CN117699748A - Preparation method of high-purity lithium bis (fluorosulfonyl) imide - Google Patents
Preparation method of high-purity lithium bis (fluorosulfonyl) imide Download PDFInfo
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- CN117699748A CN117699748A CN202410038261.6A CN202410038261A CN117699748A CN 117699748 A CN117699748 A CN 117699748A CN 202410038261 A CN202410038261 A CN 202410038261A CN 117699748 A CN117699748 A CN 117699748A
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- lithium
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- fluorosulfonyl
- imide
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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 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 31
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000000919 ceramic Substances 0.000 claims abstract description 25
- 229940070527 tourmaline Drugs 0.000 claims abstract description 25
- 229910052613 tourmaline Inorganic materials 0.000 claims abstract description 25
- 239000011032 tourmaline Substances 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 14
- ATMIHASMQFJNLZ-UHFFFAOYSA-N dichloro(imino)-$l^{4}-sulfane Chemical compound ClS(Cl)=N ATMIHASMQFJNLZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 239000012043 crude product Substances 0.000 claims abstract description 7
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims abstract description 6
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004537 pulping Methods 0.000 claims abstract description 6
- 238000007670 refining Methods 0.000 claims abstract description 6
- -1 acryl Chemical group 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- XPVRBHCXMWRJEY-UHFFFAOYSA-N difluoro(imino)-$l^{4}-sulfane Chemical compound FS(F)=N XPVRBHCXMWRJEY-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000004696 coordination complex Chemical class 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical class [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000006138 lithiation reaction Methods 0.000 claims description 7
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 claims description 7
- 125000002524 organometallic group Chemical group 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- KWBXQDNGHQLAMB-UHFFFAOYSA-N 4-sulfanyl-3h-1,3-thiazole-2-thione Chemical compound SC1=CSC(=S)N1 KWBXQDNGHQLAMB-UHFFFAOYSA-N 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000010812 mixed waste Substances 0.000 claims description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000003983 crown ethers Chemical group 0.000 claims description 2
- 239000004210 ether based solvent Substances 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical class [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical class [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 2
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 1
- 229960001701 chloroform Drugs 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 5
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 229910001510 metal chloride Inorganic materials 0.000 abstract description 3
- RKLWISLCSWAWJI-UHFFFAOYSA-L dilithium;difluoride Chemical compound [Li+].[Li+].[F-].[F-] RKLWISLCSWAWJI-UHFFFAOYSA-L 0.000 abstract 1
- 238000004334 fluoridation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 10
- 239000005935 Sulfuryl fluoride Substances 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910010941 LiFSI Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- PVMUVDSEICYOMA-UHFFFAOYSA-N n-chlorosulfonylsulfamoyl chloride Chemical compound ClS(=O)(=O)NS(Cl)(=O)=O PVMUVDSEICYOMA-UHFFFAOYSA-N 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- USPTVMVRNZEXCP-UHFFFAOYSA-N sulfamoyl fluoride Chemical compound NS(F)(=O)=O USPTVMVRNZEXCP-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of high-purity lithium bis (fluorosulfonyl) imide, and belongs to the technical fields of chemical synthesis and lithium batteries. Heating and stirring sulfamic acid, thionyl chloride and chlorosulfonic acid for reflux to obtain dichlorsulfimide, concentrating and refining dichlorsulfimide along with benign solvent after fluorination, concentrating to a certain concentration, adding poor solvent for crystallization, filtering to obtain a crude difluoride product, lithiating the crude product with alkaline lithium to form salt, pulping with dichloromethane solvent, filtering and drying to obtain the difluoride lithium. The tourmaline ceramic ball prepared by the invention carries thiazole/Sb complex and organic lithium cocatalyst, enhances the activity of the catalyst, improves the selectivity of catalyzing fluoridation reaction together with metal chloride, and reduces the occurrence of side reaction.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis and lithium batteries, and particularly relates to a preparation method of high-purity lithium bis (fluorosulfonyl) imide.
Background
The lithium bis (fluorosulfonyl) imide (LiSSI) has the advantages of high stability (not decomposed below 200 ℃), excellent low-temperature performance, good hydrolytic stability, more environment-friendly property and the like, and can be used as the electrolyte lithium salt of the next-generation secondary lithium ion battery for replacing lithium hexafluorophosphate. The difluoro sulfonimide lithium salt can be used as a lithium ion battery electrolyte additive, is applied to electrolyte of a rechargeable lithium battery, can effectively reduce high-low temperature resistance of an SEI layer formed on the surface of an electrode plate at low temperature, and reduces capacity loss of a lithium battery chemical book in the placing process, so that high battery capacity and electrochemical performance of the battery are provided, and can also be used as electrolyte for a primary battery; can be used as a polymerization catalyst; can also be used as antistatic agent in the industrial field.
CN117069075a provides a method for preparing lithium bis (fluorosulfonyl) imide, comprising the following steps: providing an aqueous solution of lithium bis (fluorosulfonyl) imide containing an alkaline lithium salt; distilling and concentrating the aqueous solution of lithium bis (fluorosulfonyl) imide to obtain a concentrated solution of lithium bis (fluorosulfonyl) imide; adding a nonaqueous organic solvent into the lithium difluorosulfimide aqueous concentrate, mixing, and distilling to remove water to obtain an organic solution of lithium difluorosulfimide.
CN116902930a discloses a preparation method of lithium bis (fluorosulfonyl) imide, comprising the following steps: s1, preparing sulfuryl fluoride; calcium fluoride and sulfur trioxide are used as raw materials, and the mixed gas containing sulfuryl fluoride is prepared by high-temperature reaction in the presence of a catalyst; the mixed gas is treated to obtain gas sulfuryl fluoride; s2, preparing lithium bis (fluorosulfonyl) imide; introducing the gas sulfuryl fluoride obtained in the step S1 into an organic solvent containing lithium nitride, and reacting to obtain slurry; solid-liquid separation is carried out on the slurry to obtain a first filtrate, and crystallization is carried out on the first filtrate after concentration to obtain a crystallization slurry; and filtering the crystallization slurry to obtain the lithium bis (fluorosulfonyl) imide.
CN116835539a discloses a method for synthesizing high-purity lithium bis (fluorosulfonyl) imide by a stepwise method. According to the invention, the thought of stepwise reaction is adopted, under the action of triethylamine in an environment filled with ammonia gas, sulfuryl fluoride is slowly introduced to generate fluorosulfonamide triethylamine salt, then the fluorosulfonamide triethylamine salt is replaced with strong acid to obtain fluorosulfonamide as an intermediate, and then the intermediate is continuously reacted with sulfuryl fluoride to obtain difluoro sulfonyl imide triethylamine salt. In the lithiation process, firstly, potassium carbonate is adopted to replace and remove triethylamine to obtain KFSI, and LiBF4 and KFSI are utilized to carry out double decomposition reaction to obtain LiFSI, so that the introduction of anion impurities is avoided, and conditions are provided for the synthesis of high-purity lithium difluorosulfimide.
CN116750733a discloses a method for preparing lithium bis-fluorosulfonyl imide from sulfuryl fluoride; the invention adopts sulfuryl fluoride, ammonia gas, organic alkali, solvent and lithium hydroxide to prepare lithium bis (fluorosulfonyl) imide; the invention firstly carries out preliminary purification by distillation and extraction, then carries out filtration, and further removes trace impurity components in the crude product after the absorption of the fluorinated peptide acid group molecular sieve, thus obtaining the high-purity lithium bis-fluorosulfonyl imide.
The current application of LiFSI has a great difficulty that the synthesis process condition is complex, the requirement on equipment in the synthesis process is high, the reaction is complex, the yield is low, the product purity is low, the pollution is large, and the synthesis cost of LiFSI is extremely expensive.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of high-purity lithium bis (fluorosulfonyl) imide, which effectively improves the selectivity of the reaction, reduces side reactions and remarkably improves the purity of lithium bis (fluorosulfonyl) imide.
The technical scheme adopted by the invention is as follows:
the preparation method of the high-purity lithium bis (fluorosulfonyl) imide comprises the following steps:
step one: synthesis of bischlorosulfonimide
Weighing 30-70 parts by mass of sulfamic acid in a round bottom flask with a condensing reflux device, weighing 90-210 parts by mass of thionyl chloride and 36-84 parts by mass of chlorosulfonic acid, stirring and refluxing for 20-30 hours at 100-120 ℃, absorbing overflow gas by alkali liquor, stopping heating after the reaction mixed liquor becomes brown yellow viscous liquid, continuously stirring until the temperature in an oil bath pot is reduced to room temperature, performing vacuum distillation under reduced pressure at 100-120 ℃, and collecting fractions at 110-114 ℃ to obtain the dichloro sulfimide.
Step two: fluorination of bischlorosulfonimide to give bisfluorosulfonimide
Adding benign solvent into a tetrafluoro reaction bottle, dripping 600-700 parts of HClSI,0.2-1 part of fluorination catalyst and 0.02-0.1 part of cocatalyst, heating to 30-100 ℃, slowly dripping 140-160 parts of anhydrous HF gas under stirring, and introducing 400-600 parts of NH 3 After 4-6 hours of reaction, sampling and analyzing that the content of the dichlorosulfimide is less than or equal to 0.25 percent, and taking the sample as qualified and transferring to the next step. Filtering and drying the fluoride waste salt to obtain mixed waste salt of ammonium chloride and ammonium fluoride, and concentrating and refining the product along with benign solvent. Concentrating to a certain concentration, adding a poor solvent for crystallization, and filtering to obtain a crude product of the difluoro sulfimide.
Step three: lithiation salt
Adding 500-600 parts of dichloromethane, 40-50 parts of alkaline lithium into a reaction bottle, cooling to 0-5 ℃, dropwise adding 170-200 parts of difluoro sulfimide under stirring, stirring for 1-3h, then heating to 20-25 ℃, dropwise adding 300-400 parts of thionyl chloride, and stirring for 10-20h. Filtering, adding 500-600 parts of dichloromethane and 0.05-0.3 part of solvent into the filter cake for pulping, filtering and drying to obtain the lithium difluorosulfimide.
Further, the alkali liquor in the step one is calcium hydroxide, cesium hydroxide, potassium hydroxide or sodium hydroxide.
Further, the benign solvent in the second step is one of acetonitrile, thionyl chloride, methyl carbonate, ethyl carbonate and methyl ethyl carbonate.
Further, the fluorination catalyst in the second step is selected from SbC1 5 、TiCl 4 、SnCl 4 、MoCl 5 One of them.
Further, the preparation method of the cocatalyst in the second step comprises the following steps:
20-40 parts of tourmaline ceramic ball containing acryl, 7-14 parts of organic metal complex, 0.001-0.02 part of lithium acrylate, 3-7 parts of potassium tert-butoxide and 200-300 parts of N-methyl pyrrolidone are mixed and stirred for 100-180 minutes at the temperature of 60-70 ℃, filtered and dried to obtain the cocatalyst.
Further, the preparation method of the organometallic complex comprises the following steps:
weighing 3-6 parts of dimercaptothiazole, 1-3 parts of SbC, adding 80-100 parts of water, mixing and stirring for 100-160 minutes at 40-50 ℃, distilling under reduced pressure to remove water, drying, standing and naturally cooling to room temperature to obtain an organic metal complex,
further, the preparation method of the acryl tourmaline ceramic ball comprises the following steps:
according to the mass portion, 100 to 140 portions of tourmaline ceramic ball are taken and dissolved in 600 to 1000 portions of water, 3 to 6 portions of 3-methacryloxypropyl trimethoxy silane are added, and the mixture is stirred for 100 to 150 minutes at the temperature of 40 to 50 ℃, filtered and dried, thus obtaining the tourmaline ceramic ball containing acryl.
Further, the poor solvent in the second step is one or more of dichloromethane, dichloroethane, chloroform, trichloroethane, carbon tetrachloride, n-hexane, cyclohexane, methanol, ethanol, trifluoroethanol, n-butanol, isopropanol or ether solvents.
Further, the alkaline lithium in step three is selected from: any one of lithium alkoxides (such as lithium methoxide, lithium ethoxide, or lithium tert-butoxide), lithium organic carboxylates (such as lithium formate, lithium acetate, etc.), lithium oxides, lithium hydroxides, lithium carbonates, etc.
Further, the drying in the third step is vacuum drying; the drying temperature is 40-50 ℃, and the drying time is 6-10 h.
Further, the solvent in the third step is crown ether, and specifically can be one or more of 18-crown ether-6, 15-crown ether-5 and 12-crown ether-4.
Reaction mechanism
The reaction mechanism for synthesizing the dichlor sulfonyl imide in the first step is as follows:
NH 2 SO 3 H+2SOCl 2 +ClSO 3 H→HN(SO 2 Cl) 2 +2SO 2 ↑+3HCl↑
the reaction mechanism of the fluorination of the dichloro sulfonyl imide to obtain the difluoro sulfonyl imide in the step two is as follows:
HN(SO2Cl)2+2HF→HN(SO2F)2+2HCl↑
the reaction mechanism of lithiation and salt formation in the third step is as follows:
reaction mechanism of the cocatalyst:
tourmaline ceramic balls containing acryl, organic metal complexes and lithium acrylate undergo a sulfhydryl addition reaction to obtain tourmaline ceramic ball-loaded thiazole/Sb complexes; the selectivity of the catalytic fluorination reaction of the organic lithium promoter and the metal chloride is improved, and the side reaction is reduced
Technical effects
Tourmaline ceramic ball loaded thiazole/Sb complex; and (3) an organolithium cocatalyst. The selectivity of the catalytic fluorination reaction with the metal chloride is improved. Thiazole and its complexes with Sb act as cocatalysts in this reaction. The organic fluorination reaction can be carried out at a lower temperature, thereby improving the selectivity of the product and reducing side reactions. The organolithium compound can interact with the thiazole complex, enhancing the activity of the catalyst and increasing the reaction rate. The selectivity of the reaction is improved, and the side reaction is reduced.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention is further illustrated by the following examples:
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%.
Example 1
Step one: synthesis of bischlorosulfonimide
30g of sulfamic acid is weighed into a round bottom flask with a condensing reflux device, 90g of thionyl chloride and 36g of chlorosulfonic acid are weighed, stirred and refluxed at 100 ℃ for 20 hours, then overflow gas is absorbed by calcium hydroxide, heating is stopped after reaction mixed liquid becomes brown yellow viscous liquid, stirring is continued until the temperature in an oil bath pot is reduced to room temperature, reduced pressure vacuum distillation is carried out, the temperature is 100 ℃, and fractions at 110 ℃ are collected to obtain the dichloro sulfimide.
Step two: fluorination of bischlorosulfonimide to give bisfluorosulfonimide
Acetonitrile is added into a tetrafluoro reaction bottle, 600g of HClSI,0.2gSbCl5 catalyst and 0.02g of promoter are added dropwise, the temperature is raised to 300 ℃, anhydrous HF gas is slowly added dropwise with stirring to about 140g, and 400g of NH is introduced 3 After the reaction is carried out for 4 hours, sampling analysis is carried out, the content of the dichlorosulfimide is less than or equal to 0.25 percent, and the reaction is regarded as qualified and then the reaction is carried out. Filtering and drying the fluoride waste salt to obtain mixed waste salt of ammonium chloride and ammonium fluoride, and concentrating and refining the product along with acetonitrile. Concentrating to a certain concentration, adding dichloromethane for crystallization, and filtering to obtain a crude product of the difluoro sulfimide.
Step three: lithiation salt
500g of dichloromethane and 40g of lithium methoxide are added into a reaction bottle, the temperature is reduced to 0 ℃, 170g of difluoro sulfimide is added dropwise under stirring, the mixture is stirred for 1h, then the temperature is increased to 20 ℃,300g of thionyl chloride is added dropwise, and the mixture is stirred for 10h. Filtering, adding 500g of dichloromethane and 0.05g of 18-crown ether-6 into the filter cake for pulping, filtering and drying to obtain the lithium difluorosulfimide.
The preparation method of the cocatalyst in the second step comprises the following steps:
20g of tourmaline ceramic ball containing acryl, 7g of organic metal complex, 0.001g of lithium acrylate, 3g of potassium tert-butoxide and 200g of N-methylpyrrolidone are mixed and stirred for 100 minutes at 60 ℃, filtered and dried to obtain a cocatalyst.
The preparation method of the organometallic complex comprises the following steps:
3g of dimercaptothiazole, 1g of SbC1 are weighed out 5 Adding 80g of water, mixing and stirring for 100 minutes at 40 ℃, distilling under reduced pressure to remove water, drying, standing and naturally cooling to room temperature to obtain an organic metal complex,
the preparation method of the acryl tourmaline ceramic ball comprises the following steps:
100g tourmaline ceramic ball is taken and dissolved in 600g water, 3g 3-methacryloxypropyl trimethoxy silane is added, and the mixture is stirred for 100 minutes at 40 ℃, filtered and dried to prepare the tourmaline ceramic ball containing acryl.
The drying in the third step is vacuum drying; the drying temperature was 40℃and the drying time was 6 hours.
Example 2
Step one: synthesis of bischlorosulfonimide
50g of sulfamic acid is weighed into a round bottom flask with a condensing reflux device, 150g of thionyl chloride and 60g of chlorosulfonic acid are weighed, stirred and refluxed at 110 ℃ for 25 hours, overflow gas is absorbed by potassium hydroxide, heating is stopped after reaction mixed liquid becomes brown yellow viscous liquid, stirring is continued until the temperature in an oil bath pot is reduced to room temperature, reduced pressure vacuum distillation is carried out, the temperature is 110 ℃, and fractions at 112 ℃ are collected to obtain the dichloro sulfimide.
Step two: fluorination of bischlorosulfonimide to give bisfluorosulfonimide
Adding thionyl chloride into a tetrafluoro reaction bottle, dropwise adding 650g of HClSI,0.6gTiCl4 catalyst and 0.06g of cocatalyst, heating to 65 ℃, slowly dropwise adding 150g of anhydrous HF gas under stirring, and introducing 500g of NH 3 After 5 hours of reaction, sampling and analyzing that the content of the dichlorosulfimide is less than or equal to 0.25 percent, and taking the sample as qualified and transferring to the next step. Filtering and drying the fluoride waste salt to obtain mixed waste salt of ammonium chloride and ammonium fluoride, and concentrating and refining the product along with sulfoxide chloride. Concentrating to a certain concentration, adding dichloroethane for crystallization, and filtering to obtain a crude product of the difluoro sulfimide.
Step three: lithiation salt
550g of dichloromethane and 45g of lithium hydroxide are added into a reaction bottle, the temperature is reduced to 3 ℃, 185g of difluoro sulfimide is added dropwise under stirring, the mixture is stirred for 2 hours, then the temperature is increased to 23 ℃, 350g of thionyl chloride is added dropwise, and the mixture is stirred for 15 hours. Filtering, adding 550g of dichloromethane and 0.2g of 15-crown ether-5 into the filter cake for pulping, filtering and drying to obtain the lithium difluorosulfimide.
The preparation method of the cocatalyst in the second step comprises the following steps:
30g of tourmaline ceramic ball containing acryl, 11g of organic metal complex, 0.01g of lithium acrylate, 5g of potassium tert-butoxide and 250g of N-methyl pyrrolidone at 65 ℃ are mixed and stirred for 140 minutes, filtered and dried to obtain the cocatalyst.
The preparation method of the organometallic complex comprises the following steps:
4.5g of dimercaptothiazole, 2g of SbC1 are weighed out 5 Adding 90g of water, mixing and stirring for 130 minutes at 45 ℃, distilling under reduced pressure to remove water, drying, standing and naturally cooling to room temperature to obtain an organic metal complex,
the preparation method of the acryl tourmaline ceramic ball comprises the following steps:
120g tourmaline ceramic ball is taken and dissolved in 800g water, 4.5g 3-methacryloxypropyl trimethoxy silane is added, and the mixture is stirred for 125 minutes at 45 ℃, filtered and dried to prepare the tourmaline ceramic ball containing acryl.
The drying in the third step is vacuum drying; the drying temperature was 45℃and the drying time was 8 hours.
Example 3
Step one: synthesis of bischlorosulfonimide
70g of sulfamic acid is weighed into a round bottom flask with a condensing reflux device, 210g of thionyl chloride and 84g of chlorosulfonic acid are weighed, stirred and refluxed at 120 ℃ for 30 hours, overflowed gas is absorbed by sodium hydroxide alkali liquor, heating is stopped after the reaction mixed liquor becomes brown yellow viscous liquid, stirring is continued until the temperature in an oil bath pot is reduced to room temperature, reduced pressure vacuum distillation is carried out, the temperature is 120 ℃, and fractions at 114 ℃ are collected to obtain the dichloro sulfimide.
Step two: fluorination of bischlorosulfonimide to give bisfluorosulfonimide
Into a tetrafluoro reaction flask, ethyl carbonate was added, and 700g of HClSI and 1g of SnCl were added dropwise 4 Catalyst, 0.1g promoter, heating to 100deg.C, slowly dropping anhydrous HF gas about 160g under stirring, and introducing 600gNH 3 After the reaction is carried out for 6 hours, sampling analysis is carried out, the content of the dichlorosulfimide is less than or equal to 0.25 percent, and the reaction is regarded as qualified and then the reaction is carried out. Filtering and drying the fluoride waste salt to obtain mixed waste salt of ammonium chloride and ammonium fluoride, and concentrating and refining the product along with good ethyl carbonate. ConcentratingAnd after a certain concentration is reached, adding trifluoroethanol for crystallization, and filtering to obtain a crude product of the difluoro sulfimide.
Step three: lithiation salt
600g of dichloromethane and 50g of alkaline lithium are added into a reaction bottle, the temperature is reduced to 5 ℃,200g of difluoro sulfimide is added dropwise under stirring, the mixture is stirred for 3 hours, then the temperature is increased to 25 ℃, 400g of thionyl chloride is added dropwise, and the mixture is stirred for 20 hours. Filtering, adding 600g of dichloromethane and 0.3g of 12-crown ether-4 into the filter cake for pulping, filtering and drying to obtain the lithium difluorosulfimide.
The preparation method of the cocatalyst in the second step comprises the following steps:
40g of tourmaline ceramic ball containing acryl, 14g of organic metal complex, 0.02g of lithium acrylate, 7g of potassium tert-butoxide and 300g of N-methylpyrrolidone are mixed and stirred for 180 minutes at 70 ℃, filtered and dried to obtain the cocatalyst.
The preparation method of the organometallic complex comprises the following steps:
6g of dimercaptothiazole, 3g of SbC1 are weighed out 5 Adding 100g of water, mixing and stirring for 160 minutes at 50 ℃, distilling under reduced pressure to remove water, drying, standing and naturally cooling to room temperature to obtain an organic metal complex,
the preparation method of the acryl tourmaline ceramic ball comprises the following steps:
140g tourmaline ceramic ball is taken and dissolved in 1000g water, 6g 3-methacryloxypropyl trimethoxy silane is added, and the mixture is stirred for 150 minutes at 50 ℃, filtered and dried to prepare the tourmaline ceramic ball containing acryl.
The drying in the third step is vacuum drying; the drying temperature was 50℃and the drying time was 10 hours.
Comparative example 1
In the second step, no cocatalyst was added, and the rest of the technical scheme was the same as in example 1.
Comparative example 2
The other technical schemes are the same as in example 1, except that no acryl tourmaline ceramic ball is added in the cocatalyst.
Comparative example 3
The cocatalyst was not added with an organometallic complex and the rest of the technical scheme was the same as in example 1.
Comparative example 4
The cocatalyst was not added with lithium acrylate and the rest of the technical scheme was the same as in example 1.
Table 1 shows the purity and yield of the target products of examples 1 to 3 and comparative examples 1 to 4.
| Purity/% | Yield/% | |
| Example 1 | 99.94 | 93.74 |
| Example 2 | 99.97 | 94.53 |
| Example 3 | 99.99 | 95.97 |
| Comparative example 1 | 82.12 | 80.77 |
| Comparative example 2 | 88.35 | 84.89 |
| Comparative example 3 | 91.53 | 87.39 |
| Comparative example 4 | 93.35 | 90.35 |
As can be seen from the above table, the yield and purity of the bisfluorosulfonyl imide obtained in examples are higher than those in comparative examples.
The above examples merely represent a few embodiments of the present application, which facilitate a specific and detailed understanding of the technical solutions of the present application, but are not to be construed as limiting the scope of the invention. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. It should be understood that those skilled in the art, based on the technical solutions provided in the present application, can obtain technical solutions through logical analysis, reasoning or limited experiments, all fall within the protection scope of the claims attached in the present application. The scope of the patent application is therefore intended to be indicated by the appended claims, and the description may be used to interpret the contents of the claims.
Claims (10)
1. The preparation method of the high-purity lithium bis (fluorosulfonyl) imide is characterized by comprising the following steps:
step one: synthesis of bischlorosulfonimide
Weighing 30-70 parts by mass of sulfamic acid in a round bottom flask with a condensing reflux device, weighing 90-210 parts by mass of thionyl chloride and 36-84 parts by mass of chlorosulfonic acid, stirring and refluxing for 20-30 hours at 100-120 ℃, absorbing overflow gas by alkali liquor, stopping heating after the reaction mixed liquor becomes brown yellow viscous liquid, continuously stirring until the temperature in an oil bath pot is reduced to room temperature, performing reduced pressure vacuum distillation at 100-120 ℃, and collecting fractions at 110-114 ℃ to obtain the dichloro sulfimide;
step two: fluorination of bischlorosulfonimide to give bisfluorosulfonimide
Adding benign solvent into a tetrafluoro reaction bottle, dripping 600-700 parts of HClSI,0.2-1 part of fluorination catalyst and 0.02-0.1 part of cocatalyst, heating to 30-100 ℃, slowly dripping 140-160 parts of anhydrous HF gas under stirring, and introducing 400-600 parts of NH 3 After the reaction is carried out for 4 to 6 hours, sampling analysis is carried out, the content of the dichlorosulfimide is less than or equal to 0.25 percent, and the reaction is regarded as qualified and then the next step is carried out; filtering and drying the fluoride waste salt to obtain mixed waste salt of ammonium chloride and ammonium fluoride, concentrating and refining the product along with benign solvent in the next step, concentrating to a certain concentration, adding a poor solvent for crystallization, and filtering to obtain a crude product of difluoro sulfimide;
step three: lithiation salt
Adding 500-600 parts of dichloromethane, 40-50 parts of alkaline lithium, cooling to 0-5 ℃, dropwise adding 170-200 parts of difluoro sulfimide under stirring, stirring for 1-3h, then heating to 20-25 ℃, dropwise adding 300-400 parts of thionyl chloride, stirring for 10-20h, filtering, adding 500-600 parts of dichloromethane and 0.05-0.3 part of solvent into a filter cake, pulping, filtering, and drying to obtain the difluoro sulfimide lithium.
2. The method for preparing high-purity lithium bis (fluorosulfonyl) imide according to claim 1, wherein the alkaline solution in the first step is calcium hydroxide, cesium hydroxide, potassium hydroxide or sodium hydroxide.
3. The method for preparing high-purity lithium bis (fluorosulfonyl) imide according to claim 1, wherein the benign solvent in the second step is one of acetonitrile, thionyl chloride, methyl carbonate, ethyl carbonate, and ethyl methyl carbonate.
4. The method for preparing high-purity lithium bis (fluorosulfonyl) imide according to claim 1, wherein the fluorination catalyst in the second step is selected from SbC1 5 、TiCl 4 、SnCl 4 、MoCl 5 One of them.
5. The method for preparing high-purity lithium bis (fluorosulfonyl) imide according to claim 1, further comprising the step of preparing a cocatalyst by:
20-40 parts of tourmaline ceramic ball containing acryl, 7-14 parts of organic metal complex, 0.001-0.02 part of lithium acrylate, 3-7 parts of potassium tert-butoxide and 200-300 parts of N-methyl pyrrolidone are mixed and stirred for 100-180 minutes at the temperature of 60-70 ℃, filtered and dried to obtain the cocatalyst.
6. The method for preparing the organometallic complex according to claim 5, comprising:
weighing 3-6 parts of dimercaptothiazole, 1-3 parts of SbC, adding 80-100 parts of water, mixing and stirring for 100-160 minutes at 40-50 ℃, distilling under reduced pressure to remove water, drying, standing and naturally cooling to room temperature to obtain the organometallic complex.
7. The preparation method of the acryl tourmaline ceramic ball in accordance with claim 5, which comprises the following steps:
according to the mass portion, 100 to 140 portions of tourmaline ceramic ball are taken and dissolved in 600 to 1000 portions of water, 3 to 6 portions of 3-methacryloxypropyl trimethoxy silane are added, and the mixture is stirred for 100 to 150 minutes at the temperature of 40 to 50 ℃, filtered and dried, thus obtaining the tourmaline ceramic ball containing acryl.
8. The method for preparing high-purity lithium bis (fluorosulfonyl) imide according to claim 1, wherein the poor solvent in the second step is one or more of dichloromethane, dichloroethane, trichloromethane, trichloroethane, carbon tetrachloride, n-hexane, cyclohexane, methanol, ethanol, trifluoroethanol, n-butanol, isopropanol or ether solvents.
9. The method for preparing high-purity lithium bis (fluorosulfonyl) imide according to claim 1, wherein the alkaline lithium in the third step is selected from the group consisting of: any one of lithium alkoxides (such as lithium methoxide, lithium ethoxide, or lithium tert-butoxide), lithium organic carboxylates (such as lithium formate, lithium acetate, etc.), lithium oxides, lithium hydroxides, lithium carbonates, etc.
10. The method for preparing high-purity lithium bis (fluorosulfonyl) imide according to claim 1, wherein the drying in the third step is vacuum drying; the drying temperature is 40-50 ℃, and the drying time is 6-10 h; the solvent is crown ether, and can be one or more of 18-crown ether-6, 15-crown ether-5 and 12-crown ether-4.
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