WO2007072763A1 - Nouveau sel d’imide de fluorosulfonyle cyclique et electrolyte - Google Patents

Nouveau sel d’imide de fluorosulfonyle cyclique et electrolyte Download PDF

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Publication number
WO2007072763A1
WO2007072763A1 PCT/JP2006/325112 JP2006325112W WO2007072763A1 WO 2007072763 A1 WO2007072763 A1 WO 2007072763A1 JP 2006325112 W JP2006325112 W JP 2006325112W WO 2007072763 A1 WO2007072763 A1 WO 2007072763A1
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ion
compound
carbon atoms
electrolyte
group
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PCT/JP2006/325112
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English (en)
Japanese (ja)
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Masao Iwaya
Hidekazu Okamoto
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Asahi Glass Company, Limited
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Priority claimed from JP2006064279A external-priority patent/JP2009054283A/ja
Application filed by Asahi Glass Company, Limited filed Critical Asahi Glass Company, Limited
Publication of WO2007072763A1 publication Critical patent/WO2007072763A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • 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
    • 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
    • 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 cyclic fluorosulfonylimide salt and an electrolyte suitably used for electrochemical devices (secondary batteries, electric double layer capacitors, fuel cells, solar cells, etc.).
  • Electrolytes used in electrochemical devices are not only superior in electrical conductivity but also in chemical stability (low corrosion resistance, heat resistance, etc.). , Operating temperature, charge / discharge cycle, durability, etc.). In order to obtain an electrolyte that achieves both electrical conductivity and chemical stability, various types of cation and anion electrolytes, and combinations thereof, have been actively studied.
  • Patent Document 1 and Patent Document 2 as an electrolyte used in the electrochemical device, wherein R F - acyclic anion represented by SO -N "-SO-R F, wherein R F - SO — N_— CO
  • R F in the above three acyclic anion formulas independently represents a monovalent perfluoro group having 1 12 carbon atoms
  • Q F in the above formula (dsi) represents 2 of 2 6 carbon atoms.
  • the valent perfluoro group is shown.
  • fluorosulfurimides there are known the following compounds (Ldsl), acyclic fluorosulfonylimides such as the following compounds (Lms 1), and cyclic fluorodisulfurimides such as the following compounds (Cdsl).
  • Ldsl acyclic fluorosulfonylimides
  • Cdsl cyclic fluorodisulfurimides
  • Patent Document 1 Japanese Patent Publication No. 11 512653
  • Patent Document 2 Japanese Patent Publication No. 01-501822
  • Patent Document 3 International Publication 2005Z001979 Pamphlet
  • Non-Patent Document 2 J. Org. Chem., 26, 4002, (1961)
  • the present inventors have conducted intensive studies on the assumption that cyclic fluoromonosulfurimides can form an ionic liquid at a lower temperature because they have an asymmetric ring structure. As a result, we succeeded in obtaining a novel cyclic fluorosulfurimide salt. Furthermore, the salt is chemically And found that it is a stable ionic liquid.
  • the inventors of the present invention provide a 4-membered cyclic anion having a -SO-N_-CO- structure
  • the cyclic anion Since the ionic radius is small, it was considered that the mobility in the electrolyte was high and the electrical conductivity was excellent. In addition, the cyclic anion has an asymmetric molecular structure and thus has a low viscosity. Furthermore, it was considered that the cyclic anion can exist in a high molar concentration in the electrolyte because of its low molecular weight. They have also found that a novel fluorine-containing compound having a 4-membered cyclic anion is useful as an electrolyte.
  • the present invention has the following gist.
  • n l, 2, 3, or 4.
  • [M] n + an n-valent cation, and when n is 1, it is an alkali metal ion, an organic ammonium ion, a sulfone ion, a positive xanthomy ion, or a phosphorous ion. Yes, when n is 2, 3, or 4, it is an n-valent metal cation.
  • X A hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a fluoroalkoxy group having 1 to 4 carbon atoms.
  • n l, 2, 3, or 4.
  • [M] n + an n-valent cation, and when n is 1, it is an alkali metal ion, an organic ammonium ion, a sulfone ion, a positive xanthomy ion, or a phosphorous ion. Yes, when n is 2, 3, or 4, it is an n-valent metal cation.
  • X A hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a fluoroalkoxy group having 1 to 4 carbon atoms.
  • n l, 2, 3, or 4.
  • Xm a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluorinated alkyl group having 1 to 4 carbon atoms, or a fluoroalkoxy group having 1 to 4 carbon atoms.
  • a novel compound which is a chemically stable ionic liquid and has low volatility, high compatibility, high conductivity, and flame retardancy. Furthermore, according to the present invention, a novel electrolyte excellent not only in electrical conductivity but also in chemical stability (low corrosion resistance, heat resistance, etc.), an electrolyte containing the electrolyte, and the electrolyte The used electrochemical device is provided.
  • a compound represented by the formula (1) is also referred to as a compound (1), and an ion represented by the formula (im) is also referred to as an ion (im).
  • an ion represented by the formula (im) is also referred to as an ion (im).
  • the symbols in the formula are as defined above unless otherwise specified.
  • the present invention provides the following compound (1).
  • Compound (1) is a salt of [M] n + which is an n-valent cation and n anions.
  • n is preferably 1
  • [M] + is a monovalent cation.
  • the monovalent cation is particularly preferably an alkali metal ion, an organic ammonium ion or a phosphonium ion! /.
  • the alkali metal ion is preferably lithium ion! /.
  • the organic ammonium ion is not particularly limited, and may be an acyclic organic ammonium ion or a cyclic organic ammonium ion.
  • the organic ammonium ion preferably has 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms.
  • An acyclic organic ammonium ion is an ion represented by the formula [(R A ) N] + (where R A is
  • a monovalent hydrocarbon group having 1 to 10 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 10 carbon atoms. ) (Hereinafter referred to as ions (Ai)).
  • the four R A in the ion (Ai) may be the same or different.
  • an etheric oxygen atom, a carbon group, or an oxycarbol group may be inserted between the carbon atom-carbon atom bond. .
  • R A is preferably an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group having 1 to 10 carbon atoms.
  • an alkyl group having 1 to 6 carbon atoms is more preferably a methyl group, an ethyl group, an n propyl group, an iso propyl group, an n butyl group, an iso butyl group, or a tert-butyl group. Is particularly preferred.
  • the cyclic organic ammonium ion is preferably an ion having a ring structure containing a positively charged nitrogen atom. Especially preferred is quinolinium or triazinium! /.
  • the carbon atom forming the ring of the cyclic organic ammonium ion contains 1 to 6 carbon atoms.
  • An alkyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms is bonded.
  • the power of imidazolium is the following ion (im—1)
  • the power of virazolium is the following ion (pi 1)
  • the power of pyradium is the following ion (pi—2).
  • ion (Py- 1) a is the force Piridaji - ⁇ beam is of the the following ions (py- 2)
  • pyrimidine - ⁇ beam is of the the following ions (P y- 3)
  • Triazolium is the following ion. (tr—l) or the ion (tr 2) below is preferred U, respectively.
  • Contact and Zeta 17 each independently represent a monovalent hydrocarbon group or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms.
  • an etheric oxygen atom, carbo- Or an oxycarbonyl group may be inserted.
  • ⁇ 1 are preferably each independently an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group having 1 to 10 carbon atoms.
  • the alkyl group having 16 carbon atoms is more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, or a tert-butyl group. Especially preferred.
  • the phosphonium ion is preferably a quaternary phosphonium ion with the formula [(R s ) P] +
  • R 4 is particularly preferably an ion represented by (wherein represents a monovalent hydrocarbon group having 120 carbon atoms or a monovalent halogenated hydrocarbon group having 120 carbon atoms). Further, when a carbon atom-carbon atom bond is present in R S , an etheric oxygen atom, a carbonyl group, or an oxycarbonyl group may be inserted between the carbon atom-carbon atom bond.
  • R s is preferably an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group having 1 to 10 carbon atoms.
  • a methyl group, an ethyl group, an n -propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a tert-butyl group is more preferable as an alkyl group having 16 carbon atoms.
  • a methyl group, an ethyl group, an n -propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a tert-butyl group is more preferable as an alkyl group having 16 carbon atoms.
  • the compound (1) when n is 2, the compound (1) is preferably the following compound (12) ([M 2 ] 2+ represents a divalent metal cation. ) When 0 n is 3, the compound (1) is preferably the following compound (13) ([M 3 ] 3+ represents a trivalent metal cation.) some cases, the compound (1) is the following compound (14) is preferably ([M 4] 4+ indicates a tetravalent metal cation.) 0
  • [ ⁇ 2 ] 2 It is preferable to use calcium ions, magnesium ions, or copper ( ⁇ ) ions.
  • [ ⁇ 3 ] 3+ is preferably an aluminum ( ⁇ ) ion.
  • X is preferably a halogen atom or a perfluoroalkyl group having 14 carbon atoms.
  • chlorine atom, fluorine atom, or trifluoromethyl Particularly preferred is a fluorine atom, which is more preferably a group! /.
  • a preferred embodiment of the compound (1) of the present invention includes the following compound (11).
  • [M 1 ] is a monovalent cation, which is a lithium ion, the ion (Ai), the ion (im 1), the ion (pi-1), the ion (pi-2), or the ion (py — 1), the ion (py—2), the ion (py—3), the ion (pr—1), the ion (pp—1), the ion (qu—1), the ion (tr—1) Or the above-mentioned ion (tr-2).
  • lithium ions, the ions (Ai), the ions (im-1), the ions (py-1), or the ions (pr-1) are particularly preferable.
  • Specific examples of compound (11) in which Mif is an organic ammonium ion include the following compounds.
  • compound (11) wherein [M 1 ] is 1,2,3-triazolium include the following compounds: Things.
  • Compound (1) is preferably produced by reacting the following compound (2) with a compound represented by the formula [ ⁇ ] ⁇ + ([ ⁇ ) (hereinafter, also referred to as compound (3)). .
  • reaction it is preferable to react 1.00 Xn to 2.OOXn times mol of compound (3) to n mol of compound (2). It is particularly preferable to react 50 ⁇ n mole.
  • the temperature in the reaction is preferably 0 to 200 ° C, particularly preferably 40 to 120 ° C.
  • the pressure in the reaction is not particularly limited. The reaction may be performed in the presence of a solvent or may be performed in the absence of a solvent.
  • the compound (3) include lithium hydroxide, tetramethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and hydroxy acid.
  • the compound (1) of the present invention is a novel compound unknown in the literature.
  • the compound (1) is a chemically stable molten salt and ionic liquid over a wide temperature range (from 1700C to + 300C). Furthermore, it was found that the compound (1) has low volatility, high compatibility with other compounds, and excellent conductivity and flame retardancy.
  • the present invention provides a composition comprising compound (1) as an active ingredient.
  • the composition of the present invention may be a composition comprising compound (1) and may be a composition comprising compound (1) and another compound.
  • the composition of the present invention preferably contains 1 to L00% by mass of the compound (1). When the composition of the present invention contains other compounds, it is more than 0 to 99% by mass of the other compounds. Is preferably included.
  • the other compound may be a liquid compound or a solid compound. Further, the other compound may be an organic compound or an inorganic compound.
  • the composition of the present invention when used as an electrolyte for a lithium secondary battery, the composition preferably contains a compound (1) in which [M] n + is a lithium ion.
  • composition of the present invention is used as an electrolyte for an electric double layer capacitor, the composition is
  • [M] It is preferable to contain a compound (1) in which n + is an organic ammonium ion or a phosphonium ion, and an organic carbonate.
  • the composition preferably comprises 40-80% by weight of compound (1) and 20-60% by weight of organic carbonate.
  • the organic carbonate is preferably ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, or methyl ethyl carbonate.
  • the composition of the present invention When the composition of the present invention is used as an antistatic agent, the composition of the present invention contains a compound (1) in which [M] n + is a lithium ion, an organic ammonium ion, or a phosphonium ion. Is preferred.
  • composition of the present invention may be used in various forms according to the application.
  • the composition of the present invention may be used alone or in combination with other materials.
  • compositions of the present invention alone include electrolytes for electrochemical devices (electrolytes for lithium secondary batteries, electrolytes for electric double layer capacitors, electrolytes for fuel cells, etc.), solvents (solvents for chemical reactions) , Solvent for extraction, solvent for electrolytic bath, etc.), heat medium, optical resolution agent, lubricant, gas detector for gas sensor, temperature sensor for temperature sensor, gas absorbent, chemical (transdermal absorption enhancer, enzyme coating) And the like in the immersion exposure method.
  • electrolytes for electrochemical devices electrolytes for lithium secondary batteries, electrolytes for electric double layer capacitors, electrolytes for fuel cells, etc.
  • solvents solvents for chemical reactions
  • solvent for extraction solvent for electrolytic bath, etc.
  • heat medium optical resolution agent
  • lubricant gas detector for gas sensor
  • temperature sensor for temperature sensor
  • gas absorbent gas absorbent
  • chemical transdermal absorption enhancer, enzyme coating
  • the composition of the present invention is particularly useful as an electrolyte for an electrochemical device, a solvent, or a heat medium from the viewpoint of its physical properties (low volatility, high compatibility, high conductivity, flame retardancy, etc.). It is. Applications for combining the composition of the present invention with other materials include electrochemical device components ( Lithium secondary battery member, electric double layer capacitor member, fuel cell member, etc. ), Antistatic agents, dispersants and the like.
  • composition of the present invention examples include a carrier obtained by impregnating a porous carrier with the composition of the present invention, and the composition of the present invention as another material. And composite materials obtained by kneading or adding to the above.
  • porous carrier examples include porous carbon materials (activated carbon and the like), porous inorganic materials (inorganic glass, silica gel, ceramics and the like), and porous resin.
  • the carrier is a carrier to which the physical properties (low volatility, high compatibility, high conductivity, flame retardancy, etc.) of the composition of the present invention are imparted, and is particularly useful as a member for an electrochemical device.
  • Specific examples of other materials in the composite material include carbon materials (carbon nanotubes, fullerenes, diamonds, etc.), thermoplastic resins (fluorine-containing resin, polychlorinated resin, cellulose, polyolefins).
  • System resin polyethylene, polypropylene, polyacetate butyl, etc.
  • styrene resin polystyrene, ABS, etc.
  • polyester resin polyethylene terephthalate, polybutylene terephthalate, etc.
  • polyamide-based resin nylon 6, nylon 66, Naiton MXD6, etc.
  • polycarbonate-based resin bisphenol A polycarbonate, etc.
  • polyether-based resin Polyphenylene ether, polyacetal, etc.
  • a composite material in which the other material is a carbon material can be a composite carbon material with improved flowability and excellent workability.
  • the composite material in which the other material is thermoplastic resin is a composite material imparted with low volatility, high compatibility, high conductivity, and flame retardancy, and is an electrochemical device member, a display element member, It is useful as an optically anisotropic film, a conductive film, an antistatic film, a photoelectric conversion element, an actuator element, a photosensitive element, and the like.
  • the present invention provides an electrolyte containing the following compound (lm).
  • the compound (lm) is a salt of [Mm] n + which is one n-valent metal cation and n anions.
  • Xm is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
  • a fluorine atom is particularly preferable from the viewpoint of the molecular weight of the compound (lm) in which a fluorine atom or a trifluoromethyl group is more preferable.
  • the compound (lm) when n is 1, the compound (lm) is represented by the following compound (11m) ([Mm 1 ] + represents a monovalent metal cation), and n is The compound (lm) when 2 is represented by the following compound (12m) ([Mm 2 ] 2+ represents a divalent metal cation), and the compound (lm) when n is 3 is The following compound (13m) ([Mm 3 ] 3+ represents a trivalent metal cation), and when n is 4, compound (1) is represented by the following compound (14m) ([Mm 4 ] 4 + represents a tetravalent metal cation.
  • [Mm 1 ] is particularly preferably a lithium ion, preferably a lithium ion, a sodium ion, or a potassium ion.
  • [Mm 2 ] is preferably calcium ion, magnesium ion, or copper (II) ion.
  • [Mm 3 ] 3+ is preferably an aluminum ( ⁇ ) ion.
  • n is 1 and [Mm] n + is preferably a monovalent metal cation.
  • Compound (lm) is preferably compound (11m).
  • the electrolyte of the present invention may be composed of a compound (lm) that may have only the compound (lm) and an electrolyte other than the compound (lm) (also referred to as other electrolyte).
  • the other electrolyte may be a compound containing a fluorine atom or a compound not containing a fluorine atom.
  • the other electrolyte may be an organic compound or an inorganic compound.
  • electrolytes include LiCl LiF Lil LiPF LiBF LiSbF LiCIO
  • Inorganic electrolyte such as 6 4 6 4; LiSO CF LiN (SO CF) LiN (SO CF CF) LiC (SO CF
  • Organic electrolytes such as CF) LiC (SO CF) LiPF (SO CF), LiPF (SO CF) I can get lost.
  • the electrolyte of the present invention contains another electrolyte
  • the electrolyte of the present invention contains 0.1 to 80% by mass of the compound (lm) with respect to the total amount of the compound (lm) and the other electrolyte. It is especially preferred to contain 1-40% by weight.
  • the compound (lm) is a molten salt that is chemically stable in a wide temperature range (from 70 ° C to + 150 ° C).
  • the compound (lm) has high compatibility with other compounds and low volatility.
  • a solution obtained by dissolving the compound (lm) in a liquid solvent capable of dissolving the compound (lm) (hereinafter also simply referred to as a liquid solvent) becomes an electrolytic solution containing the compound (lm) as an electrolyte.
  • the electrolytic solution is excellent in electrical conductivity.
  • the present invention provides an electrolytic solution comprising the electrolyte of the present invention and a liquid solvent.
  • the liquid solvent is not particularly limited as long as it has a boiling point of 25 ° C or higher, preferably 50 ° C or higher.
  • the liquid solvent is preferably a non-aqueous solvent from the viewpoint of compatibility with the electrolyte of the present invention.
  • the non-aqueous solvent is a solvent excluding water and a solvent containing water, and is not particularly limited as long as it is a solvent that does not substantially contain water.
  • the non-aqueous solvent is preferably a polar aprotic solvent from the viewpoint of compatibility with the electrolyte of the present invention.
  • polar aprotic solvents there is self-proton dissociation constant of 10 _2 molZdm 3 or less and a specific dielectric constant of 1 or more, is not preferable in particular if also a made solvates force is 10 or more limited.
  • the liquid solvent may be used alone or in combination of two or more.
  • the liquid solvent is preferably ethers, esters, nitriles, nitrohydrocarbons, amides, sulfoxides, carbonates, and at least one kind of solvent that is selected from the group power of sulfones.
  • the ability of at least one solvent selected from the group power of esters and carbonates is more preferred.
  • ethers include acyclic ethers such as jetyl ether, diethylene glycol dimethyl ether, 1,2-dimethoxyethane; tetrahydrofuran, 2-methyltetrahydrofuran, dimethyltetrahydrofuran, dioxane, dioxolane And cyclic ethers such as 4-methyldioxolane.
  • esters include acyclic ethers such as methyl formate, ethyl formate, and methyl acetate. Steal; y Cyclic esters such as butyrololataton and ⁇ -valerolataton.
  • carbonates include acyclic carbonates such as dimethyl carbonate, jetyl carbonate, and methylethyl carbonate; and cyclic carbonates such as propylene carbonate, ethylene carbonate, and butylene carbonate.
  • nitriles include acetonitrile, propio-tolyl, and benzo-tolyl.
  • nitro hydrocarbons include nitromethane and nitrobenzene.
  • amides include ⁇ , ⁇ ⁇ ⁇ ⁇ dimethylformamide, ⁇ , ⁇ ⁇ jetyl amide, and ⁇ -methylpyrrolidone.
  • sulfoxides include dimethyl sulfoxide.
  • sulfones include dimethyl sulfone and tetramethylene sulfone.
  • electrolytic solution of the present invention the electrolyte of the present invention with respect to the liquid solvent, preferably to include 0. OlmolZdm 3 or more instrument 0. ImolZdm 3 or more preferably contain instrument 0. 4 mol / dm 3 It is particularly preferable to include the above.
  • the electrolyte solution of the present invention preferably contains 5. Omol / dm 3 or less of the electrolyte of the present invention in a liquid solvent, and particularly preferably contains 2.5 mol Zdm 3 or less.
  • the compound (lm) has a low molecular weight as compared with a conventional electrolyte. Therefore, the electrolytic solution of the present invention is an electrolytic solution containing a high molar concentration of the electrolyte even if the absolute amount of the electrolyte of the present invention is small. Moreover, the electrolytic solution of the present invention becomes an electrolytic solution containing a desired molar concentration of the electrolyte by appropriately adjusting the absolute amount of the electrolyte of the present invention.
  • the electrolytic solution of the present invention is useful as an electrolytic solution used in an electrochemical device.
  • the electrochemical device of the present invention is not particularly limited as long as it has at least a pair of electrodes and a structure filled with the electrolytic solution of the present invention between the electrodes.
  • electrochemical device of the present invention examples include a primary battery, a secondary battery, an electric double layer capacitor, a fuel cell, and a solar cell.
  • the compound (lm) has sufficient electrical conductivity.
  • the compound (lm) contains a conventional electrolyte (one SO—N_—SO— structure-containing anion).
  • the electrode of the electrochemical device of the present invention has a lower acidity than The material is not easily corroded. Therefore, the electrochemical device of the present invention is an electrochemical device that has not only sufficient electrochemical performance but also excellent durability so that the electrode material is not easily corroded.
  • electrochemical devices include secondary batteries such as lithium primary batteries, lithium ion batteries, and polymer secondary batteries, electric double layer capacitors, fuel cells, solar cells, and the like.
  • secondary batteries such as lithium primary batteries, lithium ion batteries, and polymer secondary batteries, electric double layer capacitors, fuel cells, solar cells, and the like.
  • a positive electrode formed on both surfaces of an aluminum foil and a foil-shaped negative electrode are laminated or wound via a separator, and the gap between the positive electrode and the negative electrode is the present invention.
  • Examples include a primary battery having a configuration filled with an electrolytic solution.
  • Examples of the material for the positive electrode include one or more metal oxides selected from the group force consisting of manganese, conoleto, nickel, niobium, and vanadium.
  • a specific example of the lithium secondary battery of the present invention has a configuration in which a positive electrode and a negative electrode face each other via a separator, and a configuration in which a space between the positive electrode and the negative electrode is filled with the electrolytic solution of the present invention.
  • Examples include lithium secondary batteries.
  • Examples of the material for the positive electrode include composite oxides of lithium and metal atoms selected from conoretol, nickel, and iron.
  • Examples of the material for the negative electrode include lithium, aluminum, graphite, amorphous carbon material, silicon, germanium, and a composite material made of lithium and a material selected from gold.
  • each has two or more positive electrodes and negative electrodes, each of which has a configuration in which the positive electrode and the negative electrode are stacked or wound via a separator, and each of them.
  • An electric double layer capacitor having a structure in which the space between the positive electrode and the negative electrode is filled with the electrolytic solution of the present invention.
  • Each of the positive electrode and negative electrode materials is preferably a polarizable material.
  • the polarizable material is particularly preferably glassy carbon, carbon black, carbon fiber, activated carbon microbeads, or activated carbon fiber, which is preferred for carbon materials having a large specific surface area.
  • Examples of the material for the separator include organic polymers such as polyethylene, polypropylene, beylene copolymer, butylene, and polyvinylidene fluoride.
  • the electrolytic solution of the present invention is provided between the positive electrode and the negative electrode. Or may be filled with a carrier obtained by impregnating the electrolytic solution of the present invention.
  • the carrier material include organic polymers such as polyvinylidene fluoride, polyacrylonitrile, and polyethylene oxide.
  • Example 4 Production example of electrolyte Compound (l 1 ) (1.63 g) was dissolved in propylene carbonate to obtain a solution (total volume lOmL). Thereafter, while maintaining the solution temperature at 40 ° C., the solution was vacuum-reduced to completely distill off the recrystallization solvent dioxane. Next, until the total volume of the solution became 10 mL, propylene carbonate was added to the solution to obtain an electrolytic solution containing 1. OmolZdm 3 of compound (I 1 ) with respect to propylene carbonate. The electrical conductivity of the obtained electrolyte was measured at 20 ° C, 40 ° C, and 60 ° C, respectively. The results are shown in Table 1.
  • the compound (1) is a useful material as an electrolyte, and an electrolyte obtained by dissolving the compound (1) in a non-aqueous solvent is an electrolyte having both electrical conductivity and chemical stability. It can be seen that it is.
  • a solvent (a solvent for chemical reaction, a solvent for extraction, a solvent for electrolytic bath, etc.), a heat medium, an optical resolution agent, a lubricant, a gas detection agent for a gas sensor, a temperature sensor for a temperature sensor, a gas Absorber, drug (percutaneous absorption enhancer, enzyme coating agent, etc.), immersion liquid for immersion exposure method, electrolyte for electrochemical device (electrolyte for secondary battery, electrolyte for electric double layer capacitor, electrolyte for fuel cell) Etc.), electrochemical device members (secondary battery members, electric double layer capacitor members, fuel cell members, etc.), display element members, optical anisotropic films, conductive films, antistatic films, photoelectric conversion elements, Cyclic fluorosulfonylimides useful for applications such as actuator elements and photosensitive elements are provided.
  • electrolyte for electrochemical device electrochemical device
  • electrochemical device members secondary battery members, electric double layer capacitor members, fuel cell members, etc.
  • display element members optical aniso
  • electrolyte solution used in electrochemical devices such as secondary batteries such as primary batteries and lithium ion batteries, electric double layer capacitors, fuel cells and solar cells using the cyclic fluorosulfonylimides of the present invention.
  • a suitable electrolyte is provided.

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  • Engineering & Computer Science (AREA)
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  • Manufacturing & Machinery (AREA)
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Abstract

L’invention concerne un nouveau sel d’imide de fluorosulfonyle cyclique et un électrolyte. L’invention concerne notamment un composé (1) représenté ci-dessous et un électrolyte contenant un composé (1m) représenté ci-dessous. n représente 1, 2, 3 ou 4 ; [M]n+ représente un ion position n-valent, notamment un ion métallique alcalin, un ion ammonium organique, un ion sulfonium, un ion oxonium ou un ion phosphonium lorsque n vaut 1 et un ion positif métallique n-valent lorsque n vaut 2, 3 ou 4 ; [Mm]n+ représente un ion positif métallique n-valent ; et X et Xm représentent respectivement un atome d’hydrogène, un atome d’halogène, un groupement alkyle ayant de 1 à 6 atomes de carbone, un groupement fluoroalkyle ayant de 1 à 6 atomes de carbone ou un groupement fluoroalcoxy ayant de 1 à 6 atomes de carbone. (1) (1m)
PCT/JP2006/325112 2005-12-19 2006-12-15 Nouveau sel d’imide de fluorosulfonyle cyclique et electrolyte WO2007072763A1 (fr)

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JP2005-365117 2005-12-19
JP2005365117 2005-12-19
JP2006-064279 2006-03-09
JP2006064279A JP2009054283A (ja) 2005-12-19 2006-03-09 新規な含フッ素化合物を含む電解質、電解液、および電気化学デバイス

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7989635B2 (en) 2007-08-17 2011-08-02 Asahi Glass Company, Limited Method for producing purified ammonium salt of fluorinated bis-sulfonylimide
JP2018142491A (ja) * 2017-02-28 2018-09-13 国立大学法人静岡大学 プロトン伝導性電解質及び燃料電池
JP2023533050A (ja) * 2020-11-03 2023-08-01 エルジー エナジー ソリューション リミテッド リチウム二次電池用非水系電解液及びこれを含むリチウム二次電池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3091619A (en) * 1958-05-01 1963-05-28 Du Pont Nitrogen derivatives of fluoroalkyl sulfonic acid sultones
JPH01501822A (ja) * 1986-10-30 1989-06-22 サントル・ナシオナル・ドウ・ラ・ルシエルシユ・シアンテイフイク 液体電解質中に溶解した塩を含む新規のイオン伝導材料
WO2005001979A2 (fr) * 2003-06-27 2005-01-06 E.I. Dupont De Nemours And Company Composes de sulfonamide fluore et membranes d'electrolytes polymeres prepares a partir de ces composes en vue d'une utilisation dans des cellules electrochimiques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3091619A (en) * 1958-05-01 1963-05-28 Du Pont Nitrogen derivatives of fluoroalkyl sulfonic acid sultones
JPH01501822A (ja) * 1986-10-30 1989-06-22 サントル・ナシオナル・ドウ・ラ・ルシエルシユ・シアンテイフイク 液体電解質中に溶解した塩を含む新規のイオン伝導材料
WO2005001979A2 (fr) * 2003-06-27 2005-01-06 E.I. Dupont De Nemours And Company Composes de sulfonamide fluore et membranes d'electrolytes polymeres prepares a partir de ces composes en vue d'une utilisation dans des cellules electrochimiques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
IMAI Y. ET AL.: "Anionic Ring-Opening Polymerization of 4,4-Dimethyl-1,2-thiazetidin-3-one 1,1-Dioxide", POLYMER JOURNAL, vol. 11, no. 8, 1979, pages 613 - 617, XP003014287 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7989635B2 (en) 2007-08-17 2011-08-02 Asahi Glass Company, Limited Method for producing purified ammonium salt of fluorinated bis-sulfonylimide
JP2018142491A (ja) * 2017-02-28 2018-09-13 国立大学法人静岡大学 プロトン伝導性電解質及び燃料電池
JP2023533050A (ja) * 2020-11-03 2023-08-01 エルジー エナジー ソリューション リミテッド リチウム二次電池用非水系電解液及びこれを含むリチウム二次電池
JP7484009B2 (ja) 2020-11-03 2024-05-15 エルジー エナジー ソリューション リミテッド リチウム二次電池用非水系電解液及びこれを含むリチウム二次電池

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