KR20230009247A - Bis(fluorosulfonyl)imide alkali metal salt - Google Patents
Bis(fluorosulfonyl)imide alkali metal salt Download PDFInfo
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- KR20230009247A KR20230009247A KR1020210136111A KR20210136111A KR20230009247A KR 20230009247 A KR20230009247 A KR 20230009247A KR 1020210136111 A KR1020210136111 A KR 1020210136111A KR 20210136111 A KR20210136111 A KR 20210136111A KR 20230009247 A KR20230009247 A KR 20230009247A
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- fluorosulfonyl
- bis
- imide
- alkali metal
- metal salt
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- -1 Bis(fluorosulfonyl)imide alkali metal salt Chemical class 0.000 title claims abstract description 66
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 56
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 35
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims description 29
- 238000001914 filtration Methods 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 19
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 10
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 6
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 5
- PVMUVDSEICYOMA-UHFFFAOYSA-N n-chlorosulfonylsulfamoyl chloride Chemical compound ClS(=O)(=O)NS(Cl)(=O)=O PVMUVDSEICYOMA-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002198 insoluble material Substances 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 14
- 229910003002 lithium salt Inorganic materials 0.000 description 9
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910010941 LiFSI Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000012296 anti-solvent Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
- C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
Description
본 발명은 탁도가 10NTU이하인 비스(플루오로설포닐)이미드 알칼리금속염(MFSI) 및 그의 제조 방법에 관한 것이다.The present invention relates to bis(fluorosulfonyl)imide alkali metal salt (MFSI) having a turbidity of 10 NTU or less and a method for preparing the same.
모바일 기기의 대중화, 전기자동차의 상용화 및 전기저장 장치의 수요 증가에 따라 고출력, 고에너지 밀도, 고방전 전압 등의 성능을 갖춘 이차전지가 개발되고 있다.In accordance with the popularization of mobile devices, the commercialization of electric vehicles, and the increase in demand for electric storage devices, secondary batteries with performance such as high power, high energy density, and high discharge voltage are being developed.
리튬-이온 배터리는 음극, 양극, 분리막 및 전해액을 포함한다. A lithium-ion battery includes a negative electrode, a positive electrode, a separator and an electrolyte.
상기 전해액은 양극과 음극 사이에서 리튬이온 이동을 위한 매질 역할을 하면서 전지의 열적, 전기적, 물리적 안전성을 향상시키는 기능을 하는 것으로 용매(solvent), 염(salt)과 함께 다양한 첨가제(additive)로 이루어져 있다. 염(salt)으로 주로 LiPF6가 사용되며, 이것은 이온전도도(ionic conductivity), 열 안전성(thermal stability), 전기 화학적 안전성(electronical stability)과 관련이 있고 제일 중요한 리튬 공급원이다. 용매(solvent)는 염을 해리(dissociation)시키는 역할을 하며, 카보네이트(carbonate)계와 에스테르계가 주로 사용되고, 어떤 종류의 용매를 사용하느냐에 따라 벌크 이온전도도(bulk ionic conductivity), 점도(viscosity), 밀도(density), 젖음성(wettability)이 결정된다. 첨가제(additive)는 무수히 많이 존재하며 SEI(solid electrolyte interphase) 생성과 관련이 있다.The electrolyte serves as a medium for the movement of lithium ions between the positive and negative electrodes and improves the thermal, electrical, and physical safety of the battery, and is composed of a solvent, a salt, and various additives. there is. LiPF 6 is mainly used as a salt, which is related to ionic conductivity, thermal stability, and electronic stability and is the most important source of lithium. The solvent serves to dissociate the salt, and carbonate-based and ester-based solvents are mainly used. Depending on the type of solvent used, bulk ionic conductivity, viscosity, and density (density), wettability (wettability) is determined. Additives are numerous and are related to the formation of solid electrolyte interphase (SEI).
한편, 리튬염으로 리튬 헥사플루오로포스페이트(LiPF6)는 우수한 성능을 갖추고 있고 비교적 저렴한 가격으로 인하여 전해액 내의 전해질로 사용되고 있지만 플루오르화수소산 기체의 형태로 분해되는 단점을 갖는다.On the other hand, lithium hexafluorophosphate (LiPF 6 ) as a lithium salt has excellent performance and is used as an electrolyte in an electrolyte solution due to its relatively low price, but has the disadvantage of being decomposed in the form of hydrofluoric acid gas.
상기 단점을 극복하기 위하여, LiTFSI(리튬 비스(트리플루오로메탄설포닐)이미드) 및 LiFSI (리튬 비스(플루오로설포닐)이미드) 가 개발되었다. 이러한 염들은 자발적 분해를 약간 나타내거나 나타내지 않고, LiPF6 보다 가수분해에 더 안정하다.In order to overcome the above disadvantages, LiTFSI (lithium bis(trifluoromethanesulfonyl)imide) and LiFSI (lithium bis(fluorosulfonyl)imide) have been developed. These salts show little or no spontaneous degradation and are more stable to hydrolysis than LiPF 6 .
한편, LiTFSI는 알루미늄 집전기(current collector)에 대한 부식을 야기하는 단점을 갖는 것으로 알려진 반면, LiFSI는 상기와 같은 단점도 갖지 않기 때문에 종래의 다른 염들과 비교하여 탁월한 성능으로 주목을 받고 있다. 따라서 최근 전해질 특히 전기차용 전해질로는 LiPF6와 LiFSI, LiPO2F2, LiDFOP, LiBOB 등이 함께 사용되고 있다.On the other hand, while LiTFSI is known to have a disadvantage of causing corrosion to an aluminum current collector, LiFSI is attracting attention for its excellent performance compared to other conventional salts because it does not have the above disadvantage. Therefore, LiPF 6 , LiFSI, LiPO 2 F 2 , LiDFOP, LiBOB, and the like are used together as electrolytes, especially for electric vehicles.
그러나 본 발명자들은 이차전지용 전해액의 전해질 염으로서 종래의 방법으로 제조된 비스(플루오로설포닐)이미드 알칼리금속염를 사용하였을 때 전해액의 탁도가 높아지는 경우가 있고 이 경우 전지수명이 단축되는 것을 발견하였다.However, the inventors of the present invention have found that the turbidity of the electrolyte may increase when the bis(fluorosulfonyl)imide alkali metal salt prepared by the conventional method is used as the electrolyte salt of the electrolyte for a secondary battery, and in this case, the battery life is shortened.
이에 본 발명은 전지의 수명을 단축시키지 않는 비스(플루오로설포닐)이미드 알칼리금속염를 제공하고자 하였다.Accordingly, the present invention was intended to provide a bis(fluorosulfonyl)imide alkali metal salt that does not shorten the battery life.
상기 목적 달성을 위하여 노력한 바 본 발명은As an effort to achieve the above object, the present invention
비스(플루오로설포닐)이미드 알칼리금속염(MFSI) 1g을 디메틸카보네이트(DMC) 100g에 넣고, 상온에서 1시간 교반한 뒤, 즉시 샘플링하고, 네펠로미터(Nephelometer)를 사용하여 측정한 탁도가 10NTU이하인 비스(플루오로설포닐)이미드 알칼리금속염를 제공한다. 1 g of bis(fluorosulfonyl)imide alkali metal salt (MFSI) was added to 100 g of dimethyl carbonate (DMC), stirred at room temperature for 1 hour, immediately sampled, and the turbidity measured using a Nephelometer A bis(fluorosulfonyl)imide alkali metal salt having less than 10 NTU is provided.
또한 본 발명은 비스(플루오로설포닐)이미드 알칼리금속염 포함 용액을 구멍지름 1㎛이하의 필터를 사용하여 여과 후 용매를 제거하고 건조하여 제조되는 것을 특징으로 하는 비스(플루오로설포닐)이미드 알칼리금속염를 제공한다.In addition, the present invention is a bis (fluorosulfonyl) imide characterized by being prepared by filtering a solution containing bis (fluorosulfonyl) imide alkali metal salt using a filter with a pore diameter of 1 μm or less, removing the solvent and drying it. De alkali metal salts are provided.
또한 본 발명은 구멍지름 1㎛이하의 필터를 사용한 여과 이전에 구멍지름 5㎛이하의 필터를 사용하여 1차 여과를 진행하는 것을 특징으로 하는 비스(플루오로설포닐)이미드 알칼리금속염를 제공한다.In addition, the present invention provides a bis(fluorosulfonyl)imide alkali metal salt characterized in that the primary filtration is performed using a filter having a pore diameter of 5 μm or less before filtration using a filter having a pore diameter of 1 μm or less.
본 발명의 가용성 용매에서의 탁도가 10NTU이하인 비스(플루오로설포닐)이미드 알칼리금속염는 전해액의 전해질로 사용되면 전지의 수명을 연장시키는 효과가 있다.When the bis(fluorosulfonyl)imide alkali metal salt having a turbidity of 10 NTU or less in a soluble solvent of the present invention is used as an electrolyte of an electrolyte solution, it has an effect of extending battery life.
이하， 본 발명을 상세히 설명하기로 한다. 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 안되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Hereinafter, the present invention will be described in detail. The terms or words used in this specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventors can properly define the concept of terms in order to best explain their invention. Based on the principle, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.
본 발명은 가용성 용매에서 탁도가 10NTU이하인 비스(플루오로설포닐)이미드 알칼리금속염에 관한 것이다.The present invention relates to an alkali metal salt of bis(fluorosulfonyl)imide having a turbidity of 10 NTU or less in a soluble solvent.
본 발명은 가용성 용매에서 탁도가 10NTU이하인 비스(플루오로설포닐)이미드 알칼리금속염 포함 조성물에 관한 것이다.The present invention relates to a composition comprising an alkali metal salt of bis(fluorosulfonyl)imide having a turbidity of 10 NTU or less in a soluble solvent.
본 발명은 전해액에서 사용되어도 전지 수명을 단축시키지 않는 비스(플루오로설포닐)이미드 알칼리금속염를 제공하고자 노력한 바, 비스(플루오로설포닐)이미드 알칼리금속염(MFSI) 1g을 디메틸카보네이트(DMC) 100g에 넣고, 상온에서 1시간 교반한 뒤, 즉시 샘플링하고, 네펠로미터(Nephelometer)를 사용하여 측정한 탁도가 10NTU이하인 비스(플루오로설포닐)이미드 알칼리금속염의 경우 전해액에 사용되어도 전해액 탁도를 증가시키지 않고 그 결과 전지의 수명을 단축시키지 않는다는 것을 발견하고 본 발명을 완성하였다. 본 발명에서 상기 샘플링은 비스(플루오로설포닐)이미드 알칼리금속염의 DMC 용액을 1시간 교반하여 비스(플루오로설포닐)이미드 알칼리금속염는 완전히 용해된 조건에서 기타 입자가 침전되기 전에 즉시 샘플링 되는 것이 바람직하다.The present invention has tried to provide a bis(fluorosulfonyl)imide alkali metal salt that does not shorten battery life even when used in an electrolyte, and bis(fluorosulfonyl)imide alkali metal salt (MFSI) 1g is mixed with dimethyl carbonate (DMC) After putting in 100g, stirring at room temperature for 1 hour, sampling immediately, and bis(fluorosulfonyl)imide alkali metal salt having a turbidity of 10 NTU or less measured using a Nephelometer, even if used in an electrolyte solution, electrolyte turbidity The present invention was completed by finding that the life of the battery is not shortened as a result. In the present invention, the sampling is performed by stirring the DMC solution of bis(fluorosulfonyl)imide alkali metal salt for 1 hour so that the bis(fluorosulfonyl)imide alkali metal salt is completely dissolved and sampled immediately before other particles precipitate. it is desirable
또한 본 발명은 비스(플루오로설포닐)이미드 알칼리금속염 포함 용액을 구멍지름 1㎛이하의 필터를 사용하여 여과 후 용매를 제거하고 건조하여 제조되는 것을 특징으로 하는 비스(플루오로설포닐)이미드 알칼리금속염를 제공한다.In addition, the present invention is a bis (fluorosulfonyl) imide characterized by being prepared by filtering a solution containing bis (fluorosulfonyl) imide alkali metal salt using a filter with a pore diameter of 1 μm or less, removing the solvent and drying it. De alkali metal salts are provided.
상기 알칼리금속(M)은 Li, Na, K 또는 Cs 일 수 있고, 바람직하게는 Li이다.The alkali metal (M) may be Li, Na, K or Cs, and is preferably Li.
암모늄 비스(플루오로설포닐)이미드와 알칼리금속(MFSI)의 수산화물을 부틸아세테이트 용매에서 반응시켜 비스(플루오로설포닐)이미드 알칼리금속염를 제조하는 경우 미 반응 알칼리금속 수산화물, 부산물로 생성되는 NH4F, 설파믹산 유도체 등의 제거가 완벽하지 못하면 생성되는 MFSI에 잔존할 수 있고, 이러한 불순물이 존재하는 MFSI를 전해액에 첨가하게 되면, 전해액의 탁도를 증가시키고 전지수명을 단축시키는 원인이 된다.When bis(fluorosulfonyl)imide alkali metal salt is prepared by reacting ammonium bis(fluorosulfonyl)imide with alkali metal (MFSI) hydroxide in a butyl acetate solvent, unreacted alkali metal hydroxide and NH generated as a by-product If 4 F and sulfamic acid derivatives are not completely removed, they may remain in the generated MFSI, and when MFSI containing these impurities is added to the electrolyte, the turbidity of the electrolyte increases and battery life is shortened.
한편, 이러한 부산물들은 전해액 용제인 DMC에 대한 용해도가 작아서, 입자형태로 분산되어지며, 탁도 상승의 원인이 된다.On the other hand, these by-products have low solubility in DMC, which is an electrolyte solvent, and are dispersed in the form of particles, causing an increase in turbidity.
따라서 본 발명은 이러한 부산물을 필터를 이용하여 제거하면, 전해액의 탁도를 감소시키고, 전지수명 저하를 억제할 수 있음을 발견하고 본 발명을 완성하였다.Therefore, the present invention has completed the present invention by discovering that, when these by-products are removed using a filter, the turbidity of the electrolyte solution can be reduced and the decrease in battery life can be suppressed.
이하 본 발명의 비스(플루오로설포닐)이미드 알칼리금속염의 제조방법을 설명한다.Hereinafter, a method for preparing the bis(fluorosulfonyl)imide alkali metal salt of the present invention will be described.
본 발명의 비스(플루오로설포닐)이미드 알칼리금속염는 비스(클로로설포닐)이미드(HCSI) 및 NH4F를 이용하여 암모늄 비스(플루오로설포닐)이미드(NH4FSI)를 제조하는 단계 및 상기 암모늄 비스(플루오로설포닐)이미드 및 알칼리금속 수산화물을 이용하여 비스(플루오로설포닐)이미드 알칼리금속염를 제조하는 단계를 포함하여 제조될 수 있다.The bis(fluorosulfonyl)imide alkali metal salt of the present invention is prepared by using bis(chlorosulfonyl)imide (HCSI) and NH 4 F to prepare ammonium bis(fluorosulfonyl)imide (NH 4 FSI). and preparing a bis(fluorosulfonyl)imide alkali metal salt using the ammonium bis(fluorosulfonyl)imide and an alkali metal hydroxide.
구체적으로 본 발명의 비스(플루오로설포닐)이미드 알칼리금속염는Specifically, the bis(fluorosulfonyl)imide alkali metal salt of the present invention
(a) 질소분위기 하에서 비스(클로로설포닐)이미드와 NH4F를 용매 1 중에서 반응시켜서 암모늄 비스(플루오르설포닐)이미드를 제조하는 단계;(a) preparing ammonium bis(fluorosulfonyl)imide by reacting bis(chlorosulfonyl)imide with NH 4 F in solvent 1 under a nitrogen atmosphere;
(b) 상기 (a)단계의 반응 종결 후, 반응결과물을 상온까지 냉각시키고 불용성 물질을 여과 제거하여 암모늄 비스(플루오로설포닐)이미드를 얻는 단계;(b) obtaining ammonium bis(fluorosulfonyl)imide by cooling the reaction product to room temperature after completion of the reaction in step (a) and filtering out insoluble materials;
(c) 상기 (b)단계에서 얻어진 암모늄 비스(플루오르설포닐)이미드를 알칼리금속 수산화물과 반응시켜 비스(플루오르설포닐)이미드 알칼리금속염을 제조하는 단계;(c) preparing an alkali metal salt of bis(fluorosulfonyl)imide by reacting the ammonium bis(fluorosulfonyl)imide obtained in step (b) with an alkali metal hydroxide;
(d) 상기 (c)단계의 반응용액을 구멍지름 5㎛이하의 필터로 여과하는 단계 및 이후 구멍지름 1㎛이하의 필터로 여과하여 비스(플루오르설포닐)이미드 알칼리금속염을 얻는 단계를 포함하여 제조된다.(d) filtering the reaction solution in step (c) with a filter with a pore diameter of 5 μm or less, and then filtering the reaction solution with a filter with a pore diameter of 1 μm or less to obtain bis(fluorosulfonyl)imide alkali metal salt It is manufactured by
(a)단계의 반응은 하기 반응식 1과 같다.The reaction of step (a) is shown in Scheme 1 below.
식 (1)Equation (1)
상기 반응에서 NH4F는 비스(클로로설포닐)이미드 1 몰에 대하여 2 내지 10몰 바람직하게는 2.5 내지 5몰 반응시킬 수 있다. 이 경우 비스(클로로설포닐)이미드 중의 염소를 충분히 불소로 치환시킬 수 있다.In the above reaction, NH 4 F may be reacted in an amount of 2 to 10 moles, preferably 2.5 to 5 moles, based on 1 mole of bis(chlorosulfonyl)imide. In this case, chlorine in bis(chlorosulfonyl)imide can be sufficiently replaced with fluorine.
상기 반응식 1의 공정에서는 여러 가지 산들이 생성된다. 그 중 HF도 생성되는데, 이것을 질소 가스 버블링에 의하여 반응용액 안에서 제거한다면, HF가 상당히 제거된 상태에서 다음 공정을 진행할 수 있으므로, 출발물질 또는 중간생성물의 가수분해를 줄여줄 수 있다. 상기 반응용액에 질소 가스 공급은 반응 중에 할 수도 있고 반응 완료 후 (b)단계 전에 할 수도 있다. 질소 가스의 버블링은 반응용액으로부터 배출되는 가스의 pH가 6~8이 될 때까지 버블링을 실시할 수 있다. 상기 pH가 6.5~7.5가 되는 시점에서 질소 가스 버블링을 중단하는 것이 더욱 바람직하며, pH가 6.8~7.2가 되는 시점에서 질소 가스 버블링을 중단하는 것이 더 더욱 바람직하다.In the process of Scheme 1, various acids are produced. Among them, HF is also generated, and if this is removed from the reaction solution by nitrogen gas bubbling, the next process can be performed in a state in which HF is significantly removed, thereby reducing the hydrolysis of starting materials or intermediate products. Nitrogen gas may be supplied to the reaction solution during the reaction or after completion of the reaction and before step (b). Bubbling of nitrogen gas may be performed until the pH of the gas discharged from the reaction solution becomes 6 to 8. More preferably, the nitrogen gas bubbling is stopped when the pH reaches 6.5 to 7.5, and more preferably, the nitrogen gas bubbling is stopped when the pH reaches 6.8 to 7.2.
상기 (a)단계의 용매 1은 비스(플루오르설포닐)이미드 알칼리금속염을 용해시킬 수 있는 용매로 바람직하게는 디에틸에테르, 디이소프로필 에테르, 메틸-t-부틸에테르, 초산메틸, 초산에틸, 초산프로필, 및 초산부틸으로 이루어진 군으로부터 선택된 1종 이상일 수 있고 바람직하게는 초산부틸이다.Solvent 1 in step (a) is a solvent capable of dissolving bis(fluorosulfonyl)imide alkali metal salt, and is preferably diethyl ether, diisopropyl ether, methyl-t-butyl ether, methyl acetate, or ethyl acetate. , propyl acetate, and at least one selected from the group consisting of butyl acetate, preferably butyl acetate.
본 발명자들은 상기 용매가 수분을 다량 포함하는 경우 반응물 또는 생성물의 가수분해를 일으킬 수 있고 특히 반응용액에 HF와 같은 산이 존재하는 경우 하기 가수분해 반응이 촉진될 수 있다. 따라서 본 발명은 반응물 또는 생성물의 가수분해 반응을 방지하기 위하여 반응용액 중의 HF의 함량을 줄이고 또한 용매 1 내의 수분함량을 500ppm 이하, 바람직하게는 200ppm이하로 할 필요가 있다.The present inventors found that when the solvent contains a large amount of water, reactants or products may be hydrolyzed, and in particular, when an acid such as HF is present in the reaction solution, the following hydrolysis reaction may be promoted. Therefore, in the present invention, in order to prevent hydrolysis of reactants or products, it is necessary to reduce the content of HF in the reaction solution and to set the water content in solvent 1 to 500 ppm or less, preferably 200 ppm or less.
(a)단계의 불소화반응시의 온도는 반응의 진행 상황에 따라 적절히 조정할 수 있지만, 바람직하게는 -40 ℃ ∼ 200 ℃, 보다 바람직하게는 -20 ℃ ∼ 100 ℃ 이다. 반응에 필요로 하는 시간은 반응 규모에 따라 상이하지만, 바람직하게는 0.1 시간 ∼ 48 시간, 보다 바람직하게는 0.5 시간 ∼ 24 시간이다.The temperature during the fluorination reaction in step (a) can be appropriately adjusted depending on the progress of the reaction, but is preferably -40 °C to 200 °C, more preferably -20 °C to 100 °C. The time required for the reaction varies depending on the scale of the reaction, but is preferably 0.1 hour to 48 hours, more preferably 0.5 hour to 24 hours.
(b)단계는 (a)단계의 반응 종결 후, 반응결과물을 상온까지 냉각시키고 NH4Cl 등의 불용성 물질을 여과 제거하여 암모늄 비스(플루오로설포닐)이미드를 얻는 단계이다. 중간체로 얻어진 암모늄 비스(플루오르설포닐)이미드를 고체로 회수한 후 다음 단계를 진행할 수도 있고 용액 중에서 그대로 사용될 수도 있다.Step (b) is a step of obtaining ammonium bis(fluorosulfonyl)imide by cooling the reaction product to room temperature after completion of the reaction of step (a) and filtering out insoluble substances such as NH 4 Cl. Ammonium bis(fluorosulfonyl)imide obtained as an intermediate may be recovered as a solid and then proceed to the next step or may be used as it is in solution.
상기 (c)단계는 중간체로 얻어진 암모늄 비스(플루오르설포닐)이미드를 알칼리금속 수산화물과 반응시켜 비스(플루오르설포닐)이미드 알칼리금속염을 제조하는 단계이다. 상기 반응은 중간체로 얻어진 암모늄 비스(플루오르설포닐)이미드를 고체로 회수한 후 알칼리금속 수산화물과 반응시킬 수도 있으나, 중간체로 얻어진 암모늄 비스(플루오르설포닐)이미드의 고체로의 회수 없이 (b)단계의 여과액에 알칼리금속 수산화물을 추가하는 경우, 별도의 암모늄 비스(플루오르설포닐)이미드 회수 공정이 필요없어 공정 시간 및 노력을 단축할 수 있고, 생성물의 손실을 줄일 수 있는 장점이 있다.The step (c) is a step of preparing an alkali metal salt of bis(fluorosulfonyl)imide by reacting ammonium bis(fluorosulfonyl)imide obtained as an intermediate with an alkali metal hydroxide. In the above reaction, ammonium bis(fluorosulfonyl)imide obtained as an intermediate may be recovered as a solid and then reacted with an alkali metal hydroxide, but without recovery of ammonium bis(fluorosulfonyl)imide obtained as an intermediate as a solid (b) ) When alkali metal hydroxide is added to the filtrate in step, there is no need for a separate ammonium bis(fluorosulfonyl)imide recovery process, so process time and effort can be shortened, and product loss can be reduced. .
알칼리금속 수산화물의 사용량은 암모늄 비스(플루오로설포닐)이미드 1 몰에 대하여, 바람직하게는 1 몰 ∼ 10 몰, 보다 바람직하게는 1 몰 ∼ 5 몰이다.The amount of alkali metal hydroxide used is preferably 1 to 10 moles, more preferably 1 to 5 moles, based on 1 mole of ammonium bis(fluorosulfonyl)imide.
알칼리금속염으로의 반응시의 온도는 특별히 한정되지 않지만, 바람직하게는 0 ℃ ∼ 200 ℃, 보다 바람직하게는 10 ℃ ∼ 100 ℃ 이다. 반응에 필요로 하는 시간은 반응 규모에 따라 상이하지만, 바람직하게는 0.1 시간 ∼ 48 시간, 보다 바람직하게는 0.5 시간 ∼ 24 시간이다.The temperature during the reaction with the alkali metal salt is not particularly limited, but is preferably 0°C to 200°C, more preferably 10°C to 100°C. The time required for the reaction varies depending on the scale of the reaction, but is preferably 0.1 hour to 48 hours, more preferably 0.5 hour to 24 hours.
반응은 상압하에서도 실시 가능하지만, 감압하에서 실시하면 부생되는 암모니아가 제거되어 목적물이 합성되기 쉽다. 감압하는 경우, 반응 압력은 특별히 한정되지 않지만, 대기압미만 ∼ 0.01 torr 가 바람직하고, 0 ℃ ∼ 100 ℃에서 용매가 환류할 정도의 감압도가 보다 바람직하다.The reaction can be carried out even under normal pressure, but when carried out under reduced pressure, by-product ammonia is removed and the desired product is easily synthesized. In the case of reducing the pressure, the reaction pressure is not particularly limited, but is preferably less than atmospheric pressure to 0.01 torr, and more preferably a degree of pressure reduction to the extent that the solvent refluxes at 0°C to 100°C.
본 발명의 비스(플루오로설포닐)이미드 알칼리금속염 제조를 위한 반응 용기는 불소 수지나 폴리에틸렌제 등의 수지제가 보다 바람직하다.The reaction vessel for producing the bis(fluorosulfonyl)imide alkali metal salt of the present invention is more preferably made of a resin such as fluororesin or polyethylene.
상기 (d)단계는 (c)단계의 반응용액을 구멍지름 5㎛이하의 필터로 여과하는 단계 및 이후 구멍지름 1㎛이하의 필터로 여과하는 단계이다. The step (d) is a step of filtering the reaction solution of step (c) with a filter having a pore diameter of 5 μm or less and then filtering the reaction solution with a filter having a pore diameter of 1 μm or less.
비스(플루오로설포닐)이미드 알칼리금속염 제조방법에 의하여 미 반응 알칼리금속 수산화물이나 부산물로 NH4F, 설파믹산 유도체가 생성되어 잔류할 수 있는데 이러한 부산물들은 전해액 용제인 DMC등에 대한 용해도가 작아서, 입자형태로 분산되어지며, 탁도 상승의 원인이 된다. 본 발명은 먼저 구멍지름 5㎛이하의 필터, 바람직하게는 구멍지름 4-5㎛의 필터로 조대 입자를 제거하고 이후 여과액을 구멍지름 1㎛이하, 바람직하게는 구멍지름 0.5초과 1㎛이하의 필터로 여과함으로써 미세입자를 효율적으로 제거할 수 있다. 상기 여과 단계는 상압에서 진행할 수도 있지만 0.1기압이하의 압력으로 감압 여과하는 경우 여과 시간을 단축할 수 있다.By the bis(fluorosulfonyl)imide alkali metal salt production method, NH 4 F and sulfamic acid derivatives may be generated and remain as unreacted alkali metal hydroxides or by-products. These by-products have low solubility in DMC, etc. It is dispersed in the form of particles and causes an increase in turbidity. The present invention first removes coarse particles with a filter having a pore diameter of 5 μm or less, preferably a filter having a pore diameter of 4-5 μm, and then the filtrate is filtered with a pore diameter of 1 μm or less, preferably more than 0.5 and less than 1 μm. Fine particles can be efficiently removed by filtering with a filter. The filtration step may be performed at normal pressure, but the filtration time may be shortened when the filtration is performed under reduced pressure at a pressure of 0.1 atm or less.
본 발명은 비스(플루오로설포닐)이미드 알칼리금속염를 포함하는 전해액의 탁도를 개선하기 위하여 추가로 구멍지름 0.5㎛이하의 필터로 여과할 수 있다.In the present invention, in order to improve the turbidity of the electrolyte solution containing bis(fluorosulfonyl)imide alkali metal salt, it can be further filtered with a filter having a pore diameter of 0.5 μm or less.
상기 (d)단계 이후 용매 1을 진공제거하여 비스(플루오로설포닐)이미드 알칼리금속염를 얻을 수 있다.After the step (d), solvent 1 may be vacuum removed to obtain bis(fluorosulfonyl)imide alkali metal salt.
또는 (d)단계 이후 용매 1을 감압하에서 일부 제거한 다음 용매 2를 투입하여 침전으로 생성되는 비스(플루오로설포닐)이미드 알칼리금속염를 얻을 수도 있다. 상기 용매 2는 비스(플루오르설포닐)이미드 알칼리금속염을 용해시키지 않는 반용매(antisolvent)로 톨루엔, 헥세인, 헵탄, 클로로포름, 디클로로메탄 등으로 이루어진 군으로부터 선택되는 1종 이상의 것일 수 있다. Alternatively, after step (d), solvent 1 may be partially removed under reduced pressure and then solvent 2 may be added to obtain bis(fluorosulfonyl)imide alkali metal salt produced by precipitation. The solvent 2 is an antisolvent that does not dissolve the bis(fluorosulfonyl)imide alkali metal salt and may be at least one selected from the group consisting of toluene, hexane, heptane, chloroform, dichloromethane, and the like.
상기 용매 2는 비스(플루오르설포닐)이미드 알칼리금속염 100 중량부를 기준으로 50~500 중량부로 투입될 수 있으며, 더욱 바람직하게는 80~300 중량부로 투입될 수 있다. 반용매의 투입량이 상술한 범위 미만일 경우 비스(플루오르설포닐)이미드 알칼리금속염이 충분히 수득되지 않을 수 있어 바람직하지 않으며, 상술한 범위를 초과하는 경우 효과는 증가하지 않고, 여타 불필요한 부산물도 같이 침전될 수 있으므로 바람직하지 않다.The solvent 2 may be added in an amount of 50 to 500 parts by weight, more preferably 80 to 300 parts by weight, based on 100 parts by weight of the bis(fluorosulfonyl)imide alkali metal salt. When the input amount of the anti-solvent is less than the above-mentioned range, it is undesirable because sufficient bis(fluorosulfonyl)imide alkali metal salt may not be obtained. This is not desirable as it can be
본 발명의 상기 방법으로 제조된 비스(플루오로설포닐)이미드 알칼리금속염은 1g을 디메틸카보네이트(DMC) 100g에 넣고, 상온에서 1시간 교반한 뒤, 즉시 샘플링하고, 네펠로미터(Nephelometer)를 사용하여 측정한 탁도가 10NTU이하이다.1 g of the bis(fluorosulfonyl)imide alkali metal salt prepared by the above method of the present invention was added to 100 g of dimethyl carbonate (DMC), stirred at room temperature for 1 hour, immediately sampled, and measured using a Nephelometer. The turbidity measured using it is less than 10 NTU.
본 발명의 제조 방법에 따라 얻어지는 비스(플루오로설포닐)이미드 알칼리금속염은, 일차 전지, 리튬 이온 이차 전지 등의 이차 전지, 전해 콘덴서, 전기 이중층커패시터, 연료 전지, 태양 전지, 에너지저장 장치 등의 전기 화학 디바이스를 구성하는 이온 전도체의 재료로서 바람직하게 사용할 수 있다.The bis(fluorosulfonyl)imide alkali metal salt obtained according to the production method of the present invention is used in secondary batteries such as primary batteries and lithium ion secondary batteries, electrolytic capacitors, electric double layer capacitors, fuel cells, solar cells, energy storage devices, etc. It can be preferably used as a material for an ion conductor constituting an electrochemical device of
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변경 및 수정이 본 발명의 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred embodiments are presented to aid understanding of the present invention, but the following examples are merely illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. , It is natural that these changes and modifications fall within the scope of the claims of the present invention.
실시예 1. 비스(플루오로설포닐)이미드 리튬염의 합성 1Example 1. Synthesis of bis(fluorosulfonyl)imide lithium salt 1
교반장치, 콘덴서 및 온도계가 부착된 반응기에 질소분위기 하에 암모늄 비스(플루오로설포닐)이미드 198g(1mole)를 부틸아세테이트 600g에 녹이고, 수산화리튬 25.5g(1.06mole)을 첨가하고 5℃ 미만에서 반응을 4시간 진행한 후 반응을 종결시켰다. 이후 반응 용액을 1차로 구멍지름 5㎛ 필터로 여과하고, 이후 2차로 구멍지름 1㎛ 필터로 여과하여 비스(플루오로설포닐)이미드 리튬염의 부틸아세테이트 용액을 얻은 후 부틸아세테이트를 진공제거하여 비스(플루오로설포닐)이미드 리튬염를 얻었다.In a reactor equipped with a stirrer, condenser and thermometer, 198 g (1 mole) of ammonium bis(fluorosulfonyl)imide was dissolved in 600 g of butyl acetate under a nitrogen atmosphere, 25.5 g (1.06 mole) of lithium hydroxide was added, and After the reaction proceeded for 4 hours, the reaction was terminated. Thereafter, the reaction solution was firstly filtered through a filter having a pore diameter of 5 μm, and thereafter filtered through a filter having a pore diameter of 1 μm secondly to obtain a butyl acetate solution of bis(fluorosulfonyl)imide lithium salt, and then butyl acetate was vacuum-removed to obtain bis A (fluorosulfonyl)imide lithium salt was obtained.
상기 비스(플루오로설포닐)이미드 리튬염 1g을 디메틸카보네이트(DMC) 100g에 넣고, 상온에서 1시간 교반한 뒤, 즉시 샘플링하고, 네펠로미터(Nephelometer)를 사용하여 탁도를 측정하였다. 측정한 탁도는 하기 표 1에 나타내었다.1 g of the bis(fluorosulfonyl)imide lithium salt was put into 100 g of dimethyl carbonate (DMC), stirred at room temperature for 1 hour, immediately sampled, and turbidity was measured using a Nephelometer. The measured turbidity is shown in Table 1 below.
실시예 2. 비스(플루오로설포닐)이미드 리튬염의 합성 2Example 2. Synthesis of bis(fluorosulfonyl)imide lithium salt 2
실시예 1과 같이 암모늄 비스(플루오로설포닐)이미드와 수산화리튬을 부틸아세테이트에서 반응시킨 후, 1차로 구멍지름5㎛필터로 여과하고 이후2차로 구멍지름 1㎛ 필터로 여과하고, 3차로 구멍지름 0.45㎛ 필터로 여과하여 리튬 비스(플루오로설포닐)이미드의 부틸아세테이트 용액을 얻은 후 부틸아세테이트를 진공제거하여 리튬 비스(플루오로설포닐)이미드를 얻었다.As in Example 1, after reacting ammonium bis(fluorosulfonyl)imide with lithium hydroxide in butyl acetate, first filtering with a 5 μm pore diameter filter, secondly filtering with a 1 μm pore diameter filter, and thirdly After filtering with a filter having a pore diameter of 0.45 μm to obtain a butyl acetate solution of lithium bis(fluorosulfonyl)imide, the butyl acetate was removed under vacuum to obtain lithium bis(fluorosulfonyl)imide.
실시예 1과 같이 리튬 비스(플루오로설포닐)이미드의 탁도를 측정하고 하기 표 1에 나타내었다.The turbidity of lithium bis(fluorosulfonyl)imide was measured as in Example 1 and is shown in Table 1 below.
비교예 1.Comparative Example 1.
구멍지름 1㎛ 필터를 이용한 2차 여과를 실시하지 않은 것을 제외하고는 실시예 1과 같이 수행하여 비스(플루오르설포닐)이미드 리튬염을 수득하였다.Bis(fluorosulfonyl)imide lithium salt was obtained in the same manner as in Example 1, except that the secondary filtration using a filter having a pore diameter of 1 μm was not performed.
실시예 1과 같이 리튬 비스(플루오로설포닐)이미드의 탁도를 측정하고 하기 표 1에 나타내었다.The turbidity of lithium bis(fluorosulfonyl)imide was measured as in Example 1 and is shown in Table 1 below.
실시예 1 내지 2에서 제조된 비스(플루오르설포닐)이미드 리튬염의 경우 탁도가 10NTU 이하인, 반면 비교예 1에서 제조된 비스(플루오르설포닐)이미드 리튬염의 경우 탁도가 26NTU로 나타났고 이 경우 상기 물질을 전해액의 전해질로 사용할 경우 전해액의 탁도가 높아서 이후 전지의 수명을 단축시킨다.In the case of the bis(fluorosulfonyl)imide lithium salt prepared in Examples 1 and 2, the turbidity was 10 NTU or less, whereas in the case of the bis(fluorosulfonyl)imide lithium salt prepared in Comparative Example 1, the turbidity was 26 NTU, and in this case When the material is used as an electrolyte of an electrolyte solution, the turbidity of the electrolyte solution is high, thereby shortening the life of the battery.
Claims (9)
(a) 질소분위기 하에서 비스(클로로설포닐)이미드와 NH4F를 용매 1 중에서 반응시켜서 암모늄 비스(플루오르설포닐)이미드를 제조하는 단계;
(b) 상기 (a)단계의 반응 종결 후, 반응결과물을 상온까지 냉각시키고 불용성 물질을 여과 제거하여 암모늄 비스(플루오로설포닐)이미드를 얻는 단계;
(c) 상기 (b)단계에서 얻어진 암모늄 비스(플루오르설포닐)이미드를 알칼리금속 수산화물과 반응시켜 비스(플루오르설포닐)이미드 알칼리금속염을 제조하는 단계;
(d) 상기 (c)단계의 반응용액을 구멍지름 5㎛이하의 필터로 여과하는 단계 및 이후 구멍지름 1㎛이하의 필터로 여과하여 비스(플루오르설포닐)이미드 알칼리금속염을 얻는 단계를 포함하여 제조되는 것을 특징으로 하는 비스(플루오로설포닐)이미드 알칼리금속염The method according to claim 2, wherein the bis (fluorosulfonyl) imide alkali metal salt
(a) preparing ammonium bis(fluorosulfonyl)imide by reacting bis(chlorosulfonyl)imide with NH 4 F in solvent 1 under a nitrogen atmosphere;
(b) obtaining ammonium bis(fluorosulfonyl)imide by cooling the reaction product to room temperature after completion of the reaction in step (a) and filtering out insoluble materials;
(c) preparing an alkali metal salt of bis(fluorosulfonyl)imide by reacting the ammonium bis(fluorosulfonyl)imide obtained in step (b) with an alkali metal hydroxide;
(d) filtering the reaction solution in step (c) with a filter having a pore diameter of 5 μm or less and thereafter filtering the reaction solution with a filter having a pore diameter of 1 μm or less to obtain bis(fluorosulfonyl)imide alkali metal salt Bis (fluorosulfonyl) imide alkali metal salt, characterized in that produced by
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