WO2022158398A1 - Électrolyte liquide non aqueux et batterie à électrolyte liquide non aqueux - Google Patents

Électrolyte liquide non aqueux et batterie à électrolyte liquide non aqueux Download PDF

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WO2022158398A1
WO2022158398A1 PCT/JP2022/001224 JP2022001224W WO2022158398A1 WO 2022158398 A1 WO2022158398 A1 WO 2022158398A1 JP 2022001224 W JP2022001224 W JP 2022001224W WO 2022158398 A1 WO2022158398 A1 WO 2022158398A1
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group
atom
carbon atoms
general formula
ion
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Japanese (ja)
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良介 寺田
幹弘 高橋
渉 河端
克俊 鈴木
翔 山澤
玲 塚▲崎▼
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セントラル硝子株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/30—Oxygen or sulfur atoms
    • C07D233/32—One oxygen atom
    • C07D233/34—Ethylene-urea
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/056—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

Definitions

  • the present disclosure relates to non-aqueous electrolytes and non-aqueous electrolyte batteries.
  • Non-aqueous electrolyte-related technologies are no exception, and various additives have been proposed to suppress deterioration due to decomposition of the non-aqueous electrolyte on the surfaces of active positive and negative electrodes.
  • Patent Document 1 proposes to improve various battery characteristics such as high-temperature storage characteristics by adding vinylene carbonate to the non-aqueous electrolyte. This method prevents the decomposition of the non-aqueous electrolyte on the electrode surface by coating the electrode with a polymer film formed by polymerizing vinylene carbonate. is an issue.
  • Patent Document 2 the addition of lithium difluorophosphate disclosed in Patent Document 2 is effective, and by using vinylene carbonate and lithium difluorophosphate together, the internal resistance can be It is known that it is possible to obtain a battery in which an increase in the is suppressed.
  • Patent Document 3 discloses a method for improving input/output characteristics and impedance characteristics by incorporating a fluorosulfonate into a non-aqueous electrolytic solution as a single additive instead of a combination of multiple additives.
  • the present disclosure has been made in view of the above circumstances, and aims to provide a non-aqueous electrolyte and a non-aqueous electrolyte battery with a low initial resistance value.
  • component (I) one or more compounds represented by the general formula (1) (hereinafter referred to as “component (I)” or simply “(I )”.),
  • component (II) One or more of the compounds represented by the general formulas (2) to (4) and (6) (hereinafter referred to as “component (II)” or simply “ (II)”),
  • component (III) solute
  • component (IV) non-aqueous organic solvent
  • R 1 and R 2 each independently represent PO(R f ) 2 or SO 2 R f .
  • Each R f independently represents a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms or 3 to 4 carbon atoms.
  • R 3 and R 4 each independently represents a hydrogen atom, a lithium ion, a sodium ion, a potassium ion, or a linear or branched alkyl group having 1 to 12 carbon atoms or 3 to 12 carbon atoms;
  • An oxygen atom may be included between carbon atom-carbon atom bonds in the group. Any hydrogen atom of the alkyl group may be substituted with a fluorine atom.
  • R3 represents a lithium ion , sodium ion or potassium ion
  • the bond between the nitrogen atom and R3 in general formula ( 1 ) represents an ionic bond
  • R4 represents a lithium ion, sodium ion or potassium ion
  • the bond between the nitrogen atom and R4 in general formula (1) represents an ionic bond.
  • R 3 and R 4 may also form a ring structure together with the nitrogen atom to which they are attached. In this case, R 3 and R 4 together form an alkylene group having 2 to 4 carbon atoms, and an oxygen atom is included between the carbon atom-carbon atom bonds in the alkylene group. or may have an alkyl group on its side chain. Any hydrogen atom in the alkyl group and alkylene group may be substituted with a fluorine atom. ]
  • R 5 is a hydrogen atom, a lithium ion, a sodium ion, a potassium ion, an alkyl group having 5 or less carbon atoms, an alkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group, an alkynyloxy group, an aryl group having 6 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
  • any hydrogen atom of the alkyl group, the alkoxy group, the alkenyl group, the alkenyloxy group, the alkynyl group, the alkynyloxy group, the aryl group, and the aryloxy group may be substituted with a fluorine atom.
  • an oxygen atom may be included between the carbon atom-carbon atom bonds of these groups.
  • R5 represents a lithium ion, sodium ion or potassium ion
  • the bond between the oxygen atom and R5 in general formula ( 2 ) represents an ionic bond.
  • R 6 to R 9 each independently represent a fluorine atom or a group represented by —OR 10 .
  • R 10 is a straight or branched alkyl group having 1 to 10 carbon atoms, a straight or branched alkenyl group having 2 to 10 carbon atoms, a straight or branched chain having 2 to 10 carbon atoms at least one organic group selected from the group consisting of an alkynyl group, a cycloalkyl or cycloalkenyl group having 3 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms; may be substituted with a fluorine atom.
  • the organic group may contain an unsaturated bond, and an oxygen atom may be contained between the carbon atom-carbon atom bonds of the organic group.
  • M represents a lithium ion, sodium ion or potassium ion.
  • at least one of R 6 to R 9 represents a fluorine atom.
  • n represents an integer of 1 to 3
  • L represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms or OM.
  • L represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.
  • Any hydrogen atom of the aliphatic hydrocarbon group may be substituted with a fluorine atom.
  • at least one selected from the group consisting of an oxygen atom and an ester bond may be included between the carbon atom-carbon atom bonds of the aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group may contain an unsaturated bond.
  • the M represents a hydrogen atom, lithium ion, sodium ion, or potassium ion.
  • each R 14 is independently selected from the group consisting of a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or -SiR 15 3 ; and any hydrogen atom of the organic group may be substituted with a fluorine atom. Further, an oxygen atom may be included between the carbon atom-carbon atom bonds of the organic group.
  • Each R 15 is independently selected from linear or branched alkyl groups having 1 to 4 carbon atoms.
  • R 3 and R 4 in the general formula (1) are each independently a hydrogen atom, a lithium ion, a sodium ion, or a linear or branched alkyl group having 1 to 4 carbon atoms or 3 to 4 carbon atoms;
  • R 1 and R 2 each independently represent PO(R f ) 2 or SO 2 R f .
  • Each R f independently represents a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms or 3 to 4 carbon atoms.
  • R 3 and R 4 each independently represents a hydrogen atom, a lithium ion, a sodium ion, a potassium ion, or a linear or branched alkyl group having 1 to 12 carbon atoms or 3 to 12 carbon atoms;
  • An oxygen atom may be included between carbon atom-carbon atom bonds in the group. Any hydrogen atom of the alkyl group may be substituted with a fluorine atom.
  • R3 represents a lithium ion , sodium ion or potassium ion
  • the bond between the nitrogen atom and R3 in general formula ( 1 ) represents an ionic bond
  • R4 represents a lithium ion, sodium ion or potassium ion
  • the bond between the nitrogen atom and R4 in general formula (1) represents an ionic bond.
  • R 3 and R 4 may also form a ring structure together with the nitrogen atom to which they are attached. In this case, R 3 and R 4 together form an alkylene group having 2 to 4 carbon atoms, and an oxygen atom is included between the carbon atom-carbon atom bonds in the alkylene group. or may have an alkyl group on its side chain.
  • Any hydrogen atom in the alkyl group and alkylene group may be substituted with a fluorine atom.
  • Any one of [1] to [10], wherein the content of (II) with respect to the total of (I), (II), (III) and (IV) is 0.01% by mass to 10.0% by mass 1.
  • non-aqueous electrolyte solution according to any one of [1] to [11], wherein the non-aqueous organic solvent contains at least one selected from the group consisting of cyclic carbonates and chain carbonates.
  • the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate
  • the chain carbonate is the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.
  • a non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, and the non-aqueous electrolyte according to any one of [1] to [14].
  • the initial resistance value is after performing a total of three cycles of charging and discharging, including the first charging and discharging to form an electrode film and then two cycles of charging and discharging to stabilize the battery.
  • the non-aqueous electrolyte of the present disclosure is (I) a compound represented by the above general formula (1), (II) at least one compound selected from the group consisting of compounds represented by the general formulas (2) to (4) and (6); (III) a solute and (IV) a non-aqueous electrolyte containing a non-aqueous organic solvent.
  • the non-aqueous electrolyte of the present disclosure contains a compound represented by general formula (1), which is component (I).
  • component (I) When the non-aqueous electrolyte containing the component (I) is used in a non-aqueous electrolyte battery (for example, a lithium ion secondary battery or a sodium ion secondary battery), the component (I) is present on at least the positive electrode and the negative electrode. It decomposes at a high temperature and forms a film with good ion conductivity on at least one of the surfaces of the positive electrode and the negative electrode.
  • this coating suppresses direct contact between the non-aqueous organic solvent or solute and the electrode active material, and lowers the Li or Na ion dissociation energy of the solute.
  • the present inventors presume that the component (I) forms a film on the electrode surface together with the component (II), which will be described later, and as a result, the initial resistance of the non-aqueous electrolyte battery is reduced. .
  • R 1 and R 2 each independently represent PO(R f ) 2 or SO 2 R f .
  • Each R f independently represents a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms or 3 to 4 carbon atoms.
  • Specific examples of when R f represents a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms or a branched perfluoroalkyl group having 3 to 4 carbon atoms include, for example, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro Examples include propyl group, heptafluoroisopropyl group, nonafluoro-n-butyl group and the like. Among them, a trifluoromethyl group is preferred.
  • R f is preferably a fluorine atom.
  • Two R f in PO(R f ) 2 may be the same or different.
  • R 1 and R 2 are each independently preferably POF 2 or SO 2 F, and both R 1 and R 2 are preferably SO 2 F.
  • R 3 and R 4 each independently represent a hydrogen atom, a lithium ion, a sodium ion, a potassium ion, or a linear or branched alkyl group having 1 to 12 carbon atoms or 3 to 12 carbon atoms.
  • R 3 and R 4 represent a linear or branched alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group and the like.
  • An oxygen atom may be included between the carbon atom-carbon atom bonds in the alkyl group.
  • Specific examples of the alkyl group containing an oxygen atom between carbon atom-carbon atom bonds include a 2-methoxyethyl group and a 2-ethoxyethyl group.
  • any hydrogen atom in the above alkyl group may be substituted with a fluorine atom.
  • the alkyl group in which any hydrogen atom is substituted with a fluorine atom include a trifluoromethyl group, a difluoromethyl group, a fluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-difluoroethyl group, 2-fluoroethyl group, 3-fluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group , hexafluoroisopropyl group, and the like.
  • the above alkyl group is preferably an alkyl group having 6 or less carbon atoms because it can reduce the resistance when a film is formed on the electrode.
  • the alkyl group is more preferably an alkyl group having 4 or less carbon atoms, and particularly preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, or tert-butyl group. .
  • R 3 and R 4 are each independently preferably a hydrogen atom, a lithium ion, a sodium ion, or a linear or branched alkyl group having 1 to 4 carbon atoms or 3 to 4 carbon atoms; , a lithium ion, a sodium ion, or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a lithium ion, a sodium ion, or a methyl group, any of R 3 and R 4 Lithium ions are particularly preferred.
  • R 3 and R 4 may also form a ring structure together with the nitrogen atom to which they are attached.
  • R 3 and R 4 together form an alkylene group having 2 to 4 carbon atoms, and an oxygen atom is included between the carbon atom-carbon atom bonds in the alkylene group. or may have an alkyl group on its side chain. Any hydrogen atom in the alkyl group and alkylene group may be substituted with a fluorine atom.
  • the alkylene group includes, for example, an ethylene group, a propylene group, and the like, and an ethylene group is particularly preferred.
  • the compound represented by general formula (1) is preferably at least one selected from the group consisting of compounds represented by the following formulas (1a) to (1y). More preferably, a compound represented by formula (1a) (also referred to as compound (1a)), a compound represented by formula (1b) (also referred to as compound (1b)), or a compound represented by formula (1c) compound (also referred to as compound (1c)), compound represented by formula (1e) (also referred to as compound (1e)), compound represented by formula (1p) (also referred to as compound (1p)), formula at least one selected from the group consisting of a compound represented by (1w) (also referred to as compound (1w)) and a compound represented by formula (1x) (also referred to as compound (1x)); At least one selected from the group consisting of compound (1a), compound (1e), compound (1w), and compound (1x) is preferred, and compound (1a) is particularly preferred.
  • the compound represented by general formula (1) is preferably used as an additive.
  • the content of (I) with respect to the total (100% by mass) of (I), (II), (III) and (IV) (hereinafter also referred to as "concentration of (I)" ), the lower limit is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more.
  • the upper limit of the concentration of (I) is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, and even more preferably 2.0% by mass or less.
  • the concentration of (I) By setting the concentration of (I) to 0.01% by mass or more, the effect of suppressing the initial resistance increase of a non-aqueous electrolyte battery using the non-aqueous electrolyte is likely to be obtained. On the other hand, by setting the concentration of (I) to 10.0% by mass or less, the viscosity increase of the non-aqueous electrolyte can be suppressed, and the effect of improving the high-temperature cycle characteristics of a non-aqueous electrolyte battery using the non-aqueous electrolyte can be obtained. easier to get.
  • one type of compound may be used alone as component (I), or two or more types of compounds may be used by mixing them in any combination and ratio according to the application.
  • the method for synthesizing the compound represented by the general formula (1) is not particularly limited. ), 237, by reacting fluorosulfonyl isocyanate with water or by reacting phosgene with methylsulfamoyl fluoride. Furthermore, by reacting with an inorganic base such as an alkali metal hydride ion, the compound represented by the above general formula (1) in which R 3 and R 4 are lithium ion, sodium ion, or potassium ion can be synthesized. can be done.
  • the non-aqueous electrolyte of the present disclosure contains (II) at least one compound selected from the group consisting of compounds represented by general formulas (2) to (4) and (6).
  • component (I) and component (II) in combination, a higher initial resistance reduction effect can be obtained than when each component is used alone.
  • R5 is a hydrogen atom, a lithium ion, a sodium ion, a potassium ion, an alkyl group having 5 or less carbon atoms, an alkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group, an alkynyloxy group having 6 or more carbon atoms; represents an aryl group having 10 or less, or an aryloxy group having 6 or more and 10 or less carbon atoms.
  • the number of carbon atoms in the alkyl group is preferably 1 or more and 5 or less, and examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and tert-butyl group.
  • any hydrogen atom in the above alkyl group may be substituted with a fluorine atom.
  • the alkyl group in which any hydrogen atom is substituted with a fluorine atom include a trifluoromethyl group, a difluoromethyl group, a fluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-difluoroethyl group, 2-fluoroethyl group, 3-fluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group , hexafluoroisopropyl group, and the like.
  • An oxygen atom may be included between the carbon atom-carbon atom bonds in the alkyl group.
  • Specific examples of the alkyl group containing an oxygen atom between carbon atom-carbon atom bonds include a 2-methoxyethyl group and a 2-ethoxyethyl group.
  • the number of carbon atoms in the alkoxy group is 5 or less, preferably 1 or more and 5 or less, and the alkenyl group, the alkenyloxy group, the alkynyl group, and the alkynyloxy group have 5 or less carbon atoms. , is preferably 2 or more and 5 or less.
  • the aryl group and the aryloxy group have 6 or more and 10 or less carbon atoms.
  • Examples include phenyl group, tolyl group, o-xylyl group, m-butylphenyl group, p-butylphenyl group and the like. Any hydrogen atom of the alkoxy group, alkenyl group, alkenyloxy group, alkynyl group, alkynyloxy group, aryl group, and aryloxy group may be substituted with a fluorine atom. In addition, an oxygen atom may be included between the carbon atom-carbon atom bonds of these groups.
  • R 5 is preferably a lithium ion, a sodium ion or a potassium ion, particularly preferably a lithium ion.
  • Specific examples of the compound represented by formula (2) include lithium difluorophosphate.
  • R5 represents a lithium ion, sodium ion or potassium ion
  • the bond between the oxygen atom and R5 in general formula ( 2 ) represents an ionic bond.
  • R 6 to R 9 independently represents a fluorine atom or a group represented by —OR 10 .
  • R 10 is a straight or branched alkyl group having 1 to 10 carbon atoms, a straight or branched alkenyl group having 2 to 10 carbon atoms, a straight or branched chain having 2 to 10 carbon atoms It is at least one organic group selected from the group consisting of an alkynyl group, a cycloalkyl or cycloalkenyl group having 3 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
  • alkyl group examples and preferred ranges of the alkyl group, the alkenyl group, the alkynyl group, and the aryl group are the same as those described in the explanation of R 5 in the general formula (2).
  • examples of the cycloalkyl group and cycloalkenyl group include cyclopropyl group, cyclopentyl group, cyclopropenyl group, cyclopentynyl group and the like.
  • Any hydrogen atom of the organic group represented by R 10 may be substituted with a fluorine atom. Further, the organic group may contain an unsaturated bond, and an oxygen atom may be contained between the carbon atom-carbon atom bonds of the organic group.
  • R 6 to R 9 represents a fluorine atom. Any one of R 6 to R 9 preferably represents a fluorine atom.
  • M in the general formula (3) represents a lithium ion, a sodium ion or a potassium ion, preferably a lithium ion. It is particularly preferred that all of R 6 , R 7 , R 8 and R 9 in general formula (3) are fluorine atoms and M is a lithium ion.
  • Lithium bis(difluorophosphate)imide can be synthesized, for example, by reacting phosphoryl trifluoride obtained by reacting phosphoryl chloride with hydrogen fluoride, and lithium hexamethyldisilazide.
  • n represents an integer of 1 to 3
  • L represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms or OM.
  • L represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.
  • L represents an aliphatic hydrocarbon group
  • n 1, it is a monovalent aliphatic hydrocarbon group
  • n 2, it is a divalent aliphatic hydrocarbon group
  • n 3 is a trivalent aliphatic hydrocarbon group.
  • the above aliphatic hydrocarbon groups include monovalent methyl, ethyl, propyl and butyl groups, divalent methylene, ethylene, propylene and trimethylene groups, and trivalent A methine group etc. are mentioned as a thing.
  • the aliphatic hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. Any hydrogen atom in the above aliphatic hydrocarbon group may be substituted with a fluorine atom. In addition, at least one selected from the group consisting of an oxygen atom and an ester bond may be included between the carbon atom-carbon atom bonds of the aliphatic hydrocarbon group. Also, the aliphatic hydrocarbon group may contain an unsaturated bond.
  • M represents a hydrogen atom, lithium ion, sodium ion, or potassium ion.
  • n in general formula (4) is 1 and L is OLi, n is 2 and L is CH2 , or n is 1 and L is CH3 .
  • Specific examples of the compound represented by the general formula (4) include lithium fluorosulfonate, methanesulfonyl fluoride, methanedisulfonyl difluoride, ethanesulfonyl fluoride, ethanedisulfonyl fluoride, propanesulfonyl fluoride, and the like. Methanesulfonyl fluoride and methanedisulfonyl difluoride are particularly preferred.
  • the non-aqueous electrolyte of the present disclosure contains a solute.
  • the solute is not particularly limited, it is preferably an ionic salt, more preferably an ionic salt containing fluorine.
  • solute examples include at least one cation selected from the group consisting of alkali metal ions such as lithium ions and sodium ions, alkaline earth metal ions, and quaternary ammonium ions, hexafluorophosphate anions, tetrafluoro Borate anion, perchlorate anion, hexafluoroarsenate anion, hexafluoroantimonate anion, trifluoromethanesulfonate anion, bis(trifluoromethanesulfonyl)imide anion, bis(pentafluoroethanesulfonyl)imide anion, (trifluoromethanesulfonyl) ) (pentafluoroethanesulfonyl)imide anion, bis(fluorosulfonyl)imide anion, (trifluoromethanesulfonyl)(fluorosulfonyl)imide anion, (penta)
  • solutes may be used alone, or two or more types may be mixed and used in an arbitrary combination and ratio according to the application.
  • the cation is at least one selected from the group consisting of lithium, sodium, magnesium, and quaternary ammonium, and the anion is hexafluorophosphate.
  • At least one selected from the group consisting of anions, tetrafluoroborate anions, bis(trifluoromethanesulfonyl)imide anions, bis(fluorosulfonyl)imide anions, and (difluorophosphoryl)(fluorosulfonyl)imide anions is preferred.
  • the total amount of solutes in the non-aqueous electrolyte of the present disclosure (hereinafter also referred to as "solute concentration") is not particularly limited, but the lower limit is preferably 0.5 mol/L or more, more preferably 0.7 mol. /L or more, more preferably 0.9 mol/L or more. Also, the upper limit of the solute concentration is preferably 5.0 mol/L or less, more preferably 4.0 mol/L or less, and still more preferably 2.0 mol/L or less.
  • the solute concentration By setting the solute concentration to 0.5 mol/L or more, it is possible to suppress the deterioration of the cycle characteristics and output characteristics of the non-aqueous electrolyte battery due to the decrease in ionic conductivity. It is possible to suppress the decrease in ionic conductivity, the cycle characteristics of the non-aqueous electrolyte battery, and the output characteristics due to an increase in the viscosity of the electrolyte.
  • Non-aqueous organic solvent used in the non-aqueous electrolyte of the present disclosure is not particularly limited, and any non-aqueous organic solvent can be used.
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • methyl propyl carbonate ethyl propyl carbonate, methyl butyl carbonate
  • 2,2,2-trifluoroethyl methyl carbonate 2,2,2-trifluoroethyl ethyl carbonate
  • 2,2,2-trifluoroethyl propyl carbonate bis(2,2,2 -trifluoroethyl) carbonate, 1,1,1,3,3,3-hexafluoro-1-propylmethyl carbonate, 1,1,1,3,3,3-hexafluoro-1
  • the non-aqueous organic solvent is at least one selected from the group consisting of cyclic carbonates and chain carbonates from the viewpoint of excellent cycle characteristics at high temperatures. Moreover, it is preferable that the non-aqueous organic solvent is at least one selected from the group consisting of esters, because the input/output characteristics at low temperatures are excellent.
  • cyclic carbonate examples include EC, PC, butylene carbonate, FEC, etc.
  • EC EC
  • PC butylene carbonate
  • FEC fluorescence-activated carbonate
  • at least one selected from the group consisting of EC, PC, and FEC is preferable.
  • chain carbonate examples include EMC, DMC, DEC, methylpropyl carbonate, ethylpropyl carbonate, 2,2,2-trifluoroethylmethyl carbonate, 2,2,2-trifluoroethylethyl carbonate, 1,1, 1,3,3,3-hexafluoro-1-propylmethyl carbonate and 1,1,1,3,3,3-hexafluoro-1-propylethyl carbonate, among others EMC, DMC, DEC, and at least one selected from the group consisting of methyl propyl carbonate.
  • esters include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, and ethyl 2-fluoropropionate.
  • additive components generally used in the non-aqueous electrolytic solution of the present disclosure may be further added in any ratio.
  • specific examples of other additives include cyclohexylbenzene, cyclohexylfluorobenzene, fluorobenzene, biphenyl, difluoroanisole, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, 2-fluorobiphenyl, vinylene carbonate, and dimethylvinylene.
  • the non-aqueous electrolytic solution of the present disclosure may contain a compound represented by the following general formula (5) as another additive.
  • R 11 to R 13 each independently represent a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, straight-chain alkoxy groups of 1 to 10 carbon atoms, branched alkoxy groups of 3 to 10 carbon atoms, alkenyl groups of 2 to 10 carbon atoms, alkenyloxy groups of 2 to 10 carbon atoms, and 2 to 10 carbon atoms alkynyl group, alkynyloxy group having 2 to 10 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, cycloalkoxy group having 3 to 10 carbon atoms, cycloalkenyl group having 3 to 10 carbon atoms, number of carbon atoms an organic group selected from a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon carbon
  • R 11 to R 13 is a fluorine atom.
  • M m+ is an alkali metal cation, an alkaline earth metal cation, or an onium cation, where m represents an integer of the same number as the valence of the corresponding cation.
  • At least one of R 11 to R 13 is a fluorine atom; At least one of R 11 to R 13 is preferably a compound selected from hydrocarbon groups having 6 or less carbon atoms which may contain fluorine atoms.
  • At least one of R 11 to R 13 is a fluorine atom; at least one of R 11 to R 13 is a methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxyl group, vinyl group, allyl group, allyloxy group, ethynyl group, 2-propynyl group, 2-propynyloxy; group, phenyl group, phenyloxy group, 2,2-difluoroethyl group, 2,2-difluoroethyloxy group, 2,2,2-trifluoroethyl group, 2,2,2-trifluoroethyloxy group, 2 , 2,3,3-tetrafluoropropyl group, 2,2,3,3-tetrafluoropropyloxy group, 1,1,1,3,3,3-hexafluoroisopropyl group, and 1,1,1, Compounds selected from 3,3,3
  • the counter cation M m+ of the salt having the imide anion represented by the general formula (5) is preferably selected from the group consisting of lithium ion, sodium ion, potassium ion and tetraalkylammonium ion.
  • the alkyl group and alkoxyl group represented by R 11 to R 13 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tertiary butyl group, pentyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, and 1,1,1,3,3,3 Examples include alkyl groups having 1 to 10 carbon atoms such as -hexafluoroisopropyl group, fluorine-containing alkyl groups, and alkoxy groups derived from these groups.
  • the alkenyl group and alkenyloxy group include alkenyl groups having 2 to 10 carbon atoms such as vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, and 1,3-butadienyl group. Examples include fluorine alkenyl groups and alkenyloxy groups derived from these groups.
  • the alkynyl group and alkynyloxy group include alkynyl groups and fluorine-containing alkynyl groups having 2 to 10 carbon atoms such as ethynyl group, 2-propynyl group, and 1,1 dimethyl-2-propynyl group, and these groups. Examples include derivatized alkynyloxy groups.
  • Cycloalkyl groups and cycloalkoxy groups include cycloalkyl groups and fluorine-containing cycloalkyl groups having 3 to 10 carbon atoms such as cyclopentyl and cyclohexyl groups, and cycloalkoxy groups derived from these groups. .
  • the cycloalkenyl group and cycloalkenyloxy group include cycloalkenyl groups and fluorine-containing cycloalkenyl groups having 3 to 10 carbon atoms such as cyclopentenyl group and cyclohexenyl group, and cycloalkenyloxy groups derived from these groups. groups.
  • Aryl groups and aryloxy groups include aryl groups and fluorine-containing aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl, and xylyl groups, and aryloxy groups derived from these groups. .
  • the content of the other additive in the non-aqueous electrolyte is preferably 0.01% by mass or more and 8.0% by mass or less with respect to the total amount of the non-aqueous electrolyte.
  • the negative electrode coating is used as "other additives". Formation effect and positive electrode protection effect can be exhibited.
  • the content in the non-aqueous electrolyte is preferably 0.01% by mass to 5.0% by mass.
  • ionic salts in this case include lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, lithium bis(trifluoromethanesulfonyl)imide, and bis(trifluoromethanesulfonyl).
  • Alkali metal salts other than the above solutes may be used as additives.
  • Specific examples include carboxylates such as lithium acrylate, sodium acrylate, lithium methacrylate, and sodium methacrylate, and sulfate ester salts such as lithium methyl sulfate, sodium methyl sulfate, lithium ethyl sulfate, and sodium ethyl sulfate. .
  • the non-aqueous electrolyte of the present disclosure includes vinylene carbonate, lithium bis(oxalato)borate, lithium difluorooxalatoborate, lithium difluorobis(oxalato)phosphate, lithium tetrafluorooxalatophosphate, bis(fluorosulfonyl)imide It preferably contains at least one selected from lithium, (difluorophosphoryl)(fluorosulfonyl)imidelithium, 1,3-propenesultone and 1,3-propanesultone.
  • non-aqueous electrolyte of the present disclosure can also contain a polymer, and the non-aqueous electrolyte is pseudo-solidified with a gelling agent or a cross-linked polymer as in the case of using a non-aqueous electrolyte battery called a polymer battery. It is also possible to use Polymer solid electrolytes also include those containing non-aqueous organic solvents as plasticizers.
  • the polymer is not particularly limited as long as it is an aprotic polymer capable of dissolving the above (I) to (III) and other additives.
  • examples thereof include polymers having polyethylene oxide as a main chain or side chain, homopolymers or copolymers of polyvinylidene fluoride, methacrylic acid ester polymers, polyacrylonitrile, and the like.
  • an aprotic non-aqueous organic solvent is preferred among the above non-aqueous organic solvents.
  • the non-aqueous electrolyte battery of the present disclosure includes at least the non-aqueous electrolyte of the present disclosure, a negative electrode, and a positive electrode. Furthermore, it is preferable to include a separator, an outer package, and the like.
  • the negative electrode is not particularly limited, it is preferable to use a material in which alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions can be reversibly intercalated and deintercalated.
  • the positive electrode is not particularly limited, it is preferable to use a material in which alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions can be reversibly intercalated and deintercalated.
  • the cation is lithium
  • lithium metal when the cation is lithium
  • a conductive polymer or the like is used.
  • the carbon material include graphitizable carbon, non-graphitizable carbon (also called hard carbon) having a (002) plane spacing of 0.37 nm or more, and (002) plane spacing of 0.37 nm or more.
  • Graphite of 37 nm or less can be used, and the latter includes artificial graphite, natural graphite, and the like.
  • lithium-containing transition metal composite oxides such as LiCoO 2 , LiNiO 2 , LiMnO 2 and LiMn 2 O 4 are used as the positive electrode material, and the lithium-containing transition metal composite oxides such as Co, Mn and Ni are used.
  • Phosphate compounds of transition metals oxides such as TiO 2 , V 2 O 5 and MoO 3 , sulfides such as TiS 2 and FeS, conductive polymers such as polyacetylene, polyparaphenylene, polyaniline and polypyrrole, activated carbon , a polymer that generates radicals, a carbon material, or the like is used.
  • Acetylene black, ketjen black, carbon fiber, or graphite as a conductive material and polytetrafluoroethylene, polyvinylidene fluoride, or SBR resin as a binder are added to the positive electrode and negative electrode materials, and then molded into a sheet.
  • An electrode sheet can be used.
  • Nonwoven fabrics and porous sheets made of polypropylene, polyethylene, paper, glass fiber, etc. are used as separators to prevent contact between the positive and negative electrodes.
  • a coin-shaped, cylindrical, rectangular, or aluminum laminate sheet-shaped electrochemical device is assembled from the above elements.
  • LiPF 6 was added in an amount that gave a concentration of 1.0 mol/L with respect to the total amount of the non-aqueous electrolyte
  • lithium difluorophosphate was mixed with the non-aqueous organic solvent and LiPF 6 .
  • Lithium difluorophosphate was added so as to have a concentration of 0.5% by mass with respect to the total amount, and dissolved by stirring for 1 hour to prepare a comparative non-aqueous electrolyte 1-1 of Comparative Example 1-1.
  • component (IV) LiPF 6
  • Non-aqueous electrolyte 1-1 except that the type and content of component (I), the type and content of component (II), and the type and content of other additives are changed as shown in Table 1, and Non-aqueous electrolyte solutions 1-2, 1-3, comparative non-aqueous electrolyte solutions 1-2, 1-4, 1-5, reference non-aqueous electrolyte solutions were prepared in the same manner as in the preparation of comparative non-aqueous electrolyte solution 1-1. Got 1-3.
  • Example 2-1 to 2-3 Comparative Examples 2-1 to 2-2, Reference Example 2-3> (Preparation of nonaqueous electrolyte solutions 2-1 to 2-3, comparative nonaqueous electrolyte solutions 2-1 to 2-2, and reference nonaqueous electrolyte solution 2-3)
  • Non-aqueous electrolyte 1-1 and comparative non-aqueous electrolyte 1-1 except that the type and content of component (I) and the type and content of component (II) were changed as shown in Table 2.
  • Non-aqueous electrolyte solutions 2-1 to 2-3, comparative non-aqueous electrolyte solutions 2-1 to 2-2, and reference non-aqueous electrolyte solution 2-3 were obtained in the same manner as in the preparation.
  • Example 3-1 to 3-3 Comparative Examples 3-1 to 3-2, Reference Example 3-3> (Preparation of non-aqueous electrolytes 3-1 to 3-3, comparative non-aqueous electrolytes 3-1 to 3-2, and reference non-aqueous electrolyte 3-3)
  • Non-aqueous electrolyte 1-1 and comparative non-aqueous electrolyte 1-1 except that the type and content of component (I) and the type and content of component (II) were changed as shown in Table 3.
  • Non-aqueous electrolyte solutions 3-1 to 3-3, comparative non-aqueous electrolyte solutions 3-1 to 3-2, and reference non-aqueous electrolyte solution 2-3 were obtained in the same manner as in the preparation.
  • Examples 4-1 to 4-3, Comparative Examples 4-1 to 4-2> (Preparation of non-aqueous electrolyte solutions 4-1 to 4-3 and comparative non-aqueous electrolyte solutions 4-1 to 4-2)
  • Non-aqueous electrolyte solutions 4-1 to 4-3 and comparative non-aqueous electrolyte solutions 4-1 to 4-2 were obtained in the same manner as in the preparation.
  • Examples 5-1 to 5-3, Comparative Examples 5-1 to 5-2> (Preparation of non-aqueous electrolytes 5-1 to 5-3 and comparative non-aqueous electrolytes 5-1 to 5-2)
  • Non-aqueous electrolyte solutions 5-1 and 5-2 and comparative non-aqueous electrolyte solutions 5-1 and 5-2 were obtained in the same manner as in the preparation.
  • Example 6-1 to 6-3 Comparative Example 6-1> (Preparation of non-aqueous electrolytes 6-1 to 6-3 and comparative non-aqueous electrolyte 6-1)
  • Non-aqueous electrolyte solutions 6-1 to 6-3 and comparative non-aqueous electrolyte solution 6-1 were obtained in the same manner as in the preparation.
  • VC vinylene carbonate
  • DFP lithium difluorophosphate
  • BFPI lithium bis(difluorophosphate)imide
  • MSF methanesulfonyl fluoride
  • MDSDF methanedisulfonyl difluoride.
  • TFBL means lithium tetrafluoroborate
  • FS means lithium fluorosulfonate.
  • the content of component (I) represents the concentration relative to the total amount of components (I) to (IV).
  • the content of component (II) represents the concentration relative to the total amount of components (I) to (IV).
  • NCM622 positive electrode 90% by mass of LiNi 0.6 Co 0.2 Mn 0.2 O 2 powder is mixed with 5% by mass of polyvinylidene fluoride (hereinafter also referred to as PVDF) as a binder and 5% by mass of acetylene black as a conductive material, Further, N-methyl-2-pyrrolidone was added to prepare a positive electrode mixture paste. This paste was applied to both sides of an aluminum foil (A1085), dried and pressed, and then punched out to a size of 4 cm ⁇ 5 cm to obtain an NCM622 positive electrode for testing.
  • PVDF polyvinylidene fluoride
  • the non-aqueous electrolyte battery using the non-aqueous electrolyte of the present disclosure containing component (I) and component (II) has low initial resistance and is excellent.
  • component (I) and component (II) have low initial resistance and is excellent.
  • the compound (1a) and DFP are used in combination at 0.5% by mass, respectively, the vinylene carbonate disclosed in Patent Document 1 and the lithium difluorophosphate disclosed in Patent Document 2 are used in combination at 1.0% by mass. A result was obtained that the resistance value was lower than in the case.

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Abstract

La présente invention concerne un électrolyte liquide non aqueux et une batterie à électrolyte liquide non aqueux qui ont une faible valeur de résistance initiale grâce à un électrolyte liquide non aqueux contenant un solvant organique non aqueux, un soluté, et au moins un composé choisi dans le groupe constitué par les composés représentés par la formule générale (1) et des composés représentés par les formules générales (2)-(4) et (6) divulgués dans la description.
PCT/JP2022/001224 2021-01-22 2022-01-14 Électrolyte liquide non aqueux et batterie à électrolyte liquide non aqueux WO2022158398A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024197640A1 (fr) * 2023-03-29 2024-10-03 宁德时代新能源科技股份有限公司 Additif d'électrolyte, électrolyte, batterie rechargeable et dispositif électrique

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020036222A1 (fr) * 2018-08-16 2020-02-20 セントラル硝子株式会社 Solution électrolytique non aqueuse et batterie secondaire à électrolyte non aqueux
WO2021015264A1 (fr) * 2019-07-24 2021-01-28 セントラル硝子株式会社 Solution d'électrolyte non aqueux, batterie à électrolyte non aqueux et composé

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020036222A1 (fr) * 2018-08-16 2020-02-20 セントラル硝子株式会社 Solution électrolytique non aqueuse et batterie secondaire à électrolyte non aqueux
WO2021015264A1 (fr) * 2019-07-24 2021-01-28 セントラル硝子株式会社 Solution d'électrolyte non aqueux, batterie à électrolyte non aqueux et composé

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024197640A1 (fr) * 2023-03-29 2024-10-03 宁德时代新能源科技股份有限公司 Additif d'électrolyte, électrolyte, batterie rechargeable et dispositif électrique

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