CN115974015A - Synthetic method of sodium bis (fluorosulfonyl) imide - Google Patents
Synthetic method of sodium bis (fluorosulfonyl) imide Download PDFInfo
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- CN115974015A CN115974015A CN202211689675.2A CN202211689675A CN115974015A CN 115974015 A CN115974015 A CN 115974015A CN 202211689675 A CN202211689675 A CN 202211689675A CN 115974015 A CN115974015 A CN 115974015A
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- Prior art keywords
- imide
- sodium
- bis
- fluorosulfonyl
- sodium bis
- Prior art date
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- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000010189 synthetic method Methods 0.000 title claims abstract description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 24
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011780 sodium chloride Substances 0.000 claims abstract description 18
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 12
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 12
- 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 10
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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 10
- ATMIHASMQFJNLZ-UHFFFAOYSA-N dichloro(imino)-$l^{4}-sulfane Chemical compound ClS(Cl)=N ATMIHASMQFJNLZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims description 32
- 238000001914 filtration Methods 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 28
- PVMUVDSEICYOMA-UHFFFAOYSA-N n-chlorosulfonylsulfamoyl chloride Chemical compound ClS(=O)(=O)NS(Cl)(=O)=O PVMUVDSEICYOMA-UHFFFAOYSA-N 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 239000012442 inert solvent Substances 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 150000003983 crown ethers Chemical class 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- FEKGWIHDBVDVSM-UHFFFAOYSA-N 1,1,1,2-tetrachloropropane Chemical compound CC(Cl)C(Cl)(Cl)Cl FEKGWIHDBVDVSM-UHFFFAOYSA-N 0.000 claims description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical compound CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 claims description 2
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 claims description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-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
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- 230000002194 synthesizing effect Effects 0.000 claims 9
- 150000002148 esters Chemical class 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- -1 bis (chloro) sulfimide sodium Chemical compound 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- XXYVTWLMBUGXOK-UHFFFAOYSA-N [Na].FS(=N)F Chemical compound [Na].FS(=N)F XXYVTWLMBUGXOK-UHFFFAOYSA-N 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a synthetic method of sodium bis (fluorosulfonyl) imide. The synthesis method of the invention abandons the use of hydrofluoric acid, uses chlorosulfonic acid, sulfamic acid and thionyl chloride as raw materials to prepare high-purity bis (chloro) sulfimide, then uses bis (chloro) sulfimide and sodium chloride as raw materials to prepare bis (chloro) sulfimide sodium, and then uses sodium fluoride and bis (chloro) sulfimide sodium to carry out halogen replacement reaction to prepare bis (fluoro) sulfimide sodium.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a synthetic method of sodium bis (fluorosulfonyl) imide.
Background
The sodium ion battery is a secondary battery, mainly depends on sodium ions to move between a positive electrode and a negative electrode to work, and is similar to the working principle of the lithium ion battery. The electrode material used by the sodium ion battery is mainly sodium salt, and compared with lithium salt, the electrode material is richer in reserve and lower in price. Sodium ion batteries are a cost-effective alternative when the requirements on weight and energy density are not high, since sodium ions are larger than lithium ions. Compared with lithium ion batteries, sodium ion batteries have the following advantages: (1) The sodium salt raw material has abundant reserves and low price, and compared with the ternary cathode material of the lithium ion battery, the adopted ferro-manganese nickel-based cathode material has half of the raw material cost; (2) Due to the characteristics of sodium salt, the low-concentration electrolyte (the electrolyte with the same concentration and the sodium salt conductivity higher than that of the lithium electrolyte by about 20%) is allowed to be used, so that the cost is reduced; (3) Sodium ions do not form an alloy with aluminum, and the negative electrode can adopt aluminum foil as a current collector, so that the cost can be further reduced, and the weight can be further reduced; (4) The sodium ion battery is allowed to discharge to zero volts due to its no over-discharge characteristics. The energy density of the sodium ion battery is more than 100Wh/kg, and the sodium ion battery can be compared with a lithium iron phosphate battery, but the cost advantage is obvious, and the sodium ion battery is expected to replace the traditional lead-acid battery in large-scale energy storage.
Sodium bis (fluorosulfonyl) imide is also an important subject of research as an important electrolyte salt or additive in sodium ion battery electrolytes. The patent of the invention with publication number CN114572945A prepares sodium bis (fluorosulfonyl) imide by reacting bis (fluorosulfonyl) imide with a sodium source, and bis (fluorosulfonyl) imide is obtained by fluorinating bis (chlorosulfonyl) imide, and the fluorinating agent is usually anhydrous hydrofluoric acid, so that the reaction risk is increased, and after the bis (fluorosulfonyl) imide reacts with a sodium source (such as sodium hydroxide and sodium bicarbonate), reaction water is generated, and the reaction water removal process is complex, and impurities are introduced in the water removal process, and in the presence of water, bis (fluorosulfonyl) imide easily undergoes hydrolysis reaction with water, so that the yield is low.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a synthetic method of sodium bis (fluorosulfonyl) imide. The synthesis method of the invention abandons the use of hydrofluoric acid, uses chlorosulfonic acid, sulfamic acid and thionyl chloride as raw materials to prepare high-purity bis (chloro) sulfimide, then uses bis (chloro) sulfimide and sodium chloride as raw materials to prepare bis (chloro) sulfimide sodium, and then uses sodium fluoride and bis (chloro) sulfimide sodium to carry out halogen replacement reaction to prepare bis (fluoro) sulfimide sodium.
In order to achieve the technical purpose, the embodiment of the invention adopts the technical scheme that:
a synthetic method of sodium bis (fluorosulfonyl) imide comprises the following steps:
(1) Placing chlorosulfonic acid, sulfamic acid and thionyl chloride into a reaction kettle according to a certain proportion, heating to 60-80 ℃, carrying out reflux reaction for 15-30 hours, transferring into a rectifying kettle, carrying out reduced pressure distillation, and collecting main fraction at 90-110 ℃ to obtain dichlorosulfimide;
NH 2 SO 3 H+2SOCl 2 +ClSO 3 H→HN(SO 2 Cl) 2 +2SO 2 + 3HCl
(2) Mixing a certain amount of sodium chloride and an inert solvent according to a certain proportion, placing the mixture in a reaction kettle, heating to 30-50 ℃, then beginning to dropwise add the bis (chlorosulfonyl) imide in the step (1), dropwise adding the bis (chlorosulfonyl) imide for 3-5 hours, then keeping the temperature for reaction for 6-10 hours, filtering, washing the obtained filter residue with the inert solvent for multiple times, and drying to obtain a mixture of the bis (chlorosulfonyl) imide sodium and the sodium chloride; adding a benign solvent capable of dissolving the sodium dichlorosulfonimide into the mixture, and filtering to obtain filtrate for later use;
HN(SO 2 Cl) 2 +NaCl→NaN(SO 2 Cl) 2 +HCl
(3) Mixing a certain amount of sodium fluoride with the filtrate obtained in the step (2), placing the mixture in a reaction kettle, heating the mixture to 60-100 ℃, performing reflux reaction for 20-30 hours, cooling, and filtering to obtain a filtrate for later use;
NaN(SO 2 Cl) 2 +2NaF→NaN(SO 2 F) 2 +SO 2 +2NaCl
(4) Mixing a certain amount of activated carbon with the filtrate obtained in the step (3), stirring for 1 to 2 hours, decoloring, removing impurities, and filtering to obtain a filtrate for later use;
(5) Transferring the filtrate obtained in the step (4) to a crystallization kettle, distilling under reduced pressure, evaporating out the solvent, cooling and filtering when most of crystals are separated out, wherein the obtained solid is the sodium bis (fluorosulfonyl) imide, drying under reduced pressure at 50-80 ℃, and recrystallizing by using a benign solvent until the sodium bis (fluorosulfonyl) imide with the purity of more than 99% is obtained after drying;
(6) Mixing the sodium bis (fluorosulfonyl) imide obtained in the step (5) with an inert solvent, adding crown ether, heating to a reflux state, keeping for 3 hours, then performing gradient cooling, wherein each temperature stage is a gradient at 10 ℃, keeping for 2-5 hours until the temperature is reduced to 0 ℃, then filtering, and drying the obtained filter residue under reduced pressure to obtain the high-purity sodium bis (fluorosulfonyl) imide with the content being more than or equal to 99.5%.
Further, the molar ratio of the chlorosulfonic acid, the sulfamic acid and the thionyl chloride in the step (1) is as follows: 1 to 1.5.
Further, in the step (2), the molar ratio of the bischlorosulfonimide to the sodium chloride is 1.5 to 2, the mass ratio of the sodium chloride to the inert solvent is 1 to 3 to 6, the mass of the inert solvent used for washing is 20 to 40 percent of the input amount, and the ratio of the mass of the benign solvent to the theoretical obtained amount of the bischlorosulfonimide sodium is 1 to 4 to 8.
Further, the amount of sodium fluoride in the step (3) is determined by the bischlorosulfonimide obtained in the step (1), wherein the molar ratio of the bischlorosulfonimide to the sodium fluoride is 1.
Further, the adding amount of the activated carbon in the step (4) is 0.1% -0.5% of the mass of the filtrate obtained in the step (3).
Further, in the step (5), the mass of the benign solvent is 2 to 4 times of the mass of the solid sodium bis (fluorosulfonyl) imide.
Further, the mass of the inert solvent in the step (6) is 3-6 times of that of the sodium bis (fluorosulfonyl) imide obtained in the step (5), and the mass of the crown ether is 5% -10% of that of the inert solvent.
Furthermore, the inert solvent in step (2) and step (6) is halogenated alkane solvent, and is selected from one or more of dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane, trichloropropane and tetrachloropropane.
Further, the benign solvent in the step (2) and the benign solvent in the step (5) are both ester compounds, ketone compounds, nitrile compounds or ether compounds, and are selected from one or a mixture of more than two of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, acetone, methyl ethyl ketone, butanone, acetonitrile, propionitrile, diethyl ether, isopropyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 1, 4-dioxane, tetrahydrofuran and 2-methyltetrahydrofuran.
Further, the vacuum degree of the decompression operation in the steps (1), (5) and (6) is controlled to be-0.095 to-0.05 MPa; wherein the crown ether in the step (6) is one or the mixture of 15-crown ether-5 and 18-crown ether-6.
The technical scheme provided by the embodiment of the invention has the following beneficial effects:
the synthesis method of the invention abandons the use of hydrofluoric acid, adopts chlorosulfonic acid, sulfamic acid and thionyl chloride as raw materials to prepare high-purity bis (chlorosulfonyl) imide, then adopts bis (chlorosulfonyl) imide and sodium chloride as raw materials to prepare sodium bis (chlorosulfonyl) imide, and then adopts sodium fluoride and sodium bis (chlorosulfonyl) imide to carry out halogen displacement reaction to prepare sodium bis (fluorosulfonyl) imide.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A synthetic method of sodium bis (fluorosulfonyl) imide comprises the following steps:
(1) Putting 1165g of chlorosulfonic acid, 970g of sulfamic acid and 2380g of thionyl chloride into a reaction kettle, heating to 60-80 ℃, carrying out reflux reaction for 15 hours, transferring the reaction product into a rectification kettle, carrying out reduced pressure distillation, and collecting main fractions at 90-110 ℃, thereby obtaining 1490g of high-purity bischlorosulfimide;
(2) Mixing 613g of sodium chloride and 1849g of dichloromethane, then placing the mixture in a reaction kettle, heating the mixture to 35 ℃, starting to dropwise add the bis (chlorosulfonyl) imide obtained in the step (1), dropwise adding the bis (chlorosulfonyl) imide for 3 hours, then carrying out heat preservation reaction for 10 hours, filtering, washing filter residues with 500g of dichloromethane, drying to obtain a mixture of the bis (chlorosulfonyl) imide sodium and the sodium chloride, adding 6600g of dimethyl carbonate into the mixture to dissolve the bis (chlorosulfonyl) imide sodium, and filtering to obtain filtrate for later use;
(3) Mixing 585g of sodium fluoride with the filtrate obtained in the step (2), placing the mixture in the reaction kettle, heating to 90 ℃, performing reflux reaction for 20 hours, cooling, and filtering to obtain filtrate for later use;
(4) Mixing 10g of activated carbon with the filtrate obtained in the step (3), stirring, decoloring, removing impurities, stirring for 1 hour, and filtering to obtain a filtrate for later use;
(5) Transferring the filtrate obtained in the step (4) to a crystallization kettle, distilling under reduced pressure to evaporate the solvent, cooling and filtering when most crystals are separated out to obtain solid sodium bis (fluorosulfonyl) imide, and drying under reduced pressure at 50 ℃ to obtain 1022g of solid; adding 2050g of dimethyl carbonate again for dissolving, repeating the crystallization step, and recrystallizing until 830g of sodium bis (fluorosulfonyl) imide with the purity of more than 99% is obtained after drying;
(6) Mixing the higher-purity sodium bis (fluorosulfonyl) imide obtained in the step (5) with 2500g of dichloromethane, adding 18-crown ether-6125 g, heating to a reflux state, keeping the temperature at 40 ℃ for 3 hours, performing gradient cooling, keeping the temperature for 2 hours at each temperature stage with a gradient of 10 ℃ until the temperature is reduced to 0 ℃, filtering, and drying the obtained filter residue under reduced pressure to obtain 760g of high-purity sodium bis (fluorosulfonyl) imide with the purity of 99.81% and the water content of 105ppm.
The vacuum degree of the decompression operation in the steps (1), (5) and (6) is controlled to be-0.095 to-0.05 MPa.
Example 2
A synthetic method of sodium bis (fluorosulfonyl) imide comprises the following steps:
(1) Putting 1000g of chlorosulfonic acid, 1245g of sulfamic acid and 2550g of thionyl chloride into a reaction kettle, heating to 60-80 ℃, carrying out reflux reaction for 20 hours, transferring the mixture into a rectifying kettle, carrying out reduced pressure distillation, and collecting main fraction at 90-110 ℃, thereby obtaining 1432g of high-purity bischlorosulfimide;
(2) Mixing 780g of sodium chloride and 2340g of dichloroethane, placing the mixture in a reaction kettle, heating to 45 ℃, starting to dropwise add the bis (chlorosulfonyl) imide in the step (1), dropwise adding the bis (chlorosulfonyl) imide for 5 hours, then carrying out heat preservation reaction for 8 hours, filtering, washing filter residues with 500g of dichloroethane, and drying to obtain a mixture of the bis (chlorosulfonyl) imide sodium and the sodium chloride; adding 7895g of acetonitrile into the mixture to dissolve the sodium dichlorosulfonimide, and filtering to obtain filtrate for later use;
(3) Mixing 650g of sodium fluoride with the filtrate obtained in the step (2), placing the mixture in a reaction kettle, heating the mixture to 80 ℃, performing reflux reaction for 24 hours, cooling, and filtering to obtain filtrate for later use;
(4) Mixing 15g of activated carbon with the filtrate obtained in the step (3), stirring, decoloring, removing impurities, stirring for 1.5 hours, and filtering to obtain a filtrate for later use;
(5) Transferring the filtrate obtained in the step (4) to a crystallization kettle, distilling under reduced pressure to evaporate the solvent, cooling and filtering when most crystals are separated out to obtain solid sodium bis (fluorosulfonyl) imide, and drying under reduced pressure at 65 ℃ to obtain 1421g of solid; 4265g of acetonitrile is added again to dissolve the solid, the crystallization step is repeated, recrystallization is carried out, and 1279g of sodium bis (fluorosulfonyl) imide with the purity of more than 99 percent is obtained after drying;
(6) Mixing the relatively high-purity sodium bis (fluorosulfonyl) imide obtained in the step (5) with 7600g of dichloroethane, adding 15-crown ether-5760 g, heating to a reflux state at a temperature of 80 ℃, keeping for 3 hours, then performing gradient cooling, keeping for 3 hours at each temperature stage with a gradient of 10 ℃ until the temperature is reduced to 0 ℃, then filtering, and drying the obtained filter residue under reduced pressure to obtain 1190g of high-purity sodium bis (fluorosulfonyl) imide with a purity of 99.78% and a moisture content of 95ppm.
Controlling the vacuum degree of the decompression operation in the steps (1), (5) and (6) to be minus 0.095 to minus 0.05MPa.
Example 3
A synthetic method of sodium bis (fluorosulfonyl) imide comprises the following steps:
(1) Placing 150g of chlorosulfonic acid, 150g of sulfamic acid and 383g of thionyl chloride in a reaction kettle, heating to 60-80 ℃ for reflux reaction for 30 hours, transferring to a rectification kettle for reduced pressure distillation, and collecting main distillate at 90-110 ℃ to obtain 218g of high-purity dichlorosulfimide;
(2) Mixing 116g of sodium chloride and 348g of dichloromethane, placing the mixture in a reaction kettle, heating to 35 ℃, starting to dropwise add the bis (chlorosulfonyl) imide obtained in the step (1), dropwise adding the bis (chlorosulfonyl) imide for 5 hours, then carrying out heat preservation reaction for 10 hours, filtering, washing filter residues with 171g of dichloromethane, drying to obtain a mixture of the bis (chlorosulfonyl) imide sodium and the sodium chloride, adding 1500g of ethyl acetate into the mixture to dissolve the bis (chlorosulfonyl) imide sodium, and filtering to obtain filtrate for later use;
(3) Mixing 107g of sodium fluoride with the filtrate obtained in the step (2), placing the mixture in a reaction kettle, heating the mixture to 75 ℃, performing reflux reaction for 30 hours, cooling, and filtering to obtain filtrate for later use;
(4) Mixing 2g of activated carbon with the filtrate obtained in the step (3), stirring, decoloring, removing impurities, stirring for 2 hours, and filtering to obtain a filtrate for later use;
(5) Transferring the filtrate obtained in the step (4) to a crystallization kettle, distilling under reduced pressure to evaporate a solvent, cooling and filtering when most crystals are separated out to obtain a solid, namely sodium bis (fluorosulfonyl) imide, and drying under reduced pressure at 70 ℃ to obtain 221g of the solid; adding 885g of ethyl acetate again to dissolve the solid, repeating the crystallization step, recrystallizing, and drying to obtain 190g of sodium bis (fluorosulfonyl) imide with the purity of more than 99%.
(6) Mixing the higher-purity sodium bis (fluorosulfonyl) imide obtained in the step (5) with 950g of dichloromethane, adding 18-666 g of crown ether, heating to a reflux state at 40 ℃, keeping for 3 hours, performing gradient cooling, keeping for 5 hours at each temperature stage at every 10 ℃, cooling to 0 ℃, filtering, and drying the obtained filter residue under reduced pressure to obtain 182g of high-purity sodium bis (fluorosulfonyl) imide, wherein the purity is 99.83%, and the water content is 112ppm.
Controlling the vacuum degree of the decompression operation in the steps (1), (5) and (6) to be minus 0.095 to minus 0.05MPa.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A synthetic method of sodium bis (fluorosulfonyl) imide is characterized by comprising the following steps:
(1) Placing chlorosulfonic acid, sulfamic acid and thionyl chloride into a reaction kettle according to a certain proportion, heating to 60-80 ℃, carrying out reflux reaction for 15-30 hours, transferring into a rectifying kettle, carrying out reduced pressure distillation, and collecting main fraction at 90-110 ℃ to obtain dichlorosulfimide;
(2) Mixing a certain amount of sodium chloride and an inert solvent according to a certain proportion, placing the mixture in a reaction kettle, heating to 30-50 ℃, then beginning to dropwise add the bis (chlorosulfonyl) imide in the step (1), dropwise adding the bis (chlorosulfonyl) imide for 3-5 hours, then keeping the temperature for reaction for 6-10 hours, filtering, washing the obtained filter residue with the inert solvent for multiple times, and drying to obtain a mixture of the bis (chlorosulfonyl) imide sodium and the sodium chloride; adding a benign solvent capable of dissolving the sodium dichlorosulfonimide into the mixture, and filtering to obtain filtrate for later use;
(3) Mixing a certain amount of sodium fluoride with the filtrate obtained in the step (2), placing the mixture in a reaction kettle, heating to 60-100 ℃, performing reflux reaction for 20-30 hours, cooling, and filtering to obtain a filtrate for later use;
(4) Mixing a certain amount of activated carbon with the filtrate obtained in the step (3), stirring for 1 to 2 hours, decoloring, removing impurities, and filtering to obtain a filtrate for later use;
(5) Transferring the filtrate obtained in the step (4) to a crystallization kettle, distilling under reduced pressure, evaporating out the solvent, cooling and filtering when most of crystals are separated out, wherein the obtained solid is the sodium bis (fluorosulfonyl) imide, drying under reduced pressure at 50-80 ℃, and recrystallizing by using a benign solvent until the sodium bis (fluorosulfonyl) imide with the purity of more than 99% is obtained after drying;
(6) Mixing the sodium bis (fluorosulfonyl) imide obtained in the step (5) with an inert solvent, adding crown ether, heating to a reflux state, keeping for 3 hours, then performing gradient cooling, wherein each temperature stage is a gradient at 10 ℃, keeping for 2-5 hours until the temperature is reduced to 0 ℃, then filtering, and drying the obtained filter residue under reduced pressure to obtain the high-purity sodium bis (fluorosulfonyl) imide with the content being more than or equal to 99.5%.
2. The method for synthesizing sodium bis (fluorosulfonyl) imide according to claim 1, wherein the molar ratio of chlorosulfonic acid, sulfamic acid and thionyl chloride in step (1) is: 1 to 1.5.
3. The method for synthesizing sodium bis (fluorosulfonyl) imide according to claim 1, wherein in step (2), the molar ratio of bis (chlorosulfonyl) imide to sodium chloride is 1.5 to 2, the mass ratio of sodium chloride to inert solvent is 1 to 3 to 6, the mass of inert solvent used for washing is 20 to 40% of the input amount, and the ratio of the mass of benign solvent to the theoretical yield of sodium bis (chlorosulfonyl) imide is 1 to 4 to 8.
4. The method for synthesizing sodium bis (fluorosulfonyl) imide according to claim 1, wherein the amount of sodium fluoride in step (3) is determined by the bis (chlorosulfonyl) imide obtained in step (1), and the molar ratio of the bis (chlorosulfonyl) imide to the sodium fluoride is 1.
5. The method for synthesizing sodium bis (fluorosulfonyl) imide according to claim 1, wherein the amount of activated carbon added in step (4) is 0.1% -0.5% of the mass of the filtrate obtained in step (3).
6. The method for synthesizing sodium bis (fluorosulfonyl) imide according to claim 1, wherein in step (5), the mass of said benign solvent is 2 to 4 times of the mass of the solid sodium bis (fluorosulfonyl) imide.
7. The method for synthesizing sodium bis (fluorosulfonyl) imide according to claim 1, wherein the mass of the inert solvent in step (6) is 3 to 6 times of the mass of the sodium bis (fluorosulfonyl) imide obtained in step (5), and the mass of the crown ether is 5 to 10% of the mass of the inert solvent.
8. The method for synthesizing sodium bis (fluorosulfonyl) imide according to claim 1, wherein said inert solvent in step (2) and step (6) is halogenated alkane solvent selected from one or more of dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane, trichloropropane, and tetrachloropropane.
9. The method for synthesizing sodium bis (fluorosulfonyl) imide according to claim 1, wherein the benign solvents in step (2) and step (5) are esters, ketones, nitriles or ethers, and are selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, acetone, methyl ethyl ketone, acetonitrile, propionitrile, diethyl ether, isopropyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 1, 4-dioxane, tetrahydrofuran and 2-methyltetrahydrofuran.
10. The method for synthesizing sodium bis (fluorosulfonyl) imide according to claim 1, wherein the degree of vacuum in the pressure reduction operation in step (1), step (5), and step (6) is controlled to be-0.095 to-0.05 MPa; wherein the crown ether in the step (6) is one or the mixture of 15-crown ether-5 and 18-crown ether-6.
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