CN115872370A - Preparation method of bis (fluorosulfonyl) imide and bis (fluorosulfonyl) imide salt - Google Patents
Preparation method of bis (fluorosulfonyl) imide and bis (fluorosulfonyl) imide salt Download PDFInfo
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- CN115872370A CN115872370A CN202211730202.2A CN202211730202A CN115872370A CN 115872370 A CN115872370 A CN 115872370A CN 202211730202 A CN202211730202 A CN 202211730202A CN 115872370 A CN115872370 A CN 115872370A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- -1 bis-fluorosulfonyl imide Chemical class 0.000 claims abstract description 51
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 23
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 15
- 239000007791 liquid phase Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003759 ester based solvent Substances 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010626 work up procedure Methods 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 34
- 239000000126 substance Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910017855 NH 4 F Inorganic materials 0.000 description 4
- WRJWRGBVPUUDLA-UHFFFAOYSA-N chlorosulfonyl isocyanate Chemical group ClS(=O)(=O)N=C=O WRJWRGBVPUUDLA-UHFFFAOYSA-N 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 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 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012320 chlorinating reagent Substances 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 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 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- PPFAPKNCEXDZNN-UHFFFAOYSA-N N=[SH2].F.F Chemical compound N=[SH2].F.F PPFAPKNCEXDZNN-UHFFFAOYSA-N 0.000 description 1
- CQXADFVORZEARL-UHFFFAOYSA-N Rilmenidine Chemical compound C1CC1C(C1CC1)NC1=NCCO1 CQXADFVORZEARL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000005935 Sulfuryl fluoride Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRCWHGIUHLWZBK-UHFFFAOYSA-K bismuth;trifluoride Chemical compound F[Bi](F)F BRCWHGIUHLWZBK-UHFFFAOYSA-K 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ATMIHASMQFJNLZ-UHFFFAOYSA-N dichloro(imino)-$l^{4}-sulfane Chemical compound ClS(Cl)=N ATMIHASMQFJNLZ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000526 short-path distillation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of bis (fluorosulfonyl) imide and bis (fluorosulfonyl) imide salt, which comprises the following steps: sulfonyl fluoride and NH 3 And (3) carrying out reaction under the solvent-free condition to obtain the bis (fluorosulfonyl) imide. The preparation method can prepare the high-purity and high-yield bis-fluorosulfonyl imide by adopting a one-step method, and has the advantages of simple process steps, short reaction time and high preparation efficiency, so that the process cost is obviously reduced; in addition, the preparation method does not need to use an organic solvent and a complex post-treatment step, and is a more green, environment-friendly, convenient and efficient process route. The bis (fluorosulfonyl) imide prepared by the preparation method is used for preparing bis (fluorosulfonyl) imide salt, and high-quality products can be obtainedLithium salt electrolytes such as lithium bis (fluorosulfonyl) imide and the like can meet the requirements of industrial production on the capacity and quality of lithium bis (fluorosulfonyl) imide.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a preparation method of bis (fluorosulfonyl) imide and bis (fluorosulfonyl) imide salt.
Background
Lithium ion batteries are typically assembled from a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the electrolyte is referred to as "blood" of the lithium ion battery", may account for around 13% of the cost component of a lithium ion battery. The electrolyte mainly comprises lithium salt electrolyte, organic solvent, additive and the like, and the existing electrolyte lithium salt comprises lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (fluorosulfonyl) imide and the like, wherein the lithium bis (fluorosulfonyl) imide LiN (SO) 2 F) 2 The (LiFSI) has higher conductivity, excellent thermal stability and higher safety, can effectively improve the performances of high-temperature storage, low-temperature discharge and the like of the lithium ion battery, has good compatibility with electrodes, and has good application prospect.
Currently known processes for preparing LiFSI include two routes, one of which is via an exchange reaction of potassium bis-fluorosulfonylimide with other lithium salts, such as subjecting potassium bis-fluorosulfonylimide to a metathesis exchange with lithium perchlorate or lithium tetrafluoroborate in an aprotic polar solvent to obtain LiFSI, or subjecting potassium bis-fluorosulfonylimide to a metathesis exchange with an organic lithium salt (such as lithium bis-oxalato-borate or lithium oxalato-difluoroborate) in a solvent to obtain LiFSI. The other route is prepared by the neutralization reaction of the bis-fluorosulfonyl imide or the ammonium salt thereof and lithium carbonate and/or lithium hydroxide. In both of the foregoing preparative routes, bis-fluorosulfonylimide (HFSI) is a very important intermediate.
The bis (fluorosulfonyl) imide is usually obtained by reacting bis (chlorosulfonyl) imide (HClSI) with a fluorinating agent, which includes arsenic trifluoride, antimony trifluoride, zinc fluoride, anhydrous hydrogen fluoride, bismuth trifluoride, or the like. One of the methods for obtaining the bis-chlorosulfonyl imide is to use sulfamic acid, chlorosulfonic acid and a chlorinating agent to react, wherein the common chlorinating agent comprises one or a mixture of at least two of thionyl chloride, oxalyl chloride, phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride and the like. For example, CN114804043A discloses a process for preparing lithium bis (fluorosulfonyl) imide, which comprises the following steps: step 1, sequentially adding sulfamic acid, thionyl chloride and chlorosulfonic acid into a dry reaction vessel to obtain a mixed solution, reacting at 100-120 ℃ for 30 hours, then carrying out vacuum distillation under reduced pressure, and collecting fractions at 110-114 ℃/0.267kPa to obtain dichlorosulfimide; step 2, mixing the bischlorosulfonimide liquid and antimony pentachloride in the step 1, heating to 100-105 ℃, slowly introducing hydrogen fluoride gas while stirring, reacting for 18h to obtain a crude product, and performing short-path distillation to obtain the bisfluorosulfonimide; and step 3: adding dichloromethane and lithium hydroxide-hydrate in the step 2, cooling to 0-5 ℃, stirring for 2h, heating to 20-25 ℃, adding thionyl chloride, stirring for 15h, adding a crown ether solvent, pulping, filtering and drying to obtain the lithium bis (fluorosulfonyl) imide product.
Another method for obtaining bis-chlorosulfonyl imide is chlorosulfonyl isocyanate, for example, the method for preparing lithium bis-fluorosulfonyl imide disclosed in CN106044728a includes the following steps: (1) Chlorosulfonic acid and chlorosulfonyl isocyanate react in the presence of catalyst to obtain dichlorosulfonimide; (2) Reacting bis-chlorosulfonyl imine with hydrogen fluoride in the presence of a catalyst to obtain bis-fluorosulfonyl imine; (3) Reacting the bis-fluorosulfonyl imide with a lithium-containing compound to obtain LiFSI. The chlorosulfonyl isocyanate method avoids SO as compared to a method using thionyl chloride as a chlorinating agent 2 And HCl and other gases, and the environment-friendly requirement is better met. However, the yield of chlorosulfonyl isocyanate is limited, thereby limiting the overall yield of HFSI and LiFSI, which is not suitable for LiFSI industrial application.
Generally, the current process for preparing HFSI includes at least two steps of reactions, the overall process duration is over 24 hours, and multiple reaction devices are required for the multiple steps of reactions, which are high in time cost, labor cost, equipment maintenance cost and raw material cost, so that the scale application of LiFSI and lithium ion batteries using the same is greatly limited. Therefore, the technical route for preparing HFSI and LiFSI is simplified, and the production cost is reduced, so as to realize the high-efficiency preparation of HFSI and LiFSI.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of bis-fluorosulfonyl imide and bis-fluorosulfonyl imide salt, wherein the preparation method uses sulfonyl fluoride and NH 3 (liquid ammonia and/or ammonia) is used as a raw material, the bis-fluorosulfonyl imide is obtained by a one-step method, the process steps are simple, the reaction time is short, an organic solvent is not required to be used, the characteristics of environmental protection and high efficiency are realized, and the full satisfaction of the requirements on environment friendliness and high efficiency can be realizedLarge-scale industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing bis (fluorosulfonyl) imide, comprising: sulfonyl fluoride and NH 3 The reaction is carried out under the solvent-free condition to obtain the bis-fluorosulfonyl imide (HFSI).
The reaction formula of the preparation method provided by the invention is as follows:
2SO 2 F 2 +NH 3 →HN(SO 2 F) 2 +2HF；
HF+NH 3 →NH 4 F；
wherein the sulfonyl fluoride is reacted with NH 3 Reacting in one step to obtain a target product HFSI and simultaneously generate HF; HF and NH in the system 3 React to form NH 4 F，NH 4 F is solid, and then the HFSI (liquid) can be separated by adopting a solid-liquid separation method. The preparation method can obtain the target product HFSI with high purity and high yield through one-step reaction, has simple process steps, short preparation time and high preparation efficiency, thereby obviously reducing the time cost and the raw material cost, and being a green, environment-friendly, convenient and efficient preparation process of the difluoride sulfimide without using an organic solvent or a complex post-treatment step.
Preferably, the preparation method comprises any one of method A, method B, method C and method D.
The method A comprises the following steps: and introducing ammonia gas into the liquefied sulfonyl fluoride for reaction to obtain the bis (fluorosulfonyl) imide.
The method B comprises the following steps: and (3) introducing sulfonyl fluoride into liquid ammonia for reaction to obtain the bis-fluorosulfonyl imide.
The method C comprises the following steps: and mixing the liquefied sulfonyl fluoride with liquid ammonia for reaction to obtain the bis-fluorosulfonyl imide.
The method D comprises the following steps: and mixing the gaseous sulfonyl fluoride with ammonia gas for reaction to obtain the bis (fluorosulfonyl) imide.
Preferably, the preparation method is a method A, a method B and a methodAny one of the methods C; whereby said sulfonyl fluoride is liquefied sulfonyl fluoride and/or said NH 3 The reaction is carried out in a liquid phase environment for liquid ammonia, so that the two raw materials can be fully contacted and reacted, the reaction rate and the preparation efficiency are improved, and the reaction time is shortened.
Preferably, the sulfonyl fluoride is reacted with NH 3 The molar ratio of (1.5-4), for example, can be 1.6, 1.8, 1:2, 1.2, 1, 2.5, 1, 2.8, 1:3, 1.
As a preferred embodiment of the present invention, the sulfonyl fluoride and NH 3 The molar ratio of (1), (1.5-4), NH 3 In a suitable excess, the hydrogen fluoride produced is completely replaced by NH 3 Absorbing to improve the conversion rate of the raw material and obtain the target product HFSI with high purity and high yield.
Preferably, the reaction temperature is 0 to 100 ℃, for example, 5 ℃,10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃, and the specific values therebetween are limited for space and simplicity, and the invention is not exhaustive.
Preferably, the reaction time is 0.1 to 12h, for example 0.2h, 0.5h, 0.8h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 11h, and specific values therebetween, not exhaustive enumeration of the ranges included therein is included herein for reasons of brevity and conciseness.
Preferably, the pressure of the reaction is 2.0 to 8.0MPa, for example, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa, 5MPa, 5.5MPa, 6MPa, 6.5MPa, 7MPa or 7.5MPa, and specific values therebetween are not exhaustive, and for the sake of brevity, the invention is not intended to list the specific values included in the range, and more preferably 3.0 to 6.0MPa.
As a preferred embodiment of the present invention, the reaction is carried out under a high pressure condition, preferably a pressure of 2.0 to 8.0MPa, to react the starting sulfuryl fluoride with NH 3 Fully contact and react in a liquid phase environment to obtain the HFSI with high purity and high yield.
Preferably, the means for reacting comprises a batch reactor or a continuous reactor.
Preferably, the reaction also comprises a post-treatment step after the reaction is finished.
Preferably, the method of work-up comprises solid-liquid separation, optionally distillation and optionally rectification.
Preferably, the solid-liquid separation method comprises filtration, and the solid phase obtained by filtration is NH 4 F, the liquid phase is the target product HFSI.
Preferably, the liquid phase (HFSI) obtained after the solid-liquid separation is subjected to purification treatment by distillation and/or rectification, so that impurities in the system are removed, and the high-purity HFSI is obtained.
Preferably, the distillation is a vacuum distillation.
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, and specific values therebetween, and the invention is not exhaustive and for the sake of brevity only specific values included in the stated range are not enumerated.
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 specific values therebetween are limited for space and simplicity, and the invention is not exhaustive.
Preferably, the reduced pressure distillation time is 0.5 to 3h, for example, 0.75h, 1h, 1.25h, 1.5h, 1.75h, 2h, 2.25h, 2.5h or 2.75h, and the specific values therebetween are not exhaustive, and for the sake of brevity and clarity, the invention is not intended to include the specific values within the stated ranges.
Preferably, the preparation method specifically comprises: sulfonyl fluoride and NH 3 Reacting for 0.1-12h at 0-100 ℃ under the pressure of 2.0-8.0MPa, and then carrying out solid-liquid separation on the product to obtain a liquid phase of the bis (fluorosulfonyl) imide; the sulfonyl fluoride and NH 3 In a molar ratio of1, (1.5-4); the reaction is carried out in the absence of a solvent.
In a second aspect, the present invention provides a method for preparing a bis-fluorosulfonyl imide salt, comprising the steps of:
(1) Preparing the bis-fluorosulfonyl imide by the preparation method of the first aspect;
(2) Reacting the bis (fluorosulfonyl) imide obtained in the step (1) with a metal source to obtain the bis (fluorosulfonyl) imide salt.
Preferably, the metal source of step (2) comprises an alkali metal hydroxide and/or an alkali metal salt.
Preferably, the bis-fluorosulfonyl imide salt includes lithium bis-fluorosulfonyl imide (LiFSI), sodium bis-fluorosulfonyl imide, or potassium bis-fluorosulfonyl imide, and further preferably lithium bis-fluorosulfonyl imide.
Preferably, the metal source in step (2) is a lithium source, including lithium hydroxide and/or a lithium salt.
Preferably, the metal source in step (2) comprises any one or a combination of at least two of lithium hydroxide, lithium carbonate, lithium hexafluorophosphate and lithium fluoride, and lithium fluoride is more preferred.
Preferably, the molar ratio of the bis-fluorosulfonyl imide to the metal source is 1 (1.0-1.3), and may be, for example, 1:1, 1.05, 1.1, 1.15, 1.
Preferably, the reaction temperature in step (2) is 90-165 ℃, for example, 95 ℃,100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃,140 ℃, 145 ℃,150 ℃, 155 ℃ or 160 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive listing the specific values included in the range.
Preferably, the reaction time in step (2) is 0.1-12h, for example, 0.2h, 0.5h, 0.8h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 11h, and the specific values therebetween, and the invention is not exhaustive for the specific values included in the range in the interest of brevity and conciseness.
In the preparation method of the bis (fluorosulfonyl) imide salt, the reaction in the step (2) does not need to use an organic solvent, and a metal source and the bis (fluorosulfonyl) imide (liquid) react at 90-165 ℃ to obtain the bis (fluorosulfonyl) imide salt; as the reaction is a solvent-free process, a large amount of waste liquid is avoided, the waste liquid treatment capacity is obviously reduced, and the method is more environment-friendly.
Preferably, the reaction in step (2) generates a bis-fluorosulfonyl imide salt, and the bis-fluorosulfonyl imide salt is mixed with a solvent to obtain the bis-fluorosulfonyl imide salt solution.
Preferably, the solvent comprises an ester solvent, further preferably a carbonate solvent and/or a carboxylate 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 acetate, or a combination of at least two thereof.
Preferably, the bis-fluorosulfonyl imide salt solution further comprises a purification step.
Preferably, the method of purification comprises: removing any one or a combination of at least two of acidic species (e.g., HF), solid-liquid separation, extraction, or recrystallization.
Preferably, the metal source is a lithium salt (e.g., liF) that reacts with HFSI to form an acidic species (HF); 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 bis (fluorosulfonyl) imide salt 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 solid impurities in the system.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention providesIn the preparation method of the bis-fluorosulfonyl imide, sulfonyl fluoride and NH are used 3 The raw material is adopted, the high-purity and high-yield bis-fluorosulfonyl imide can be obtained by a one-step method, the process steps are simple, the reaction time is short, and the preparation efficiency is high, so that the process cost is obviously reduced; in addition, the preparation method does not need to use an organic solvent or a complex post-treatment step, the yield of the target product, namely the bis-fluorosulfonyl imide, is more than or equal to 95 percent, the purity of the target product, namely the bis-fluorosulfonyl imide, is more than or equal to 99.5 percent, and is a more environment-friendly, convenient and efficient process route, and the large-scale industrial production requirements can be fully met.
(2) The bis-fluorosulfonyl imide obtained by the preparation method is used for preparing bis-fluorosulfonyl imide salt, the bis-fluorosulfonyl imide salt can be obtained by a solvent-free process, a large amount of chemical waste liquid is avoided, the process is green and environment-friendly, high-quality lithium salt electrolytes such as bis-fluorosulfonyl imide can be obtained, and the requirements of industrial production on the capacity and quality of the bis-fluorosulfonyl imide can be met.
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 "either" 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 not intended to limit 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, the schematic representations of the terms used above 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, and the reaction apparatus used is a high-pressure reactor. The structures of all products are tested and confirmed by a nuclear magnetic resonance analyzer, the purity data is obtained by testing through a gas chromatography, and the yield is the mass yield.
Example 1
A preparation method of bis (fluorosulfonyl) imide comprises the following specific steps: adding liquefied sulfonyl fluoride into a high-pressure reaction kettle, controlling the pressure in the kettle to be 3MPa, and introducing ammonia gas into the kettle to ensure that the molar ratio of the liquefied sulfonyl fluoride to the ammonia gas is 1.8; and (2) after ammonia gas is completely introduced, reacting for 2 hours at 30 ℃ and 3MPa, filtering the obtained product, and removing solid impurities to obtain a liquid phase of the bis (fluorosulfonyl) imide (HFSI), wherein the yield is 97% and the purity is 99.7%.
Structure detection of HFSI: F-NMR (CDCl) 3 -d，400MHz)：δ59.10ppm。
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following steps: adding lithium fluoride LiF into a reactor, heating to 120 ℃, and adding the HFSI prepared in the embodiment into the reactor, wherein the molar ratio of the HFSI to the LiF is 1:1; after HFSI is added, reacting for 5h at 140 ℃ to obtain lithium bis (fluorosulfonyl) imide (LiFSI); liFSI was added to Ethyl Methyl Carbonate (EMC) to obtain an EMC solution of LiFSI. The purity of the LiFSI is 99.5%, and the yield is 95%.
Example 2
A preparation method of bis (fluorosulfonyl) imide comprises the following specific steps: adding liquefied sulfonyl fluoride into a high-pressure reaction kettle, controlling the pressure in the kettle to be 6.0MPa, and introducing ammonia gas into the kettle to ensure that the molar ratio of the liquefied sulfonyl fluoride to the ammonia gas is 1:3; after ammonia gas is completely introduced, the mixture reacts for 1.5 hours at the temperature of 25 ℃ and under the pressure of 6.0MPa, the obtained product is filtered, solid impurities are removed, the obtained liquid phase is the target product HFSI, the yield is 97.2%, and the purity is 99.6%.
The structure of the target product is characterized by F-NMR, and the chemical shift data are the same as example 1 and are not repeated.
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following steps: adding LiF into a reactor, heating to 120 ℃, and adding the HFSI prepared in the embodiment into the reactor, wherein the molar ratio of the HFSI to the LiF is 1; after HFSI is added, reacting for 5 hours at 140 ℃ to obtain LiFSI; liFSI was added to the solvent EMC to obtain an EMC solution of LiFSI. The purity of the LiFSI is 99.2%, and the yield is 94.8%.
Example 3
A preparation method of bis (fluorosulfonyl) imide comprises the following specific steps: adding liquid ammonia into a high-pressure reaction kettle, controlling the pressure in the kettle to be 3.5MPa, and introducing sulfonyl fluoride into the kettle to ensure that the molar ratio of the sulfonyl fluoride to the liquid ammonia is 1:2; after the sulfonyl fluoride is completely introduced, the obtained product is filtered after the reaction is carried out for 1.5h under the conditions of 25 ℃ and 3.5MPa, solid impurities are removed, the obtained liquid phase is the target product HFSI, the yield is 96 percent, and the purity is 99.5 percent.
The structure of the target product is characterized by F-NMR, and the chemical shift data are the same as example 1 and are not repeated.
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following steps: adding lithium fluoride LiF into a reactor, heating to 120 ℃, adding the HFSI prepared in the embodiment into the reactor, wherein the molar ratio of the HFSI to the LiF is 1:1; after HFSI is added, reacting for 5 hours at 140 ℃ to obtain LiFSI; liFSI was added to the solvent EMC to obtain an EMC solution of LiFSI. The purity of the LiFSI is 99.6%, and the yield is 96%.
Example 4
A preparation method of bis (fluorosulfonyl) imide comprises the following specific steps: adding liquid ammonia into a high-pressure reaction kettle, controlling the pressure in the kettle to be 2.8MPa, and introducing sulfonyl fluoride into the kettle so that the molar ratio of the sulfonyl fluoride to the liquid ammonia is 1; after sulfonyl fluoride is completely introduced, reacting for 3.5 hours at 20 ℃ under the pressure of 2.8MPa, filtering the obtained product, removing solid impurities, and obtaining a liquid phase which is the target product HFSI, wherein the yield is 96.3 percent and the purity is 99.7 percent.
The structure of the target product is characterized by F-NMR, and the chemical shift data are the same as example 1 and are not repeated.
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following steps: adding lithium fluoride LiF into a reactor, heating to 120 ℃, and adding the HFSI prepared in the embodiment into the reactor, wherein the molar ratio of the HFSI to the LiF is 1:1; after HFSI is added, reacting for 5 hours at 140 ℃ to obtain LiFSI; liFSI was added to the solvent EMC to obtain an EMC solution of LiFSI. The purity of the LiFSI is 99.5%, and the yield is 96.3%.
Example 5
A preparation method of bis (fluorosulfonyl) imide comprises the following specific steps: controlling the pressure in the high-pressure reaction kettle to be 3.5MPa, and introducing liquid ammonia and liquefied sulfonyl fluoride into the kettle to ensure that the molar ratio of the liquefied sulfonyl fluoride to the liquid ammonia is 1:2; after all the materials are introduced, the reaction is carried out for 1h under the conditions of 25 ℃ and 3.5MPa, the obtained product is filtered, solid impurities are removed, the obtained liquid phase is the target product HFSI, the yield is 97.1%, and the purity is 99.6%.
The structure of the target product is characterized by F-NMR, and the chemical shift data are the same as example 1 and are not repeated.
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following steps: adding lithium fluoride LiF into a reactor, heating to 120 ℃, and adding the HFSI prepared in the embodiment into the reactor, wherein the molar ratio of HFSI to LiF is 1.1; after HFSI is added, reacting for 4.5h at 150 ℃ to obtain LiFSI; liFSI was added to the solvent EMC to obtain an EMC solution of LiFSI. The purity of the LiFSI is 99.7%, and the yield is 95%.
Example 6
A preparation method of bis (fluorosulfonyl) imide comprises the following specific steps: controlling the pressure in the high-pressure reaction kettle to be 4.0MPa, and introducing liquid ammonia and liquefied sulfonyl fluoride into the kettle to ensure that the molar ratio of the liquefied sulfonyl fluoride to the liquid ammonia is 1:3; after all the materials are introduced, the reaction is carried out for 2 hours at the temperature of 30 ℃ and under the pressure of 4.0MPa, the obtained product is filtered, solid impurities are removed, the obtained liquid phase is the target product HFSI, the yield is 96.7 percent, and the purity is 99.7 percent.
The structure of the target product is characterized by F-NMR, and the chemical shift data are the same as example 1 and are not repeated.
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following steps: adding LiF into a reactor, heating to 120 ℃, and adding the HFSI prepared in the embodiment into the reactor, wherein the molar ratio of the HFSI to the LiF is 1; after HFSI is added, reacting for 5 hours at 150 ℃ to obtain LiFSI; liFSI was added to the solvent EMC to obtain an EMC solution of LiFSI. The purity of the LiFSI is 99.5%, and the yield is 95.7%.
Example 7
A method for preparing bis (fluorosulfonyl) imide comprises the following steps: controlling the pressure in the high-pressure reaction kettle to be 3.5MPa, and introducing ammonia gas and sulfonyl fluoride into the kettle to ensure that the molar ratio of the sulfonyl fluoride to the ammonia gas is 1:2; after all the materials are introduced, the reaction is carried out for 2 hours at the temperature of 25 ℃ and under the pressure of 3.5MPa, the obtained product is filtered, solid impurities are removed, the obtained liquid phase is the target product HFSI, the yield is 94.8 percent, and the purity is 99.3 percent.
The structure of the target product is characterized by F-NMR, and the chemical shift data are the same as example 1 and are not repeated.
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following steps: adding LiF into a reactor, heating to 120 ℃, adding the HFSI prepared in the embodiment into the reactor, wherein the molar ratio of the HFSI to the LiF is 1:1; after HFSI is added, reacting for 5 hours at 140 ℃ to obtain LiFSI; liFSI was added to the solvent EMC to obtain an EMC solution of LiFSI. The purity of the LiFSI was 98.9% and the yield was 93%.
Example 8
A preparation method of bis (fluorosulfonyl) imide comprises the following specific steps: controlling the pressure in the high-pressure reaction kettle to be 2MPa, and introducing liquid ammonia and liquefied sulfonyl fluoride into the kettle to ensure that the molar ratio of the liquefied sulfonyl fluoride to the liquid ammonia is 1:2; after all the materials are introduced, reacting for 2 hours at 25 ℃ and 2MPa, filtering the obtained product, removing solid impurities, and obtaining a liquid phase which is a target product HFSI, wherein the yield is 94.5 percent and the purity is 99.1 percent.
The structure of the target product is characterized by F-NMR, and the chemical shift data are the same as example 1 and are not repeated.
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following steps: adding lithium fluoride LiF into a reactor, heating to 120 ℃, and adding the HFSI prepared in the embodiment into the reactor, wherein the molar ratio of the HFSI to the LiF is 1.1; after HFSI is added, reacting for 4.5h at 150 ℃ to obtain LiFSI; liFSI was added to the solvent EMC to obtain an EMC solution of LiFSI. The purity of the LiFSI is 99%, and the yield is 92.1%.
Comparative example 1
A preparation method of bis (fluorosulfonyl) imide comprises the following specific steps: adding 200mL of acetonitrile serving as a solvent into a reaction bottle, adding 184g of triethylamine, uniformly stirring, cooling the reaction bottle, introducing 150g of sulfonyl fluoride gas, uniformly stirring, introducing 9.0g of dry ammonia gas into the system, stirring for reacting for 24h, introducing nitrogen into the reaction bottle after the reaction is finished, and purging the reaction bottle with nitrogen to remove waste gas; after purging is finished, filtering out fluoride salt, evaporating and recovering the solvent, adding diethyl ether and water after all the solvent is evaporated, extracting, combining organic phases, and drying by anhydrous sodium sulfate to obtain a target product HFSI; the yield was 91% and the purity was 99.1%.
A preparation method of lithium bis (fluorosulfonyl) imide comprises the following specific steps: to the HFSI, 100mL of acetonitrile was added as a solvent, and 25g of lithium hydroxide was added and stirred for 1 hour, and undissolved portions were filtered off to remove the organic solvent, and further, high-purity LiFSI was obtained by recrystallization, with a yield of 82%.
The applicant states that the present invention is illustrated by the above examples of the preparation of bis-fluorosulfonylimide and bis-fluorosulfonylimide salts of the present invention, but the present invention is not limited to the above examples, i.e., it is not meant to be construed as being limited thereto. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, 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 bis (fluorosulfonyl) imide, which is characterized by comprising the following steps: sulfonyl fluoride and NH 3 And (3) carrying out reaction under the solvent-free condition to obtain the bis (fluorosulfonyl) imide.
2. The production method according to claim 1, characterized in that the production method includes any one of method a, method B, method C, method D;
the method A comprises the following steps: introducing ammonia gas into the liquefied sulfonyl fluoride for reaction to obtain the bis-fluorosulfonyl imide;
the method B comprises the following steps: introducing sulfonyl fluoride into liquid ammonia to react to obtain the bis-fluorosulfonyl imide;
the method C comprises the following steps: mixing liquefied sulfonyl fluoride with liquid ammonia to react to obtain the bis-fluorosulfonyl imide;
the method D comprises the following steps: mixing gaseous sulfonyl fluoride with ammonia gas for reaction to obtain the bis-fluorosulfonyl imide;
preferably, the preparation method is any one of method A, method B and method C.
3. The process according to claim 1 or 2, wherein the sulfonyl fluoride is reacted with NH 3 The molar ratio of (1) to (4) is 1.
4. The method according to any one of claims 1 to 3, wherein the reaction temperature is 0 to 100 ℃;
preferably, the reaction time is 0.1 to 12 hours.
5. The process according to any one of claims 1 to 4, wherein the pressure of the reaction is 2.0 to 8.0MPa, preferably 3.0 to 6.0MPa.
6. The method according to any one of claims 1 to 5, wherein the reaction further comprises a post-treatment step after completion of the reaction;
preferably, the method of work-up comprises solid-liquid separation, optionally distillation and optionally rectification.
7. The preparation method according to any one of claims 1 to 6, characterized in that it comprises in particular: sulfonyl fluoride and NH 3 Reacting for 0.1-12h at 0-100 ℃ and 2.0-8.0MPa, and then carrying out solid-liquid separation on the product to obtain a liquid phase of the bis (fluorosulfonyl) imide;
the sulfonyl fluoride and NH 3 The molar ratio of (1), (1.5) to (4); the reaction is carried out in the absence of a solvent.
8. A preparation method of bis (fluorosulfonyl) imide salt is characterized by comprising the following steps:
(1) The bis-fluorosulfonyl imide is prepared by the preparation method according to any one of claims 1 to 7;
(2) Reacting the bis (fluorosulfonyl) imide obtained in the step (1) with a metal source to obtain the bis (fluorosulfonyl) imide salt.
9. The method of claim 8, wherein the metal source of step (2) comprises an alkali metal hydroxide and/or an alkali metal salt, preferably a lithium hydroxide and/or a lithium salt;
preferably, the metal source in step (2) comprises any one of lithium hydroxide, lithium carbonate, lithium hexafluorophosphate and lithium fluoride or a combination of at least two of the above;
preferably, the temperature of the reaction of step (2) is 90-165 ℃;
preferably, the reaction time of the step (2) is 0.1-12h.
10. The method according to claim 8 or 9, wherein the reaction in the step (2) produces a bis-fluorosulfonyl imide salt, and the bis-fluorosulfonyl imide salt is mixed with a solvent to obtain the bis-fluorosulfonyl imide salt solution;
preferably, the solvent comprises an ester solvent, further preferably a carbonate solvent and/or a carboxylic acid ester solvent;
preferably, the ester-based solvent includes any one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 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 acetate, or a combination of at least two thereof.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102378755A (en) * | 2009-03-31 | 2012-03-14 | 中央硝子株式会社 | Method for producing imidic acid compound |
| CN104495767A (en) * | 2014-11-21 | 2015-04-08 | 湖南有色郴州氟化学有限公司 | Preparation method of lithium bis(fluorosulfonyl)amide |
| CN115140716A (en) * | 2022-06-17 | 2022-10-04 | 九江天赐高新材料有限公司 | Preparation method of bis (fluorosulfonyl) imide compound, bis (fluorosulfonyl) imide ionic liquid and lithium bis (fluorosulfonyl) imide |
| CN115259112A (en) * | 2022-07-04 | 2022-11-01 | 浙江中欣氟材股份有限公司 | Production method of bis-fluorosulfonyl imide and lithium salt thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102378755A (en) * | 2009-03-31 | 2012-03-14 | 中央硝子株式会社 | Method for producing imidic acid compound |
| CN104495767A (en) * | 2014-11-21 | 2015-04-08 | 湖南有色郴州氟化学有限公司 | Preparation method of lithium bis(fluorosulfonyl)amide |
| CN115140716A (en) * | 2022-06-17 | 2022-10-04 | 九江天赐高新材料有限公司 | Preparation method of bis (fluorosulfonyl) imide compound, bis (fluorosulfonyl) imide ionic liquid and lithium bis (fluorosulfonyl) imide |
| CN115259112A (en) * | 2022-07-04 | 2022-11-01 | 浙江中欣氟材股份有限公司 | Production method of bis-fluorosulfonyl imide and lithium salt thereof |
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