CN114348978A - 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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- 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 51
- 239000003792 electrolyte Substances 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910001868 water Inorganic materials 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 61
- 238000001704 evaporation Methods 0.000 claims abstract description 59
- 230000008020 evaporation Effects 0.000 claims abstract description 49
- 238000000605 extraction Methods 0.000 claims abstract description 40
- 230000018044 dehydration Effects 0.000 claims abstract description 23
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 23
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 238000007670 refining Methods 0.000 claims abstract description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 127
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 119
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000012071 phase Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 24
- NTJBWZHVSJNKAD-UHFFFAOYSA-N triethylazanium;fluoride Chemical compound [F-].CC[NH+](CC)CC NTJBWZHVSJNKAD-UHFFFAOYSA-N 0.000 claims description 23
- 229910006095 SO2F Inorganic materials 0.000 claims description 22
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 238000011084 recovery Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- 239000011552 falling film Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- 230000003068 static effect Effects 0.000 claims description 13
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims description 12
- 239000005935 Sulfuryl fluoride Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 8
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003456 sulfonamides Chemical class 0.000 claims description 6
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- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 4
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 4
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 4
- 229940017219 methyl propionate Drugs 0.000 claims description 4
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 4
- 229940124530 sulfonamide Drugs 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-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
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000003759 ester based solvent Substances 0.000 claims description 3
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical group CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010626 work up procedure Methods 0.000 claims description 3
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000002699 waste material Substances 0.000 abstract description 5
- 229910010941 LiFSI Inorganic materials 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910006145 SO3Li Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 238000004064 recycling Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- SAPIQCCFEBULSH-UHFFFAOYSA-M lithium;sulfamate Chemical compound [Li+].NS([O-])(=O)=O SAPIQCCFEBULSH-UHFFFAOYSA-M 0.000 description 1
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- 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
- H01M10/0567—Liquid materials characterised by the additives
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- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The application relates to a method for preparing lithium bis (fluorosulfonyl) imide, which comprises the following steps: (a) a synthesis step; (b) an evaporation step; (c) an extraction step; (d) alkalization; (e) a dehydration step; (f) desolventizing; and optionally (g) a refining step. The method can solve the problems of low product purity, high water content, high production cost and more three wastes in the prior art for preparing LiFSI.
Description
Technical Field
The present application relates to a method of preparing lithium bis (fluorosulfonyl) imide, and lithium bis (fluorosulfonyl) imide prepared by the method, an electrolyte containing the lithium bis (fluorosulfonyl) imide, and a secondary battery thereof.
Background
Due to the special molecular structure of the lithium bis (fluorosulfonyl) imide (LiFSI), the electrolyte added with LiFSI can obtain higher conductivity. Meanwhile, LiFSI also has the characteristics of high thermal stability, wider electrochemical window and lower corrosion rate, and particularly in a power battery, the cycle performance and the rate capability of the power battery can be improved, so that LiFSI is an excellent choice for electrolyte lithium salt of a lithium ion battery.
In the prior art, many problems exist in the industrial large-scale production of LiFSI synthesis and purification, the synthesis process is complicated, the flow is long, the product conversion rate is low, the consumption of raw and auxiliary materials is high, and the raw and auxiliary materials are difficult to recover, so the economy is not high. The application aims to solve at least some of the problems, and provides a novel continuous method for producing LiFSI, so that the purity and the moisture of the LiFSI reach the battery-level standard, the production cost is low, three wastes are less, and the method is suitable for industrial production.
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 solves the problems of low product purity, high moisture content, high production cost, and large amounts of three wastes, which are involved in the production of LiFSI in the prior art.
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 containing the lithium bis (fluorosulfonyl) imide, and a secondary battery thereof.
A first aspect of the present application provides a method for preparing lithium bis (fluorosulfonyl) imide, comprising the steps of:
(a) the synthesis steps are as follows: sulfuryl fluoride, ammonia gas and triethylamine react in a reaction device in the presence of a solvent to obtain a product containing (SO)2F-NH-SO2F)·Et3N, triethylamine hydrogen fluoride and triethylamine stream α 1;
(b) and (3) an evaporation step: the stream α 1 is subjected to evaporation to give a mixture comprising (SO)2F-NH-SO2F)·Et3N and triethylamine hydrogen fluoride, optionally after work-up with distilled solvent and triethylamine, is recycled to step (a);
(c) an extraction step: mixing the stream α 2 obtained in step (b) in an extraction column or staticallyWashing the reactor with water to obtain a solution containing (SO)2F-NH-SO2F)·Et3N oil phase alpha 3 and water phase alpha containing triethylamine hydrogen fluorideWater (W)Separating out an oil phase alpha 3;
(d) alkalization step: sending the oil phase alpha 3 obtained in the step (c) to an evaporator, mixing the oil phase alpha 3 with an aqueous solution of lithium hydroxide to obtain a mixture material flow beta 1-1, and then performing reduced pressure evaporation on the material flow beta 1-1 to obtain a material flow beta 1-2 containing lithium bis (fluorosulfonyl) imide;
(e) a dehydration step: mixing the material flow beta 1-2 containing the lithium bis (fluorosulfonyl) imide with an ester solvent, and then evaporating in an evaporator to obtain a material flow beta 2 containing the lithium bis (fluorosulfonyl) imide;
(f) desolventizing: mixing the material flow beta 2 obtained in the step (e) with an ester solvent, and then evaporating in an evaporator to obtain bis (fluorosulfonyl) imide lithium beta 3; and optionally
(g) Refining: and (f) sending the lithium bis (fluorosulfonyl) imide beta 3 obtained in the step (f) to a dissolution deacidification kettle, adding an ester solvent and lithium hydroxide, then carrying out centrifugal filtration, sending the obtained filtrate g-1 to a dehydration kettle containing a molecular sieve for dehydration, removing the molecular sieve through filtration, sending the obtained filtrate g-2 to a product preparation kettle, and optionally carrying out demagnetizing and filtering treatment.
The preparation method can be used for obtaining LiFSI with high purity and less moisture. Meanwhile, the production cost is low and the three wastes are less.
In any embodiment, in step (a), the ratio of sulfuryl fluoride: ammonia gas: the molar ratio of triethylamine is (1.5-3.5) to 1 (1-6), and can be (2-3) to 1 (1-5).
In any embodiment, in step (a), the solvent is selected from acetonitrile, propionitrile, isopropionitrile, diethyl ether, propyl ether, isopropyl ether, tetrahydrofuran, acetone, butanone, methyl isobutyl ketone, methyl pyrrolidone, or a mixture of any two or more thereof; preferably, the solvent contains at least acetonitrile.
In any embodiment, in step (a), the reaction temperature of the reaction is no greater than 25 ℃, optionally from 3 ℃ to 20 ℃; and/or the reaction pressure of the reaction is not higher than 0.4MPa, optionally not higher than 0.25 MPa.
In any embodiment, a step of filtering the stream α 1 is also included between steps (a) and (b) to remove by-product sulfonamides (NH)2-SO2-NH2) And (3) a solid. Optionally, the step of filtering comprises filtering with a tetrafluoro filter bag having a pore size of 5 μm to 20 μm.
In any embodiment, in step (b), the stream α 1 is evaporated using a falling film evaporator.
In any embodiment, in step (c), the aqueous phase α comprising triethylamine hydrogen fluoride is contacted with a solventWater (W)And (3) recycling the water phase, wherein triethylamine obtained after the water phase is subjected to alkalization and purification treatment can be recycled.
In any embodiment, in step (d), oil phase α 3 is mixed with an aqueous solution of lithium hydroxide and stirred to react for 0.5 to 3 hours, optionally 1 to 2 hours.
In any embodiment, in the step (d), standing and liquid separation are carried out on the condensate obtained by evaporating the material flow beta 1-1, the upper layer liquid is triethylamine aqueous solution, and the upper layer liquid is sent to recovery treatment; the lower layer liquid is condensed water, and the lower layer liquid is recycled for preparing the lithium hydroxide aqueous solution required by the alkalization step.
In any embodiment, in step (d), the volume ratio of stream α 3 to the aqueous solution of lithium hydroxide therein is (0.8 to 5):1, optionally (1-1.2): 1.
in any embodiment, in steps (e) and (f), the aqueous solution of ester solvent obtained by condensation is sent to a recovery treatment.
In any embodiment, in step (e), the resulting stream β 2 contains 0.1% to 2% by volume of water and 20% to 40% by volume of ester solvent.
In any embodiment, the lithium bis (fluorosulfonylimide) β 3 obtained in step (f) has a water content of 2000ppm to 4000ppm, preferably 2300ppm to 2700 ppm.
In any embodiment, the evaporation in step (b), step (d), step (e) and step (f) may be performed in one or more evaporators.
In any embodiment, in steps (f) and (g), the centrifugation is performed using a scraper centrifuge or a disk centrifuge.
In any embodiment, in step (e), step (f) and step (g), the ester solvents are each independently selected from organic solvents having a boiling point greater than 70 ℃, preferably greater than 80 ℃, preferably 100-130 ℃ and being immiscible with water. Optionally, the ester solvent contains a carbonate solvent, and further optionally, the carbonate solvent is selected from ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, or a mixture of two or more thereof. And/or the ester solvent contains a carboxylic ester solvent, and further optionally, the carboxylic ester solvent is selected from propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate or a mixture of two or more of the above. Optionally, the ester solvent is selected from at least one of ethyl methyl carbonate, dimethyl carbonate and diethyl carbonate.
In any embodiment, the evaporation temperature in the basifying step (d) is controlled at 30 ℃ to 40 ℃, optionally 30 ℃ to 35 ℃; and/or, controlling the evaporation temperature of the dehydration step (e) at 40-55 ℃, optionally 45-50 ℃; and/or, the evaporation temperature in the desolventizing step (f) is controlled at 60 ℃ to 80 ℃, optionally 65 ℃ to 75 ℃.
In any embodiment, in step (d), step (e) and step (f), the pH of the mixture is maintained during evaporation at 7-9, preferably 8-9, by the addition of an aqueous solution of lithium hydroxide.
In any embodiment, in step (d), step (e) and step (f), the concentration of the aqueous lithium hydroxide solution is from 1mol/L to 15mol/L, optionally from 2mol/L to 10 mol/L.
In any embodiment, in step (f), the lithium bis (fluorosulfonyl) imide β 3 has an HF of 50 μ g/g or less and a water content of 20 μ g/g or less.
In any embodiment, the ester solvent used in step (e), step (f) and step (g) is the same.
The second aspect of the present application also provides a lithium bis-fluorosulfonylimide prepared by the method of the first aspect of the present application.
The third aspect of the present application also provides an electrolyte comprising lithium bis (fluorosulfonylimide) prepared by the method of the first aspect of the present application.
The fourth aspect of the present application also provides a secondary battery comprising the electrolyte solution according to the third aspect of the present application.
The electrolyte or secondary battery of the present application comprises the lithium bis-fluorosulfonylimide prepared by the first aspect of the present application, and therefore has at least the same advantages as the method described in the first aspect of the present application.
Drawings
Fig. 1 shows a schematic flow diagram of the α -stage process (synthesis → evaporation → extraction), in which an extraction column is used for the extraction process.
Fig. 2 shows a schematic flow diagram of the alpha stage process (synthesis → evaporation → extraction) in which a static mixer is used for the extraction process.
FIG. 3 is a schematic flow diagram of the beta stage process (alkalization → dehydration → exsolution).
FIG. 4 is a schematic flow diagram of a refining process.
Detailed Description
Hereinafter, embodiments of the method for producing lithium bis (fluorosulfonyl) imide according to the present invention will be specifically disclosed with reference to the drawings. 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 drawings and the following description are provided for those skilled in the art to fully understand the present application, and are not intended to limit the subject matter recited 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.
As used herein, the terms "above," "below," and "including numbers, such as" more than one, "mean one or more," more than one of A and B "mean" A, "" B, "or" A and B.
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).
Unless otherwise indicated, the contents and percentages in the context of the present application are based on mass.
The process route of the application is as follows: synthesis → evaporation → extraction → basification → dehydration → exsolution → refining (the refining step is an optional step). The individual steps will be described further below.
[ Synthesis procedure ]
In the synthesis step (a) of the present application, sulfuryl fluoride, ammonia gas and triethylamine are reacted in the presence of a solvent in a reaction apparatus to obtain a mixture containing (SO)2F-NH-SO2F)·Et3N, triethylamine hydrogen fluoride and triethylamine stream α 1;
in some embodiments, in step (a), the reaction between sulfuryl fluoride, ammonia and triethylamine involves primarily the following main reactions:
6SO2F2+3NH3+5Et3N→3(SO2F-NH-SO2F)·Et3N+2Et3N·(HF)n
wherein n is an integer of 1 to 12;
at the same time, the following side reactions are also accompanied:
6NH3+3SO2F2+5Et3N→3NH2-SO2-NH2+2Et3N·(HF)n
wherein n is an integer of 1 to 12.
In some embodiments, in step (a), the ratio of sulfuryl fluoride: ammonia gas: the molar ratio of triethylamine is (1.5-3.5) to 1 (1-6), and can be (2-3) to 1 (1-5). In the present application, when the ammonia gas is excessive, side reactions are liable to occur, so that the reaction mixture becomes turbid, resulting in difficulty in subsequent filtration. Meanwhile, in order to lighten the color of the material, the contact between sulfuryl fluoride and triethylamine for a long time needs to be avoided. Therefore, preferably, in step (a), acetonitrile and triethylamine are firstly added into the reaction device, then partial ammonia gas is introduced, preferably 2% -15%, preferably 3% -10% of the total amount of ammonia gas is introduced, and finally the reaction is carried out by introducing ammonia gas and sulfuryl fluoride simultaneously.
In some embodiments, in step (a), the solvent is selected from acetonitrile, propionitrile, isopropionitrile, diethyl ether, propyl ether, isopropyl ether, tetrahydrofuran, acetone, butanone, methyl isobutyl ketone, methyl pyrrolidone, or a mixture of any two or more thereof, preferably, the solvent contains at least acetonitrile.
In the present application, in the step (a), the reaction apparatus may be a reaction apparatus conventionally used in the art, such as a reaction tank. In general, the reaction in (a) may be carried out in any suitable manner. For example, the reaction can be carried out in a batch reactor or in at least one semicontinuous-operated reactor or in at least one continuously operated reactor.
In some embodiments, in step (a), the reaction temperature of the reaction is no greater than 25 ℃, optionally from 3 ℃ to 20 ℃; and/or the reaction pressure of the reaction is not higher than 0.4MPa, optionally not higher than 0.25 MPa. Too high temperature and pressure can lead to more side reactions, and in addition, too high temperature and solvent are easy to vaporize, thus causing too large pressure in the reaction kettle and influencing safe production.
The inventors of the present application have found that particularly good yields and color shades are obtained when the molar ratio of sulfuryl fluoride to ammonia gas in step (a) is from (1.5-4):1, preferably from (2-3): 1.
In some embodiments, in step (a), at the end of the reaction, a composition comprising from 30 to 50% by weight of (SO) is obtained2F-NH-SO2F)·Et3N, 15 to 30% by weight of triethylamine hydrogen fluoride salt (Et)3N (HF) N) and from 0 to 10% by weight of triethylamine.
In some embodiments, the α 1 stream may be filtered more than once, preferably 2-5 times, optionally 2 times, with the downstream filtration using filter bags having a smaller pore size than the upstream filter bags.
[ Evaporation step ]
In the evaporation step (b) of the present application, the stream α 1 is subjected to evaporation to obtain a mixture comprising (SO)2F-NH-SO2F)·Et3N and triethylamine hydrogen fluoride, optionally after work-up, is recycled to step (a).
In some embodiments, a step of filtering the stream α 1 is also included between steps (a) and (b) to remove by-product sulfonamides (NH)2-SO2-NH2) The step of filtering optionally comprises filtering with a tetrafluoro filter bag having a pore size of 5 to 20 μm, optionally 6 to 15 μm.
In some embodiments, in step (b), stream α 1 is evaporated using a falling film evaporator. The heat exchange medium used by the falling film evaporator can be hot water, and the temperature of a hot water barrel is 50-100 ℃, preferably 60-80 ℃.
In some embodiments, in step (b), the evaporation may be performed using one or two or more evaporators in series, preferably falling film evaporators.
In some embodiments, in step (b), the gas stream distilled off by the evaporator is condensed using a condenser, preferably a condenser comprising a pre-condenser and a post-condenser, the pre-condenser being condensed with water at 0 ℃ and the post-condenser being condensed with water at-15 ℃. Optionally, the internal pressure of the evaporator is from-0.01 MPa to-0.1 MPa. In this context, it will be understood by those skilled in the art that the water used in the condenser contains 30-50% by weight of an anti-freezing liquid, which may be ethylene glycol, glycerol.
In some embodiments, the evaporation in step (b) may be performed in one or more evaporators.
In some embodiments, in step (b), stream α 2 comprises from 60 wt% to 80 wt% (SO)2F-NH-SO2F)·Et3N and 20 to 40% by weight triethylamine hydrogen fluoride.
[ extraction procedure ]
In the extraction step (c) of the present application, the stream α 2 obtained in step (b) is washed with water in an extraction column or a static mixer to obtain a mixture comprising (SO)2F-NH-SO2F)·Et3N oil phase alpha 3 and water phase alpha containing triethylamine hydrogen fluorideWater (W)Separating out an oil phase alpha 3;
in some embodiments, in step (c), the mass ratio of water to stream α 2 entering the extraction column or static mixer is 1: (1-2), optionally 1: (1.1-1.5).
In some embodiments, in step (c), oil phase α 3 further comprises 5 wt.% to 15 wt.% water.
In some embodiments, in step (c), αWater (W)Comprises 75-80 wt% of water and 20-25 wt% of triethylamine hydrogen fluoride salt.
In some embodiments, in step (c), the aqueous phase α comprising triethylamine hydrogen fluoride is contacted with a solventWater (W)Sent to a recovery treatment, the water phase alphaWater (W)The triethylamine obtained after alkalization and purification can be recycled. The aqueous phase contains impurity ions (e.g. F) in addition to triethylamine hydrogen fluoride-、SO4 2-、FSO3 -Or Cl-) After alkalization and purification treatment in the recovery section, triethylamine can be recycled, and KF can produce extra economic benefit for sale.
In the present application, the extraction column may be an extraction column conventionally used in the art, such as a packed extraction column, a sieve plate extraction column, a rotating disk extraction column, a vibrating sieve plate column, a multistage centrifugal extraction column, preferably a rotating disk extraction column.
In some embodiments, the extraction step is carried out in an extraction column (stirring frequency 15. + -. 1 HZ; wherein a weight ratio of deionized water to. alpha.2 of 1 (1 to 1.6), preferably 1 (1 to 1.4)) is used, whereinThe light phase (with low density) enters from the bottom of the side surface of the extraction tower and is discharged from the top of the extraction tower; the heavy phase enters from the top of the side surface of the extraction tower and is discharged from the bottom of the extraction tower, and the middle stirring is spiral (the stirring effect is better, and the cleaning and separation conditions are better). Unexpectedly, the inventors have discovered that extraction with an extraction column can be achieved for impurity ions (e.g., F)-) Better separation. After the treatment of the static mixer, the content of F ions in alpha 3 is more than or equal to 1000ppm, and more LiOH needs to be consumed in the subsequent alkalization process; however, the content of F ions in alpha 3 is less than or equal to 100ppm after the treatment of the extraction tower.
In the present application, the determination of the F ion content and the water content in the stream is a method well known to the art, for example the determination of the F ion content by alizarin complex colorimetry, the determination of the water content by Karl Fischer's method.
In some embodiments, in step (c), the stream α 2 obtained in step (b) is washed with water in an extraction column.
In the present application, the static mixer may be a static mixer conventionally used in the art, such as a static mixer of a pipeline type. In the case of using a static mixer, the resulting mixture is pumped into a layering tank to be subjected to standing layering, and it is usually allowed to stand for 1 to 10 hours, preferably 2 to 6 hours.
In the present application, the water used herein is deionized water, unless otherwise specified, so that the kind and content of impurities contained in the final product can be minimized.
[ alkalization step ]
In the alkalization step (d) of the present application, the oil phase α 3 obtained in step (c) is sent to an evaporator, and after mixing with an aqueous solution of lithium hydroxide, a mixture stream β 1-1 is obtained, and then the stream β 1-1 is subjected to reduced pressure evaporation to obtain a stream β 1-2 comprising lithium bis-fluorosulfonylimide.
In some embodiments, the alkalization of step (d) is performed according to the following reaction scheme:
(SO2F-NH-SO2F)·Et3N+LiOH→(SO2F-N-SO2F)-Li+(LiFSI)+Et3N+H2O。
the reaction principle is that strong base replaces weak base, and the alkalinity of LiOH is higher than (SO)2F-NH-SO2F)·Et3Triethylamine in N, SO that triethylamine is replaced, and LiOH and (SO)2F-NH-SO2F)·Et3The N reacts to form lithium bis (fluorosulfonyl) imide, LiFSI for short, and triethylamine is removed by evaporation.
In some embodiments, in step (d), oil phase α 3 is mixed with an aqueous solution of lithium hydroxide and stirred for 0.5 to 3 hours, optionally 1 to 2 hours.
In some embodiments, in step (d), the concentration of the aqueous lithium hydroxide solution is from 1mol/L to 15mol/L, optionally from 2mol/L to 10 mol/L.
In some embodiments, in step (d), the condensate obtained by evaporating the stream β 1-1 is subjected to standing liquid separation, and the supernatant is an aqueous triethylamine solution and is sent to a recovery treatment; the lower layer liquid is condensed water, and the lower layer liquid is recycled for preparing the lithium hydroxide aqueous solution required by the alkalization step.
In some embodiments, in step (d), wherein the volume ratio of oil phase α 3 to the aqueous solution of lithium hydroxide is (0.8-5): 1, optionally (1-1.2): 1.
in some embodiments, in step (d), during the evaporation under reduced pressure of stream β 1-1, the pH of the mixture is maintained at 7 to 9, preferably 8 to 9, during the evaporation by addition of an aqueous lithium hydroxide solution.
In some embodiments, in step (d), the evaporation is performed using a falling film evaporator, the evaporation temperature being controlled between 30 ℃ and 40 ℃, optionally between 30 ℃ and 35 ℃.
In some embodiments, the evaporation in step (d) may be performed in one or more evaporators.
In some embodiments, in step (d), wherein stream β 1-2 comprises 70 to 90 weight percent lithium bis-fluorosulfonylimide and 5 to 25 weight percent water, the balance being LiF, Li2SO4And lithium sulfamate, etc., based on 100% by weight of the stream β 1-2.
[ dehydration step ]
In the dehydration step (e) of the present application, the stream β 1-2 comprising lithium bis-fluorosulfonylimide is mixed with an ester solvent and then evaporated in an evaporator to obtain a stream β 2 comprising lithium bis-fluorosulfonylimide.
In some embodiments, in step (e), the aqueous solution of ester solvent obtained by condensation is sent to a recovery treatment.
In some embodiments, in step (e), stream β 1-2 is mixed with an ester solvent in a ratio of 1: (0.4-0.8), preferably 1: (0.5-0.7) in a volume ratio.
In some embodiments, in step (e), the resulting stream β 2 further comprises 0.1% to 2% by volume of water and 20% to 40% by volume of an ester solvent.
In some embodiments, in step (e), the evaporator is a falling film evaporator, the evaporation temperature being controlled between 40 ℃ and 55 ℃, optionally between 45 ℃ and 50 ℃.
In some embodiments, the evaporation in step (e) may be performed in one or more evaporators.
Since the lithium salt is very water-absorbent, it is difficult to reduce the moisture to the required standard only by evaporation. For example, the adsorption of lithium salts to water can be reduced by adding a large amount of an ester-based organic solvent (e.g., carbonates and carboxylates, preferably DEC and EMC) which is insoluble in water and preferably has a boiling point greater than that of water (e.g., 105-. The mixture of the ester organic solvent and water obtained by condensation can be recycled after being purified by a recovery section.
In some embodiments, the following side reactions also occur during the addition of lithium hydroxide during step (d), step (e) and step (f):
(SO2F-N-SO2F)-Li++4LiOH→NH2SO3Li+Li2SO4+2LiF+H2O
thus, after the dehydration step (e) and the desolventizing stepOptionally, before step (f), a byproduct lithium compound (e.g., NH)2SO3Li、Li2SO4And LiF), such as by a scraper centrifuge or a disk centrifuge.
In some embodiments, an ester solvent is mixed with stream β 1-2, the pH of the mixture is maintained between 7-9 while evaporating to dehydrate, and optionally centrifugally filtered to obtain stream β 2 comprising 60 to 80 wt% lithium bis-fluorosulfonylimide, 20 to 40 wt% ester solvent, and 0.2 to 1.5 wt% water.
In some embodiments, in step (e), the pH of the mixture is maintained at 7-9, preferably 8-9, during evaporation by the addition of aqueous lithium hydroxide.
In some embodiments, in step (e), the concentration of the aqueous lithium hydroxide solution is from 1mol/L to 15mol/L, optionally from 2mol/L to 10 mol/L.
[ desolventizing step ]
In desolventizing step (f) herein, the stream β 2 obtained in step (e) is mixed with an ester solvent and then evaporated in an evaporator to obtain lithium bis (fluorosulfonylimide) β 3.
In some embodiments, after the dehydration step (e) and before the desolventizing step (f), optionally, a byproduct lithium compound (e.g., NH)2SO3Li、Li2SO4And 2LiF), such as by a scraper centrifuge or a disk centrifuge, to obtain a stream β 2-1.
In some embodiments, in step (f), the stream β 2 or stream β 2-1 is mixed with the ester solvent in a volume ratio of 1 (0.1 to 0.4), preferably 1 (0.2 to 0.3).
In some embodiments, in step (f), the evaporator is a wiped film evaporator, and the evaporation temperature is controlled at 60 to 80 ℃, optionally 65 to 75 ℃.
In some embodiments, the evaporation in step (f) may be performed in one or more evaporators.
In some embodiments, the lithium bis (fluorosulfonyl) imide β 3 obtained in step (f) has a water content of 2000ppm to 4000ppm, preferably 2300ppm to 2700 ppm. By continuing to mix the stream β 2 or the stream β 2-1 obtained by filtration with the ester solvent in step (e) and then continuing to evaporate, it is possible to remove the water from the stream β 2 or the stream β 2-1 even further.
In some embodiments, in step (f), lithium bis (fluorosulfonyl) imide β 3 comprises 80 to 90 weight percent lithium bis (fluorosulfonyl) imide and 10 to 20 weight percent ester solvent.
In some embodiments, in step (f), the aqueous solution of ester solvent obtained by condensation is sent to a recovery treatment.
In some embodiments, in step (f), the lithium bis (fluorosulfonyl) imide β 3 has an HF of 50 μ g/g or less and a water content of 20 μ g/g or less. When the content of the lithium bis (fluorosulfonyl) imide β 3 is not more than the above, a purification treatment, that is, a purification step (g), may be performed.
In the present application, the pH of the mixture is maintained during the steps of alkalization, dehydration and desolventization at 7-9, preferably 8-9, by adding an aqueous solution of lithium hydroxide during evaporation. Decomposition of the product is preferably inhibited by adding a lithium hydroxide solvent to maintain a weakly basic system.
In some embodiments, the pH of the evaporated mixture is maintained in the range of 7 to 9, preferably 8 to 9, by the addition of aqueous lithium hydroxide solution.
In some embodiments, in step (f), the concentration of the aqueous lithium hydroxide solution is from 1mol/L to 15mol/L, optionally from 2mol/L to 10 mol/L.
In some embodiments, the process of the present application does not include crystallizing lithium bis (fluorosulfonyl) imide β 3.
[ refining step ]
In the refining step (g) of the present application, the lithium bis (fluorosulfonyl) imide β 3 obtained in the step (f) is sent to a dissolution deacidification kettle, an ester solvent and lithium hydroxide are added, then centrifugal filtration is performed, the obtained filtrate g-1 is sent to a dehydration kettle containing a molecular sieve for dehydration, the molecular sieve is removed by filtration, and the obtained filtrate g-2 is sent to a product preparation kettle, and optionally subjected to demagnetization and filtration treatment.
In the present application, a refining operation may optionally be performed to meet the final product requirements, depending on the specific composition of lithium bis (fluorosulfonyl) imide β 3. For example, when the lithium bis (fluorosulfonyl) imide β 3 has HF > 50 μ g/g and/or a water content > 20 μ g/g, acid and water removal operations may be required. First, lithium hydroxide is added according to the determined HF content, for example, according to the determined HF content, and then the ratio of the hydrogen in terms of HF: lithium hydroxide 1: (1.05-1.10) adding lithium hydroxide. Then, impurities (LiF, LiF generated by reaction of HF and LiOH) are filtered out by centrifugation, and a molecular sieve is added for removing water, wherein the molecular sieve is a 4A molecular sieve, and the weight of the adsorbed water of the 4A molecular sieve is 15-20% of the weight of the molecular sieve.
In some embodiments, in step (g), the lithium hydroxide is in solid form.
In some embodiments, in step (g), the filtrate g-1 has HF ≦ 50 μ g/g.
In some embodiments, in step (g), the filtrate g-2 has HF of 50 μ g/g or less and a water content of 20 μ g/g or less.
In some embodiments, in step (g), the demagnetizing operation is performed, for example, by using a demagnetizing filter (e.g., vertical, horizontal, high efficiency permanent magnet, drum, or electromagnetic), which may have a magnetic field strength of 5,000-12,000 gauss, preferably 6,000-9,000 gauss.
In some embodiments, in steps (f) and (g), the centrifugation is performed using a scraper centrifuge or a disk centrifuge.
In some embodiments, in step (e), step (f) and step (g), the ester solvents are each independently selected from organic solvents having a boiling point greater than 70 ℃, preferably greater than 80 ℃, preferably 100-130 ℃ and being immiscible with water. Alternatively, for example, the ester solvent contains a carbonate solvent, and further alternatively, the carbonate solvent is selected from ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, or a mixture of two or more thereof. And/or the ester solvent contains a carboxylic ester solvent, and further optionally, the carboxylic ester solvent is selected from propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate or a mixture of two or more of the above. Optionally, the ester solvent is selected from at least one of ethyl methyl carbonate, dimethyl carbonate and diethyl carbonate.
In some embodiments, the ester solvent used in step (e), step (f) and step (g) is the same.
The second aspect of the present application also provides a lithium bis-fluorosulfonylimide prepared by the method of the first aspect of the present application.
The third aspect of the present application also provides an electrolyte comprising lithium bis (fluorosulfonylimide) prepared by the method of the first aspect of the present application.
The fourth aspect of the present application also provides a secondary battery comprising the electrolyte solution according to the third aspect of the present application.
The electrolyte or secondary battery of the present application comprises the lithium bis-fluorosulfonylimide prepared by the first aspect of the present application, and therefore has at least the same advantages as the method described in the first aspect of the present application.
The raw and auxiliary materials used in the LiFSI synthesis process route are common chemical products, the production cost is low, the reaction process has no high temperature and high pressure, the heat generated in the front-end synthesis reaction is cooled through a refrigerator, the reaction at low temperature is guaranteed, and the reaction safety coefficient is high. The production cost of LiFSI is low, the three wastes are less, the purity is high, the raw materials can be fully recycled, and the byproduct can generate extra economic benefit after being purified, so that the method is suitable for industrial production. By recycling the raw materials, the consumption of raw and auxiliary materials is reduced, the utilization rate of reaction raw materials is improved, the discharge treatment cost of compounds is reduced, the production cost is effectively reduced, and the economic benefit is improved.
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
[ Synthesis step → Evaporation step → extraction step ]
The α -stage process (synthesis → evaporation → extraction) is described in conjunction with fig. 1, wherein the extraction process employs an extraction column.
Will be 40m3Triethylamine 35m3Acetonitrile is pumped in with a volume of 100m3The temperature in the synthesis kettle was lowered to 15 deg.C, then 120kg of ammonia gas was introduced first, and finally ammonia gas (2000kg) and sulfuryl fluoride (26000kg) were introduced simultaneously, maintaining the pressure in the kettle at 0.3MPa, and maintaining the temperature in the kettle at 15 deg.C. After the reaction is continued for 4 hours, the pressure in the kettle is reduced to 0.1MPa, and the stirring is stopped. The reaction mixture stream α 1 obtained, which comprises 40% by weight of (SO)2F-NH-SO2F)·Et3N, 18% by weight of triethylamine hydrogen fluoride and 6% by weight of triethylamine) was filtered through a tetrafluoro filter bag having a pore size of 5 μm, and a solid by-product sulfonamide was filtered out. Pumping the filtrate into a falling-film evaporator (hot water tank temperature is 75 deg.C, and evaporating solvent in the filtrate under-0.02 MPa vacuum degree (vacuum pump front stage is condensed with 0 deg.C water, and rear stage is condensed with-15 deg.C water) to obtain a filtrate containing (SO)2F-NH-SO2F)·Et3Stream α 2 of N and triethylamine hydrogen fluoride (which comprises 70% by weight of (SO)2F-NH-SO2F)·Et3N, 28% by weight triethylamine hydrogen fluoride) and a condensate containing acetonitrile. The condensate is recycled for use in the first step of the synthesis vessel. Pumping the material flow alpha 2 to a rotary disc extraction tower (the stirring frequency is 15 +/-1 Hz, the flow is controlled so that the weight ratio of deionized water to alpha 2 is 1: 1.2), and fully mixing the material flow alpha 2 with the deionized water in the extraction tower to obtain a water phase alpha containing triethylamine hydrogen fluoride serving as an upper layer liquidWater (W)(which contains 77% by weight of water + 22% by weight of triethylamine hydrogen fluoride salt), and (SO) as a lower liquid2F-NH-SO2F)·Et3N oil phase α 3 (which also contains 15 wt% water). Will be provided withThe upper aqueous phase is sent to a recovery workshop for treatment, and the lower oil phase is sent to an alkalization step. The oil phase alpha 3 was also detected to contain 100ppm of F-。
[ alkalization step → dehydration step → desolventizing step ]
The beta stage process (basification → dehydration → exsolution) is described in conjunction with fig. 3.
The material flow alpha 3 is directly alkalized in a falling-film evaporator B (hot water barrel steam heating temperature is 35 ℃), and a lithium hydroxide aqueous solution (with the concentration of 5mol/L, wherein the volume ratio of the material flow alpha 3 to the lithium hydroxide aqueous solution is 1.1: 1) is added dropwise while continuously stirring. After 1 hour of reaction, a mixture stream β 1-1 (crude lithium salt) is obtained. At the same time, hot water with the temperature of 35 ℃ is used for heating material flow beta 1-1, the vacuum is started, the vacuum degree in the kettle is kept at-0.08 MPa, and the steaming time is 6 hours. The front stage and the rear stage of the vacuum pump respectively use water at 25 ℃ and water at 0 ℃ to carry out five-stage condensation. And standing and separating the condensate liquid, wherein the upper layer liquid is triethylamine aqueous solution, pumping the triethylamine aqueous solution to a recovery workshop for recovery, and the lower layer liquid is recovered for use in the alkalization process to prepare the lithium hydroxide aqueous solution. After evaporation in a falling-film evaporator B, a stream β 1-2 comprising lithium bis-fluorosulfonylimide (which comprises 85% by weight of lithium bis-fluorosulfonylimide and 10% by weight of water) is obtained. During the evaporation in the falling-film evaporator B, an aqueous lithium hydroxide solution (concentration 5mol/L) is added so that the pH of the stream β 1-2 is maintained at 8.
The stream β 1-2 is continued to be evaporated in a falling-film evaporator C (hot-water drum steam heating temperature 50 ℃). Simultaneously, metering and pumping diethyl carbonate (DEC) (controlling a flow meter to ensure that the volume ratio of the DEC to the material flow beta 1-2 is 0.6:1), continuously heating and evaporating in vacuum (-0.08MPa), respectively carrying out five-stage condensation on the front stage and the rear stage of a vacuum pump by using normal temperature (25 ℃) water and 0 ℃ water, wherein the condensate is an aqueous solution containing the DEC. And sending the condensate to a recovery workshop for recovery. After evaporation in a falling-film evaporator C, a stream β 2 comprising lithium bis-fluorosulfonylimide (which comprises 70% by weight of lithium bis-fluorosulfonylimide and 29% by weight of diethyl carbonate and 1% by weight of water) is obtained. During the evaporation in the falling-film evaporator C, an aqueous lithium hydroxide solution (concentration 5mol/L) is metered in, so that the pH of the stream β 2 is maintained at 8.
And (3) centrifuging the material flow beta 2 obtained after evaporation by the falling-film evaporator C by using a disc centrifuge (the rotating speed is 1500rpm), filtering out a byproduct lithium compound to obtain a material flow beta 2-1 containing 1 wt% of water, 30 wt% of diethyl carbonate and 69 wt% of lithium bis (fluorosulfonyl) imide. The material flow beta 2-1 is pumped into a scraper evaporator D (the steam heating temperature of a hot water barrel is 75 ℃), simultaneously, diethyl carbonate (DEC) is metered and pumped (the flow meter is controlled, the volume ratio of the DEC to the material flow beta 2-1 is 0.25:1), and the heating, the evaporation and the dehydration are continued under vacuum (the vacuum degree is-0.08 MPa). A lithium hydroxide solution (5 mol/L concentration) was also added simultaneously with the evaporation by means of the scraper evaporator D, so that the pH of the resulting stream β 3 was maintained at 8. The condensate, which mainly comprises DEC and a small amount of water, is sent to a recovery plant for recovery. After 6 hours of evaporation, lithium bis (fluorosulfonylimide) β 3 (which contains 85% by weight of lithium bis (fluorosulfonylimide) and 15% by weight of diethyl carbonate) was obtained with a water content of 3000 ppm.
[ refining step ]
An optional refining step is described in connection with fig. 4.
70L of diethyl carbonate and 0.1kg of lithium hydroxide were added to 30kg of lithium bis-fluorosulfonylimide beta 3. Then, a disc centrifuge is used for centrifugation (the rotating speed is 1500rpm) to remove solids, then, the filtrate g-1(HF is less than or equal to 50 mu g/g) is sent to a dehydration kettle, 20kg of molecular sieve is added into the dehydration kettle, the stirring rotating speed is 800rpm, and the treatment is carried out for 2 hours. Then a filter is used for filtering out the molecular sieve, and the obtained filtrate g-2 (the water content is less than or equal to 20 mu g/g) is sent to a product blending kettle. Finally, demagnetizing (vertical demagnetizing filter, 8000 Gauss) and filtering (respectively passing through 1 micron filter, 0.5 micron filter and 0.1 micron filter) to obtain 28 wt% concentration diethyl carbonate solution of lithium bis (fluorosulfonyl) imide, and finally canning.
Through detection, the purity of the powder obtained by drying the lithium bis (fluorosulfonyl) imide with the concentration of 28 weight percent is 99.4 percent, the yield is 95 percent, wherein the content of free acid is 20 mug/g, and the content of water is 25 mug/g.
Example 2: the technical solution of example 2 is the same as that of example 1, except that in the extraction step, a static mixer is adopted for the extraction process (the ratio of the length to the pipe diameter L/D is 10; the flow rate is controlled so that the weight ratio of deionized water to alpha 2 is equal to1: 1.2). According to the scheme shown in figure 2, a material flow alpha 2 is pumped to a static mixer, is fully mixed with deionized water in the static mixer, is sent to a layering tank, and is kept stand for layering for 2 hours to obtain a water phase alpha containing triethylamine hydrogen fluoride serving as an upper layer liquidWater (W)And as a subbing liquid, a liquid containing (SO)2F-NH-SO2F)·Et3And the oil phase alpha 3 of the N, the upper water phase is sent to a recovery workshop for treatment, and the lower oil phase is sent to an alkalization step. The alpha 3 oil phase was found to contain 1000ppm of F-。
Through detection, the purity of the powder obtained by drying the lithium bis (fluorosulfonyl) imide beta 3 is 99.0%, the yield is 92%, wherein the content of free acid is 25 mug/g, and the content of water is 30 mug/g.
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 (24)
1. A method for preparing lithium bis (fluorosulfonyl) imide, comprising the steps of:
(a) the synthesis steps are as follows: sulfuryl fluoride, ammonia gas and triethylamine react in a reaction device in the presence of a solvent to obtain a product containing (SO)2F-NH-SO2F)·Et3N, triethylamine hydrogen fluoride and triethylamine stream α 1;
(b) and (3) an evaporation step: evaporating the stream alpha 1 to obtain a product containing (SO)2F-NH-SO2F)·Et3N and triethylamine hydrogen fluoride, optionally after work-up with distilled solvent and triethylamine, is recycled to step (a);
(c) an extraction step: washing the stream α 2 obtained in step (b) with water in an extraction column or a static mixer to obtain a product comprising (SO)2F-NH-SO2F)·Et3N oil phase alpha 3 and water phase alpha containing triethylamine hydrogen fluorideWater (W)Separating out the oil phase alpha 3;
(d) alkalization step: sending the oil phase alpha 3 obtained in the step (c) to an evaporator, mixing the oil phase alpha 3 with an aqueous solution of lithium hydroxide to obtain a mixture material flow beta 1-1, and then carrying out reduced pressure evaporation on the material flow beta 1-1 to obtain a material flow beta 1-2 containing lithium bis (fluorosulfonyl) imide;
(e) a dehydration step: mixing the material flow beta 1-2 containing the lithium bis (fluorosulfonyl) imide with an ester solvent, and then evaporating in an evaporator to obtain a material flow beta 2 containing the lithium bis (fluorosulfonyl) imide;
(f) desolventizing: mixing the material flow beta 2 obtained in the step (e) with an ester solvent, and then evaporating in an evaporator to obtain bis (fluorosulfonyl) imide lithium beta 3; and optionally
(g) Refining: and (f) sending the lithium bis (fluorosulfonyl) imide beta 3 obtained in the step (f) to a dissolution deacidification kettle, adding an ester solvent and lithium hydroxide, then carrying out centrifugal filtration, sending the obtained filtrate g-1 to a dehydration kettle containing a molecular sieve for dehydration, removing the molecular sieve through filtration, sending the obtained filtrate g-2 to a product preparation kettle, and optionally carrying out demagnetizing and filtering treatment.
2. The process according to claim 1, wherein, in step (a), the ratio of sulfuryl fluoride: ammonia gas: the molar ratio of triethylamine is (1.5-3.5) to 1 (1-6), and can be (2-3) to 1 (1-5).
3. The process according to claim 1 or 2, wherein in step (a) the solvent is selected from acetonitrile, propionitrile, isopropionitrile, diethyl ether, propyl ether, isopropyl ether, tetrahydrofuran, acetone, butanone, methyl isobutyl ketone, methyl pyrrolidone, or a mixture of any two or more thereof; preferably, the solvent contains at least acetonitrile.
4. A process according to any one of claims 1 to 3, wherein in step (a) the reaction is carried out at a reaction temperature of no more than 25 ℃, optionally 3 ℃ to 20 ℃; and/or the presence of a gas in the gas,
the reaction pressure of the reaction is not higher than 0.4MPa, and optionally not higher than 0.25 MPa.
5. The process according to any one of claims 1 to 4, wherein between step (a) and step (b) further comprising a step of filtering the stream α 1 to remove by-product sulfonamide solids, optionally the step of filtering comprises filtering with a tetrafluoro filter bag having a pore size of 5 to 20 μm.
6. The process according to any one of claims 1 to 5, wherein, in step (b), the stream α 1 is evaporated using a falling-film evaporator.
7. The process according to any one of claims 1 to 6, wherein in step (c) the aqueous phase comprising triethylamine hydrogen fluoride is subjected to aWater (W)Sent to a recovery treatment, the water phase alphaWater (W)The triethylamine obtained after alkalization and purification can be recycled.
8. The process according to any one of claims 1 to 7, wherein in step (d) the oil phase α 3 is mixed with an aqueous solution of lithium hydroxide and stirred for 0.5-3 hours, optionally 1-2 hours.
9. The process according to any one of claims 1 to 8, wherein in step (d), the condensate resulting from the evaporation of the stream β 1-1 is subjected to a static liquid separation, the supernatant being an aqueous triethylamine solution, said supernatant being sent to a recovery treatment; and the lower layer liquid is condensed water, and is recycled for preparing the lithium hydroxide aqueous solution required by the alkalization step.
10. The process according to any one of claims 1 to 9, wherein, in step (d), the volume ratio of the oil phase α 3 to the aqueous solution of lithium hydroxide is (0.8-5): 1, optionally (1-1.2): 1.
11. the process according to any one of claims 1 to 10, wherein in steps (e) and (f), the aqueous solution of the ester solvent obtained by condensation is sent to a recovery treatment.
12. The process according to any one of claims 1 to 11, wherein, in step (e), the stream β 2 obtained contains 0.1 to 2 vol.% of water and 20 to 40 vol.% of ester solvent.
13. The process according to any one of claims 1 to 12, wherein the lithium bis-fluorosulfonylimide β 3 obtained in step (f) has a water content of 2000 to 4000ppm, preferably 2300 to 2700 ppm.
14. The process according to any one of claims 1 to 13, wherein the evaporation in step (b), step (d), step (e) and step (f) can be carried out in one or more evaporators.
15. The process of any one of claims 1 to 14, wherein in step (g), the centrifugation is performed using a scraper centrifuge or a disk centrifuge.
16. The process according to any one of claims 1 to 15, wherein in step (e), step (f) and step (g), the ester solvents are each independently selected from organic solvents having a boiling point of more than 70 ℃, preferably more than 80 ℃, preferably 100-;
optionally, the ester solvent contains a carbonate solvent, and further optionally, the carbonate solvent is selected from ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, or a mixture of two or more thereof; and/or the presence of a gas in the gas,
the ester solvent contains a carboxylic ester solvent, and further optionally, the carboxylic ester solvent is selected from propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate or a mixture of two or more of the propyl propionate, the methyl propionate, the ethyl propionate and the methyl butyrate;
optionally, the ester solvent is selected from at least one of ethyl methyl carbonate, dimethyl carbonate and diethyl carbonate.
17. The process according to any one of claims 1 to 16, wherein the evaporation temperature in the alkalization step (d) is controlled at 30-40 ℃, optionally 30-35 ℃; and/or, controlling the evaporation temperature of the dehydration step (e) at 40-55 ℃, optionally 45-50 ℃; and/or, the evaporation temperature in the desolventizing step (f) is controlled at 60 ℃ to 80 ℃, optionally 65 ℃ to 75 ℃.
18. The process according to any one of claims 1 to 17, wherein in step (d), step (e) and step (f) the pH of the mixture is maintained at 7-9, preferably 8-9, during evaporation by addition of an aqueous solution of lithium hydroxide.
19. The process of any one of claims 1 to 18, wherein in step (d), step (e) and step (f), the concentration of the aqueous lithium hydroxide solution is from 1 to 15mol/L, optionally from 2 to 10 mol/L.
20. The process according to any one of claims 1 to 19, wherein in step (f) the lithium bis (fluorosulfonylimide) β 3 has an HF of 50 μ g/g or less and a water content of 20 μ g/g or less.
21. The process according to any one of claims 1 to 20, wherein in step (e), step (f) and step (g) the ester solvent used is the same.
22. Lithium bis-fluorosulfonylimide prepared by the process of any one of claims 1 to 21.
23. An electrolyte comprising lithium bis-fluorosulfonylimide prepared by the method of any one of claims 1-21.
24. A secondary battery comprising the electrolyte of claim 23.
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| WO2024065156A1 (en) * | 2022-09-27 | 2024-04-04 | 上海东庚化工技术有限公司 | Production method and production system for lithium bisfluorosulfonylimide |
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