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WO2012115112A1 - Solution électrolytique non aqueuse pour pile secondaire et pile secondaire - Google Patents

Solution électrolytique non aqueuse pour pile secondaire et pile secondaire Download PDF

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Publication number
WO2012115112A1
WO2012115112A1 PCT/JP2012/054153 JP2012054153W WO2012115112A1 WO 2012115112 A1 WO2012115112 A1 WO 2012115112A1 JP 2012054153 W JP2012054153 W JP 2012054153W WO 2012115112 A1 WO2012115112 A1 WO 2012115112A1
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Prior art keywords
carbon atoms
compound
fluorine
mass
group
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English (en)
Japanese (ja)
Inventor
真男 岩谷
祐 小野崎
隆之 金子
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AGC Inc
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Asahi Glass Co Ltd
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Priority to JP2013501075A priority Critical patent/JPWO2012115112A1/ja
Publication of WO2012115112A1 publication Critical patent/WO2012115112A1/fr
Anticipated expiration legal-status Critical
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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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three solvents
    • 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 secondary battery.
  • lithium salt is dissolved well to express high lithium ion conductivity, and from the point of having a wide potential window, ethylene carbonate, dimethyl carbonate, etc.
  • Carbonate solvents have been widely used.
  • carbonate-based solvents are flammable and may ignite due to battery heat generation.
  • addition of a fluorine-based solvent has been proposed (see Patent Document 1).
  • the fluorine-based solvent has a low lithium salt solubility and tends to deteriorate rate characteristics.
  • a fluorine-based solvent is used as a main component for the purpose of improving nonflammability (flame retardancy), and a glyme-based solvent is added for the purpose of improving the solubility of lithium salt, It has been proposed to form a complex with a lithium salt and a glyme solvent (see Patent Document 2).
  • An object of the present invention is to provide a non-aqueous electrolyte for a secondary battery having excellent cycle characteristics and a secondary battery using the non-aqueous electrolyte for a secondary battery.
  • a nonaqueous electrolytic solution comprising an electrolyte and a liquid composition
  • the electrolyte is a lithium salt
  • the liquid composition comprises at least one fluorine-containing ether compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), and represented by the following formula (3):
  • the fluorine-containing ether compound has a mass of 40 to 90% by mass with respect to the total mass of the non-aqueous electrolyte, A non-aqueous electrolyte for a secondary battery, wherein a mass of the fluorine-containing cyclic carbonate compound is 0.2 to 10% by mass with respect to a total mass of the non-aqueous electrolyte.
  • 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
  • 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 1 to 5 carbon atoms having one or more etheric oxygen atoms between carbon atoms and carbon atoms, or carbon A fluorinated alkylene group having 1 to 5 carbon atoms having one or more etheric oxygen atoms between atoms and carbon atoms.
  • m is an integer of 1 to 10.
  • Q 1 represents a linear alkylene group having 1 to 4 carbon atoms, or one or more hydrogen atoms of the linear alkylene group are alkyl groups having 1 to 5 carbon atoms, or one or more carbon atoms between carbon atoms.
  • R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms or an alkylene group having 1 to 10 carbon atoms formed by linking R 3 and R 4 .
  • R 5 to R 8 are each independently a hydrogen atom, a fluorine atom, a saturated hydrocarbon group having 1 to 4 carbon atoms, or a saturated one having 1 to 4 carbon atoms having one or more etheric oxygen atoms between carbon atoms.
  • a saturated hydrocarbon group, and at least one of R 5 to R 8 is a fluorine atom or a group having a fluorine atom;
  • the molar amount of the electrolyte with respect to the total volume of the non-aqueous electrolyte is 0.1 to 3.0 mol / L, and the mass of the non-fluorinated ether compound is 1 with respect to the total mass of the non-aqueous electrolyte.
  • N O / N Li which is a ratio of the total number of moles of lithium atoms derived from the lithium salt (N Li ) to the total number of moles of etheric oxygen atoms derived from the non-fluorine ether compound (N O ) is 1
  • N B the total number of moles of etheric oxygen atoms derived from the non-fluorine ether compound (N O ) there (N a + N B + N O) / N Li is 2-6 [1] - non-aqueous electrolyte solution for a secondary battery according to any one of [5].
  • the non-aqueous electrolyte contains a compound represented by the following formula (5), and the mass of the compound represented by the formula (5) with respect to the total mass of the non-aqueous electrolyte is 0 to 30
  • R 9 to R 14 are each independently a hydrogen atom, a halogen atom, a saturated hydrocarbon group, or a halogenated saturated hydrocarbon group.
  • R 5 to R 8 of the fluorine-containing cyclic carbonate compound represented by the formula (4) are each independently a hydrogen atom, a fluorine atom, —CF 3 , —CHF 2 , —CH 2 F, —CF 2.
  • the nonaqueous electrolyte for secondary batteries according to one item.
  • the fluorine-containing ether compound is CF 3 CH 2 OCF 2 CF 2 H, CHF 2 CF 2 CH 2 OCF 2 CF 2 H, CF 3 CF 2 CH 2 OCF 2 CHF 2 , CF 3 CH 2 OCF 2 CHFCF 3 and the nonaqueous electrolyte for secondary batteries according to any one of [1] to [8], which is one or more compounds selected from the group consisting of CHF 2 CF 2 CH 2 OCF 2 CFHCF 3 .
  • Any one of [1] to [9], wherein Q 1 of the non-fluorinated ether compound represented by the formula (3) is —CH 2 CH 2 —, and m is 1 to 3.
  • the non-aqueous electrolyte for secondary batteries as described in the item.
  • the positive electrode using a material capable of inserting and extracting lithium ions as an active material
  • the negative electrode using a carbon material capable of inserting and extracting lithium ions as an active material
  • any one of [1] to [10] A secondary battery having a non-aqueous electrolyte for a secondary battery.
  • a secondary battery having excellent cycle characteristics can be obtained by using the non-aqueous electrolyte for a secondary battery of the present invention.
  • 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 batteries of the present invention (hereinafter sometimes simply referred to as “non-aqueous electrolyte”) is composed of an electrolyte and a liquid composition, the electrolyte is a lithium salt, and the liquid composition is One or more fluorine-containing ether compounds selected from the group consisting of compound (1) and compound (2) described later, compound (3) which is a non-fluorine ether compound, and compound (4) which is a fluorine-containing cyclic carbonate compound ).
  • the non-aqueous electrolyte of the present invention may contain other components as necessary. Examples of other components include components selected from non-fluorinated cyclic carbonate compounds, cyclic ester compounds, and surfactants described below; and other compounds.
  • a non-aqueous electrolyte is an electrolyte that uses a solvent that does not substantially contain water, and even if water is included, the water content of the secondary battery using the non-aqueous electrolyte does not deteriorate. It is an electrolyte solution in an amount that cannot be seen.
  • 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 electrolyte. 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 only one type may be used, or two or more types may be used.
  • 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 contains LiPF 6 and particularly preferably LiPF 6 .
  • Examples of the compound (A) include the following compound (A-1) to compound (A-4).
  • the compound (A) preferably includes the compound (A-2) in which k is 2, and is composed of the compound (A-2) in which k is 2, from the viewpoint of easily obtaining a non-aqueous electrolyte with high electrical conductivity. It is more preferable.
  • the lower limit of the total number of moles of the lithium salt relative to the total volume of the non-aqueous electrolyte is not particularly limited, and is preferably 0.1 mol / L (liter), more preferably 0.3 mol / L, and 0.5 mol / L. More preferred is 0.7 mol / L.
  • the upper limit of the total number of moles of the lithium salt is preferably 3.0 mol / L, more preferably 2.0 mol / L, and even more preferably 1.5 mol / L. If the total number of moles of the lithium salt relative to the total volume of the non-aqueous electrolyte is equal to or greater than the lower limit, a non-aqueous electrolyte having a high electrical conductivity can be easily obtained. Moreover, if the total number of moles of the lithium salt relative to the total volume of the non-aqueous electrolyte is not more than the above upper limit value, the lithium salt is likely to be uniformly dissolved in the liquid composition.
  • fluorine-containing ether compound One or more fluorine-containing ether compounds selected from the group consisting of the following compound (1) and the following compound (2) are used as a solvent that imparts nonflammability to the nonaqueous electrolytic solution.
  • the fluorine-containing ether compound contained in the nonaqueous electrolytic solution of the present invention may be one type or two or more types. The ratio when there are 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
  • one or both of R 1 and R 2 is a fluorinated alkyl group.
  • X is an alkylene group having 1 to 5 carbon atoms, a fluorinated alkylene group having 1 to 5 carbon atoms, or a carbon atom having 1 or more etheric oxygen atoms between carbon atoms. Or a fluorinated alkylene group having 1 to 5 carbon atoms having one or more etheric oxygen atoms between carbon atoms.
  • alkyl group and the alkyl group having an etheric oxygen atom between carbon atoms a group having a linear structure, a branched structure, or a partially cyclic structure (for example, a cycloalkylalkyl group), respectively. Is mentioned.
  • R 1 and R 2 in the compound (1) is a fluorinated alkyl group. By making one or both of R 1 and R 2 a fluorinated alkyl group, the solubility and nonflammability of the lithium salt in the non-aqueous electrolyte are improved. R 1 and R 2 in the compound (1) may be the same or different.
  • Compound (1) includes a compound (1-A) in which each of R 1 and R 2 is a fluorinated alkyl group having 1 to 10 carbon atoms, and R 1 is one or more carbon atoms between carbon atoms
  • a compound (1-B) which is a fluorinated alkyl group having 1 to 10 carbon atoms having an etheric oxygen atom and R 2 is a fluorinated alkyl group having 1 to 10 carbon atoms is preferred, and R 1 and R 2 are In any case, the compound (1-A) which is a fluorinated alkyl group having 1 to 10 carbon atoms 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 compound (1) can affect flammability. Therefore, 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.
  • the compound (1) is preferably a compound in which one or both ends of R 1 and R 2 are —CF 2 H groups from the viewpoint of improving the solubility of the lithium salt in the solvent. Furthermore, since the compound (1) has improved solubility in a lithium salt solvent, a compound in which both R 1 and R 2 are fluorinated alkyl groups in which part of the hydrogen atoms of the alkyl group is fluorinated is obtained. preferable.
  • compounds other than the compound (1-A), the compound (1-B), the compound (1-A) and the compound (1-B) include, for example, the compounds described in International Publication No. 2009/133899, etc. Is mentioned.
  • the nonaqueous electrolytic solution of the present invention can easily dissolve a lithium salt and easily obtain a nonaqueous electrolytic solution having excellent nonflammability and high conductivity.
  • 1 and R 2 are preferably composed of the compound (1-A) in the case of a fluorinated alkyl group having 1 to 10 carbon atoms, and CF 3 CH 2 OCF 2 CF 2 H (trade name: AE-3000, Asahi Glass Co., Ltd.) Manufactured by Co., Ltd.), CHF 2 CF 2 CH 2 OCF 2 CF 2 H, CF 3 CF 2 CH 2 OCF 2 CF 2 H, CF 3 CH 2 OCF 2 CHFCF 3 , and CHF 2 CF 2 CH 2 OCF 2 CFHCF 3 more preferably contains at least one element selected from the group, CF 3 CH 2 OCF 2 CF 2 H and CHF 2 CF 2 CH 2 OCF 2 CFHCF 3 of (HFE5510) It is particularly preferred to include one even without.
  • 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.
  • X is —CH 2 —, —CH 2 CH 2 — as the compound (2).
  • Compound (2) which is one selected from the group consisting of, —CH (CH 3 ) CH 2 —, and —CH 2 CH 2 CH 2 —, is preferred.
  • Specific examples of the compound (2) include a compound represented by the following formula.
  • the fluorine-containing ether compound may be any one of the use of only the compound (1), the use of only the compound (2), or the combined use of the compound (1) and the compound (2), and the use of only the compound (1). Or the use of only compound (2).
  • the compound (1) may be only one type or two or more types.
  • 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 mass of the fluorine-containing ether compound relative to the total mass (100% by mass) of the non-aqueous electrolyte is 40 to 90% by mass.
  • 50 mass% is preferable, as for the lower limit of the mass of the said fluorine-containing ether compound, 60 mass% is more preferable, and 65 mass% is further more preferable.
  • 85 mass% is preferable, as for the upper limit of the mass of the said fluorine-containing ether compound, 80 mass% is more preferable, and 75 mass% is further more preferable. If the mass of the fluorine-containing ether compound is not more than the upper limit value, the lithium salt is easily dissolved uniformly.
  • the mass of the said fluorine-containing ether compound is more than a lower limit, the nonaqueous electrolyte solution excellent in nonflammability will be easy to be obtained.
  • the mass ratio (Vb / Va) is preferably 0.01 to 100 0.1 to 10 is more preferable.
  • the non-aqueous electrolyte of the present invention further contains the following compound (3) which is a non-fluorine ether compound.
  • Compound (3) is a solvent that plays a role of uniformly dissolving the lithium salt in the fluorinated ether compound by efficiently solvating with the lithium salt. Part or all of the compound (3) is considered to form a complex with the lithium salt in the electrolytic solution.
  • m is an integer of 1 to 10.
  • Q 1 represents a linear alkylene group having 1 to 4 carbon atoms, or one or more hydrogen atoms of the linear alkylene group are alkyl groups having 1 to 5 carbon atoms, or one or more carbon atoms between carbon atoms. And an alkyl group having 1 to 5 carbon atoms containing an etheric oxygen atom.
  • R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms or an alkylene group having 1 to 10 carbon atoms formed by linking R 3 and R 4 .
  • m is preferably an integer of 1 to 6, more preferably an integer of 1 to 5, still more preferably an integer of 1 to 4, particularly preferably an integer of 1 to 3, and most preferably 1 or 2.
  • Q 1 is preferably a linear alkylene group having 1 to 4 carbon atoms, particularly preferably —CH 2 CH 2 —. Further, when m is 1, Q 1 is preferably —CH 2 CH 2 —, and when m is 2 or more, the types of Q 1 may be the same or different. 1, -CH 2 CH 2 - preferably set to the essential, -CH 2 CH 2 - and more preferably consists only.
  • R 3 and R 4 are each preferably a methyl group or an ethyl group, and more preferably a methyl group.
  • the compound (3) preferably contains the following compound (3A), and more preferably consists of the compound (3A).
  • m is an integer of 1 to 10.
  • R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms or an alkylene group having 1 to 10 carbon atoms formed by linking R 3 and R 4 .
  • m is preferably an integer of 1 to 6, more preferably an integer of 1 to 5, further preferably an integer of 1 to 4, and an integer of 1 to 3.
  • R 3 and R 4 are each preferably a methyl group or an ethyl group, and more preferably a methyl group.
  • the compound (3) since the viscosity (20 ° C.) is 5 cP or less and the practical solvent viscosity of the nonaqueous electrolytic solution is excellent and shows good conductivity, m is 1 in the compound (3A).
  • Compounds of ⁇ 5 are preferred.
  • the compound is preferably monoglyme, diglyme, triglyme, tetraglyme, pentaglime, diethylene glycol diethyl ether, triethylene glycol diethyl ether, tetraethylene glycol diethyl ether, or pentaethylene glycol diethyl ether.
  • the compound (3A) is preferably a compound having m of 1 to 3.
  • monoglyme, diglyme, triglyme, diethylene glycol diethyl ether, triethylene glycol diethyl ether, or tetraethylene glycol diethyl ether is more preferable. Furthermore, monoglyme, diglyme, or triglyme is more preferable, and monoglyme or diglyme is particularly preferable in terms of excellent balance between both properties of viscosity and flash point.
  • compounds in which R 3 and R 4 are linked to form an alkylene group having 1 to 10 carbon atoms include, for example, 12-crown-4, 14-crown-4, 15- Crown-5, 18-crown-6 and the like.
  • the compound (3A) in which m is 1 to 3 is preferably essential, and more preferably composed of the compound.
  • the compound (3A) is more preferably composed of at least one of monoglyme and diglyme, and particularly preferably composed of monoglyme.
  • the mass of the compound (3) with respect to the total mass (100 mass%) of the nonaqueous electrolytic solution of the present invention is preferably 1 to 20 mass%. 15 mass% is preferable, as for the upper limit of the mass of the said compound (3), 12 mass% is more preferable, and 10 mass% is further more preferable. Moreover, 1 mass% is preferable, as for the lower limit of the mass of the said compound (3), 2 mass% is more preferable, and 3 mass% is further more preferable.
  • the compound (3) contained in the nonaqueous electrolytic solution of the present invention may be only one type or two or more types.
  • the ratio of the molar amount of the compound (3) to the molar amount of the lithium salt in the nonaqueous electrolytic solution of the present invention is preferably 0.2 to 4.0 times, more preferably 0.5 to 3.0 times, and preferably 0.00. 5 to 2.0 times is particularly preferable.
  • the molar ratio of the compound (3) to the lithium salt is not less than the lower limit of the above range, the lithium salt is easily dissolved uniformly in the fluorinated ether solvent.
  • the molar ratio of the compound (3) to the lithium salt is not more than the upper limit of the above range, a nonaqueous electrolytic solution excellent in oxidation resistance and nonflammability can be easily obtained.
  • N O / N which is the ratio of the total number of moles of etheric oxygen atoms (N O ) derived from the compound (3) to the total number of moles of lithium atoms derived from the lithium salt (N Li ) in the non-aqueous electrolyte of the present invention
  • the lower limit of Li is preferably 1, more preferably 1.5, and even more preferably 2.
  • the upper limit of the N 2 O 3 / N Li is preferably 6, more preferably 5, and even more preferably 4.
  • the N 2 O 3 / N Li is at least the lower limit value, it is easy to dissolve the lithium salt in the fluorine-containing ether solvent.
  • the N 2 O 3 / N Li is not more than the upper limit value, it is easy to improve the cycle characteristics at high voltage, and it is easy to obtain a non-aqueous electrolyte excellent in nonflammability.
  • the nonaqueous electrolytic solution of the present invention further contains the following compound (4) which is a fluorine-containing cyclic carbonate compound.
  • compound (4) which is a fluorine-containing cyclic carbonate compound.
  • the types of effective compounds and the optimum addition amount differ greatly depending on the components of the nonaqueous electrolytic solution.
  • the inventors then added 40 to 90 one or more fluorine-containing ether solvents selected from the group consisting of the compound (1) and the compound (2) as in the non-aqueous electrolyte for secondary batteries of the present invention. It has been found that in a non-aqueous electrolyte containing a mass%, it is extremely effective for improving the cycle characteristics to contain the compound (4) in a specific ratio. In addition, since the compound (4) efficiently solvates with the lithium salt, it is considered that the lithium salt is uniformly dissolved by assisting the dissolution of the lithium salt in the fluorine-containing ether solvent.
  • R 5 to R 8 are each independently a hydrogen atom, a fluorine atom, a saturated hydrocarbon group having 1 to 4 carbon atoms, or a carbon atom having 1 to 4 carbon atoms having one or more etheric oxygen atoms between carbon atoms.
  • 4 is a saturated hydrocarbon group
  • at least one of R 5 to R 8 is a fluorine atom or a group having a fluorine atom.
  • R 5 to R 8 include a hydrogen atom, a fluorine atom, a saturated hydrocarbon group having 1 to 4 carbon atoms having a fluorine atom, or a fluorine atom, and one or more etheric groups between the carbon atom and the carbon atom.
  • a saturated hydrocarbon group having 1 to 4 carbon atoms having an oxygen atom is preferable, and a hydrogen atom, a fluorine atom, —CF 3 , —CHF 2 , —CH 2 F, —CF 2 CF 3 , —CH 2 CF 3 or —CH 2 OCH 2 CF 2 CF 3 is more preferable, and from the viewpoint of availability, a fluorine atom or —CF 3 is more preferable, and a fluorine atom is particularly preferable.
  • the compound (4) the following compounds (4-1) to (4-7) are preferable, and the compound (4-1) or the compound (4-4) is more preferable from the viewpoint of availability, etc., and the compound (4- 1) is more preferable.
  • Specific examples of the compound (4) other than the compounds (4-1) to (4-7) include the following compound (4-8).
  • the compound (4) contained in the nonaqueous electrolytic solution of the present invention may be only one type or two or more types.
  • the lower limit of the mass of the compound (4) with respect to the total mass (100% by mass) of the nonaqueous electrolytic solution of the present invention is 0.2% by mass and 0.5% by mass from the viewpoint of obtaining excellent cycle characteristics. Is preferable, and 1.0 mass% is more preferable.
  • the upper limit of the mass of the compound (4) is 10.0% by mass, preferably 8.0% by mass, and more preferably 5.0% by mass from the viewpoint of obtaining excellent cycle characteristics.
  • the nonaqueous electrolytic solution of the present invention preferably contains at least one selected from the group consisting of a non-fluorinated cyclic carbonate compound and a cyclic ester compound.
  • the non-fluorine-based cyclic carbonate compound is a compound having no ring and having a ring structure composed of a carbon atom and an oxygen atom, and the ring structure is represented by —O—C ( ⁇ O) —O—. It is a compound having a carbonate bond.
  • the cyclic ester compound is a compound having a ring structure composed of a carbon atom and an oxygen atom, and the ring structure is a compound having an ester bond represented by —O—C ( ⁇ O) —C—.
  • the non-fluorinated cyclic carbonate compound and the cyclic ester compound have high polarity, promote dissociation of lithium ions in the electrolytic solution, and improve the conductivity of the non-aqueous electrolytic solution. It becomes easy to suppress the fall of the.
  • the non-fluorinated cyclic carbonate compound and the cyclic ester compound assist in dissolving the lithium salt uniformly in the fluorinated ether solvent by efficiently solvating with the lithium salt.
  • the non-fluorinated cyclic carbonate compound is preferably a compound that does not contain a carbon-carbon unsaturated bond in the molecule.
  • the ring structure in the non-fluorinated 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 non-fluorinated cyclic carbonate compound is preferably a ring structure having one carbonate bond, and more preferably a ring structure formed by linking a carbonate bond to a linear alkylene group.
  • the linear alkylene group preferably has 1 to 7 carbon atoms, more preferably 1 to 4, more preferably 2 or 3, particularly preferably 2.
  • the non-fluorinated cyclic carbonate compound may be a compound in which one or more hydrogen atoms of the linear alkylene group are substituted with a substituent.
  • a substituent for example, a chlorine atom, an alkyl group, and a halogenated alkyl group (excluding a fluorinated alkyl group) are preferable.
  • the halogen atom in the halogenated alkyl group is preferably a chlorine atom.
  • the non-fluorinated cyclic carbonate compound the following compound (6) is preferable.
  • R 15 to R 18 are each independently a hydrogen atom, a chlorine atom, an alkyl group, or a chlorinated alkyl group.
  • the alkyl group preferably has 1 to 6 carbon atoms
  • the chlorinated alkyl group preferably has 1 to 6 carbon atoms.
  • non-fluorinated cyclic carbonate compound propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, or 4-chloro-1,3-dioxolan-2-one corresponding to the compound (6) is preferable, and propylene carbonate, ethylene Carbonate or butylene carbonate is more preferred.
  • propylene carbonate, ethylene Carbonate or butylene carbonate is more preferable from the viewpoint of easy availability and the properties of the nonaqueous electrolytic solution.
  • examples of the non-fluorinated cyclic carbonate compound other than the compound (6) include vinylene carbonate.
  • the non-aqueous electrolyte of the present invention contains a non-fluorine-type cyclic carbonate compound
  • the non-fluorine-type cyclic carbonate compound may be only one type or two or more types.
  • the non-fluorinated cyclic carbonate compound preferably contains the compound (6), and more preferably consists of the compound (6).
  • the cyclic ester compound is preferably a compound that does not contain a carbon-carbon unsaturated bond in the molecule.
  • the cyclic structure in the cyclic 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 ester compound is preferably a ring structure having one ester bond, and more preferably a ring structure formed by linking an ester bond with a linear alkylene group.
  • the linear alkylene group preferably has 1 to 7 carbon atoms, more preferably 1 to 4, more preferably 2 or 3, and particularly preferably 2.
  • the cyclic 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.
  • the alkyl group preferably has 1 to 6 carbon atoms
  • the halogenated alkyl group preferably has 1 to 6 carbon atoms.
  • the halogen atom or the halogen atom in the halogenated alkyl group is preferably at least one of a chlorine atom and a fluorine atom.
  • the cyclic ester compound the following compound (7) is preferable.
  • n is an integer of 1 to 5
  • R 19 to R 22 are each independently a hydrogen atom, a halogen atom, an alkyl group, or a halogenated alkyl group.
  • the alkyl group preferably has 1 to 6 carbon atoms
  • the halogenated alkyl group preferably has 1 to 6 carbon atoms.
  • the halogen atom in the halogen atom and the halogenated alkyl group is preferably at least one of a fluorine atom and a chlorine atom.
  • R 19 may be the same group or a different group, and R 19 may be the same group or a different group.
  • n is preferably an integer of 1 to 4, more preferably 2 or 3, and particularly preferably 2.
  • R 19 and R 20 are preferably a hydrogen atom. When n is 2 or more, R 19 and R 20 are preferably all hydrogen atoms.
  • R 21 and R 22 are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.
  • the compound (7) include cyclic ester compounds such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexanolactone, ⁇ -valerolactone, and carbon atoms forming the ring structure of the cyclic ester compound. And 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 ester compound may be only one type or two or more types.
  • the cyclic ester compound preferably contains the compound (7), and more preferably consists of the compound (7-1).
  • the non-aqueous electrolyte of the present invention contains at least one selected from the group consisting of a non-fluorine cyclic carbonate compound and a cyclic ester compound
  • the non-fluorine cyclic relative to the total mass (100% by mass) of the non-aqueous electrolyte
  • the lower limit of the total mass of the carbonate compound and the cyclic ester compound is preferably more than 0% by mass, more preferably 5% by mass, and still more preferably 10% by mass.
  • the upper limit of the total mass of the non-fluorinated cyclic carbonate compound and the cyclic ester compound is preferably 30% by mass, more preferably 25% by mass, and even more preferably 20% by mass.
  • the total mass of the non-fluorine-based cyclic carbonate compound and the cyclic ester compound is equal to or higher than the lower limit value, it is easy to suppress a decrease in battery capacity during charge / discharge at a high rate. In addition, the dissociation degree of the lithium salt is improved, and the electrical conductivity becomes better.
  • the total mass of the non-fluorine-based cyclic carbonate compound and the cyclic ester compound is not more than the upper limit value, a non-aqueous electrolyte solution excellent in nonflammability is easily obtained.
  • the non-aqueous electrolyte of the present invention contains at least one selected from the group consisting of the non-fluorinated cyclic carbonate compound and the cyclic ester compound
  • the total number of lithium atoms derived from the lithium salt (N Li ) the fluorine-containing cyclic carbonate compounds the total number of moles derived from the carbonyl oxygen atom (N a)
  • the total moles of the non-fluorine-containing cyclic carbonate compounds the total number of moles derived from the carbonyl oxygen atoms and the cyclic ester compound derived from the carbonyl oxygen atom
  • the lower limit of (N A + N B + N O ) / N Li is the ratio of the sum of numbers (N B ) and the total number of moles of etheric oxygen atoms (N O ) derived from the non-fluorine ether compound is 2 Is preferable, 3 is more preferable, and 3.5 is more preferable.
  • the upper limit of (N A + N B + N O) / N Li is preferably 6, more preferably from 5.5, more preferably 5.0, 4.5 is particularly preferred. If the (N A + N B + N O) / N Li is less than the lower limit, the lithium salt is easily uniformly dissolved in the non-aqueous electrolyte solution of the present invention. On the other hand, the long (N A + N B + N O) / N Li is not more than the upper limit, it is easy to suppress a decrease in battery capacity in charge and discharge at high rate conditions, also tends to improve the cycle characteristics at high voltage .
  • nonaqueous electrolytic solution of the present invention may contain the following compound (5) which is a chain carbonate compound.
  • R 9 to R 14 are each independently a hydrogen atom, a halogen atom, an alkyl group, or a halogenated alkyl group.
  • R 9 to R 14 in the compound (5) are preferably a hydrogen atom or an alkyl group.
  • One or more compounds selected from the group consisting of isopropyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, and 3-fluoropropyl methyl carbonate are preferred, and properties such as availability and viscosity are given to the performance of the non-aqueous electrolyte. From the viewpoint, dimethyl carbonate, diethyl carbonate, or methyl ethyl carbonate is particularly preferable.
  • the non-aqueous electrolyte of this invention contains a compound (5)
  • the upper limit of the mass of the compound (5) with respect to the total mass (100 mass%) of a non-aqueous electrolyte 30 mass% is preferable, 25 % By mass is more preferable, 20% by mass is more preferable, 15% by mass is particularly preferable, and 10% by mass is most preferable.
  • the lower limit of the mass of the compound (5) with respect to the total mass (100 mass%) of the nonaqueous electrolytic solution is 0 mass%.
  • the compound (5) is a chain carbonate compound and has a low polarity unlike the cyclic carbonate compounds such as the compound (4) and the compound (6).
  • the amount of the compound (5) contained in the nonaqueous electrolytic solution of the present invention is increased, the lithium salt solubility is improved, but the flame retardancy is improved without improving the charge / discharge characteristics at a high rate. There is a risk of lowering.
  • the nonaqueous electrolytic solution of the present invention preferably contains a surfactant for improving the wettability between the nonaqueous electrolytic solution and the electrode active material.
  • a surfactant 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 (8-1) or compound (8-2) is preferred.
  • R 23 and R 24 are each independently a perfluoroalkyl group having 4 to 20 carbon atoms, or a perfluoroalkyl group having 1 or more etheric oxygen atoms between carbon atoms and carbon atoms.
  • a fluoroalkyl group; M 1 and M 2 are each independently an alkali metal or NH (R 25 ) 3 (R 25 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and may be the same group or different groups. Good.)
  • R 23 and R 24 are each a perfluoroalkyl group having 4 to 20 carbon atoms, or one or more etheric groups between carbon atoms and carbon atoms from the viewpoint that the degree of reducing the surface tension of the nonaqueous electrolytic solution is good.
  • a perfluoroalkyl group having 4 to 20 carbon atoms having an oxygen atom is preferable. From the viewpoint of solubility and environmental storage properties, a perfluoroalkyl group having 4 to 8 carbon atoms, or one or more carbon atoms between carbon atoms.
  • a C 4-8 perfluoroalkyl group having an etheric oxygen atom is more preferred.
  • the structures of R 23 and R 24 may be linear or branched, and may contain a ring structure.
  • R 23 and R 24 are preferably a straight chain 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 (8-1) 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.
  • Specific examples of the compound (8-2) is, for example, C 4 F 9 SO 3 - NH 4 +, C 5 F 11 SO 3 - NH 4 +, C 6 F 13 SO 3 - NH 4 +, C 4 F 9 SO 3 - NH (CH 3 ) 3 +, C 5 F 11 SO 3 - NH (CH 3) 3 +, C 6 F 13 SO 3 - NH (CH 3) 3 +, C 4 F 9 SO 3 - Li +, C 5 F 11 SO 3 - Li +, C 6 F 13 SO 3 - Li +, C 3 F 7 OCF (CF 3) CF 2 OC (CF 3) FSO 3 - NH 4 +, C 3 F 7 OCF (CF 3) CF 2 OCF ( CF 3) CF 2 OCF (CF 3) SO 3 - NH 4 +, HCF 2 CF 2 OCF 2 CF 2 SO 3 - NH 4 +, CF 3 CFHCF 2 OCF 2 CF 2 SO 3 - NH 4 +, C 3 F 7 OC
  • 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 mass of the surfactant relative to the total mass (100% by mass) of the non-aqueous electrolyte is preferably 5% by mass, more preferably 3% by mass. More preferred is 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 , One or more lithium salts selected from the group consisting of Compound (B), Compound (C), and LiBF 4 ; one or more selected from the group consisting of Compound (1) and Compound (2); Compound (3A) A nonaqueous electrolytic solution for a secondary battery containing the compound (4).
  • composition 2 LiPF 6 , the above 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 , one or more lithium salts selected from the group consisting of Compound (B), Compound (C), and LiBF 4 ; one or more selected from the group consisting of Compound (1) and Compound (2); Compound (3A Nonaqueous electrolyte for secondary batteries containing compound (4); one or more selected from the group consisting of compound (6) and compound (7).
  • composition 3 is more preferable.
  • Composition 3 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 , LiBF 4 ; CF 3 CH 2 OCF 2 CF 2 H, CHF 2 CF 2 CH 2 OCF 2 CF 2 H, CF 3 CF 2 CH 2 OCF 2 CF 2 H, CF 3 CH 2 OCF 2 CHFCF 3, CHF 2 CF 2 CH 2 OCF 2 CFHCF 3 , a compound represented by the formula (2) and X is CH 2 CH 2 and a group represented by the formula (2) and X is CH (CH 3 ) CH 2 One or more selected; one or more selected from the group consisting of monoglyme, diglyme and triglyme; fluoroethylene carbonate (compound (4-1 ), Non-aqueous electrolyte secondary battery containing.
  • composition 4 is particularly preferred.
  • Composition 4 A nonaqueous electrolytic solution for a secondary battery, comprising: a lithium salt containing LiPF 6 ; HFE5510; monoglyme or diglyme; fluoroethylene carbonate (compound (4-1)).
  • the non-aqueous electrolyte in the present invention does not undergo phase separation and does not interfere with the effects of the present invention, so long as the lithium salt, the fluorinated ether solvent, the non-fluorinated ether compound, the fluorinated cyclic carbonate compound, the non-fluorine-based A compound other than the cyclic carbonate compound, the cyclic ester compound and the surfactant (hereinafter referred to as “other compound”) may be included.
  • Other compounds include fluorine-containing alkanes; chain carboxylic acid esters such as propionic acid alkyl esters, malonic acid dialkyl esters, and acetic acid alkyl esters; cyclic sulfonic acid esters such as propane sultone; sulfonic acid alkyl esters; acetonitrile, isobutyl Examples thereof include carbonitrile such as ronitrile and pivalonitrile.
  • the volume of the other compound with respect to the total mass (100% by mass) of the non-aqueous electrolyte is preferably more than 0% by mass to 20% by mass, More than 15% by mass is more preferable, and more than 0.01% by mass to 10% by mass is particularly preferable.
  • the non-aqueous electrolyte of the present invention contains a fluorine-containing alkane
  • the vapor pressure of the non-aqueous electrolyte can be suppressed and the nonflammability of the non-aqueous electrolyte can be further improved.
  • 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.
  • a fluorine-containing alkane having 4 to 12 carbon atoms is preferred.
  • the fluorine content in the fluorinated alkane (the fluorine content means the proportion of the mass of fluorine atoms in the molecular weight) is preferably 50 to 80%. If the fluorine content in the fluorine-containing alkane is 50% or more, the nonflammability is further increased. When the fluorine content in the fluorine-containing alkane is 80% or less, the solubility of the lithium salt is easily maintained.
  • the fluorine-containing alkane a compound having a linear structure is preferable.
  • These fluorine-containing alkanes may be used alone or in combination of two or more.
  • the mass of the fluorinated alkane is preferably from 5 to 30% by mass relative to the total mass (100% by mass) of the non-aqueous electrolyte.
  • content of the said fluorine-containing alkane is 5 mass% or more, it will be easy to reduce a vapor pressure and to express nonflammability. If the mass of the fluorine-containing alkane is 30% by mass or less, it is easy to maintain the solubility of the lithium salt.
  • the non-aqueous electrolyte of the present invention may contain other components as required in order to improve the function of the non-aqueous electrolyte.
  • the other components include an overcharge preventing agent, a dehydrating agent, a deoxidizing agent, a capacity maintenance aid for improving capacity maintenance characteristics and cycle characteristics after high-temperature storage.
  • 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 Partially fluorinated products of the above aromatic compounds such as biphenyl, o-cyclohexylfluorobenzene, p-cyclohexylfluorobenzene; fluorinated anisole such as 2,4-difluoroanisole, 2,5-difluoroanisole and 2,6-difluoroaniol Compounds.
  • aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl
  • An overcharge inhibitor may be used individually by 1 type, and may use 2 or more types together.
  • the mass of the overcharge inhibitor with respect to the total mass (100% by mass) of the non-aqueous electrolyte is preferably 0.01 to 5% by mass.
  • the dehydrating agent examples include molecular sieves, mirabilite, magnesium sulfate, calcium hydride, sodium hydride, potassium hydride, lithium aluminum hydride and the like.
  • the solvent used in the nonaqueous electrolytic solution of the present invention it is preferable to use a solvent obtained by performing rectification after dehydrating with the dehydrating agent. Moreover, you may use the solvent which performed only the dehydration by the said dehydrating agent, without performing rectification.
  • Properties improving aids for improving capacity retention characteristics and cycle characteristics after high temperature storage include, for example, succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, di-anhydride Carboxylic anhydrides 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-
  • Hydrocarbon compounds such as fluorobenzene, difluorobenzene, hexafluorobenzene, benzotrifluoride and the like can be mentioned.
  • These characteristic improvement aids may be used alone or in combination of two or more.
  • the mass of the characteristic improving auxiliary with respect to the total mass (100% by mass) of the nonaqueous electrolytic solution is preferably 0.01 to 5% by mass.
  • the non-aqueous electrolyte of the present invention can be suitably used as a non-aqueous electrolyte in a lithium ion secondary battery having a positive electrode, a negative electrode containing a carbon material capable of inserting and extracting lithium ions as an active material, and a separator.
  • the non-aqueous electrolyte solution of the present invention described above contains the compound (4), whereby excellent cycle characteristics can be obtained.
  • the secondary battery of this invention is a secondary battery which has a negative electrode and a positive electrode, and the non-aqueous electrolyte of this invention.
  • the negative electrode is a negative electrode using a carbon material capable of inserting and extracting lithium ions as an active material.
  • the carbon material include artificial or natural graphite (graphite) and amorphous carbon. These carbon materials may be used individually by 1 type, and may use 2 or more types together.
  • graphite or a carbon material in which the surface of graphite is coated with amorphous carbon as compared with the graphite is particularly preferable.
  • the positive electrode examples include an electrode having a material capable of inserting and extracting lithium ions as an active material.
  • the positive electrode active material known positive electrode active materials for lithium ion secondary batteries can be used.
  • lithium-containing transition metal oxide examples include lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide.
  • the metal contained in the lithium-containing transition metal composite oxide is preferably Al, V, Ti, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Si, Yb, etc.
  • some of the transition metal atoms that are the main components of these lithium transition metal composite oxides are Al
  • Examples include those substituted with other metals such as Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Si, and Yb.
  • the transition metal oxide include TiO 2 , MnO 2 , MoO 3 , V 2 O 5 , V 6 O 13 , and examples of the transition metal sulfide include TiS 2 , FeS, MoS 2, etc. Includes SnO 2 , SiO 2 and the like.
  • 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.
  • a positive electrode active material 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 main constituent of the positive electrode active material is attached to the surface of the positive electrode active material can be used.
  • Surface adhesion substances include oxides such as aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide; 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 ppm, more preferably 1 ppm, and particularly preferably 10 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 non-aqueous electrolyte 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.
  • the secondary battery of the present invention has a negative electrode and a positive electrode, one of which is a nonpolarizable electrode and the other is a polarizable electrode, or both are nonpolarizable electrodes, and the nonaqueous electrolytic solution of the present invention.
  • the polarizable electrode is preferably composed mainly of a material having a high specific surface area that is electrochemically inactive, and particularly preferably composed of activated carbon, carbon black, metal fine particles, or conductive oxide fine particles.
  • an electrode layer made of a carbon material powder having a high specific surface area such as activated carbon is formed on the surface of the metal current collector.
  • a binder that binds the negative electrode active material or the positive electrode active material is used.
  • the binder for binding the negative electrode active material and the positive electrode active material any binder can be used as long as it is a material that is stable with respect to the solvent and the electrolytic solution used during electrode production.
  • the binder is, for example, a fluororesin such as polyvinylidene fluoride or polytetrafluoroethylene, a polyolefin such as polyethylene or polypropylene, a polymer having an unsaturated bond such as styrene / butadiene rubber, isoprene rubber or butadiene rubber, and a copolymer thereof. Examples thereof include acrylic polymers such as polymers, acrylic acid copolymers, and methacrylic acid copolymers, and copolymers thereof. These binders may be used individually by 1 type, and may use 2 or more types together.
  • the electrode may contain a thickener, a conductive material, a filler and the like in order to increase mechanical strength and electrical conductivity.
  • a thickener examples include carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and polyvinylpyrrolidone. These thickeners may be used individually by 1 type, and may use 2 or more types together.
  • Examples of the conductive material include carbonaceous materials such as acetylene black, graphite, carbon black, and carbon fiber. These electrically conductive materials may be used individually by 1 type, and may use 2 or more types together.
  • a binder, a thickener, a conductive material, a solvent, etc. are added to a negative electrode active material or a positive electrode active material to form a slurry, which is then applied to a current collector and dried. It can.
  • the electrode is preferably consolidated by pressing after drying. If the density of the positive electrode active material layer is too low, the capacity of the secondary battery may be insufficient.
  • the current collector various current collectors can be used, but usually a metal or an alloy is used.
  • the negative electrode current collector include copper, nickel, and stainless steel, with copper being preferred.
  • the current collector of the positive electrode include metals such as aluminum, titanium, and tantalum or alloys thereof, and aluminum or alloys thereof are preferable, and aluminum is more preferable.
  • the shape of the secondary battery may be selected according to the application, and may be a coin type, a cylindrical type, a square type or a laminate type. Further, the shapes of the positive electrode and the negative electrode can be appropriately selected according to the shape of the secondary battery.
  • the charging voltage of the secondary battery of the present invention is preferably 3.4 V or higher, more preferably 4.0 V or higher, and particularly preferably 4.2 V or higher.
  • 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 4.0 V or more.
  • 4.2V or more is more preferable.
  • the charging voltage when the positive electrode active material is an olivine-type metal lithium salt is preferably 3.2 V or more, and more preferably 3.4 V or more.
  • a porous film is usually interposed as a separator between the positive electrode and the negative electrode of the secondary battery.
  • a non-aqueous electrolyte is used by impregnating the porous membrane.
  • the separator is preferably a porous sheet or non-woven fabric made of polyvinylidene fluoride, polytetrafluoroethylene, a fluororesin such as a copolymer of ethylene and tetrafluoroethylene, a polyimide, or a polyolefin such as polyethylene or polypropylene.
  • the material is preferably a polyolefin such as polyethylene or polypropylene. Moreover, you may use as a gel electrolyte what impregnated the electrolyte solution in the porous film and made it gelatinize.
  • the material of the battery casing used in the non-aqueous electrolyte 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 secondary battery of the present invention described above has excellent cycle characteristics because it uses the non-aqueous electrolyte of the present invention. 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 used for various applications such as satellites, submarines, ships, uninterruptible power supplies, robots, and power storage systems.
  • the secondary battery of the present invention has particularly preferable characteristics for large-sized secondary batteries such as electric vehicles, hybrid vehicles, trains, airplanes, artificial satellites, submarines, ships, uninterruptible power supply devices, robots, and power storage systems. .
  • Example 1 LiPF 6 (0.137 g) which is a lithium salt is dispersed in HFE5510 (CF 2 HCF 2 CH 2 OCF 2 CFHCF 3 , 1.178 g) which is a fluorine-containing ether solvent, and then monoglyme which is a non-fluorine ether compound.
  • the slurry was applied to a thickness of 150 ⁇ m on a copper foil having a thickness of 20 ⁇ m, dried and pressed, and then punched into a circle having a diameter of 19 mm to obtain an evaluation electrode (positive electrode). Further, a lithium metal foil was punched into a circle having a diameter of 19 mm to obtain a counter electrode (negative electrode). Evaluation of a single electrode cell comprising a graphite electrode-lithium metal foil by adding a polyolefin microporous membrane as an electrode separator for evaluation between the positive electrode and the negative electrode, adding the prepared non-aqueous electrolyte 1 (0.5 mL) Cell 1 was produced.
  • Non-aqueous electrolytes 2 to 6 were prepared in the same manner as in Example 1 except that non-aqueous electrolytes having the compositions shown in Table 1 were used as non-aqueous electrolytes, and evaluation cells 2 to 6 were produced.
  • test methods For the evaluation cells 1 to 6, the cycle characteristics were evaluated by the following test methods.
  • the evaluation cells 1 to 4 were evaluated for the cycle characteristics under the test method 1, the evaluation cell 5 for the test method 2, and the evaluation cell 6 for the test method 3.
  • Test Method 1 Evaluation of Evaluation Cells 1 to 4 (Examples 1 to 4): The secondary battery was discharged at 25 ° C.
  • Cycle 4 was charged at a constant current of 0.2C, cycle 5 at 0.5C, cycle 6 at 1.0C, and cycle 7 at a constant current of 2.0C up to 1.0V.
  • Cycles 8 to 30 were discharged to 0.05 V with a constant current of 0.2 C, and further discharged until the current value reached 0.02 C at the discharge lower limit voltage, and after a pause of 10 minutes, a constant current of 0.2 C To 1.0V.
  • the cycle characteristics were evaluated from the maintenance rate of the charge capacity of cycle 30 with respect to the charge capacity of cycle 1. Note that 1C represents a current value for discharging the reference capacity of the battery in one hour, and 0.2C represents a current value of 1/5 thereof.
  • Test Method 2 (Evaluation of Evaluation Cell 5 (Example 5): Test method 1 except that the discharge in cycle 1 was changed to discharge to 0.05 V at a constant current of 0.2 C at 25 ° C. and further to discharge until the current value reached 0.02 C at the discharge lower limit voltage. As well as.
  • Test Method 3 Evaluation of Evaluation Cell 6 (Example 6) Cycle 1 discharge was changed to discharge to 1.0 V at a constant current of 0.04 C at 25 ° C., hold for 5 hours at the discharge lower limit voltage, and then discharge to 0.05 V at a constant current of 0.2 C. The test was performed in the same manner as in Test Method 1 except that. Table 1 shows the evaluation results of the cycle characteristics of the evaluation cells in each example.
  • HFE5510 CF 2 HCF 2 CH 2 OCF 2 CFHCF 3.
  • FEC Fluoroethylene carbonate.
  • PC Propylene carbonate.
  • VC vinylene carbonate.
  • N 2 O 3 / N Li Ratio of the total number of moles of lithium atoms derived from lithium salt (N Li ) and the total number of moles of etheric oxygen atoms derived from non-fluorinated ether compounds (N 2 O 3 ).
  • N A + N B + N O total number of moles of lithium atoms from the lithium salt (N Li) for the total number of moles of the carbonyl oxygen atoms from the fluorine-containing cyclic carbonate compounds (N A), a non-fluorinated Sum of the total number of moles of carbonyl oxygen atoms derived from the cyclic carbonate compound and the total number of moles of carbonyl oxygen atoms derived from the cyclic ester compound (N B ), and the total number of moles of etheric oxygen atoms derived from the non-fluorinated ether compound (N O ) ratio.
  • Charge capacity maintenance rate The maintenance rate of the charge capacity of cycle 30 relative to the charge capacity of cycle 1
  • the nonaqueous electrolytic solution of the present invention can be used as an electrolytic solution for a nonaqueous secondary battery such as a lithium ion secondary battery.
  • a nonaqueous secondary battery such as a lithium ion secondary battery.

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Abstract

L'objet de la présente invention est de fournir une solution électrolytique non aqueuse présentant d'excellentes caractéristiques de cyclage et une pile secondaire utilisant la solution électrolytique non aqueuse. Une solution électrolytique non aqueuse pour une pile secondaire est composée d'un électrolyte et d'une composition liquide, l'électrolyte étant du sel de lithium ; la composition liquide contient un composé d'éther spécifique fluoré, un composé d'éther spécifique non fluoré et un composé de carbonate cyclique spécifique fluoré ; la masse du composé d'éther fluoré est de 40-90 % par rapport à la masse totale de la solution électrolytique ; et la masse du composé carbonate cyclique fluoré est de 0,2-10 % par rapport à la masse totale de la solution électrolytique non aqueuse. Elle concerne également une pile secondaire présentant la solution électrolytique non aqueuse pour une pile secondaire.
PCT/JP2012/054153 2011-02-23 2012-02-21 Solution électrolytique non aqueuse pour pile secondaire et pile secondaire Ceased WO2012115112A1 (fr)

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Publication number Priority date Publication date Assignee Title
JP6500775B2 (ja) * 2013-04-18 2019-04-17 日本電気株式会社 リチウムイオン二次電池
JP6740147B2 (ja) 2017-02-01 2020-08-12 トヨタ自動車株式会社 非水電解液および非水電解液二次電池の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008096729A1 (fr) * 2007-02-06 2008-08-14 Daikin Industries, Ltd. Solution électrolytique non aqueuse
JP2008218387A (ja) * 2006-12-22 2008-09-18 Daikin Ind Ltd 非水系電解液
WO2009035085A1 (fr) * 2007-09-12 2009-03-19 Daikin Industries, Ltd. Solution d'électrolyte
JP2010146740A (ja) * 2008-12-16 2010-07-01 Daikin Ind Ltd 電解液
JP2010238510A (ja) * 2009-03-31 2010-10-21 Daikin Ind Ltd リチウム二次電池の非水電解液用溶媒

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008218387A (ja) * 2006-12-22 2008-09-18 Daikin Ind Ltd 非水系電解液
WO2008096729A1 (fr) * 2007-02-06 2008-08-14 Daikin Industries, Ltd. Solution électrolytique non aqueuse
WO2009035085A1 (fr) * 2007-09-12 2009-03-19 Daikin Industries, Ltd. Solution d'électrolyte
JP2010146740A (ja) * 2008-12-16 2010-07-01 Daikin Ind Ltd 電解液
JP2010238510A (ja) * 2009-03-31 2010-10-21 Daikin Ind Ltd リチウム二次電池の非水電解液用溶媒

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