-04-18 | ダイキン工業株式会社 | Lithium fluorosulfonate production method |
| CN109928371A (en) * | 2019-04-12 | 2019-06-25 | 广州理文科技有限公司 | A kind of preparation method of imidodisulfuryl fluoride lithium salt |
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