WO2020235336A1 - ビス（フルオロスルホニル）イミド化合物及びその製造方法 - Google Patents

ビス（フルオロスルホニル）イミド化合物及びその製造方法 Download PDF

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WO2020235336A1
WO2020235336A1 PCT/JP2020/018424 JP2020018424W WO2020235336A1 WO 2020235336 A1 WO2020235336 A1 WO 2020235336A1 JP 2020018424 W JP2020018424 W JP 2020018424W WO 2020235336 A1 WO2020235336 A1 WO 2020235336A1
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solvent
metal
less
mass ppm
carbonate
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French (fr)
Japanese (ja)
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知恵 小野田
貴之 小畠
裕大 勝山
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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Priority to US17/613,460 priority Critical patent/US12319571B2/en
Priority to EP20810728.4A priority patent/EP3967656B1/en
Priority to JP2021520691A priority patent/JP7266092B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/02—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
    • C07C255/03—Mononitriles
    • 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
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/02—Magnesium compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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

Definitions

  • the present invention relates to a novel bis (fluorosulfonyl) imide compound and the like.
  • Lithium bis (fluorosulfonyl) imide is used as an electrolyte for a lithium ion secondary battery (Patent Document 1).
  • An object of the present invention is to provide a novel bis (fluorosulfonyl) imide compound and the like.
  • an alkali metal salt such as lithium bis (fluorosulfonyl) imide is conventionally known.
  • the present inventor attempted to synthesize a non-alkali metal salt of bis (fluorosulfonyl) imide.
  • the counter ions of bis (fluorosulfonyl) imide are completely different between alkali metal ions and non-alkali metal ions, and in the first place, it may not even be possible to stably obtain non-alkali metal salts. Ion.
  • the present inventor has undergone a specific method (step) to carry out a non-alkali metal salt of bis (fluorosulfonyl) imide containing a solvent (solvent molecule) as a ligand.
  • the present invention was completed after further studies, finding that a relatively stable solution can be obtained.
  • a compound represented by the following formula (1) M a X b Y c (1)
  • M is a metal (ion, cation) other than alkali metal
  • X is -N (SO 2 F) 2 (bis (fluorosulfonyl) imide (ion, anion))
  • Y is a coordinating solvent. (Molecular), where a, b and c are positive numbers.)
  • the metal M contains at least one metal (polyvalent metal) selected from the metals of Groups 2, 10 to 13 of the periodic table.
  • Metal M is magnesium
  • Coordinating solvent Y is acetonitrile, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, Includes at least one selected from 1,4-dioxane, 1,3-dioxolane, methyl acetate, ethyl acetate, ethyl propionate, propyl propionate, ⁇ -butyrolactone, valerolactone, and sulfolane.
  • a reaction step of reacting a salt (compound) of metal M, which does not generate water during the reaction reaction with bis (fluorosulfonyl) imide
  • reaction with bis (fluorosulfonyl) imide bis (fluorosulfonyl) imide
  • the salt of metal M is at least one selected from halides, sulfates, nitrates, phosphates, chlorates, chromates, formates, acetates and trifluoromethanesulfonates, [9].
  • the manufacturing method described in. [11] The production method according to [9] or [10], wherein 0.3 to 1.5 equivalents of the salt of the metal M is used with respect to the bis (fluorosulfonyl) imide.
  • the coordinating solvent Y1 is used to obtain a compound in which the coordinating solvent Y is Y1 in the formula (1), and then at least a part of the coordinating solvent Y1 is added to the coordinating solvent Y2.
  • the coordinating solvent Y1 is a nitrile solvent, and the coordinating solvent Y2 is at least one selected from a carbonate solvent, an ether solvent, an ester solvent, and a sulfone solvent. Manufacturing method.
  • a novel bis (fluorosulfonyl) imide compound or the like can be provided.
  • Such a compound of the present invention is a non-alkali metal salt (for example, magnesium salt) of bis (fluorosulfonyl) imide. Therefore, it is useful as a compound (for example, an electrolyte, an additive, etc.) applicable to non-alkali metal ion applications, for example, a non-alkali metal ion battery (for example, a magnesium ion battery).
  • a non-alkali metal ion battery for example, a magnesium ion battery.
  • such compounds for example, magnesium salts
  • characteristics such as a wide potential window, high stability (thermal stability, etc.), high conductivity, and the ability to insert and remove non-alkali metals. It has and can be suitably applied as a compound for non-alkali metal ion batteries and the like.
  • the compound of the present invention contains a solvent (coordinating solvent) as a ligand, and by using such a solvent as a solvent used for an electrolytic solution or the like, an electrolyte for an electrolytic solution or the like can be used. It can be used as it is as an additive or the like.
  • the above-mentioned bis (fluorosulfonyl) imide compound can be efficiently produced.
  • the produced compound for example, a compound having acetonitrile as a ligand
  • the bis for example, a compound containing a solvent suitable for the purpose as a ligand
  • a non-alkali metal salt of fluorosulfonyl) imide can be efficiently obtained.
  • FIG. 1 is a chart obtained by 19 F-NMR measurement of the white powder obtained in Example 1.
  • FIG. 2 is a chart obtained by 1 H-NMR measurement of the white powder obtained in Example 1.
  • FIG. 3 is a chart obtained by Raman measurement of white crystals and acetonitrile obtained in Example 2.
  • FIG. 4 is a chart obtained by Raman measurement of white crystals and acetonitrile obtained in Example 2.
  • FIG. 5 is a chart obtained by Raman measurement of the white viscous solid product obtained in Example 8 and triglime.
  • the compound of the present invention is represented by the following formula (1).
  • the compound of the present invention (sometimes referred to as compound (1), etc.) is a non-alkali metal salt of bis (fluorosulfonyl) imide containing a solvent (as a ligand) [bis (fluorosulfonyl) imide ( A salt of an anion) and a non-alkali metal (cation)].
  • M is a metal other than an alkali metal
  • X is -N (SO 2 F) 2
  • Y is a coordinating solvent
  • a, b and c are positive numbers.
  • M is a metal other than alkali metal (non-alkali metal).
  • metal M include typical metals [for example, alkaline earth metals or Group 2 metals of the periodic table (eg, beryllium, magnesium, calcium, strontium, barium, etc.), and metals of Group 12 of the periodic table (for example, barium).
  • Periodic Table Group 13 metals eg, aluminum, gallium, indium, tallium, etc.
  • Periodic Table Group 14 metals eg, silicon, germanium, tin, lead, etc.
  • Periodic Table 15 Group metals eg, antimon, bismuth, etc.
  • transition metals eg, periodic table Group 3 metals (eg, scandium, yttrium, lanthanoid, etc.), periodic table Group 4 metals (eg, titanium, zirconium, hafnium, etc.)) , Periodic Table Group 5 metals (eg vanadium, niobium, tantalum, etc.), Periodic Table Group 6 metals (eg chromium, molybdenum, tungsten, etc.), Periodic Table Group 7 metals (eg manganese, etc.), Periodic Table Group 8 metal (eg iron, ruthenium, etc.), Group 9 metal of the periodic table (eg cobalt,
  • the metal M may be contained in the compound represented by the formula (1) alone or in combination of two or more.
  • the metal M may contain an alkali metal as long as it contains a non-alkali metal, but usually does not contain an alkali metal in many cases.
  • Group 2 metals, Group 10 metals, Group 11 metals, Group 12 metals, Group 13 metals, Group 14 metals, etc. of the Periodic Table are typical, and Group 2 metals and Group 2 metals of the Periodic Table.
  • Group 10 metals, Group 11 metals, Group 13 metals and Group 14 metals are preferable, Group 2 metals (calcium, magnesium, etc.) and Group 13 metals (aluminum, etc.) in the periodic table are more preferable, and magnesium is particularly preferable. ..
  • the metal M is at least selected from such metals (for example, Group 2 metal, Group 10 metal, Group 11 metal, Group 12 metal, Group 3 metal, Group 14 metal in the periodic table). 1 type, Group 2 metal of the periodic table) may be included.
  • the metal (non-alkali metal) M may be a multivalent metal (ion) in the formula (1).
  • the valence of such a metal M is not particularly limited and can be selected according to the type of the metal M. For example, divalent (2+) to octavalent (8+), preferably divalent to hexavalent, and more preferably. It may be divalent to tetravalent, or divalent or trivalent (particularly divalent).
  • Specific metal include, for example, divalent metal cations (for example, Mg 2+ , Ca 2+ , Zn 2+ , Pd 2+ , Sn 2+ , Hg 2+ , Rh 2+ , Cu 2+ , Be 2+ , Sr 2+ , Ba. 2+ etc.), trivalent metal cations (eg, Al 3+ , Ga 3+, etc.).
  • divalent metal cations for example, Mg 2+ , Ca 2+ , Zn 2+ , Pd 2+ , Sn 2+ , Hg 2+ , Rh 2+ , Cu 2+ , Be 2+ , Sr 2+ , Ba. 2+ etc.
  • trivalent metal cations eg, Al 3+ , Ga 3+, etc.
  • alkaline earth metal cations and Al 3+ are preferable, and Mg 2+, Ca 2+ , and Al 3+ are more preferable because they have a small ionic radius and are easily used in batteries and the like
  • X is ⁇ N (SO 2 F) 2 (sometimes referred to as FSI).
  • This X can be called a bis (fluorosulfonyl) imide (anion) (the following formula), so to speak.
  • Y is a solvent (molecule).
  • the solvent (coordinating solvent) is not particularly limited as long as it exhibits coordinating property [or can be a ligand (ligand of metal M)], but for example, a nitrogen-containing solvent, etc. Examples thereof include a hetero atom (hetero element) -containing solvent (hetero atom-containing non-aqueous solvent) such as an oxygen-containing solvent and a sulfur-containing solvent, and water.
  • nitrogen-containing solvent examples include a nitrile solvent, an amide solvent, a nitro solvent (nitromethane and the like), an amine solvent [for example, a chain amine (for example, an aliphatic amine such as methyl amine and dimethyl amine), and a cyclic amine (for example). , Piperidine, etc.)], aromatic solvents [for example, pyridine-based solvents (for example, pyridine, etc.)] and the like.
  • nitrile-based solvent examples include aliphatic nitriles [for example, cyano such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile, methoxypropionitrile, glutaronitrile, adiponitrile, and 2-methylglutaronitrile.
  • Alcans eg, mono or dicyanoalkane
  • aromatic nitriles eg, benzonitrile, tolnitrile
  • amide-based solvent examples include chain amides [for example, chain aliphatic amides (for example, alkanoic acid amides such as dimethylformamide and dimethylacetamide)], cyclic amides (or lactam, for example, N-methylpyrrolidone, etc.). And so on.
  • chain amides for example, chain aliphatic amides (for example, alkanoic acid amides such as dimethylformamide and dimethylacetamide)], cyclic amides (or lactam, for example, N-methylpyrrolidone, etc.). And so on.
  • oxygen-containing solvent examples include carbonate-based solvent, ether-based solvent, ester-based solvent, ketone-based solvent, alcohol-based solvent [for example, chain alcohol (for example, alkanol such as methanol and ethanol), cyclic alcohol (for example, cyclo). Hexanol, etc.), etc.] and the like.
  • Examples of the carbonate-based solvent include chain carbonates [for example, di-C 1-4 alkyl carbonates such as dialkyl carbonates (eg, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), etc., preferably di-alkyl carbonates.
  • chain carbonates for example, di-C 1-4 alkyl carbonates such as dialkyl carbonates (eg, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), etc., preferably di-alkyl carbonates.
  • C 1-2 alkyl carbonate alkylaryl carbonate (eg, C 1-4 alkylphenyl carbonate such as methylphenyl carbonate), diaryl carbonate (eg, diphenyl carbonate), etc.], cyclic carbonate ⁇ eg, saturated cyclic carbonate [eg, eg, saturated cyclic carbonate] Ethylene carbonate, propylene carbonate, ethylene 2,3-dimethylcarbonate, alkylene carbonate such as 1,2-butylene carbonate (eg, C 2-6 alkylene carbonate, preferably C 2-4 alkylene carbonate), erythritan carbonate, etc.], Unsaturated cyclic carbonates (eg, alkenylene carbonates such as vinylene carbonate, methylvinylene carbonate, ethylvinylene carbonate; 2-vinylethylene carbonate), fluorine-containing cyclic carbonates (eg, fluoroethylene carbonate, 4,5-difluoroethylene carbonate, trifluoro) Prop
  • ether-based solvent examples include chain ethers ⁇ for example, chain aliphatic ethers [for example, C 2- of alcandiol dialkyl ethers (eg, 1,2-dimethoxyethane (ethylene glycol dimethyl ether), ethylene glycol diethyl ethers and the like).
  • chain ethers for example, chain aliphatic ethers [for example, C 2- of alcandiol dialkyl ethers (eg, 1,2-dimethoxyethane (ethylene glycol dimethyl ether), ethylene glycol diethyl ethers and the like).
  • ester-based solvent examples include chain esters ⁇ for example, aliphatic esters [for example, alkanoic acid esters such as methyl acetate, ethyl acetate, ethyl propionate, propyl propionate (for example, C 1-5 alkanoate C 1-). 4 Alkyl esters), etc.], aromatic esters (eg, methyl benzoate, ethyl benzoate), etc. ⁇ , cyclic esters [or lactones, such as ⁇ -butyrolactone, valerolactone ( ⁇ -valerolactone, ⁇ -valerolactone, etc.) Etc.] etc.
  • chain esters for example, aliphatic esters [for example, alkanoic acid esters such as methyl acetate, ethyl acetate, ethyl propionate, propyl propionate (for example, C 1-5 alkanoate C 1-). 4 Alkyl esters), etc.], aromatic esters (e
  • ketone solvent examples include chain ketones (for example, dialkyl ketones such as acetone, methyl ethyl ketone and methyl isopropyl ketone), cyclic ketones [for example, cycloalkanones (for example, cyclohexanone), and heterocyclic ketones (for example, for example). 1,3-Dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 3-methyl-2-oxazolidinone, etc.)] and the like. ..
  • chain ketones for example, dialkyl ketones such as acetone, methyl ethyl ketone and methyl isopropyl ketone
  • cyclic ketones for example, cycloalkanones (for example, cyclohexanone)
  • heterocyclic ketones for example, for example
  • sulfur-containing solvent examples include chain sulfone (or chain sulfone solvent, for example, dialkyl sulfone such as dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone), cyclic sulfone [for example, sulfolanes (or sulfolane solvent, for example, for example). , Sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane), etc.] and other sulfones (sulfone-based solvents).
  • chain sulfone or chain sulfone solvent, for example, dialkyl sulfone such as dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone
  • cyclic sulfone for example, sulfolanes (or sulfolane solvent, for example, for example. , Sulfolane,
  • Solvent Y may be contained in the compound represented by the formula (1) alone or in combination of two or more.
  • nitrile-based solvents carbonate-based solvents, ether-based solvents, ester-based solvents, sulfone-based solvents and the like are preferable, and among them, aliphatic nitriles, chain carbonates, cyclic carbonates, chain aliphatic ethers, cyclic ethers and chains.
  • State esters for example, aliphatic esters such as C 1-5 alkanoic acid C 1-4 alkyl esters), cyclic esters, cyclic sulfones (sulfolanes, etc.) and the like are preferable.
  • More typical solvents include acetonitrile, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran. , 1,4-dioxane, 1,3-dioxolane, methyl acetate, ethyl acetate, ethyl propionate, propyl propionate, ⁇ -butyrolactone, valerolactone, sulfolane and the like.
  • Such a solvent is suitable because it has a stable coordination structure. Further, in many cases, it is a solvent that can be used (or can be allowed to be contained) in a battery, an electrolytic solution, etc., and by using such a solvent, the compound represented by the formula (1) can be made into an electrolytic solution or the like. Can be used as it is in.
  • a solvent such as acetonitrile is relatively easily replaced as described later, and a compound having such a solvent Y can be suitably used as a compound for obtaining a compound having a different solvent as Y.
  • the solvent Y is at least such a solvent [for example, a nitrile solvent (aliphatic nitrile, etc.), a carbonate solvent (chain carbonate, cyclic carbonate, etc.), an ether solvent (for example, a chain aliphatic ether, cyclic). At least one selected from ether and the like) and ester-based solvents] may be included.
  • a solvent for example, a nitrile solvent (aliphatic nitrile, etc.), a carbonate solvent (chain carbonate, cyclic carbonate, etc.), an ether solvent (for example, a chain aliphatic ether, cyclic). At least one selected from ether and the like) and ester-based solvents] may be included.
  • the compound or solvent Y represented by the formula (1) may contain at least an aprotic solvent (for example, a solvent other than water, an alcohol solvent and an amine solvent), and (substantially) protons. It does not have to contain a sex solvent (water, etc.).
  • an aprotic solvent for example, a solvent other than water, an alcohol solvent and an amine solvent
  • protons it does not have to contain a sex solvent (water, etc.).
  • a protonic solvent its content is not particularly limited, and may be contained as (a part of) the solvent Y, for example.
  • the proportion of water is 20000 mass ppm or less (for example, 10000 mass ppm or less), preferably 5000 mass ppm or less (for example, 3000 mass ppm or less), and more preferably 2000 mass ppm or less. It may be mass ppm or less, particularly 1500 mass ppm or less, 1000 mass ppm or less, 500 mass ppm or less, 250 mass ppm or less, 100 mass ppm or less, 50 mass ppm or less, 0 mass ppm (or detection limit), etc. There may be.
  • the ratio of water is 20000 mass ppm or less (for example, 10000 mass ppm or less), preferably 5000 mass ppm or less (for example, 3000 mass ppm or less), more preferably 2000 mass ppm or less, particularly 1500 mass ppm or less. It may be 1000 mass ppm or less, 500 mass ppm or less, 250 mass ppm or less, 100 mass ppm or less, 50 mass ppm or less, 0 mass ppm (or detection limit) and the like.
  • the water content can be measured by, for example, the Karl Fischer method.
  • a compound having such a small amount of water is unlikely to cause a reaction such as hydrolysis, and it is easy to ensure high stability (hydrolysis stability) as a compound. Further, if the amount of water is about this level, it can be stably removed even when it is necessary to remove it. Further, it is easy to use as an electrolyte or the like and is suitable.
  • a, b and c are all positive numbers. That is, the compound represented by the formula (1) always contains the metal M, X, and the solvent Y, and the abundance ratio (composition ratio) of these in the compound can be represented by a / b / c.
  • b is, for example, 0.1 or more (for example, 0.1 or more), although it depends on the type of the metal M and the solvent Y. It may be 0.1 to 10), preferably 0.3 or more (for example, 0.3 to 9), more preferably 0.5 or more (for example, 0.5 to 8), and usually 1 or more [for example, 1, 1 to 5, 1.2 or more (for example, 1.2 to 4.5), 1.5 or more (for example, 1.5 to 4), 1.7 or more (for example, 1.7 to 3.5) , 2 or more (for example, 2 to 2.5), 2 etc.].
  • c is, for example, 0.1 or more (for example, 0.1 to 25), preferably 0, although it depends on the type of the metal M and the solvent Y. It may be .2 or more (for example, 0.2 to 20), more preferably 0.3 or more (for example, 0.3 to 18), and usually 0.4 or more [for example, 0.4 to 15, 0. .7 or more (for example, 0.7 to 12), 0.8 or more (for example, 0.8 to 10), 1 or more (for example, 1 to 8), 1.5 or more (for example, 1.8 to 8) , 2 or more (for example, 2 to 7.5), etc.].
  • a / b / c 1 / 0.1 to 10 (for example, 0.5 to 8) / 0.1 to 25 (for example, 0.2 to). 20), preferably 1/1 to 5 (eg, 1.2 to 4.5) /0.3 to 18 (eg, 0.4 to 15), and even more preferably 1 / 1.5 to 4 (eg, 1 / 1.5 to 4). 1.7 to 3.5) /0.7 to 12 (for example, 0.8 to 10), especially 1/2 to 3 (for example, 2 to 2.5) / 1 to 8 (for example, 2 to 7. 5) may be used.
  • the method for producing the compound represented by the formula (1) is not particularly limited, but it can be efficiently produced by the method described later.
  • the present invention also includes a method for producing a bis (fluorosulfonyl) imide compound.
  • a bis (fluorosulfonyl) imide compound may be, in particular, the above-exemplified compound (bis (fluorosulfonyl) imide compound).
  • At least a reaction step of reacting a metal salt (or a metal compound) with a bis (fluorosulfonyl) imide in the presence of a coordinating solvent is performed.
  • examples of the coordinating solvent include the above-exemplified coordinating solvent Y, and preferred embodiments are the same as described above.
  • the metal salt (or metal compound) is not particularly limited as long as it can react with bis (fluorosulfonyl) imide, but does not generate water during the reaction [during reaction with bis (fluorosulfonylimide)]. It is preferable that it is one.
  • Specific metal salts include, for example, salts (compounds) of the above-exemplified metal (metal M), for example, halides (or hydrogen halides), inorganic acid salts (for example, sulfates, nitrates, phosphates). , Chlorate, oxoate such as chromate), organic acid salt [eg, carboxylate (eg, alcanate such as formate, acetate), sulfonate (eg, trifluoromethanesulfonate) ) Etc.] and so on.
  • halides may be preferably used.
  • the halogen is not particularly limited, but may be chlorine (atom), bromine (atom), iodine (atom) or the like, and may be chlorine in particular.
  • the metal halide include alkali halogenated earth metals [for example, magnesium halide such as magnesium chloride (MgCl 2 )] and the like.
  • the bis (fluorosulfonyl) imide can be said to be a compound represented by HN (SO 2 F) 2 (sometimes referred to as HFSI) (the following formula).
  • the bis (fluorosulfonyl) imide compound (the compound (1) and the like) may be a protonic solvent as a coordinating solvent, particularly a compound having a small amount of water.
  • the coordinating solvent, the metal salt and / or the bis (fluorosulfonyl) imide used as a raw material may also have a low content of such a solvent.
  • the content of water contained in such a coordinating solvent is, for example, 20000 mass ppm or less (for example, 10000 mass ppm or less), preferably 5000 mass ppm or less (for example, 3000 mass ppm or less), and more preferably 2000 mass ppm or less. It may be mass ppm or less, particularly 1500 mass ppm or less, 1000 mass ppm or less, 500 mass ppm or less, 250 mass ppm or less, 100 mass ppm or less, 50 mass ppm or less, 0 mass ppm (or detection limit), etc. There may be.
  • the content of water (including the case where it is contained as a hydrate or the like) contained in the metal salt is, for example, 20000 mass ppm or less (for example, 10000 mass ppm or less), preferably 5000 mass ppm or less (for example, 3000 mass ppm or less). (ppm or less), more preferably 2000 mass ppm or less, particularly 1500 mass ppm or less, 1000 mass ppm or less, 500 mass ppm or less, 250 mass ppm or less, 100 mass ppm or less, 50 mass ppm or less, 0 mass It may be ppm (or detection limit) or the like.
  • the content of water contained in bis (fluorosulfonyl) imide is, for example, 20000 mass ppm or less (for example, 10000 mass ppm or less), preferably 5000 mass ppm or less (for example, 3000 mass ppm or less), more preferably 3000 mass ppm or less. It may be 2000 mass ppm or less, particularly 1500 mass ppm or less, 1000 mass ppm or less, 500 mass ppm or less, 250 mass ppm or less, 100 mass ppm or less, 50 mass ppm or less, 0 mass ppm (or detection limit), etc. It may be.
  • the reaction step may be carried out in the presence of an appropriate medium [for example, a solvent that is not a coordinating solvent, an inert (non-reactive) solvent in the reaction (reaction between the metal salt and the coordinating solvent), etc.]. Well, it may be done in the absence. In the present invention, since a solvent (coordinating solvent) can be used as the reaction component, the reaction can be efficiently proceeded without adding a separate solvent.
  • an appropriate medium for example, a solvent that is not a coordinating solvent, an inert (non-reactive) solvent in the reaction (reaction between the metal salt and the coordinating solvent), etc.
  • the ratio (use ratio) of each component can be appropriately selected according to the type of the target bis (fluorosulfonyl) imide compound and the like.
  • the ratio of the bis (fluorosulfonyl) imide to the metal salt is such that the metal salt is added to the bis (fluorosulfonyl) imide.
  • 05 equivalents or more for example, 0.1 equivalents or more
  • preferably 0.2 equivalents or more for example, 0.3 equivalents or more
  • more preferably 0.4 equivalents or more for example, 0.5 equivalents or more.
  • the ratio of bis (fluorosulfonyl) imide to the metal salt is, for example, 2 equivalents or less (for example, 1.8 equivalents or less) of the metal salt, preferably 1.6 equivalents, relative to bis (fluorosulfonyl) imide.
  • Equivalent or less for example, 1.5 equivalents or less
  • more preferably 1.4 equivalents or less for example, 1.3 equivalents or less
  • 1.2 equivalents or less for example, 1.15 equivalents or less, 1.1.
  • Equivalent or less, 1 equivalent or less, etc. may be used.
  • the “equivalent” can be selected according to the valence of the metal (metal salt). For example, in the case of a divalent metal (magnesium, etc.), “1 equivalent” is used with respect to bis (fluorosulfonyl) imide (monovalent). Means "0.5 mol” for 1 mol of bis (fluorosulfonyl) imide.
  • the ratio of the solvent is not particularly limited and can be selected according to the amount (ratio) of the solvent contained in the target product, for example, 0.05 equivalent or more (with respect to the metal salt).
  • it may be 0.1 equivalent or more, preferably 0.2 equivalent or more (for example, 0.3 equivalent or more), more preferably 0.4 equivalent or more (for example, 0.5 equivalent or more), and 0. 6.6 equivalents or more (for example, 0.7 equivalents or more, 0.8 equivalents or more, 0.9 equivalents or more, 0.95 equivalents or more, 1 equivalents or more, 1.5 equivalents or more, 2 equivalents or more, 3 equivalents or more, 5 It may be equivalent or more).
  • the upper limit of the ratio of the solvent to the metal salt is not particularly limited, and may be a large excess, or may be 1000 equivalents, 500 equivalents, 300 equivalents, 200 equivalents, 100 equivalents, or the like.
  • the bis (fluorosulfonyl) imide compound (the compound (1), etc.) may be a protonic solvent, particularly a compound having a small amount of water.
  • the amount of water (water content) in the reaction system is preferably relatively small, and the reaction may be carried out in the absence of (substantially) water.
  • the water content in the reaction system is, for example, 20000 mass ppm or less (for example, 10000 mass ppm or less), preferably 5000 mass ppm or less (for example, 3000 mass ppm or less), more preferably 2000 mass ppm or less, particularly 1500 mass ppm or less, 1000 mass ppm or less, 500 mass ppm or less.
  • it may be 250 mass ppm or less, 100 mass ppm or less, 50 mass ppm or less, 0 mass ppm (or detection limit), or the like.
  • each component may be charged in the reaction system (reactor) at the first stage of the reaction process, or may be charged (added) in stages.
  • the order, timing and speed of addition of each component can be appropriately selected.
  • HFSI may be added to a system containing a metal halide and a coordinating solvent.
  • the temperature is not particularly limited, and may be any of heating, normal temperature, and cooling.
  • the temperature is 100 ° C. or lower (for example, 80 ° C. or lower, 60 ° C. or lower, etc.), preferably 50 ° C. or lower (for example, 30 ° C. or lower), and more preferably 20 ° C. or lower (for example, 10 ° C. or lower). It may be 0 ° C. or lower (-10 ° C. or lower, -20 ° C. or lower, etc.).
  • the lower limit of the reaction temperature is not particularly limited, and may be, for example, ⁇ 100 ° C., ⁇ 80 ° C., ⁇ 70 ° C., ⁇ 60 ° C., ⁇ 40 ° C., ⁇ 20 ° C., 0 ° C. and the like. Typically, the temperature may be about ⁇ 20 ° C. to 100 ° C. (for example, 0 ° C. to 60 ° C.).
  • the reaction may be carried out under stirring. Further, the reaction is preferably carried out in an atmosphere having a low dew point. In such a case, the dew point may be, for example, 0 ° C. or lower, more preferably ⁇ 10 ° C. or lower, ⁇ 20 ° C. or lower, still more preferably ⁇ 30 ° C. or lower, and particularly preferably ⁇ 50 ° C. or lower. Further, the reaction may be carried out in an inert atmosphere (in nitrogen, helium, argon, etc.).
  • acid can usually be generated by the reaction. Since such an acid may decompose the product, it is preferable to react while removing the generated acid.
  • the method for removing the generated acid is not particularly limited, and may be selected depending on the type of generated acid and the like. For example, when hydrogen halide is generated, a method of flowing with an atmospheric gas, bubbling with an atmospheric gas, removing with an alkaline trap or the like is preferable.
  • the reaction time can be appropriately selected depending on the type and amount of each component, and is not particularly limited, but is, for example, 0.1 hours or more (for example, 0.5 hours or more), preferably 3 hours or more, and more preferably 5. It may be more than an hour. Typically, the reaction time may be about 0.1 hour to 48 hours (for example, 0.1 hour to 24 hours).
  • a product (the compound (1) or the like) is obtained.
  • the product may be appropriately purified and recovered from the reaction mixture after the reaction (after the reaction step).
  • the purification method is not particularly limited, and a conventional method (for example, filtration, distillation, concentration, recrystallization, etc.) can be used.
  • the reaction mixture may be concentrated for the purpose of removing the solvent (coordinating solvent).
  • Purification concentration, etc. may be performed under heating or reduced pressure. In such a case, the temperature and pressure at the time of concentration may be relatively gentle. By purifying (concentrating) under such conditions, decomposition of the product and the like can be suppressed as much as possible, and the product can be efficiently obtained (recovered).
  • the temperature during purification is 100 ° C. or lower, preferably 90 ° C. or lower (for example, 85 ° C. or lower), more preferably 80 ° C. or lower (for example, 75 ° C. or lower), still more preferably 70 ° C. or lower (for example, 70 ° C. or lower).
  • the lower limit of the temperature is not particularly limited and may be appropriately set at a temperature at which concentration is possible (for example, room temperature (for example, 35 ° C., 30 ° C., 20 ° C., 15 ° C., etc.), 10 ° C., 0 ° C., etc. It may be -10 ° C, -20 ° C, etc.).
  • the temperature at the time of purification (concentration, etc.) may be about 0 to 100 ° C. (for example, 20 to 60 ° C.).
  • the pressure (decompression degree) can be selected from the range below atmospheric pressure. For example, 900 hPa or less, 800 hPa or less, 700 hPa or less, 600 hPa, 500 hPa or less, 400 hPa or less, 300 hPa or less. , 200 hPa or less, 150 hPa or less, 120 hPa or less, 100 hPa or less, 80 hPa or less, and the like.
  • the lower limit of the pressure may be, for example, 3 hPa, 5 hPa, 10 hPa, 20 hPa, 30 hPa, 40 hPa, 50 hPa, 60 hPa, or the like.
  • the product (compound (1), etc.) obtained through the reaction step contains a coordinating solvent (as a ligand) corresponding to the coordinating solvent used.
  • a coordinating solvent may be replaced with another coordinating solvent to obtain another product (ligand or a compound (1) different in its composition, etc.).
  • the production method of the present invention may include a step of substituting the coordinating solvent (ligand substitution step) after the above reaction step.
  • Such a method uses the coordinating solvent Y1 in the reaction step, and the product (or compound, the first compound, the first production) in which the coordinating solvent Y is Y1 in the formula (1). It can be said that the method includes a ligand substitution step of substituting at least a part of the coordinating solvent Y1 with the coordinating solvent Y2 after obtaining the substance or the like.
  • the combination of the coordinating solvent Y1 and the coordinating solvent Y2 is not particularly limited, and may be any solvent different from each other.
  • the coordinating solvent Y1 is a nitrile solvent (for example, acetonitrile) or the like, substitution with the coordinating solvent Y2 proceeds relatively easily.
  • the coordinating solvent Y1 is a nitrile solvent (aliphatic nitrile, acetonitrile), and the coordinating solvent Y2 is a non-nitrile solvent (for example, a carbonate solvent, an ether solvent). , At least one selected from ester-based solvent and sulfone-based solvent), and the like, but are not particularly limited.
  • the ligand replacement step at least a part of the coordinating solvent Y1 in the first compound is replaced with the coordinating solvent Y2 (a solvent different from the coordinating solvent Y1).
  • the substitution method is not particularly limited, and for example, the first compound and the coordinating solvent Y2 may be brought into contact with each other (for example, mixed).
  • the amount of the coordinating solvent Y2 (the amount of the coordinating solvent Y2 brought into contact with 1 mol of the first compound (or Y1)) is not particularly limited, but is, for example, the first compound.
  • 0.1 mol or more for example, 0.2 mol or more
  • 0.5 mol or more for example, 0.7 mol or more
  • 1 mol or more for example, 1.2 mol or more
  • the above for example, 1.8 mol or more
  • 2 mol or more, and the like may be used.
  • the ligand replacement step may be performed under heating, normal temperature, or cooling. Moreover, the ligand replacement step may be performed under stirring.
  • the ligand replacement step is preferably carried out in a low dew point atmosphere, and may be carried out in an inert atmosphere (in nitrogen, helium, argon, etc.). These conditions may be selected from the same range as described above.
  • the time for contacting the first compound with the coordinating solvent in the ligand substitution step can be appropriately selected depending on the type and amount of each component, and is not particularly limited, but is, for example, 1 minute or more, preferably 10. It may be minutes or more, more preferably 30 minutes or more, particularly 1 hour or more.
  • the pressure may be reduced during or after the contact. By reducing the pressure, the coordinating solvent can be replaced and the desorbed coordinating solvent can be efficiently removed (purified).
  • the boiling point Y1 of the coordinating solvent Y1 is lower or the same as the boiling point Y2 of the coordinating solvent Y2, or even if it is higher, it is not too high.
  • the difference (Y2-Y1) between the boiling point Y2 and the boiling point Y1 may be -30 ° C or higher, -20 ° C or higher, -10 ° C or higher, -5 ° C or higher, -3 ° C or higher, 0 ° C or higher, or the like. Good.
  • the pressure (decompression degree) may be selected from the same range as described above.
  • a product (or a compound, a second compound, a second product, etc.) in which at least a part of the coordinating solvent Y1 is replaced with the coordinating solvent Y2 is obtained.
  • the second product may be appropriately purified and recovered from the mixture (reaction mixture) after such a ligand substitution step.
  • the purification method the same method as described above may be selected.
  • the products may be purified by a method such as recrystallization, if necessary. Good. By such purification, a high-purity target compound (first compound, second compound) can be efficiently obtained.
  • the recrystallization method is not particularly limited, and a conventional method can be used. For example, it may be recrystallized in the same coordinating solvent Y as the coordinating solvent Y constituting the product.
  • ICP emission spectroscopy A multi-type ICP emission spectroscopic analyzer (“ICPE-9000” manufactured by Shimadzu Corporation) was used to analyze the magnesium substance contained in the product.
  • IR measurement The IR measurement was performed using "Scimitar 2000 FT-IR” manufactured by Varian and "MIRale ATR” manufactured by PIKE.
  • KF Karl Fischer
  • Raman measurement was performed using "NRS-3100" manufactured by JASCO Corporation.
  • Example 1 A 100 ml reaction vessel equipped with a synthetic agitator, a thermometer, and a dropping device for Mg (FSI) 2 (MeCN) 7 was placed under a nitrogen stream, and 2.09 g (22.0 mmol, 1.00 eq.) Of magnesium chloride (MgCl 2 ). ) And 30.0 ml (574 mmol, 26.1 eq., Moisture content 7.8 mass ppm) of super-dehydrated acetonitrile (MeCN) were added, and the mixture was cooled to 4 ° C. in an ice bath.
  • Mg (FSI) 2 (MeCN) 7 Mg (FSI) 2 (MeCN) 7 was placed under a nitrogen stream, and 2.09 g (22.0 mmol, 1.00 eq.) Of magnesium chloride (MgCl 2 ).
  • Example 2 Synthesis of Mg (FSI) 2 (MeCN) 6 To the product obtained in Example 1, an excess amount of super-dehydrated acetonitrile (MeCN) (water content 7.8 mass ppm) was added, and the mixture was heated to 50 ° C. , Cooled overnight in a freezer at ⁇ 10 ° C. to obtain white crystals.
  • MeCN super-dehydrated acetonitrile
  • Example 3 Synthesis of Mg (FSI) 2 (MeCN) 5
  • the product obtained in Example 1 was depressurized in a vacuum oven (complete vacuum) at room temperature for 2 hours to obtain a white powder.
  • Example 4 Synthesis of Mg (FSI) 2 (MeCN) 4
  • the product obtained in Example 1 was depressurized in a vacuum oven (complete vacuum) at 50 ° C. for 3 hours to obtain a translucent viscous liquid.
  • Example 5 Synthesis of Mg (FSI) 2 (DMC) 3 To the product obtained in Example 1, a large excess amount (about 80 equivalents) of dimethyl carbonate (DMC, water content 20.7 mass ppm) was added, and two layers were added. The lower layer divided into two was collected. Then, the pressure was reduced in a reduced pressure oven (complete vacuum) at room temperature for 2 hours to obtain a pale yellow, highly viscous liquid product.
  • DMC dimethyl carbonate
  • Example 6 Synthesis of Mg (FSI) 2 (G1) 3
  • 1,2-dimethoxyethane G1, water content 143 mass ppm
  • the obtained mixed solution was concentrated by an evaporator, and then depressurized at 70 ° C. for 30 minutes in a reduced pressure oven (complete vacuum) to obtain a pale yellow, highly viscous liquid product.
  • Example 7 Synthesis of Mg (FSI) 2 (MeCN) 1 (G3) 1 1 equivalent of triethylene glycol dimethyl ether (triglime, G3, water content 254 mass ppm) was added to the product obtained in Example 1 to obtain the product. The mixed solution was concentrated with an evaporator (55 ° C., 30 hPa) to obtain a colorless viscous liquid product.
  • Example 8 Synthesis of Mg (FSI) 2 (G3) 2 To the product obtained in Example 1, 2 equivalents of triethylene glycol dimethyl ether (triglime, G3, water content 254 mass ppm) was added, and the obtained mixed solution was added. Concentration was carried out on an evaporator (60 ° C., 10 hPa) to obtain a white viscous solid product.
  • Example 9 Synthesis of Mg (FSI) 2 (G3) 3 To the product obtained in Example 1, 3 equivalents of triethylene glycol dimethyl ether (triglime, G3, water content 254 mass ppm) was added, and the obtained mixed solution was added. Concentration was carried out with an evaporator (60 ° C., 10 hPa) to obtain a colorless transparent liquid product.
  • Example 10 Synthesis of Mg (FSI) 2 (G3) 5 To the product obtained in Example 1, 5 equivalents of triethylene glycol dimethyl ether (triglime, G3, water content 254 mass ppm) was added, and the obtained mixed solution was added. Concentration was carried out with an evaporator (60 ° C., 10 hPa) to obtain a colorless transparent liquid product.
  • a novel bis (fluorosulfonyl) imide compound or the like can be provided.
  • a compound can be used, for example, as an electrolyte or an additive for an electrolytic solution.
  • a compound in which the metal M is magnesium can be used as a compound (electrolyte or the like) for a magsium (ion) battery (secondary battery).

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CN106430129A (zh) 2016-08-30 2017-02-22 九江天赐高新材料有限公司 一种二氟磺酰亚胺盐的制备方法

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GLEB VERYASOV; KAZUHIKO MATSUMOTO; RIKA HAGIWARA: "Homoleptic octahedral coordination of CH 3 CN to Mg 2+ in the Mg[N(SO 2 CF 3 ) 2 ] 2 -CH 3 CN system", DALTON TRANSACTIONS, vol. 45, 2016, pages 2810 - 2813, XP055595732 *
PIETER GEYSENS, VIJAY SHANKAR RANGASAMY, SAVITHA THAYUMANASUNDARAM, KOEN ROBEYNS, LUC VAN MEERVELT, JEAN-PIERRE LOCQUET, JAN FRANS: "Solvation Structure of Sodium Bis(fluorosulfonyl)imide-Glyme Solvate Ionic Liquids and Its Influence on Cycling of Na-MNC Cathodes", THE JOURNAL OF PHYSICAL CHEMISTRY B, vol. 122, 2018, pages 275 - 289, XP055762905 *
SANG-DON HAN, OLEG BORODIN, DANIEL M. SEO, ZHI-BIN ZHOU, WESLEY A. HENDERSON: "Electrolyte Solvation and Ionic Association : V. Acetonitrile-Lithium Bis(fluorosulfonyl)imide (LiFSI) Mixtures", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 161, no. 14, 2014, pages A2042 - A2053, XP055762902 *
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SINGH, SUKHJINDER ET AL.: "Bis(fluorosulphuryl)imide derivatives of zinc(II), cadmium(II), mercury(II) and their coordination complexes with oxygen and nitrogen donors", INDIAN JOURNAL OF CHEMISTRY, vol. 28A, 1989, pages 890 - 892, XP008132308 *
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