CN117430094A - Preparation method of high-purity lithium bis (fluorosulfonyl) imide liquid salt - Google Patents
Preparation method of high-purity lithium bis (fluorosulfonyl) imide liquid salt Download PDFInfo
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- lithium
- difluoro
- imide
- salt
- fluorosulfonyl
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- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000003839 salts Chemical class 0.000 title claims abstract description 15
- 239000007788 liquid Substances 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 21
- -1 difluoro sulfonimide Chemical compound 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000012043 crude product Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- 239000002516 radical scavenger Substances 0.000 claims abstract description 7
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 4
- 125000005587 carbonate group Chemical group 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 3
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000003660 carbonate based solvent Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 3
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
-
- 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
-
- 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
Abstract
The invention relates to the field of organic chemistry, and provides a preparation method of high-purity lithium bis (fluorosulfonyl) imide liquid salt, which comprises the following steps: mixing and reacting the difluoro-sulfonyl imide with lithium fluoride, and then carrying out first filtering treatment to obtain a difluoro-sulfonyl imide lithium salt crude product; dissolving the crude product of the lithium difluorosulfimide in a benign solvent, adding an acid scavenger for treatment, and performing a second filtration treatment to obtain the lithium difluorosulfimide liquid salt; wherein the benign solvent is a carbonate solvent; in the invention, the difluoro sulfonimide is used as a raw material and a reaction solvent, and reacts with lithium fluoride at a certain temperature to generate difluoro sulfonimide lithium salt, after the reaction is finished, the difluoro sulfonimide lithium salt crude product can be obtained through first filtering treatment, and the filtrate obtained through the first filtering treatment of the reaction liquid is unreacted difluoro sulfonimide and can be reused; the preparation method has the advantages of less three wastes, economy, environmental protection, simple process, high yield and good product quality, and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of organic chemistry, in particular to a preparation method of high-purity lithium bis (fluorosulfonyl) imide liquid salt.
Background
The lithium ion battery is an important secondary battery, and has been widely used in the aspects of modern production and life due to the characteristics of high working voltage, small volume, light weight, high energy, no memory effect, no pollution, small self-discharge, long cycle life and the like. Lithium bis-fluorosulfonimide (LiLSI) with conventional electrolyte salt LiPF 6 Compared with the prior art, the polymer has better conductivity, higher electrochemical and thermal stability and hydrolysis resistance. The addition of LiFSI can greatly improve the charge and discharge times of the battery, and can ensure that electrode materials with extremely strong activity such as a high-nickel positive electrode, a high-voltage positive electrode and the like are kept stable, thereby prolonging the service life of the battery, improving the flame retardant property of electrolyte and improving the safety.
Most LiFeSI is synthesized by synthesizing dichloro-sulfonyl-imide (HClSI) and then reacting with MFn to prepare the corresponding salt intermediate of metal or organic alkali difluoro-sulfonyl-imide, and then reacting with LiOH and Li 2 CO 3 The disadvantages of these methods are that it is difficult to complete the exchange reaction after it reaches an equilibrium, and that the unreacted intermediate MSFI is difficult to completely separate from LiSFI, resulting in a high quality product.
With purified potassium bis-fluorosulfonyl imide (KFSI) and LiClO 4 、LiBF 4 Lithium bisoxalato borate, liPF 6 The lithium salt is subjected to metal exchange to prepare LiFeSI, potassium ions in the product are often very high, which affects practical application, in particular LiClO 4 And KClO produced 4 There is a certain explosion risk.
US8377406 discloses a method for preparing LiFSI by directly reacting bis-fluorosulfonyl imide (HFSI) with lithium carbonate in an aqueous solution, but the method has obvious defects that HFSI is severely exothermic when dissolved in water, so that HFSI is decomposed, and the method for preparing the HFSI aqueous solution at ultralow temperature (-78 ℃) is adopted to solve the technical problem of violent exothermic when HFSI is dissolved in water, but the method increases a large amount of energy consumption, and more importantly, liFSI has very good water solubility and very low extraction efficiency, so that the method is not suitable for industrial production.
Therefore, there is a need for a preparation method that is simple in process and can improve the yield and quality of lithium bis-fluorosulfonyl imide.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and provides a preparation method of high-purity lithium bis (fluorosulfonyl) imide liquid salt.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the high-purity lithium bis (fluorosulfonyl) imide liquid salt comprises the following steps: mixing and reacting the difluoro-sulfonyl imide with lithium fluoride, and then carrying out first filtering treatment to obtain a difluoro-sulfonyl imide lithium salt crude product; dissolving the crude product of the lithium difluorosulfimide in a benign solvent, adding an acid scavenger for treatment, and performing a second filtration treatment to obtain lithium difluorosulfimide liquid salt;
wherein the benign solvent is a carbonate solvent;
wherein the acid scavenger is an alkaline reagent;
wherein, the equation of the reaction is:
preferably, the mass ratio of the bis-fluorosulfonyl imide to the lithium fluoride is (15-50): 1.
preferably, the temperature of the reaction is 80 ℃ to 150 ℃; the reaction time is 1h-8h.
Preferably, the carbonate-based solvent comprises: at least one of dimethyl carbonate, ethylmethyl carbonate or diethyl carbonate.
Preferably, the mass ratio of the benign solvent to the crude lithium bis (fluorosulfonyl) imide salt is (1-5): 1.
preferably, the acid scavenger comprises: at least one of an inorganic base or an organic base.
More preferably, the inorganic base comprises: at least one of lithium hydride, calcium hydride, or ammonia; the organic base includes: at least one of butyllithium, triethylamine, tripropylamine, tributylamine, or diisopropylethylamine.
Preferably, the materials used in the second filtering treatment include: at least one of vinylidene fluoride resin film, polytetrafluoroethylene folding filter element or ceramic film.
More preferably, the pore size of the material is 1nm-1000nm.
Compared with the prior art, the invention has the following technical effects:
in the invention, the difluoro sulfonimide is used as a raw material and a reaction solvent, and reacts with lithium fluoride at a certain temperature to generate difluoro sulfonimide lithium salt, after the reaction is finished, the difluoro sulfonimide lithium salt crude product can be obtained through first filtering treatment, and the filtrate obtained through the first filtering treatment of the reaction liquid is unreacted difluoro sulfonimide and can be reused; the hydrogen fluoride overflowed in the reaction can react with lithium carbonate to prepare lithium fluoride, so that the recycling of the byproducts is realized; the preparation method has the advantages of less three wastes, economy, environmental protection, simple process, high yield and good product quality, and is suitable for industrial production.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention will be further illustrated, but is not limited, by the following examples.
Example 1
The embodiment provides a preparation method of high-purity lithium bis (fluorosulfonyl) imide liquid salt, which comprises the following steps: 750g of difluoro-sulfonyl imide (HFSI) and 30g of lithium fluoride (LiF) are placed in a reaction kettle to be mixed and reacted for 5 hours at the temperature of 110 ℃, and Hydrogen Fluoride (HF) tail gas generated in the reaction is introduced into a reaction kettle through a PFA resin tube to be filled with sufficient Li 2 CO 3 And deionized water in a PFA reaction kettle; after the reaction is finished, the reaction kettle is cooled to room temperature, and is subjected to first filtration treatment, so that 540.2g of filtrate and 215.9g of crude product of lithium bis (fluorosulfonyl) imide salt (LiFSI) are obtained, and the acid value (HF meter) is 476ppm; when the pH value of the PFA reaction kettle system is 6-7, filtering and drying materials in the PFA reaction kettle to obtain recovered LiF;
490g of methyl ethyl carbonate (EMC) with the water content less than 5ppm is placed in a reaction kettle, 210g of LiSI crude product and 0.04g of lithium hydride (LiH) are added, and after stirring for 1h at room temperature, a ceramic membrane with the pore diameter of 50nm is adopted for carrying out secondary filtration treatment, thus obtaining LiSI solution; the concentration of LiSSI solution was detected to be 29.8%, the acid value (HF) was 12ppm, the water was 8ppm, the chloride ion concentration was less than 1ppm, the fluoride ion concentration was 5ppm, the sulfate ion concentration was less than 1ppm, the sodium concentration was 2ppm, and the potassium concentration was 1ppm.
Example 2
The embodiment provides another preparation method of high-purity lithium bis (fluorosulfonyl) imide liquid salt, which comprises the following steps: 520g of HFSI, 230g of HFSI and 30g of LiF in the filtrate of example 1 are placed in a reaction kettle to be mixed and reacted for 4 hours at 120 ℃, and HF tail gas generated in the reaction is introduced into a reactor filled with sufficient Li through a PFA resin tube 2 CO 3 And deionized water in a PFA reaction kettle; after the reaction is finished, the reaction kettle is cooled to room temperature, and is subjected to first filtering treatment to obtain 538.4g of filtrate and 217.9g of LiFSI crude product, wherein the acid value (HF meter) is 506ppm;
490g of dimethyl carbonate (DMC) with the water content less than 5ppm is placed in a reaction kettle, 210g of LiFSI crude product and 0.51g of triethylamine are added, and after stirring is carried out for 1h at room temperature, a vinylidene fluoride resin film with the aperture of 450nm is adopted for carrying out secondary filtration treatment, thus obtaining a LiFSI solution; the concentration of LiSSI solution was detected to be 30.0%, the acid value (HF) was 9ppm, the water was 11ppm, the chloride ion concentration was less than 1ppm, the fluoride ion concentration was 12ppm, the sulfate ion concentration was less than 1ppm, the sodium concentration was 1ppm, and the potassium concentration was 1ppm.
Example 3
The embodiment provides another preparation method of high-purity lithium bis (fluorosulfonyl) imide liquid salt, which comprises the following steps: 750g HFSI and 30g recovered LiF described in the example were mixed in a reaction vessel and reacted at 120℃for 4 hours, the HF tail gas produced in the reaction was introduced into a reactor containing a sufficient amount of Li via a PFA resin tube 2 CO 3 And deionized water in a PFA reaction kettle; after the reaction is finished, the reaction kettle is cooled to room temperature, and is subjected to first filtering treatment, 539.0g of filtrate and 216.1g of LiFSI crude product are obtained, and the acid value (HF meter) is 480ppm;
490g of diethyl carbonate (DEC) having a water content of less than 5ppm are placed in a reaction vessel and 210g of crude LiFSI and 0.11g of calcium hydride (CaH 2 ) Stirring for 1h at room temperature, and then adopting a polytetrafluoroethylene folding filter element with the aperture of 200nm to carry out secondary filtration treatment to obtain a LiFSI solution; the concentration of LiSSI solution was detected to be 29.8%, the acid value (HF) was 5ppm, the moisture was 15ppm, the chloride ion concentration was less than 1ppm, the fluoride ion concentration was 3ppm, the sulfate ion concentration was less than 1ppm, the sodium concentration was 3ppm, and the potassium concentration was 1ppm.
In summary, the difluoro sulfonimide is used as a raw material and a reaction solvent, and reacts with lithium fluoride at a certain temperature to generate difluoro sulfonimide lithium salt, after the reaction is finished, the difluoro sulfonimide lithium salt crude product can be obtained through first filtering treatment, and the filtrate obtained through the first filtering treatment of the reaction liquid is unreacted difluoro sulfonimide and can be reused; the hydrogen fluoride overflowed in the reaction can react with lithium carbonate to prepare lithium fluoride, so that the recycling of the byproducts is realized; the preparation method has the advantages of less three wastes, economy, environmental protection, simple process, high yield and good product quality, and is suitable for industrial production.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, and it will be appreciated by those skilled in the art that equivalent substitutions and obvious variations may be made using the teachings of the present invention, which are intended to be included within the scope of the invention.
Claims (9)
1. The preparation method of the high-purity lithium bis (fluorosulfonyl) imide liquid salt is characterized by comprising the following steps: mixing and reacting the difluoro-sulfonyl imide with lithium fluoride, and then carrying out first filtering treatment to obtain a difluoro-sulfonyl imide lithium salt crude product; dissolving the crude product of the lithium difluorosulfimide in a benign solvent, adding an acid scavenger for treatment, and performing a second filtration treatment to obtain lithium difluorosulfimide liquid salt;
wherein the benign solvent is a carbonate solvent;
wherein the acid scavenger is an alkaline reagent.
2. The method according to claim 1, wherein the mass ratio of the bis-fluorosulfonyl imide to the lithium fluoride is (15-50): 1.
3. the method of claim 1, wherein the temperature of the reaction is 80 ℃ to 150 ℃; the reaction time is 1h-8h.
4. The method according to claim 1, wherein the carbonate-based solvent comprises: at least one of dimethyl carbonate, ethylmethyl carbonate or diethyl carbonate.
5. The preparation method according to claim 1, wherein the mass ratio of the benign solvent to the crude lithium bis (fluorosulfonyl) imide salt is (1-5): 1.
6. the method of preparing according to claim 1, wherein the acid scavenger comprises: at least one of an inorganic base or an organic base.
7. The method according to claim 6, wherein the inorganic base comprises: at least one of lithium hydride, calcium hydride, or ammonia; the organic base includes: at least one of butyllithium, triethylamine, tripropylamine, tributylamine, or diisopropylethylamine.
8. The method according to claim 1, wherein the materials used for the second filtering treatment include: at least one of vinylidene fluoride resin film, polytetrafluoroethylene folding filter element or ceramic film.
9. The method according to claim 8, wherein the pore size of the material is 1nm to 1000nm.
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| CN202311336288.5A CN117430094A (en) | 2023-10-16 | 2023-10-16 | Preparation method of high-purity lithium bis (fluorosulfonyl) imide liquid salt |
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| CN202311336288.5A CN117430094A (en) | 2023-10-16 | 2023-10-16 | Preparation method of high-purity lithium bis (fluorosulfonyl) imide liquid salt |
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| CN117430094A true CN117430094A (en) | 2024-01-23 |
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