WO2022158400A1 - Électrolyte non aqueux, et batterie à électrolyte non aqueux - Google Patents

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

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WO2022158400A1
WO2022158400A1 PCT/JP2022/001227 JP2022001227W WO2022158400A1 WO 2022158400 A1 WO2022158400 A1 WO 2022158400A1 JP 2022001227 W JP2022001227 W JP 2022001227W WO 2022158400 A1 WO2022158400 A1 WO 2022158400A1
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group
atom
carbon atoms
general formula
aqueous electrolyte
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PCT/JP2022/001227
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English (en)
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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    • 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 discloses a method for improving cycle characteristics by including methanesulfonic anhydride in a non-aqueous electrolyte. Further, Patent Document 2 discloses a method for improving cycle characteristics by including ethylene sulfate in a non-aqueous electrolytic solution.
  • non-aqueous electrolytes are required to improve battery characteristics from various perspectives.
  • a methanesulfonic anhydride or an ethylene sulfate-containing non-aqueous electrolytic solution is used, while the cycle characteristics are improved, there is still room for improvement in other characteristics. It turned out that there was
  • 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 that can exhibit a well-balanced effect of improving cycle characteristics and reducing the initial resistance value.
  • the present inventors have made intensive studies, and found that the compound represented by the general formula (1) as the component (I), the general formulas (2) to (3) as the component (II), ( 5) a non-aqueous electrolytic solution containing at least one compound selected from the group consisting of the compounds represented by (III), a solute as component (III), and a non-aqueous organic solvent as component (IV), thereby improving cycle characteristics and It has been found that a non-aqueous electrolyte battery can be obtained which can exhibit, in a well-balanced manner, the effect of reducing the initial resistance value and the effect of reducing the initial resistance value.
  • 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 of the alkyl group and the alkylene group may be substituted with a fluorine atom. ]
  • the compound represented by the general formula (2) is a compound having a cyclic skeleton composed of 4 to 7 atoms selected from carbon atoms, oxygen atoms, and sulfur atoms. It has a sulfonyl group and at least one oxygen atom.
  • the cyclic skeleton may contain an unsaturated bond.
  • the state of sulfur atoms forming the cyclic skeleton is selected from S, SO and SO2.
  • n represents the number of carbon atoms contained in the cyclic skeleton.
  • R 5 is bonded to a carbon atom forming the cyclic skeleton and each independently represents a hydrogen atom, a fluorine atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms, the aliphatic hydrocarbon group being oxygen It may contain at least one of an atom and an unsaturated bond, and any hydrogen atom of the aliphatic hydrocarbon group may be substituted with a fluorine atom. Further, when the carbon atoms forming the cyclic skeleton are adjacent to each other, those carbon atoms may constitute a part of an aromatic ring, and the aromatic ring has 1 to 4 carbon atoms.
  • a hydrocarbon group may be attached. The hydrocarbon group bonded to the aromatic ring may contain at least one of an oxygen atom and an unsaturated bond, and any hydrogen atom of the hydrocarbon group may be substituted with a fluorine atom. ]
  • X represents a sulfonyl group or a ketone group
  • R 6 and R 7 each independently represent a hydrocarbon group having 1 to 10 carbon atoms
  • the hydrocarbon group is a fluorine atom, an oxygen It may have at least one selected from the group consisting of atoms, unsaturated bonds, and ester bonds.
  • each R 11 is independently a vinyl group, an allyl group, a 1-propenyl group, an ethynyl group, or a 2-propynyl group. Plural R 11 may be the same or different.
  • Each R 12 is independently a fluorine atom, an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group, an alkynyloxy group, an aryl group, or an aryloxy group, and these groups other than the fluorine atom may have at least one of a fluorine atom and an oxygen atom. When there is more than one R 12 , they may be the same or different.
  • y is 2-4.
  • R 1 and R 2 in the general formula (1) are each independently POF 2 or SO 2 F.
  • 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;
  • 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.
  • non-aqueous electrolyte and a non-aqueous electrolyte battery that can exhibit the effect of improving cycle characteristics and the effect of reducing the initial resistance value in a well-balanced manner.
  • the initial resistance value refers to the initial charge and discharge for forming the electrode film, and then the non-aqueous electrolyte battery after performing two cycles of charge and discharge for stabilizing the battery.
  • the discharge capacity after storage for a week is the remaining capacity after storage
  • the discharge capacity after charging and discharging after that is the recovery capacity after storage
  • the ratio of the discharge capacity performed immediately before storage at 60 ° C. and the remaining capacity after storage is stored.
  • the post-remaining capacity retention ratio and the ratio of the discharge capacity immediately before storage at 60° C. to the post-storage recovery capacity are expressed as the post-storage recovery capacity retention ratio.
  • the resistance value obtained by impedance measurement performed thereafter is referred to as the resistance value after storage
  • the ratio between the initial resistance value and the resistance value after storage is referred to as the resistance value retention rate after storage.
  • 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 (3) and (5); (III) a solute and (IV) a non-aqueous electrolyte containing a non-aqueous organic solvent.
  • the non-aqueous electrolytic solution of the present disclosure includes a compound represented by general formula (1) (hereinafter sometimes referred to as "component (I)” or simply “(I)”).
  • component (I) a compound represented by general formula (1)
  • 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 component (I) forming a film on the electrode surface together with the component (II) described later the effect of improving the cycle characteristics of the non-aqueous electrolyte battery and the effect of reducing the initial resistance value can be exhibited in a well-balanced manner. The inventors presume that.
  • 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, and any of R 3 and R 4 is more preferably a lithium ion.
  • 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) a compound (also referred to as compound (1c)), a compound represented by formula (1e) (also referred to as compound (1e)), a compound represented by formula (1p) (also referred to as compound (1p)), and At least one selected from the group consisting of compounds represented by formula (1w) (also referred to as compound (1w)), more preferably compound (1a), compound (1e), and compound (1w) It is at least one selected from the group, and particularly preferably compound (1a) or compound (1e).
  • 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 the non-aqueous electrolyte battery using the non-aqueous electrolyte and the effect of improving each characteristic after storage are easily obtained. .
  • the concentration of (I) 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 is at least one compound selected from the group consisting of compounds represented by general formulas (2) to (3) and (5) (hereinafter referred to as "component (II)” or simply " (II)”).
  • the non-aqueous electrolyte containing the component (II) is used in a non-aqueous electrolyte battery (for example, a lithium ion secondary battery), the component (II) is decomposed at least on either the positive electrode or the negative electrode, and durability At least one of the surfaces of the positive electrode and the negative electrode is coated with a coating excellent in This coating improves the cycle characteristics of the non-aqueous electrolyte battery.
  • the component (II) forming a film on the electrode surface together with the component (I) described above, the effect of improving the cycle characteristics of the non-aqueous electrolyte battery and the effect of reducing the initial resistance value can be exhibited in a well-balanced manner.
  • the inventors presume that.
  • the compounds represented by formula (2) are described below.
  • the compound represented by the general formula (2) is a compound having a cyclic skeleton composed of 4 to 7 atoms selected from carbon atoms, oxygen atoms, and sulfur atoms, and a sulfonyl group adjacent to the cyclic skeleton. and at least one oxygen atom.
  • the cyclic skeleton may contain an unsaturated bond.
  • the state of the sulfur atom forming the cyclic skeleton is selected from S, SO and SO2.
  • n represents the number of carbon atoms contained in the cyclic skeleton.
  • R 5 is bonded to a carbon atom forming a cyclic skeleton and each independently represents a hydrogen atom, a fluorine atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms, the aliphatic hydrocarbon group being an oxygen atom; and at least one unsaturated bond, and hydrogen atoms of the aliphatic hydrocarbon group may be substituted with fluorine atoms.
  • the carbon atoms forming the cyclic skeleton are adjacent to each other, those carbon atoms may constitute a part of the aromatic ring, and the aromatic ring may be carbonized with 1 to 4 carbon atoms.
  • a hydrogen group may be attached.
  • the hydrocarbon group bonded to the aromatic ring may contain at least one of an oxygen atom and an unsaturated bond, and a hydrogen atom of the hydrocarbon group may be substituted with a fluorine atom.
  • the cyclic skeleton of general formula (2) has 4 to 7 atoms selected from carbon atoms, oxygen atoms, and sulfur atoms as ring members.
  • the compound represented by general formula (2) is preferably at least one selected from the group consisting of 1,3-propanesultone, 1,3-propenesultone, and ethylene sulfate.
  • X represents a sulfonyl group or a ketone group
  • R 6 and R 7 are each independently selected from hydrocarbon groups having 1 to 10 carbon atoms, and the hydrocarbon groups are fluorine atoms, oxygen atoms, unsaturated bonds, and It may have at least one selected from the group consisting of an ester bond.
  • the compound represented by the general formula (3) is preferably at least one selected from the group consisting of methanesulfonic anhydride, ethanesulfonic anhydride, and trifluoromethanesulfonic anhydride. , especially methanesulfonic anhydride.
  • Each R 11 is independently a vinyl group, an allyl group, a 1-propenyl group, an ethynyl group, or a 2-propynyl group.
  • Plural R 11 may be the same or different. It is preferred that at least one of R 11 is a vinyl group.
  • Each R 12 is independently a fluorine atom, an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group, an alkynyloxy group, an aryl group, or an aryloxy group, and these groups other than the fluorine atom may have at least one of a fluorine atom and an oxygen atom. When there is more than one R 12 , they may be the same or different.
  • y is 2 to 4, preferably 3 to 4, more preferably 4.
  • the compound represented by the general formula (5) is preferably at least one selected from the group consisting of the following compounds (1-1) to (1-28), especially (1- 1), (1-2), (1-3), (1-4), (1-6), (1-7), (1-8), (1-10), (1-12) , (1-15), (1-22), (1-23), (1-24), (1-25), (1-26), (1-27), and (1-28) From the viewpoint of ease of synthesis and stability of the compound, at least one selected from the group consisting of is more preferable.
  • (1-1), (1-2), (1-4), (1-10), (1-12), (1-15), (1-22), (1-24) ), (1-25), and (1-28) are preferably at least one selected from the group consisting of (1-1), (1-2), ( 1-12), (1-15), and (1-24), more preferably at least one selected from the group consisting of (1-15) tetravinylsilane and (1-24) methyl At least one selected from the group consisting of trivinylsilane is more preferred, and tetravinylsilane is particularly preferred.
  • the content of (II) with respect to the total (100% by mass) of (I), (II), (III) and (IV) (hereinafter also referred to as "concentration of (II)" ), 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 (II) 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 (II) By setting the concentration of (II) to 0.01% by mass or more, the effect of improving the cycle characteristics 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 (II) to 10.0% by mass or less, the viscosity increase of the non-aqueous electrolyte can be suppressed, and the effect of improving the cycle characteristics of the non-aqueous electrolyte battery using the non-aqueous electrolyte can be obtained. easier to get.
  • 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, since 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 at 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 (4) as another additive.
  • R 8 to R 10 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
  • R 8 to R 10 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.
  • the compound (salt having an imide anion) represented by the general formula (4) has at least one PF bond or SF bond, excellent low temperature properties can be obtained.
  • At least one of R 8 to R 10 is a fluorine atom; At least one of R 8 to R 10 is preferably a compound selected from hydrocarbon groups having 6 or less carbon atoms which may contain fluorine atoms.
  • At least one of R 8 to R 10 is a fluorine atom; at least one of R 8 to R 10 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 (4) 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 8 to R 10 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, 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 nonaqueous electrolyte is preferably 0.01% by mass or more and 8.0% by mass or less with respect to the total amount of the nonaqueous 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 and (difluorophosphoryl)(fluorosulfonyl)imidelithium.
  • 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.
  • Examples 1-2 to 1-3, Comparative Examples 1-1 to 1-4, Reference Examples 1-1 to 1-3> (Preparation of nonaqueous electrolytes 1-2 to 1-3, comparative nonaqueous electrolytes 1-1 to 1-4, and reference nonaqueous electrolytes 1-1 to 1-3)
  • a non-aqueous electrolyte was prepared in the same manner as the non-aqueous electrolyte 1-1, except that the type and amount of component (I) and the type and amount of component (II) were changed as shown in Table 1.
  • 1-2 to 1-3, comparative nonaqueous electrolytes 1-1 to 1-4, and reference nonaqueous electrolytes 1-1 to 1-3 were obtained.
  • Example 2-1 to 2-3 Comparative Example 2-1> (Preparation of non-aqueous electrolyte solutions 2-1 to 2-3 and comparative non-aqueous electrolyte solution 2-1)
  • a non-aqueous electrolyte was prepared in the same manner as the non-aqueous electrolyte 1-1 except that the type and amount of component (I) and the type and amount of component (II) were changed as shown in Table 2.
  • 2-1 to 2-3 and Comparative Nonaqueous Electrolyte 2-1 were obtained.
  • Example 3-1 to 3-3 Comparative Example 3-1> (Preparation of non-aqueous electrolyte solutions 3-1 to 3-3 and comparative non-aqueous electrolyte solution 3-1)
  • a non-aqueous electrolyte was prepared in the same manner as the non-aqueous electrolyte 1-1 except that the type and amount of component (I) and the type and amount of component (II) were changed as shown in Table 3.
  • 3-1 to 3-3 and a comparative non-aqueous electrolyte 3-1 were obtained.
  • 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)
  • a non-aqueous electrolyte was prepared in the same manner as the non-aqueous electrolyte 1-1 except that the type and amount of component (I) and the type and amount of component (II) were changed as shown in Table 4. 4-1 to 4-3, and comparative non-aqueous electrolytes 4-1 to 4-2 were obtained.
  • Examples 5-1 to 5-3, Comparative Examples 5-1 to 5-2> (Preparation of nonaqueous electrolytes 5-1 to 5-3 and comparative nonaqueous electrolytes 5-1 to 5-2) A non-aqueous electrolyte was prepared in the same manner as the non-aqueous electrolyte 1-1, except that the type and amount of component (I) and the type and amount of component (II) were changed as shown in Table 5. 5-1 to 5-3, and comparative non-aqueous electrolytes 5-1 to 5-2 were obtained.
  • PS 1,3-propanesultone
  • Esa ethylene sulfate
  • MSA methanesulfonic anhydride
  • TVSi tetravinylsilane
  • MTVSi methyltrivinylsilane.
  • the content of component (I) is a value relative to the total amount of components (I) to (IV).
  • the content of component (II) is a value 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 the component (I) and the component (II) has the effect of improving the cycle characteristics and the effect of reducing the initial resistance value. It can be seen that it is excellent in terms of For example, the combined use of 0.5% by mass of compound (1a) and methanesulfonic anhydride, respectively, is faster than the case of containing 1.0% by mass of methanesulfonic anhydride alone disclosed in Patent Document 1. An unexpected result was obtained that the resistance value could be reduced and the capacity retention rate after cycling was higher.
  • non-aqueous electrolyte and a non-aqueous electrolyte battery that can exhibit the effect of improving cycle characteristics and the effect of reducing the initial resistance value in a well-balanced manner.

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Abstract

L'invention concerne (I) un composé représenté par la formule générale (1), (II) un composé d'au moins une sorte choisie dans un groupe constitué d'un composé représenté par les formules générales (2) à (3) et (5), (III) un soluté, et (IV) un électrolyte non aqueux comprenant un solvant organique non aqueux. Plus précisément, l'invention fournit un électrolyte non aqueux permettant de développer un équilibre satisfaisant entre effets améliorant les caractéristiques de cycle et effets réduisant la valeur de résistance initiale, et fournit également une batterie à électrolyte non aqueux. Ｓｉ（Ｒ１１）ｙ（Ｒ１２）４－ｙ（５）
PCT/JP2022/001227 2021-01-22 2022-01-14 Électrolyte non aqueux, et batterie à électrolyte non aqueux WO2022158400A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114552015A (zh) * 2022-02-25 2022-05-27 珠海市赛纬电子材料股份有限公司 电解液添加剂、锂离子电池电解液及锂离子电池

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018078103A (ja) * 2016-11-02 2018-05-17 株式会社豊田自動織機 非水系二次電池並びにこれに用いられるガス発生抑制剤及び非水系電解液
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
JP2018078103A (ja) * 2016-11-02 2018-05-17 株式会社豊田自動織機 非水系二次電池並びにこれに用いられるガス発生抑制剤及び非水系電解液
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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114552015A (zh) * 2022-02-25 2022-05-27 珠海市赛纬电子材料股份有限公司 电解液添加剂、锂离子电池电解液及锂离子电池
CN114552015B (zh) * 2022-02-25 2024-04-05 珠海市赛纬电子材料股份有限公司 电解液添加剂、锂离子电池电解液及锂离子电池

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