CN114368733A - Lithium bis (fluorosulfonyl) imide, preparation method thereof, electrolyte and secondary battery - Google Patents
Lithium bis (fluorosulfonyl) imide, preparation method thereof, electrolyte and secondary battery Download PDFInfo
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- CN114368733A CN114368733A CN202210111168.4A CN202210111168A CN114368733A CN 114368733 A CN114368733 A CN 114368733A CN 202210111168 A CN202210111168 A CN 202210111168A CN 114368733 A CN114368733 A CN 114368733A
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- Prior art keywords
- imide
- fluorosulfonyl
- lithium
- lithium bis
- bis
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- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003792 electrolyte Substances 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 124
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 50
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 49
- 239000002250 absorbent Substances 0.000 claims abstract description 45
- 230000002745 absorbent Effects 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- -1 lithium imide Chemical class 0.000 claims abstract description 18
- 229910006095 SO2F Inorganic materials 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 229940124530 sulfonamide Drugs 0.000 claims description 7
- 150000003456 sulfonamides Chemical class 0.000 claims description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011552 falling film Substances 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 3
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical class CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-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
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims 2
- 239000000243 solution Substances 0.000 description 36
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 32
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 32
- 239000000047 product Substances 0.000 description 22
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000005935 Sulfuryl fluoride Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 229910010941 LiFSI Inorganic materials 0.000 description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 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 2
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ZVVSSOQAYNYNPP-UHFFFAOYSA-N olaflur Chemical compound F.F.CCCCCCCCCCCCCCCCCCN(CCO)CCCN(CCO)CCO ZVVSSOQAYNYNPP-UHFFFAOYSA-N 0.000 description 2
- 229960001245 olaflur Drugs 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910006024 SO2Cl2 Inorganic materials 0.000 description 1
- 229910006145 SO3Li Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003759 ester based solvent Substances 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
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 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
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- NTJBWZHVSJNKAD-UHFFFAOYSA-N triethylazanium;fluoride Chemical compound [F-].CC[NH+](CC)CC NTJBWZHVSJNKAD-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000000007 visual effect Effects 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- C01P2006/40—Electric properties
-
- 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
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/65—Chroma (C*)
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
Abstract
The application provides a method for preparing lithium bis (fluorosulfonyl) imide, which comprises (1) adding an organic solvent and an absorbent A into a reaction kettle, then adding a part of ammonia source, and finally adding SO at the same time2X2Reacting with the rest ammonia source to obtain Salt (SO) containing bis (fluorosulfonyl) imide and absorbent A2F‑NH‑SO2F) Solution of A in the SO2X2Wherein X is independently of each other fluorine or chlorine; (2) filtering, concentrating and cleaning the solution obtained in the step (1) to obtain a Salt (SO) of the purified bis (fluorosulfonyl) imide and an absorbent A2F‑NH‑SO2F) A; (3) adding a Salt (SO) of the purified bis-fluorosulfonylimide obtained in step (2) with an absorbent A2F‑NH‑SO2F) Adding a lithium source into the solution A to react to obtain the product containing the diflunisalA solution of lithium imide; and (4) dehydrating the solution obtained in the step (3), concentrating, crystallizing by using a non-aqueous poor solvent, and drying to obtain the lithium bis (fluorosulfonyl) imide.
Description
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to a method for preparing lithium bis (fluorosulfonyl) imide, lithium bis (fluorosulfonyl) imide prepared by the method, electrolyte containing lithium bis (fluorosulfonyl) imide prepared by the method and a secondary battery.
Background
In recent years, with the application range of lithium ion batteries becoming wider, lithium ion batteries are widely used in energy storage power systems such as hydraulic power, thermal power, wind power and solar power stations, and in a plurality of fields such as electric tools, electric bicycles, electric motorcycles, electric automobiles, military equipment and aerospace. As lithium ion batteries have been greatly developed, higher requirements are also put forward on energy density, cycle performance, safety performance and the like. Lithium bis (fluorosulfonyl) imide is expected to be a novel electrolyte salt for lithium ion batteries due to its high conductivity, high thermal stability, wide electrochemical window, and low corrosion rate. However, the existing method for preparing lithium bis (fluorosulfonyl) imide still needs to be improved.
Disclosure of Invention
The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing lithium bis (fluorosulfonyl) imide, which is simple in operation, mild in reaction conditions, easy in removal of impurity ions, and high in yield, and which can produce lithium bis (fluorosulfonyl) imide having high purity and low chroma.
In order to achieve the above objects, the present application provides a method of preparing lithium bis (fluorosulfonyl) imide, and lithium bis (fluorosulfonyl) imide prepared by the method, an electrolyte solution and a secondary battery including lithium bis (fluorosulfonyl) imide prepared by the method.
In a first aspect of the present application, there is provided a process for preparing lithium bis (fluorosulfonyl) imide, comprising
(1) Adding an organic solvent and an absorbent A into a reaction kettle, then adding part of ammonia source, and finally adding SO at the same time2X2Reacting with the rest ammonia source to obtain Salt (SO) containing bis (fluorosulfonyl) imide and absorbent A2F-NH-SO2F) Solution of A in the SO2X2In, X are independent of each otherIs fluorine or chlorine;
(2) filtering, concentrating and cleaning the solution obtained in the step (1) to obtain a Salt (SO) of the purified bis (fluorosulfonyl) imide and an absorbent A2F-NH-SO2F)·A；
(3) Adding a Salt (SO) of the purified bis-fluorosulfonylimide obtained in step (2) with an absorbent A2F-NH-SO2F) Adding a lithium source into the solution A, and reacting to obtain a solution containing lithium bis (fluorosulfonyl) imide; and
(4) and (4) dehydrating the solution obtained in the step (3), concentrating, crystallizing by using a non-aqueous poor solvent, and drying to obtain the lithium bis (fluorosulfonyl) imide.
The application relates to the preparation of Salts (SO) of bis (fluorosulfonyl) imide with an absorbent A2F-NH-SO2F) When A, part of the ammonia source is added first and then SO is added simultaneously2X2And the reaction with the residual ammonia source realizes the preparation of the lithium bis (fluorosulfonyl) imide with high yield, and ensures that the prepared lithium bis (fluorosulfonyl) imide has high purity and low chroma.
In any embodiment, in step (1), the portion of the ammonia source comprises 3% to 10% of the total mass of the ammonia source. When the proportion of part of the ammonia source to the total mass of the ammonia source is in a given range, the yield of the lithium bis (fluorosulfonyl) imide can be further improved, the purity of the lithium bis (fluorosulfonyl) imide can be further improved, and the chroma of the lithium bis (fluorosulfonyl) imide can be reduced.
In any embodiment, in step (1), the SO2X2The molar ratio to the ammonia source is (greater than 2 to less than or equal to 3) to 1, optionally (2.01-2.1) to 1. When SO2X2When the molar ratio to the ammonia source is within the given range, the yield of lithium bis (fluorosulfonyl) imide can be further improved.
In any embodiment, in step (1), the molar ratio of absorbent A to the ammonia source is (1-5): 1.
In any embodiment, in step (1), the temperature of the reaction is from-10 ℃ to 50 ℃, optionally from 5 ℃ to 35 ℃; the reaction time is 2h to 8 h. When the temperature and time of the reaction in step (1) are controlled within the given ranges, the yield of lithium bis (fluorosulfonyl) imide can be further improved.
In any embodiment, in step (1), the ammonia source is one or more of ammonia gas, amine fluoride, sulfonamide, sulfamic acid, and difluorohydrinamine.
In any embodiment, in step (1), the absorbent a is one or more of pyridine, picoline, N-methylpyrrolidone, imidazole, trimethylamine, triethylamine, tri-N-propylamine, tri-N-butylamine, and diisopropylethylamine.
In any embodiment, in step (1), the organic solvent is one or more of acetonitrile, propionitrile, isopropionitrile, diethyl ether, propyl ether, isopropyl ether, tetrahydrofuran, acetone, butanone, methyl isobutyl ketone, and methyl pyrrolidone.
In any embodiment, in step (3), the lithium source is one or more of lithium hydroxide, lithium carbonate, lithium nitride, lithium oxide, and lithium hydride.
In any embodiment, in step (3), the temperature of the reaction is from 15 ℃ to 40 ℃; the reaction time is 0.5h to 6 h.
In any embodiment, in the step (2) and the step (4), the concentration includes reduced pressure distillation, falling film evaporation, or blade evaporation.
In any embodiment, in step (4), the poor solvent is C1-C8One or more of alkanes, benzene, toluene, xylene, methylene chloride, dichloroethane, trichloroethane, tetrachloroethane, and carbon tetrachloride.
A second aspect of the present application provides lithium bis (fluorosulfonylimide) prepared by the process of the first aspect of the present application.
In a third aspect of the present application, an electrolyte is provided, which includes lithium bis-fluorosulfonylimide, where the lithium bis-fluorosulfonylimide is the lithium bis-fluorosulfonylimide of the second aspect of the present application or the lithium bis-fluorosulfonylimide prepared by the method of the first aspect of the present application.
A fourth aspect of the present application provides a secondary battery comprising the electrolyte of the third aspect of the present application.
In the application, the preparation method of the lithium bis (fluorosulfonyl) imide is simple to operate, mild in reaction conditions, easy to remove impurity ions, and high in yield. The lithium bis (fluorosulfonyl) imide prepared by the method has high purity and low chroma, and can exert better performance in electrolyte.
Detailed Description
Hereinafter, the method for producing lithium bis (fluorosulfonyl) imide of the present application is specifically disclosed. But a detailed description thereof will be omitted. For example, detailed descriptions of already known matters and repetitive descriptions of actually the same configurations may be omitted. This is to avoid unnecessarily obscuring the following description, and to facilitate understanding by those skilled in the art. The following description is provided for those skilled in the art to fully understand the present application, and is not intended to limit the subject matter described in the claims.
The "ranges" disclosed herein are defined in terms of lower limits and upper limits, with a given range being defined by a selection of one lower limit and one upper limit that define the boundaries of the particular range. Ranges defined in this manner may or may not include endpoints and may be arbitrarily combined, i.e., any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is only a shorthand representation of the combination of these numbers. In addition, when a parameter is an integer of 2 or more, it is equivalent to disclose that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or the like.
All embodiments and alternative embodiments of the present application may be combined with each other to form new solutions, if not specifically stated.
All technical and optional features of the present application may be combined with each other to form new solutions, if not otherwise specified.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, if not specifically stated. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, and may also comprise steps (b) and (a) performed sequentially. For example, reference to the process further comprising step (c) means that step (c) may be added to the process in any order, for example, the process may comprise steps (a), (b) and (c), may also comprise steps (a), (c) and (b), may also comprise steps (c), (a) and (b), etc.
The terms "comprises" and "comprising" as used herein mean either open or closed unless otherwise specified. For example, the terms "comprising" and "comprises" may mean that other components not listed may also be included or included, or that only listed components may be included or included.
In this application, the term "or" is inclusive, if not otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or not present); a is false (or not present) and B is true (or present); or both a and B are true (or present).
Lithium bis (fluorosulfonylimide) (chemical formula Li [ N (SO) ]2F)2]Acronym LiFSI) is an important new material containing fluorine, due to its special molecular structure, Li+Has lower binding energy with FSI-, is beneficial to Li+So that the higher conductivity can be obtained by adding LiFSI into the electrolyte; meanwhile, LiFSI also has the characteristics of high thermal stability, wider electrochemical window and lower corrosion rate, and particularly in a power battery, the LiFSI can improve the cycle performance and the rate capability of the power battery and is expected to become a novel electrolyte lithium salt of a lithium ion battery.
At present, LiFSI cannot be used in large scale, mainly because the restriction of synthesis process conditions causes high production cost, and in the synthesis process, the defects of complex process, long flow, low product conversion rate, high energy consumption, environmental pollution and the like exist. In addition, as an electrolyte for a lithium ion secondary battery, it is required to satisfy severe requirements such as high purity and no water, and in particular, it is difficult to completely remove the electrolyte by heating to bring water after introducing water, drying to remove water until decomposition, and a large yield is lost even if the electrolyte can be removed.
In order to overcome the defects of harsh process conditions, serious corrosion to equipment, incapability of effectively controlling impurity ions and high energy consumption of the conventional LiFSI preparation method, the application provides the method for preparing LiFSI, which is simple to operate, mild in reaction conditions and easy to remove the impurity ions.
In one embodiment, the present application provides a method for preparing lithium bis (fluorosulfonyl) imide, comprising
(1) Adding an organic solvent and an absorbent A into a reaction kettle, then adding part of ammonia source, and finally adding SO at the same time2X2Reacting with the rest ammonia source to obtain Salt (SO) containing bis (fluorosulfonyl) imide and absorbent A2F-NH-SO2F) Solution of A in the SO2X2Wherein X is independently of each other fluorine or chlorine;
(2) filtering, concentrating and cleaning the solution obtained in the step (1) to obtain a Salt (SO) of the purified bis (fluorosulfonyl) imide and an absorbent A2F-NH-SO2F)·A；
(3) Adding a Salt (SO) of the purified bis-fluorosulfonylimide obtained in step (2) with an absorbent A2F-NH-SO2F) Adding a lithium source into the solution A, and reacting to obtain a solution containing lithium bis (fluorosulfonyl) imide; and
(4) and (4) dehydrating the solution obtained in the step (3), concentrating, crystallizing by using a non-aqueous poor solvent, and drying to obtain the lithium bis (fluorosulfonyl) imide.
Although the mechanism is not clear, the applicant has surprisingly found that: in the preparation of Salts (SO) of bis-fluorosulfonyl imides with absorbents A2F-NH-SO2F) When A, part of the ammonia source is added first and then SO is added simultaneously2X2And the reaction with the residual ammonia source realizes the preparation of the lithium bis (fluorosulfonyl) imide with high yield, and ensures that the prepared lithium bis (fluorosulfonyl) imide has high purity and low chroma.
Alternatively, the SO2X2Can be SO2F2、SO2Cl2Or SO2FxClyX + y is 2, x > 0, and y > 0.
In step (1), the following reaction mainly occurs:
main reaction (B is ammonia source):
SO2X2+B+A→(SO2F-NH-SO2F)·A+A·(HX)n(n＝1-12)；
side reaction 1:
SO2X2+B+A→NH2-SO2-NH2+A·(HX)n(n＝1-12)
side reaction 2:
SO2X2+A→[XSO2·A]+X-+X-[A-SO2-A]2+X-
the by-products formed in the side reaction 2 may be coloured, SO being avoided in order to lighten the colour of the material, i.e. to reduce the colour strength2X2With absorbent A for a prolonged period of time, SO that part of the ammonia source is added at the time of feeding, and then SO is added simultaneously2X2And the remaining ammonia source, directly starting the main reaction.
In some embodiments, in step (1), the portion of the ammonia source comprises 3% to 10% of the total mass of the ammonia source. When the proportion of part of the ammonia source to the total mass of the ammonia source is in a given range, the yield of the lithium bis (fluorosulfonyl) imide can be further improved, the purity of the lithium bis (fluorosulfonyl) imide can be further improved, and the chroma of the lithium bis (fluorosulfonyl) imide can be reduced.
In some embodiments, in step (1), the SO2X2The molar ratio to the ammonia source is (greater than 2 to less than or equal to 3) to 1, optionally (2.01-2.1) to 1. In the step (1), if the ammonia gas is excessive, the above-mentioned easily occursSide reaction 1, the formation of solid sulfonamide, which not only affects the yield, but also makes the material cloudy, making subsequent filtration difficult. When the SO is present2X2When the molar ratio to the ammonia source is within the given range, the yield of lithium bis (fluorosulfonyl) imide can be further improved.
In some embodiments, in step (1), the molar ratio of absorbent a to the ammonia source is (1-5): 1.
In some embodiments, in step (1), the temperature of the reaction is from-10 ℃ to 50 ℃, optionally from 5 ℃ to 35 ℃; the reaction time is 2h to 8 h. When the temperature and time of the reaction in step (1) are controlled within the given ranges, the yield of lithium bis (fluorosulfonyl) imide can be further improved. When the reaction temperature is lower than-10 ℃, the reaction speed is slowed down; when the reaction temperature is higher than 50 ℃, side reactions are increased, so that the yield is influenced, and in addition, the temperature is too high, the solvent is easy to vaporize, so that the pressure in the reaction kettle is too high, and the safety production is influenced.
In some embodiments, in step (1), the ammonia source is one or more of ammonia gas, amine fluoride, sulfonamide, sulfamic acid, and difluorohydrinamine.
In some embodiments, in step (1), the absorbent a is one or more of pyridine, picoline, N-methylpyrrolidone, imidazole, trimethylamine, triethylamine, tri-N-propylamine, tri-N-butylamine, and diisopropylethylamine.
In some embodiments, in step (1), the organic solvent is one or more of acetonitrile, propionitrile, isopropionitrile, diethyl ether, propyl ether, isopropyl ether, tetrahydrofuran, acetone, butanone, methyl isobutyl ketone, and methyl pyrrolidone.
In the examples of the present application, in the step (1), the reaction pressure is not particularly limited, and the reaction may be carried out under normal pressure conditions, pressurized conditions or reduced pressure conditions.
In some embodiments, in step (2), the solution obtained in step (1) is filtered to remove the by-product sulfonamide formed from side reaction 1. The filtration is carried out, for example, using a tetrafluoro filter bag having a pore size of 5 to 20 μm, optionally 6 to 15 μm.
In some embodiments, in step (2), the solution after filtration is concentrated to remove the organic solvent and unreacted absorbent a, this concentration step also being referred to as "falling film" in the chemical industry. The removed organic solvent and the unreacted absorbent A are respectively recycled for the reaction in the step (1) to reduce the production cost. If the organic solvent and the unreacted absorbent A are not removed after the step (1) but are removed after the step (3), lithium bis (fluorosulfonyl) imide is decomposed during the process, thereby reducing the product yield.
In some embodiments, the concentrating comprises vacuum distillation, falling film evaporation, or blade evaporation.
In the examples of the present application, the vacuum degree of the reduced pressure distillation was from-0.05 MPa to-0.09 MPa.
In some embodiments, in step (2), the concentrated solution is washed with water to remove A. (HX) produced in the reactionnAnd impurity ions (e.g. F)-、SO4 2-、FSO3 -、Cl-) Wherein A, X is as defined above, and n is an arbitrary number from 1 to 12. This washing step is also known in the chemical field as extraction. Removed A (HX)nAfter treatment, the absorbent A can be reused in the reaction of the step (1), thereby further reducing the production cost. If there is no washing step, in step (3), A. (HX)nWill react with the lithium source to produce byproducts, thereby consuming excessive lithium source and affecting production costs.
In some embodiments, the mass ratio of water used for washing to the concentrated solution is 1: 1-2, optionally 1: 1.1-1.5.
In some embodiments, the water used for washing is deionized water.
In some embodiments, in step (3), the lithium source is one or more of lithium hydroxide, lithium carbonate, lithium nitride, lithium oxide, and lithium hydride.
In some embodiments, the lithium hydroxide comprises a solvate, such as a hydrate.
In step (3), the following reaction mainly occurs (M is a lithium source):
(SO2F-NH-SO2F)·A+M→(SO2F-N-SO2F)-Li+(LiFSI)+A
in some embodiments, in step (3), the temperature of the reaction is from 15 ℃ to 40 ℃; the reaction time is 0.5h to 6 h.
In some embodiments, the lithium source is used in solid form.
In some embodiments, the lithium source is used in the form of an aqueous solution having a concentration of 5 wt% to 15 wt%.
In some embodiments, in step (4), the solution obtained in step (3) is dehydrated using an ester solvent to bring the product to a moisture content of 50ppm or less, alternatively 20ppm or less. The ester solvent is, for example, diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC) or dimethyl carbonate (DMC). And (4) adding an ester solvent into the solution obtained in the step (3), and then evaporating the ester solvent under-0.05 MPa to-0.09 MPa while supplementing the ester solvent.
Because lithium bis (fluorosulfonyl) imide has very strong water absorption, it is difficult to reduce water content to target requirements with conventional evaporation processes. The ester solvent can reduce the moisture adsorption of the lithium salt, and therefore, in the present application, the moisture can be reduced to the target level by evaporating the ester solvent while supplementing the ester solvent.
In some embodiments, in step (4), the total mass of ester solvents used for dehydration is 50% to 70%, optionally 55% to 65%, of the mass of the solution obtained in step (3).
In some embodiments, in the step (4), the dehydrated solution is concentrated to evaporate the ester solvent used in the dehydration step to 20-40% (mass ratio) to ensure the normal operation of the subsequent crystallization process.
In the examples of the present application, in step (4), the concentration is reduced pressure distillation, falling film evaporation or blade evaporation. Optionally, the reduced pressure distillation is performed at a vacuum of-0.05 MPa to-0.09 MPa.
In some embodiments, in step (4), a byproduct lithium compound (e.g., NH) is added before and/or after dehydration and evaporation of the ester solvent2SO3Li、Li2SO42LiF) by centrifugal filtration, for example by a scraper centrifuge or a disk centrifuge.
In some embodiments, in step (4), the solution after concentration is crystallized using a non-aqueous poor solvent.
In some embodiments, in step (4), the poor solvent is C1-C8One or more of alkanes, benzene, toluene, xylene, methylene chloride, dichloroethane, trichloroethane, tetrachloroethane, and carbon tetrachloride.
In some embodiments, in step (4), the crystals after crystallization are filtered. The filtration was performed using a 100-300 mesh filter plate.
In some embodiments, in step (4), the crystals after filtration are dried. Optionally, the drying is vacuum drying.
In some embodiments, the purity of the crystals after drying is 98.8% or more, alternatively 99.0% or more, further alternatively 99.4% or more, Cl-3ppm or less, HF 50ppm or less, optionally 25ppm or less, and a color of 50Hazen or less, optionally 25Hazen or less.
In one embodiment of the present application, lithium bis (fluorosulfonylimide) is provided, which is prepared by the method as described above.
In one embodiment of the present application, an electrolyte is provided, which comprises lithium bis-fluorosulfonylimide, wherein the lithium bis-fluorosulfonylimide is lithium bis-fluorosulfonylimide as described above or lithium bis-fluorosulfonylimide as prepared by the method as described above.
In one embodiment of the present application, there is provided a secondary battery comprising the electrolyte as described above.
In the application, the method for preparing the lithium bis (fluorosulfonyl) imide has the advantages of simple operation, mild reaction conditions, easy removal of impurity ions and high yield. The lithium bis (fluorosulfonyl) imide prepared by the method has high purity and low chroma, and can exert better performance in electrolyte.
Examples
Hereinafter, examples of the present application will be described. The following description of the embodiments is merely exemplary in nature and is in no way intended to limit the present disclosure. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
(1) Firstly, adding 310g of triethylamine (3mol) as an absorbent A and 300g of acetonitrile as an organic solvent into a reactor, starting stirring at the speed of 1500rpm, cooling to 15 ℃, slowly introducing 1g of ammonia gas (0.06mol), finally simultaneously introducing 16g of ammonia gas (0.94mol) and 209g of sulfuryl fluoride (2.05mol), and preserving heat for 4 hours to obtain a solution containing the bisfluorosulfonyl imide triethylamine salt;
(2) filtering the solution obtained in the step (1) by using a tetrafluoro filter bag with the aperture of 5 mu m, carrying out vacuum distillation on the filtrate under-0.07 MPa to remove an organic solvent and an unreacted absorbent, and washing the filtrate by using deionized water to remove impurities such as fluorine ions, triethylamine hydrogen fluoride salt and the like so as to obtain purified bis (fluorosulfonyl) imide triethylamine salt;
(3) adding 42g of lithium hydroxide monohydrate (LiOH. H) to the purified bis (fluorosulfonyl) imide triethylamine salt obtained in the step (2)2O), stirring for 2 hours at room temperature to obtain a solution containing lithium bis (fluorosulfonyl) imide; and
(4) and (3) settling the solution obtained in the step (3) by using a centrifugal machine to separate solid residues, adding diethyl carbonate into the filtrate, and evaporating diethyl carbonate at-0.07 MPa while replenishing diethyl carbonate to dehydrate, wherein the total mass of the added diethyl carbonate accounts for 60% of the mass of the solution obtained in the step (3), and carrying out reduced pressure distillation on the dehydrated solution at-0.09 MPa to ensure that the mass of diethyl carbonate accounts for 30% of the mass of the solution obtained in the step (3) so as to ensure the normal operation of the subsequent crystallization process. And (3) settling and separating solid residues by using a centrifugal machine, adding 200g of dichloromethane for crystallization, filtering by using a filter plate with the filtering aperture of 250 meshes, cleaning the crystals by using 100g of dichloromethane, and drying in vacuum to obtain 172.1g of lithium bis (fluorosulfonyl) imide, wherein the yield is 92%, the purity is 99.8%, the content of HF (hydrogen fluoride) is 15ppm, and the chroma is 10 Hazen.
Example 2
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in step (1), firstly, slowly introducing 0.5g of ammonia gas (0.03mol), and then simultaneously introducing 16.5g of ammonia gas (0.97mol) and 209g of sulfuryl fluoride (2.05 mol);
in step (4), 166.5g of lithium bis (fluorosulfonyl) imide were obtained in 89% yield, 99.5% purity, HF 20ppm, and color 15 Hazen.
Example 3
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in step (1), firstly, 1.7g of ammonia gas (0.1mol) is slowly introduced, and then 15.3g of ammonia gas (0.9mol) and 209g of sulfuryl fluoride (2.05mol) are simultaneously introduced;
in step (4), 168.4g of lithium bis (fluorosulfonylimide) was obtained in a yield of 90%, a purity of 99.6%, HF 18ppm and a color of 15 Hazen.
Example 4
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in step (1), firstly, slowly introducing 0.3g of ammonia gas (0.02mol), and then simultaneously introducing 16.7g of ammonia gas (0.98mol) and 209g of sulfuryl fluoride (2.05 mol);
in step (4), 149.7g of lithium bis (fluorosulfonylimide) was obtained in 80% yield with a purity of 98.7%, HF of 30ppm and a color of 35 Hazen.
Example 5
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in step (1), first, 3.4g of ammonia gas (0.2mol) was slowly introduced, and then 13.6g of ammonia gas (0.8mo1) and 209g of sulfuryl fluoride (2.05mol) were simultaneously introduced;
in step (4), 151.5g of lithium bis (fluorosulfonylimide) was obtained in 81% yield with a purity of 98.9%, HF 28ppm and a color of 35 Hazen.
Example 6
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in the step (1), firstly, 1g of ammonia gas (0.06mol) is slowly introduced, and then 16g of ammonia gas (0.94mol) and 205g of sulfuryl fluoride (2.01mol) are simultaneously introduced;
in step (4), 164.6g of lithium bis (fluorosulfonyl) imide were obtained in 88% yield with a purity of 99.4%, HF 20ppm and a color of 20 Hazen.
Example 7
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in step (1), firstly, slowly introducing 1g of ammonia gas (0.06mol), and then simultaneously introducing 16g of ammonia gas (0.94mol) and 214g of sulfuryl fluoride (2.1 mol);
in step (4), 166.5g of lithium bis (fluorosulfonyl) imide were obtained in 89% yield, 99.5% purity, HF 18ppm, and color 20 Hazen.
Example 8
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in step (1), first, 1g of ammonia gas (0.06mol) was slowly introduced, and then 16g of ammonia gas (0.94mol) and 204g of sulfonyl fluoride (2mol) were simultaneously introduced;
in the step (4), 153.4g of lithium bis (fluorosulfonylimide) was obtained in a yield of 82%, a purity of 98.7%, HF 25ppm and a chroma of 35Hazen
Example 9
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in the step (1), firstly, 1g of ammonia gas (0.06mol) is slowly introduced, and then 16g of ammonia gas (0.94mol) and 225g of sulfuryl fluoride (2.2mol) are simultaneously introduced;
in step (4), 149.7g of lithium bis (fluorosulfonylimide) was obtained in 80% yield with a purity of 98.4%, HF 28ppm and a color of 35 Hazen.
Example 10
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in the step (1), 101g of triethylamine (1mol) is added as an absorbent A;
in step (4), 164.6g of lithium bis (fluorosulfonyl) imide were obtained in 88% yield with a purity of 99.5%, HF 17ppm and a color of 15 Hazen.
Example 11
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in the step (1), 506g of triethylamine (5mol) is added as an absorbent A;
in step (4), 166.5g of lithium bis (fluorosulfonyl) imide were obtained in 89% yield, 99.6% purity, HF 15ppm, and color 15 Hazen.
Example 12
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in the step (1), 51g of triethylamine (0.5mol) is added as an absorbent A;
in step (4), 140.3g of lithium bis (fluorosulfonyl) imide were obtained in a yield of 75%, a purity of 95.9%, HF 35ppm and a color number of 45 Hazen.
Example 13
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in the step (1), 607g of triethylamine (6mol) is added as an absorbent A;
in step (4), 149.7g of lithium bis (fluorosulfonylimide) was obtained in 80% yield with a purity of 96.7%, HF 30ppm and a color of 40 Hazen.
Example 14
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in the step (1), firstly, adding 310g of triethylamine (3mol) as an absorbent A and 300g of acetonitrile as an organic solvent into a reactor, starting stirring at a stirring speed of 1500rpm, cooling to 14 ℃, then adding 2.2g of ammonium fluoride (0.06mol), finally adding 34.8g of ammonium fluoride (0.94mol) and simultaneously introducing 209g of sulfuryl fluoride (2.05mol), and preserving heat for 4 hours to obtain a solution containing the difluorosulfimide triethylamine salt;
in step (4), 164.6g of lithium bis (fluorosulfonyl) imide were obtained in 88% yield with a purity of 99.5%, HF 18ppm and a color of 15 Hazen.
Example 15
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in the step (1), firstly, adding 310g of triethylamine (3mol) as an absorbent A and 300g of acetonitrile as an organic solvent into a reactor, starting stirring at a stirring speed of 1500rpm, cooling to 15 ℃, then adding 5.8g of sulfonamide (0.06mol), finally adding 90.2g of sulfonamide (0.94mol) and simultaneously introducing 209g of sulfuryl fluoride (2.05mol), and preserving heat for 4 hours to obtain a solution containing the bisfluorosulfonyl imide triethylamine salt;
in step (4), 162.8g of lithium bis (fluorosulfonyl) imide was obtained in 87% yield with a purity of 99.2%, HF 20ppm and a color of 20 Hazen.
Example 16
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in the step (1), firstly, adding 310g of triethylamine (3mol) as an absorbent A and 300g of acetonitrile as an organic solvent into a reactor, starting stirring at the stirring speed of 1500rpm, cooling to 15 ℃, then slowly introducing 1g of ammonia gas (0.06mol), finally introducing 16g of ammonia gas (0.94mol) and adding 243g of fluorochlorosulfonyl chloride (2.05mol), and preserving heat for 4 hours to obtain a solution containing the difluorosulfimide triethylamine salt;
in step (4), 166.5g of lithium bis (fluorosulfonyl) imide were obtained in 89% yield and 99.5% purity in HF 18ppm and color 15 Hazen.
Example 17
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in step (1), 237g of pyridine (3mol) was added as absorbent A;
in step (4), 168.4g of lithium bis (fluorosulfonylimide) was obtained in a yield of 90%, a purity of 99.6%, HF 16ppm and a color of 15 Hazen.
Example 18
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in the step (1), 300g of diethyl ether is added as an organic solvent;
in step (4), 164.6g of lithium bis (fluorosulfonyl) imide were obtained in 88% yield with a purity of 99.4%, HF 19ppm and a color of 20 Hazen.
Example 19
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in the step (3), 36.9g of lithium carbonate is added into the purified bis (fluorosulfonyl) imide triethylamine salt obtained in the step (2), and the mixture is stirred at room temperature for 2 hours to obtain a solution containing lithium bis (fluorosulfonyl) imide;
in step (4), 160.9g of lithium bis (fluorosulfonylimide) was obtained in 86% yield, 99.0% purity, HF 22ppm, color 25 Hazen.
Example 20
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in the step (4), 400g of carbon tetrachloride was used for the crystallization to finally obtain 160.9g of lithium bis (fluorosulfonylimide) in a yield of 86%, a purity of 98.8%, HF 25ppm, and a chroma of 25 Hazen.
Comparative example 1
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in the step (1), firstly, adding 310g of triethylamine (3mol) as an absorbent A and 300g of acetonitrile as an organic solvent into a reactor, starting stirring at the stirring speed of 1500rpm, cooling to 15 ℃, then slowly introducing 17g of ammonia gas (1mol), finally introducing 209g of sulfuryl fluoride (2.05mol), and preserving heat for 4 hours to obtain a solution containing the bisfluorosulfonyl imide triethylamine salt;
in step (4), 127.2g of lithium bis (fluorosulfonyl) imide were obtained in 68% yield, 88.7% purity, HF 50ppm, and color 50 Hazen.
Comparative example 2
Lithium bis (fluorosulfonylimide) preparation referring to example 1 in its entirety, with the difference,
in the step (1), firstly, adding 310g of triethylamine (3mol) as an absorbent A and 300g of acetonitrile as an organic solvent into a reactor, starting stirring at the stirring speed of 1500rpm, cooling to 15 ℃, then introducing 209g of sulfuryl fluoride (2.05mol), finally slowly introducing 17g of ammonia gas (1mol), and preserving heat for 4 hours to obtain a solution containing the bisfluorosulfonyl imide triethylamine salt;
in step (4), 97.3g of lithium bis (fluorosulfonylimide) was obtained in 52% yield, 81.9% purity, HF 65ppm, and color 300 Hazen.
Test method
1. The purity test method of the product lithium bis (fluorosulfonyl) imide comprises the following steps
The measurement was carried out by ion chromatography quantitative analysis (IC).
w＝[(c×V×187)/(m×180.06)]×10-6×100％
w: purity of lithium bis (fluorosulfonyl) imide in percent (%)
c: calculating the concentration of the bis-fluorosulfonyl imide radical ion by ion chromatography curve, wherein the unit is milligram per liter (mg/L)
V: volume of sample pre-treatment constant volume, unit is milliliter (mL)
m: the sample mass is weighed in grams (g)
187: molar mass of lithium bis (fluorosulfonyl) imide in unit of g/moL
180.06: molar mass of bis (fluorosulfonyl) imide radical, unit g/moL
2. The test method of HF in the product lithium bis (fluorosulfonyl) imide comprises
The free HF content can be determined by titration with standard sodium hydroxide solution in an ice-water mixture.
HF(μg/g)＝(V-V0)×0.01×20×106/1000m＝(V-V0)×200/m
In the formula:
0.01: concentration of NaOH Standard solution, mol/L
V0: titration of blank background (100ml pure water +50g ice) to endpoint, volume reading of burette, ml
V: after addition of the sample, when titration is to the end point, the volume reading of the burette, ml
20: molar molecular weight of HF, g/mol
m: amount of sample weighed, g
106: conversion to. mu.g/g
3. The method for testing the chroma of the product lithium bis (fluorosulfonyl) imide comprises the following steps
A series of standard solutions of 10, 20, 30 to 200 Hazen are prepared from 500 Hazen units of Pt-Co standard solution
Calculating formula V is 100N/500N/5
V: volume of 500 Gionce reference fluid required (ml)
N: the amount of the prepared color code Heishiao is 100ml
A series of Pt-Co standard colorimetric solutions filled in a colorimetric tube of 50ml are put on a colorimetric frame according to the colorimetric size,
placing a white background in a light source box, placing a sample of 25ml in a 50ml colorimetric tube at the middle position of a bottom plate of the light box, and comparing the sample with the platinum-cobalt standard solution in the standard light source box along the axis direction of the colorimetric tube by a visual method, wherein the color of the sample is not darker than that of the platinum-cobalt standard solution.
The results of examples 1 to 20 and comparative examples 1 to 2 are summarized in tables 1 to 4.
Table 1: effect of Ammonia Source on yield and product
Table 2: SO (SO)2X2Effect of molar ratio to Ammonia Source on yield and product
Table 3: effect of the molar ratio of absorbent A to Ammonia Source on yield and product
As is clear from tables 1 to 4, the yield and the product purity of all the above examples are higher than those of the comparative examples, and the HF and the color of the product are lower than those of the comparative examples.
As can be seen from Table 1, in the preparation of the salts of bis-fluorosulfonylimide with absorbent A, part of the ammonia source is added first and then SO is added simultaneously2X2The reaction with the residual ammonia source can obviously improve the yield of the method for preparing the lithium bis (fluorosulfonyl) imide and the purity of the product, and simultaneously reduce the HF and the chroma of the product. When part of the ammonia source accounts for 3% -10% of the total mass of the ammonia source, the yield and the product purity can be further improved, and the product chromaticity is reduced.
As can be seen from Table 2, when SO is added2X2When the molar ratio of the ammonia source to the ammonia source is more than 2 to less than or equal to 3: 1, the yield and the product purity are both higher. When SO2X2When the molar ratio of the ammonia source to the ammonia source is (2.01-2.1) to 1, the yield and the product purity can be further improved, and the product chromaticity and HF can be reduced.
As is clear from Table 3, when the molar ratio of the absorbent A to the ammonia source is (1-5): 1, the yield and the product purity can be further improved while the product hue and HF can be reduced.
As can be seen from Table 4, the process described is for different ammonia sources, SO2X2Good compatibility of absorbent, organic solvent, lithium salt and poor solvent.
The present application is not limited to the above embodiments. The above embodiments are merely examples, and embodiments having substantially the same configuration as the technical idea and exhibiting the same operation and effect within the technical scope of the present application are all included in the technical scope of the present application. In addition, various modifications that can be conceived by those skilled in the art are applied to the embodiments and other embodiments are also included in the scope of the present application, in which some of the constituent elements in the embodiments are combined and constructed, without departing from the scope of the present application.
Claims (15)
1. A process for preparing lithium bis (fluorosulfonyl) imide, which comprises
(1) Adding an organic solvent and an absorbent A into a reaction kettle, then adding part of ammonia source, and finally adding SO at the same time2X2Reacting with the rest ammonia source to obtain Salt (SO) containing bis (fluorosulfonyl) imide and absorbent A2F-NH-SO2F) Solution of A in the SO2X2Wherein X is independently of each other fluorine or chlorine;
(2) filtering, concentrating and cleaning the solution obtained in the step (1) to obtain a Salt (SO) of the purified bis (fluorosulfonyl) imide and an absorbent A2F-NH-SO2F)·A；
(3) Adding a Salt (SO) of the purified bis-fluorosulfonylimide obtained in step (2) with an absorbent A2F-NH-SO2F) Adding a lithium source into the solution A, and reacting to obtain a solution containing lithium bis (fluorosulfonyl) imide; and
(4) and (4) dehydrating the solution obtained in the step (3), concentrating, crystallizing by using a non-aqueous poor solvent, and drying to obtain the lithium bis (fluorosulfonyl) imide.
2. The method of claim 1, wherein, in step (1), the portion of the ammonia source comprises 3% to 10% of the total mass of the ammonia source.
3. The method of claim 1 or 2, wherein, in step (1), the SO2X2The molar ratio to the ammonia source is (greater than 2 to less than or equal to 3) to 1, optionally (2.01-2.1) to 1.
4. The process of any one of claims 1 to 3, wherein in step (1), the molar ratio of absorbent A to the ammonia source is (1-5) to 1.
5. The process of any one of claims 1 to 4, wherein in step (1), the temperature of the reaction is from-10 ℃ to 50 ℃, optionally from 5 ℃ to 35 ℃; the reaction time is 2h to 8 h.
6. The process of any one of claims 1 to 5, wherein in step (1), the ammonia source is one or more of ammonia gas, fluorinated amines, sulfonamides, sulfamic acid and difluorohydrogenated amines.
7. The process according to any one of claims 1 to 6, wherein, in step (1), the absorbent A is one or more of pyridine, picoline, N-methylpyrrolidone, imidazole, trimethylamine, triethylamine, tri-N-propylamine, tri-N-butylamine, and diisopropylethylamine.
8. The process according to any one of claims 1 to 7, wherein in step (1), the organic solvent is one or more of acetonitrile, propionitrile, isopropionitrile, diethyl ether, propyl ether, isopropyl ether, tetrahydrofuran, acetone, butanone, methyl isobutyl ketone, and methyl pyrrolidone.
9. The method of any one of claims 1 to 8, wherein, in step (3), the lithium source is one or more of lithium hydroxide, lithium carbonate, lithium nitride, lithium oxide, and lithium hydride.
10. The process according to any one of claims 1 to 9, wherein, in step (3), the temperature of the reaction is 15 ℃ to 40 ℃; the reaction time is 0.5h to 6 h.
11. The method according to any one of claims 1 to 10, wherein in the step (2) and the step (4), the concentration comprises reduced pressure distillation, falling film evaporation or blade evaporation.
12. The process according to any one of claims 1 to 11, wherein, in step (4), the poor solvent is C1-C8One or more of alkanes, benzene, toluene, xylene, methylene chloride, dichloroethane, trichloroethane, tetrachloroethane, and carbon tetrachloride.
13. Lithium bis (fluorosulfonyl) imide, wherein said lithium bis (fluorosulfonyl) imide is prepared by the process of any one of claims 1 to 12.
14. An electrolyte comprising lithium bis-fluorosulfonylimide, said lithium bis-fluorosulfonylimide being the lithium bis-fluorosulfonylimide according to claim 13 or being prepared according to the method of any one of claims 1 to 12.
15. A secondary battery comprising the electrolyte of claim 14.
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