CN115893337A - Preparation method of lithium bis (fluorosulfonyl) imide - Google Patents
Preparation method of lithium bis (fluorosulfonyl) imide Download PDFInfo
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- imide
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- fluorosulfonyl
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- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 63
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 56
- -1 bis-chlorosulfonyl imine Chemical class 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 50
- 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 33
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 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 26
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 230000035484 reaction time Effects 0.000 claims abstract description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 35
- 238000004821 distillation Methods 0.000 claims description 28
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 27
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 27
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 239000012295 chemical reaction liquid Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- PVMUVDSEICYOMA-UHFFFAOYSA-N n-chlorosulfonylsulfamoyl chloride Chemical compound ClS(=O)(=O)NS(Cl)(=O)=O PVMUVDSEICYOMA-UHFFFAOYSA-N 0.000 claims description 14
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 13
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 230000007797 corrosion Effects 0.000 claims description 8
- 238000005260 corrosion Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000012805 post-processing Methods 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 abstract description 46
- 239000002994 raw material Substances 0.000 abstract description 18
- 150000003949 imides Chemical class 0.000 abstract description 4
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- ATMIHASMQFJNLZ-UHFFFAOYSA-N dichloro(imino)-$l^{4}-sulfane Chemical compound ClS(Cl)=N ATMIHASMQFJNLZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 43
- 239000000047 product Substances 0.000 description 22
- 230000002572 peristaltic effect Effects 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 229910000856 hastalloy Inorganic materials 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- PPFAPKNCEXDZNN-UHFFFAOYSA-N N=[SH2].F.F Chemical compound N=[SH2].F.F PPFAPKNCEXDZNN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 2
- 229910000792 Monel Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005935 Sulfuryl fluoride Substances 0.000 description 2
- HMPLAFKHRANTGF-UHFFFAOYSA-N [Li].NS(F)(=O)=O Chemical compound [Li].NS(F)(=O)=O HMPLAFKHRANTGF-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical class [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of lithium bis (fluorosulfonyl) imide, which comprises the following steps: (1) Placing a mixture of sulfamic acid, chlorosulfonic acid and thionyl chloride in a dynamic tubular reactor for reaction to obtain dichlorosulfimide; (2) Reacting the bis-chlorosulfonyl imine with hydrogen fluoride in a continuous reactor to obtain bis-fluorosulfonyl imine; (3) And reacting the bis-fluorosulfonyl imide with lithium fluoride to obtain the bis-fluorosulfonyl imide lithium. According to the preparation method, HClSI and HFSI are efficiently obtained by continuous equipment, and then the LiFSI is prepared from HFSI and LiF under the solvent-free condition, so that the reaction time is short, the reaction efficiency and selectivity are high, the raw material conversion rate is high, complex solvent removal and purification steps are not needed, the high-purity and high-yield LiFSI can be efficiently prepared, the preparation method is a convenient, efficient and environment-friendly process, the requirements of large-scale production are fully met, and the product quality meets the industrial standards of batteries.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a preparation method of lithium bis (fluorosulfonyl) imide.
Background
In recent years, the development of high performance power batteries and energy storage batteries is greatly promoted by the vigorous development of new energy industries, and liquid lithium ion batteries are regarded as important branches in the industries and are paid much attention in the industries. In a liquid lithium ion battery, an electrolyte is a key material determining the final performance of the battery, and the core of the electrolyte is a lithium salt electrolyte. Lithium bis (fluorosulfonylimide) LiN (SO) 2 F) 2 (LiFSI) is the most promising new generation lithium salt electrolyte material at present, and has high thermal stability,Hydrolysis resistance, high conductivity and the like, and is acknowledged to be expected to replace the lithium hexafluorophosphate which currently occupies the leading position of the industrial market. With the rapid development of lithium ion batteries, the demand of LiFSI is gradually increased, the preparation process of LiFSI is optimized, and the product quality and the productivity of LiFSI are improved, which are important research points in the industry at present.
The current process route for preparing LiFSI can be divided into two categories: firstly, preparing the lithium bis (chloro-fluoro-sulfonyl) imide, and then fluorinating the lithium bis (chloro-fluoro-sulfonyl) imide to obtain LiFSI; and the other one is to obtain the bis (fluorosulfonyl) imide (HFSI) and then react the bis (fluorosulfonyl) imide with other lithium salts to obtain LiFSI.
CN103524387A discloses a preparation method of lithium bis (fluorosulfonyl) imide, which comprises the following steps: firstly, thionyl chloride, sulfamic acid and chlorosulfonic acid react for 18 hours at 120-130 ℃ to obtain a dichlorosulfonimide compound HN (SO) 2 Cl) 2 (ii) a Then, without isolation of the product, the obtained HN (SO) was directly used 2 Cl) 2 Reacting with thionyl chloride and anhydrous lithium salt to obtain lithium bis (chlorosulfonyl) imide; removing the thionyl chloride solvent, adding an organic solvent and a small amount of triethylamine, and carrying out fluorination reaction by using anhydrous zinc fluoride to obtain the lithium bis (fluorosulfonyl) imide. The method has good continuous operability, but the preparation process comprises two steps of introduction of metal salt, so that the separation of the metal salt which is not completely reacted from the final product is difficult, and high-purity LiFSI is difficult to obtain.
CN101747242A discloses a method for preparing bis-fluorosulfonyl imide and alkali metal salt of perfluoroalkylsulfonyl fluorosulfonyl imide, which comprises the following steps: firstly, reacting sulfonamide, thionyl chloride and chlorosulfonic acid to obtain dichlorosulfimide; then reacting the bis-chlorosulfonyl imine with antimony trifluoride to obtain bis-fluorosulfonyl imine; reacting the difluoride sulfimide with potassium carbonate to obtain difluoride sulfimide sylsalt; finally, the potassium bis (fluorosulfonyl) imide salt and lithium perchlorate or lithium tetrafluoroborate are subjected to double decomposition exchange reaction in an aprotic polar solvent to obtain the lithium bis (fluorosulfonyl) imide. In the method, antimony trifluoride used as a fluorinating reagent has high price and high industrialization cost; furthermore, potassium ions and perchlorate residues in the target product are difficult to remove, and high-quality LiFSI cannot be obtained.
CN107188138A discloses a preparation method of lithium bis (fluorosulfonyl) imide, which comprises the following steps: 1) Preparing lithium fluorosulfonamide; 2) Preparing sulfuryl fluoride, namely introducing the sulfuryl fluoride into a lithium fluorosulfonamide solution, and adding an acid-binding agent to prepare bis (fluorosulfonyl) imide ammonium salt; 3) Dissolving the ammonium bis (fluorosulfonyl) imide salt into an aqueous solution, and exchanging by acidic resin to obtain a bis (fluorosulfonyl) imide aqueous solution; 4) Adding lithium carbonate to react with the bis (fluorosulfonyl) imide, adjusting the pH value to be neutral, filtering to remove insoluble substances, removing most of water under reduced pressure, adding a weak-polarity organic solvent to precipitate a crude product of the bis (fluorosulfonyl) imide, and further drying under reduced pressure; 5) And purifying the crude product of the lithium bis (fluorosulfonyl) imide. The preparation method is simple, short in reaction time and high in yield, and can effectively control metal ions and anion impurities to obtain a high-purity product. According to the preparation method, liFSI is obtained through the neutralization reaction of lithium carbonate and HFSI, water is generated through the reaction, a product of complex crystal water is obtained, and the difficulty in purification and water removal in the later period is high, so that the product is difficult to meet the use standard of a battery.
At present, the preparation route of LiFSI is generally longer, the overall process time is usually more than 48h, the reaction efficiency is not high, a large amount of organic solvent is needed to be used as a reaction medium or a treatment/purification reagent in the preparation process, the treatment difficulty and the cost of chemical waste liquid are higher, and the development trend of low VOC at present is not met in the aspect of environmental protection.
Therefore, the preparation method of lithium bis (fluorosulfonyl) imide, which has higher development efficiency, shorter time and better environmental protection property, is an urgent problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of lithium bis (fluorosulfonyl) imide, which can enhance the mass and heat transfer efficiency among raw materials, improve the reaction rate, shorten the reaction time and quickly obtain the high-yield lithium bis (fluorosulfonyl) imide by using continuous equipment such as a dynamic tubular reactor, a continuous reactor and the like; the bis-fluorosulfonyl imide reacts with lithium fluoride to generate the bis-fluorosulfonyl imide lithium, so that the reaction rate is increased, the use of an organic solvent is avoided, the introduction of impurities is reduced, and the preparation efficiency and the quality of a target product are remarkably improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of lithium bis (fluorosulfonyl) imide, which comprises the following steps:
(1) Placing a mixture of sulfamic acid, chlorosulfonic acid and thionyl chloride in a dynamic tubular reactor for reaction to obtain dichlorosulfonimide;
(2) Reacting the bischlorosulfonimide obtained in the step (1) with hydrogen fluoride in a continuous reactor to obtain the bisfluorosulfonimide;
(3) Reacting the bis-fluorosulfonyl imide obtained in the step (2) with lithium fluoride to obtain the lithium bis-fluorosulfonyl imide.
The preparation method provided by the invention comprises three steps: preparing bis (chlorosulfonyl) imide (HClSI), bis (fluorosulfonyl) imide (HFSI) and bis (fluorosulfonyl) imide Lithium (LiFSI); the reaction formula is as follows:
ClHSO 3 +NH 2 SO 3 H+SOCl 2 →NH(SO 2 Cl) 2 +SO 2 +HCl；
NH(SO 2 Cl) 2 +2HF→NH(SO 2 F) 2 +2HCl；
NH(SO 2 F) 2 +LiF→LiN(SO 2 F) 2 +HF。
the reaction of generating HClSI in the step (1) is carried out in a dynamic tubular reactor, so that the mass transfer and heat transfer efficiency among materials is enhanced, and particularly, the mass transfer and heat transfer of a solid-liquid interface between sulfamic acid and chlorosulfonic acid/thionyl chloride are improved, so that the reaction rate is effectively improved, the reaction time is shortened, the reaction is promoted to be completely carried out, and the conversion rate of raw materials and the yield of products are improved. The reaction of HClSI and HF in step (2) is carried out in a continuous reactor, so that the heat and mass transfer of a gas-liquid interface is promoted, the mass and heat transfer effects of the reaction are improved, the reaction rate is increased, the reaction time is shortened, and the production safety is improved. Reacting HFSI and LiF under the solvent-free condition to obtain LiFSI, and increasing the reaction rate and the reaction efficiency and selectivity so as to improve the conversion rate of raw materials and the yield of target products; because no organic solvent is used in the whole process flow, the introduction of impurities is reduced, the step of removing the solvent is not needed, and the post-treatment process is simplified. In addition, the step (1) and the step (2) are continuous reaction processes, no solvent is used in the whole process flow, the utilization rate and the conversion rate of raw materials are high, and the reaction degree is more sufficient, so that the raw materials are fed in a molar ratio close to the stoichiometric ratio, and the loss of the raw materials is reduced.
In conclusion, the preparation method provided by the invention can be used for quickly and efficiently preparing HFSI by continuous equipment (a dynamic tubular reactor and a continuous reactor), so that LiFSI can be prepared by HFSI and LiF under the solvent-free condition, the reaction time is short, the reaction efficiency and selectivity are high, the raw material conversion rate is high, complex solvent removal and purification steps are not needed, and a large amount of waste liquid is avoided, so that LiFSI with high purity and high yield can be efficiently prepared, the preparation method is a convenient, efficient and environment-friendly preparation process, the requirement of large-scale production can be fully met, and the product quality meets the industrial standards of batteries.
Preferably, the molar ratio of sulfamic acid to chlorosulfonic acid in step (1) is 1 (1-1.5), and may be, for example, 1.
Preferably, the molar ratio of sulfamic acid to thionyl chloride in step (1) is 1 (2-5), and can be, for example, 1.
Preferably, the sulfamic acid, the chlorosulfonic acid and the thionyl chloride are mixed in a mixing kettle provided with an emulsification pump to obtain the mixture in the step (1).
Preferably, the mixing comprises a cyclic milling and dispersion process.
Preferably, the temperature of the mixing is 10 to 50 ℃, for example, 12 ℃, 15 ℃, 18 ℃, 20 ℃, 22 ℃, 25 ℃, 28 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃, 42 ℃, 45 ℃, 48 ℃, and the specific values therebetween, are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.
As a preferable technical scheme of the invention, sulfamic acid, chlorosulfonic acid and thionyl chloride are mixed and ground in a mixing kettle provided with an emulsification pump for pretreatment, particularly, solid-phase sulfamic acid is fully ground, so that the three raw materials can be fully mixed and uniformly dispersed to form slurry (the mixture) with good uniformity, the reaction rate in the step (1) is further improved, and the reaction time is shortened.
Preferably, in the mixing kettle, sulfamic acid (solid) is fed by a spiral feeding device, thionyl chloride and chlorosulfonic acid solution are fed by a plunger type feeding pump, and after the feeding is finished, the system is protected by nitrogen displacement.
Preferably, the mixing kettle provided with the emulsifying pump comprises a grinding system and a circulating system, so that the sulfamic acid, the chlorosulfonic acid and the thionyl chloride can be more fully mixed, ground and dispersed.
Preferably, the particle size of the sulfamic acid in the mixture of step (1) is less than or equal to 100 μm, such as 90 μm, 80 μm, 70 μm, 60 μm, 50 μm, 40 μm, 30 μm, 20 μm, 10 μm, 5 μm, or 1 μm, and the like. That is, when the particle size of the sulfamic acid is 100 μm or less, the mixing step accompanied by the circulating grinding and dispersion is completed.
Preferably, the grinding step further comprises a sieving step to remove large-sized particles in the mixture.
Preferably, the length of the tube of the dynamic tube reactor in step (1) is 500-10000mm, such as 600mm, 800mm, 1000mm, 2000mm, 3000mm, 4000mm, 5000mm, 6000mm, 7000mm, 8000mm or 9000mm, and specific values therebetween, which are not intended to limit the disclosure and for the sake of brevity, the invention is not exhaustive.
Preferably, the equivalent diameter of the dynamic tube reactor of step (1) is 50-800mm, for example, 60mm, 80mm, 100mm, 150mm, 200mm, 250mm, 300mm, 350mm, 400mm, 450mm, 500mm, 550mm, 600mm, 650mm, 700mm or 750mm, and specific values therebetween are not exhaustive, and for the sake of brevity and clarity, the invention is not intended to be exhaustive of the specific values included in the ranges.
Preferably, the inner wall material of the dynamic tube reactor in the step (1) is a corrosion-resistant material, and comprises silicon carbide and/or a corrosion-resistant alloy.
Preferably, the corrosion resistant alloy comprises hastelloy (e.g., hastelloy C-276 alloy) and/or monel.
Preferably, the mixture of step (1) is fed into the dynamic tube reactor by a peristaltic pump.
Preferably, the feeding rate of the mixture of step (1) is 0.1-50mL/min, such as 0.5mL/min, 1mL/min, 3mL/min, 5mL/min, 8mL/min, 10mL/min, 15mL/min, 20mL/min, 25mL/min, 30mL/min, 35mL/min, 40mL/min or 45mL/min, and the specific points between the above points are limited by space and for simplicity, and the invention is not exhaustive.
Preferably, the reaction temperature in step (1) is 70-150 ℃, for example, it may be 75 ℃,80 ℃, 85 ℃, 90 ℃,95 ℃,100 ℃, 105 ℃,110 ℃, 115 ℃,120 ℃, 125 ℃,130 ℃, 135 ℃, 140 ℃ or 145 ℃, and the specific values between the above values, are limited by space and for the sake of brevity, and the invention is not exhaustive enumeration of the specific values included in the range.
Preferably, the reaction time of step (1) is 5-120min, for example, 6min, 8min, 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min or 110min, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive.
Wherein the reaction time in the step (1) is the residence time of the mixture in the dynamic tubular reactor.
Preferably, the reaction in step (1) further comprises a post-treatment step after the reaction is completed.
Preferably, the method of post-processing comprises: placing the reaction liquid obtained by the reaction in a gas-liquid separator for gas-liquid separation and aging, and introducing inert gas to remove hydrogen chloride and sulfur dioxide to obtain a bischlorosulfimide solution; and distilling the bis-chlorosulfonyl imide solution to obtain the bis-chlorosulfonyl imide.
As the preferred technical scheme of the invention, the preparation of the bis (chlorosulfonyl) imide in the step (1) breaks through the traditional batch kettle type reactor, and the HClSI is prepared by combining a dynamic tubular reactor, a gas-liquid separation aging device and a distillation device, and has the characteristics of high efficiency, high quality and continuity. Specifically, through the combination of reaction and aging in the dynamic tubular reactor, the complete progress of the reaction is promoted, and the conversion rate of raw materials and the yield of products are improved. Meanwhile, the distillation technology can improve the quality of HClSI, reduce energy consumption, reduce the possibility of side reaction of products in the distillation process and realize batch continuous production. Moreover, the gas-liquid separation and aging device is integrated, the device adopts a corrosion-resistant material, and a large amount of acid tail gas is collected uniformly, so that the problems of strong reaction corrosivity and difficulty in treatment of a large amount of acid gas are solved.
Preferably, the inert gas comprises nitrogen.
Preferably, the inert gas (nitrogen) is a dry gas with a moisture content of < 50ppm.
Preferably, the aging temperature is 75-150 ℃, for example, 80 ℃, 85 ℃, 90 ℃,95 ℃,100 ℃, 105 ℃,110 ℃, 115 ℃,120 ℃, 125 ℃,130 ℃, 135 ℃, 140 ℃ or 145 ℃, and the specific values therebetween, are not exhaustive and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the scope.
Preferably, the aging time is 0.1 to 12 hours, for example, 0.5 hour, 1.0 hour, 1.5 hour, 2.0 hour, 2.5 hour, 3.0 hour, 3.5 hour, 4.0 hour, 4.5 hour, 5.0 hour, 5.5 hour, 6 hour, 6.5 hour, 7 hour, 7.5 hour, 8 hour, 8.5 hour, 9 hour, 9.5 hour, 10 hour or 11 hour, and specific values between the above values, which are not exhaustive and included in the range, are further preferred to be 0.5 to 10 hours, for the sake of brevity.
Preferably, the distillation device is a reduced pressure evaporation kettle.
Preferably, the distillation temperature is 70-150 ℃, for example, it may be 75 ℃,80 ℃, 85 ℃, 90 ℃,95 ℃,100 ℃, 105 ℃,110 ℃, 115 ℃,120 ℃, 125 ℃,130 ℃, 135 ℃, 140 ℃ or 145 ℃, and the specific values therebetween, are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.
Preferably, the distillation pressure is between 1 Pa and 200Pa, for example 5Pa, 10Pa, 20Pa, 30Pa, 50Pa, 70Pa, 90Pa, 100Pa, 110Pa, 130Pa, 150Pa, 170Pa or 190Pa, and specific values therebetween, not to be limited by space and for reasons of brevity, the invention is not exhaustive of the specific values included in the range, further preferably 80 to 120Pa.
Preferably, the molar ratio of the bis-chlorosulfonyl imide to hydrogen fluoride in step (2) is 1 (2-50), and can be, for example, 1.
Preferably, the continuous reactor of step (2) comprises a microchannel reactor and/or a dynamic tube reactor.
Preferably, the inner wall material of the continuous reactor in the step (2) comprises silicon carbide and/or corrosion-resistant alloy.
Preferably, the corrosion resistant alloy comprises hastelloy (e.g., hastelloy C-276 alloy) and/or monel.
Preferably, the reaction temperature in the step (2) is 80-150 ℃, for example, 85 ℃, 90 ℃,95 ℃,100 ℃, 105 ℃,110 ℃, 115 ℃,120 ℃, 125 ℃,130 ℃, 135 ℃, 140 ℃ or 145 ℃, and the specific values therebetween, for brevity and conciseness, the invention is not exhaustive and does not include the specific values included in the range, and more preferably 90-120 ℃.
Preferably, the reaction time of step (2) is 0.1-24h, such as 0.2h, 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23h, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive.
Preferably, the reaction in step (2) further comprises a post-treatment step after the reaction is completed.
The reaction in the step (2) can generate hydrogen chloride, and residual hydrogen fluoride also exists in the system, so that the reaction in the step (2) can obtain a mixed gas of hydrogen chloride and hydrogen fluoride. Preferably, after the reaction in the step (2) is completed, an inert gas is introduced into the system to remove hydrogen chloride and hydrogen fluoride.
Preferably, the inert gas comprises nitrogen.
Preferably, the time for introducing the inert gas is 2 to 6 hours, and for example, may be 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or the like.
Preferably, the method of post-processing comprises: pressurizing and separating the mixed gas generated in the step (2) to respectively obtain hydrogen fluoride and hydrogen chloride; the hydrogen fluoride is used in the reaction in the step (2) and the hydrogen chloride is mixed with water to obtain hydrochloric acid.
Preferably, the pressure of the pressure separation is between 0.1 and 5.0MPa, and may be, for example, 0.3MPa, 0.5MPa, 0.8MPa, 1.0MPa, 1.5MPa, 2.0MPa, 2.5MPa, 3.0MPa, 3.5MPa, 4.0MPa or 4.5MPa, and specific values therebetween, not to be limiting in space and for the sake of brevity, the invention is not exhaustive and does not list the specific values included in the range.
Preferably, the hydrochloric acid has a HCl content of 15-35% by mass, for example, 16%, 18%, 20%, 22%, 25%, 28%, 30%, 32% or 34%, and the specific values therebetween are not exhaustive for the purpose of space and brevity.
Preferably, the hydrogen fluoride is condensed and then used in the reaction in step (2).
Preferably, the bis-fluorosulfonyl imide obtained in step (2) is further subjected to a purification step.
Preferably, the method of purification comprises distillation and/or rectification.
Preferably, the distillation is reduced pressure distillation, and the obtained fraction is purified bis-fluorosulfonylimide.
Preferably, the fraction which is not distilled in the distillation is discharged into water for hydrolysis, and the hydrolysate is neutralized by an alkaline solution (such as NaOH solution) and then treated as solid waste.
Preferably, the vacuum degree of the reduced pressure distillation is-0.05 MPa to-0.09 MPa, and may be, for example, -0.055MPa, -0.06MPa, -0.065MPa, -0.07MPa, -0.075MPa, -0.08MPa or-0.085 MPa, etc.
Preferably, the temperature of the reduced pressure distillation is 90-120 ℃, for example, 92 ℃,95 ℃, 98 ℃,100 ℃, 102 ℃, 105 ℃, 108 ℃,110 ℃, 112 ℃, 115 ℃ or 118 ℃ and the like.
Preferably, the reduced pressure distillation time is 0.5 to 3 hours, and for example, may be 0.75 hour, 1 hour, 1.25 hour, 1.5 hour, 1.75 hour, 2 hours, 2.25 hours, 2.5 hours, 2.75 hours, or the like.
Preferably, the fraction obtained at the top of the rectification tower is purified bis-fluorosulfonyl imide, and the heavy component at the bottom of the rectification tower is recovered and used in the reaction in the step (2).
Preferably, fluorosulfonic acid is also generated as a byproduct in the reaction in the step (2), and the fluorosulfonic acid has a similar boiling point to HFSI and is difficult to separate and remove by a conventional process; by adopting a separation process of adding sodium chloride to remove impurities and then distilling/rectifying, trace fluorosulfonic acid can be removed, and the purity of HFSI is improved.
Preferably, the molar ratio of the bis-fluorosulfonyl imide to lithium fluoride in step (3) is 1 (0.8-1.3), and can be, for example, 1.
Preferably, the temperature of the reaction in the step (3) is 110-200 ℃, for example, 115 ℃,120 ℃, 125 ℃,130 ℃, 135 ℃, 140 ℃,145 ℃, 150 ℃, 155 ℃,160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃ or 195 ℃, and the specific values therebetween are limited in space and for the sake of brevity, and the invention is not exhaustive enumeration of the specific values included in the range, and more preferably 125-165 ℃.
Preferably, the reaction time in step (3) is 0.1-24h, such as 0.2h, 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23h, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive and specific values included in the range are further preferably 0.1-12h.
Preferably, the lithium bis (fluorosulfonyl) imide obtained in the step (3) is mixed with a solvent to obtain a lithium bis (fluorosulfonyl) imide solution.
As LiFSI is mostly used as a lithium salt electrolyte/additive in the electrolyte, liFSI obtained by a solvent-free process can be further dissolved in a solvent as a preferred technical scheme of the invention, thereby facilitating the preparation of the subsequent electrolyte.
Preferably, the solvent includes an ester solvent, more preferably a carbonate solvent and/or a carboxylic acid ester solvent, and more preferably a carbonate solvent.
Preferably, the ester-based solvent includes any one of dimethyl carbonate (DMC), diethyl carbonate, ethyl Methyl Carbonate (EMC), ethylene carbonate, propylene carbonate, butylene carbonate, γ -butyrolactone, dipropyl carbonate, vinylene carbonate, methyl propyl carbonate, ethyl acetate, methyl butyrate, ethyl butyrate, methyl propionate, ethyl propionate, propyl propionate, or propyl acetate, or a combination of at least two thereof.
Preferably, the lithium bis (fluorosulfonyl) imide solution further comprises a purification step.
Preferably, the method of purification comprises: removal of any one or a combination of at least two of acidic species (e.g., HF), solid-liquid separation, extraction, or recrystallization.
Acidic species (HF) are generated due to the reaction of LiF with HFSI; preferably, the agent for removing acidic substances is lithium carbonate (Li) 2 CO 3 )。
Preferably, the method for removing acidic substances comprises: and mixing the lithium bis (fluorosulfonyl) imide solution with lithium carbonate to remove residual acidic substances (HF) in the solution.
Preferably, the solid-liquid separation method is filtration, so as to filter out solid impurities in the system.
Preferably, the preparation method specifically comprises the following steps:
(1) The preparation method of the bis-chlorosulfonyl imide comprises the following steps:
(a) Mixing sulfamic acid, chlorosulfonic acid and thionyl chloride in a molar ratio of 1 (1-1.5) to 2-5 in a mixing kettle provided with an emulsification pump, wherein the mixing comprises the processes of circular grinding and dispersion until the particle size of the sulfamic acid is less than or equal to 100 mu m to obtain a mixture;
(b) Introducing the mixture into a dynamic tubular reactor, and reacting at 70-150 ℃ for 5-120min to obtain a reaction solution;
(c) Placing the reaction liquid in a gas-liquid separator for gas-liquid separation and aging, and introducing nitrogen to remove hydrogen chloride and sulfur dioxide to obtain a bis (chlorosulfonyl) imide solution; the aging temperature is 75-150 ℃, and the aging time is 0.5-10h;
(d) Distilling the bis-chlorosulfonyl imide solution to obtain the bis-chlorosulfonyl imide; the distillation pressure is 1-200Pa, and the temperature is 75-150 ℃;
(2) Reacting the bis-chlorosulfonyl imine obtained in the step (1) with hydrogen fluoride in a continuous reactor at the temperature of 80-150 ℃ for 0.1-24h to obtain bis-fluorosulfonyl imine; the molar ratio of the bis (chlorosulfonyl) imide to the hydrogen fluoride is 1 (2-50);
(3) Reacting the bis (fluorosulfonyl) imide obtained in the step (2) with lithium fluoride at the temperature of 110-200 ℃ for 0.1-24h to obtain the bis (fluorosulfonyl) imide lithium; the molar ratio of the bis-fluorosulfonyl imide to the lithium fluoride is 1 (0.8-1.3).
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method provided by the invention, HFSI is prepared quickly and efficiently by continuous equipment, and then the HFSI and LiF are reacted under the solvent-free condition to prepare LiFSI, so that the reaction time is short, the reaction efficiency and selectivity are high, the conversion rate of raw materials is high, complex solvent removal and purification steps are not needed, a large amount of waste liquid is avoided, and the high-purity and high-yield LiFSI is prepared efficiently.
(2) According to the invention, through the design of the process and the optimization of the parameters, the purity of the target product LiFSI is more than 98%, and the yield is more than 90% on the premise of no need of complicated purification and post-treatment, so that the preparation method is a convenient, efficient and environment-friendly process, can fully meet the requirements of large-scale production, and the product quality meets the industrial standards of batteries.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
"optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
The indefinite articles "a" and "an" preceding an element or component of the invention are used without limitation to the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
Reference throughout this specification to "one embodiment," "some embodiments," "exemplary," "specific examples" or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this document, schematic representations of the above terms are not necessarily intended to refer to the same embodiment or example.
Further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
In the following embodiments of the present invention, all chemical reagents such as raw materials are commercially available chemical products. Purity data of all products were obtained by ion chromatography tests, and the yield is mass yield.
In the following embodiment of the invention, the length of the dynamic tube reactor is 1000mm, the equivalent diameter is 150mm, and the inner wall material is Hastelloy C-276 alloy.
Example 1
A preparation method of lithium bis (fluorosulfonyl) imide specifically comprises the following steps:
(1) Bis-chlorosulfonylimide (HClSI) was prepared by the following procedure:
(a) Feeding sulfamic acid, chlorosulfonic acid and thionyl chloride in a molar ratio of 1.2;
(b) Introducing the mixture into a dynamic tubular reactor through a peristaltic pump, and reacting for 50min at 120 ℃ to obtain a reaction solution;
(c) Placing the reaction liquid in a gas-liquid separator for gas-liquid separation and aging, and introducing dry nitrogen to remove hydrogen chloride and sulfur dioxide to obtain a bis (chlorosulfonyl) imide solution; the aging temperature is 120 ℃, and the aging time is 7 hours;
(d) Distilling the bis-chlorosulfonyl imide solution in a reduced pressure evaporation kettle at 100Pa and 100 ℃ to obtain HClSI;
(2) Introducing HClSI obtained in the step (1) into a continuous reactor, and introducing HF gas at 95 ℃ to ensure that the molar ratio of HF to HClSI is 2.2; reacting at 95 ℃ for 8h, and cooling to room temperature; introducing nitrogen into the reactor for 3 hours, removing mixed gas of HCl and HF, then carrying out reduced pressure distillation for 2 hours at-0.05 MPa and 100 ℃, and collecting fractions to obtain the bis (fluorosulfonyl) imide (HFSI);
(3) Adding the HFSI obtained in the step (2) into a reactor, heating to 120 ℃, and adding lithium fluoride (LiF) into the reactor to ensure that the molar ratio of the HFSI to the LiF is 1.05; after LiF is added, reacting for 5 hours at 145 ℃ to obtain difluoride sulfimide (LiFSI); liFSI was added to Ethyl Methyl Carbonate (EMC) to obtain an EMC solution of LiFSI.
Example 2
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following steps:
(1) HClSI was prepared as follows:
(a) Feeding sulfamic acid, chlorosulfonic acid and thionyl chloride in a molar ratio of 1.4;
(b) Introducing the mixture into a dynamic tubular reactor through a peristaltic pump, and reacting for 100min at 110 ℃ to obtain a reaction solution;
(c) Placing the reaction liquid in a gas-liquid separator for gas-liquid separation and aging, and introducing dry nitrogen to remove hydrogen chloride and sulfur dioxide to obtain a bis (chlorosulfonyl) imide solution; the aging temperature is 110 ℃, and the aging time is 10 hours;
(d) Distilling the bis-chlorosulfonyl imide solution in a reduced pressure evaporation kettle at the pressure of 120Pa and the temperature of 130 ℃ to obtain HClSI;
(2) Introducing the HClSI obtained in the step (1) into a continuous reactor, and introducing HF gas at 80 ℃ to ensure that the molar ratio of HF to HClSI is 2.5; reacting at 80 ℃ for 12h, and cooling to room temperature; introducing nitrogen into the reactor for 3 hours, removing the mixed gas of HCl and HF, then carrying out reduced pressure distillation for 2 hours at-0.05 MPa and 100 ℃, and collecting fractions to obtain the HFSI;
(3) Adding the HFSI obtained in the step (2) into a reactor, heating to 120 ℃, and adding LiF into the reactor to ensure that the molar ratio of the HFSI to the LiF is 1.2; after LiF is added, reacting for 3.5h at 160 ℃ to obtain LiFSI; liFSI was added to the EMC solvent to obtain an EMC solution of LiFSI.
Example 3
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following steps:
(1) HClSI was prepared as follows:
(a) Feeding sulfamic acid, chlorosulfonic acid and thionyl chloride in a molar ratio of 1.05;
(b) Introducing the mixture into a dynamic tubular reactor through a peristaltic pump, and reacting for 20min at 130 ℃ to obtain a reaction solution;
(c) Placing the reaction liquid in a gas-liquid separator for gas-liquid separation and aging, and introducing dry nitrogen to remove hydrogen chloride and sulfur dioxide to obtain a bis (chlorosulfonyl) imide solution; the aging temperature is 130 ℃, and the aging time is 5h;
(d) Distilling the bis-chlorosulfonyl imide solution in a reduced pressure evaporation kettle at 80Pa and 80 ℃ to obtain HClSI;
(2) Introducing HClSI obtained in the step (1) into a continuous reactor, and introducing HF gas at 100 ℃ to ensure that the molar ratio of HF to HClSI is 2.1; reacting at 100 ℃ for 7h, and cooling to room temperature; introducing nitrogen into the reactor for 3h, removing the mixed gas of HCl and HF, then carrying out reduced pressure distillation at-0.05 MPa and 100 ℃ for 2h, and collecting fractions to obtain HFSI;
(3) Adding the HFSI obtained in the step (2) into a reactor, heating to 120 ℃, and adding LiF into the reactor to ensure that the molar ratio of the HFSI to the LiF is 1; after LiF is added, reacting for 8 hours at 130 ℃ to obtain LiFSI; liFSI was added to the solvent EMC to obtain an EMC solution of LiFSI.
Example 4
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following steps:
(1) Bis-chlorosulfonylimide (HClSI) was prepared by the following procedure:
(a) Feeding sulfamic acid, chlorosulfonic acid and thionyl chloride in a molar ratio of 1.2;
(b) Introducing the mixture into a dynamic tubular reactor through a peristaltic pump, and reacting for 130min at 120 ℃ to obtain a reaction solution;
(c) Placing the reaction liquid in a gas-liquid separator for gas-liquid separation and aging, and introducing dry nitrogen to remove hydrogen chloride and sulfur dioxide to obtain a bis (chlorosulfonyl) imide solution; the aging temperature is 120 ℃, and the aging time is 7 hours;
(d) Distilling the bis-chlorosulfonyl imide solution in a reduced pressure evaporation kettle at 100Pa and 100 ℃ to obtain HClSI;
(2) The HClSI obtained in step (1) was subjected to the same procedures as in steps (2) and (3) of example 1 to prepare HFSI and LiFSI in this order.
Example 5
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following steps:
(1) Bis-chlorosulfonyl imide (HClSI) was prepared by the following procedure:
(a) Feeding sulfamic acid, chlorosulfonic acid and thionyl chloride in a molar ratio of 1.2;
(b) Introducing the mixture into a dynamic tubular reactor through a peristaltic pump, and reacting for 50min at 120 ℃ to obtain a reaction solution;
(c) Placing the reaction liquid in a gas-liquid separator for gas-liquid separation and aging, and introducing dry nitrogen to remove hydrogen chloride and sulfur dioxide to obtain a bis (chlorosulfonyl) imide solution; the aging temperature is 60 ℃, and the aging time is 7 hours;
(d) Distilling the bis-chlorosulfonyl imide solution in a reduced pressure evaporation kettle at 100Pa and 100 ℃ to obtain HClSI;
(2) The HClSI obtained in step (1) was used to prepare HFSI and LiFSI in the same manner as in steps (2) and (3) of example 1.
Example 6
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following steps:
(1) Bis-chlorosulfonyl imide (HClSI) was prepared by the following procedure:
(a) Feeding sulfamic acid, chlorosulfonic acid and thionyl chloride in a molar ratio of 1.2;
(b) Introducing the mixture into a dynamic tubular reactor through a peristaltic pump, and reacting for 50min at 120 ℃ to obtain a reaction solution;
(c) Placing the reaction liquid in a gas-liquid separator for gas-liquid separation and aging, and introducing dry nitrogen to remove hydrogen chloride and sulfur dioxide to obtain a bis (chlorosulfonyl) imide solution; the aging temperature is 120 ℃, and the aging time is 20min;
(d) Distilling the bis-chlorosulfonyl imide solution in a reduced pressure evaporation kettle at 100Pa and 100 ℃ to obtain HClSI;
(2) The HClSI obtained in step (1) was subjected to the same procedures as in steps (2) and (3) of example 1 to prepare HFSI and LiFSI in this order.
Example 7
A preparation method of lithium bis (fluorosulfonyl) imide specifically comprises the following steps:
(1) Bis-chlorosulfonylimide (HClSI) was prepared by the following procedure:
(a) Feeding sulfamic acid, chlorosulfonic acid and thionyl chloride in a molar ratio of 1.2;
(b) Introducing the mixture into a dynamic tubular reactor through a peristaltic pump, and reacting for 50min at 120 ℃ to obtain a reaction solution;
(c) Placing the reaction liquid in a gas-liquid separator for gas-liquid separation and aging, and introducing dry nitrogen to remove hydrogen chloride and sulfur dioxide to obtain a bis (chlorosulfonyl) imide solution; the aging temperature is 120 ℃, and the aging time is 12 hours;
(d) Distilling the bis-chlorosulfonyl imide solution in a reduced pressure evaporation kettle at 100Pa and 100 ℃ to obtain HClSI;
(2) The HClSI obtained in step (1) was used to prepare HFSI and LiFSI in the same manner as in steps (2) and (3) of example 1.
Example 8
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following steps:
(1) Bis-chlorosulfonyl imide (HClSI) was prepared by the following procedure:
(a) Feeding sulfamic acid, chlorosulfonic acid and thionyl chloride in a molar ratio of 1.2;
(b) Introducing the mixture into a dynamic tubular reactor through a peristaltic pump, and reacting for 50min at 120 ℃ to obtain a reaction solution;
(c) Putting the reaction liquid into a gas-liquid separator for gas-liquid separation, introducing nitrogen to remove hydrogen chloride and sulfur dioxide, introducing the reaction liquid into a reduced pressure evaporation kettle for distillation, wherein the pressure is 100Pa, and the temperature is 100 ℃, so as to obtain HClSI;
(2) The HClSI obtained in step (1) was used to prepare HFSI and LiFSI in the same manner as in steps (2) and (3) of example 1.
Example 9
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following steps:
(1) Bis-chlorosulfonyl imide (HClSI) was prepared by the following procedure:
(a) Feeding sulfamic acid, chlorosulfonic acid and thionyl chloride in a molar ratio of 1.2;
(b) Introducing the mixture into a dynamic tubular reactor through a peristaltic pump, and reacting for 120min at 120 ℃ to obtain a reaction solution;
(c) Putting the reaction liquid into a gas-liquid separator for gas-liquid separation, introducing nitrogen to remove hydrogen chloride and sulfur dioxide, and introducing the reaction liquid into a reduced pressure evaporation kettle for distillation at the pressure of 100Pa and the temperature of 100 ℃ to obtain HClSI;
(2) The HClSI obtained in step (1) was subjected to the same procedures as in steps (2) and (3) of example 1 to prepare HFSI and LiFSI in this order.
Comparative example 1
A preparation method of lithium bis (fluorosulfonyl) imide specifically comprises the following steps:
(1) Adding sulfamic acid, chlorosulfonic acid and thionyl chloride into a batch type reaction kettle according to a molar ratio of 1.2;
the HClSI obtained in step (1) was subjected to the same procedures as in steps (2) and (3) of example 1 to prepare HFSI and LiFSI in this order.
Comparative example 2
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following steps:
HClSI and HFSI were prepared in the same manner as in step (1) and step (2) of example 1 in this order;
(3) Dissolving LiF in a dimethyl carbonate solvent to form uniform suspension; adding the HFSI obtained in the step (2) into the mixture, wherein the molar ratio of the HFSI to the LiF is 1.05; after HFSI is added, reacting for 12 hours at 70 ℃ to obtain LiFSI solution; and (4) concentrating by reduced pressure distillation, and recrystallizing the concentrated solution by EMC to obtain the target product LiFSI.
Comparative example 3
A preparation method of lithium bis (fluorosulfonyl) imide specifically comprises the following steps:
(1) Adding sulfamic acid, chlorosulfonic acid and thionyl chloride into a batch type reaction kettle according to a molar ratio of 1.2;
(2) Introducing HClSI obtained in the step (1) into a reaction kettle, introducing HF gas at 95 ℃ to ensure that the molar ratio of HF to HClSI is 2.2; reacting at 95 ℃ for 8 hours, and cooling to room temperature; introducing nitrogen into the kettle for 3h, removing the mixed gas of HCl and HF, then carrying out reduced pressure distillation for 2h at-0.05 MPa and 100 ℃, and collecting fractions to obtain HFSI;
(3) Dissolving LiF in a dimethyl carbonate solvent to form uniform suspension; adding the HFSI obtained in the step (2) into the mixture, wherein the molar ratio of the HFSI to the LiF is 1.05; after HFSI is added, reacting for 16h at 70 ℃ to obtain LiFSI solution; and (4) concentrating by reduced pressure distillation, and recrystallizing the concentrated solution by EMC to obtain the target product LiFSI.
The purity and yield data of the target products (HClSI, HFSI, liFSI) obtained in examples 1-9 and comparative examples 1-3 are summarized; wherein the yields of HFSI and LiFSI are the total yields of this example/comparative example, as shown in table 1:
TABLE 1
According to the data in the table 1, the method for preparing lithium bis (fluorosulfonyl) imide provided by the invention has the advantages that HClSI and HFSI are quickly and efficiently prepared by continuous equipment, the yield of HClSI obtained in the step (1) is more than 96%, and the purity is more than or equal to 99%; the yield (total yield of two-step reaction) of the HClSI and the HF for generating the HFSI is more than or equal to 94 percent, and the purity is more than or equal to 99 percent; the HFSI is used as a raw material and reacts with LiF under the solvent-free condition to prepare LiFSI, the yield of the LiFSI (the total yield of three steps of reactions) is more than or equal to 90 percent, and the purity is more than or equal to 99 percent. Therefore, the preparation method provided by the invention has the advantages of higher reaction efficiency and reaction selectivity, high raw material conversion rate, no need of complex solvent removal and purification steps, and capability of quickly and efficiently obtaining the high-purity and high-yield LiFSI. In addition, the invention can obtain HClSI with high purity and high yield by the design and mutual combination of the reaction time and the aging step in the dynamic tubular reactor, and further obtain HFSI and LiFSI by using HClSI as a raw material; if the reaction time in the dynamic tube reactor is too long (example 4), the formation of byproducts in the reaction can be caused, and the yield and purity of HClSI are affected; if the aging temperature is too low (example 5) or the aging time is too short (example 6), the yield of HClSI is lowered, and the subsequent distillation process cannot completely remove by-products and unreacted raw materials, resulting in a decrease in purity; if the aging time is too long (example 7), on one hand, the whole process flow is prolonged, the efficiency is affected, and on the other hand, some byproduct impurities are generated in HClSI; without the aging step (examples 8-9), HClSI with high purity and high yield could not be obtained even if the reaction time in the dynamic tube reactor was extended (example 9), which in turn affected the yield of HFSI and LiFSI for subsequent production.
Comparative example 1 the conventional batch reactor is used to prepare HClSI, and the poor heat and mass transfer effect in the system results in low conversion rate of raw materials, long reaction time and significantly reduced HClSI yield, thereby affecting the total yield of the subsequent HFSI and LiFSI.
In comparative example 2, the reaction between HFSI and LiF is performed in the presence of a solvent, the reaction rate is slow, the time consumption is long, and the obtained LiFSI contains many impurities, and the impurities cannot be effectively removed even if the purification is performed by a recrystallization method, so that the yield and the purity of the target product are low.
Comparative example 3 HClSI and HFSI were prepared using a conventional batch reactor, the heat and mass transfer efficiency in the system was low, the reaction speed was slow, the reaction time was long, and the yields of HClSI and HFSI were low; and the reaction of HFSI and LiF is carried out in the presence of a solvent, the time consumption of the whole process is long, impurities cannot be effectively removed by recrystallization, the purification difficulty is high, the total yield of the target product LiFSI is low, and the quality cannot meet the standard of the battery industry easily.
The applicant states that the present invention is illustrated by the above examples to the preparation method of lithium bis (fluorosulfonylimide) according to the present invention, but the present invention is not limited to the above examples, which does not mean that the present invention is implemented by relying on the above examples. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of lithium bis (fluorosulfonyl) imide is characterized by comprising the following steps:
(1) Placing a mixture of sulfamic acid, chlorosulfonic acid and thionyl chloride in a dynamic tubular reactor for reaction to obtain dichlorosulfonimide;
(2) Reacting the bischlorosulfonimide obtained in the step (1) with hydrogen fluoride in a continuous reactor to obtain the bisfluorosulfonimide;
(3) And (3) reacting the bis-fluorosulfonyl imide obtained in the step (2) with lithium fluoride to obtain the lithium bis-fluorosulfonyl imide.
2. The method according to claim 1, wherein the molar ratio of the sulfamic acid to the chlorosulfonic acid in the step (1) is 1 (1-1.5);
preferably, the molar ratio of the sulfamic acid to the thionyl chloride in the step (1) is 1 (2-5);
preferably, the sulfamic acid, the chlorosulfonic acid and the thionyl chloride are mixed in a mixing kettle provided with an emulsification pump to obtain the mixture in the step (1);
preferably, the mixing comprises a process of cyclic grinding and dispersion;
preferably, the temperature of the mixing is 10-50 ℃;
preferably, the particle size of the sulfamic acid in the mixture of step (1) is less than or equal to 100 μm.
3. The production method according to claim 1 or 2, wherein the dynamic tube reactor of step (1) has a tube length of 500 to 10000mm;
preferably, the equivalent diameter of the dynamic tubular reactor of step (1) is 50 to 800mm;
preferably, the inner wall material of the dynamic tube reactor in the step (1) comprises silicon carbide and/or corrosion-resistant alloy.
4. The method according to any one of claims 1 to 3, wherein the temperature of the reaction in step (1) is 70 to 150 ℃;
preferably, the reaction time of step (1) is 5-120min.
5. The production method according to any one of claims 1 to 4, characterized in that the step (1) further comprises a step of post-treatment after the completion of the reaction;
preferably, the method of post-processing comprises: placing the reaction liquid obtained by the reaction in a gas-liquid separator for gas-liquid separation and aging, and introducing inert gas to remove hydrogen chloride and sulfur dioxide to obtain a bischlorosulfimide solution; distilling the bis-chlorosulfonyl imide solution to obtain the bis-chlorosulfonyl imide;
preferably, the inert gas comprises nitrogen;
preferably, the temperature of aging is 75 to 150 ℃;
preferably, the aging time is 0.5-10h;
preferably, the distillation device is a reduced pressure evaporation kettle;
preferably, the temperature of the distillation is 70-150 ℃;
preferably, the distillation pressure is between 1 and 200Pa.
6. The process according to any one of claims 1 to 5, wherein the molar ratio of the bis-chlorosulfonyl imide to hydrogen fluoride in the step (2) is 1 (2 to 50);
preferably, the continuous reactor of step (2) comprises a microchannel reactor and/or a dynamic tube reactor;
preferably, the inner wall material of the continuous reactor in the step (2) comprises silicon carbide and/or corrosion-resistant alloy.
7. The process according to any one of claims 1 to 6, wherein the temperature of the reaction in step (2) is 80 to 150 ℃, further preferably 90 to 120 ℃;
preferably, the reaction time of the step (2) is 0.1-24h.
8. The method according to any one of claims 1 to 7, wherein the step (2) further comprises a post-treatment step after the reaction is completed;
preferably, the method of post-processing comprises: pressurizing and separating the mixed gas generated in the step (2) to respectively obtain hydrogen fluoride and hydrogen chloride; the hydrogen fluoride is used in the reaction in the step (2) and the hydrogen chloride is mixed with water to obtain hydrochloric acid;
preferably, the pressure for the pressure separation is 0.1 to 5.0MPa;
preferably, the mass percentage of HCl in the hydrochloric acid is 15-35%;
preferably, the bis-fluorosulfonyl imide obtained in step (2) is further subjected to a purification step;
preferably, the method of purification comprises distillation and/or rectification.
9. The process according to any one of claims 1 to 8, wherein the molar ratio of the bis-fluorosulfonylimide to the lithium fluoride in the step (3) is 1 (0.8 to 1.3);
preferably, the temperature of the reaction of step (3) is 110 to 200 ℃, further preferably 125 to 165 ℃;
preferably, the reaction time of the step (3) is 0.1 to 24 hours, and further preferably 0.1 to 12 hours;
preferably, the lithium bis (fluorosulfonyl) imide obtained in the step (3) is mixed with a solvent to obtain a lithium bis (fluorosulfonyl) imide solution;
preferably, the solvent includes an ester solvent, and further preferably a carbonate solvent and/or a carboxylic acid ester solvent.
10. The preparation method according to any one of claims 1 to 9, characterized in that it comprises in particular the steps of:
(1) The preparation method of the bis-chlorosulfonyl imide comprises the following steps:
(a) Mixing sulfamic acid, chlorosulfonic acid and thionyl chloride in a molar ratio of 1 (1-1.5) to 2-5 in a mixing kettle provided with an emulsification pump, wherein the mixing comprises the processes of circular grinding and dispersion until the particle size of the sulfamic acid is less than or equal to 100 mu m to obtain a mixture;
(b) Introducing the mixture into a dynamic tubular reactor, and reacting at 70-150 ℃ for 5-120min to obtain a reaction solution;
(c) Placing the reaction liquid in a gas-liquid separator for gas-liquid separation and aging, and introducing nitrogen to remove hydrogen chloride and sulfur dioxide to obtain a bis (chlorosulfonyl) imide solution; the aging temperature is 75-150 ℃, and the aging time is 0.5-10h;
(d) Distilling the bis-chlorosulfonyl imide solution to obtain the bis-chlorosulfonyl imide; the distillation pressure is 1-200Pa, and the temperature is 70-150 ℃;
(2) Reacting the bis-chlorosulfonyl imine obtained in the step (1) with hydrogen fluoride in a continuous reactor at the temperature of 80-150 ℃ for 0.1-24h to obtain bis-fluorosulfonyl imine; the molar ratio of the bis (chlorosulfonyl) imide to the hydrogen fluoride is 1 (2-50);
(3) Reacting the bis (fluorosulfonyl) imide obtained in the step (2) with lithium fluoride at the temperature of 110-200 ℃ for 0.1-24h to obtain the bis (fluorosulfonyl) imide lithium; the molar ratio of the bis-fluorosulfonyl imide to the lithium fluoride is 1 (0.8-1.3).
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