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WO2014128940A1 - Solution d'électrolyte non aqueux pour batteries secondaires et batterie secondaire au lithium-ion - Google Patents

Solution d'électrolyte non aqueux pour batteries secondaires et batterie secondaire au lithium-ion Download PDF

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Publication number
WO2014128940A1
WO2014128940A1 PCT/JP2013/054614 JP2013054614W WO2014128940A1 WO 2014128940 A1 WO2014128940 A1 WO 2014128940A1 JP 2013054614 W JP2013054614 W JP 2013054614W WO 2014128940 A1 WO2014128940 A1 WO 2014128940A1
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compound
carbon atoms
group
ocf
lithium
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Japanese (ja)
Inventor
真男 岩谷
祐 小野崎
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AGC Inc
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Asahi Glass Co Ltd
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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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or 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 non-aqueous electrolyte for a secondary battery and a lithium ion secondary battery.
  • a non-aqueous electrolyte used for a lithium ion secondary battery (hereinafter sometimes simply referred to as “secondary battery”) generally exhibits high lithium ion conductivity by dissolving a lithium salt well,
  • carbonate solvents such as ethylene carbonate and dimethyl carbonate have been widely used because they have a wide potential window.
  • carbonate-based solvents are flammable and may ignite due to battery heat generation.
  • a fluorinated solvent Patent Document 1
  • the fluorine-based solvent has a low lithium salt solubility and tends to have poor cycle characteristics.
  • Non-aqueous electrolysis with excellent solubility of lithium salt which is composed mainly of fluorine-based solvent with high incombustibility (flame retardant), and complexed with lithium salt and glyme solvent by adding glyme solvent.
  • Patent Document 2 A liquid has been proposed (Patent Document 2).
  • a lithium ion secondary battery is charged and discharged at a voltage of about 4.3 V in terms of the withstand voltage characteristics of the nonaqueous electrolyte.
  • a non-aqueous electrolyte that can be charged and discharged at a higher voltage is required in order to be applied to an in-vehicle power source of an electric vehicle that requires larger energy.
  • the present invention relates to a non-aqueous electrolyte for a secondary battery having sufficient cycle characteristics and excellent withstand voltage characteristics that enables charging and discharging at a higher voltage, and the non-aqueous electrolysis for the secondary battery.
  • An object is to provide a lithium ion secondary battery using the liquid.
  • a non-aqueous electrolyte comprising a lithium salt and a liquid composition
  • the liquid composition comprises a medium containing one or more fluorine-containing ether compounds selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), and a donor number of 10
  • the ligand compound includes a phosphate ester compound represented by the following formula (3):
  • the ratio N O / N Li of the total number of moles of oxygen atoms (N O ) of the phosphonyl group in the phosphate compound to the total number of moles of lithium atoms derived from the lithium salt (N Li ) is 1 or more, Wherein for N Li, the ratio N A / N Li of the total number of moles of coordinating atoms to the lithium atoms of the ligand compound (N A) is 4
  • R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a fluorinated alkyl group having 1 to 10 carbon atoms, or 3 to 10 carbon atoms
  • R 1 and R 2 each represents one or both of a fluorinated alkyl group having 1 to 10 carbon atoms, a fluorinated cycloalkyl group having 3 to 10 carbon atoms, or a carbon number of 2 to 1 having one or more etheric oxygen atoms.
  • X is an alkylene group having 1 to 5 carbon atoms, a fluorinated alkylene group having 1 to 5 carbon atoms, an alkylene group having 2 to 5 carbon atoms having one or more etheric oxygen atoms, or one or more etheric oxygen atoms And a fluorinated alkylene group having 2 to 5 carbon atoms.
  • R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms, a fluorinated alkyl group having 1 to 5 carbon atoms, an alkylene group having 1 to 10 carbon atoms formed by linking R 3 and R 4 , or A fluorinated alkylene group having 1 to 10 carbon atoms formed by linking R 3 and R 4 ;
  • Y is a halogen atom, an alkoxy group having 1 to 5 carbon atoms, or a fluorinated alkoxy group having 1 to 5 carbon atoms; is there.
  • the phosphate compound is trimethyl phosphate, triethyl phosphate, tris phosphate (2,2,2-trifluoroethyl), tris phosphate (2,2,3,3-tetrafluoropropyl),
  • the non-aqueous electrolyte for secondary batteries according to the above [1] which is one or more compounds selected from the group consisting of compounds represented by the following formulas (3-1) to (3-3).
  • the fluorine-containing ether compound is CF 3 CH 2 OCF 2 CHF 2 , CF 3 CH 2 OCF 2 CHFCF 3 , CHF 2 CF 2 CH 2 OCF 2 CHF 2 , CH 3 CH 2 CH 2 OCF 2 CHF 2 , CH 3 CH 2 OCF 2 CHF 2 , CH 3 CH 2 OCF 2 CHFCF 3, CH 3 CH 2 CH 2 OCF 2 CHF 2, CH 3 CH 2 CH 2 OCF 2 CHFCF 3, and CHF 2 CF 2 CH 2 OCF 2 CHFCF
  • the nonaqueous electrolytic solution for a secondary battery according to any one of the above [1] to [5], which is one or more compounds selected from the group consisting of 3 .
  • the liquid composition further includes at least one coordination selected from the group consisting of a cyclic carbonate compound, a chain monocarbonate compound, a cyclic carboxylic acid ester compound, a chain carboxylic acid ester compound, and a cyclic sulfone compound.
  • the nonaqueous electrolytic solution for a secondary battery according to any one of the above [1] to [6], which contains a child compound.
  • a negative electrode using as an active material a positive electrode having a material capable of inserting and extracting lithium ions as an active material and one or more selected from the group consisting of lithium metal, a lithium alloy, and a carbon material capable of inserting and extracting lithium ions.
  • a non-aqueous electrolyte for a secondary battery according to any one of [1] to [7] above.
  • the non-aqueous electrolyte for a secondary battery of the present invention has sufficient cycle characteristics and has excellent withstand voltage characteristics that enable charging and discharging at a higher voltage.
  • the lithium ion secondary battery of the present invention has sufficient cycle characteristics and can be charged and discharged at a higher voltage.
  • fluorination means that a part or all of hydrogen atoms bonded to a carbon atom is substituted with a fluorine atom.
  • the fluorinated alkyl group is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.
  • the partially fluorinated group there are a hydrogen atom and a fluorine atom.
  • the perfluoroalkyl group is a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.
  • the carbon-carbon unsaturated bond is a carbon-carbon double bond or a carbon-carbon triple bond.
  • Non-aqueous electrolyte for secondary battery comprises a lithium salt and a liquid composition.
  • the liquid composition has a medium containing one or more fluorine-containing ether compounds selected from the group consisting of the compound (1) and the compound (2) described later, a donor number of 10 or more, and a withstand voltage of 5. 1 or more types of ligand compounds which are 5V or more.
  • a non-aqueous electrolyte is an electrolyte that does not substantially contain water, and even if it contains water, the amount of water is in a range where performance degradation of a secondary battery using the non-aqueous electrolyte is not observed.
  • the amount of water that can be contained in the non-aqueous electrolyte is preferably 500 ppm by mass or less, more preferably 100 ppm by mass or less, and 50 ppm by mass or less with respect to the total mass of the non-aqueous electrolyte. It is particularly preferred.
  • the lower limit of the moisture content is 0 mass ppm.
  • Lithium salt is an electrolyte that dissociates in a non-aqueous electrolyte and supplies lithium ions.
  • the lithium salt LiPF 6 , the following compound (A) (where k is an integer of 1 to 5), FSO 2 N (Li) SO 2 F, CF 3 SO 2 N (Li) SO 2 CF 3 CF 3 CF 2 SO 2 N (Li) SO 2 CF 2 CF 3 , LiClO 4 , the following compound (B), the following compound (C), and LiBF 4 are preferably used.
  • the lithium salt contained in the nonaqueous electrolytic solution of the present invention may be only one type or two or more types.
  • the combination in the case of using 2 or more types of lithium salt together includes the combination disclosed in International Publication No. 2009/133899.
  • the lithium salt preferably comprises LiPF 6, and particularly preferably composed of only LiPF 6.
  • Examples of the compound (A) include the following compound (A-1) to compound (A-4).
  • the compound (A) preferably includes a compound (A-2) in which k is 2 from the viewpoint of easily obtaining a non-aqueous electrolyte having high conductivity, and only from the compound (A-2) in which k is 2 More preferably.
  • the content of the lithium salt in the nonaqueous electrolytic solution is not particularly limited, but is preferably 0.5 to 1.5 mol / L.
  • the lower limit value of the lithium salt content is more preferably 0.7 mol / L.
  • the upper limit of the lithium salt content is more preferably 1.2 mol / L.
  • the content of the lithium salt in the non-aqueous electrolyte is preferably 5 to 20 mass%.
  • the lower limit of the content of the lithium salt in the non-aqueous electrolyte is more preferably 7% by mass, and still more preferably 8% by mass. Moreover, 18 mass% is more preferable, and, as for the upper limit of content of the said lithium salt, 16 mass% is further more preferable.
  • the medium of the liquid composition in the nonaqueous electrolytic solution of the present invention contains one or more fluorine-containing ether compounds selected from the group consisting of the following compound (1) and the following compound (2).
  • the fluorine-containing ether compound has excellent withstand voltage characteristics and flame retardancy that enable charging and discharging at high voltage.
  • the fluorine-containing ether compound contained in the liquid composition may be one type or two or more types. The ratio in the case of two or more fluorine-containing ether compounds can be arbitrarily determined.
  • R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a fluorinated alkyl group having 1 to 10 carbon atoms, or a carbon number of 3
  • R 1 and R 2 is a fluorinated alkyl group having 1 to 10 carbon atoms, a fluorinated cycloalkyl group having 3 to 10 carbon atoms, or a carbon number having one or more etheric oxygen atoms 2 to 10 fluorinated alkyl groups.
  • X is an alkylene group having 1 to 5 carbon atoms, a fluorinated alkylene group having 1 to 5 carbon atoms, an alkylene group having 2 to 5 carbon atoms having one or more etheric oxygen atoms, or A fluorinated alkylene group having 2 to 5 carbon atoms having one or more etheric oxygen atoms.
  • Examples of the alkyl group and the alkyl group having an etheric oxygen atom include groups each having a linear structure, a branched structure, or a partially cyclic structure (for example, a cycloalkylalkyl group).
  • One or both of R 1 and R 2 in the compound (1) has a fluorinated alkyl group having 1 to 10 carbon atoms, a fluorinated cycloalkyl group having 3 to 10 carbon atoms, or one or more etheric oxygen atoms A fluorinated alkyl group having 2 to 10 carbon atoms. When one or both of R 1 and R 2 are these groups, the solubility of the lithium salt in the non-aqueous electrolyte and the flame retardancy are excellent.
  • R 1 and R 2 in the compound (1) may be the same or different.
  • compound (1) a compound in which R 1 and R 2 are both fluorinated alkyl groups having 1 to 10 carbon atoms (hereinafter referred to as compound (1-A)), and R 1 is one or more compounds.
  • a compound having a etheric oxygen atom and having 2 to 10 carbon atoms and R 2 being a fluorinated alkyl group having 1 to 10 carbon atoms (hereinafter referred to as compound (1-B)) is preferable.
  • compound (1-A) is more preferred.
  • the molecular weight of the compound (1) is preferably 150 to 800, more preferably 150 to 500, and particularly preferably 200 to 500.
  • the number of etheric oxygen atoms in the compound (1) having an etheric oxygen atom is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1. When the etheric oxygen atom in the compound (1) is in this range, the non-aqueous electrolyte is excellent in flame retardancy.
  • the fluorine content in the compound (1) refers to the ratio of the total mass of fluorine atoms in the molecular weight
  • the non-aqueous electrolyte is excellent in withstand voltage characteristics and flame retardancy. . 50 mass% or more is preferable and, as for the fluorine content in a compound (1), 60 mass% or more is more preferable.
  • the compound (1) is preferably a compound in which both R 1 and R 2 are alkyl groups in which some of the hydrogen atoms of the alkyl group are fluorinated.
  • the compound (1) is more preferably a compound in which one or both ends of R 1 and R 2 are —CF 2 H groups.
  • the liquid composition has excellent lithium salt solubility.
  • Specific examples of the compound (1-A), the compound (1-B), and the compound other than the compound (1-A) and the compound (1-B) include, for example, compounds described in International Publication No. 2009/133899 Etc.
  • the compound (1-A) is preferable, and CF 3 CH 2 OCF 2 CHF 2 (trade name: AE-3000, manufactured by Asahi Glass Co., Ltd.), CF 3 CH 2 OCF 2 CHFCF 3 , CHF 2 CF 2 CH 2 OCF 2 CHF 2, CH 3 CH 2 CH 2 OCF 2 CHF 2, CH 3 CH 2 OCF 2 CHF 2, CH 3 CH 2 OCF 2 CHFCF 3, CH 3 CH 2 CH 2 OCF 2 CHF 2, CH 3 CH
  • One or more selected from the group consisting of 2 CH 2 OCF 2 CHFCF 3 and CHF 2 CF 2 CH 2 OCF 2 CHFCF 3 is more preferred, and CF 3 CH 2 OCF 2 CHF 2 , CHF 2 CF 2 CH 2 OCF 2 CHFCF 3 or a mixture thereof is particularly preferred.
  • CF 3 CH 2 OCF 2 CHF 2 , CHF 2 CF 2 CH 2 OCF 2 CHFCF 3 or a mixture thereof is particularly preferred. If compound (1) is the said compound, a non-aqueous
  • X may have a linear structure or a branched structure.
  • X is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms.
  • the alkylene group preferably has a linear structure or a branched structure.
  • the side chain is preferably an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms having an etheric oxygen atom.
  • compound (2) is the said compound, a non-aqueous electrolyte will be excellent in the solubility of a lithium salt, a withstand voltage characteristic, and a flame retardance.
  • Specific examples of the compound (2) include a compound represented by the following formula.
  • the fluorine-containing ether compound compound (1), compound (2), or a mixture of compound (1) and compound (2) is preferred, and compound (1) alone or compound (2) alone is more preferred.
  • the nonaqueous electrolytic solution of the present invention contains the compound (1)
  • the compound (1) may be used alone or in combination of two or more.
  • the non-aqueous electrolyte of this invention contains a compound (2), only 1 type may be sufficient as a compound (2) and 2 or more types may be sufficient as it.
  • the compound (1) (mass: Va) and the compound (2) (mass: Vb) are used in combination as the fluorine-containing ether compound, their mass ratio (Vb / Va) is preferably 0.01 to 100, and 0 1 to 10 is more preferable.
  • the medium in the nonaqueous electrolytic solution of the present invention may contain a medium other than the above-described fluorine-containing ether compound.
  • the other medium include a fluorine-containing alkane.
  • the non-aqueous electrolyte of the present invention contains a fluorinated alkane, the non-aqueous electrolyte is further excellent in withstand voltage characteristics and flame retardancy.
  • the fluorine-containing alkane refers to a compound in which one or more hydrogen atoms in the alkane are substituted with fluorine atoms and hydrogen atoms remain.
  • the fluorine-containing alkane preferably has 4 to 12 carbon atoms.
  • the liquid composition can dissolve lithium salt if the vapor pressure of the non-aqueous electrolyte is low and the fluorine-containing alkane having 12 or less carbon atoms. Excellent in properties.
  • the fluorine content in the fluorine-containing alkane is preferably 50 to 80% by mass.
  • the fluorine content in the fluorine-containing alkane is 50% by mass or more, the non-aqueous electrolyte is excellent in voltage resistance characteristics and flame retardancy.
  • the fluorine content in the fluorine-containing alkane is 80% by mass or less, the liquid composition has excellent lithium salt solubility.
  • fluorine-containing alkane a compound having a linear structure is preferable.
  • a fluorine-containing alkane may be used individually by 1 type, and may use 2 or more types together.
  • the ratio W 1 / W of the mass (W 1 ) of the fluorinated ether compound to the mass (W) of the medium in the nonaqueous electrolytic solution of the present invention is 0.80 or more.
  • the W 1 / W is preferably 0.85 or more, and more preferably 0.90 or more.
  • the upper limit value of W 1 / W is 1. When the W 1 / W is within this range, the non-aqueous electrolyte of the present invention is excellent in withstand voltage characteristics and flame retardancy.
  • the content of the fluorine-containing ether compound in the liquid composition is preferably 30 to 80% by mass.
  • the lower limit of the content of the fluorine-containing ether compound is more preferably 35% by mass, and still more preferably 40% by mass.
  • the upper limit of the content of the fluorine-containing ether compound is more preferably 70% by mass and even more preferably 65% by mass. If content of the said fluorine-containing ether compound is below an upper limit, a liquid composition is excellent in the solubility of lithium salt. Moreover, if content of the said fluorine-containing ether compound is more than a lower limit, a withstand voltage characteristic and a flame retardance will be excellent.
  • the ratio W 2 / W of the mass (W 2 ) of the other medium to the mass (W) of the entire medium in the nonaqueous electrolytic solution is a withstand voltage.
  • 0.01 to 0.2 is preferable, and 0.01 to 0.1 is more preferable.
  • the content of the fluorinated alkane in the liquid composition is preferably 5 to 40% by mass.
  • the withstand voltage characteristics and flame retardancy are excellent.
  • a liquid composition is excellent in the solubility of lithium salt.
  • the content of the medium in the liquid composition is preferably 0.01 to 40% by mass, more preferably 0.01 to 30% by mass.
  • the content is preferably 0.01% by mass to 20% by mass.
  • the content of the medium in the liquid composition is preferably 30 to 80% by mass, more preferably 35 to 78% by mass, further preferably 38 to 75% by mass, and particularly preferably 40 to 70% by mass. Further, the content of the medium in the non-aqueous electrolyte is preferably 25 to 76% by mass, more preferably 30 to 73% by mass, further preferably 33 to 69% by mass, and particularly preferably 34 to 65% by mass. When the content of the medium is not less than the lower limit value, the withstand voltage characteristics and flame retardancy are excellent. If content of the said medium is below an upper limit, a liquid composition is excellent in the solubility of lithium salt.
  • the liquid composition in the nonaqueous electrolytic solution of the present invention has a donor compound having a donor number of 10 or more and a withstand voltage by a linear sweep voltammetry method of 5.5 V (potential with respect to lithium metal, hereinafter the same) or more. , "Ligand Compound (A)").
  • the ligand compound (A) in the present invention has an atom coordinated to a lithium atom, that is, an electron pair of an atom having an electron pair donating ability, and coordinated to a lithium atom derived from a lithium salt to form a complex. To solvate the lithium salt. Due to the ligand compound (A), the liquid composition is excellent in the solubility of the lithium salt.
  • the number of donors is a parameter relating to the electron pair donating ability of a solvent molecule, defined by V. Gutmann, E. Wychera, Inorg. Nucl. Chem. Lett., 2, 257 (1996), and 1,2-dichloroethane. It is the - ⁇ H value (unit: kcal ⁇ mol ⁇ 1 ) of the equilibrium when a 1: 1 complex of antimony pentachloride and a measuring molecule is formed.
  • the withstand voltage is a decomposition voltage of the ligand compound measured using a linear sweep voltammetry method with platinum as a working electrode.
  • the ligand compound (A) forms a complex by donating electrons to the lithium salt, and the non-aqueous electrolyte is excellent in the solubility of the lithium salt.
  • the number of donors is preferably 12 or more, and more preferably 14 or more.
  • the withstand voltage of the ligand compound (A) by the linear sweep voltammetry method is 5.5 V or more, the non-aqueous electrolyte can be charged and discharged at a high voltage.
  • the withstand voltage is preferably 5.6 V or more, and more preferably 5.8 V or more.
  • the ligand compound (A) includes a phosphate ester compound (compound (3)) represented by the following formula (3).
  • compound (3) phosphate ester compound represented by the following formula (3).
  • R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms, a fluorinated alkyl group having 1 to 5 carbon atoms, or the number of carbon atoms formed by linking R 3 and R 4.
  • Y is a halogen atom, an alkoxy group having 1 to 5 carbon atoms, or 1 carbon atom; -5 fluorinated alkoxy groups.
  • the alkyl group, fluorinated alkyl group, alkylene group, and fluorinated alkylene group in R 3 and R 4 of the compound (3) may each have a linear structure or a branched structure.
  • R 3 and R 4 in the compound (3) may be the same or different when they are not linked.
  • R 3 and R 4 in the compound (3) are preferably a methyl group, an ethyl group, CF 3 CH 2 —, or CHF 2 CF 2 CH 2 — when they are not linked.
  • an ethylene group is preferred.
  • the alkoxy group for Y may have a linear structure or a branched structure.
  • Y is preferably a fluorine atom, a methoxy group, an ethoxy group, CF 3 CH 2 —O—, or CHF 2 CF 2 CH 2 —O—.
  • the compound (3) includes trimethyl phosphate, triethyl phosphate, tris phosphate (2,2,2-trifluoroethyl), tris phosphate (2,2,3,3-tetrafluoropropyl). And at least one selected from the group consisting of the following compounds (3-1) to (3-3), more preferably trimethyl phosphate or triethyl phosphate.
  • the compound (3) is any of these compounds, the nonaqueous electrolytic solution is excellent in withstand voltage characteristics.
  • Compound (3) may be used alone or in combination of two or more.
  • the liquid composition is a compound other than the compound (3), the number of donors is 10 or more, and the other withstand voltage is 5.5 V or more (hereinafter referred to as “other coordination”).
  • other ligand compounds (A1) include cyclic carbonate compounds, chain monocarbonate compounds, cyclic carboxylic acid ester compounds, chain carboxylic acid ester compounds, and cyclic sulfone compounds.
  • the cyclic carbonate compound is a compound in which the ring skeleton has a ring structure composed of carbon atoms and oxygen atoms, and the ring structure has a carbonate bond represented by —O—C ( ⁇ O) —O—. .
  • the ring structure in the cyclic carbonate compound is preferably a 4- to 10-membered ring, more preferably a 4- to 7-membered ring, more preferably a 5- to 6-membered ring, and particularly preferably a 5-membered ring from the viewpoint of availability.
  • the ring structure of the cyclic carbonate compound is preferably a ring structure having one carbonate bond.
  • a ring structure in which a carbonate bond is formed by linking with a linear alkylene group or vinylene group is more preferable.
  • the linear alkylene group preferably has 1 to 7 carbon atoms, more preferably 1 to 4, more preferably 2 or 3. 2 is particularly preferable.
  • Specific examples include propylene carbonate (PC), ethylene carbonate (EC), and butylene carbonate (BC).
  • Examples of the carbonate compound having a ring structure formed by linking a carbonate bond to a vinylene group include vinylene carbonate and dimethyl vinylene carbonate, with vinylene carbonate being particularly preferred.
  • the cyclic carbonate compound is also preferably a compound in which one or more hydrogen atoms of the linear alkylene group are substituted with a substituent.
  • a substituent for example, a halogen atom, an alkyl group, a halogenated alkyl group, a vinyl group, or an allyl group is preferable.
  • Specific examples include fluoroethylene carbonate (FEC).
  • FEC fluoroethylene carbonate
  • the ligand compound (A) includes a cyclic carbonate compound
  • the cyclic carbonate compound may be only one type or two or more types.
  • the non-aqueous electrolyte contains a cyclic carbonate compound, it is preferable because the dielectric constant of the non-aqueous electrolyte is increased.
  • the chain monocarbonate compound is a chain compound having no carbonate structure and having one carbonate bond represented by —O—C ( ⁇ O) —O—.
  • Examples of the chain monocarbonate include dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC).
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • the chain monocarbonate compound may be only one kind or two or more kinds. It is preferable that the non-aqueous electrolyte contains a chain monocarbonate compound because the viscosity of the non-aqueous electrolyte is low.
  • a cyclic carboxylic acid ester compound is a compound in which the ring skeleton has a ring structure composed of carbon atoms and oxygen atoms, and the ring structure has an ester bond.
  • the cyclic carboxylic acid ester compound is preferably a compound containing no carbon-carbon unsaturated bond in the molecule.
  • the ring structure in the cyclic carboxylic acid ester compound is preferably a 4- to 10-membered ring, more preferably a 4- to 7-membered ring, more preferably a 5- to 6-membered ring, and particularly preferably a 5-membered ring from the viewpoint of availability.
  • the ring structure of the cyclic carboxylic acid ester compound is preferably a ring structure having one ester bond.
  • the cyclic carboxylic acid ester compound may be a compound in which one or more hydrogen atoms of the linear alkylene group are substituted with a substituent.
  • substituent include a halogen atom, an alkyl group, and a halogenated alkyl group.
  • cyclic carboxylic acid ester compounds such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexanolactone, and ⁇ -valerolactone, and carbon atoms forming the ring structure of the cyclic carboxylic acid ester compound.
  • examples thereof include compounds in which one or more hydrogen atoms are substituted with a halogen atom, an alkyl group, or a halogenated alkyl group.
  • ⁇ -butyrolactone or ⁇ -valerolactone is preferable, and ⁇ -butyrolactone is particularly preferable from the viewpoint of easy availability and properties of the electrolytic solution.
  • the cyclic carboxylic acid ester compound may be only one type or two or more types.
  • the stability of the nonaqueous electrolytic solution is excellent.
  • a chain carboxylic acid ester compound is a chain compound having no ester structure and having an ester bond.
  • the chain carboxylic acid ester compound is preferably a chain monoester having one ester bond. Examples of the chain monoester include ethyl acetate, ethyl butyrate, butyl acetate and the like.
  • the chain carboxylic acid ester compound may be only one kind or two or more kinds. It is preferable to contain a chain carboxylic acid ester compound because the viscosity of the nonaqueous electrolytic solution is low.
  • the cyclic sulfone compound is a compound in which the ring skeleton has a ring structure composed of a carbon atom and a sulfur atom, and the ring structure has a sulfone bond represented by —C—S ( ⁇ O) 2 —C—. is there.
  • the cyclic sulfone compound is preferably a compound that does not contain a carbon-carbon unsaturated bond in the molecule.
  • the ring structure in the cyclic sulfone compound is preferably a 4- to 10-membered ring, more preferably a 4- to 7-membered ring, more preferably a 5- to 6-membered ring, and particularly preferably a 5-membered ring from the viewpoint of availability.
  • the ring structure of the cyclic sulfone compound is preferably a ring structure having one sulfone bond.
  • the cyclic sulfone compound may be a compound in which one or more hydrogen atoms of the linear alkylene group are substituted with a substituent. Examples of the substituent include a halogen atom, an alkyl group, and a halogenated alkyl group. Specific examples include sulfolane.
  • the ligand compound (A) includes a cyclic sulfone compound
  • the cyclic sulfone compound may be only one type or two or more types. A cyclic sulfone compound is preferable because the dielectric constant of the non-aqueous electrolyte is large.
  • the ligand compound (A) only the compound (3) may be used, or the compound (3) and another ligand compound (A1) may be used in combination. 40 mass% or more is preferable, as for the ratio of the mass of the compound (3) with respect to the total mass of a ligand compound (A), 50 mass% or more is more preferable, and 55 mass% or more is further more preferable. If the ratio of a compound (3) is this range, a non-aqueous electrolyte will be excellent in the solubility of a lithium salt, and a withstand voltage characteristic.
  • the content of the ligand compound (A) in the liquid composition is preferably 10 to 70% by mass.
  • the lower limit of the content of the ligand compound (A) is more preferably 15% by mass, further preferably 18% by mass, and particularly preferably 20% by mass.
  • the upper limit of the content of the ligand compound (A) is more preferably 65% by mass, further preferably 62% by mass, and particularly preferably 60% by mass.
  • the content of the ligand compound (A) in the nonaqueous electrolytic solution is preferably 8 to 67% by mass.
  • the lower limit of the content of the ligand compound (A) is more preferably 13% by mass, further preferably 16% by mass, and particularly preferably 17% by mass.
  • the upper limit of the content of the ligand compound (A) is more preferably 61% by mass, further preferably 57% by mass, and particularly preferably 56% by mass. If content of the said ligand compound (A) is more than a lower limit, a liquid composition is excellent in the solubility of lithium salt. Further, if the content of the ligand compound (A) is not more than the upper limit value, the content of the medium, particularly the fluorinated ether compound, is increased, so that the non-aqueous electrolyte has a withstand voltage characteristic and flame retardancy. Excellent.
  • the content of the compound (3) in the liquid composition is preferably 10 to 70% by mass.
  • the lower limit of the content of the compound (3) is more preferably 15% by mass, further preferably 18% by mass, and particularly preferably 20% by mass.
  • the upper limit of the content of the compound (3) is more preferably 65% by mass, further preferably 60% by mass, and particularly preferably 55% by mass. If content of the said compound (3) is more than a lower limit, lithium salt will melt
  • the lower limit value of / N Li is 1, 2 is preferable, and 3 is more preferable.
  • 6 is preferable, as for the upper limit of the ratio N 2 O / N Li , 5 is more preferable, and 4 is particularly preferable. If the N 2 O 3 / N Li is not less than the lower limit value, the solubility of the lithium salt is excellent. If the ratio N 2 O / N Li is not more than the upper limit value, excellent withstand voltage characteristics can be easily obtained.
  • the total number of moles of atoms coordinated to lithium atoms in the ligand compound (A) relative to the total number of moles of lithium atoms derived from lithium salt (N Li ) contained in the non-aqueous electrolyte of the present invention ( The ratio N A / N Li of N A ) is 4-8 .
  • the upper limit of the ratio N A / N Li is preferably 6. If the ratio N A / N Li is not less than the lower limit, the liquid composition is excellent in the solubility of the lithium salt. If the ratio N A / N Li is equal to or less than the upper limit value, the non-aqueous electrolyte is excellent in voltage endurance characteristics and flame retardancy.
  • ligand compound total moles of coordinating atoms to lithium atoms in (A) and (N A), each of the ligand compound (A) coordinating the lithium atom in a molecule It is the sum total of the products of the number of atoms that are positioned, that is, the coordination number T of the ligand compound (A) to the lithium atom and the number of moles of the ligand compound (A).
  • the N A is the coordination number T of the ligand compound (A)
  • the ligand compound It is a product of the number of moles of A).
  • the N A for each of the ligand compound (A), the coordination number of the ligand compound (A) T And the product of the number of moles of the ligand compound (A), and the sum of them.
  • the method for calculating the coordination number T to the lithium atom of the ligand compound (A) will be described in detail in the Examples section.
  • the nonaqueous electrolytic solution of the present invention may contain other components as necessary.
  • Other components include, for example, conventionally known overcharge prevention agents, dehydrating agents, deoxidizing agents, characteristic improvement aids for improving capacity retention characteristics and cycle characteristics after high-temperature storage, and electrode combinations of non-aqueous electrolytes. Examples thereof include surfactants that help impregnate the material and separator.
  • overcharge inhibitor examples include aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, and dibenzofuran; 2-fluoro Fluorinated products of the above aromatic compounds such as biphenyl, o-cyclohexylfluorobenzene, p-cyclohexylfluorobenzene; fluorinated anisole compounds such as 2,4-difluoroanisole, 2,5-difluoroanisole and 2,6-difluoroaniol Etc.
  • aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether,
  • the liquid composition contains an overcharge inhibitor
  • only one overcharge inhibitor may be used, or two or more overcharge inhibitors may be used.
  • the content of the overcharge inhibitor in the liquid composition is preferably 0.01 to 5% by mass.
  • the dehydrating agent examples include molecular sieves, sodium sulfate, magnesium sulfate, calcium hydride, sodium hydride, potassium hydride, lithium aluminum hydride and the like.
  • the medium used for the non-aqueous electrolyte of the present invention it is preferable to use a medium which has been subjected to rectification after dehydration with the dehydrating agent. Moreover, you may use the medium which performed only the dehydration by the said dehydrating agent, without performing rectification.
  • Examples of the characteristic improvement aid for improving capacity maintenance characteristics and cycle characteristics after high-temperature storage include succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, dihydrate Carboxylic anhydride such as glycolic acid, cyclohexanedicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phenylsuccinic anhydride; ethylene sulfite, methyl methanesulfonate, busulfan, sulfolane, sulfolene, dimethylsulfone, diphenylsulfone Sulfur-containing compounds such as methylphenylsulfone, dibutyldisulfide, dicyclohexyldisulfide, tetramethylthiuram monosulfide, N, N-dimethylmethanesulfonamide, N, N-diethy
  • Hydrocarbon compounds; fluorine-containing aromatic compounds such as fluorobenzene, difluorobenzene, hexafluorobenzene, benzotrifluoride and the like can be mentioned.
  • the property improving aid may be only one kind or two or more kinds.
  • the content of the property improving aid in the liquid composition is preferably 0.01 to 5% by mass.
  • any of a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant may be used. Agents are preferred.
  • a fluorine-containing surfactant is preferable from the viewpoint of high oxidation resistance and good cycle characteristics and rate characteristics.
  • the anionic fluorine-containing surfactant the following compound (4-1) or compound (4-2) is preferable.
  • R 5 and R 6 are each independently a perfluoroalkyl group having 4 to 20 carbon atoms or a perfluoroalkyl group having 4 to 20 carbon atoms having one or more etheric oxygen atoms.
  • M 1 and M 2 are each independently an alkali metal or NH (R 7 ) 3 (R 7 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which may be the same group or different groups. Good.)
  • R 5 and R 6 are each a C 4-20 perfluoroalkyl group or a C 4 carbon atom having one or more etheric oxygen atoms from the viewpoint of a good degree of reducing the surface tension of the non-aqueous electrolyte.
  • a perfluoroalkyl group having 20 to 20 carbon atoms is preferred.
  • An alkyl group is more preferred.
  • the structure of R 5 and R 6 may be a linear structure or a branched structure, and may contain a ring structure.
  • R 5 and R 6 are preferably linear structures because they are readily available and have a good surface activity.
  • the alkali metal of M 1 and M 2 Li, Na, or K is preferable.
  • M 1 and M 2 NH 4+ is particularly preferable.
  • Specific examples of the compound (4-1) include, for example, C 4 F 9 COO — NH 4 + , C 5 F 11 COO — NH 4 + , C 6 F 13 COO — NH 4 + , C 5 F 11 COO ⁇ .
  • C 5 F 11 COO ⁇ NH 4 + , C 5 F 11 COO ⁇ Li + , and C 6 F 13 COO ⁇ Li are preferred because of their good solubility in non-aqueous electrolytes and the effect of reducing surface tension.
  • solubility in the nonaqueous electrolytic solution from the viewpoint of satisfactory effect of reducing the surface tension, C 4 F 9 SO 3 - NH 4 +, C 6 F 13 SO 3 - NH 4 +, C 4 F 9 SO 3 - Li +, C 6 F 13 SO 3 - Li +, C 8 F 17 SO 3 - Li +, C 3 F 7 OCF (CF 3) CF 2 OCF (CF 3) SO 3 - NH 4 +, C 3 F 7 OCF (CF 3) CF 2 OCF (CF 3) SO 3 - Li +, C 3 F 7 OCF (CF 3) SO 3 - NH 4 +, or C 3 F 7 OCF (CF 3 ) SO 3 - Li + is preferred.
  • the surfactant may be only one type or two or more types.
  • the upper limit of the content of the surfactant in the liquid composition is preferably 5% by mass, more preferably 3% by mass, and even more preferably 2% by mass.
  • the lower limit is preferably 0.05% by mass.
  • composition 1 LiPF 6 , compound (A), FSO 2 N (Li) SO 2 F, CF 3 SO 2 N (Li) SO 2 CF 3 , CF 3 CF 2 SO 2 N (Li) SO 2 CF 2 CF 3 , LiClO 4
  • LiPF 6 LiPF 6 , compound (A), FSO 2 N (Li) SO 2 F, CF 3 SO 2 N (Li) SO 2 CF 3 , CF 3 CF 2 SO 2 N (Li) SO 2 CF 2 CF 3 , LiClO 4
  • LiPF 6 LiPF 6 , compound (A), FSO 2 N (Li) SO 2 F, CF 3 SO 2 N (Li) SO 2 CF 3 , CF 3 CF 2 SO 2 N (Li) SO 2 CF 2 CF 3 , LiClO 4
  • LiPF 6 LiPF 6 , compound (A), FSO 2 N (Li) SO 2 F, CF 3 SO 2 N (Li) SO 2 CF 3 ,
  • composition 2 is more preferable.
  • Composition 2 One or more lithium salts selected from the group consisting of LiPF 6 , CF 3 SO 2 N (Li) SO 2 CF 3 , CF 3 CF 2 SO 2 N (Li) SO 2 CF 2 CF 3 , LiClO 4 and LiBF 4 And; CF 3 CH 2 OCF 2 CHF 2 , CF 3 CH 2 OCF 2 CHFCF 3 , CHF 2 CF 2 CH 2 OCF 2 CHF 2 , CH 3 CH 2 CH 2 OCHF 2 , CH 3 CH 2 OCF 2 CHF 2 , CHF 2 CF 2 CH 2 OCF 2 CHFCF 3 , CH 3 CH 2 OCF 2 CHFCF 3 , CH 3 CH 2 CH 2 OCF 2 CHFCF 3 , CH 3 CH 2 CH 2 OCF 2 CHF 2 , CH 3 CH 2 CH 2 OCF 2 CHFCF 3 , represented by the formula (2) and compounds wherein X is CH 2 CH 2, and wherein is represented by formula (2) and X is CH (CH
  • composition 3 is particularly preferred.
  • Composition 3 A nonaqueous electrolytic solution for a secondary battery containing LiPF 6 , CHF 2 CF 2 CH 2 OCF 2 CFHCF 3 and trimethyl phosphate.
  • the lithium ion secondary battery of this invention is a secondary battery characterized by having a positive electrode, a negative electrode, and the non-aqueous electrolyte of this invention.
  • the positive electrode include an electrode in which a positive electrode layer containing a positive electrode active material, a conductivity-imparting agent, and a binder is formed on a current collector.
  • the positive electrode active material may be any material that can occlude and release lithium ions, and known positive electrode active materials for lithium ion secondary batteries can be employed. Examples thereof include lithium-containing transition metal oxides, lithium-containing transition metal composite oxides using one or more transition metals, transition metal oxides, transition metal sulfides, metal oxides, and olivine-type metal lithium salts.
  • transition metal oxides include TiO 2 , MnO 2 , MoO 3 , V 2 O 5 , V 6 O 13 , transition metal sulfides TiS 2 , FeS, MoS 2 , metal oxides SnO 2 , Examples thereof include SiO 2 .
  • the olivine-type metallic lithium salt is Li L X x Y y O z F g (where X is Fe (II), Co (II), Mn (II), Ni (II), V (II), or Cu ( II), Y represents P or Si, and represents numbers satisfying 0 ⁇ L ⁇ 3, 1 ⁇ x ⁇ 2, 1 ⁇ y ⁇ 3, 4 ⁇ z ⁇ 12, and 0 ⁇ g ⁇ 1, respectively. Or a complex thereof.
  • the active material which forms a positive electrode may be used individually by 1 type, and may use 2 or more types together.
  • a material in which a substance having a composition different from that of the substance constituting the main cathode active material is attached to the surface of the cathode active material can be used.
  • Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, etc .; lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate And sulfates such as aluminum sulfate; carbonates such as lithium carbonate, calcium carbonate, and magnesium carbonate.
  • the lower limit of the mass with respect to the positive electrode active material is preferably 0.1 mass ppm, more preferably 1 mass ppm, and particularly preferably 10 mass ppm.
  • the upper limit is preferably 20% by mass, more preferably 10% by mass, and particularly preferably 5% by mass.
  • the surface adhering substance can suppress the oxidation reaction of the nonaqueous electrolytic solution on the surface of the positive electrode active material, and can improve the battery life.
  • a lithium-containing composite oxide based on an ⁇ -NaCrO 2 structure such as LiCoO 2 , LiNiO 2 , LiMnO 2, or the like, LiMn 2 O, because of its high discharge voltage and high electrochemical stability
  • LiCoO 2 , LiNiO 2 , LiMnO 2, or the like, LiMn 2 O because of its high discharge voltage and high electrochemical stability
  • a lithium-containing composite oxide based on a spinel structure such as 4 is preferred.
  • Examples of the conductivity-imparting agent include carbon materials and conductive oxide powders.
  • Examples of the binder include resin binders such as polyvinylidene fluoride, and rubber binders such as hydrocarbon rubber and fluorine rubber.
  • Examples of the current collector include a metal thin film mainly composed of Al or the like.
  • Examples of the negative electrode include an electrode in which a negative electrode layer containing a powdered negative electrode active material, a conductivity-imparting agent, and a binder is formed on a current collector.
  • Examples of the negative electrode active material include one or more selected from the group consisting of a lithium metal, a lithium alloy, and a carbon material capable of inserting and extracting lithium ions.
  • Examples of the carbon material include graphite, coke, and hard carbon.
  • Examples of the lithium alloy include a Li—Al alloy, a Li—Pb alloy, a Li—Si alloy, and a Li—Sn alloy.
  • the negative electrode binder and the conductivity-imparting agent can be the same as those for the positive electrode.
  • a metal thin film mainly composed of Cu or the like can be used.
  • a negative electrode active material can maintain a shape in itself (for example, lithium metal thin film)
  • a negative electrode can be formed only with a negative electrode active material.
  • a separator is interposed between the positive electrode and the negative electrode to prevent a short circuit.
  • An example of the separator is a porous film.
  • a non-aqueous electrolyte is used by impregnating the porous membrane.
  • you may use as a gel electrolyte what impregnated the porous film with the nonaqueous electrolyte solution, and was made to gelatinize.
  • porous film those which are stable with respect to the non-aqueous electrolyte and excellent in liquid retention can be used, such as polyvinylidene fluoride, polytetrafluoroethylene, a copolymer of ethylene and tetrafluoroethylene, a fluorine resin, polyimide, Or the porous sheet or nonwoven fabric which uses polyolefin, such as polyethylene and a polypropylene, as a raw material is preferable.
  • the material of the porous film is preferably a polyolefin such as polyethylene or polypropylene.
  • separator inorganic fine particles such as silica, alumina, titania, etc.
  • the material of the battery casing used in the lithium ion secondary battery of the present invention include nickel-plated iron, stainless steel, aluminum or an alloy thereof, nickel, titanium, a resin material, and a film material.
  • the shape of the secondary battery may be selected according to the application, and may be any shape such as a coin shape, a cylindrical shape, a square shape, and a laminate shape. Moreover, the shape of a positive electrode and a negative electrode can be suitably selected according to the shape of a secondary battery.
  • the charging voltage of the secondary battery of the present invention is preferably 3.4 V or more, more preferably 4.0 V or more, further preferably 4.2 V or more, and particularly preferably 4.5 V or more.
  • the positive electrode active material of the secondary battery is a lithium-containing transition metal oxide, a lithium-containing transition metal composite oxide, a transition metal oxide, a transition metal sulfide, or a metal oxide
  • the charging voltage is preferably 4.2 V or more, 4.5V or more is more preferable.
  • the positive electrode active material is an olivine type lithium metal salt
  • the charging voltage is preferably 3.2 V or higher, and more preferably 3.4 V or higher.
  • the secondary battery of the present invention since the secondary battery of the present invention described above uses the non-aqueous electrolyte of the present invention, it has excellent withstand voltage characteristics in addition to sufficient cycle characteristics. Therefore, the secondary battery of the present invention includes a mobile phone, a portable game machine, a digital camera, a digital video camera, an electric tool, a notebook computer, a portable information terminal, a portable music player, an electric vehicle, a hybrid vehicle, a train, an aircraft, an artificial It can be applied to various uses such as satellites, submarines, ships, uninterruptible power supplies, robots, and power storage systems. In addition, the secondary battery of the present invention is particularly effective as a large-sized secondary battery for electric vehicles, hybrid vehicles, trains, airplanes, artificial satellites, submarines, ships, uninterruptible power supply devices, robots, power storage systems, and the like.
  • Examples 1 to 7 are production examples
  • Examples 8 to 11 are examples
  • Examples 12 and 13 are comparative examples.
  • the coordination number T of the ligand compound (A) was calculated from the obtained equivalent number Q by the above formula (I). Table 1 shows the coordination number T to the lithium atom of the ligand compound (A) obtained by the coordination number measurement test 1.
  • the coordination number T to the lithium atom was determined by the following coordination number measurement test 2.
  • the coordination number measurement test 2 is the same as the coordination number measurement test 1, in which the complex of LiPF 6 and the ligand compound is precipitated in CHF 2 CF 2 CH 2 OCF 2 CHFCF 3 or is in a two-layer separation state. By doing so, it can be used for a ligand compound whose coordination number T to a lithium atom is not required.
  • the reason why the coordination number T to the lithium atom calculated by the coordination number measurement tests 1 and 2 is not an integer is that the ligand compound (A) having a plurality of atoms that can coordinate to the lithium atom (for example, diethyl carbonate) If this is the case, one carbonyl oxygen and two ether oxygens) may be due to a mixture of atoms involved in coordination and atoms not involved in coordination.
  • the withstand voltage of the ligand compound was measured by the linear sweep voltammetry method shown below.
  • a 1 cm square platinum plate was used as a working electrode, a 1.5 cm square lithium metal foil as a counter electrode, and a lithium ribbon as a reference electrode.
  • a non-aqueous electrolyte prepared by mixing ethylene carbonate and ethyl methyl carbonate in equal volumes and dissolving LiPF 6 so as to have a concentration of 1M
  • a non-aqueous electrolyte prepared by mixing ligand compounds in the same volume Each of the electrodes described above was impregnated, and the voltage was swept from the open circuit voltage to a noble voltage up to 8 V at a sweep rate of 5 mV / sec.
  • Nonaqueous electrolytes 2 to 6 were obtained in the same manner as in Example 1 except that the composition of each compound was changed as shown in Table 4.
  • Example 7 To 10 mL of HFE5510, 10 mmol of LiPF 6 was added with stirring, and the mixture was stirred for 30 minutes under sealing. Thereafter, a part thereof was dissolved in deuterated acetonitrile (CD 3 CN), and 19 F-NMR measurement was performed. As a result, dissolution of LiPF 6 could not be confirmed.
  • CD 3 CN deuterated acetonitrile
  • AE-3000 CF 3 CH 2 OCF 2 CHF 2 (trade name: AE-3000, manufactured by Asahi Glass Co., Ltd.).
  • HFE5510 CHF 2 CF 2 CH 2 OCF 2 CHFCF 3.
  • TMP Trimethyl phosphate (withstand voltage 6.8 V, donor number 23).
  • EC ethylene carbonate (withstand voltage 6.6 V, donor number 16).
  • PC propylene carbonate (withstand voltage 6.8 V, donor number 15).
  • EMC Ethyl methyl carbonate (withstand voltage 6.6 V).
  • the number of donors of EMC is considered to be approximately equal to the number of donors of diethyl carbonate because of its structure.
  • the donor number of diethyl carbonate is 15.
  • Example 8 4.48 g of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as a positive electrode active material, 0.56 g of acetylene black as a conductivity-imparting agent, and polyvinylidene fluoride (PVdF) as a binder 4.67 g was added to 12.55 g of N-methylpyrrolidone (NMP) as a solvent and mixed to form a slurry. Thereafter, the slurry was coated on an aluminum foil having a thickness of 20 ⁇ m, dried and pressed, and punched into a circle having a diameter of 18 mm to obtain a positive electrode.
  • NMP N-methylpyrrolidone
  • a lithium metal foil was punched into a circle having a diameter of 19 mm to form a negative electrode.
  • a polyolefin microporous membrane was used as a separator. The polyolefin microporous membrane was sandwiched between the positive electrode and the negative electrode, and 0.5 mL of the nonaqueous electrolyte solution 1 prepared in Example 1 was added thereto to prepare an evaluation cell 1. .
  • Example 9 An evaluation cell 2 was prepared in the same manner as in Example 8, except that the nonaqueous electrolytic solution 2 prepared in Example 2 was used as the nonaqueous electrolytic solution.
  • Example 10 An evaluation cell 3 was prepared in the same manner as in Example 8 except that the nonaqueous electrolytic solution 3 prepared in Example 3 was used as the nonaqueous electrolytic solution.
  • Example 11 An evaluation cell 4 was prepared in the same manner as in Example 8 except that the nonaqueous electrolytic solution 4 prepared in Example 4 was used as the nonaqueous electrolytic solution.
  • Example 12 An evaluation cell 5 was prepared in the same manner as in Example 8 except that the nonaqueous electrolytic solution 5 prepared in Example 5 was used.
  • Example 13 An evaluation cell 6 was prepared in the same manner as in Example 8 except that the nonaqueous electrolytic solution 6 prepared in Example 6 was used as the nonaqueous electrolytic solution.
  • a charge / discharge cycle test of 50 cycles was performed in such a flow that the above-described charge / discharge cycle was one cycle and the next cycle under the same condition was started after a 10-minute pause after discharge.
  • the ratio of the discharge capacity of cycle 50 to the discharge capacity of cycle 1 was defined as the discharge capacity retention rate, and the cycle characteristics were evaluated. The results are shown in Table 5.
  • the secondary batteries of Examples 8 to 10 using the nonaqueous electrolytic solution of the present invention have excellent cycle characteristics compared to the secondary battery of Example 12 using a carbonate-based solvent. Indicated.
  • the secondary batteries of Examples 8 and 11 using the non-aqueous electrolyte of the present invention did not contain a phosphate ester compound, and Examples 12 and 13 using carbonate solvents were used. Compared to the secondary battery, it showed excellent withstand voltage characteristics.
  • the non-aqueous electrolyte for a secondary battery of the present invention can be used for a lithium ion secondary battery that has sufficient cycle characteristics and can be charged and discharged at a high voltage.

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Abstract

L'invention concerne : une solution d'électrolyte non aqueux pour batteries secondaires, qui possède des caractéristiques de cycle suffisantes et d'excellentes caractéristiques de tension de résistance qui permettent une charge et une décharge à une tension supérieure ; et une batterie secondaire au lithium-ion. L'invention concerne une solution d'électrolyte non aqueux pour batterie secondaire, qui contient un sel de lithium, un milieu qui est principalement composé d'un composé spécifique d'éther contenant du fluor, et d'un composé ligand spécifique contenant un constituant spécifique d'ester d'acide phosphorique. Le rapport du nombre total de moles d'atomes d'oxygène (NO) dans les groupements phosphonyle dans le composé d'ester d'acide phosphorique par rapport au nombre total de moles d'atomes de lithium (NLi) dérivés du sel de lithium, à savoir NO/NLi est 1 ou plus, et le rapport du nombre total de moles d'atomes (NA) dans le composé ligand, lesdits atomes étant coordonnés aux atomes de lithium, par rapport au nombre NLi décrit ci-dessus, à savoir NA/NLi est de 4 à 8. L'invention concerne également une batterie secondaire au lithium-ion qui utilise cette solution d'électrolyte non aqueux.
PCT/JP2013/054614 2013-02-22 2013-02-22 Solution d'électrolyte non aqueux pour batteries secondaires et batterie secondaire au lithium-ion Ceased WO2014128940A1 (fr)

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WO2019093411A1 (fr) * 2017-11-08 2019-05-16 国立大学法人 東京大学 Électrolyte présentant des propriétés d'extinction d'incendie, et batterie secondaire comprenant ledit électrolyte
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WO2016199823A1 (fr) * 2015-06-09 2016-12-15 ステラケミファ株式会社 Solution d'électrolyte non aqueux pour batteries secondaires et batterie secondaire la comportant
WO2019093411A1 (fr) * 2017-11-08 2019-05-16 国立大学法人 東京大学 Électrolyte présentant des propriétés d'extinction d'incendie, et batterie secondaire comprenant ledit électrolyte
JPWO2019093411A1 (ja) * 2017-11-08 2020-11-19 国立大学法人 東京大学 消火性電解液及び当該電解液を含む二次電池
WO2019188360A1 (fr) * 2018-03-26 2019-10-03 Tdk株式会社 Électrolyte d'accumulateur et accumulateur
JPWO2019188360A1 (ja) * 2018-03-26 2021-03-11 Tdk株式会社 二次電池用電解液および二次電池
JP7014290B2 (ja) 2018-03-26 2022-02-01 Tdk株式会社 二次電池用電解液および二次電池
WO2020203148A1 (fr) * 2019-03-29 2020-10-08 株式会社村田製作所 Solution électrolytique pour pile secondaire et pile secondaire
JPWO2020203148A1 (fr) * 2019-03-29 2020-10-08
CN113632282A (zh) * 2019-03-29 2021-11-09 株式会社村田制作所 二次电池用电解液及二次电池
JP7201074B2 (ja) 2019-03-29 2023-01-10 株式会社村田製作所 二次電池用電解液および二次電池
CN113632282B (zh) * 2019-03-29 2023-10-03 株式会社村田制作所 二次电池用电解液及二次电池

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