CN116654883A - Method for preparing lithium bis (fluorosulfonyl) imide from methylsilazane - Google Patents
Method for preparing lithium bis (fluorosulfonyl) imide from methylsilazane Download PDFInfo
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- CN116654883A CN116654883A CN202310669223.6A CN202310669223A CN116654883A CN 116654883 A CN116654883 A CN 116654883A CN 202310669223 A CN202310669223 A CN 202310669223A CN 116654883 A CN116654883 A CN 116654883A
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- resin
- imide
- fluorosulfonyl
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- lithium bis
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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 48
- 238000000034 method Methods 0.000 title claims abstract description 45
- QKDIBALFMZCURP-UHFFFAOYSA-N 1-methyl-1$l^{3}-silinane Chemical compound C[Si]1CCCCC1 QKDIBALFMZCURP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 108
- 229920005989 resin Polymers 0.000 claims abstract description 108
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 54
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003463 adsorbent Substances 0.000 claims abstract description 37
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005935 Sulfuryl fluoride Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 77
- 238000001179 sorption measurement Methods 0.000 claims description 53
- 238000003756 stirring Methods 0.000 claims description 44
- 238000005342 ion exchange Methods 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- -1 lithium bis-fluorosulfonyl imide Chemical class 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 18
- 239000012454 non-polar solvent Substances 0.000 claims description 18
- 239000002798 polar solvent Substances 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 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 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- RFHDPGSALHDJTN-UHFFFAOYSA-N 2,5-difluoro-3,6-bis(sulfanyl)terephthalic acid Chemical compound SC1=C(C(=O)O)C(=C(C(=C1F)C(=O)O)S)F RFHDPGSALHDJTN-UHFFFAOYSA-N 0.000 claims description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 8
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- FIADVASZMLCQIF-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octamethyl-1,3,5,7,2,4,6,8-tetrazatetrasilocane Chemical group C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N[Si](C)(C)N1 FIADVASZMLCQIF-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 239000003849 aromatic solvent Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical group 0.000 claims description 4
- 150000008282 halocarbons Chemical group 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- WGGNJZRNHUJNEM-UHFFFAOYSA-N 2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6-triazatrisilinane Chemical compound C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N1 WGGNJZRNHUJNEM-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- UKJACMXXELMBEE-UHFFFAOYSA-N [N].C[Si] Chemical compound [N].C[Si] UKJACMXXELMBEE-UHFFFAOYSA-N 0.000 abstract description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000072 sodium resin Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 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
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 229910010941 LiFSI Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- HSASJEUDAQEILE-UHFFFAOYSA-N 2,3-difluoroterephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C(F)=C1F HSASJEUDAQEILE-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 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
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
- C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
- C01P2006/40—Electric properties
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention relates to the technical field of lithium batteries, in particular to a method for preparing lithium bis (fluorosulfonyl) imide by methyl silazane; the invention adopts sulfuryl fluoride, methyl silicon nitrogen, alkaline lithium and resin-based diacid adsorbent as raw materials to react and synthesize the difluoro lithium sulfonyl imide, the raw materials are easy to obtain, the price is substantial, the operation is simple, and the total yield is high; the invention adopts a low-temperature method to react when adding alkaline lithium, thereby avoiding the heating operation of the final product and ensuring the quality of the product; the invention has low production cost, less byproducts and simple post-treatment, and the purity of the lithium bis (fluorosulfonyl) imide prepared by the invention is up to 99.99 percent, the yield is up to 95.96 percent, thus being suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a method for preparing lithium bis (fluorosulfonyl) imide from methyl silazane.
Background
Along with the decrease of reserves of traditional fossil energy and the increasing of atmospheric pollution, new energy automobiles with the main characteristics of energy conservation and environmental protection are generated, and lithium batteries are gradually and widely applied as energy storage devices of the new energy automobiles. The key materials of the lithium ion battery comprise: positive electrode, negative electrode, binder, separator and electrolyte. The electrolyte plays a role in transmitting charges between the anode and the cathode in the battery, is a key component of the lithium ion battery, and has significant influence on the cycle and service life of the battery, safety performance and energy. The lithium bis (fluorosulfonyl) imide (LiWSI) is a novel electrolyte lithium salt used in lithium battery electrolyte, is environment-friendly, has good safety performance, and has the basic condition of industrial application. Compared with the traditional lithium hexafluorophosphate (LiPF 6), lithium ions in LiFSI are more easily dissociated, so that the lithium hexafluorophosphate has higher conductivity; the decomposition temperature of LiFeSI is higher than 200 ℃, and the thermal stability and the safety performance are obviously better than those of LiPF6; in addition, the lithium ion battery has unique effects in improving performances such as high-temperature storage, low-temperature discharge and the like, and has excellent characteristics such as good compatibility with an electrode, so that LiFSI is an electrolyte with good prospect in the lithium ion battery.
Chinese patent CN202211740521.1: provided are a method for preparing a bis-fluorosulfonyl imide and a method for preparing a bis-fluorosulfonyl imide salt, the method for preparing the bis-fluorosulfonyl imide comprising the steps of: (1) The sulfonyl chloride reacts with NH3 to obtain dichloro sulfonyl imide, and the reaction pressure is more than or equal to 0.7MPa; (2) The dichloro-sulphonyl-imine reacts with HF to obtain difluoro-sulphonyl-imine.
Chinese patent CN202211652000.0: a preparation method of lithium bis (fluorosulfonyl) imide and a lithium ion battery are provided. The preparation method comprises the following steps: (1) Adding lithium fluoride into liquid difluoro-sulfonyl imide to react, and mixing the generated product with an organic solvent to obtain a difluoro-sulfonyl imide lithium solution; (2) And (3) reacting the lithium bis (fluorosulfonyl) imide solution with lithium carbonate, and performing solid-liquid separation on the obtained product to obtain the lithium bis (fluorosulfonyl) imide. The invention adopts the lithium carbonate acid removal process, improves the product quality and reduces the cost, and prepares the high-purity lithium bis (fluorosulfonyl) imide.
Chinese patent CN202211139496.1: the invention discloses a method for preparing lithium bis (fluorosulfonyl) imide, which belongs to the technical field of synthesis of lithium ion battery chemicals and comprises the following steps: washing the primary or secondary amine type ion exchange resin with a solvent having a moisture content of less than 10ppm until the moisture content of the discharged solvent is less than 10ppm; preparing a solution A; the solution A is circulated to the mixing device A after passing through primary amine or secondary amine type ion exchange resin, and the circulation reaction is carried out until the concentration of the SuFEx reagent in the mixing device A is not changed; forming a resin/lithium carbonate mixed bed; preparing a solution B; introducing the solution B into a resin reactor, preserving the heat of the resin reactor, discharging reaction tail gas, circulating the solution B into a mixing device B after passing through the resin reactor, and performing a cyclic reaction until no reaction tail gas is discharged from an exhaust system, thereby obtaining the solution of lithium difluorosulfimide salt in the mixing device B.
The purity of the lithium-bis-fluorosulfonyl imide lithium is very high in the lithium ion battery, and the impurity ions and the moisture content in the lithium-bis-fluorosulfonyl imide lithium are required to be controlled at ppm level. The impurity ions in the lithium bis (fluorosulfonyl) imide have metal ion impurities, are not easy to separate by adopting a common metal ion adsorbent, and need the steps of reduced pressure distillation, recrystallization and the like, thereby improving the production cost.
Disclosure of Invention
Based on the problems, the invention aims to provide a method for preparing lithium bis (fluorosulfonyl imide) by using methylsilazane, which adopts sulfuryl fluoride, methylsilazane, alkaline lithium and resin-based diacid adsorbent as raw materials to react and synthesize lithium bis (fluorosulfonyl imide), and adopts a low-temperature method to react when alkaline lithium is added, so that the heating operation of a final product is avoided, the quality of the product is ensured, and the method is suitable for industrial production.
In order to achieve the above object, the first aspect of the present invention provides a method for preparing lithium bis (fluorosulfonyl) imide from methylsilazane, comprising the following steps:
s1: weighing 10-50 parts of sulfuryl fluoride and 100-150 parts of solvent according to parts by weight, stirring and mixing, heating, and slowly adding 5-10 parts of methyl silazane for reaction;
s2: after the reaction is finished, cooling, slowly dropwise adding 15-20 parts of alkaline lithium for reaction, after the reaction is finished, adding 0.02-0.5 part of resin-based diacid adsorbent, stirring for 20-40 minutes, and then filtering to remove unreacted alkaline lithium and resin-based diacid adsorbent;
s3: and (3) evaporating and concentrating the filtrate, adding 100-150 parts of a weak polar solvent or a nonpolar solvent, separating out solid lithium bis (fluorosulfonyl) imide, and drying to obtain the lithium bis (fluorosulfonyl) imide.
Further, the methyl silazane is octamethyl cyclotetrasilazane or hexamethyldisilazane or hexamethyl cyclotrisilazane.
Further, the solvent is esters, amides or nitriles;
further, esters include ethyl acetate, butyl acetate; further amides include N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone;
further, nitriles include acetonitrile, propionitrile.
Preferably, the reaction temperature of S1 is 80-110 ℃ and the reaction time is 5-10h.
Preferably, the alkaline lithium is LiF, liOH, liHCO 3 Or Li (lithium) 2 CO 3 One or more of the following.
Preferably, the reaction temperature of the S2 is 0-20 ℃ and the reaction time is 5-10h.
Preferably, the weak polar solvent or the nonpolar solvent is halogenated hydrocarbon solvent, alkane solvent or halogenated aromatic solvent;
further, the halogenated hydrocarbon solvent comprises dichloromethane and dichloroethane;
further, the alkane solvent comprises n-hexane, cyclohexane and n-heptane;
further, the halogenated aromatic solvents include toluene, ethylbenzene, chlorobenzene.
The second aspect of the present invention provides a method for preparing a resin-based diacid adsorbent comprising:
s1: according to the mass parts, nitrogen is introduced into a closed reaction kettle, 2-5 parts of 2, 3-dimercapto malonic acid, 10-15 parts of 2, 5-difluoro-3, 6-dimercapto terephthalic acid and 100-200 parts of sodium hydroxide solution with the mass percent concentration of 5-10% are added into the kettle, stirred for 30-60min at the temperature of 30-40 ℃, and the water is removed by reduced pressure distillation;
s2: adding 1000-1500 parts of ethanol, 100-130 parts of propenyl adsorption resin and 3-6 parts of triethylamine into a stirring kettle, stirring at 60-72 ℃ for 100-150min, and filtering to obtain resin-based sodium diacid;
s3: ion exchange is carried out, and sodium ions are replaced by hydrogen ions, wherein the process conditions are as follows: adding resin base sodium diacid into an ion exchange column, wherein the adding amount is 30-60% of the volume of the ion exchange column, adding 100-200 parts of hydrochloric acid solution with the mass percent concentration of 5-10% into the ion exchange column at the flow rate of 0.5-2BV/h, distilling effluent liquid to remove ethanol, and drying to obtain the resin base diacid adsorbent.
Further, the preparation method of the propylene-based adsorption resin comprises the following steps:
according to the mass portions, introducing nitrogen into a closed reaction kettle, adding 12-15 parts of adsorption resin, 100-150 parts of acryloyl chloride and 5-10 parts of anhydrous aluminum chloride into the kettle, stirring for 10-20 hours at 40-50 ℃, filtering, and drying to obtain the allyl adsorption resin.
Further, the adsorption resin comprises one or more of styrene-divinylbenzene adsorption resin, styrene-divinylbenzene adsorption resin modified resin, polystyrene adsorption resin modified resin, polyacrylate adsorption resin and polyacrylate adsorption resin modified resin;
further, the first macroporous adsorption resin comprises nonpolar D101, LX-100B, LX-T28 and weak polar AB-8.
Reaction mechanism:
in the invention, 2, 3-dimercapto malonic acid and 2, 5-difluoro-3, 6-dimercapto terephthalic acid firstly generate sodium salt; then, the catalyst is subjected to sulfhydryl addition reaction with propenyl adsorption resin, then, sodium ions are replaced by hydrogen ions through ion exchange, and the obtained adsorbent contains malonic acid and difluoro terephthalic acid functional groups.
The technical effects are as follows:
compared with the prior art, the method for preparing the lithium bis (fluorosulfonyl) imide from the methylsilazane has the following remarkable effects:
1. the invention adopts sulfuryl fluoride, methyl silicon nitrogen, alkaline lithium and resin-based diacid adsorbent as raw materials to react and synthesize the difluoro lithium sulfonyl imide, the raw materials are easy to obtain, the price is substantial, the operation is simple, and the total yield is high;
2. the invention has low production cost, less byproducts and simple post-treatment, and is suitable for industrial production;
3. the invention adopts low temperature method reaction when adding alkaline lithium, avoids heating operation of the final product, thereby ensuring the quality of the product.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The method for preparing lithium bis (fluorosulfonyl) imide from methyl silazane comprises the following operation steps:
s1: weighing 10g of sulfuryl fluoride and 100g of solvent, stirring and mixing, heating, and slowly adding 5g of methyl silazane for reaction;
s2: after the reaction is finished, cooling, slowly dropwise adding 15g of alkaline lithium for reaction, after the reaction is finished, adding 0.02g of resin-based diacid adsorbent, stirring for 20 minutes, and then filtering to remove unreacted alkaline lithium and resin-based diacid adsorbent;
s3: and (3) evaporating and concentrating the filtrate, adding 100g of a weak polar solvent or a nonpolar solvent, separating out solid lithium bis (fluorosulfonyl) imide, and drying to obtain the lithium bis (fluorosulfonyl) imide.
The methyl silazane is octamethyl cyclotetra-silazane.
The solvent is ethyl acetate.
The reaction temperature of S1 is 80 ℃ and the reaction time is 5h.
The alkaline lithium is LiF.
The reaction temperature of the S2 is 0 ℃, and the reaction time is 5 hours.
The weak polar solvent or the nonpolar solvent is dichloromethane.
The preparation method of the resin-based diacid adsorbent comprises the following steps:
s1: introducing nitrogen into a closed reaction kettle, adding 2g of 2, 3-dimercapto malonic acid, 10g of 2, 5-difluoro-3, 6-dimercapto terephthalic acid and 100g of sodium hydroxide solution with the mass percent concentration of 5% into the kettle, stirring for 30min at 30 ℃, and distilling under reduced pressure to remove water;
s2: 1000g of ethanol, 100g of propenyl adsorption resin and 3g of triethylamine are added into a stirring kettle, stirred at 60 ℃ for 100min, and filtered to obtain resin-based sodium diacid;
s3: ion exchange is carried out, and sodium ions are replaced by hydrogen ions, wherein the process conditions are as follows: adding sodium resin-based diacid into an ion exchange column, wherein the adding amount is 30 percent of the volume of the ion exchange column, adding 100g of hydrochloric acid solution with the mass percent concentration of 5 percent into the ion exchange column at the flow rate of 0.5BV/h, distilling effluent liquid to remove ethanol, and drying to obtain the resin-based diacid adsorbent.
The preparation method of the propenyl adsorption resin comprises the following steps:
in a closed reaction kettle, introducing nitrogen, adding 12g of adsorption resin, 100g of acryloyl chloride and 5g of anhydrous aluminum chloride into the kettle, stirring for 10 hours at 40 ℃, filtering and drying to obtain the allyl adsorption resin.
The adsorption resin is nonpolar D101.
Example 2
The method for preparing lithium bis (fluorosulfonyl) imide from methyl silazane comprises the following operation steps:
s1: weighing 20g of sulfuryl fluoride and 110g of solvent, stirring and mixing, heating, and slowly adding 6g of methyl silazane for reaction;
s2: after the reaction is finished, cooling, slowly dropwise adding 16g of alkaline lithium for reaction, after the reaction is finished, adding 0.2g of resin-based diacid adsorbent, stirring for 25 minutes, and then filtering to remove unreacted alkaline lithium and resin-based diacid adsorbent;
s3: and (3) evaporating and concentrating the filtrate, adding 110g of a weak polar solvent or a nonpolar solvent, separating out solid lithium bis (fluorosulfonyl) imide, and drying to obtain the lithium bis (fluorosulfonyl) imide.
The methyl silazane is hexamethyldisilazane.
The solvent is N, N-dimethylformamide.
The reaction temperature of the S1 is 90 ℃, and the reaction time is 7h.
The alkaline lithium is LiOH.
The reaction temperature of the S2 is 5 ℃, and the reaction time is 7h.
The weak polar solvent or the nonpolar solvent is n-hexane.
The preparation method of the resin-based diacid adsorbent comprises the following steps:
s1: introducing nitrogen into a closed reaction kettle, adding 3g of 2, 3-dimercapto malonic acid, 12g of 2, 5-difluoro-3, 6-dimercapto terephthalic acid and 140g of sodium hydroxide solution with the mass percent concentration of 6% into the kettle, stirring for 40min at 35 ℃, and distilling under reduced pressure to remove water;
s2: adding 1200g of ethanol, 110g of propenyl adsorption resin and 4g of triethylamine into a stirring kettle, stirring at 65 ℃ for 110min, and filtering to obtain resin-based sodium diacid;
s3: ion exchange is carried out, and sodium ions are replaced by hydrogen ions, wherein the process conditions are as follows: adding sodium resin-based diacid into an ion exchange column, wherein the adding amount is 40 percent of the volume of the ion exchange column, adding 140g of hydrochloric acid solution with the mass percent concentration of 6 percent into the ion exchange column at the flow rate of 1BV/h, distilling effluent liquid to remove ethanol, and drying to obtain the resin-based diacid adsorbent.
The preparation method of the propenyl adsorption resin comprises the following steps:
in a closed reaction kettle, introducing nitrogen, adding 13g of adsorption resin, 110g of acryloyl chloride and 6g of anhydrous aluminum chloride into the kettle, stirring for 14h at 45 ℃, filtering and drying to obtain the allyl adsorption resin.
The adsorption resin is nonpolar LX-100B.
Example 3
The method for preparing lithium bis (fluorosulfonyl) imide from methyl silazane comprises the following operation steps:
s1: weighing 40g of sulfuryl fluoride and 140g of solvent, stirring and mixing, heating, and slowly adding 9g of methyl silazane for reaction;
s2: after the reaction is finished, cooling, slowly dropwise adding 18g of alkaline lithium for reaction, after the reaction is finished, adding 0.4g of resin-based diacid adsorbent, stirring for 35 minutes, and then filtering to remove unreacted alkaline lithium and resin-based diacid adsorbent;
s3: and (3) evaporating and concentrating the filtrate, adding 140g of a weak polar solvent or a nonpolar solvent, separating out solid lithium bis (fluorosulfonyl) imide, and drying to obtain the lithium bis (fluorosulfonyl) imide.
The methyl silazane is hexamethyldisilazane.
The solvent is acetonitrile.
The reaction temperature of S1 is 100 ℃, and the reaction time is 9h.
The alkaline lithium is LiHCO 3 。
The reaction temperature of the S2 is 15 ℃, and the reaction time is 9h.
The weak polar solvent or the nonpolar solvent is toluene.
The preparation method of the resin-based diacid adsorbent comprises the following steps:
s1: introducing nitrogen into a closed reaction kettle, adding 4g of 2, 3-dimercapto malonic acid, 14g of 2, 5-difluoro-3, 6-dimercapto terephthalic acid and 180g of sodium hydroxide solution with the mass percent concentration of 9% into the kettle, stirring for 50min at 35 ℃, and distilling under reduced pressure to remove water;
s2: adding 1400g of ethanol, 120g of propenyl adsorption resin and 5g of triethylamine into a stirring kettle, stirring at 70 ℃ for 140min, and filtering to obtain resin-based sodium diacid;
s3: ion exchange is carried out, and sodium ions are replaced by hydrogen ions, wherein the process conditions are as follows: adding sodium resin-based diacid into an ion exchange column, wherein the addition amount is 50 percent of the volume of the ion exchange column, adding 180g of hydrochloric acid solution with the mass percent concentration of 9 percent into the ion exchange column at the flow rate of 1.5BV/h, distilling effluent liquid to remove ethanol, and drying to obtain the resin-based diacid adsorbent.
The preparation method of the propenyl adsorption resin comprises the following steps:
in a closed reaction kettle, introducing nitrogen, adding 14g of adsorption resin, 140g of acryloyl chloride and 8g of anhydrous aluminum chloride into the kettle, stirring for 18h at 45 ℃, filtering and drying to obtain the allyl adsorption resin.
The adsorption resin is nonpolar LX-T28.
Example 4
The method for preparing lithium bis (fluorosulfonyl) imide from methyl silazane comprises the following operation steps:
s1: weighing 50g of sulfuryl fluoride and 150g of solvent, stirring and mixing, heating, and slowly adding 10g of methyl silazane for reaction;
s2: after the reaction is finished, cooling, slowly dropwise adding 0g of alkaline lithium for reaction, after the reaction is finished, adding 0.5g of resin-based diacid adsorbent, stirring for 40 minutes, and then filtering to remove unreacted alkaline lithium and resin-based diacid adsorbent;
s3: and (3) evaporating and concentrating the filtrate, adding 150g of a weak polar solvent or a nonpolar solvent, separating out solid lithium bis (fluorosulfonyl) imide, and drying to obtain the lithium bis (fluorosulfonyl) imide.
The methyl silazane is hexamethyl cyclotrisilazane.
The solvent is propionitrile.
The reaction temperature of S1 is 110 ℃, and the reaction time is 0h.
The alkaline lithium is Li 2 CO 3 。
The reaction temperature of the S2 is 20 ℃ and the reaction time is 10 hours.
The weak polar solvent or the nonpolar solvent is ethylbenzene.
The preparation method of the resin-based diacid adsorbent comprises the following steps:
s1: introducing nitrogen into a closed reaction kettle, adding 5g of 2, 3-dimercapto malonic acid, 15g of 2, 5-difluoro-3, 6-dimercapto terephthalic acid and 200g of 10% sodium hydroxide solution by mass percent into the kettle, stirring for 60min at 40 ℃, and distilling under reduced pressure to remove water;
s2: adding 1500g of ethanol, 30g of propenyl adsorption resin and 6g of triethylamine into a stirring kettle, stirring at 72 ℃ for 150min, and filtering to obtain resin-based sodium diacid;
s3: ion exchange is carried out, and sodium ions are replaced by hydrogen ions, wherein the process conditions are as follows: adding sodium resin-based diacid into an ion exchange column, wherein the adding amount is 60 percent of the volume of the ion exchange column, adding 200g of hydrochloric acid solution with the mass percent concentration of 10 percent into the ion exchange column at the flow rate of 2BV/h, distilling effluent liquid to remove ethanol, and drying to obtain the resin-based diacid adsorbent.
The preparation method of the propenyl adsorption resin comprises the following steps:
in a closed reaction kettle, introducing nitrogen, adding 15g of adsorption resin, 150g of acryloyl chloride and 10g of anhydrous aluminum chloride into the kettle, stirring for 20h at 50 ℃, filtering and drying to obtain the allyl adsorption resin.
The adsorption resin is weak-polarity AB-8.
Comparative example 1
The method for preparing lithium bis (fluorosulfonyl) imide from methyl silazane comprises the following operation steps:
s1: weighing 10g of sulfuryl fluoride and 100g of solvent, stirring and mixing, heating, and slowly adding 5g of methyl silazane for reaction;
s2: after the reaction is finished, cooling, slowly dropwise adding 15g of alkaline lithium for reaction, and filtering to remove unreacted alkaline lithium after the reaction is finished;
s3: and (3) evaporating and concentrating the filtrate, adding 100g of a weak polar solvent or a nonpolar solvent, separating out solid lithium bis (fluorosulfonyl) imide, and drying to obtain the lithium bis (fluorosulfonyl) imide.
The methyl silazane is octamethyl cyclotetra-silazane.
The solvent is ethyl acetate.
The reaction temperature of S1 is 80 ℃ and the reaction time is 5h.
The alkaline lithium is LiF.
The reaction temperature of the S2 is 0 ℃, and the reaction time is 5 hours.
The weak polar solvent or the nonpolar solvent is dichloromethane.
Comparative example 2
The method for preparing lithium bis (fluorosulfonyl) imide from methyl silazane comprises the following operation steps:
s1: weighing 10g of sulfuryl fluoride and 100g of solvent, stirring and mixing, heating, and slowly adding 5g of methyl silazane for reaction;
s2: after the reaction is finished, cooling, slowly dropwise adding 15g of alkaline lithium for reaction, after the reaction is finished, adding 0.02g of resin-based diacid adsorbent, stirring for 20 minutes, and then filtering to remove unreacted alkaline lithium and resin-based diacid adsorbent;
s3: and (3) evaporating and concentrating the filtrate, adding 100g of a weak polar solvent or a nonpolar solvent, separating out solid lithium bis (fluorosulfonyl) imide, and drying to obtain the lithium bis (fluorosulfonyl) imide.
The methyl silazane is octamethyl cyclotetra-silazane.
The solvent is ethyl acetate.
The reaction temperature of S1 is 80 ℃ and the reaction time is 5h.
The alkaline lithium is LiF.
The reaction temperature of the S2 is 0 ℃, and the reaction time is 5 hours.
The weak polar solvent or the nonpolar solvent is dichloromethane.
The preparation method of the resin-based diacid adsorbent comprises the following steps:
s1: introducing nitrogen into a closed reaction kettle, adding 10g of 2, 5-difluoro-3, 6-dimercapto terephthalic acid and 100g of sodium hydroxide solution with the mass percent concentration of 5% into the kettle, stirring for 30min at 30 ℃, and distilling under reduced pressure to remove water;
s2: 1000g of ethanol, 100g of propenyl adsorption resin and 3g of triethylamine are added into a stirring kettle, stirred at 60 ℃ for 100min, and filtered to obtain resin-based sodium diacid;
s3: ion exchange is carried out, and sodium ions are replaced by hydrogen ions, wherein the process conditions are as follows: adding sodium resin-based diacid into an ion exchange column, wherein the adding amount is 30 percent of the volume of the ion exchange column, adding 100g of hydrochloric acid solution with the mass percent concentration of 5 percent into the ion exchange column at the flow rate of 0.5BV/h, distilling effluent liquid to remove ethanol, and drying to obtain the resin-based diacid adsorbent.
The preparation method of the propenyl adsorption resin comprises the following steps:
in a closed reaction kettle, introducing nitrogen, adding 12g of adsorption resin, 100g of acryloyl chloride and 5g of anhydrous aluminum chloride into the kettle, stirring for 10 hours at 40 ℃, filtering and drying to obtain the allyl adsorption resin.
The adsorption resin is nonpolar D101.
Comparative example 3
The method for preparing lithium bis (fluorosulfonyl) imide from methyl silazane comprises the following operation steps:
s1: weighing 10g of sulfuryl fluoride and 100g of solvent, stirring and mixing, heating, and slowly adding 5g of methyl silazane for reaction;
s2: after the reaction is finished, cooling, slowly dropwise adding 15g of alkaline lithium for reaction, after the reaction is finished, adding 0.02g of resin-based diacid adsorbent, stirring for 20 minutes, and then filtering to remove unreacted alkaline lithium and resin-based diacid adsorbent;
s3: and (3) evaporating and concentrating the filtrate, adding 100g of a weak polar solvent or a nonpolar solvent, separating out solid lithium bis (fluorosulfonyl) imide, and drying to obtain the lithium bis (fluorosulfonyl) imide.
The methyl silazane is octamethyl cyclotetra-silazane.
The solvent is ethyl acetate.
The reaction temperature of S1 is 80 ℃ and the reaction time is 5h.
The alkaline lithium is LiF.
The reaction temperature of the S2 is 0 ℃, and the reaction time is 5 hours.
The weak polar solvent or the nonpolar solvent is dichloromethane.
The preparation method of the resin-based diacid adsorbent comprises the following steps:
s1: introducing nitrogen into a closed reaction kettle, adding 2g of 2, 3-dimercapto malonic acid and 100g of sodium hydroxide solution with the mass percent concentration of 5% into the kettle, stirring for 30min at 30 ℃, and distilling under reduced pressure to remove water;
s2: 1000g of ethanol, 100g of propenyl adsorption resin and 3g of triethylamine are added into a stirring kettle, stirred at 60 ℃ for 100min, and filtered to obtain resin-based sodium diacid;
s3: ion exchange is carried out, and sodium ions are replaced by hydrogen ions, wherein the process conditions are as follows: adding sodium resin-based diacid into an ion exchange column, wherein the adding amount is 30 percent of the volume of the ion exchange column, adding 100g of hydrochloric acid solution with the mass percent concentration of 5 percent into the ion exchange column at the flow rate of 0.5BV/h, distilling effluent liquid to remove ethanol, and drying to obtain the resin-based diacid adsorbent.
The preparation method of the propenyl adsorption resin comprises the following steps:
in a closed reaction kettle, introducing nitrogen, adding 12g of adsorption resin, 100g of acryloyl chloride and 5g of anhydrous aluminum chloride into the kettle, stirring for 10 hours at 40 ℃, filtering and drying to obtain the allyl adsorption resin.
The adsorption resin is nonpolar D101.
The purity and yield of the product in particular embodiments of the invention are calculated by the following method:
1. purity: purity of lithium bis (fluorosulfonyl) imide = mass of lithium bis (fluorosulfonyl) imide in mixture ≡mass of mixture x 100%;
2. yield: yield of lithium bis (fluorosulfonyl) imide = actual yield of lithium bis (fluorosulfonyl) imide/theoretical yield of lithium bis (fluorosulfonyl) imide x 100%.
| Purity/% | Yield/% | |
| Example 1 | 99.95 | 93.72 |
| Example 2 | 99.97 | 94.53 |
| Example 3 | 99.99 | 95.96 |
| Example 4 | 99.98 | 95.03 |
| Comparative example 1 | 88.12 | 91.78 |
| Comparative example 2 | 91.35 | 92.85 |
| Comparative example 3 | 93.36 | 92.26 |
Compared with the data of the comparative example, the method has the advantages of simple operation, less byproducts, simple post-treatment, high purity and high total yield, and is suitable for industrial production.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The method for preparing lithium bis (fluorosulfonyl) imide from methyl silazane comprises the following operation steps:
s1: weighing 10-50 parts of sulfuryl fluoride and 100-150 parts of solvent according to parts by weight, stirring and mixing, heating, and slowly adding 5-10 parts of methyl silazane for reaction;
s2: after the reaction is finished, cooling, slowly dropwise adding 15-20 parts of alkaline lithium for reaction, after the reaction is finished, adding 0.02-0.5 part of resin-based diacid adsorbent, stirring for 20-40 minutes, and then filtering to remove unreacted alkaline lithium and resin-based diacid adsorbent;
s3: and (3) evaporating and concentrating the filtrate, adding 100-150 parts of a weak polar solvent or a nonpolar solvent, separating out solid lithium bis (fluorosulfonyl) imide, and drying to obtain the lithium bis (fluorosulfonyl) imide.
2. A method for preparing lithium bis-fluorosulfonyl imide from methylsilazane according to claim 1, wherein: the methyl silazane is octamethyl cyclotetrasilazane or hexamethyldisilazane or hexamethyl cyclotrisilazane.
3. A method for preparing lithium bis-fluorosulfonyl imide from methylsilazane according to claim 1, wherein: the solvent is esters, amides and nitriles; further esters include ethyl acetate, butyl acetate; further amides include N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone; further nitriles include acetonitrile, propionitrile.
4. A method for preparing lithium bis-fluorosulfonyl imide from methylsilazane according to claim 1, wherein: the reaction temperature of the S1 is 80-110 ℃ and the reaction time is 5-10h.
5. A method for preparing lithium bis-fluorosulfonyl imide from methylsilazane according to claim 1, wherein: the alkaline lithium is LiF, liOH, liHCO 3 Or Li (lithium) 2 CO 3 One or more of the following.
6. A method for preparing lithium bis-fluorosulfonyl imide from methylsilazane according to claim 1, wherein: the reaction temperature of the S2 is 0-20 ℃ and the reaction time is 5-10h.
7. A method for preparing lithium bis-fluorosulfonyl imide from methylsilazane according to claim 1, wherein: the weak polar solvent or the nonpolar solvent is halogenated hydrocarbon solvent, alkane solvent and halogenated aromatic solvent;
further halogenated hydrocarbon solvents include dichloromethane, dichloroethane;
further alkane solvents include n-hexane, cyclohexane, n-heptane;
further halogenated aromatic solvents include toluene, ethylbenzene, chlorobenzene.
8. A method for preparing lithium bis-fluorosulfonyl imide from methylsilazane according to claim 1, wherein: the preparation method of the resin-based diacid adsorbent comprises the following steps:
s1: according to the mass parts, nitrogen is introduced into a closed reaction kettle, 2-5 parts of 2, 3-dimercapto malonic acid, 10-15 parts of 2, 5-difluoro-3, 6-dimercapto terephthalic acid and 100-200 parts of sodium hydroxide solution with the mass percent concentration of 5-10% are added into the kettle, stirred for 30-60min at the temperature of 30-40 ℃, and the water is removed by reduced pressure distillation;
s2: adding 1000-1500 parts of ethanol, 100-130 parts of propenyl adsorption resin and 3-6 parts of triethylamine into a stirring kettle, stirring at 60-72 ℃ for 100-150min, and filtering to obtain resin-based sodium diacid;
s3: ion exchange is carried out, and sodium ions are replaced by hydrogen ions, wherein the process conditions are as follows: adding resin base sodium diacid into an ion exchange column, wherein the adding amount is 30-60% of the volume of the ion exchange column, adding 100-200 parts of hydrochloric acid solution with the mass percent concentration of 5-10% into the ion exchange column at the flow rate of 0.5-2BV/h, distilling effluent liquid to remove ethanol, and drying to obtain the resin base diacid adsorbent.
9. The method for preparing lithium bis (fluorosulfonyl) imide from methylsilazane according to claim 8, wherein the method comprises the steps of: the preparation method of the propenyl adsorption resin comprises the following steps:
according to the mass portions, introducing nitrogen into a closed reaction kettle, adding 12-15 parts of adsorption resin, 100-150 parts of acryloyl chloride and 5-10 parts of anhydrous aluminum chloride into the kettle, stirring for 10-20 hours at 40-50 ℃, filtering, and drying to obtain the allyl adsorption resin.
10. A method for preparing lithium bis-fluorosulfonyl imide from methylsilazane according to claim 9, wherein: the adsorption resin comprises one or more of styrene-divinylbenzene adsorption resin, styrene-divinylbenzene adsorption resin modified resin, polystyrene adsorption resin modified resin, polyacrylate adsorption resin and polyacrylate adsorption resin modified resin;
further, the first macroporous adsorption resin comprises nonpolar D101, LX-100B, LX-T28 and weak polar AB-8.
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| CN117229463B (en) * | 2023-11-15 | 2024-01-30 | 国家电投集团氢能科技发展有限公司 | Non-fluorine sulfonic acid resin, proton exchange membrane and preparation method and application thereof |
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