KR101800299B1 - Method for preparing lithium fluorosulfonylimide using alcohol solvents - Google Patents
Method for preparing lithium fluorosulfonylimide using alcohol solvents Download PDFInfo
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- fluorosulfonylimide
- solvent
- lithium
- alcohol
- fsi
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- 238000000034 method Methods 0.000 title claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 18
- 239000005456 alcohol based solvent Substances 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 13
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 29
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 21
- 239000012141 concentrate Substances 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006184 cosolvent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 229940035429 isobutyl alcohol Drugs 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 4
- 150000003863 ammonium salts Chemical class 0.000 abstract 1
- 125000005463 sulfonylimide group Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000013557 residual solvent Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 150000001350 alkyl halides Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 238000001159 Fisher's combined probability test Methods 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 238000004401 flow injection analysis Methods 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PVMUVDSEICYOMA-UHFFFAOYSA-N n-chlorosulfonylsulfamoyl chloride Chemical compound ClS(=O)(=O)NS(Cl)(=O)=O PVMUVDSEICYOMA-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/02—Lithium compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to a process for preparing lithium fluorosulfonylimide, and more particularly to a process for producing lithium fluorosulfonylimide from a mixture comprising a fluorosulfonylimide ammonium salt or a salt containing a metal salt and a lithium salt and an alcohol, The method comprising: Since the method of preparing lithium fluorosulfonylimide according to an embodiment of the present invention easily removes water and solvent and crystallizes the lithium fluorosulfonylimide, the lithium fluorosulfonylimide used as the electrolyte of the secondary battery Economical mass production of sulfonylimide is possible.
Description
The invention relates to a process for the preparation of lithium fluorosulfonylimide.
Lithium bis-fluorosulfonylimide (LiFSI) is a material used as an electrolyte of a secondary battery.
Bisfluorosulfonylimide inorganic salts, especially lithium bisfluorosulfonyl imide (LiFSI), have advantages over other fluorine compounds due to their high thermal stability, high conductivity, and low corrosion resistance. However, many researchers have studied the manufacturing method, but it has not been commercialized to date because of difficulty in manufacturing and handling.
The preparation of alkali metal bis (fluorosulfonyl) imide (MFSI) containing lithium salts is described in non-patent document 1 (Beran et al., Polyhedron 25: 1292-1298, 2006). It is described in the above paper that LiFSI can be prepared by LiClO4 reaction with KFSI. However, this non-patent article describes that LiFSI was not crystallized in an oxygen-containing solvent.
U.S. Patent No. 7,253,317 discloses a method for producing LiFSI from the reaction of a monovalent fluorine salt such as potassium fluoride with bis (chlorosulfonyl) imide. However, there is a large amount of potassium remaining for use as a battery, , There is a disadvantage of using nitromethane which generates toxic gas as a reaction solvent.
U.S. Patent No. 8,926,930 discloses a method of reacting LiFSI in an organic layer by reacting bis (fluorosulfonyl) imide of an organic layer with lithium hydroxide in a water layer, and then concentrating the organic layer to obtain LiFSI . However, the butyl acetate solvent used has a boiling point of 125 ° C which is considerably high in temperature, and is not environmentally friendly as a solvent causing respiratory or skin diseases. In addition, this patent discloses a method of producing a thin film using a thin-film evaporator, which comprises the steps of injecting nitrogen in order to avoid moisture contact during the concentration process, concentrating it with expensive equipment in order to remove moisture, .
U.S. Patent No. 8,377,406 discloses that bis (fluorosulfonyl) imide is cooled to -78 ° C, water is slowly added to room temperature, the pH is adjusted by adding lithium carbonate, the aqueous layer is extracted with ethyl acetate, and the ethyl acetate layer is concentrated However, this patent also has a disadvantage that it has to be cooled to -78 ° C in order to avoid the by-products generated in the reaction with water.
On the other hand, in order for the alkali metal fluorosulfonylimide to be used as an electrolyte of a battery, there should be no moisture and residual solvent other than the above-mentioned thermal stability, high conductivity, low corrosion resistance. In the production of the alkali metal fluorosulfonylimide, water and the residual solvent inhibit the crystallization of the alkali metal fluorosulfonylimide, particularly LiFSI, and thus the production becomes impossible. Further, even if crystallization is performed, Moisture and residual solvents act to lower the efficiency of the battery.
The above-mentioned U.S. patents do not disclose any particular content of residual solvent and moisture.
It is an object of the present invention to solve the various problems including the above problems, and it is an object of the present invention to provide a method of manufacturing a semiconductor device having thermal stability, high conductivity and low causticity, especially, residual solvent of 5 ppm or less, moisture of 30 ppm or less, The present invention provides a process for producing lithium fluorosulfonylimide suitable for use as an electrolyte of a secondary battery.
According to one aspect of the present invention,
A first step of reacting a fluorosulfonylimide inorganic salt (M (FSI) x) represented by the following formula (1) with a lithium salt in a solvent containing an alcohol having 1 to 10 carbon atoms;
Wherein M is H, NH4, Na and R is a fluoroalkyl group having 1 to 6 carbon atoms or fluorine.
A second step of filtering the unreacted compound in the first step;
A third step of concentrating the filtrate of the second step;
A fourth step of crystallizing or precipitating the concentrate of the third step; And
And a fifth step of drying the precipitate, wherein the fourth step crystallization or the precipitation is carried out. The process for producing lithium fluorosulfonylimide represented by the following Chemical Formula 2 is provided:
(2)
According to one embodiment of the present invention, it is possible to produce lithium fluorosulfonylimide which has thermal stability, high conductivity, low corrosiveness, and particularly low moisture and residual solvent which can be used as an electrolyte of a secondary battery, Therefore, mass production is possible.
Figures 1 and 2 show the FTIR spectra and differential scanning calorimetry (DSC) analysis results of NH 4 FSI, respectively.
According to one aspect of the present invention,
A first step of reacting a fluorosulfonylimide inorganic salt (M (FSI) x) represented by the following formula (1) with a lithium salt in a solvent containing an alcohol having 1 to 10 carbon atoms;
(Formula 1)
(Wherein, M is H, NH 4, Na, and R is an alkyl group or a fluorine-fluoroalkyl having 1 to 6 carbon atoms.)
A second step of filtering the unreacted compound in the first step;
A third step of concentrating the filtrate of the second step;
A fourth step of crystallizing or precipitating the concentrate of the third step; And
And a fifth step of drying the precipitate, wherein the fourth step crystallization or the precipitation is carried out. The process for producing lithium fluorosulfonylimide represented by the following Chemical Formula 2 is provided:
(2)
In the above production process, the reaction time of the first step may be in the range of 20 minutes to 25 hours, preferably 1 to 8 hours, in the time of melting the mixture or almost completely dissolving therein.
One of the advantages of the present invention is that the reaction progress can be easily confirmed.
For example, in the case of the reaction between ammonium bis (fluorosulfonyl) imide and lithium hydroxide salt (
(Scheme 1)
On the other hand, a method of producing LiFSI by removing ammonia produced in the reaction under vacuum while reacting is also an example.
In the above method, and the lithium salt is lithium hydroxide (LiOH) or a hydrate (LiOH o H 2 O), LiCO 3, LiF, or LiClO 4 Number of day, but, preferably, commercially useful and safe lithium hydroxide to.
In the above method, in the first step, the lithium salt may be used in an amount of 0.9 to 10 equivalents based on 1 equivalent of the fluorosulfonylimide inorganic salt (M (FSI) x), preferably, Can be used within the range of 1 to 2 equivalents. If 10 equivalents or more is used, it may be difficult to remove excess lithium salt by filtration, and when 0.9 equivalents or less is used, sticky liquid may remain after solvent removal, which may be difficult to crystallize.
In the above production method, the solvent used in the first step should be capable of dissolving the fluorosulfonylimide inorganic salt (M (FSI) x) and the lithium salt or dissolving the reaction while proceeding. Also, it should be non-reactive with lithium fluorosulfonylimide as a target material, and it is preferably a solvent which removes water easily by azeotropy with water or forms a layer with water.
In this connection, according to the results of research conducted by the inventors of the present invention, unlike the result of the above-mentioned Non-Patent
In the above production method, the solvent may be a cosolvent in which a co-solvent of an alcohol having 1 to 10 carbon atoms and water is mixed with 2 to 4 kinds of alcohols having 1 to 10 carbon atoms or 2 to 4 kinds of alcohols having 1 to 10 carbon atoms, Can be public daily. At this time, in the case of a co-solvent in which alcohol and water are mixed, the mixing ratio of alcohol to water is preferably 1: 1 to 100: 1 by volume.
In the above production method, the amount of the FSI added may be 1 to 20 wt% (w / v%), and preferably 3 to 10 (w / v%), based on the volume of the solvent.
In the manufacturing method, the step of filtering the unreacted compound in the first step, which is the second step, is a step of removing foreign substances which may be present in the unreacted compound or mass production after the reaction, May be further included.
In the above production method, the third step (the step of concentrating the filtrate in the second step) may be a condensation temperature of 30 to 90 ° C, preferably 30 to 80 ° C. When concentrated at 90 ° C or higher, the color turns yellow and by-products can be produced. In addition, in the third step, crystallization can easily be performed without using a thin-film evaporator, which is an expensive equipment, which is an advantage according to an embodiment of the present invention.
In the above manufacturing method, the fourth step may include a step of crystallizing the concentrate of the third step, a step of adding a solvent to the concentrate of the third step to precipitate the concentrate, or seeding the concentrate of the third step The crystals can be generated by adding a further solvent. In the fourth step, the crystallization or precipitation solvent is preferably a haloalkane, and the haloalkane may be methylene chloride, chloroform, carbon tetrachloride or dichloroethane, preferably methylene chloride.
The crystallization or precipitation solvent may be from 0.5 to 10 vol% (v / w%), preferably from 1 to 5 vol% (v / w%), based on the weight of the concentrate.
In the above manufacturing method, the fifth step is a step of drying the crystal or precipitate, and the drying temperature is 20 to 80 캜, preferably 30 to 60 캜 under vacuum.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
First, prior to the embodiment of the present invention, the fluorosulfonylimide inorganic salt (M (FSI) x) represented by the above formula (1) was prepared according to the following general example.
General Example 1: Ammonium bis (fluorosulfonyl) imide (NH 4 FSI)
NH 4 FSI expressed by the following
(Formula 3)
General Example 2: Preparation of bis (fluorosulfonyl) imide (HFSI)
HFSI represented by the following Chemical Formula 4 was prepared according to
(Formula 4)
Example 1: Preparation of NH 4 Manufacture of LiFSI from FSI
100 g of NH 4 FSI obtained from General Example 1, 31.4 g of lithium hydroxide monohydrate, and 750 ml of isopropyl alcohol were added and reacted at about 20 ° C for 7 hours. After the reaction was completed, it was filtered and concentrated by rotary evaporation at 50 ° C to give a concentrate. After the precipitate was formed by adding 200 ml of methylene chloride to the concentrate, the mixture was stirred for 1 hour, filtered, and vacuum-dried at 50 ° C to obtain 85.4 g of LiFSI crystals (yield: 91%).
Example 2: Preparation of NH 4 Manufacture of LiFSI from FSI
100 g of NH 4 FSI obtained from General Example 1, 31.4 g of lithium hydroxide monohydrate, and 750 ml of butyl alcohol were added and reacted at about 20 ° C for 7 hours. After the reaction was completed, it was filtered and concentrated by rotary evaporation at 50 ° C to give a concentrate. After the precipitate was formed by adding 200 ml of methylene chloride to the concentrate, the mixture was stirred for 1 hour, filtered, and vacuum-dried at 50 ° C to obtain 70.4 g of LiFSI crystals (yield: 75%).
Example 3: Preparation of NH 4 Manufacture of LiFSI from FSI
100 g of NH 4 FSI obtained from General Example 1, 31.4 g of lithium hydroxide monohydrate, and 750 ml of isobutyl alcohol were added and reacted at about 20 ° C for 7 hours. After the reaction was completed, it was filtered and concentrated by rotary evaporation at 50 ° C to give a concentrate. After the precipitate was formed by adding 200 ml of methylene chloride to the concentrate, stirring was performed for 1 hour, followed by filtration and vacuum drying at 50 ° C to obtain 80.7 g (yield: 86%).
Example 4: Preparation of NH 4 Manufacture of LiFSI from FSI
100 g of NH 4 FSI obtained from General Example 1, 31.4 g of lithium hydroxide monohydrate, 75 mL of water and 750 mL of isopropyl alcohol were added and reacted at about 20 ° C for 7 hours. After the reaction was completed, it was filtered and concentrated by rotary evaporation at 50 ° C to give a concentrate. After the precipitate was formed by adding 200 ml of methylene chloride to the concentrate, the mixture was stirred for 1 hour, filtered, and vacuum-dried at 50 ° C to obtain 85.4 g of LiFSI crystals (yield: 91%).
Example 5: Preparation of LiFSI from HFSI
100 g of HFSI obtained from General Example 3, 34.36 g of lithium hydroxide, and 750 ml of isopropyl alcohol were added and reacted at about 20 DEG C for 7 hours. After the reaction was completed, it was filtered and concentrated by rotary evaporation at 50 ° C to give a concentrate. After the precipitate was formed by adding 200 ml of methylene chloride to the concentrate, the mixture was stirred for 1 hour, then filtered, and vacuum dried at 50 ° C to obtain 75 g (yield: 73%).
Comparative Example 1: Reaction using toluene as a solvent
100 g of NH 4 FSI, 31.38 g of lithium hydroxide and 750 ml of toluene were added and reacted at about 20 ° C. for 7 hours, but the reaction did not proceed because the reaction did not dissolve.
Comparative Example 2: Reaction using water as a solvent
100 g of NH 4 FSI, 31.38 g of lithium hydroxide and 750 ml of water were added and reacted at about 20 ° C for 7 hours, but the product was not solidified.
Measurement of Residual Solvent
1 g of the LiFSI prepared in Examples 1 to 5 was dissolved in N, N -dimethylacetamide and diluted to 4 ml. The remaining solvent was purified by gas chromatography (Pyroprobe 5000, YL Instrument) under the following conditions The results are shown in Table 1.
[Gas chromatograph conditions]
Detector: Flame Ionization Detector (FID)
USP G43 (DB-624, Agilent co.) Column for gas chromatography coated with 3 μm of dimethylpolysiloxane at a temperature of 200 ° C. and a diameter of about 0.53 mm, a length of about 30 m, and 6% , 8 ° C / 100 ° C, 13 ° C / 240 ° C (10 min.), And a split column min, total 30.27 min, head space conditions: GC cycle time: 45.00 min, valve oven temp .: 105 ° C, transfer line temperature: 110 ° C, (Platen / Sample temp.): 100 ° C, Platen temp. Equil. Time: 1.00 min, Specimen Temperature Equilibration Time (Sample) Mixture Stabilization Time: 0.50 min, Pressurize: 10 PSIG, Pressurize Equil. Time: 0.20 min, Equil. Time: 30.00 min, Mixing Time: 5.00 min, Mixture Stabilization Time: , Loop fill pressure (Loop Fill Pressur e): 5 PSIG, Loop Fill Time: 2.00 min, Inject Time: 1.00 min
(ppm)
As shown in Table 1, when LiFSI was prepared by the production method according to the example of the present invention, only a very small amount of residual solvent was detected at 5 ppm or less.
Residual moisture measurement
In a glover box under a nitrogen atmosphere, the LiFSI prepared in Examples 1 to 5 were each taken in a vial, the lid was closed, and the mass was measured. 3.1215 g in Example 1, 3.2432 g in Example 2, 3.1338 g in Example 3, 3.1931 g in Example 4, and 3.1795 g in Example 5, respectively. Each vial was dissolved in 5 ml of methanol for HPLC, and 1 ml was taken with a syringe and the residual moisture was measured using the Karl-Fisher method. The measurement results are shown in Table 2.
(ppm)
As shown in Table 2, LiFSI produced by the production method according to one embodiment of the present invention has a moisture content of 10 ppm or less, which is easier to remove moisture than the conventional method, and thus is suitable as an electrolyte synthesis method.
Metal content measurement
The present inventors measured metal contents using an inductively coupled plasma optical emission spectrometer (ICP-OES, PerkinElmer OPTIMA ICP-OES 5300 DV, Flow Injection System FIAS 400, Autosampler AS 93plus). Specifically, plasma-on was performed to optimize the spectrometer and the detector before using the device, and then warm-up was performed for 1 hour or more. The instrument was then checked with various calibrations and optimizations (Detector calibration, wavelength calibration, Torch View Optimization). We have designed a method to perform BEC, Detection Limits, and Precision tests to check the performance of the equipment. It was measured by mainly using
After preparation, the method for analysis was designed. The purge gas flow was set at 1 L / min of nitrogen gas and the delay time was set at about 90 s after inputting the element to be analyzed and setting the wavelength, time and repetition degree. Since the autosampler is used, the conditional command is input when the sample is injected. After designing the method, measurement was started. The order of measurement was <Analyze Blank -
As shown in Table 3, LiFSI produced by the method according to an embodiment of the present invention has a residual metal content of 20 ppm or less.
Claims (9)
(Formula 1)
(Wherein, M is H, NH 4, Na, and R is an alkyl group or a fluorine-fluoroalkyl having 1 to 6 carbon atoms.)
A second step of filtering the unreacted compound in the first step;
A third step of concentrating the filtrate of the second step;
A fourth step of crystallizing or precipitating the concentrate of the third step; And
And a fifth step of drying the precipitate or the fourth step crystal. The method of producing lithium fluorosulfonylimide according to claim 1,
(2)
Wherein the lithium salt is lithium hydroxide or a hydrate thereof, Li 2 CO 3 , LiF, or LiClO 4 .
Wherein the lithium salt is lithium hydroxide or a hydrate thereof.
Wherein the lithium salt is added in an amount of 0.9 to 2 equivalents based on 1 equivalent of the compound of the formula (1).
Wherein the amount of the fluorosulfonylimide inorganic salt (M (FSI) x) is in the range of 1 to 20 wt% (w / v%) based on the volume of the solvent.
Wherein the alcohol is isopropyl alcohol, butyl alcohol, or isobutyl alcohol.
Wherein the solvent is a mixture of 2 to 4 kinds of alcohols having 1 to 10 carbon atoms.
Wherein the solvent is a co-solvent comprising a co-solvent containing an alcohol having 1 to 10 carbon atoms and water, a mixture of 2 to 4 types of an alcohol having 1 to 10 carbon atoms, and water.
Wherein the volume ratio of the alcohol to water is 1: 1 to 100: 1. 7. A process for preparing lithium fluorosulfonylimide,
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102064905B1 (en) * | 2018-01-08 | 2020-01-10 | 주식회사 천보 | Manufacturing Method For bis-Fluoro Sulfonyl Imide Salt |
| WO2023025776A1 (en) * | 2021-08-27 | 2023-03-02 | Solvay Sa | Reactive distillation process for preparing fluorosulfonylimide salts |
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| KR102223112B1 (en) * | 2017-11-24 | 2021-03-04 | 파미셀 주식회사 | Fluorosulfonyl imide alkali metal salt and preparing method thereof |
| JP6921464B2 (en) | 2018-04-10 | 2021-08-18 | エルジー・ケム・リミテッド | Method for producing lithium bis (fluorosulfonyl) imide salt |
| KR102275418B1 (en) * | 2018-07-09 | 2021-07-12 | 이피캠텍 주식회사 | method for preparing lithium bisfluorosulfonylimide |
| US11267707B2 (en) | 2019-04-16 | 2022-03-08 | Honeywell International Inc | Purification of bis(fluorosulfonyl) imide |
| CN110697668B (en) * | 2019-11-20 | 2021-08-06 | 上海如鲲新材料有限公司 | Preparation method of high-purity bis (fluorosulfonyl) imide salt |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102064905B1 (en) * | 2018-01-08 | 2020-01-10 | 주식회사 천보 | Manufacturing Method For bis-Fluoro Sulfonyl Imide Salt |
| WO2023025776A1 (en) * | 2021-08-27 | 2023-03-02 | Solvay Sa | Reactive distillation process for preparing fluorosulfonylimide salts |
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