CN115676855B - Preparation method of sodium ion battery electrolyte sodium salt - Google Patents
Preparation method of sodium ion battery electrolyte sodium salt Download PDFInfo
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Abstract
The invention discloses a preparation method of sodium salt of an electrolyte of a sodium-ion battery, which comprises the steps of dissolving lithium salt of the electrolyte of a lithium-ion battery in a first polar solvent to obtain a lithium salt solution; adding anhydrous sodium fluoride, 15-crown-5 and a second polar solvent into a reaction vessel; adding a lithium salt solution into a reaction container under normal pressure, and reacting for 1-12 hours at the temperature of 0-60 ℃ under stirring; and after the reaction is finished, filtering under reduced pressure, concentrating and crystallizing the filtrate, washing with a nonpolar solvent, filtering, and drying to obtain the sodium salt of the sodium ion battery electrolyte. The method has the advantages of mild reaction conditions, simple and convenient process operation, almost quantitative reaction and high reaction efficiency; has the advantages of high yield and high quality; meanwhile, the by-product lithium fluoride can be simply purified to obtain an electronic-grade lithium fluoride product, and the method can be applied to the field of lithium ion batteries and can improve the utilization rate of raw materials.
Description
Technical Field
The invention belongs to the technical field of electrolyte sodium salt preparation, and particularly relates to a preparation method of sodium ion battery electrolyte sodium salt.
Background
Sodium and lithium are elements of the same main group, the chemical properties are similar, the sodium ion battery has the advantages of similar energy storage principle and process technology as the lithium ion battery, and the like, and the recycling of sodium resources is more mature and cheap, so the sodium ion battery has very wide application prospect. At present, sodium salts (sodium salts for short) of electrolytes of sodium ion batteries mainly comprise sodium hexafluorophosphate, sodium tetrafluoroborate, sodium bifluorosulfonimide and the like. The preparation method is basically the same as the lithium ion battery electrolyte lithium salt (lithium salt for short), and the difference is that the lithium source of the synthetic raw material is replaced by the sodium source. For example, the synthesis method of sodium hexafluorophosphate adopts phosphorus pentafluoride and sodium fluoride to react under anhydrous hydrofluoric acid, and the solid sodium hexafluorophosphate product is obtained after crystallization and drying. For example, the synthesis method of the sodium bis (fluorosulfonyl) imide comprises the steps of carrying out neutralization reaction on the sodium bis (fluorosulfonyl) imide and alkaline sodium salt such as sodium carbonate and sodium hydroxide, and then carrying out dehydration, purification and the like to obtain a sodium bis (fluorosulfonyl) imide solid product. Although the sodium salt can use a mature lithium salt production technology for reference and even share the same production line with the lithium salt, the sodium salt obtained has more impurities due to the solubility difference between the sodium salt and the lithium salt, trace metal ions, acidity and the like are easy to exceed the standard, the consistency of the product quality is poor, and the large-scale application of the sodium salt in a sodium ion battery system is limited.
Disclosure of Invention
The invention aims to provide a preparation method of sodium salt of sodium ion battery electrolyte, which is mild in reaction, simple in process, high in product quality and good in stability and aims to solve the problems that the solubility difference between sodium salt and lithium salt in the prior art causes more impurities in sodium salt obtained by applying a mature lithium salt production technology for reference, trace metal ions, acidity and the like are easy to exceed standards, the consistency of product quality is poor, and the large-scale application of the sodium salt in a sodium ion battery system is limited.
In order to achieve the purpose and achieve the technical effect, the invention adopts the following technical scheme:
a preparation method of sodium salt of sodium ion battery electrolyte is characterized in that: dissolving lithium ion battery electrolyte lithium salt (lithium salt for short) in a first polar solvent to obtain a lithium salt solution; anhydrous sodium fluoride, 15-crown-5 and a second polar solvent are added into a reaction vessel; adding a lithium salt solution into a reaction container under normal pressure, and reacting for 1-12 hours at the temperature of 0-60 ℃ under stirring;
after the reaction is finished, filtering under reduced pressure to obtain a first filter cake, and concentrating, crystallizing, washing with a nonpolar solvent, filtering and drying the filtrate to obtain sodium ion battery electrolyte sodium salt;
the lithium ion battery electrolyte lithium salt is selected from one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethyl) sulfonyl imide, lithium trifluoromethanesulfonate, lithium bis (oxalato) borate, lithium difluoro (oxalato) phosphate and lithium tetrafluoro (oxalato) phosphate;
the sodium ion battery electrolyte sodium salt is sodium hexafluorophosphate, sodium tetrafluoroborate, sodium bifluorosulfonylimide, sodium bis (trifluoromethyl) sulfonylimide, sodium trifluoromethanesulfonate, sodium bisoxalate, sodium bifluorodioxalato phosphate and sodium tetrafluorooxalato phosphate corresponding to lithium ion battery electrolyte lithium salt.
Further, when the lithium ion battery electrolyte lithium salt is one of lithium hexafluorophosphate, lithium difluorooxalato borate, lithium difluorobis-oxalato phosphate and lithium tetrafluorooxalato phosphate, the first polar solvent and the second polar solvent are non-aqueous organic solvents; when the lithium ion battery electrolyte lithium salt is one of lithium tetrafluoroborate, lithium bifluorosulfonimide, lithium bis (trifluoromethyl) sulfimide, lithium trifluoromethanesulfonate and lithium bis (oxalato) borate, the first polar solvent and the second polar solvent further comprise water.
Further, the non-aqueous organic solvent is selected from one or a mixture of methanol, ethanol, n-propanol, isopropanol, butanol, acetonitrile, propionitrile, methyl acetate, ethyl acetate, propyl acetate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, acetone, methyl ethyl ketone, 1, 4-dioxane, 1, 4-butyrolactone, tetrahydrofuran, ethylene glycol dimethyl ether, dimethyl sulfoxide, and dimethylformamide.
Further, the total amount of the first polar solvent and the second polar solvent is the minimum standard which can fully dissolve sodium salt of the sodium-ion battery electrolyte obtained by the reaction.
Further, the purity of the anhydrous sodium fluoride is electronic grade; the molar ratio of the anhydrous sodium fluoride to the lithium ion battery electrolyte lithium salt is (1-1.5) to 1; preferably (1-1.2) to 1; more preferably (1-1.1): 1.
Further, the addition amount of the 15-crown ether-5 is 0.01 to 1 mass percent of the anhydrous sodium fluoride; preferably 0.1 to 1 percent; more preferably 0.1% to 0.5%.
Further, the lithium salt dissolving solution is added dropwise or at a time, and is preferably added dropwise in view of the progress of the reaction.
Further, the nonpolar solvent is one or more selected from benzene, toluene, chlorobenzene, n-hexane, cyclohexane, n-heptane, n-octane, dichloromethane, 1, 2-dichloroethane, 1, 2-trichloroethane, 1, 2-tetrachloroethane, and petroleum ether.
Further, the first filter cake is purified in the following manner: drying the first filter cake, removing the first polar solvent and the second polar solvent remained on the first filter cake, stirring and washing for 0.5-1 hour at room temperature by using 1-3 times of pure water, and removing sodium fluoride, lithium ion battery electrolyte lithium salt and other soluble impurities; and filtering to obtain a second filter cake, leaching with pure water for several times, and drying in vacuum to obtain the lithium fluoride.
According to the technical scheme provided by the invention, anhydrous sodium fluoride and lithium ion battery electrolyte lithium salt react in a contact manner in a polar solvent to generate insoluble solid lithium fluoride and sodium ion battery electrolyte sodium salt. 15-crown-5 (CAS number: 33100-27-5) as phase transfer catalyst can effectively complex sodium positive ion (Na) in anhydrous sodium fluoride + ) So that anhydrous sodium fluorideMiddle fluorine anion (F) - ) Exposed in the second polar solvent and/or the first polar solvent, and lithium positive ions (Li) in the lithium salt solution + ) The rapid combination generates insoluble and stable lithium fluoride crystal, and the reaction is more thorough. Meanwhile, in the technical scheme of the invention, the adopted lithium ion battery electrolyte lithium salt is a mature industrial product in the industry, has high quality specification meeting the industrial standard of the existing lithium ion battery, reacts with anhydrous sodium fluoride to obtain the corresponding sodium salt (sodium ion battery electrolyte sodium salt), has few impurities, is easy to purify and has high purity, and can fully meet the application standard of the sodium ion battery.
Compared with the prior art, the invention has the following beneficial effects: the reaction condition is mild, the process operation is simple and convenient, the quantitative reaction can be almost realized, and the reaction efficiency is high; has the advantages of high yield and high quality; meanwhile, the by-product lithium fluoride can be simply purified to obtain an electronic-grade lithium fluoride product, and the electronic-grade lithium fluoride product can be applied to the field of lithium ion batteries and has high raw material utilization rate.
Detailed Description
The present invention will be described in further detail with reference to specific examples, so that the advantages of the present invention will be more apparent. It should be understood that the description is intended for purposes of illustration only and is not intended to limit the scope of the present disclosure. The experimental procedures, in which specific conditions are not specified, in the following examples are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
In the following examples, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorosulfonimide, lithium bis (trifluoromethyl) sulfonimide, lithium trifluoromethanesulfonate, lithium bis (oxalato) borate, lithium difluorooxalato borate, lithium difluorobis (oxalato) phosphate, and lithium tetrafluorooxalato phosphate are all qualified lithium salt products that meet the current standards in the industry or the market, and have high-quality specifications that meet the current standards in the lithium ion battery industry.
In the following examples, reagents such as dimethyl carbonate, anhydrous sodium fluoride, 15-crown-5, methylene chloride and the like were commercially available.
Example 1
A preparation method of sodium hexafluorophosphate comprises the steps of adding 152g (1 mol) of lithium hexafluorophosphate into dimethyl carbonate with the mass being 2 times that of the lithium hexafluorophosphate under the nitrogen atmosphere, and stirring for dissolving; 42g (1 mol) of anhydrous sodium fluoride is added into a three-neck flask, then 0.21g of 15-crown-5 (phase transfer catalyst) and 100g of dimethyl carbonate are added into the three-neck flask, the temperature is controlled to be 0-10 ℃, dimethyl carbonate solution of lithium hexafluorophosphate is dropwise added into the three-neck flask under stirring, white turbidity appears after dropwise addition, and after 1 hour, the stirring reaction is continued for 1 hour and is stopped.
And filtering the reaction solution under nitrogen atmosphere to obtain a first filter cake and a clear filtrate, concentrating the clear filtrate under reduced pressure until more crystals appear, adding 300g of dichloromethane into the filtrate, stirring and washing the mixture, filtering the mixture, and drying the mixture in vacuum to obtain 160g of a sodium hexafluorophosphate product with the yield of 95.2%. The lithium ion residue is 4.6ppm and the other metal ion residues are less than 1ppm through ICP spectral analysis. Titration was carried out at 4 ℃ under ice water using 0.01mol/L aqueous potassium hydroxide solution, and the acidity was calculated as HF and the acid value was 13.8ppm.
And drying the first filter cake at 65 ℃ under reduced pressure for 2 hours, adding the first filter cake into 80g of pure water, stirring for 0.5 hour, filtering to obtain a second filter cake, leaching the second filter cake twice with the pure water, drying, and weighing 24g to obtain the lithium fluoride, wherein the recovery rate is 92.3%. The quality of the lithium fluoride battery meets the standard requirement of the battery-grade lithium fluoride industry through detection.
Example 2
A preparation method of sodium bis (fluorosulfonyl) imide comprises the steps of adding 187g (1 mol) of lithium bis (fluorosulfonyl) imide into 3 times of methanol in a nitrogen atmosphere, and stirring to dissolve the lithium bis (fluorosulfonyl) imide; adding 46g (1.1 mol) of sodium fluoride into a three-neck flask, adding 0.05g of 15-crown ether-5 (phase transfer catalyst) and 100g of methanol into the three-neck flask, controlling the temperature to be 15-25 ℃, dropwise adding a methanol solution of lithium bis (fluorosulfonyl) imide into the three-neck flask under stirring, wherein the dropwise adding is white turbid, and after 3 hours, continuously stirring for reacting for 2 hours and stopping.
And filtering the reaction liquid under nitrogen atmosphere to obtain a first filter cake and a clear filtrate, concentrating the clear filtrate under reduced pressure until more crystals appear, adding 200g of toluene into the filtrate, stirring and washing, filtering, and drying in vacuum to obtain 191g of the sodium bis (fluorosulfonyl) imide product, wherein the yield is 94.1%. The residual lithium ions are 11ppm and the residual other metal ions are less than 5ppm through ICP spectral analysis. Titration was carried out with a 0.01mol/L aqueous potassium hydroxide solution, and the acidity was found to be 22ppm in terms of HF.
And drying the first filter cake at 40 ℃ under reduced pressure for 1 hour, adding the first filter cake into 100g of pure water, stirring for 1 hour, filtering to obtain a second filter cake, leaching the second filter cake twice with the pure water, drying, and weighing 23g to obtain the lithium fluoride, wherein the recovery rate is 88.5%. The quality of the product meets the standard requirement of battery-grade lithium fluoride industry through detection.
Example 3
A method for preparing bis (trifluoromethyl) sulfimide sodium, which is similar to the operation method of lithium bis (trifluoromethyl) sulfimide in example 2, from lithium bis (trifluoromethyl) sulfimide and sodium fluoride.
Example 4
A preparation method of sodium trifluoromethanesulfonate, which is the same as the operation method of the lithium bis (fluorosulfonyl) imide in example 2, and the sodium trifluoromethanesulfonate is prepared from lithium trifluoromethanesulfonate and sodium fluoride.
Example 5
A preparation method of sodium bisoxalateborate comprises the steps of adding 291g (1.5 mol) of lithium bisoxalateborate into dimethylformamide with the mass being 5 times that of the lithium bisoxalateborate in a nitrogen atmosphere, and stirring for dissolving; adding 66g (1.57 mol) of sodium fluoride into a three-neck flask, then adding 0.3g of 15-crown ether-5 (phase transfer catalyst) and 200g of dimethylformamide into the three-neck flask, controlling the temperature to be 50-60 ℃, dropwise adding an acetonitrile dissolving solution of lithium bis (oxalato) borate while stirring, wherein the solution is white and turbid after dropwise adding, and after 5 hours, continuously stirring and reacting for 3 hours and stopping.
And filtering the reaction liquid to obtain a first filter cake and a clear filtrate, concentrating the clear filtrate under reduced pressure until more crystals appear, adding 500g1, 2-dichloroethane, stirring, washing, filtering, and drying in vacuum to obtain 287g of the sodium bisoxalateproduct with the yield of 91.1%. The residual lithium ions are 13ppm and the residual other metal ions are less than 10ppm by ICP spectral analysis. The titration is carried out by gamma-butyrolactone titration with anhydrous triethylamine, neutral red-methylene blue is used as indicator, acidity is calculated by HF, and acid value is 32ppm.
And drying the first filter cake at 90 ℃ under reduced pressure for 1 hour, adding the first filter cake into 150g of pure water, stirring for 2 hours, filtering to obtain a second filter cake, leaching the second filter cake once with the pure water, drying, and weighing 34g to obtain the lithium fluoride, wherein the recovery rate is 87.2%. The quality of the product meets the standard requirement of battery-grade lithium fluoride industry through detection.
Example 6
288g (2 mol) of lithium difluoro-oxalato-borate is added into 3 times of acetonitrile by mass under the nitrogen atmosphere, and stirred to be dissolved clearly; adding 92g (2.2 mol) of sodium fluoride into a three-neck flask, then adding 0.092g of 15-crown-5 (phase transfer catalyst) and 150g of acetonitrile into the three-neck flask, controlling the temperature to be 30-35 ℃, dropwise adding an acetonitrile dissolving solution of lithium difluorooxalate borate into the three-neck flask under stirring, wherein the solution is white and turbid after dropwise adding, and continuing to stir for 1.5 hours and stop the reaction after dropwise adding is finished after 4 hours.
And filtering the reaction liquid to obtain a first filter cake and a clear filtrate, concentrating the clear filtrate under reduced pressure until more crystals appear, adding 350g of cyclohexane into the filtrate, stirring and washing the mixture, filtering the mixture, and drying the mixture in vacuum to obtain 295g of sodium difluorooxalate product with the yield of 92.2%. The lithium ion residue is 4.6ppm and other metal ion residues are less than 10ppm through ICP spectral analyzer detection. The titration is carried out by gamma-butyrolactone titration with anhydrous triethylamine, neutral red-methylene blue is used as indicator, acidity is calculated by HF, and acid value is 28ppm.
And drying the first filter cake at 50 ℃ under reduced pressure for 1 hour, adding the first filter cake into 100g of pure water, stirring for 1 hour, filtering to obtain a second filter cake, leaching the second filter cake once with pure water, drying, and weighing 46g to obtain the lithium fluoride, wherein the recovery rate is 88.5%. The quality of the product meets the standard requirement of battery-grade lithium fluoride industry through detection.
Example 7
A preparation method of sodium difluorobis (oxalate) phosphate comprises the steps of adding 252g (1 mol) of lithium difluorobis (oxalate) phosphate into 2 times of glycol dimethyl ether in a nitrogen atmosphere, and stirring for dissolving; 42g (1 mol) of sodium fluoride is added into a three-neck flask, then 0.15g of 15-crown ether-5 (phase transfer catalyst) and 160g of ethylene glycol dimethyl ether are added into the three-neck flask, the temperature is controlled to be 25-32 ℃, ethylene glycol dimethyl ether solution of lithium difluorobis (oxalato) phosphate is dropwise added into the three-neck flask under stirring, white turbidity appears when the dropwise addition is finished after 2.5 hours, and the stirring reaction is continued for 1.5 hours and is stopped.
And filtering the reaction liquid to obtain a first filter cake and a clear filtrate, concentrating the clear filtrate under reduced pressure until more crystals appear, adding 350g of cyclohexane into the filtrate, stirring and washing the mixture, filtering the mixture, and drying the mixture in vacuum to obtain 295g of sodium difluorooxalate product with the yield of 92.2%. The lithium ion residue is 4.6ppm and other metal ion residues are less than 10ppm through ICP spectral analyzer detection.
The acid value is 69ppm calculated by HF and neutral red-methylene blue is used as indicator by gamma-butyrolactone titration of anhydrous triethylamine.
And drying the first filter cake at 50 ℃ under reduced pressure for 1 hour, adding the first filter cake into 100g of pure water, stirring for 1 hour, filtering to obtain a second filter cake, rinsing the second filter cake once with pure water, drying, and weighing 46g to obtain the lithium fluoride, wherein the recovery rate is 88.5%. The quality of the product meets the standard requirement of battery-grade lithium fluoride industry through detection.
Example 8
A method for preparing sodium tetrafluoro oxalate phosphate, which was prepared from lithium tetrafluoro oxalate phosphate and sodium fluoride by the same method as that used in example 5.
Example 9
A preparation method of sodium tetrafluoroborate is characterized in that 94g (1 mol) of lithium tetrafluoroborate and 46g (1.1 mol) of sodium fluoride are added into a three-neck flask, then 300g of pure water and 0.05g of 15-crown-5 (phase transfer catalyst) are added, and the temperature is controlled between 10 ℃ and 20 ℃ to stir and react for 2 hours.
And filtering to obtain a first filter cake after the reaction is finished, and concentrating the filtrate under reduced pressure until more crystals appear. And (3) cooling, filtering, leaching with 200g of petroleum ether for three times, and drying at 65-70 ℃ under reduced pressure for 12 hours to obtain 89g of sodium tetrafluoroborate with the yield of 80.1%. The lithium ion residue is 6.8ppm and the other metal ion residues are less than 5ppm by ICP spectral analysis. Titration was carried out with a 0.01mol/L aqueous potassium hydroxide solution, and the acidity was measured in terms of HF, and the acid value was 9.6ppm.
And directly leaching the first filter cake twice with pure water, drying and weighing 24g to obtain the lithium fluoride, wherein the recovery rate is 92.3%. The quality of the product meets the standard requirement of battery-grade lithium fluoride industry through detection.
It will be appreciated that various alterations and modifications of the invention will occur to those skilled in the art upon reading the above teachings, and that such equivalents are intended to fall within the scope of the invention as defined by the appended claims.
Claims (9)
1. A preparation method of sodium salt of sodium ion battery electrolyte is characterized in that: dissolving lithium ion battery electrolyte lithium salt in a first polar solvent to obtain a lithium salt solution; anhydrous sodium fluoride, 15-crown-5 and a second polar solvent are added into a reaction vessel; adding a lithium salt solution into a reaction container under normal pressure, and reacting for 1-12 hours at the temperature of 0-60 ℃ under stirring;
after the reaction is finished, filtering under reduced pressure to obtain a first filter cake, and concentrating, crystallizing, washing with a nonpolar solvent, filtering and drying the filtrate to obtain sodium salt of the sodium ion battery electrolyte;
the lithium ion battery electrolyte lithium salt is selected from one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethyl) sulfonyl imide, lithium trifluoromethanesulfonate, lithium bis (oxalato) borate, lithium difluoro (oxalato) phosphate and lithium tetrafluoro (oxalato) phosphate;
the sodium ion battery electrolyte sodium salt is sodium hexafluorophosphate, sodium tetrafluoroborate, sodium bifluorosulfonylimide, sodium bis (trifluoromethyl) sulfonylimide, sodium trifluoromethanesulfonate, sodium bisoxalato, sodium bifluoroxalato, sodium bifluorodioxalato and sodium tetrafluorooxalato which correspond to lithium ion battery electrolyte lithium salt.
2. The method for preparing sodium salt of sodium-ion battery electrolyte according to claim 1, characterized in that: when the lithium ion battery electrolyte lithium salt is one of lithium hexafluorophosphate, lithium difluorooxalato borate, lithium difluorobis (oxalato) phosphate and lithium tetrafluorooxalato phosphate, the first polar solvent and the second polar solvent are non-aqueous organic solvents; when the lithium ion battery electrolyte lithium salt is one of lithium tetrafluoroborate, lithium bifluorosulfonimide, lithium bis (trifluoromethyl) sulfimide, lithium trifluoromethanesulfonate and lithium bis (oxalato) borate, the first polar solvent and the second polar solvent further comprise water.
3. The method for preparing sodium salt of sodium-ion battery electrolyte according to claim 2, characterized in that: the non-aqueous organic solvent is selected from one or a mixture of methanol, ethanol, n-propanol, isopropanol, butanol, acetonitrile, propionitrile, methyl acetate, ethyl acetate, propyl acetate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, acetone, methyl ethyl ketone, 1, 4-dioxane, 1, 4-butyrolactone, tetrahydrofuran, ethylene glycol dimethyl ether, dimethyl sulfoxide and dimethylformamide.
4. The method for preparing sodium salt of sodium-ion battery electrolyte according to claim 3, wherein: the total amount of the first polar solvent and the second polar solvent is the lowest standard which can fully dissolve sodium salt of the sodium-ion battery electrolyte obtained by reaction.
5. The method for preparing sodium salt of sodium-ion battery electrolyte according to claim 1, wherein: the purity of the anhydrous sodium fluoride is electronic grade; the molar ratio of the anhydrous sodium fluoride to the lithium ion battery electrolyte lithium salt is (1-1.5) to 1.
6. The method for preparing sodium salt of sodium-ion battery electrolyte according to claim 1, characterized in that: the addition amount of the 15-crown ether-5 is 0.01-1% of the mass multiple of the anhydrous sodium fluoride.
7. The method for preparing sodium salt of sodium-ion battery electrolyte according to claim 1, wherein: the lithium salt dissolving solution is added dropwise or added at one time.
8. The method for preparing sodium salt of sodium-ion battery electrolyte according to claim 1, characterized in that: the nonpolar solvent is selected from one or more of benzene, toluene, chlorobenzene, n-hexane, cyclohexane, n-heptane, n-octane, dichloromethane, 1, 2-dichloroethane, 1, 2-trichloroethane, 1, 2-tetrachloroethane and petroleum ether.
9. The method for preparing sodium salt of sodium-ion battery electrolyte according to claim 1, wherein: and the first filter cake is purified in the following mode: drying the first filter cake, removing the first polar solvent and the second polar solvent remained on the first filter cake, stirring and washing for 0.5-1 hour at room temperature by using 1-3 times of pure water, and removing sodium fluoride, lithium ion battery electrolyte lithium salt and other soluble impurities; and filtering to obtain a second filter cake, leaching with pure water for several times, and drying in vacuum to obtain the lithium fluoride.
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| CN115092944A (en) * | 2022-06-29 | 2022-09-23 | 张家港博威新能源材料研究所有限公司 | Synthesis method of hexafluorophosphate |
| CN114988437A (en) * | 2022-08-04 | 2022-09-02 | 江苏蓝固新能源科技有限公司 | Preparation method of hexafluorophosphate electrolyte solution |
| CN115477308A (en) * | 2022-08-28 | 2022-12-16 | 兰州理工大学 | Method for preparing sodium tetrafluoroborate at normal temperature by one-step method |
| CN115304629A (en) * | 2022-10-09 | 2022-11-08 | 江苏国泰超威新材料有限公司 | Preparation method of sodium difluorooxalate |
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