KR20200061058A - Method for producing bisfluorosulfonyl imide alkali metal salt and bisfluorosulfonyl imide alkali metal salt produced by same - Google Patents

Abstract

The present specification relates to a method for producing a bis(fluorosulfonyl)imide alkali metal salt and a bis(fluorosulfonyl)imide alkali metal salt produced thereby. The method for producing a bis(fluorosulfonyl)imide alkali metal salt comprises the steps of: synthesizing an ammonium bis(fluorosulfonyl)imide salt; and synthesizing a bis(fluorosulfonyl)imide alkali metal salt from the ammonium bis(fluorosulfonyl)imide salt. The bis(fluorosulfonyl)imide alkali metal salt has thermal stability, high conductivity and low corrosiveness.

Description

Method for manufacturing bisfluorosulfonyl imide alkali metal salt and bisfluorosulfonyl imide alkali metal salt prepared thereby

The present specification relates to a method for producing a bisfluorosulfonyl imide alkali metal salt and a bisfluorosulfonyl imide alkali metal salt prepared thereby.

Bisfluorosulfonyl imide alkali metal salt is a material used as an electrolyte in a secondary battery. Among them, lithium fluorosulfonyl imide (LiFSI) has an advantage over other fluorine compounds due to its high thermal stability, high conductivity, and low corrosiveness. However, despite these advantages, many researchers have studied the manufacturing method, but have not been commercialized to date due to difficulties in manufacturing and handling.

U.S. Patent No. 7,253,317 discloses a method for preparing lithium bisfluorosulfonylimide (LiFSI) from the reaction of a monovalent fluorine salt such as potassium fluoride with bis(chlorosulfonyl)imide, but with a battery. There is a lot of potassium remaining for use, and there is also a disadvantage of using nitromethane, which generates toxic gas as a reaction solvent.

In U.S. Patent No. 8,926,930, two phases, i.e., bis(fluorosulfonyl)imide of an organic layer and lithium hydroxide in a water layer are reacted to move LiFSI to the organic layer, and then the organic layer is concentrated to obtain LiFSI. Is disclosed. However, the butyl acetate solvent used has a very high temperature at which the boiling point is concentrated to 125°C, and is not environmentally friendly as a solvent that causes respiratory and skin diseases. In addition, this patent goes through a process of injecting nitrogen to avoid contact with moisture during the concentration process, and on the other hand, it has the disadvantage of producing by using a thin-filmevaporator by concentrating with expensive equipment to remove moisture. have.

In general, the production process of the bisfluorosulfonyl imide alkali metal salt is a process for producing an ammonium bisfluorosulfonyl imide and a bisfluorosulfonyl alkali metal salt from the ammonium bisfluorosulfonyl imide. Proceeding to the process, the yield and purity of the bisfluorosulfonyl alkali metal salt produced are determined according to the type of solvent used in the manufacturing process/type of neutralizer/reaction time/reaction temperature.

Particularly, in the case of ammonium bisfluorosulfonyl imide, the acidity is high, and when it is used to synthesize the bisfluorosulfonyl alkali metal salt, a low pH causes side reactions, resulting in a decrease in yield and purity, and the intermediate ammonium bisfluor In some cases, the quality may be improved by neutralizing rosulfonyl imide with an ammonia water neutralizer, but even in this case, loss of yield occurs due to solubility in water even though purity is improved by neutralization and purification effects.

Therefore, there is a need for research on a new manufacturing method capable of simultaneously improving the yield and purity of bisfluorosulfonyl alkali metal salt, which is a material used as an electrolyte in a secondary battery.

U.S. Patent No. 7,253,317

The present invention provides a method for producing a bisfluorosulfonyl imide alkali metal salt and a bisfluorosulfonyl imide alkali metal salt prepared thereby.

In one embodiment of the present application, (1) synthesizing an ammonium bisfluorosulfonyl imide salt; And (2) synthesizing a bisfluorosulfonyl imide alkali metal salt from the ammonium bisfluorosulfonyl imide salt. Synthesizing the phenyl imide salt includes reacting bis(chlorosulfonyl)imide with ammonium fluoride (NH ₄ F) to form an ammonium bisfluorosulfonyl imide salt; Neutralizing the ammonium bisfluorosulfonyl imide salt with a neutralizing agent represented by Formula 1 below; And recrystallizing the neutralized ammonium bisfluorosulfonyl imide salt as a first organic solvent, wherein the first organic solvent comprises ethyl acetate (EA, ethyl acetate) and methylene chloride (MC, Metylenechloride). It provides a method for producing a bisfluorosulfonyl imide alkali metal salt.

[Formula 1]

R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In another exemplary embodiment, a bisfluorosulfonyl imide alkali metal salt prepared by a manufacturing method according to an exemplary embodiment of the present application is provided.

In the production of a bisfluorosulfonyl imide alkali metal salt having thermal stability, high conductivity, and low corrosive characteristics, which can be used as an electrolyte for a secondary battery, a yield including neutralizing with a neutralizing agent represented by Chemical Formula 1 It has a feature that can minimize the loss (loss).

In addition, in the preparation of the bisfluorosulfonyl imide alkali metal salt according to the present application, in the step of synthesizing the ammonium bisfluorosulfonyl imide salt, the neutralized product is recrystallized with a specific first organic solvent and a specific ratio. Including the step, it has the characteristics of improving the yield and forming a white powder in appearance. That is, the color of the resulting powder affects the color of the bisfluorosulfonyl imide alkali metal salt which is finally formed in the step of reacting with the alkali metal salt, and forms the white powder by the above manufacturing method to form the final bisfluor. It has characteristics that can improve the properties of the rosulfonyl imide alkali metal salt.

1 is a diagram showing a purity/yield/pH graph of ammonium bisfluorosulfonyl imide salt according to the type/concentration of the neutralizing agent in Examples and Comparative Examples of the present application.
FIG. 2 is a graph showing the purity/yield/pH graph of the ammonium bisfluorosulfonyl imide salt according to the type/ratio of the first organic solvent in Examples and Comparative Examples of the present application.
3 is a graph showing the purity/yield/pH graph of ammonium bisfluorosulfonyl imide salt according to the recrystallization temperature of Examples and Comparative Examples of the present application.

Hereinafter, the present application will be described in detail.

In the present specification, when a part “includes” a certain component, it means that the component may further include other components, rather than excluding other components, unless otherwise specified.

In one embodiment of the present application, (1) synthesizing an ammonium bisfluorosulfonyl imide salt; And (2) synthesizing a bisfluorosulfonyl imide alkali metal salt from the ammonium bisfluorosulfonyl imide salt. Synthesizing the phenyl imide salt includes reacting bis(chlorosulfonyl)imide with ammonium fluoride (NH ₄ F) to form an ammonium bisfluorosulfonyl imide salt; Neutralizing the ammonium bisfluorosulfonyl imide salt with a neutralizing agent represented by Formula 1 below; And recrystallizing the neutralized ammonium bisfluorosulfonyl imide salt as a first organic solvent, wherein the first organic solvent comprises ethyl acetate (EA, ethyl acetate) and methylene chloride (MC, Metylenechloride). It provides a method for producing a bisfluorosulfonyl imide alkali metal salt.

[Formula 1]

R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In the preparation of the bisfluorosulfonyl imide alkali metal salt of the present application, including the step of neutralizing with a neutralizing agent represented by the formula (1) has a characteristic that can minimize the loss (loss) of the yield.

In one embodiment of the present application, the bisfluorosulfonyl imide alkali metal salt is lithium bisfluorosulfonyl imide (LiFSI), potassium bisfluorosulfonyl imide (KFSI), sodium bisfluorosulfonyl Imide (NaFSI) and the like, and bisfluorosulfonyl imide containing an alkali metal salt is not limited thereto.

In one embodiment of the present application, the step of synthesizing (1) ammonium bisfluorosulfonyl imide salt may be represented by the following general formula (1).

[Formula 1]

In one embodiment of the present application, the step of synthesizing the ammonium bisfluorosulfonyl imide salt is by reacting bis(chlorosulfonyl)imide with ammonium fluoride (NH ₄ F) to form ammonium bisfluorosulfonyl already. Forming a rare salt;

Neutralizing the ammonium bisfluorosulfonyl imide salt with a neutralizing agent represented by Formula 1; And

And recrystallizing the neutralized ammonium bisfluorosulfonyl imide salt with a first organic solvent.

In particular, in the production of the bisfluorosulfonyl imide alkali metal salt according to the present application, the yield loss (loss) of the ammonium bisfluorosulfonyl imide salt produced by the step of neutralizing with a neutralizing agent represented by the formula (1) It has features that can be minimized.

In addition, in the preparation of the bisfluorosulfonyl imide alkali metal salt according to the present application, in the step of synthesizing the ammonium bisfluorosulfonyl imide salt, the neutralized ammonium bisfluorosulfonyl imide salt is identified as a specific first organic Including the step of recrystallization with a solvent has a characteristic that can form a white powder (white powder).

That is, the color of the resulting powder affects the color of the finally formed bisfluorosulfonyl imide alkali metal salt, and forms the white powder by the above manufacturing method to form the final bisfluorosulfonyl imide alkali metal salt. It has the characteristics to improve the appearance of the.

In an exemplary embodiment of the present application, the first organic solvent satisfies a 1:99 to 99:1 ratio of ethyl acetate (EA, ethyl acetate) and methylene chloride (MC). A method for producing phosphorus bisfluorosulfonyl imide alkali metal salt is provided.

When the ratio (Volume weight mole) of ethyl acetate (EA, Ethyl acetate) and methylene chloride (MC) of the first organic solvent satisfies the above range, the yield of ammonium bisfluorosulfonyl imide salt produced And the purity is increased, thereby improving the yield and purity of the bisfluorosulfonyl imide alkali metal salt prepared accordingly.

In one embodiment of the present application, the first organic solvent includes ethyl acetate (EA, Ethyl acetate) and methylene chloride (MC, Metylenechloride), and the content of the methylene chloride (MC) is ethyl acetate (EA, Ethyl It provides a method for producing a bisfluorosulfonyl imide alkali metal salt that is higher than the acetate) content.

In particular, in the ratio (Volume weight mole) of ethyl acetate (EA, Ethyl acetate) and methylene chloride (MC, Methylenechloride) of the first organic solvent during the recrystallization step, purity and yield are higher when MC ratio is higher than EA In particular, it has an effect of increasing, and if it is recrystallized using ethyl acetate (EA) alone, the product is dissolved and concentrated, so that crystals are not produced.

In addition, it has a characteristic that can form a white powder (white powder) by including a first organic solvent of a specific content.

In an exemplary embodiment of the present application, the neutralizing agent provides a method for producing an alkali metal salt of bisfluorosulfonyl imide that is based on 100 parts by weight of bis(chlorosulfonyl) imide, based on 100 parts by weight or more and 60 parts by weight or less. .

In another embodiment, the neutralizing agent is based on 100 parts by weight of the bis(chlorosulfonyl) imide, 0.01 parts by weight or more and 60 parts by weight or less, preferably 10 parts by weight or more and 60 parts by weight or less, more preferably It may be 10 parts by weight or more and 50 parts by weight or less.

As the content of the neutralizing agent satisfies the above range, the purity of the resulting ammonium bisfluorosulfonyl imide salt is improved, and thus the purity and yield of the bisfluorosulfonyl imide alkali metal salt formed are increased. .

In one embodiment of the present application, the reaction temperature of the step of recrystallizing the neutralized ammonium bisfluorosulfonyl imide salt with the first organic solvent is 0°C or more and 100°C or less. Provides a method of manufacturing a metal salt.

In another embodiment, the reaction temperature of the step of recrystallizing the neutralized ammonium bisfluorosulfonyl imide salt with the first organic solvent is 0°C or more and 100°C or less, preferably 10°C or more and 50°C or less, More preferably, it may be 10°C or more and 20°C or less.

As the reaction temperature of the step of recrystallizing the neutralized ammonium bisfluorosulfonyl imide salt with the first organic solvent satisfies the above range, the yield and purity of the resulting bisfluorosulfonyl imide alkali metal salt are improved. In particular, in the recrystallization step, as the reaction temperature is lowered, the amount of crystal precipitation increases and the yield is improved.

In one embodiment of the present application, R ₁ to R ₄ in Formula 1 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In another exemplary embodiment, R ₁ to R ₄ in Formula 1 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group.

In another exemplary embodiment, R ₁ to R ₄ in Formula 1 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted C1 to C40 alkyl group; A substituted or unsubstituted C6 to C40 aryl group; Or a substituted or unsubstituted C2 to C40 heteroaryl group.

In another exemplary embodiment, R ₁ to R ₄ in Formula 1 are the same or different from each other, and each independently a substituted or unsubstituted C1 to C40 alkyl group.

In another exemplary embodiment, R ₁ to R ₄ in Formula 1 are the same as or different from each other, and each independently a C1 to C40 linear alkyl group.

In another exemplary embodiment, R ₁ to R ₄ of Formula 1 may be a methyl group.

The neutralizing agent represented by Chemical Formula 1 may be TMAH (Tetrametyl ammoniym hydroxide).

In an exemplary embodiment of the present application, the neutralizing agent represented by Chemical Formula 1 may be dissolved in water to be used, and the neutralizing agent represented by Chemical Formula 1 may be 0.01 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of water, more preferably It may be 0.1 parts by weight or more and 25 parts by weight or less.

In the present application, the term "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited if the position at which the hydrogen atom is substituted, that is, the position at which the substituent is substitutable, When two or more are substituted, two or more substituents may be the same or different from each other.

In the present specification, "substituted or unsubstituted" means C1 to C60 straight or branched chain alkyl; C2 to C60 straight or branched chain alkenyl; C2 to C60 straight or branched chain alkynyl; C3 to C60 monocyclic or polycyclic cycloalkyl; C2 to C60 monocyclic or polycyclic heterocycloalkyl; C6 to C60 monocyclic or polycyclic aryl; C2 to C60 monocyclic or polycyclic heteroaryl; -SiRR'R"; -P(=O)RR'; C1 to C20 alkylamine; C6 to C60 monocyclic or polycyclic arylamine; and C2 to C60 monocyclic or polycyclic heteroarylamine Means substituted or unsubstituted with one or more substituents, or substituted or unsubstituted with two or more substituents selected from the substituents exemplified above,

R, R'and R" are the same as or different from each other, and each independently hydrogen; deuterium; -CN; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; or substituted Or it may be an unsubstituted heteroaryl group.

In the present specification, the alkyl group includes a straight chain or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. Carbon number of the alkyl group may be 1 to 60, specifically 1 to 40, more specifically, 1 to 20. Specific examples are methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , Isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, and the like, but are not limited thereto.

In the present specification, the aryl group includes 6 to 60 carbon atoms or a monocyclic ring, and may be further substituted by other substituents. Here, polycyclic means a group in which an aryl group is directly connected or condensed with another ring group. Here, the other cyclic group may be an aryl group, but may be another kind of cyclic group, for example, a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group. The aryl group includes a spiro group. The number of carbon atoms of the aryl group may be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of the aryl group include a phenyl group, biphenyl group, triphenyl group, naphthyl group, anthryl group, chrysenyl group, phenanthrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, phenenyl group, pyre Neil group, tetrasenyl group, pentasenyl group, fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, 2,3-dihydro-1H-indenyl group, and condensed ring groups thereof And the like, but are not limited thereto.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may combine with each other to form a ring.

,

,

,

,

,

등이 될 수 있으나, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

,

And the like, but is not limited thereto.

In the present specification, the heteroaryl group includes S, O, Se, N or Si as a hetero atom, monocyclic or polycyclic having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic group refers to a group in which a heteroaryl group is directly connected or condensed with another ring group. Here, the other ring group may be a heteroaryl group, but may be another type of ring group, for example, a cycloalkyl group, a heterocycloalkyl group, an aryl group, or the like. The heteroaryl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 3 to 25 carbon atoms. Specific examples of the heteroaryl group include pyridyl group, pyrrolyl group, pyrimidyl group, pyridazinyl group, furanyl group, thiophene group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, thiazolyl Group, isothiazolyl group, triazolyl group, furazanyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group , Thiazinyl group, deoxynyl group, triazinyl group, tetrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolinyl group, naphthyridyl group, acridinyl group, phenanthridy Niyl group, imidazopyridinyl group, diazanaphthalenyl group, triazinden group, indolyl group, indolizinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophene group, benzofuran group , Dibenzothiophene group, dibenzofuran group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, phenazinyl group, dibenzosilol group, spirobi(dibenzosilol), dihydrophenazinyl group, Phenoxazinyl group, phenanthridyl group, imidazopyridinyl group, thienyl group, indolo[2,3-a]carbazolyl group, indolo[2,3-b]carbazolyl group, indolinyl group, 10, 11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenanthrazinyl group, phenothiathiazinyl group, phthalazinyl group, naphthilidinyl group, phenanthrolinyl group, Benzo[c][1,2,5]thiadiazolyl group, 5,10-dihydrodibenzo[b,e][1,4]azasilinyl, pyrazolo[1,5-c]quinazolinyl group , Pyrido[1,2-b]indazolyl group, pyrido[1,2-a]imidazo[1,2-e]indolinyl group, 5,11-dihydroindeno[1,2-b ]Carbazolyl group, and the like, but is not limited thereto.

In one embodiment of the present application, the step of synthesizing the bisfluorosulfonyl imide alkali metal salt from the (2) ammonium bisfluorosulfonyl imide salt may be represented by the following General Formula 2.

[Formula 2]

In one embodiment of the present application, the step of synthesizing the bisfluorosulfonyl imide alkali metal salt from the ammonium bisfluorosulfonyl imide salt includes a metal salt containing the ammonium bisfluorosulfonyl imide salt and M ⁺ . Reacting; And adding a second solvent to the product, wherein the M is an onium cation compound, transition metal, group 1 element, group 2 element, group 13 It provides a method for producing a bisfluorosulfonyl imide salt selected from the group consisting of elements and group 15 elements.

In one embodiment of the present application, M may be an ion containing H.

In another exemplary embodiment, M may be an onium cation compound, specifically H; NH ₄ ; It may be HN(CH ₃ ) ₃ , HN(CH ₂ CH ₃ ) ₃ or HN(CH ₂ CH ₂ CH ₃ ) ₃ , but is not limited to these if it is an onium cation compound combined with hydrogen.

In another exemplary embodiment, the M may be a group 1 alkali metal such as Li, Na, K, or the like.

In another exemplary embodiment, M may be K or Li.

In another exemplary embodiment, M may be Li.

In an exemplary embodiment of the present application, the metal salt containing M ⁺ may be lithium hydroxide (LiOH), a hydrate thereof (LiOHH ₂ O), Li ₂ CO ₃ , LiHCO ₃ , LiF, or LiCl.

In one embodiment of the present application, the metal salt containing M ⁺ may be lithium hydroxide or potassium hydroxide.

The onium cation compound refers to a compound formed by coordination of protons or other cationic reagents or the like in a compound containing an element having an isolated electron pair.

In one embodiment of the present application, the metal salt containing M ⁺ may be 10 parts by weight or more and 50 parts by weight or less based on 100 parts by weight of the ammonium bisfluorosulfonyl imide salt.

In another exemplary embodiment, the metal salt containing M ⁺ may be 15 parts by weight or more and 45 parts by weight or less based on 100 parts by weight of the ammonium bisfluorosulfonyl imide salt, preferably 20 parts by weight or more and 40 parts by weight It may be:

When the metal salt containing the M ⁺ is included in the weight range, it is convenient to remove the extra metal salt to be progressed later, and after the reaction is completed, no residue remains, so it can have an excellent effect in crystallization.

In one embodiment of the present application, the second solvent is an organic solvent; Or it provides a method for producing a bisfluorosulfonyl imide alkali metal salt containing water (H ₂ O).

In one embodiment of the present application, the organic solvent is acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, Ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1 ,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloroethene, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol , Propanol, butanol, t-butanol, 2-ethoxy propanol, 2-methoxy propanol, 3-methoxy butanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3- It may be one or more selected from the group consisting of methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether. , It is not limited to this.

In one embodiment of the present application, the organic solvent is specifically, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methylethylketone, cyclohexanone, cyclopentanone, 4-hydroxy- Ketones such as 4-methyl-2-pentanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Glycol ethers such as dipropylene glycol diethyl ether and triethylene glycol monoethyl ether (cellosolve); Ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethanol, propanol, ethylene glycol, propylene glycol, carbitol, dimethyl Acetamide (DMAc), N,N-diethylacetamide, dimethylformamide (DMF), diethylformamide (DEF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) , N-ethylpyrrolidone (NEP), 1,3-dimethyl-2-imidazolidinone, N,N-dimethylmethoxyacetamide, dimethylsulfoxide, pyridine, dimethylsulfone, hexamethylphosphoamide, tetra Methylurea, N-methylcaractam, tetrahydrofuran, m-dioxane, P-dioxane, 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, 1,2-bis(2- Any one selected from the group consisting of methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)]ether and mixtures thereof can be used.

In one embodiment of the present application, the second solvent may be water (H ₂ O).

In one embodiment of the present application, the second solvent may be used in a cleaning process for purifying impurities during the process of preparing an alkali metal salt of bis fluorosulfonyl imide.

In one embodiment of the present application, after the step of adding a second solvent to the product, filtering; And it provides a method of producing a bisfluorosulfonyl imide alkali metal salt further comprising the step of concentrating the filtrate of the filtering step to form a concentrate.

In one embodiment of the present application, the concentration temperature of the step of forming a concentrate by concentrating the filtrate is 30°C or more and 90°C or less, preferably 30°C or more and 80°C or less, more preferably 40°C or more and 70°C or less Can be.

When having the above range, it is possible to prevent the suppression of by-products, it has the effect of preventing the color change that may occur in the step of concentrating the filtrate.

In one embodiment of the present application, after the step of forming the concentrate, the method of producing a bisfluorosulfonyl imide alkali metal salt further comprising crystallizing or precipitating the concentrate to obtain a crystal or precipitate to provide.

In addition, after the step of obtaining the crystal or precipitate, there is provided a method for producing a bisfluorosulfonyl imide alkali metal salt further comprising the step of drying the crystal or precipitate.

In one embodiment of the present application, the step of drying the crystal or precipitate is a step of drying the crystal or precipitate under vacuum, and the drying temperature may be 20°C or more and 80°C or less, preferably 40°C or more and 60°C or less. .

In one embodiment of the present application, the reaction time of the step of reacting the ammonium bisfluorosulfonyl imide salt with the metal salt containing M ⁺ is made within a range of 20 minutes to 6 hours, and ranges from 60 minutes to 1 hour It is particularly preferred to be made within.

When the reaction time proceeds within the above range, the yield and purity of the product are particularly excellent.

In one embodiment of the present application, after the step of reacting the metal salt containing the ammonium bisfluorosulfonyl imide salt and M ⁺ , as a step of removing unreacted reactants or foreign substances that may be present in the mass production process After filtration, a washing step or a purification step may be further included.

In one embodiment of the present application, the yield of the bisfluorosulfonyl imide alkali metal salt is 70% or more.

In another exemplary embodiment, the yield of the bisfluorosulfonyl imide alkali metal salt may be 70% or more and 99% or less, preferably 70% or more and 95% or less.

In one embodiment of the present application, the purity of the bisfluorosulfonyl imide alkali metal salt is 95% or more.

In another exemplary embodiment, the purity of the bisfluorosulfonyl imide alkali metal salt may be 95% or more and 99% or less.

In an exemplary embodiment of the present application, a bisfluorosulfonyl imide alkali metal salt prepared by a manufacturing method according to an exemplary embodiment of the present application is provided.

Hereinafter, the present invention will be described in more detail through production examples and experimental examples. However, the present invention is not limited to the manufacturing examples and experimental examples disclosed below, but can be implemented in various different forms, and the following manufacturing examples and experimental examples make the disclosure of the present invention complete, and provide common knowledge. It is provided to fully inform the possessor of the scope of the invention.

< Manufacturing example >

<ammonium Bisfluorosulfonyl  Synthesis of imide>

< Example  1 to 16, Comparative example  1 to 3>

[ Example  One]

To a 500 ml three-necked flask equipped with a stirrer, condenser, and thermometer, 175 g of acetonitrile and 30.3 g (0.81 mol) of ammonium fluoride were quantitatively charged and stirred under nitrogen atmosphere. Subsequently, 50 g (0.24 mol) of bis(chlorosulfonyl)imide was slowly added dropwise at room temperature for 30 minutes or more, and the internal temperature was raised to 80° C. to react for 5 hours. After cooling to room temperature, the reactants were filtered to filter by-products and the filtrate was concentrated under reduced pressure to obtain Crude ammonium bisfluorosulfonylimide. Here, 60 g of butyl acetate was added to dissolve the reactant in the Crude state, and 24 g of 0.1% aqueous solution of TMAH (Tetramethyl ammonium hydroxide) was added to neutralize it by stirring for 30 minutes at room temperature. The organic layer was separated, concentrated under reduced pressure, and recrystallized by feeding 60 g of dichloromethane. The precipitated crystals were filtered through a filter paper to obtain a white powder.

Elemental analysis confirmed that it was ammonium bis fluorosulfonyl imide and 43.4 g was obtained. (Purity 98.7%, yield 93.7%)

[ Example  3]

To a 500 ml three-necked flask equipped with a stirrer, condenser and thermometer, 245 g of acetonitrile and 42.4 g (1.15 mol) of ammonium fluoride were quantitatively charged and stirred under nitrogen atmosphere. Subsequently, 70 g (0.33 mol) of bis(chlorosulfonyl)imide was slowly added dropwise at room temperature for 30 minutes or more, and the internal temperature was raised to 80°C to react for 5 hours. After cooling to room temperature, the reaction product was filtered to filter by-products, and the filtrate was concentrated under reduced pressure to obtain Crude ammonium bisfluorosulfonylimide. To this, 110 g of butyl acetate was added to dissolve the reactant in the Crude state, and 34.1 g of a 1.0% aqueous solution of TMAH was added to neutralize the mixture by sufficiently stirring at room temperature for 30 minutes. The organic layer was separated, concentrated under reduced pressure, and recrystallized by feeding 70 g of dichloromethane. The precipitated crystals were filtered through a filter paper to obtain a white powder.

Elemental analysis confirmed that it was ammonium bis fluorosulfonyl imide and 60.7 g was obtained. (Purity 98.8%, yield 93.7%)

[ Example  5]

In a 500 ml three-necked flask equipped with a stirrer, condenser, and thermometer, 175 g of acetonitrile and 30.3 g (0.82 mol) of ammonium fluoride were quantitatively charged and stirred under nitrogen atmosphere. Subsequently, 50 g (0.23 mol) of bis(chlorosulfonyl)imide was slowly added dropwise at room temperature for 30 minutes or more, and the internal temperature was raised to 80° C. to react for 5 hours. After cooling to room temperature, the reaction product was filtered to filter by-products, and the filtrate was concentrated under reduced pressure to obtain Crude ammonium bisfluorosulfonylimide. Here, 120 g of butyl acetate was added to dissolve the reactants in the Crude state, and 20.4 g of a 10.0% aqueous solution of TMAH was added to neutralize the mixture by sufficiently stirring at room temperature for 30 minutes. The organic layer was separated, concentrated under reduced pressure, and recrystallized by feeding 100 g of dichloromethane. The precipitated crystals were filtered through a filter paper to obtain a white powder.

Elemental analysis confirmed that ammonium bis fluorosulfonyl imide and 39.9 g were obtained. (Purity 98.4%, Yield 86.2%)

[ Example  2, 4, 6, Comparative example  1 and 2]

In Example 1, ammonium bisfluorosulfonyl imide was synthesized in the same manner as in Example 1, except that the neutralizing agent of Table 1 below was used instead of using the TMAH aqueous solution.

NH ₄ FSI Neutralizer concentration water yield(%) pH Comparative Example 1 2% ammonia water 98.9 55.0 6.1 Comparative Example 2 H ₂ O 93.6 81.0 5.4 Example 1 TMAH 0.1% 98.7 93.7 5.8 Example 2 TMAH 0.5% 98.6 92.7 6.0 Example 3 TMAH 1.0% 98.8 94.6 6.4 Example 4 TMAH 5.0% 98.9 83.3 6.3 Example 5 TMAH 10.0% 98.4 86.2 6.4 Example 6 TMAH 25.0% 99.5 63.0 6.5

As can be seen from Table 1, when TMAH was used as a neutralizing agent, it was confirmed that both the purity and yield of the resulting ammonium bisfluorosulfonyl imide (NH ₄ FSI) were excellent, and Comparative Example 1 contained 2% ammonia water. As used, the purity is similar, but the yield is particularly low, and in the case of Comparative Example 2, it was confirmed that the water was used alone as a neutralizing agent, and the purity was lowered. Specifically, FIG. 1 is a diagram showing a purity/yield/pH graph of an ammonium bisfluorosulfonyl imide salt according to the type of neutralizing agent in Examples and Comparative Examples of the present application.

As can be seen in Figure 1, when the specific gravity of water to the neutralizing agent is high, the purity by purification is improved due to solubility in water, but it can be confirmed that the specific gravity of the yield decrease. When the ammonium bis fluorosulfonyl imide salt was purified by using water alone in [Comparative Example 2] for the neutralizing agent, it was confirmed that yields of 10 to 15% Loss were generated compared to the case of using the neutralizing agent.

[ Example  7]

As in Example 3, ammonium bis fluorosulfonyl imide was prepared based on 30 g of bis chlorosulfonyl imide and neutralized with 1% aqueous solution of TMAH. After separating the organic layer and concentrating under reduced pressure, 70 g of a mixed solvent of EA:MC=5:95 was introduced to induce recrystallization. At this time, the recrystallization temperature induces recrystallization at room temperature (20°C) and, when crystals are formed, through filter paper. Filtered. Thereafter, a white powder filtered on a filter paper was obtained.

Elemental analysis confirmed that it was ammonium bis fluorosulfonyl imide and 26.2 g was obtained. (Purity 99.0%, yield 94.4%)

[ Example  8 to 16 and Comparative example  3]

In Example 7, in the same manner as in Example 7, except that the ratio of EA:MC uses a recrystallization solvent that satisfies the range of Table 2 below, and the recrystallization temperature satisfies the temperature range of Table 2 below. Then, ammonium bisfluorosulfonyl imide was synthesized.

NH ₄ FSI Recrystallized solvent
EA:MC Temperature water yield(%) pH Comparative Example 3 100:0 Room temperature Crystal non-production Example 7 5:95 99.0 94.4 6.4 Example 8 10:90 98.2 93.6 6.2 Example 9 20:80 98.0 90.0 6.3 Example 10 30:70 96.7 85.8 6.2 Example 11 50:50 88.6 76.5 6.1 Example 12 80:20 87.5 74.5 5.7 Example 13 90:10 86.1 70.4 5.1 Example 14 5:95 20℃ 98.8 92.0 6.0 Example 15 5:95 50℃ 95.7 87.5 5.4 Example 16 5:95 100℃ 67.0 68.7 4.6

As can be seen from Table 2, when a specific range was satisfied with the recrystallization solvent, it was confirmed that the purity and yield of the resulting ammonium bisfluorosulfonyl imide (NH ₄ FSI) increased. In particular, in the ratio (Volume weight mole) of ethyl acetate (EA, Ethyl acetate) and methylene chloride (MC, Methylenechloride) of the first organic solvent during the recrystallization step, purity and yield are higher when MC ratio is higher than EA In particular, it has an effect of increasing, and it can be confirmed that crystallization is not generated even if the product is dissolved and concentrated by recrystallization using ethyl acetate (EA) alone.

In addition, as the reaction temperature of the step of recrystallizing the neutralized ammonium bisfluorosulfonyl imide salt with the first organic solvent satisfies a specific range, the yield and purity of the resulting bisfluorosulfonyl imide alkali metal salt It was confirmed that the improvement was made. In particular, it was confirmed that the crystallization amount increased as the reaction temperature was lower in the recrystallization step, thereby improving the yield.

2 is a diagram showing a purity/yield/pH graph of ammonium bisfluorosulfonyl imide salt according to the type/ratio of the first organic solvent in Examples and Comparative Examples of the present application, and FIG. 3 is an example of the present application and This is a graph showing the purity/yield/pH graph of the ammonium bisfluorosulfonyl imide salt according to the recrystallization temperature of the comparative example.

2, the recrystallization solvent was found to improve the yield and purity when EA and MC were mixed in an appropriate ratio. In particular, as shown in [Example 7], it was confirmed that the smaller the EA ratio, the higher the yield and purity.

In addition, as can be seen in FIG. 3, in the recrystallization temperature, after the recrystallization solvent was introduced into the crude product, the solubility in the solvent increased as the temperature reached a high temperature, and the yield was lowered, especially at room temperature (17 to 25°C) The method was the best.

<ammonium Bis From fluorosulfonylimide Bisfluorosulfonyl  Synthesis of imide alkali metal salt>

[Example 17]

To a 300 ml three-necked flask equipped with a stirrer, condenser, and thermometer, 20 g (0.1 mol) of ammonium bis fluorosulfonyl imide prepared in the same manner as in Example 15 was added under nitrogen atmosphere, and 40 g of ethyl acetate was added and stirred. Subsequently, 6.4 g (0.15 mol) of lithium hydroxide monohydrate was added and reacted at room temperature for 4 hours. After the reaction was completed, tertiary distilled water was added to the reaction mixture, and 0.1 times (4 g) of ethyl acetate was added thereto, followed by stirring at room temperature for 30 minutes. Thereafter, after separating the organic layer, the obtained organic layer was concentrated, dichloromethane was added three times, and gradually cooled and filtered to form a filter paper to obtain 16.0 g of lithium bis fluorosulfonyl imide as a white crystal. (Purity 99.6 %, Yield 85.0%)

[Example 18]

To a 300 ml three-necked flask equipped with a stirrer, condenser, and thermometer, 20 g (0.1 mol) of ammonium bis fluorosulfonyl imide prepared in the same manner as in Example 16 was added under nitrogen atmosphere, and 40 g of ethyl acetate was added and stirred. Subsequently, 6.4 g (0.15 mol) of lithium hydroxide monohydrate was added and reacted at room temperature for 4 hours. After the reaction was completed, tertiary distilled water was added to the reaction mixture, and 0.1 times (4 g) of ethyl acetate was added thereto, followed by stirring at room temperature for 30 minutes. Thereafter, after separating the organic layer, the obtained organic layer was concentrated, dichloromethane was added three times, and gradually cooled and filtered to form a filter paper to obtain 14.1 g of lithium bis fluorosulfonyl imide as a white crystal. (Purity 97.6 %, yield 75.0%)

LiFSI RM LiOH
(1.5eq, g) EA
(3T, ml) IC anion (%) yield NH ₄ FSI Cl SO4 water Example 17 Example 15 6.4 60 0.13 0.16 99.6 85.0 Example 18 Example 16 4.1 40 0.02 1.82 97.9 75.0

As can be seen from Table 3, after the production of ammonium bisfluorosulfonyl imide as in the present invention, the synthesis of bisfluorosulfonyl imide alkali metal salt, the final formed bisfluorosulfonyl imide alkali metal salt The purity of 97 or more, the yield was also 75% or more, it was confirmed that the yield and purity was improved. For the purity analysis of the final product for each example, Ion chromatography manufactured by Thermo Fisher was used, and the sample was analyzed by diluting 10,000 times.

Claims (15)

(1) synthesizing ammonium bisfluorosulfonyl imide salt; And
(2) synthesizing a bisfluorosulfonyl imide alkali metal salt from the ammonium bisfluorosulfonyl imide salt;
As a method for producing bisfluorosulfonyl imide alkali metal salt containing,
The step of synthesizing the ammonium bisfluorosulfonyl imide salt comprises reacting bis(chlorosulfonyl)imide with ammonium fluoride (NH ₄ F) to form an ammonium bisfluorosulfonyl imide salt;
Neutralizing the ammonium bisfluorosulfonyl imide salt with a neutralizing agent represented by Formula 1 below; And
Recrystallizing the neutralized ammonium bisfluorosulfonyl imide salt with a first organic solvent,
The first organic solvent is ethyl acetate (EA, Ethyl acetate) and methylene chloride (MC, Metylenechloride) containing bisfluorosulfonyl imide alkali metal salt production method:
[Formula 1]

R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group. The method according to claim 1,
The first organic solvent is a bisfluorosulfonyl imide alkali in which the ratio (Volume weight mole) of ethyl acetate (EA, Ethyl acetate) and methylene chloride (MC) satisfies 1:99 to 99:1. Method of manufacturing a metal salt. The method according to claim 1, The first organic solvent includes ethyl acetate (EA, Ethyl acetate) and methylene chloride (MC, Metylenechloride), the content of the methylene chloride (MC) is more than ethyl acetate (EA, Ethyl acetate) content Method for producing bisfluorosulfonyl imide alkali metal salt which is high. The method according to claim 1,
Synthesizing the bisfluorosulfonyl imide alkali metal salt from the ammonium bisfluorosulfonyl imide salt comprises reacting the ammonium bisfluorosulfonyl imide salt with a metal salt containing M ⁺ ; And
Adding a second solvent to the product;
As a method for producing a bisfluorosulfonyl imide alkali metal salt containing,
The M is an onium cation compound, a transition metal, a group 1 element, a group 2 element, a group 13 element, and a group 15 element selected from the group consisting of bisfluorosulfonyl imide alkali metal salt. The method according to claim 4,
The second solvent is an organic solvent; Or a method of producing a bisfluorosulfonyl imide alkali metal salt containing water (H ₂ O). The method according to claim 1,
The R ₁ to R ₄ are the same or different from each other, and each independently, a substituted or unsubstituted C1 to C40 alkyl group is a method for producing an alkali metal salt of bisfluorosulfonyl imide. The method according to claim 1,
The neutralizing agent is a method for producing an alkali metal salt of bisfluorosulfonyl imide, which is based on 100 parts by weight of the bis(chlorosulfonyl) imide, based on 100 parts by weight or more and 50 parts by weight or less. The method according to claim 1,
The reaction temperature of the step of recrystallization of the neutralized ammonium bisfluorosulfonyl imide salt with a first organic solvent is a method of producing an alkali metal salt of bisfluorosulfonyl imide that is 0°C or more and 100°C or less. The method according to claim 4,
The metal salt containing M ⁺ is lithium bis or potassium hydroxide, a method for preparing an alkali metal salt of bisfluorosulfonyl imide. The method according to claim 4, After the step of adding a second solvent to the product, filtering; And
The method of producing a bisfluorosulfonyl imide alkali metal salt further comprising the step of concentrating the filtrate of the filtering step to form a concentrate. The method according to claim 10, After the step of forming the concentrate, the method of producing a bisfluorosulfonyl imide alkali metal salt further comprising the step of crystallizing or precipitating the concentrate to obtain a crystal or precipitate. The method of claim 11, further comprising drying the crystal or precipitate after the step of obtaining the crystal or precipitate. The method according to claim 1,
The method for producing an alkali metal salt of bisfluorosulfonyl imide, wherein the yield of the bisfluorosulfonyl imide alkali metal salt is 70% or more. The method according to claim 1,
The method of producing a bisfluorosulfonyl imide alkali metal salt having a purity of 95% or more of the bisfluorosulfonyl imide alkali metal salt. Bisfluorosulfonyl imide alkali metal salt prepared by the production method according to any one of claims 1 to 14.

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