Classifications

• • 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
• • 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
• • 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
  • H01M10/0568—Liquid materials characterised by the solutes
• • 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
  • H01M10/0569—Liquid materials characterised by the solvents
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0025—Organic electrolyte
  • H01M2300/0028—Organic electrolyte characterised by the solvent
• • 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 disclosure relates to a composition manufacturing method and a non-aqueous electrolyte.
• Patent Literature 1 proposes a method for producing a non-aqueous electrolyte having a low water content. This method comprises combining an acid containing an anion of an alkali metal salt (e.g., bis(fluorosulfonyl)imide (HFSI)), an alkali metal base (e.g., lithium carbonate), and a non-aqueous solvent with a non-aqueous solvent, water, and an acid.
• an alkali metal salt e.g., bis(fluorosulfonyl)imide (HFSI)
• an alkali metal base e.g., lithium carbonate
• step (a) mixing under conditions sufficient to produce a solution mixture comprising the alkali metal salt produced from the reaction of the alkali metal salt with an alkali metal base; and (b) generating a liquid. Moreover, in this method, a non-aqueous solvent is added to the generated non-aqueous electrolytic solution, and step (b) is repeated.
• step (b) the thermal stability of the solution mixture obtained in step (a) is not sufficient. It is necessary to perform step (b) at Therefore, in this method, the step (b) must be repeated many times in order to sufficiently reduce the water content of the non-aqueous electrolyte, and the efficiency of dehydration and replacement with a non-aqueous solvent is insufficient. there were.
• the present disclosure has been made in view of such points, and the object thereof is to provide a method for producing a composition that is highly efficient in dehydration and substitution with a non-aqueous solvent, and a non-aqueous electrolyte solution containing the composition. to provide.
• the present applicant discloses an electrolyte composition containing a sulfonylimide compound and an amidosulfuric acid component in International Publication No. 2020/241161 (application specification of PCT/JP2020/18124).
• the applicant also discloses a composition comprising an electrolyte, a solvent and an anion component in application specification PCT/JP2021/004071.
• the electrolyte contains a sulfonylimide salt (sulfonylimide compound), and the anion component is an acid having an acid dissociation constant pKa (acid dissociation constant pKa1 of the first stage for an acid that ionizes multiple times) of 0 or more and 6.5 or less.
• the component is contained at a concentration of 50 ppm by mass or more and 10000 ppm by mass or less with respect to the electrolyte.
• the composition containing the sulfonylimide compound has excellent storage stability even at high temperatures (the property that the decomposition reaction of the sulfonylimide compound is suppressed even when stored for a long period of time).
• the disclosed technique utilizes the above-described effect produced by the addition of an anion component and adds an anion component to a solution containing a sulfonylimide compound to improve the thermal stability of the solution.
• An operation of dehydration and replacement with a non-aqueous solvent was performed.
• the present disclosure is specifically as follows.
• a method for producing a composition of the present disclosure is a method for producing a composition containing an electrolyte, a non-aqueous solvent and an anion component
• the electrolyte has the general formula (1): LiN(XSO 2 )(FSO 2 ) (X represents a fluorine atom, an alkyl group having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon atoms.) (1) including a sulfonylimide compound represented by The anion component has an acid dissociation constant pKa of its conjugate acid (acid dissociation constant pKa1 of the first stage for an acid that ionizes multiple times) of 0 or more and 6.5 or less, and a concentration of 10000 mass ppm or less with respect to the electrolyte. is contained in A dehydration step of adding the anion component to a solution containing the electrolyte and the non-aqueous solvent, dehydrating the solution, and substituting the solvent.
• the anion component in the manufacturing method, in the dehydration step, may be contained at a concentration of 4000 ppm by mass or more relative to the electrolyte. Moreover, the dehydration step may include a step of adding the anion component to the electrolyte at a concentration of 1000 ppm by mass or more.
• the anion component may be at least one selected from the group consisting of an amidosulfuric acid component, an acetic acid (carboxylic acid) component, a carbonic acid component and a phosphoric acid component.
• the anion component is at least one selected from the group consisting of a sulfonic acid component, a sulfinic acid component, a carboxylic acid component, a carbonic acid component, a phosphoric acid component, a phosphonic acid component, derivatives thereof, and salts thereof.
• the anion component contains at least one selected from the group consisting of amidosulfuric acid and salts thereof, amidosulfuric acid derivatives and salts thereof, and the amidosulfuric acid derivatives and salts thereof have the general formula (2):
• R 1 and R 2 are H (hydrogen atom), a hydroxyl group, an optionally substituted alkyl group having 1 to 10 carbon atoms, a cyclo represents an alkyl group, an aryl group having 6 to 16 carbon atoms, an aralkyl group having 7 to 16 carbon atoms or an alkanoyl group having 2 to 16 carbon atoms, which may contain a hetero atom, and R 1 and R 2 form a ring structure;
• R 1 and R 2 are the above groups other than H, they may be the same or different (R 1 and R 2 are not the same when H (R 1 and R 2 is not H at the same time)).
• M represents H (hydrogen atom) or metal atom.) It may be a compound represented by.
• the anion component may contain at least one selected from the group consisting of amidosulfuric acid and alkali metal salts of amidosulfuric acid.
• the anion component may contain an alkali metal amide sulfate.
• the non-aqueous solvent may contain a chain carbonate solvent.
• the moisture content of the composition may be 10000 ppm by mass or less.
• the non-aqueous electrolyte of the present disclosure includes the composition obtained by the production method described above.
• the method for producing the composition according to this embodiment includes at least a preparation step and a dehydration step. Through these steps, a composition containing an electrolyte, a non-aqueous solvent and an anion component, which will be described later, is obtained.
• a preparation step is a step of preparing a solution containing an electrolyte and water and/or a non-aqueous solvent. That is, in the preparation step, an aqueous electrolyte solution containing an electrolyte and water may be prepared, an electrolyte solution containing an electrolyte and a non-aqueous solvent may be prepared, or a hydrous electrolyte containing an electrolyte, water and a non-aqueous solvent may be prepared.
• a solution may be prepared.
• the electrolyte aqueous solution, the electrolyte solution, and the water-containing electrolyte solution are collectively referred to as "water-containing sulfonylimide solution".
• the method for producing a composition according to the present embodiment is a method premised on using a hydrous sulfonylimide solution.
• the electrolyte has the general formula (1): [Chemical 2] LiN( XSO2 )( FSO2 ) (1) (hereinafter referred to as "sulfonylimide compound (1)", fluorine-containing sulfonylimide salt).
• the sulfonylimide compound (1) is an electrolyte contained in the composition obtained by the production method according to this embodiment.
• X represents a fluorine atom, an alkyl group having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon atoms.
• alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group and hexyl group.
• alkyl groups having 1 to 6 carbon atoms linear or branched alkyl groups having 1 to 6 carbon atoms are preferred, and linear alkyl groups having 1 to 6 carbon atoms are more preferred.
• fluoroalkyl group having 1 to 6 carbon atoms examples include those in which some or all of the hydrogen atoms of an alkyl group having 1 to 6 carbon atoms are substituted with fluorine atoms.
• the fluoroalkyl group having 1 to 6 carbon atoms includes fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, pentafluoroethyl group and the like.
• the fluoroalkyl group may be a perfluoroalkyl group.
• the substituent X is preferably a fluorine atom and a perfluoroalkyl group (for example, a perfluoroalkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, etc.), a fluorine atom, A trifluoromethyl group and a pentafluoroethyl group are more preferred, a fluorine atom and a trifluoromethyl group are even more preferred, and a fluorine atom is even more preferred.
• a perfluoroalkyl group for example, a perfluoroalkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, etc.
• the sulfonylimide compound (1) include lithium bis(fluorosulfonyl)imide (LiN(FSO 2 ) 2 , LiFSI), lithium (fluorosulfonyl)(methylsulfonyl)imide, lithium (fluorosulfonyl)(ethylsulfonyl) imide, lithium(fluorosulfonyl)(trifluoromethylsulfonyl)imide, lithium(fluorosulfonyl)(pentafluoroethylsulfonyl)imide, lithium(fluorosulfonyl)(heptafluoropropylsulfonyl)imide and the like.
• the sulfonylimide compounds may be used alone or in combination of two or more.
• lithium bis(fluorosulfonyl)imide lithium bis(fluorosulfonyl)imide, lithium (fluorosulfonyl)(trifluoromethylsulfonyl)imide, and lithium (fluorosulfonyl)(pentafluoroethylsulfonyl) ) imide, more preferably lithium bis(fluorosulfonyl)imide.
• lithium bis(fluorosulfonyl)imide lithium (fluorosulfonyl)(trifluoromethylsulfonyl)imide
• lithium (fluorosulfonyl)(pentafluoroethylsulfonyl) ) imide more preferably lithium bis(fluorosulfonyl)imide.
• hydrous sulfonylimide solutions those in which the sulfonylimide compound (1) contains LiN(FSO 2 ) 2 are preferred.
• sulfonylimide compound (1) a commercially available product may be used, or one synthesized by a conventionally known method may be used.
• a method for synthesizing the sulfonylimide compound (1) is not particularly limited, and all conventionally known methods can be employed.
• a powder (solid) of the sulfonylimide compound (1) is obtained by the conventionally known method described above.
• the sulfonylimide compound (1) can be used in the production solvent used for the production of the sulfonylimide compound (1) (the sulfonylimide compound (1) obtained by the above-described conventionally known production method) within the range that does not hinder the object of the present invention. contained residual solvent).
• the residual solvent includes the solvent used in the production reaction of the sulfonylimide compound (1), the solvent used in the purification step, and the like.
• water For example, water; alcohol solvents such as methanol, ethanol, propanol and butanol; carboxylic acid solvents such as formic acid and acetic acid; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone; Nitrile solvents such as nitrile and benzonitrile; Ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate; Aliphatic ether solvents such as diethyl ether, diisopropyl ether, t-butyl methyl ether and cyclopentyl methyl ether; Halogen-based solvents; nitro group-containing solvents such as nitromethane and nitrobenzene; nitrogen-containing organic solvents such as ethylformamide and N-methylpyrrolidone; dimethyl sulfoxide; glyme-based solvents, tolu
• aromatic hydrocarbon solvents pentane, hexane, heptane, octane, decane, dodecane, undecane, tridecane, decalin, 2,2,4,6,6-pentamethylheptane, isoparaffin (e.g., "Marcazol R” (Maruzen 2,2,4,6,6-pentamethylheptane manufactured by Petrochemical Co., Ltd., a mixture of 2,2,4,4,6-pentamethylheptane), "Isopar (registered trademark) G” (manufactured by ExxonMobil C9-C11 mixed isoparaffins), “Isopar (registered trademark) E” (C8-C10 mixed isoparaffins manufactured by ExxonMobil) Chain aliphatic hydrocarbon solvents such as dichloromethane, chloroform, 1,2-dichloroethane; cyclohexane, methylcyclohexane , 1,2-di
• the content of the sulfonylimide compound (1) in the hydrous sulfonylimide solution is preferably 10% by mass or more, from the viewpoint of sufficiently reducing the water content of the composition. More preferably 20% by mass or more, still more preferably 30% by mass or more.
• the content is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, and even more preferably 60% by mass or more.
• the upper limit of the content is preferably 80% by mass or less from the viewpoint of sufficiently reducing the moisture content of the composition.
• the dehydration efficiency means the efficiency of dehydrating the hydrous sulfonylimide solution and substituting it with a non-aqueous solvent in the dehydration step described later, specifically by the method described in the examples below. It means the dehydration efficiency based on the obtained numerical value.
• Non-aqueous solvent The non-aqueous solvent is not particularly limited as long as it can dissolve and disperse the electrolyte (hereinafter also referred to as "electrolyte solvent").
• electrolyte solvent a non-aqueous solvent having a large dielectric constant, a high solubility of the electrolyte salt, a boiling point of 60° C. or higher at normal pressure, and a wide electrochemical stability range is suitable. More preferably, it is an organic solvent with a low water content.
• organic solvents examples include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 2,6-dimethyltetrahydrofuran, tetrahydropyran, crown ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, Ether solvents such as 1,4-dioxane and 1,3-dioxolane; Chain carbonates such as dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), diphenyl carbonate, and methylphenyl carbonate ) solvent; saturated cyclic carbonate solvent such as ethylene carbonate, propylene carbonate, 2,3-dimethylethylene carbonate, 1,2-butylene carbonate and erythritan carbonate; vinylene carbonate, methyl vinylene carbonate, ethyl vinylene carbonate, 2- cyclic carbonate solvents having uns
• non-aqueous solvents chain carbonate solvents, carbonate solvents such as cyclic carbonate solvents, lactone solvents, ether solvents and chain ester solvents are preferred, and dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate.
• ethylene carbonate, propylene carbonate, ⁇ -butyrolactone and ⁇ -valerolactone are more preferable, and carbonate solvents such as dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate are more preferable, and dimethyl carbonate, ethylmethyl carbonate, Chain carbonate-based solvents such as diethyl carbonate are even more preferred.
• the non-aqueous solvent preferably contains a carbonate solvent, more preferably a chain carbonate solvent, and even more preferably a chain carbonate solvent alone.
• the hydrous sulfonylimide solution may or may not contain an anion component, which will be described later.
• the content of the anion component is preferably 10000 ppm by mass or less, more preferably 7500 ppm by mass or less, and even more preferably 5500 ppm by mass or less relative to the electrolyte. It is preferably 4500 mass ppm or less, more preferably 4000 mass ppm or less, and particularly preferably 4000 mass ppm or less.
• the method of preparing the hydrous sulfonylimide solution is not particularly limited, and a method of dissolving the powder (solid) of the sulfonylimide compound (1) in water and/or a non-aqueous solvent; water and/or a non-aqueous solvent, LiOH or A method of mixing and reacting a lithium salt such as Li 2 CO 3 and HFSI [bis(fluorosulfonyl)imide] may be mentioned. Examples of the lithiation reaction of HFSI include methods described in International Publication No. 2014-035464.
• ⁇ Dehydration process> In the dehydration step, a non-aqueous solvent was added to the hydrous sulfonylimide solution obtained in the preparation step, and the water contained in the hydrous sulfonylimide solution and the added non-aqueous solvent were azeotropically removed for dehydration and addition. This is the step of substituting with a non-aqueous solvent.
• the term "water contained in the water-containing sulfonylimide solution” refers to the water used in the preparation step as well as the water contained in raw materials such as the sulfonylimide compound (1) and the non-aqueous solvent.
• the method for producing the composition according to the present embodiment is characterized in that an anion component is further added to the hydrous sulfonylimide solution together with the non-aqueous solvent before the operation of dehydration and replacement with the non-aqueous solvent.
• the solution for performing the operation of dehydration and substitution with a non-aqueous solvent contains, in addition to the sulfonylimide compound (1), water and a non-aqueous solvent, an anion component contains
• an anion component contains, when the hydrous sulfonylimide solution obtained in the preparation step is an electrolyte solution containing a non-aqueous solvent or a hydrous electrolyte solution (other than an aqueous electrolyte solution), when an anion component is added to these electrolyte solutions or hydrous electrolyte solutions, the non-aqueous No solvent may be added.
• a solution obtained by adding only an anion component to an electrolyte solution or a hydrous electrolyte solution may be used as the hydrous sulfonylimide solution for dehydration.
• the hydrous sulfonylimide solution for dehydration prepared as described above contains an anion component and is therefore excellent in thermal stability. As a result, even if the hydrous sulfonylimide solution for dehydration is dehydrated at a relatively high temperature and replaced with a non-aqueous solvent, the decomposition of LiFSI is suppressed.
• the addition of the anion component also improves the efficiency (dehydration efficiency) of dehydrating the hydrous sulfonylimide solution for dehydration and substituting it with a non-aqueous solvent.
• Advantageous effects of the addition of the anionic component reduce the labor required for the dehydration step and improve the productivity of the composition.
• the content of the sulfonylimide compound (1) in the hydrous sulfonylimide solution for dehydration is preferably 10% by mass from the viewpoint of sufficiently reducing the water content of the composition. Above, more preferably 20% by mass or more, still more preferably 30% by mass or more. Moreover, the content is preferably 40% by mass or more, more preferably 45% by mass or more, and still more preferably 50% by mass or more, from the viewpoint of improving dehydration efficiency.
• the upper limit of the content is preferably 60% by mass or less from the viewpoint of sufficiently reducing the moisture content of the composition.
• Non-aqueous solvent the same solvent (electrolyte solvent) as the non-aqueous solvent used in the preparation step can be used as the non-aqueous solvent (hereinafter also referred to as "addition solvent") added to the hydrous sulfonylimide solution as necessary.
• the water-containing sulfonylimide solution is an electrolyte solution containing a non-aqueous solvent or a water-containing electrolyte solution (other than an aqueous electrolyte solution)
• the added solvent may be the same as or different from the non-aqueous solvent used in the preparation step.
• chain carbonate (chain carbonate) solvents preferably contains a chain carbonate-based solvent, and more preferably contains only a chain carbonate-based solvent.
• the hydrous sulfonylimide solution obtained in the preparation step is used as a raw material, so the additive solvent does not need to be "completely" non-aqueous, and may contain water.
• the upper limit of the water content of the solvent to be added may be the saturated water content or less, preferably 1000 mass ppm or less, more preferably 500 mass ppm or less.
• the total amount of the added solvent is not particularly limited in terms of the lower limit, and may be adjusted as appropriate according to the type and amount of the residual solvent in the sulfonylimide compound (1). For example, it is preferably 10000 g or less, more preferably 1000 g or less, even more preferably 500 g or less, and still more preferably 200 g or less per 100 g of the sulfonylimide compound (1).
• the total amount of the additive solvent (the amount used) is, for example, preferably 1 to 1000 parts by mass, more preferably 5 to 500 parts by mass, and still more preferably 100 parts by mass of the sulfonylimide compound (1). is 10 to 300 parts by mass, more preferably 30 to 200 parts by mass.
• the anion component added to the hydrous sulfonylimide solution (hereinafter also referred to as “additional anion component”) has an acid dissociation constant pKa of its conjugate acid (acid dissociation constant pKa1 of the first stage for an acid that ionizes multiple times) ( Temperature: room temperature (25° C.), solvent: water) is an acid component (hereinafter also referred to as “specific acid component”) having a temperature of 0 to 6.5.
• the hydrous sulfonylimide solution for dehydration is excellent in thermal stability, since decomposition of LiFSI is suppressed even at relatively high temperatures (for example, 50° C. or higher). Further, the composition obtained after the dehydration step contains a specific acid component, so that the thermal stability is improved.
• an anion component means a specific acid (for example, amidosulfuric acid described later) or a salt thereof (for example, lithium amidosulfate described later) that can become an anion by dissociating ions in a solution. It refers to the partial structure of the acid component (in the case of the above example, the amidosulfate ion).
• the pKa of the conjugate acid means, for example, the pKa of “HA” when the anion (A ⁇ ) has a valence of 1, and the first dissociation constant pKa1 of “H 2 A” when it has a valence of 2.
• the specific acid components may be used alone (may be included), or may be used in combination of two or more (may be included in combination).
• the specific acid component is at least one selected from the group consisting of an amidosulfuric acid component, an acetic acid (carboxylic acid) component, a carbonic acid component and a phosphoric acid component. Further, the specific acid component (anion component) is selected from the group consisting of a sulfonic acid component, a sulfinic acid component, a carboxylic acid component, a carbonic acid component, a phosphoric acid component and a phosphonic acid component; derivatives thereof; and salts thereof. At least one. When two or more types of anion components are used in combination, a plurality of the same anion components may be selected, or a plurality of different types of anion components may be combined.
• the structure of the specific acid component is not particularly limited in the solution, and it may exist (contain) in the form of ions (may not be dissolved) or may be dissolved.
• the sulfonic acid component refers to a compound having a sulfonic acid group (sulfo group, —SO 3 H). mentioned.
• Amidosulfuric acid component Amidosulfuric acid components (amidosulfuric acid compounds, amidosulfuric compounds, amidosulfuric acid compounds) include amidosulfuric acid (sulfamic acid), amidosulfuric acid derivatives, salts thereof, and the like.
• Amidosulfuric acid derivatives include N-substituted amidosulfuric acid (N-substituted sulfamic acid, etc.).
• amidosulfuric acid derivatives may be compounds represented by general formula (2) (N-substituted amidosulfuric acid and salts thereof).
• general formula (2) is represented as a neutral type (R 1 R 2 NSO 2 (OM)), it may be a zwitterionic type, or both of these may be included.
• R 1 and R 2 are ⁇ H (hydrogen atom), a hydroxyl group, or an optionally substituted alkyl group having 1 to 10 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, aryl group having 6 to 16 carbon atoms, or aralkyl group having 7 to 16 carbon atoms. or an alkanoyl group having 2 to 16 carbon atoms, may contain a heteroatom, and may form a ring structure with R 1 and R 2 .
• R 1 and R 2 are the above groups other than H, they may be the same or different (R 1 and R 2 are not the same when they are H (R 1 and R 2 are not H at the same time )).
• M represents H (hydrogen atom) or a metal atom.
• examples of the alkyl group having 1 to 10 carbon atoms include a methyl group.
• the cycloalkyl group having 3 to 10 carbon atoms includes cyclopropyl group and the like.
• examples of the aryl group having 6 to 16 carbon atoms include a phenyl group and a naphthyl group.
• Examples of the aralkyl group having 7 to 16 carbon atoms include a benzyl group and a phenethyl group.
• the alkanoyl group having 2 to 16 carbon atoms includes benzoyl group and the like.
• These may be groups containing heteroatoms (nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, etc.).
• groups containing heteroatoms include groups in which some of the carbon atoms are substituted with heteroatoms, thiocycloalkyl groups (groups corresponding to thiocycloalkanes such as thiepane, thiocane, thietane, thiane, and dithiane).
• substituents for these groups include, but are not particularly limited to, hydroxyl groups, halogen atoms, amino groups, carboxyl groups, alkoxy groups, acyl groups, and the like. These may be substituted singly or in combination of two or more.
• metal atoms examples include alkali metal atoms such as lithium, sodium, and potassium; alkaline earth metal atoms such as magnesium, calcium, and barium; and aluminum.
• amidosulfuric acid derivatives and salts thereof [N-substituted amidosulfuric acid and salts thereof (or compounds represented by the formula (2))] include N-hydroxyamidosulfuric acid; N-mono- or dialkylamidosulfuric acid [N - methylamidosulfuric acid, N-ethylamidosulfuric acid, N-(1-methylpropyl)amidosulfuric acid, N-(2-methylbutyl)amidosulfuric acid, N-(2,2-dimethylpropyl)amidosulfuric acid, N,N-diethylamidosulfuric acid, N-(3-hydroxypropyl)amidosulfuric acid, N-methyl-N-(2,3-dihydroxypropyl)amidosulfuric acid, N,N-bis(2-hydroxyethyl)amidosulfuric acid, N-(2,3-dihydroxy Propyl)amidosulfuric acid, N-(3-methoxy-4-methylphenyl
• N-mono- or dialkylamidosulfuric acid [N-benzylamidosulfuric acid, N-( ⁇ -methylphenethyl)amidosulfuric acid, etc.]; N-alkyl-N-arylamidosulfuric acid (N-ethyl-N-phenylamidosulfuric acid, etc.
• N-mono- or diacylamidosulfuric acid [N-benzoylamidosulfuric acid, N-(3-chloroalanyl)amidosulfuric acid, N-(3-chloro-3-methylalanyl)amidosulfuric acid, etc.]; N-thiocycloalkylamidosulfuric acid [ N-(thiepan-4-yl)amidosulfuric acid, N-thiocan-4-ylamidosulfuric acid, thiocan-5-ylamidosulfuric acid, N-thietane-3-ylamidosulfuric acid, N-1,3-dithian-5-ylamidosulfuric acid, N-(thiane-3-yl)amidosulfuric acid, N-(thiolan-3-yl)amidosulfuric acid, etc.]; and salts thereof.
• Amidosulfuric acid derivatives and salts thereof may be used alone, respectively, or two or more of them may be used in combination.
• the salt of the amidosulfuric acid component is not particularly limited.
• it may be a salt that uses amidosulfuric acid or an amidosulfuric acid derivative as either a base or an acid. a salt of an amidosulfuric acid derivative and a base).
• Specific salts include alkali metal salts such as lithium salts, sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts, calcium salts and barium salts; and metal salts such as aluminum salts.
• alkali metal salts are preferred, and lithium salts are more preferred.
• the salt may also be a salt corresponding to the cation of the electrolyte with which it is combined. For example, when a lithium salt is used as the electrolyte, a lithium salt (lithium amidosulfate, etc.) may be used.
• the amidosulfuric acid component preferably contains at least one selected from the group consisting of amidosulfuric acid and its salts (alkali metal salts), amidosulfuric acid derivatives and its salts (alkali metal salts), amidosulfuric acid and alkali metal amidosulfuric acid More preferably, it contains at least one selected from the group consisting of salts (for example, lithium amidosulfate, etc.), and more preferably contains an alkali metal amidosulfate.
• salts for example, lithium amidosulfate, etc.
• the heteroatom-containing alkylsulfonic acid component is not particularly limited, and may be represented by general formula (4): [Chemical 4] R 4 —SO 2 (OM) (4) Compounds represented by and the like.
• R 4 represents an alkyl group having 1 to 6 carbon atoms containing a heteroatom (nitrogen atom, oxygen atom, sulfur atom, etc.). M is the same as above.
• heteroatom-containing alkylsulfonic acid components include isethionic acid (R 4 : C 2 H 4 OH, pKa: 1.4) and 3-hydroxypropanesulfonic acid (R 4 : C 3 H 6 OH, pKa: 1.7), taurine (2-aminoethanesulfonic acid, R 4 : C 2 H 4 NH 2 , pKa: 0.5), 2-mercaptoethanesulfonic acid (R 4 : C 2 H 4 SH, pKa: 1 .5); and salts thereof.
• the heteroatom-containing alkylsulfonic acid components may be used alone or in combination of two or more.
• alkali metal salts are preferred, and lithium salts are more preferred.
• the salt may also be a salt corresponding to the cation of the electrolyte with which it is combined.
• a lithium salt such as lithium heteroatom-containing alkylsulfonate
• a lithium salt such as lithium heteroatom-containing alkylsulfonate
• heteroatom-containing alkylene disulfonic acid component The heteroatom-containing alkylenedisulfonic acid component is not particularly limited and may be represented by general formula (5): [Chemical 5] (MO)SO2 - R5 - SO2(OM) ( 5 ) Compounds represented by and the like.
• R 5 represents a C 1-6 alkylene group containing a heteroatom (nitrogen atom, oxygen atom, sulfur atom, etc.).
• M is the same as above.
• heteroatom-containing alkylenedisulfonic acid component examples include general formula (5a): [Chemical 6] (HO)SO2 - CH2SCH2 - SO2 ( OH) (5a) A compound represented by (pKa: 0.2), general formula (5b): [Chemical 7] (HO)SO2 - CH2OCH2 - SO2 ( OH) (5b) Compound represented by (pKa: 0.2); and salts thereof and the like.
• the heteroatom-containing alkylenedisulfonic acid components may be used alone or in combination of two or more.
• alkali metal salts are preferred, and lithium salts are more preferred.
• the salt may also be a salt corresponding to the cation of the electrolyte with which it is combined.
• a lithium salt such as lithium heteroatom-containing alkylenedisulfonate
• a lithium salt such as lithium heteroatom-containing alkylenedisulfonate
• a sulfinic acid component refers to a compound having a —SO 2 H group, such as general formula (6): [Chemical 8] R6-SO(OM) ( 6 ) Compounds represented by and the like.
• R 6 represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms (halogenated alkyl group) optionally having a halogen atom as a substituent, or an aryl group having 6 to 16 carbon atoms.
• the aryl group having 6 to 16 carbon atoms includes phenyl group, tolyl group, xylyl group, naphthyl group and the like.
• M is the same as above.
• the sulfinic acid component examples include sulfurous acid (R 6 : OH, pKa: 1.9), p-toluenesulfinic acid (R 6 : (CH 3 )C 6 H 3 (p-tolyl group), pKa: 2 .0), trifluoromethanesulfinic acid (R 6 : CF 3 , pKa: 2.1); and salts thereof.
• the sulfinic acid components may be used singly or in combination of two or more.
• the salt may also be a salt corresponding to the cation of the electrolyte with which it is combined.
• a lithium salt lithium sulfinate, etc.
• a lithium salt lithium sulfinate, etc.
• Carboxylic acids and salts thereof represented by the acetic acid component may be compounds represented by the general formula (3).
• R 3 is H (hydrogen atom), optionally substituted alkyl group having 1 to 10 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, 6 to 16 carbon atoms represents an aryl group, an aralkyl group having 7 to 16 carbon atoms, or an alkanoyl group having 2 to 16 carbon atoms, which may contain a heteroatom.
• M is the same as above.
• examples of the alkyl group having 1 to 10 carbon atoms include a methyl group.
• the cycloalkyl group having 3 to 10 carbon atoms includes cyclopropyl group and the like.
• examples of the aryl group having 6 to 16 carbon atoms include a phenyl group and a naphthyl group.
• Examples of the aralkyl group having 7 to 16 carbon atoms include a benzyl group and a phenethyl group.
• the alkanoyl group having 2 to 16 carbon atoms includes benzoyl group and the like.
• These may be groups containing heteroatoms (nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, etc.).
• groups containing heteroatoms include groups in which some of the carbon atoms are substituted with heteroatoms, thiocycloalkyl groups (groups corresponding to thiocycloalkanes such as thiepane, thiocane, thietane, thiane, and dithiane).
• substituents for these groups include, but are not particularly limited to, hydroxyl groups, halogen atoms, amino groups, carboxyl groups, alkoxy groups, acyl groups, and the like. These may be substituted singly or in combination of two or more.
• carboxylic acids and salts thereof include saturated fatty acids (formic acid, acetic acid, propionic acid, butyric acid, etc.), unsaturated fatty acids (linolenic acid, linoleic acid, olein acid, etc.), hydroxy acids (lactic acid, citric acid, salicylic acid, etc.), dicarboxylic acids (oxalic acid, tartaric acid, phthalic acid, itaconic acid, maleic acid, etc.), amino acids (glycine, alanine, etc.), and salts thereof. be done. More specifically, alkyl monocarboxylic acids and salts thereof include acetic acid, trifluoroacetic acid; and salts thereof.
• Alkyldicarboxylic acids and salts thereof include malonic acid, maleic acid, succinic acid; and salts thereof.
• aromatic carboxylic acids and salts thereof include benzoic acid, salicylic acid; and salts thereof.
• aromatic dicarboxylic acids and salts thereof include phthalic acid, maleic acid; and salts thereof.
• Carboxylic acid and its salt may be used independently, respectively, and may use two or more types together.
• Specific salts include alkali metal salts (lithium salts, sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, calcium salts, barium salts, etc.), aluminum salts, and the like. Among these, alkali metal salts are preferred, and lithium salts are more preferred.
• the salt may also be a salt corresponding to the cation of the electrolyte with which it is combined. For example, when using a lithium salt as the electrolyte, a lithium salt (such as lithium acetate) may be used.
• the carbonic acid component is not particularly limited, and examples thereof include carbonates, hydrogen carbonates, and the like. Carbonic acid components may be used alone or in combination of two or more.
• Specific salts include alkali metal salts (lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, etc.), alkaline earth metal salts (beryllium salts, magnesium salts, calcium salts, strontium salts, barium salts, etc.). etc. Among these, alkali metal salts are preferred, and lithium salts are more preferred.
• the salt may also be a salt corresponding to the cation of the electrolyte with which it is combined. For example, when using a lithium salt as the electrolyte, a lithium salt (such as lithium carbonate) may be used.
• the phosphoric acid component is not particularly limited, and includes various phosphates such as phosphates, hydrogen phosphates and dihydrogen phosphates; phosphate ester components and the like. Each phosphoric acid component may be used alone, or two or more of them may be used in combination.
• Specific salts include alkali metal salts (lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, etc.), alkaline earth metal salts (beryllium salts, magnesium salts, calcium salts, strontium salts, barium salts, etc.). etc. Among these, alkali metal salts are preferred, and lithium salts are more preferred.
• the salt may also be a salt corresponding to the cation of the electrolyte with which it is combined. For example, when using a lithium salt as the electrolyte, a lithium salt (such as lithium phosphate) may be used.
• the phosphate ester component is not particularly limited, and general formula (7): [Chemical 10] R 7 O-PO(OM) 2 (7)
• Examples include a phosphate diester component represented by the above.
• R 7 is an alkyl group having 1 to 6 carbon atoms (halogenated alkyl group) optionally having a halogen atom as a substituent or an aryl group having 6 to 16 carbon atoms. show.
• the aryl group having 6 to 16 carbon atoms includes phenyl group, tolyl group, xylyl group, naphthyl group and the like.
• two R 7 may form a ring structure.
• M is the same as above.
• two Ms may be the same (both are H (hydrogen atom) or metal atom) or may be different.
• phosphoric acid monoester component examples include monomethyl phosphate (R 7 : methyl group, pKa: 1.8); and salts thereof.
• phosphate diester component examples include formula (8a): [Chemical 12] (CF 3 O) 2 -PO(OH) (8a) A compound represented by (R 7 : CF 3 , pKa: 0.6), formula (8b):
• the phosphate ester component may be used alone or in combination of two or more.
• the salt may also be a salt corresponding to the cation of the electrolyte with which it is combined.
• a lithium salt lithium phosphate, etc.
• a lithium salt lithium phosphate, etc.
• R 8 is an alkyl group having 1 to 6 carbon atoms (halogenated alkyl group) optionally having a halogen atom as a substituent, an aryl group having 6 to 16 carbon atoms, a halogen atom or hydrogen. represents an atom.
• the aryl group having 6 to 16 carbon atoms includes phenyl group, tolyl group, xylyl group, naphthyl group and the like.
• M is the same as above. Two M may be the same (both are H (hydrogen atom) or metal atom) or may be different.
• the phosphonic acid component examples include methylphosphonic acid (R 8 : methyl group, pKa: 2.4), trifluoromethanephosphonic acid (R 8 : CF 3 , pKa: 1.2), phosphorous acid/ phosphite, R 8 : H, pKa: 1.3); and salts thereof.
• alkali metal salts are preferred, and lithium salts are more preferred.
• the salt may also be a salt corresponding to the cation of the electrolyte with which it is combined.
• a lithium salt such as lithium phosphonate
• Each of the phosphonic acid components may be used alone, or two or more of them may be used in combination.
• the salt may also be a salt corresponding to the cation of the electrolyte with which it is combined.
• a lithium salt such as lithium phosphonate
• a lithium salt such as lithium phosphonate
• a sulfonic acid component, a carbonic acid component and a phosphoric acid component are preferable from the viewpoint of improving the thermal stability of the hydrous sulfonylimide solution for dehydration and improving the dehydration efficiency. More preferred.
• the sulfonic acid components amidosulfuric acid components and heteroatom-containing alkyl sulfonic acid components are preferred.
• a combination of a sulfonic acid component (an amidosulfuric acid component or a heteroatom-containing alkylsulfonic acid component) and a carbonic acid component is preferred, and a combination of an amidosulfuric acid component and a carbonic acid component is more preferred.
• the added amount of the added anion component (specific acid component) (the total added amount when two or more types are used together) is determined by the thermal stability of the hydrous sulfonylimide solution for dehydration with respect to the electrolyte (sulfonylimide compound (1)). It is preferably 1000 ppm by mass or more, more preferably 2000 ppm by mass or more, and still more preferably 4000 ppm by mass or more, from the viewpoint of improving dehydration efficiency by improving properties.
• the upper limit of the amount added is preferably 30000 mass ppm or less, more preferably 25000 mass ppm or less, and even more preferably 10000 mass ppm or less.
• the addition amount of the additional anion component refers to the addition amount of the anion component intentionally added to the hydrous sulfonylimide solution in the dehydration step. That is, the dehydration step includes a step of adding (to the hydrous sulfonylimide solution or the hydrous sulfonylimide solution for dehydration) the added anion component at the above concentration (for example, a concentration of 1000 ppm by mass or more relative to the electrolyte). good too.
• the anion component (specific acid component) concentration in the hydrated sulfonylimide solution for dehydration is preferably 4000 ppm by mass or more, more preferably 4000 ppm by mass or more, relative to the electrolyte. is 5000 mass ppm or more, more preferably 8000 mass ppm or more, still more preferably 10000 mass ppm or more, still more preferably 20000 mass ppm or more.
• the concentration of the anion component is not the amount of the anion component added in the dehydration step, but the amount of the anion component present (the content of the anion component contained in the hydrous sulfonylimide solution for dehydration).
• the above addition amount may be a ratio in terms of a non-salt form (or free form, such as acid or acid derivative).
• the salts of the acids and derivatives thereof described above may be commercially available products or manufactured products.
• the method for dehydrating the hydrous sulfonylimide solution is not particularly limited.
• a hydrous sulfonylimide solution for dehydration which is obtained by adding a non-aqueous solvent and an anion component to the hydrous sulfonylimide solution, is distilled by a distillation method such as simple distillation, flash distillation, or continuous distillation. A dehydration method and the like can be mentioned.
• the same amount of the non-aqueous solvent as the distillate to be removed is continuously added.
• the distillate may be phase separated to remove the aqueous phase while the organic phase (the phase containing the non-aqueous solvent) is allowed to reflux.
• the reflux liquid may be returned to the fractionating tube (distillation column, column, etc.) or to the distillation bottoms containing the hydrous sulfonylimide solution for dehydration.
• the reflux liquid may be subjected to a separate dehydration operation and then returned to the distillation apparatus (either the fractionating tube or the distillation bottom liquid may be used).
• the dehydration operation includes the use of dehydrating agents such as molecular sieves.
• the temperature at which the distillate is phase-separated is not particularly limited, and may be appropriately adjusted depending on the non-aqueous solvent used. °C, more preferably 10°C to 40°C.
• the positional relationship between the organic phase to be refluxed and the aqueous phase to be removed may change depending on the type of non-aqueous solvent used. For example, when butyl acetate is used as the non-aqueous solvent, the organic phase is positioned at the top, and when dimethyl carbonate is used, the organic phase is positioned at the bottom.
• the distillation apparatus may be appropriately selected.
• the waste water phase removed to the outside of the system contains not a little non-aqueous solvent.
• the production method of the present disclosure may include a recovery step of recovering the non-aqueous solvent from the discarded aqueous phase after the dehydration step.
• a method for recovering the non-aqueous solvent from the waste water phase is not particularly limited, and an example thereof includes a method of distilling the waste water phase.
• the hydrous sulfonylimide solution for dehydration is dehydrated to obtain a composition containing the added non-aqueous solvent and the anion component.
• the dehydration step can be said to be a step of replacing the water in the hydrous sulfonylimide solution with a non-aqueous solvent.
• the dehydration step can be carried out under normal pressure or under reduced pressure (the dehydration step may be carried out under a combination of normal pressure and reduced pressure), but from the viewpoint of suppressing decomposition of the sulfonylimide compound (1) due to heat. Therefore, it is preferable to carry out the reaction under reduced pressure (dehydration under reduced pressure).
• the degree of pressure reduction is not particularly limited and may be adjusted appropriately according to the concentration of the sulfonylimide compound (1), the type and amount of the non-aqueous solvent, etc. For example, it is preferably 200 kPa or less, more preferably 40 kPa or less, and still more preferably 15 kPa. Below, it is particularly preferably 10 kPa or less. Moreover, the lower limit of the degree of pressure reduction is more than 5 kPa.
• the degree of pressure reduction in the dehydration process may be constant during the dehydration process, or may be changed within the above range.
• the heating temperature in the dehydration step may be adjusted as appropriate according to the degree of pressure reduction, the type and amount of the non-aqueous solvent, and is not particularly limited, but from the viewpoint of improving the dehydration efficiency, For example, it is preferably 20 to 110°C, more preferably 30 to 100°C.
• the hydrous sulfonylimide solution for dehydration has improved thermal stability due to the addition of an anion component.
• the hydrolysis of 1) is suppressed. That is, in order to improve the dehydration efficiency, the lower limit of the heating temperature may be set to 50° C. or higher.
• the heating temperature in the dehydration process may be constant during the dehydration process, or may be changed within the above range.
• the temperature may be gradually increased within the above range.
• the heating method is not particularly limited, and for example, by raising the oil bath temperature while a container such as a flask containing the hydrous sulfonylimide solution for dehydration is immersed in the oil bath, the internal temperature of the container (heating temperature equivalent) is raised.
• the temperature difference ( ⁇ t) between the flask internal temperature and the oil bath temperature during the dehydration operation is preferably 5 to 40°C, more preferably 10 to 40°C. , more preferably from 20 to 40°C, and even more preferably from 30 to 40°C.
• the treatment time in the dehydration step is not particularly limited and may be appropriately adjusted according to the degree of pressure reduction, heating temperature, type and amount of non-aqueous solvent, etc. For example, it is preferably 1 to 40 hours, more preferably 2 to 35 hours. hours, more preferably 5 to 30 hours.
• the device for decompression and/or heating used in the dehydration process may be appropriately selected according to the amount of solution, degree of decompression, heating temperature, and the like.
• a tank reactor, a pressure-reduced tank reactor, and the like can be mentioned.
• the dehydration efficiency in the dehydration step is specified by the dehydration efficiency obtained by the method for quantifying the dehydration efficiency described later and the method described in Examples in the method for producing a composition according to the present embodiment.
• the dehydration efficiency in the dehydration step is preferably 80 or less, more preferably 60 or less, still more preferably 50 or less, and even more preferably 30 or less.
• the total amount of non-aqueous solvent required to reach the target water content of the composition for example, 50 mass ppm or less
• total weight for quantification.
• the “total amount of non-aqueous solvent” in the formula (1) refers to the total amount of non-aqueous solvent (addition solvent) added to the hydrous sulfonylimide solution in the dehydration step.
• total amount of non-aqueous solvent may be the total amount of solvent added to the system for simple distillation, and the total amount of vapor evaporated from the reactor/still can (distillation device) for continuous distillation (hereinafter referred to as “total rise (also called steam volume).
• total rise also called steam volume.
• the method for producing the composition may contain other steps as long as the object of the present invention is not impaired. Other steps include filtration, column purification, activated carbon treatment, molecular sieve treatment, etc., in addition to the recovery step described above.
• a hydrous sulfonylimide solution containing the sulfonylimide compound (1) and water and/or a non-aqueous solvent (electrolyte solvent) is prepared, and the solution is A composition containing the sulfonylimide compound (1) as an electrolyte, a non-aqueous solvent and an anion component through a step (operation) of dehydrating a hydrous sulfonylimide solution for dehydration by adding an anion component and, if necessary, a non-aqueous solvent to you get something.
• the hydrous sulfonylimide solution for dehydration has high thermal stability due to the addition of an anion component, the dehydration operation can be performed at a relatively high temperature (for example, 50° C. or higher), resulting in excellent dehydration efficiency and productivity. also improve.
• the resulting composition not only has a sufficiently low moisture content, but also has excellent thermal stability.
• composition (Electrolytes)
• the content of the sulfonylimide compound (1) in the composition (relative to the total amount of 100% by mass of the components contained in the composition) (the total content when two or more are used in combination) makes the composition suitable for a wide range of electrolytic solution compositions. From the viewpoint of application, it is preferably 30% by mass or more, more preferably 35% by mass or more.
• the upper limit of the content is preferably 60% by mass or less, more preferably 55% by mass or less, from the viewpoint of improving the storage stability of the composition even at high temperatures.
• the composition may contain the sulfonylimide compound (1), but may contain other electrolytes (electrolytes other than the sulfonylimide compound (1)).
• Other electrolytes may be mixed with the composition, or may be mixed with the hydrous sulfonylimide solution and/or the hydrous sulfonylimide solution for dehydration in the manufacturing process of the composition.
• Other electrolytes include imide salts, non-imide salts, and the like.
• Examples of the imide salt include fluorine-containing sulfonylimide salts different from the sulfonylimide compound (1) (hereinafter referred to as "another sulfonylimide compound").
• Other sulfonylimide compounds include lithium bis(trifluoromethylsulfonyl)imide (LiN(CF 3 SO 2 ) 2 , hereinafter also referred to as “LiTFSI”); lithium bis(pentafluoroethylsulfonyl)imide; lithium bis(heptafluoro propylsulfonyl)imide; non-lithium salts of fluorine-containing sulfonylimides listed as sulfonylimide compound (1) (for example, salts in which lithium (ion) is substituted with a cation other than lithium ion in sulfonylimide compound (1)), etc.
• Salts substituted with cations other than lithium ions include alkali metal salts such as sodium salts, potassium salts, rubidium salts and cesium salts; alkaline earth metal salts such as beryllium salts, magnesium salts, calcium salts, strontium salts and barium salts. aluminum salts; ammonium salts; phosphonium salts and the like.
• alkali metal salts such as sodium salts, potassium salts, rubidium salts and cesium salts
• alkaline earth metal salts such as beryllium salts, magnesium salts, calcium salts, strontium salts and barium salts.
• aluminum salts such as ammonium salts; phosphonium salts and the like.
• Other sulfonylimide compounds may be used alone, respectively, or two or more of them may be used in combination.
• other sulfonylimide compounds may be commercially available products, or may be synthesized by conventionally known methods.
• Non-imide salts include salts of non-imide anions and cations (lithium ions and cations exemplified above).
• Examples of non-imide salts include fluorophosphorus salts such as LiPF 6 , LiPF 3 (CF 3 ) 3 , LiPF 3 (C 2 F 5 ) 3 , LiPF 3 (C 3 F 7 ) 3 and LiPF 3 (C 4 F 9 ) 3 .
• Acid compounds Fluoroboric acid compounds such as LiBF4 , LiBF( CF3 ) 3 , LiBF( C2F5 ) 3 , LiBF( C3F7 ) 3 , lithium hexafluoroarsenate ( LiAsF6 ), LiSbF6 , LiClO 4 , LiSCN, LiAlF4 , CF3SO3Li , LiC[(CF3SO2)3 ] , LiN ( NO2), LiN[(CN) 2 ;
• salts include salts in which lithium (ions) are substituted with the above-exemplified cations (e.g., NaBF 4 , NaPF 6 , NaPF 3 (CF 3 ) 3 , etc.)
• Non-imide salts may be used alone. Alternatively, two or more types may be used in combination.
• the non-imide salt may be a commercially available product or one synthesized by a conventionally known method.
• electrolytes sulfonylimide compound (1), other electrolytes, etc.
• electrolytes may exist (contain) in the form of ions in the composition.
• the non-aqueous solvent preferably contains a carbonate solvent, more preferably contains a chain carbonate solvent, and particularly preferably consists of only a chain carbonate solvent.
• the ratio of the carbonate-based solvent (preferably chain carbonate-based solvent) to the total non-aqueous solvent is not particularly limited, and is 10% by volume or more, 20% by volume or more, 30% by volume or more, 40% by volume or more, 50% by volume or more. , 60% by volume or more, 70% by volume or more, 80% by volume or more, 90% by volume or more, 95% by volume or more, 99% by volume or more, or 100% by volume (substantially only carbonate solvent (preferably substantially Only a chain carbonate-based solvent)) may be used.
• the concentration of the anion component (specific acid component) is 10000 mass ppm (1 mass%) or less with respect to the electrolyte (sulfonylimide compound (1)).
• the concentration of the anion component (specific acid component) relative to the electrolyte (sulfonylimide compound (1)) is preferably 50 ppm by mass or more from the viewpoint of improving the storage stability of the composition even at high temperatures. , more preferably 60 mass ppm or more.
• the upper limit of the concentration is 10000 mass ppm or less, preferably 8000 mass ppm or less, more preferably 6000 mass ppm or less, still more preferably 4000 mass ppm or less, and even more preferably 2000 mass ppm or less.
• the concentration of the specific acid component is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and even more preferably 400 mass ppm or less.
• the above concentration may be a ratio in terms of non-salt form (or free form, such as acid or acid derivative).
• the composition may contain additives for the purpose of improving various characteristics of the lithium ion secondary battery.
• the additive may be added to the composition, or may be added to the hydrous sulfonylimide solution and/or the hydrous sulfonylimide solution for dehydration in the production process of the composition.
• Additives include succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, diglycolic anhydride, cyclohexanedicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phenyl Carboxylic anhydride such as succinic anhydride; ethylene sulfite, 1,3-propanesultone, 1,4-butanesultone, methyl methanesulfonate, busulfan, sulfolane, sulfolene, dimethylsulfone, tetramethylthiuram monosulfide, trimethylene sulfur-containing compounds such as glycol sulfate; 1-methyl-2-pyrrolidinone, 1-methyl-2-piperidone, 3-methyl-2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone, N-methylsuccinimide, etc
• saturated hydrocarbon compounds such as heptane, octane, and cycloheptane
• carbonate compounds such as vinylene carbonate, fluoroethylene carbonate (FEC), trifluoropropylene carbonate, phenylethylene carbonate and erythritan carbonate; , H 3 NSO 3
• sulfamate alkali metal salts such as lithium salt, sodium salt, potassium salt; alkaline earth metal salts such as calcium salt, strontium salt, barium salt; manganese salt, copper salt, zinc salt, other metal salts such as iron salts , cobalt salts , nickel salts; ammonium salts; guanidine salts , etc.
• fluorosulfonic acid compounds such as magnesium fluorosulfonate (Mg(FSO3)2 )
• fluorophosphate compounds such as lithium monofluorophosphate ( Li2PO3F ) and lithium difluorophosphate ( LiPO2F2 ); lithium Bis
• the moisture content (water concentration, water content) of the composition is preferably 10000 ppm by mass or less, more preferably 3000 ppm by mass, 1000 ppm by mass, 900 ppm by mass, 800 mass ppm, 700 mass ppm, 600 mass ppm, 500 mass ppm, 400 mass ppm, 300 mass ppm, 200 mass ppm, 100 mass ppm and 50 mass ppm.
• the water content of the composition is preferably as low as possible, may be below the detection limit, and may be substantially free of water (0 mass ppm).
• the water concentration can be measured by the method described in Examples below, for example, using a Karl Fischer moisture analyzer.
• the composition contains water content of 0.1 mass ppm or more, 0.3 mass ppm or more, 0.5 mass ppm or more, 0.7 mass ppm or more, 0.8 mass ppm or more, 1 mass ppm or more, 1 It may be contained at a concentration of 5 mass ppm or more, 2 mass ppm or more, 3 mass ppm or more, 5 mass ppm or more, 7 mass ppm or more, or 10 mass ppm or more.
• Each concentration of anionic impurities such as fluoride ion (F ⁇ ), chloride ion (Cl ⁇ ), sulfate ion (SO 4 2 ⁇ ), FSO 3 ⁇ (fluorosulfonate ion), etc.
• F ⁇ fluoride ion
• Cl ⁇ chloride ion
• SO 4 2 ⁇ sulfate ion
• FSO 3 ⁇ fluorosulfonate ion
• it is preferably 300 mass ppm or less, more preferably 200 mass ppm or less, even more preferably 100 mass ppm or less, still more preferably 80 mass ppm or less, and even more preferably 60 mass ppm. Below, particularly preferably, it is 40 mass ppm or less.
• Each concentration of anionic impurities is preferably as low as possible, may be below the detection limit, and may be substantially free of anionic impurities (0 mass ppm).
• the concentration of anionic impurities can be measured by the methods described in Examples below, such as ion chromatography and NMR.
• the composition configured as described above is a solution (liquid) composition because it contains the electrolyte, solvent, and anion component described above.
• the liquid composition may be used as a non-aqueous electrolyte or as a raw material for a non-aqueous electrolyte (electrolyte solution, electrolyte material).
• the non-aqueous electrolytic solution according to this embodiment includes the composition (liquid composition) obtained by the manufacturing method according to this embodiment described above. That is, the non-aqueous electrolyte is prepared using the composition.
• the composition may be used as it is, or the composition may be diluted by mixing the above-described non-aqueous solvent (electrolyte solvent).
• electrolyte solvents include carbonate-based solvents and other non-aqueous solvents.
• the solvent mixed with the composition may be the same solvent as the solvent constituting the composition, or may be a different solvent.
• the non-aqueous electrolytic solution may contain only the composition (consisting of only the composition), and if necessary, the composition may contain the above-described electrolyte or solvent, and the above-described additives as long as they are not harmful. It may further contain.
• all the items described in the manufacturing method and the obtained composition described above also apply to the non-aqueous electrolyte.
• LiFSI LiFSI aqueous solution
• LiFSI/H 2 O lithium bis(fluorosulfonyl)imide
• the quantitative lower limits are, for example, F ⁇ , Cl ⁇ , SO 4 2 ⁇ : 5 mass ppm, H 2 NSO 3 Li: 10 mass ppm. These lower limits of determination are the concentration in the solution, not the standard concentration of the electrolyte.
• the LiFSI concentration in the LiFSI aqueous solution was measured by 19 F-NMR.
• 19 F-NMR measurement was performed using "Unity Plus-400" manufactured by Varian (internal standard substance: trifluorotoluene, number of integrations: 64 times).
• the hydrous LiFSI solution is diluted 100 times with ultrapure water (over 18.2 ⁇ cm) to obtain a measurement solution, and an ion chromatography system ICS-3000 (manufactured by Nippon Dionex Co., Ltd.) is used to measure the content in the hydrous LiFSI solution.
• concentrations of H 2 NSO 3 Li (anion component), anionic impurities (F ⁇ , Cl ⁇ , SO 4 2 ⁇ , FSO 3 ⁇ etc.) and other impurities (FSO 2 NH 2 etc.) were measured.
• the measurement conditions are as follows.
• Example 1 In a dry room (dew point: ⁇ 40° C.), a 2-liter three-necked flask equipped with a thermometer for measuring the internal temperature, a solvent inlet, and a distillation column (filler: Sulzer EX, manufactured by Sulzer Japan Co., Ltd.; the same shall apply hereinafter).
• LiFSI aqueous solution LiFSI/H 2 O obtained in Synthesis Example 1 (preparation step) obtained in Synthesis Example 1 (preparation step)
• 678 g of DMC and 1.2 g of lithium carbonate as an anion component (2691 mass ppm per electrolyte) and 0.8 g of lithium amide sulfate (electrolyte 1792 mass ppm per unit) was added to prepare a hydrous LiFSI/DMC solution containing 28% by mass of LiFSI (a hydrous sulfonylimide solution for dehydration).
• a cooling pipe for condensing volatilized vapor is provided at the top of the distillation column.
• a Dean-Stark apparatus is provided as a phase separation tank for oil-water separation of the condensed liquid.
• the flask is immersed in an oil bath, and the temperature inside the flask is heated to 32° C. in the oil bath to azeotropically distill water together with DMC. rice field.
• the distillate gas passed through a distillation column, was condensed in a condenser (2° C.), and was phase-separated into an aqueous phase and a DMC phase in a Dean Stark chamber as a distillate.
• the aqueous phase was removed out of the system, and the DMC phase was returned to the top of the distillation column using a reflux pump and refluxed.
• Example 2 It was dehydrated and replaced with DMC under the same conditions as in Example 1, except that ⁇ t was changed from 15 to 20°C (dehydration step). The resulting suspension was filtered through a membrane filter to obtain a colorless and transparent LiFSI/DMC solution. The results of measuring the solution composition of the LiFSI/DMC solution and the concentration of anionic impurities in the electrolyte in the same manner as described above are shown below.
• Example 3 In a dry room (dew point: ⁇ 40° C.), 699 g of the LiFSI aqueous solution (LiFSI/H 2 O) obtained in Synthesis Example 1 (preparation step), 712 g of EMC, and lithium carbonate as an anion component were placed in the same apparatus as in Example 1. 1.2 g (3368 mass ppm per electrolyte) and 0.6 g lithium amidosulfate (1757 mass ppm per electrolyte) were added to prepare an EMC solution of hydrated LiFSI containing 25% by mass of LiFSI (hydrous sulfonylimide solution for dehydration). .
• the flask is immersed in an oil bath, and the temperature inside the flask is heated to 33° C. in the oil bath to azeotropically distill water together with EMC. rice field.
• the distillate gas passed through a distillation column, was condensed in a condenser (2° C.), and was phase-separated into a water phase and an EMC phase in a Dean Stark chamber as a distillate. Among them, the water phase was removed out of the system, and the EMC phase was returned to the top of the distillation column using a reflux pump and refluxed.
• Vacuum distillation (continuous distillation) was carried out for a total of 30 hours while gradually raising the temperature of the oil bath, thereby dehydrating and replacing with EMC.
• the internal temperature of the flask varied between 33°C and 64°C, and ⁇ t varied between 15 and 30°C.
• the above dehydration operation was defined as a dehydration step.
• the resulting suspension was filtered through a membrane filter to obtain a colorless and transparent LiFSI/EMC solution.
• the results of measuring the solution composition of the LiFSI/EMC solution and the concentration of anionic impurities in the electrolyte in the same manner as described above are shown below.
• Example 4 It was dehydrated and replaced with EMC under the same conditions as in Example 3, except that ⁇ t was changed from 15 to 20°C (dehydration step). The resulting suspension was filtered through a membrane filter to obtain a colorless and transparent LiFSI/EMC solution. The results of measuring the solution composition of the LiFSI/EMC solution and the concentration of anionic impurities in the electrolyte in the same manner as described above are shown below.
• Example 5 In a dry room (dew point: ⁇ 40° C.), 812 g of the LiFSI aqueous solution (LiFSI/H 2 O) obtained in Synthesis Example 2 (preparation step), 665 g of DMC and 15 of lithium carbonate as an anion component were placed in the same apparatus as in Example 1. 0 g (23383 mass ppm per electrolyte) was added to prepare a hydrous LiFSI/DMC solution containing 44 wt % LiFSI (a hydrous sulfonylimide solution for dehydration).
• the pressure in the flask was reduced to 8.5 kPa using a vacuum pump, the flask was immersed in an oil bath, and the temperature inside the flask was heated to 52 ° C. in the oil bath. operation was performed. While gradually raising the temperature of the oil bath, vacuum distillation (continuous distillation) was carried out for a total of 25 hours to dehydrate and replace with DMC. During the dehydration, the temperature inside the flask varied between 52°C and 84°C, and ⁇ t varied between 7 and 20°C. The above dehydration operation was defined as a dehydration step. The resulting suspension was filtered through a membrane filter to obtain a colorless and transparent LiFSI/DMC solution.
• Example 6 In a dry room (dew point: ⁇ 40° C.), 1263 g of the LiFSI aqueous solution (LiFSI/H 2 O) obtained in Synthesis Example 2 (preparation step), 1994 g of EMC, and 4 lithium carbonate as an anion component were placed in the same apparatus as in Example 1. .1 g (4108 wt ppm per electrolyte) was added to prepare a hydrous LiFSI/EMC solution containing 31 wt % LiFSI (a hydrous sulfonylimide solution for dehydration).
• Example 2 the pressure in the flask was reduced to 8 kPa using a vacuum pump, the flask was immersed in an oil bath, and the same operation as in Example 1 was performed except that the temperature inside the flask was heated to 71 ° C. in the oil bath. did Vacuum distillation (continuous distillation) was performed for a total of 15 hours while gradually raising the temperature of the oil bath to dehydrate and replace with EMC. During dehydration, the internal temperature of the flask varied between 49°C and 59°C, and ⁇ t varied between 22 and 31°C. The above dehydration operation was defined as a dehydration step. The resulting suspension was filtered through a membrane filter to obtain a colorless and transparent LiFSI/EMC solution.
• Example 7 In a dry room (dew point: ⁇ 40° C.), 1477 g of the hydrous LiFSI/EMC solution obtained in Synthesis Example 4 (preparation step) and 15.0 g of lithium carbonate as an anion component (25647 g per electrolyte) were placed in the same apparatus as in Example 1. mass ppm) was added to prepare a hydrous LiFSI/EMC solution containing 40% by mass of LiFSI (a hydrous sulfonylimide solution for dehydration).
• the pressure in the flask was reduced to 5.5 kPa using a vacuum pump, the flask was immersed in an oil bath, and the temperature inside the flask was heated to 58 ° C. in the oil bath. operation was performed. While gradually raising the temperature of the oil bath, vacuum distillation (continuous distillation) was performed for a total of 7 hours to dehydrate and replace with EMC. During dehydration, the internal temperature of the flask varied between 57°C and 64°C, and ⁇ t varied between 5 and 25°C. The above dehydration operation was defined as a dehydration step. The resulting suspension was filtered through a membrane filter to obtain a colorless and transparent LiFSI/EMC solution.
• Example 8> In a dry room (dew point: -40 ° C.), 51 g of the LiFSI aqueous solution obtained in Synthesis Example 5 (FSI concentration: 70 wt%, anion component content: 5822 ppm), 212 g of EMC, and lithium phosphate as an anion component were added to a 500 mL eggplant flask. 1.1 g (manufactured by Sigma-Aldrich, amount of anion component added during process (per electrolyte): 14233 ppm) was added to prepare a hydrous LiFSI/EMC solution containing 14% by mass of LiFSI (a hydrous sulfonylimide solution for dehydration).
• Example 9 In a dry room (dew point: -40 ° C.), 50 g of the LiFSI aqueous solution obtained in Synthesis Example 5 (FSI concentration: 70 wt%, anion component content: 5822 ppm) in a 500 mL eggplant flask, EMC 230 g, and lithium carbonate 0 as an anion component .52 g (addition amount of anion component during process (per electrolyte): 14733 ppm) and 0.63 g of 70% by mass isethionic acid aqueous solution (manufactured by Fuji Film Wako Pure Chemical, amount of anion component addition during process (per electrolyte): 12495 ppm)
• a hydrous LiFSI/EMC solution a hydrous sulfonylimide solution for dehydration
• the flask was immersed in an oil bath and heated to 25° C. (oil bath temperature: 60° C.) in the oil bath. Water was azeotropically distilled with DMC. After 20 minutes, the flask was depressurized and non-aqueous DMC (water content ⁇ 30 ppm by mass) was added, followed by distillation under reduced pressure again. This operation was repeated, and a cumulative total of 606.0 g of DMC was added.
• a part of the obtained solution was filtered with a membrane filter to obtain a colorless and transparent LiFSI/DMC solution containing 56% by mass of LiFSI.
• the water content of the LiFSI/EMC solution was measured in the same manner as described above, the water content was 115 mass ppm.
• Table 1 shows the number of times DMC was added, the total amount of DMC (additional total amount) at each time, the water content of the solution at each time, and the dehydration efficiency at each time.
• the dehydration efficiency in each time was calculated
• the dehydration efficiency means that the smaller the value, the higher the efficiency of dehydration and replacement with DMC.
• Dehydration efficiency "total amount of DMC required to reach the water content at each time” / "weight of LiFSI" (2)
• the flask was immersed in an oil bath and heated to 25° C. (oil bath temperature: 50° C.) in the oil bath. azeotropically distilled water with EMC.
• the distillate gas passed through a distillation column, was condensed in a condenser (2° C.), and was phase-separated into a water phase and an EMC phase in a Dean Stark chamber as a distillate. Among them, the water phase was removed out of the system, and the EMC phase was returned to the top of the distillation column using a reflux pump and refluxed. After 4.5 hours, the flask internal temperature reached 35 ° C.
• the LiFSI/EMC solution obtained above was concentrated at a pressure of 2.5 KPa and an oil bath temperature of 50°C. The resulting solution was filtered through a membrane filter to obtain 263.3 g of a colorless and transparent LiFSI/EMC solution.
• the solution composition of the concentrated LiFSI/EMC solution and the concentration of anionic impurities in the electrolyte were measured in the same manner as described above, and the results are shown below.
• Table 2 shows the type of solvent, the type and amount of anion component added, and the dehydration efficiency of each LiFSI solution (composition) obtained through the adjustment process and the dehydration process.
• the amount of anion component added during the dehydration process per electrolyte is the weight of the anion component added to the hydrous LiFSI solution when preparing the hydrous sulfonylimide solution for dehydration before dehydration (a plurality of anion components is added, the sum of these weights).
• the anion component content during the dehydration process per electrolyte is a calculated value based on the total amount of the anion component content in the raw material of the hydrous LiFSI solution and the above anion component addition amount.
• the dehydration efficiency was determined by the following formula (3).
• the dehydration efficiency means that the smaller the value, the higher the efficiency of dehydration and replacement with a non-aqueous solvent.
• [Number 3] Dehydration efficiency "Total amount of added solvent or total amount of rising steam required for water content to reach 50 ppm by mass”/"Weight of LiFSI" (3)
• the total amount of the non-aqueous solvent in Comparative Example 1 is the amount required for the water content to reach 115 ppm by mass.
• the anion component in the production method of each example, in the dehydration step, is contained at a concentration of 4000 ppm by mass or more with respect to LiFSI (electrolyte) (the total concentration when two or more types are used together). It can be said that the dehydration efficiency is high.
• the set pressure degree of pressure reduction
• the heating temperature can be set relatively high (for example, 50 ° C. or higher), so not only the dehydration efficiency , the production efficiency (productivity) of the composition is also excellent.
• the present disclosure is suitable for non-aqueous electrolytes used in lithium-ion secondary batteries and the like, and compositions that can be used as raw materials thereof.

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