CN116750733A - Method for preparing lithium bis (fluorosulfonyl) imide by utilizing sulfuryl fluoride - Google Patents
Method for preparing lithium bis (fluorosulfonyl) imide by utilizing sulfuryl fluoride Download PDFInfo
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- CN116750733A CN116750733A CN202310694627.0A CN202310694627A CN116750733A CN 116750733 A CN116750733 A CN 116750733A CN 202310694627 A CN202310694627 A CN 202310694627A CN 116750733 A CN116750733 A CN 116750733A
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- China
- Prior art keywords
- imide
- fluorosulfonyl
- lithium bis
- sulfuryl fluoride
- molecular sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000005935 Sulfuryl fluoride Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 43
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 87
- 239000002808 molecular sieve Substances 0.000 claims abstract description 65
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002253 acid Substances 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 239000012043 crude product Substances 0.000 claims abstract description 31
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims abstract description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 108090000765 processed proteins & peptides Proteins 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 lithium bis-fluorosulfonyl imide Chemical class 0.000 claims description 39
- 150000001447 alkali salts Chemical class 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000001704 evaporation Methods 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 24
- XPVRBHCXMWRJEY-UHFFFAOYSA-N difluoro(imino)-$l^{4}-sulfane Chemical compound FS(F)=N XPVRBHCXMWRJEY-UHFFFAOYSA-N 0.000 claims description 19
- 150000007530 organic bases Chemical class 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- IBWXKMBLEOLOLY-UHFFFAOYSA-N dimethoxy(prop-2-enyl)silicon Chemical compound CO[Si](OC)CC=C IBWXKMBLEOLOLY-UHFFFAOYSA-N 0.000 claims description 8
- 150000003949 imides Chemical class 0.000 claims description 8
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 claims description 2
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000004821 distillation Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 description 33
- 229910021645 metal ion Inorganic materials 0.000 description 13
- 230000007935 neutral effect Effects 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 238000006138 lithiation reaction Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WRJWRGBVPUUDLA-UHFFFAOYSA-N chlorosulfonyl isocyanate Chemical compound ClS(=O)(=O)N=C=O WRJWRGBVPUUDLA-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 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
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910021654 trace metal Inorganic materials 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 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 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of lithium batteries, in particular to a method for preparing lithium bis (fluorosulfonyl) imide by utilizing sulfuryl fluoride; the invention adopts sulfuryl fluoride, ammonia gas, organic alkali, solvent and lithium hydroxide to prepare lithium bis (fluorosulfonyl) imide; the method comprises the steps of firstly carrying out distillation and extraction, carrying out preliminary purification, then filtering, and further removing trace impurity components in the crude product after adsorbing by a fluorinated peptide acid-based molecular sieve to obtain high-purity lithium bis (fluorosulfonyl) imide; the process route of the invention avoids SO 2 And the generation of waste gases such as HCl and the like, thereby meeting the environmental protection requirement; the method has the advantages of simple process, strong operability, obvious purification effect and the like, and has the condition of industrial production.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a method for preparing lithium bis (fluorosulfonyl) imide by utilizing sulfuryl fluoride.
Background
Lithium ion batteries are a new type of high energy secondary battery developed in the 90 s of the 20 th century, and have become one of the most promising systems in all battery products at present. The energy-saving high-energy-density energy-saving high-power discharge lamp has the excellent performances of high specific energy, small volume, light weight, high-rate discharge, low self-discharge rate, long cycle life, no toxicity, no memory effect and the like, and is widely applied to the fields of portable electronic products, new energy automobiles and energy storage.
Lithium bis-fluorosulfonyl imide is a novel lithium electrolyte salt that is considered to be the most likely lithium electrolyte salt to replace lithium hexafluorophosphate. In addition, lithium bis (fluorosulfonyl) imide has the following characteristics: compared with lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide is easier to dissociate lithium ions, so that the lithium bis (fluorosulfonyl) imide has higher conductivity; the decomposition temperature of the lithium bis (fluorosulfonyl) imide is higher than 200 ℃, so that the lithium bis (fluorosulfonyl) imide has higher thermal stability and safety; the lithium bis (fluorosulfonyl) imide has better compatibility with an electrode, and has unique advantages in the aspects of improving low-temperature discharge, high-temperature storage and the like; environmental friendliness and high safety, has basic conditions of industrialization, and is also becoming a focus of attention in the field of batteries.
Chinese patent CN202211723748.5: the preparation method of the lithium bis (fluorosulfonyl) imide comprises the following steps: (1) Mixing chlorosulfonyl isocyanate and fluorosulfonic acid, continuously introducing anhydrous hydrogen fluoride gas under stirring, and reacting for 4-30 hours at 25-130 ℃ under the action of a catalyst to synthesize difluoro sulfonyl imide; (2) Mixing the difluoro sulfimide with an organic solvent, adding a lithium alloy, reacting at 15-120 ℃ for 0.5-15 hours, and filtering and distilling the product under reduced pressure to obtain the difluoro sulfimide lithium.
Chinese patent CN202211730109.1: the preparation method of the difluoro-sulfonyl imide, the lithium difluoro-sulfonyl imide, the preparation method and the application thereof are provided, and the preparation method of the difluoro-sulfonyl imide comprises the following steps: the sulfonyl fluoride and hexamethyl silazane react in inert atmosphere to obtain an intermediate product, and the intermediate product is subjected to gas phase separation to obtain the difluoro sulfonyl imide.
Chinese patent CN202111101717.1: belongs to the field of preparation of lithium bis (fluorosulfonyl) imide, and in particular relates to a preparation method of lithium bis (fluorosulfonyl) imide. The method comprises the following steps: and (3) reacting the difluoro-sulfonyl imide with lithium phosphate in a nonaqueous solvent to obtain a reaction solution containing the difluoro-sulfonyl imide lithium, and performing aftertreatment to obtain the difluoro-sulfonyl imide lithium.
The above patent and the prior art all adopt the production process of synthesizing LiFSI by taking dichlorsulfimide (HClSI) as a raw material and carrying out fluorination and lithiation (salification) reactions. The industrialized synthesis process of HClSI mainly comprises two methods of sulfamic acid/chlorosulfonic acid method and sulfamic acid/chlorosulfonyl isocyanate method; the fluorinating agent mainly comprises hydrogen fluoride, ammonium fluoride, potassium fluoride and the like; the lithiation agent mainly comprises lithium hydroxide monohydrate, lithium acetate, lithium carbonate, lithium halide and the like; the lithiation reaction solvent mainly comprises methylene dichloride, ether, carbonic ester and the like. The lithium bis (fluorosulfonyl) imide prepared by the prior art has the defects of low purity, low yield, complex process, high cost and the like.
The residual metal ions in the lithium bis (fluorosulfonyl) imide are out of standard, and most of the metal ions are non-heavy metal ions, such as potassium, sodium, magnesium, iron, calcium, lead and the like; the method for removing the metal ion residues mainly adopts a metal ion adsorbent, utilizes the algae soil or zeolite powder to adsorb the metal ions, adds cation exchange resin and the like in the preparation process, but has the defects of poor removal effect, aggravation of the metal ion residues, easy exceeding of acid value and the like although the method can effectively remove the metal ions. While sulfoxide chloride can remove water from lithium difluorosulfimide, but simultaneously introduces SO which is difficult to remove 3 2- Ions can increase the purification difficulty of subsequent lithium bis (fluorosulfonyl) imide. Therefore, further improvements are needed for the purification of lithium bis-fluorosulfonyl imide.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a method for preparing lithium difluorosulfimide by using sulfuryl fluoride, ammonia gas, organic base, solvent and lithium hydroxide, wherein the method comprises the steps of preparing lithium difluorosulfimide by using sulfuryl fluoride, extracting, primarily purifying, filtering, adsorbing by using a perfluoropeptide acid-based molecular sieve, and further removing trace impurity components in the crude product to obtain high-purity lithium difluorosulfimide.
To achieve the above and other related objects, the present invention provides a method for preparing lithium bis (fluorosulfonyl) imide using sulfuryl fluoride, comprising the steps of:
s1: weighing sulfuryl fluoride, ammonia gas, organic alkali and a solvent according to parts by weight, and reacting in a reaction kettle to obtain organic alkali salt of difluoro sulfimide;
s2: evaporating the organic alkali salt of the difluoro sulfimide, and recycling the evaporated solvent and the organic alkali;
s3: extracting and evaporating organic alkali salt of the difluoro-sulfonyl imide, adding a lithium hydroxide aqueous solution, and reacting for 1-3 hours to obtain a difluoro-sulfonyl imide lithium crude product;
s4: and (3) evaporating the crude product of the lithium bis (fluorosulfonyl) imide, adding an ester solvent and a lithium hydroxide aqueous solution with the mass concentration of 10-20%, mixing and stirring, filtering, and adsorbing by a fluoropeptidic acid-based molecular sieve with the mass percentage of 3-8% of the crude product of the lithium bis (fluorosulfonyl) imide to obtain the lithium bis (fluorosulfonyl) imide.
Preferably, said sulfuryl fluoride: ammonia gas: organic base: the molar ratio of the solvent is (1-3): 1: (1-5): (30-50).
Preferably, the organic base is one or more of triethylamine, triethylene diamine, 1, 8-diazabicyclo undec-7-ene, 1, 5-diazabicyclo [4.3.0] -5-nonene, 4-dimethylaminopyridine, pyridine, N-methylmorpholine and tetramethyl ethylenediamine.
Preferably, the solvent is a mixture of acetonitrile and any two or more of propionitrile, isopropyl nitrile, diethyl ether, propyl ether, isopropyl ether, tetrahydrofuran, acetone, butanone, methyl isobutyl ketone and methyl pyrrolidone.
Preferably, the reaction temperature of the S1 is 5-25 ℃, and the reaction pressure is 0.2-0.3MPa.
Preferably, the volume of the organic alkali salt of the bis (fluorosulfonyl) imide and lithium hydroxide in the step S3 is 1: (1-1.2).
Preferably, the evaporation temperature is 30-50 ℃.
Preferably, the ester solvent is at least one of methyl ethyl carbonate, dimethyl carbonate and diethyl carbonate.
Preferably, the preparation method of the fluoropeptidic acid-based molecular sieve comprises the following steps:
s1: 0.1 to 1 part of H according to the parts by weight 2 PtCl 6 .6H 2 O and 100-500 parts of isopropanol are added into a reactor protected by nitrogen at one time, and stirred for 1-5 hours at room temperature to obtain a Speiers catalyst;
s2: according to the mass portion, 2-5 portions of 3,4,5, 6-tetrafluoro peptide acid, 10-15 portions of 4-vinyl-1, 2-phthalic acid, 100-200 portions of allyl modified MCM-41 mesoporous molecular sieve, 1000-1500 portions of N, N-dimethylformamide and 0.03-0.6 portion of Speiers catalyst are added into a stirring kettle, stirred for 50-100min at 70-80 ℃, benzoyl peroxide is then added, stirring is continued for 100-140min, filtering and deionized water washing is carried out until neutrality, and Jin Fu peptide acid based molecular sieve is obtained after drying.
Preferably, the preparation method of the allyl modified MCM-41 mesoporous molecular sieve comprises the following steps:
according to the mass portion, 2-5 portions of allyl dimethoxy silane, 2-5 portions of MCM-41 mesoporous molecular sieve, 2-5 portions of deionized water and 70-80 ℃ are stirred for 50-100min, filtered and dried to obtain the allyl modified MCM-41 mesoporous molecular sieve.
Compared with the prior art, the method for preparing the lithium bis (fluorosulfonyl) imide by utilizing the sulfuryl fluoride has the following remarkable effects:
1. the method comprises the steps of firstly carrying out preliminary purification by distillation and extraction, then carrying out filtration, and further removing trace metal impurity components in the crude product after passing through the fluopeptide acid-based molecular sieve, wherein a plurality of functional groups can be combined with metal ions in the fluopeptide acid-based molecular sieve at the same time, so that the adsorption rate and selectivity of the metal ions are greatly improved. Most metal ions can form complex chelate structures on the surface of the chelating agent; because the fluoropeptidic acid group molecular sieve has very wide aperture and specific surface area, various metal ions can be efficiently adsorbed; obtaining high-purity low-metal ion residual lithium bis (fluorosulfonyl) imide;
2. the process route of the invention avoids SO 2 And the generation of waste gases such as HCl and the like, thereby meeting the environmental protection requirement;
3. the method has the advantages of simple process, strong operability, obvious purification effect and the like, and has the condition of industrial production.
Detailed Description
The technical scheme of the invention is further specifically described by the following specific examples. It should be understood that the practice of the invention is not limited to the following examples, but is intended to be within the scope of the invention in any form and/or modification thereof.
In the present invention, unless otherwise specified, all parts and percentages are by weight, and the equipment, materials, etc. used are commercially available or are conventional in the art. The methods in the following examples are conventional in the art unless otherwise specified.
The purity and yield of the product in particular embodiments of the invention are calculated by the formula:
1. purity: purity of lithium bis (fluorosulfonyl) imide = mass of lithium bis (fluorosulfonyl) imide in mixture ≡mass of mixture x 100%;
2. yield: yield of lithium bis (fluorosulfonyl) imide = actual yield of lithium bis (fluorosulfonyl) imide/theoretical yield of lithium bis (fluorosulfonyl) imide x 100%.
Example 1
A method for preparing lithium bis (fluorosulfonyl) imide by utilizing sulfuryl fluoride comprises the following operation steps:
s1: weighing sulfuryl fluoride, ammonia gas, organic alkali and a solvent, and reacting in a reaction kettle to obtain organic alkali salt of difluoro sulfimide;
s2: evaporating the organic alkali salt of the difluoro sulfimide, and recycling the evaporated solvent and the organic alkali;
s3: extracting and evaporating organic alkali salt of the difluoro-sulfonyl imide, adding a lithium hydroxide aqueous solution, and reacting for 1h to obtain a difluoro-sulfonyl imide lithium crude product;
s4: and (3) evaporating the crude product of the lithium difluorosulfimide, adding an ester solvent and a lithium hydroxide aqueous solution with the mass concentration of 10%, mixing and stirring, filtering, and adsorbing by a fluoropeptidic acid group molecular sieve with the mass percentage of 3% of the crude product of the lithium difluorosulfimide to obtain the lithium difluorosulfimide.
The sulfuryl fluoride: ammonia gas: organic base: the molar ratio of the solvent is 1:1:1:30.
the organic base is triethylamine.
The solvent is a mixture of acetonitrile and propionitrile.
The reaction temperature of the S1 is 5 ℃, and the reaction pressure is 0.2MPa.
The volume of the organic alkali salt of the bisfluorosulfonyl imide and lithium hydroxide in the S3 is 1:1.
the evaporation temperature was 30 ℃.
The ester solvent is methyl ethyl carbonate.
The preparation method of the fluoropeptidic acid group molecular sieve comprises the following steps:
s1: will be 0.1gH 2 PtCl 6 .6H 2 O and 100g of isopropanol are added into a reactor protected by nitrogen at one time, and stirred for 1 hour at room temperature to obtain a Speiers catalyst;
s2: 2g of 3,4,5, 6-tetrafluoro peptide acid, 10g of 4-vinyl-1, 2-phthalic acid, 100g of allyl modified MCM-41 mesoporous molecular sieve, 1000g of N, N-dimethylformamide and 0.03g of Speiers catalyst are added into a stirring kettle, stirred for 50min at 70 ℃, then benzoyl peroxide is added, stirring is continued for 100min, filtering, deionized water is washed to be neutral, and drying is carried out, thus obtaining the Jin Fu peptide acid-based molecular sieve.
The preparation method of the allyl modified MCM-41 mesoporous molecular sieve comprises the following steps:
2g of allyl dimethoxy silane, 2g of MCM-41 mesoporous molecular sieve and 2g of deionized water are stirred at 70 ℃ for 50min, filtered and dried to obtain the allyl modified MCM-41 mesoporous molecular sieve.
In this example, the purity of lithium difluorosulfimide was found to be 99.95% by analytical calculation, and the reaction yield was 94.07%.
Example 2
A method for preparing lithium bis (fluorosulfonyl) imide by utilizing sulfuryl fluoride comprises the following operation steps:
s1: weighing sulfuryl fluoride, ammonia gas, organic alkali and a solvent, and reacting in a reaction kettle to obtain organic alkali salt of difluoro sulfimide;
s2: evaporating the organic alkali salt of the difluoro sulfimide, and recycling the evaporated solvent and the organic alkali;
s3: extracting and evaporating organic alkali salt of the difluoro-sulfonyl imide, adding a lithium hydroxide aqueous solution, and reacting for 2 hours to obtain a difluoro-sulfonyl imide lithium crude product;
s4: and (3) evaporating the crude product of the lithium difluorosulfimide, adding an ester solvent and a lithium hydroxide aqueous solution with the mass concentration of 15%, mixing and stirring, filtering, and adsorbing by a fluoropeptidic acid group molecular sieve with the mass percentage of 5% of the crude product of the lithium difluorosulfimide to obtain the lithium difluorosulfimide.
The sulfuryl fluoride: ammonia gas: organic base: the molar ratio of the solvent is 2:1:2:35.
the organic base is triethylamine.
The solvent is a mixture of acetonitrile and diethyl ether.
The reaction temperature of the S1 is 10 ℃, and the reaction pressure is 0.25MPa.
The volume of the organic alkali salt of the bisfluorosulfonyl imide and lithium hydroxide in the S3 is 1:1.1.
the evaporation temperature was 35 ℃.
The ester solvent is dimethyl carbonate.
The preparation method of the fluoropeptidic acid group molecular sieve comprises the following steps:
s1: will be 0.4gH 2 PtCl 6 .6H 2 O and 200g of isopropanol are added into a reactor protected by nitrogen at one time, and stirred at room temperature for 2 hours to obtain a Speiers catalyst;
s2: 3g of 3,4,5, 6-tetrafluoro peptide acid, 12g of 4-vinyl-1, 2-phthalic acid, 140g of allyl modified MCM-41 mesoporous molecular sieve, 1100g of N, N-dimethylformamide and 0.2g of Speiers catalyst are added into a stirring kettle, stirred for 60min at 75 ℃, benzoyl peroxide is then added, stirring is continued for 110min, filtering, deionized water is washed to be neutral, and drying is carried out, thus obtaining the Jin Fu peptide acid-based molecular sieve.
The preparation method of the allyl modified MCM-41 mesoporous molecular sieve comprises the following steps:
3g of allyl dimethoxy silane, 3g of MCM-41 mesoporous molecular sieve and 3g of deionized water are stirred at 75 ℃ for 60min, filtered and dried to obtain the allyl modified MCM-41 mesoporous molecular sieve.
In this example, the purity of lithium difluorosulfimide was found to be 99.96% by analytical calculation, and the reaction yield was found to be 93.91%.
Example 3
A method for preparing lithium bis (fluorosulfonyl) imide by utilizing sulfuryl fluoride comprises the following operation steps:
s1: weighing sulfuryl fluoride, ammonia gas, organic alkali and a solvent, and reacting in a reaction kettle to obtain organic alkali salt of difluoro sulfimide;
s2: evaporating the organic alkali salt of the difluoro sulfimide, and recycling the evaporated solvent and the organic alkali;
s3: extracting and evaporating organic alkali salt of the difluoro-sulfonyl imide, adding a lithium hydroxide aqueous solution, and reacting for 2 hours to obtain a difluoro-sulfonyl imide lithium crude product;
s4: and (3) evaporating the crude product of the lithium difluorosulfimide, adding an ester solvent and a lithium hydroxide aqueous solution with the mass concentration of 15%, mixing and stirring, filtering, and adsorbing by a fluoropeptidic acid-based molecular sieve with the mass percentage of 7% of the crude product of the lithium difluorosulfimide to obtain the lithium difluorosulfimide.
The sulfuryl fluoride: ammonia gas: organic base: the molar ratio of the solvent is 2:1:4:45.
the organic base is triethylamine.
The solvent is a mixture of acetonitrile and tetrahydrofuran.
The reaction temperature of the S1 is 15 ℃, and the reaction pressure is 0.25MPa.
The volume of the organic alkali salt of the bisfluorosulfonyl imide and lithium hydroxide in the S3 is 1:1.1.
the evaporation temperature was 45 ℃.
The ester solvent is dimethyl carbonate.
The preparation method of the fluoropeptidic acid group molecular sieve comprises the following steps:
s1: will be 0.8gH 2 PtCl 6 .6H 2 O and 400g of isopropanol are added into a reactor protected by nitrogen at one time, and stirred for 4 hours at room temperature to obtain a Speiers catalyst;
s2: 4g of 3,4,5, 6-tetrafluoro peptide acid, 14g of 4-vinyl-1, 2-phthalic acid, 180g of allyl modified MCM-41 mesoporous molecular sieve, 1400g of N, N-dimethylformamide and 0.4g of Speiers catalyst are added into a stirring kettle, stirred for 80min at 75 ℃, benzoyl peroxide is then added, stirring is continued for 130min, filtering, deionized water is washed to be neutral, and drying is carried out, thus obtaining the Jin Fu peptide acid-based molecular sieve.
The preparation method of the allyl modified MCM-41 mesoporous molecular sieve comprises the following steps:
4g of allyl dimethoxy silane, 4g of MCM-41 mesoporous molecular sieve and 4g of deionized water are stirred at 75 ℃ for 80min, filtered and dried to obtain the allyl modified MCM-41 mesoporous molecular sieve.
In this example, the purity of lithium difluorosulfimide was found to be 99.99% by analytical calculation, and the reaction yield was 96.02%.
Example 4
A method for preparing lithium bis (fluorosulfonyl) imide by utilizing sulfuryl fluoride comprises the following operation steps:
s1: weighing sulfuryl fluoride, ammonia gas, organic alkali and a solvent, and reacting in a reaction kettle to obtain organic alkali salt of difluoro sulfimide;
s2: evaporating the organic alkali salt of the difluoro sulfimide, and recycling the evaporated solvent and the organic alkali;
s3: extracting and evaporating organic alkali salt of the difluoro-sulfonyl imide, adding a lithium hydroxide aqueous solution, and reacting for 3 hours to obtain a difluoro-sulfonyl imide lithium crude product;
s4: and (3) evaporating the crude product of the lithium difluorosulfimide, adding an ester solvent and a lithium hydroxide aqueous solution with the mass concentration of 20%, mixing and stirring, filtering, and adsorbing by a fluoropeptidic acid group molecular sieve with the mass percentage of 8% of the crude product of the lithium difluorosulfimide to obtain the lithium difluorosulfimide.
The sulfuryl fluoride: ammonia gas: organic base: the molar ratio of the solvent is 3:1:5:50.
the organic base is triethylamine.
The solvent is a mixture of acetonitrile and acetone.
The reaction temperature of the S1 is 25 ℃, and the reaction pressure is 0.3MPa.
The volume of the organic alkali salt of the bisfluorosulfonyl imide and lithium hydroxide in the S3 is 1:1.2.
the evaporation temperature was 50 ℃.
The ester solvent is diethyl carbonate.
The preparation method of the fluoropeptidic acid group molecular sieve comprises the following steps:
s1: will 1gH 2 PtCl 6 .6H 2 O and 500g of isopropanol are added into a reactor protected by nitrogen at one time, and stirred for 5 hours at room temperature to obtain a Speiers catalyst;
s2: 5g of 3,4,5, 6-tetrafluoro-peptide acid, 15g of 4-vinyl-1, 2-phthalic acid, 200g of allyl modified MCM-41 mesoporous molecular sieve, 1500g of N, N-dimethylformamide and 0.6g of Speiers catalyst are added into a stirring kettle, stirred for 100min at 80 ℃, benzoyl peroxide is then added, stirring is continued for 140min, filtering, deionized water is washed to be neutral, and drying is carried out, so as to obtain the Jin Fu peptide acid-based molecular sieve.
The preparation method of the allyl modified MCM-41 mesoporous molecular sieve comprises the following steps:
5g of allyl dimethoxy silane, 5g of MCM-41 mesoporous molecular sieve and 5g of deionized water are stirred at 80 ℃ for 100min, filtered and dried to obtain the allyl modified MCM-41 mesoporous molecular sieve.
In this example, the purity of lithium difluorosulfimide was found to be 99.98% by analytical calculation, and the reaction yield was found to be 95.33%.
Comparative example 1
A method for preparing lithium bis (fluorosulfonyl) imide by utilizing sulfuryl fluoride comprises the following operation steps:
s1: weighing sulfuryl fluoride, ammonia gas, organic alkali and a solvent, and reacting in a reaction kettle to obtain organic alkali salt of difluoro sulfimide;
s2: evaporating the organic alkali salt of the difluoro sulfimide, and recycling the evaporated solvent and the organic alkali;
s3: extracting and evaporating organic alkali salt of the difluoro-sulfonyl imide, adding a lithium hydroxide aqueous solution, and reacting for 1h to obtain a difluoro-sulfonyl imide lithium crude product;
s4: and (3) evaporating the crude product of the lithium difluorosulfimide, adding an ester solvent and a lithium hydroxide aqueous solution with the mass concentration of 10%, mixing and stirring, filtering, and adsorbing by a fluoropeptidic acid group molecular sieve with the mass percentage of 3% of the crude product of the lithium difluorosulfimide to obtain the lithium difluorosulfimide.
The sulfuryl fluoride: ammonia gas: organic base: the molar ratio of the solvent is 1:1:1:30.
the organic base is triethylamine.
The solvent is a mixture of acetonitrile and propionitrile.
The reaction temperature of the S1 is 5 ℃, and the reaction pressure is 0.2MPa.
The volume of the organic alkali salt of the bisfluorosulfonyl imide and lithium hydroxide in the S3 is 1:1.
the evaporation temperature was 30 ℃.
The ester solvent is methyl ethyl carbonate.
The preparation method of the fluoropeptidic acid group molecular sieve comprises the following steps:
s1: will be 0.1gH 2 PtCl 6 .6H 2 O and 100g of isopropanol are added into a reactor protected by nitrogen at one time, and stirred for 1 hour at room temperature to obtain a Speiers catalyst;
s2: 2g of 3,4,5, 6-tetrafluoro-peptide acid, 10g of 4-vinyl-1, 2-phthalic acid, 1000g of N, N-dimethylformamide and 0.03g of Speiers catalyst are added into a stirring kettle, stirred for 50min at 70 ℃, benzoyl peroxide is then added, stirring is continued for 100min, filtering, deionized water is washed to be neutral, and drying is carried out, thus obtaining the Jin Fu peptide-acid-based molecular sieve.
In this example, the purity of lithium difluorosulfimide was 87.96% and the reaction yield was 92.55% by analytical calculation.
Comparative example 2
A method for preparing lithium bis (fluorosulfonyl) imide by utilizing sulfuryl fluoride comprises the following operation steps:
s1: weighing sulfuryl fluoride, ammonia gas, organic alkali and a solvent, and reacting in a reaction kettle to obtain organic alkali salt of difluoro sulfimide;
s2: evaporating the organic alkali salt of the difluoro sulfimide, and recycling the evaporated solvent and the organic alkali;
s3: extracting and evaporating organic alkali salt of the difluoro-sulfonyl imide, adding a lithium hydroxide aqueous solution, and reacting for 1h to obtain a difluoro-sulfonyl imide lithium crude product;
s4: and (3) evaporating the crude product of the lithium difluorosulfimide, adding an ester solvent and a lithium hydroxide aqueous solution with the mass concentration of 10%, mixing and stirring, filtering, and adsorbing by a fluoropeptidic acid group molecular sieve with the mass percentage of 3% of the crude product of the lithium difluorosulfimide to obtain the lithium difluorosulfimide.
The sulfuryl fluoride: ammonia gas: organic base: the molar ratio of the solvent is 1:1:1:30.
the organic base is triethylamine.
The solvent is a mixture of acetonitrile and propionitrile.
The reaction temperature of the S1 is 5 ℃, and the reaction pressure is 0.2MPa.
The volume of the organic alkali salt of the bisfluorosulfonyl imide and lithium hydroxide in the S3 is 1:1.
the evaporation temperature was 30 ℃.
The ester solvent is methyl ethyl carbonate.
The preparation method of the fluoropeptidic acid group molecular sieve comprises the following steps:
s1: will be 0.1gH 2 PtCl 6 .6H 2 O and 100g of isopropanol are added into a reactor protected by nitrogen at one time, and stirred for 1 hour at room temperature to obtain a Speiers catalyst;
s2: 2g of 3,4,5, 6-tetrafluoro peptide acid, 100g of allyl modified MCM-41 mesoporous molecular sieve, 1000g of N, N-dimethylformamide and 0.03g of Speiers catalyst are added into a stirring kettle, stirred for 50min at 70 ℃, benzoyl peroxide is then added, stirring is continued for 100min, filtering, deionized water is washed to be neutral, and drying is carried out, so as to obtain the Jin Fu peptide acid-based molecular sieve.
The preparation method of the allyl modified MCM-41 mesoporous molecular sieve comprises the following steps:
2g of allyl dimethoxy silane, 2g of MCM-41 mesoporous molecular sieve and 2g of deionized water are stirred at 70 ℃ for 50min, filtered and dried to obtain the allyl modified MCM-41 mesoporous molecular sieve.
In this example, the purity of lithium difluorosulfimide was 90.13% and the reaction yield was 93.37% by analytical calculation.
Comparative example 3
A method for preparing lithium bis (fluorosulfonyl) imide by utilizing sulfuryl fluoride comprises the following operation steps:
s1: weighing sulfuryl fluoride, ammonia gas, organic alkali and a solvent, and reacting in a reaction kettle to obtain organic alkali salt of difluoro sulfimide;
s2: evaporating the organic alkali salt of the difluoro sulfimide, and recycling the evaporated solvent and the organic alkali;
s3: extracting and evaporating organic alkali salt of the difluoro-sulfonyl imide, adding a lithium hydroxide aqueous solution, and reacting for 1h to obtain a difluoro-sulfonyl imide lithium crude product;
s4: and (3) evaporating the crude product of the lithium difluorosulfimide, adding an ester solvent and a lithium hydroxide aqueous solution with the mass concentration of 10%, mixing and stirring, filtering, and adsorbing by a fluoropeptidic acid group molecular sieve with the mass percentage of 3% of the crude product of the lithium difluorosulfimide to obtain the lithium difluorosulfimide.
The sulfuryl fluoride: ammonia gas: organic base: the molar ratio of the solvent is 1:1:1:30.
the organic base is triethylamine.
The solvent is a mixture of acetonitrile and propionitrile.
The reaction temperature of the S1 is 5 ℃, and the reaction pressure is 0.2MPa.
The volume of the organic alkali salt of the bisfluorosulfonyl imide and lithium hydroxide in the S3 is 1:1.
the evaporation temperature was 30 ℃.
The ester solvent is methyl ethyl carbonate.
The preparation method of the fluoropeptidic acid group molecular sieve comprises the following steps:
s1: will be 0.1gH 2 PtCl 6 .6H 2 O and 100g of isopropanol are added into a reactor protected by nitrogen at one time, and stirred for 1 hour at room temperature to obtain a Speiers catalyst;
s2: 2g of 3,4,5, 6-tetrafluoro peptide acid, 10g of 4-vinyl-1, 2-phthalic acid, 100g of allyl modified MCM-41 mesoporous molecular sieve and 1000g of N, N-dimethylformamide are added into a stirring kettle, stirred for 50min at 70 ℃, benzoyl peroxide is then added, stirring is continued for 100min, filtering, deionized water is washed to be neutral, and drying is carried out, thus obtaining the Jin Fu peptide acid based molecular sieve.
The preparation method of the allyl modified MCM-41 mesoporous molecular sieve comprises the following steps:
2g of allyl dimethoxy silane, 2g of MCM-41 mesoporous molecular sieve and 2g of deionized water are stirred at 70 ℃ for 50min, filtered and dried to obtain the allyl modified MCM-41 mesoporous molecular sieve.
In this example, the purity of lithium difluorosulfimide was calculated to be 92.52% by analysis and the reaction yield was 93.32%.
By comparing the data of the above examples with the data of the comparative examples, the invention obtains the high-purity low-metal ion residual lithium bis-fluorosulfonyl imide by performing preliminary purification by distillation and extraction, filtering, and further removing trace metal impurity components in the crude product after the fluorine-peptide acid-based molecular sieve.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related arts are included in the scope of the present invention.
Claims (10)
1. A method for preparing lithium bis (fluorosulfonyl) imide by utilizing sulfuryl fluoride comprises the following operation steps:
s1: weighing sulfuryl fluoride, ammonia gas, organic alkali and a solvent according to parts by weight, and reacting in a reaction kettle to obtain organic alkali salt of difluoro sulfimide;
s2: evaporating the organic alkali salt of the difluoro sulfimide, and recycling the evaporated solvent and the organic alkali;
s3: extracting and evaporating organic alkali salt of the difluoro-sulfonyl imide, adding a lithium hydroxide aqueous solution, and reacting for 1-3 hours to obtain a difluoro-sulfonyl imide lithium crude product;
s4: and (3) evaporating the crude product of the lithium bis (fluorosulfonyl) imide, adding an ester solvent and a lithium hydroxide aqueous solution with the mass concentration of 10-20%, mixing and stirring, filtering, and adsorbing by a fluoropeptidic acid-based molecular sieve with the mass percentage of 3-8% of the crude product of the lithium bis (fluorosulfonyl) imide to obtain the lithium bis (fluorosulfonyl) imide.
2. A method for preparing lithium bis-fluorosulfonyl imide from sulfuryl fluoride according to claim 1, wherein: the sulfuryl fluoride: ammonia gas: organic base: the molar ratio of the solvent is (1-3): 1: (1-5): (30-50).
3. A method for preparing lithium bis-fluorosulfonyl imide from sulfuryl fluoride according to claim 1, wherein: the organic base is one or more of triethylamine, triethylene diamine, 1, 8-diazabicyclo undec-7-ene, 1, 5-diazabicyclo [4.3.0] -5-nonene, 4-dimethylaminopyridine, pyridine, N-methylmorpholine and tetramethyl ethylenediamine.
4. A method for preparing lithium bis-fluorosulfonyl imide from sulfuryl fluoride according to claim 1, wherein: the solvent is a mixture of acetonitrile and any two or more of propionitrile, isopropyl nitrile, diethyl ether, propyl ether, isopropyl ether, tetrahydrofuran, acetone, butanone, methyl isobutyl ketone and methyl pyrrolidone.
5. A method for preparing lithium bis-fluorosulfonyl imide from sulfuryl fluoride according to claim 1, wherein: the reaction temperature of the S1 is 5-25 ℃, and the reaction pressure is 0.2-0.3MPa.
6. A method for preparing lithium bis-fluorosulfonyl imide from sulfuryl fluoride according to claim 1, wherein: the volume of the organic alkali salt of the bisfluorosulfonyl imide and lithium hydroxide in the S3 is 1: (1-1.2).
7. A method for preparing lithium bis-fluorosulfonyl imide from sulfuryl fluoride according to claim 1, wherein: the evaporation temperature is 30-50 ℃.
8. A method for preparing lithium bis-fluorosulfonyl imide from sulfuryl fluoride according to claim 1, wherein: the ester solvent is at least one of methyl ethyl carbonate, dimethyl carbonate and diethyl carbonate.
9. A method for preparing lithium bis-fluorosulfonyl imide from sulfuryl fluoride according to claim 1, wherein: the preparation method of the fluoropeptidic acid group molecular sieve comprises the following steps:
s1: 0.1 to 1 part of H according to the parts by weight 2 PtCl 6 .6H 2 O and 100-500 parts of isopropanol are added into a reactor protected by nitrogen at one time, and stirred for 1-5 hours at room temperature to obtain a Speiers catalyst;
s2: according to the mass portion, 2-5 portions of 3,4,5, 6-tetrafluoro peptide acid, 10-15 portions of 4-vinyl-1, 2-phthalic acid, 100-200 portions of allyl modified MCM-41 mesoporous molecular sieve, 1000-1500 portions of N, N-dimethylformamide and 0.03-0.6 portion of Speiers catalyst are added into a stirring kettle, stirred for 50-100min at 70-80 ℃, benzoyl peroxide is then added, stirring is continued for 100-140min, filtering and deionized water washing is carried out until neutrality, and Jin Fu peptide acid based molecular sieve is obtained after drying.
10. A method for preparing lithium bis-fluorosulfonyl imide from sulfuryl fluoride according to claim 9, wherein: the preparation method of the allyl modified MCM-41 mesoporous molecular sieve comprises the following steps:
according to the mass portion, 2-5 portions of allyl dimethoxy silane, 2-5 portions of MCM-41 mesoporous molecular sieve, 2-5 portions of deionized water and 70-80 ℃ are stirred for 50-100min, filtered and dried to obtain the allyl modified MCM-41 mesoporous molecular sieve.
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2023
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