WO2014024990A1 - Solution électrolytique non aqueuse et batterie secondaire électrolytique non aqueuse l'utilisant - Google Patents

Solution électrolytique non aqueuse et batterie secondaire électrolytique non aqueuse l'utilisant Download PDF

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WO2014024990A1
WO2014024990A1 PCT/JP2013/071547 JP2013071547W WO2014024990A1 WO 2014024990 A1 WO2014024990 A1 WO 2014024990A1 JP 2013071547 W JP2013071547 W JP 2013071547W WO 2014024990 A1 WO2014024990 A1 WO 2014024990A1
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compound
aqueous electrolyte
group
mass
carbonate
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PCT/JP2013/071547
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English (en)
Japanese (ja)
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大橋　洋一
古田土　稔
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三菱化学株式会社
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Priority claimed from JP2012177498A external-priority patent/JP6089487B2/ja
Priority claimed from JP2013067182A external-priority patent/JP6064735B2/ja
Application filed by 三菱化学株式会社 filed Critical 三菱化学株式会社
Priority to KR1020157002235A priority Critical patent/KR102202221B1/ko
Priority to CN201380041629.4A priority patent/CN104584309B/zh
Publication of WO2014024990A1 publication Critical patent/WO2014024990A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—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
    • H01M10/0567—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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
    • 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 and a non-aqueous electrolyte secondary battery using the same.
  • Non-aqueous systems such as lithium ion secondary batteries with higher energy density than nickel / cadmium batteries and nickel / hydrogen batteries.
  • Electrolyte batteries are widely used and actively researched.
  • the electrolytic solution used for a non-aqueous electrolyte battery is usually composed mainly of an electrolyte and a non-aqueous solvent.
  • an electrolyte such as LiPF 6 , LiBF 4 , LiN (CF 3 SO 2 ) 2 , a high dielectric constant solvent such as ethylene carbonate and propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl
  • a non-aqueous electrolyte solution dissolved in a mixed solvent with a low viscosity solvent such as methyl carbonate is used.
  • the gel electrolyte which made the matrix polymer contain the above electrolyte solutions and was made into the gel state is also used.
  • Non-aqueous electrolyte secondary batteries typified by lithium ion secondary batteries, etc.
  • the electrolyte decomposes on the electrodes and the materials that make up the battery deteriorate, reducing the battery capacity To do.
  • the safety against swelling, ignition, or explosion of the battery may be reduced. So far, a method for improving battery characteristics of a non-aqueous electrolyte secondary battery by incorporating an acid anhydride in the non-aqueous electrolyte has been proposed.
  • Patent Document 1 proposes a non-aqueous electrolyte solution comprising a non-aqueous solvent containing a carboxylic anhydride having a carbon-carbon unsaturated bond and / or an aromatic ring in the molecule and an electrolyte. Yes. According to this, leakage current when a coin cell using Li metal and a natural graphite negative electrode is kept at 60 ° C. in a charged state is suppressed.
  • Patent Document 2 0.0005 to 0.7% by weight of hydrogen fluoride with respect to the total amount of the non-aqueous solvent, the electrolyte, the non-aqueous solvent and the electrolyte, and the total amount of the non-aqueous solvent and the electrolyte
  • a non-aqueous electrolyte solution containing 0.01 to 4.0% by weight of a compound having a carboxyl group or a carboxylic anhydride group has been proposed. According to it, when a coin cell using a natural graphite negative electrode and a LiCoO 2 positive electrode is used, the load characteristics and the remaining capacity after storage at 4.2 ° C. at 60 ° C. for 7 days are improved.
  • a negative electrode and a positive electrode that can occlude and release lithium ions and a non-aqueous electrolyte solution are provided, and the negative electrode has at least one atom selected from the group consisting of Si atoms, Sn atoms, and Pb atoms.
  • Non-aqueous electrolytes characterized by the above have been proposed. According to this, the cycle characteristics are improved by satisfying the conditions of a specific negative electrode, a carbonate having at least one of an unsaturated bond and a halogen atom, and an acid anhydride having a specific structure.
  • Patent Documents 1 and 2 describes a carboxylic acid in a nonaqueous electrolytic solution, and also has a carbon-carbon unsaturated bond and / or a certain content of an aromatic ring in the molecule. There is no description or suggestion that the combination of a specific compound with a specific compound improves the properties specifically.
  • Patent Document 3 also has no description regarding carboxylic acid in non-aqueous electrolyte, and among the many acid anhydrides, the characteristics are specifically improved by combining an acid anhydride having a specific structure with a specific compound. There is no suggestion about. In addition, none of these Patent Documents 1 to 3 suggests that the cycle characteristics may be deteriorated by the carboxylic acid in the non-aqueous electrolyte solution.
  • the present invention provides a non-aqueous electrolyte solution that improves cycle characteristics and load characteristics in a non-aqueous electrolyte solution secondary battery, and a non-aqueous electrolyte solution secondary battery using this non-aqueous electrolyte solution. This is the issue. Another object is to suppress gas generation when the secondary battery is cycled.
  • the present inventors have combined non-aqueous electrolytic solutions containing a specific structure acid anhydride and a specific compound, or containing a specific structure acid anhydride.
  • the inventors have found that the above-mentioned problems can be solved by controlling the carboxylic acid content, and have completed the present invention. That is, the gist of the present invention resides in the following ⁇ 1> to ⁇ 12>.
  • a non-aqueous electrolyte used in a non-aqueous electrolyte secondary battery including a positive electrode having a positive electrode active material capable of inserting and extracting metal ions and a negative electrode having a negative electrode active material capable of absorbing and releasing metal ions.
  • Benzene compound compound having Si—Si bond without an aliphatic substituent having an unsaturated bond, compound having S ⁇ O group, compound represented by the following general formula (6), monofluorophosphate And a non-aqueous electrolyte solution containing at least one selected from the group consisting of difluorophosphates.
  • R 1 to R 6 each independently represents a hydrogen atom, a fluorine atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group.
  • M represents a transition metal, a group 13, 14 or 15 element of the periodic table, or a hydrocarbon group having 1 to 6 carbon atoms which may have a hetero atom.
  • Z a + is a metal ion, a proton, or an onium ion
  • a is 1 to 3
  • b is 1 to 3
  • l is b / a
  • m represents 1 to 4
  • n represents 1 to 8
  • t represents 0 to 1
  • p represents 0 to 3
  • q represents 0 to 2
  • r represents 0 to 2.
  • the M may have a hetero atom.
  • R 21 represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom, or X 3 R 24 , and n R 21 s are bonded to form a ring. May be.
  • R 22 represents a direct bond or a hydrocarbon group having 1 to 6 carbon atoms which may have a hetero atom, and X 1 to X 3 each independently represents O, S, or NR 25 .
  • R 23 and R 24 or R 25 in R 21 or R 22 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a hetero atom, and R 23 to When a plurality of R 25 are present, each may be bonded to form a ring.
  • Y 1 and Y 2 each independently represent C, S, or Si. However, when Y 1 or Y 2 is C or Si, q or r is 0 or 1, respectively, and when Y 1 or Y 2 is S, q or r is 2, respectively. )
  • ⁇ 2> The nonaqueous electrolytic solution according to ⁇ 1>, wherein the nonaqueous electrolytic solution contains at least one selected from the group consisting of a nitrile compound, an isocyanate compound, a monofluorophosphate, and a difluorophosphate.
  • ⁇ 3> The nonaqueous electrolytic solution according to ⁇ 1> or ⁇ 2>, wherein the nitrile compound is a dinitrile compound.
  • ⁇ 4> Any of the above ⁇ 1> to ⁇ 3>, wherein the nitrile compound is at least one selected from the group consisting of succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, sebacononitrile, and 2-methylglutaronitrile.
  • ⁇ 7> The non-reactive material according to any one of ⁇ 1> to ⁇ 6>, wherein the aromatic hydrocarbon is at least one selected from the group consisting of cyclohexylbenzene, t-butylbenzene, and t-pentylbenzene.
  • the fluorinated benzene compound is at least one selected from the group consisting of fluorobenzene, difluorobenzene, trifluorobenzene, tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene, and benzotrifluoride.
  • the non-aqueous electrolyte solution according to any one of the above. ⁇ 12> The compound represented by the general formula (6) is selected from the group consisting of lithium (bisoxalato) borate, lithium difluorooxalatoborate, lithium (trisoxalato) phosphate, lithium difluoro (bisoxalato) phosphate and lithium tetrafluorooxalatophosphate.
  • the non-aqueous electrolyte solution according to any one of the above items ⁇ 1> to ⁇ 11> which is at least one compound selected.
  • a non-aqueous electrolyte used in a non-aqueous electrolyte secondary battery comprising a positive electrode having a positive electrode active material capable of occluding and releasing metal ions and a negative electrode having a negative electrode active material capable of occluding and releasing metal ions.
  • it contains a compound represented by the following general formula (1) and a carboxylic acid, and the content of the carboxylic acid is 0.00001% by mass or more and less than 0.01% by mass with respect to the entire non-aqueous electrolyte.
  • a non-aqueous electrolyte solution is 0.00001% by mass or more and less than 0.01% by mass with respect to the entire non-aqueous electrolyte.
  • R 1 to R 6 each independently represents a hydrogen atom, a fluorine atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group.
  • R 1 to R 3 each independently represents a hydrogen atom, a fluorine atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group.
  • the content of the compound represented by the general formula (1) is 0.01% by mass or more and 10% by mass or less with respect to the entire non-aqueous electrolyte solution.
  • a non-aqueous electrolyte secondary battery comprising a positive electrode having a positive electrode active material capable of occluding and releasing metal ions and a negative electrode having a negative electrode active material capable of occluding and releasing metal ions, wherein ⁇ 1> A nonaqueous electrolyte secondary battery comprising the nonaqueous electrolyte solution according to any one of to ⁇ 16>.
  • a non-aqueous electrolyte secondary battery comprising a positive electrode having a positive electrode active material capable of occluding and releasing metal ions, and a negative electrode having a negative electrode active material occluding and releasing metal ions and containing carbon.
  • a non-aqueous electrolyte secondary battery comprising the non-aqueous electrolyte solution according to any one of ⁇ 1> to ⁇ 16>.
  • the present invention it is possible to obtain a non-aqueous electrolyte secondary battery excellent in load characteristics and cycle characteristics. Moreover, the gas generation amount at the time of repeating a charging / discharging cycle can be suppressed.
  • Non-aqueous electrolyte ⁇ contains an electrolyte and a non-aqueous solvent that dissolves the electrolyte in the same manner as a general non-aqueous electrolyte, and is a compound represented by the following general formula (1) (hereinafter referred to as “compound”).
  • a cyclic carbonate compound having an unsaturated bond a cyclic carbonate compound having a fluorine atom, a nitrile compound, an isocyanate compound, an aromatic hydrocarbon, a fluorinated benzene compound, A compound having an Si—Si bond without an aliphatic substituent having an unsaturated bond, a compound having an S ⁇ O group, a compound represented by the following general formula (6), a monofluorophosphate, and difluorophosphorus It contains at least one selected from the group consisting of acid salts.
  • R 1 to R 6 each independently represents a hydrogen atom, a fluorine atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group.
  • M represents a transition metal, a group 13, 14 or 15 element of the periodic table, or a hydrocarbon group having 1 to 6 carbon atoms which may have a hetero atom.
  • Z a + is a metal ion, a proton, or an onium ion
  • a is 1 to 3
  • b is 1 to 3
  • l is b / a
  • m represents 1 to 4
  • n represents 1 to 8
  • t represents 0 to 1
  • p represents 0 to 3
  • q represents 0 to 2
  • r represents 0 to 2.
  • the M may have a hetero atom.
  • R 21 represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom, or X 3 R 24 , and n R 21 s are bonded to form a ring. May be.
  • R 22 represents a direct bond or a hydrocarbon group having 1 to 6 carbon atoms which may have a hetero atom, and X 1 to X 3 each independently represents O, S, or NR 25 .
  • R 23 and R 24 or R 25 in R 21 or R 22 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a hetero atom, and R 23 to When a plurality of R 25 are present, each may be bonded to form a ring.
  • Y 1 and Y 2 each independently represent C, S, or Si. However, when Y 1 or Y 2 is C or Si, q or r is 0 or 1, respectively, and when Y 1 or Y 2 is S, q or r is 2, respectively. )
  • R 1 to R 6 in the general formula (1) each independently represent a hydrogen atom, a fluorine atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, preferably a hydrogen atom, an alkyl group or an aryl group. More preferably a hydrogen atom or an alkyl group.
  • R 1 to R 6 are an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, some or all of the hydrogen atoms contained therein may be substituted with fluorine atoms.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, amyl group, t-amyl group, 2-ethylhexyl group and the like. Is mentioned.
  • alkenyl group examples include a vinyl group, an allyl group, and a 2-butenyl group.
  • alkynyl group examples include ethynyl group and propargyl group.
  • aryl group examples include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2-t-butylphenyl group, 3-t-butylphenyl group, 4-t-butylphenyl group, Examples include 2-t-amylphenyl group, 3-t-amylphenyl group, 4-t-amylphenyl group and the like.
  • Specific examples of the compound (1) include the following compounds.
  • the following compounds A to D are preferably used.
  • the nonaqueous electrolytic solution ⁇ of the present invention is characterized by containing the compound (1), but the compound (1) to be contained is not limited to one type, and a plurality of types may be used in combination.
  • the content of the compound (1) (the total amount when a plurality of types are used in combination) is not particularly limited, but is usually 0.01% by mass or more, preferably 0 with respect to the total amount of the non-aqueous electrolyte ⁇ . .1% by mass or more, more preferably 0.2% by mass or more, and usually 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less. .
  • the content of the compound (1) is not particularly limited, but is usually 0.01% by mass or more, preferably 0 with respect to the total amount of the non-aqueous electrolyte ⁇ . .1% by mass or more, more preferably 0.2% by mass or more, and usually 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less.
  • the non-aqueous electrolyte ⁇ of the present invention is a cyclic carbonate compound having an unsaturated bond, a cyclic carbonate compound having a fluorine atom, a nitrile compound, an isocyanate compound, an aromatic hydrocarbon, a fluorinated benzene compound, an aliphatic having an unsaturated bond.
  • Cyclic carbonate compound having an unsaturated bond examples include vinylene carbonate (VC), methyl vinylene carbonate, ethyl vinylene carbonate, 1,2-dimethyl vinylene carbonate, 1,2-diethyl vinylene carbonate, fluoro vinylene carbonate, trifluoromethyl.
  • VC vinylene carbonate
  • methyl vinylene carbonate methyl vinylene carbonate
  • ethyl vinylene carbonate 1,2-dimethyl vinylene carbonate
  • 1,2-diethyl vinylene carbonate 1,2-dimethyl vinylene carbonate
  • fluoro vinylene carbonate trifluoromethyl
  • Vinylene carbonate compounds such as vinylene carbonate; vinyl ethylene carbonate, 1-methyl-2-vinylethylene carbonate, 1-ethyl-2-vinylethylene carbonate, 1-n-propyl-2-vinylethylene carbonate, 1-methyl-2 -Vinyl ethylene carbonate compounds such as vinyl ethylene carbonate, 1,1-divinyl ethylene carbonate, 1,2-divinyl ethylene carbonate; 1,1-dimethyl-2 Methylene ethylene carbonate, methylene ethylene carbonate compounds such as 1,1-diethyl-2-methylene ethylene carbonate; ethynyl ethylene carbonate compounds such as ethynyl ethylene carbonate. These may be used alone or in combination of two or more.
  • the content in the non-aqueous electrolyte ⁇ is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.3% by mass or more. Usually, it is 10 mass% or less, Preferably it is 8 mass% or less, More preferably, it is 6 mass% or less, More preferably, it is 3 mass% or less.
  • the content of the cyclic carbonate compound having a carbon-carbon unsaturated bond is within the above range, the effect of improving the cycle characteristics of the battery and the capacity maintenance characteristics after high-temperature storage is sufficiently exerted. The increase in the amount of gas generated is suppressed.
  • Cyclic carbonate compound having a fluorine atom examples include fluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,2-difluoroethylene carbonate, 1,1,2-trifluoroethylene carbonate, tetrafluoroethylene carbonate, 1- Fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1,2-difluoro-1-methylethylene carbonate, 1,1,2-trifluoro-2-methylethylene carbonate, trifluoromethylethylene carbonate Etc.
  • fluoroethylene carbonate, difluoroethylene carbonate, and 1-fluoro-2-methylethylene carbonate are preferable from the viewpoint of improving cycle characteristics and high-temperature storage characteristics, more preferably fluoroethylene carbonate and difluoroethylene carbonate, and more preferably fluoroethylene carbonate. Further preferred. These may be used alone or in combination of two or more.
  • the content in the non-aqueous electrolyte ⁇ is usually 0.001% by mass or more, preferably 0.1% by mass or more, more preferably 0. .3% by mass or more, more preferably 0.5% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.
  • fluoroethylene carbonate may be used as a solvent, and in that case, the content is not limited to the above.
  • the nitrile compound is not limited as long as it has a nitrile group (CN group). Specifically, acetonitrile, propionitrile, butyronitrile, pentanenitrile, hexanenitrile, heptanenitrile, octanenitrile, Nonane nitrile, decane nitrile, dodecane nitrile (lauronitrile), tridecane nitrile, tetradecane nitrile (myristonitrile), hexadecane nitrile, pentadecane nitrile, heptadecane nitrile, octadecane nitrile (stearonitrile), nonadecane nitrile, icosonitrile , Mononitrile compounds such as acrylonitrile, crotononitrile, methacrylonitrile, cinnamonitrile, 3-methoxyacrylonitrile, 3-e
  • CN group
  • mononitrile compounds such as butyronitrile and lauronitrile; dinitrile compounds such as succinonitrile, glutaronitrile, adiponitrile, pimeonitrile, sebacononitrile, and 2-methylglutaronitrile are preferable, and succinonitrile and glutaronitrile Dinitrile compounds such as adiponitrile, pimelonitrile, sebaconitrile, 2-methylglutaronitrile are more preferred.
  • These nitrile compounds are preferably used together with the compound (1) in the present invention because the battery characteristics are particularly improved.
  • the nitrile compound is not limited to one type, and a plurality of types may be used in combination.
  • the content of the nitrile compound with respect to the total amount of the non-aqueous electrolyte ⁇ is usually 0.01% by mass or more and usually 10% by mass or less.
  • it is 0.1 mass% or more, More preferably, it is 0.5 mass% or more,
  • it is 8 mass% or less as an upper limit, More preferably, it is 5 mass% or less, Most preferably, it is 3 mass% or less.
  • the isocyanate compound is not limited as long as it has an isocyanato group (NCO group). Specifically, isocyanatomethane, isocyanatoethane, 1-isocyanatopropane, 1-isocyanatobutane, 1-isocyanatopentane, 1-isocyanatohexane, 1-isocyanatoheptane, 1-isocyanatooctane, 1-isocyanatononane, 1-isocyanatodecane, isocyanatocyclohexane, methoxycarbonyl isocyanate, ethoxycarbonyl isocyanate, propoxycarbonyl Isocyanate, butoxycarbonyl isocyanate, methoxysulfonyl isocyanate, ethoxysulfonyl isocyanate, propoxysulfonyl isocyanate, butoxysulfonyl isocyanate, fluorosulfur Com
  • compounds having one isocyanato group such as methoxycarbonyl isocyanate, ethoxycarbonyl isocyanate, propoxycarbonyl isocyanate, butoxycarbonyl isocyanate, methoxysulfonyl isocyanate, ethoxysulfonyl isocyanate, propoxysulfonyl isocyanate, butoxysulfonyl isocyanate, fluorosulfonyl isocyanate; 1,4 -Diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane, 1,7-diisocyanatoheptane, 1,8-diisocyanatooctane, 1,9-diisocyanatononane 1,10-diisocyanatodecane, toluene diisocyanate, xylene diisocyanate, tolylene diisocyan
  • the content in the non-aqueous electrolyte ⁇ is usually 0.001% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more. More preferably, it is 0.3% by mass or more, usually 10% by mass or less, preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.
  • the isocyanate content is within the above range, the effect of improving the cycle characteristics of the battery and the capacity maintenance characteristics after high-temperature storage is sufficiently exhibited, and an increase in internal resistance is suppressed.
  • the aromatic hydrocarbon is not limited as long as it is aromatic, and specifically, toluene, cumene, cyclohexylbenzene, t-butylbenzene, t-pentylbenzene, tri (t-butylphenyl) phosphate. , Methylphenyl carbonate, diphenyl carbonate, biphenyl and the like.
  • cyclohexylbenzene, t-butylbenzene, t-pentylbenzene, tri (t-butylphenyl) phosphate, methylphenyl carbonate, diphenyl carbonate, and biphenyl are preferred, such as cyclohexylbenzene, t-butylbenzene, and t-pentylbenzene.
  • the alkylbenzene compound is more preferable.
  • aromatic hydrocarbons are preferably used together with the compound (1) in the present invention because the battery characteristics are particularly improved.
  • the non-aqueous electrolyte ⁇ of the present invention contains an aromatic hydrocarbon, the aromatic hydrocarbon is not limited to one type, and a plurality of types may be used in combination.
  • the content of aromatic hydrocarbons relative to the total amount of the non-aqueous electrolyte ⁇ (the total amount when a plurality of types are used in combination) is usually 0.01% by mass or more and usually 10% by mass or less.
  • the value is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and the upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and most preferably 2% by mass or less. .
  • the battery characteristics are particularly improved without impairing the effect of the compound (1).
  • the fluorinated benzene compound is not limited as long as it is a fluorinated benzene compound. Specifically, fluorobenzene, difluorobenzene, trifluorobenzene, tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene. And benzotrifluoride.
  • fluorobenzene pentafluorobenzene, hexafluorobenzene, and benzotrifluoride are preferable.
  • fluorinated benzene compounds are preferably used together with the compound (1) in the present invention because the battery characteristics are particularly improved.
  • the non-aqueous electrolyte ⁇ of the present invention contains a fluorinated benzene compound
  • the fluorinated benzene compound is not limited to one type, and a plurality of types may be used in combination.
  • the content of the fluorinated benzene compound with respect to the total amount of the non-aqueous electrolyte ⁇ is usually 0.01% by mass or more and usually 20% by mass or less.
  • the value is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 3% by mass or less. .
  • the battery characteristics are particularly improved without impairing the effect of the compound (1).
  • the “compound having an Si—Si bond without an aliphatic substituent having an unsaturated bond” (hereinafter sometimes referred to as “specific Si compound”) used in the present invention may be used alone. Two or more kinds may be optionally used in combination. Hereinafter, the “specific Si compound” in the present invention will be described more specifically.
  • the “specific Si compound” in the present invention is not particularly limited as long as it is a compound having an Si—Si bond without having an aliphatic substituent having an unsaturated bond. From the viewpoint of properties, a compound represented by the following general formula (4) is preferable.
  • a 1 to A 6 each independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a hetero atom, or a substituent.
  • a 1 to A 6 are each independently preferably a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and particularly preferably a hydrocarbon group having 1 to 10 carbon atoms.
  • the hydrocarbon group having 1 to 10 carbon atoms is a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, a phenyl group, or a hydrogen atom. It is particularly preferably a methyl group, an ethyl group, a phenyl group, or a hydrogen atom.
  • the specific compound having a Si—Si bond does not have an aliphatic substituent having an unsaturated bond because the high resistance film formed by self-polymerization of the aliphatic substituent is This is to prevent the effect of suppressing the internal resistance of the battery by the “specific Si compound” from being impaired.
  • the “specific Si compound” include compounds represented by the following formulas (a) to (q), and the formulas (a), (b), (e), (g), (i ) To (k) or (n) are more preferred, compounds represented by the formula (a), (e), (j), (k) or (n) are more preferred, and the compound represented by the formula (a) ), (E), (j) or (k) is most preferred.
  • formula (a) is hexamethyldisilane
  • formula (e) is hexaethyldisilane
  • formula (j) is 1,2-diphenyltetramethyldisilane
  • formula (k) is 1,1,2 , 2-tetraphenyldisilane.
  • Me represents a methyl group.
  • the reason why the compounds represented by the above formulas (a) to (q) are preferable is that the production cost of the electrolytic solution can be suppressed due to industrial availability, and that the “specific Si compound” is contained in the non-aqueous electrolytic solution. Therefore, the effect of suppressing the internal resistance of the battery is more effectively exhibited by a high-quality film formed of the “specific Si compound”.
  • the blending amount of the “specific Si compound” is arbitrary as long as the effects of the present invention are not significantly impaired, but the lower limit relative to the whole non-aqueous electrolytic solution.
  • the value is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass. % Or less, most preferably 1% by mass or less.
  • the effect of the “specific Si compound” can be sufficiently obtained, but it is particularly excellent in terms of inhibiting an unnecessary reaction.
  • Examples of the compound having an S ⁇ O group in the present invention include compounds represented by the following formula (5).
  • L represents a ⁇ -valent organic group which may have a substituent
  • R 7 represents a halogen atom, a hydrocarbon group having 1 to 4 carbon atoms or an alkoxy group.
  • ⁇ is 1 or more.
  • a plurality of R 7 may be the same or different from each other, and R 7 and L may be bonded to each other to form a ring.
  • sulfate ester there is no restriction
  • the sulfate ester may be contained alone in the nonaqueous electrolytic solution of the present invention, or two or more may be used in any combination and ratio.
  • the amount of sulfate ester added to the non-aqueous electrolyte solution of the present invention is contained at a concentration of 0.1% by mass or more, more preferably 0.2% by mass or more, and usually 70% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less. .
  • the sulfate ester include compounds represented by formulas (B15) to (B22), and among them, compounds represented by formulas (B15), (B17), (B18), and (B22) are more preferable.
  • sulfonic acid ester there is no restriction
  • the sulfonic acid ester may be included alone in the nonaqueous electrolytic solution of the present invention, or two or more may be combined in any combination and ratio.
  • the amount of sulfonate ester added to the non-aqueous electrolyte solution of the present invention is no limitation on the amount of sulfonate ester added to the non-aqueous electrolyte solution of the present invention, and it is optional as long as the effects of the present invention are not significantly impaired. Above, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and usually 70% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less. desirable. Within the above range, when the non-aqueous electrolyte solution of the present invention is used for a non-aqueous electrolyte secondary battery, the effect of improving the cycle characteristics can be more sufficiently exhibited. Furthermore, high-temperature storage characteristics and continuous charge characteristics tend to be improved.
  • sulfonic acid ester examples include compounds represented by formulas (B23) to (B36). Among them, formulas (B23), (B24), (B27), (B28), (B31) to (B36) are exemplified. ) Is more preferred.
  • M represents a transition metal, a group 13, 14 or 15 element of the periodic table, or a hydrocarbon group having 1 to 6 carbon atoms which may have a hetero atom.
  • Z a + is a metal ion, a proton, or an onium ion
  • a is 1 to 3
  • b is 1 to 3
  • l is b / a
  • m represents 1 to 4
  • n represents 1 to 8
  • t represents 0 to 1
  • p represents 0 to 3
  • q represents 0 to 2
  • r represents 0 to 2.
  • the M may have a hetero atom.
  • R 21 represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom, or X 3 R 24 , and n R 21 s are bonded to form a ring. May be.
  • R 22 represents a direct bond or a hydrocarbon group having 1 to 6 carbon atoms which may have a hetero atom, and X 1 to X 3 each independently represents O, S, or NR 25 .
  • R 23 and R 24 or R 25 in R 21 or R 22 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a hetero atom, and R 23 to When a plurality of R 25 are present, each may be bonded to form a ring.
  • Y 1 and Y 2 each independently represent C, S, or Si. However, when Y 1 or Y 2 is C or Si, q or r is 0 or 1, respectively, and when Y 1 or Y 2 is S, q or r is 2, respectively. )
  • the compound represented by the said General formula (6) may be included alone in the non-aqueous electrolyte solution of the present invention, or two or more of them may be combined in any combination and ratio. You may let them.
  • the compound represented by the formula (6) include compounds represented by the formulas (B8) to (B14), and among them, compounds represented by the formulas (B9), (B11), and (B13). Is more preferable.
  • the counter cations of monofluorophosphate and difluorophosphate are not particularly limited, but lithium, sodium, potassium, magnesium, calcium, and NR 11 R 12 R 13 R 14 (wherein R 11 to R 14 Each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms).
  • the organic group having 1 to 12 carbon atoms represented by R 11 to R 14 of ammonium is not particularly limited.
  • the alkyl group may be substituted with a halogen atom, a halogen atom or an alkyl group
  • examples thereof include an cycloalkyl group which may be substituted, an aryl group which may be substituted with a halogen atom or an alkyl group, and a nitrogen atom-containing heterocyclic group which may have a substituent.
  • R 11 to R 14 are each independently preferably a hydrogen atom, an alkyl group, a cycloalkyl group, or a nitrogen atom-containing heterocyclic group.
  • the monofluorophosphate include lithium monofluorophosphate, sodium monofluorophosphate, potassium monofluorophosphate, tetramethylammonium monofluorophosphate, and tetraethylammonium monofluorophosphate.
  • the difluorophosphate include lithium difluorophosphate, sodium difluorophosphate, potassium difluorophosphate, tetramethylammonium difluorophosphate, tetraethylammonium difluorophosphate, and the like. Of these, lithium monofluorophosphate and lithium difluorophosphate are preferable, and lithium difluorophosphate is more preferable. These may be used alone or in combination of two or more.
  • the total content in the non-aqueous electrolyte ⁇ is usually 0.001% by mass or more, preferably 0.01. It is at least mass%, more preferably at least 0.1 mass%, even more preferably at least 0.2 mass%, usually at most 5 mass%, preferably at most 3 mass%, more preferably at most 2 mass%.
  • the battery is disassembled and the non-aqueous electrolyte is extracted again.
  • the content is often significantly reduced. Therefore, those in which at least one monofluorophosphate and / or difluorophosphate can be detected from the non-aqueous electrolyte extracted from the battery are detected in the non-aqueous electrolyte at a predetermined ratio defined in the present invention. It is considered to be a non-aqueous electrolyte solution.
  • Electrolytes ⁇ There is no restriction
  • a lithium salt is usually used as an electrolyte.
  • the electrolyte include inorganic lithium salts such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiSbF 6 , LiSO 3 F, and LiN (FSO 2 ) 2 ; LiCF 3 SO 3 , LiN (FSO 2 ) (CF 3 SO 2 ), LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , lithium cyclic 1,3-hexafluoropropanedisulfonylimide, Lithium cyclic 1,2-tetrafluoroethanedisulfonylimide, LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiC (CF 3 SO 2 ) 3 , LiPF 4 (CF 3 ) 2 , LiPF 4 (C 2 F 5 ) 2 , LiPF 4 (CF 3 SO 2 ) 2 , LiPF 4 (C 2 F 5 SO 2 ) 2 , LiBF 2 (CF 3 ) 2
  • LiPF 6 , LiBF 4 , LiSO 3 F, LiN (FSO 2 ) 2 , LiN (FSO 2 ) (in terms of solubility / dissociation in non-aqueous solvents, electrical conductivity, and battery characteristics obtained) CF 3 SO 2 ), LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , lithium bis (oxalato) borate, lithium difluorooxalatoborate, lithium tris (oxalato) phosphate, lithium difluorobis ( Oxalato) phosphate and lithium tetrafluoro (oxalato) phosphate are preferable, and LiPF 6 and LiBF 4 are particularly preferable.
  • electrolyte may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
  • electrolyte may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
  • two types of specific inorganic lithium salts are used in combination, or when inorganic lithium salts and fluorine-containing organic lithium salts are used in combination, gas generation during trickle charging is suppressed, and deterioration after high-temperature storage is suppressed. Therefore, it is preferable.
  • the combination and the LiPF 6 and LiBF 4, and an inorganic lithium salt such as LiPF 6, LiBF 4, LiCF 3 SO 3, LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) 2, etc.
  • the combined use with a fluorine-containing organic lithium salt is preferred.
  • LiBF 4 is usually contained at a ratio of 0.01% by mass to 50% by mass with respect to the entire electrolyte.
  • the ratio is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, while preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass or less, Most preferably, it is 3 mass% or less.
  • inorganic lithium salts such as LiPF 6 and LiBF 4 are replaced with inorganic lithium salts such as LiSO 3 F and LiN (FSO 2 ) 2 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , and LiN (C 2 F 5.
  • the proportion of the inorganic lithium salt in the total electrolyte is usually 70% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more, and usually 99% by mass or less. Preferably, it is 95 mass% or less.
  • the concentration of the lithium salt in the non-aqueous electrolyte ⁇ of the present invention is arbitrary as long as the gist of the present invention is not impaired, but is usually 0.5 mol / L or more, preferably 0.6 mol / L or more, more preferably 0. 0.8 mol / L or more. Moreover, it is 3 mol / L or less normally, Preferably it is 2 mol / L or less, More preferably, it is 1.8 mol / L or less, More preferably, it is the range of 1.6 mol / L or less.
  • the concentration of the lithium salt is in the above range, the electrical conductivity of the non-aqueous electrolyte is sufficient, and the electrical conductivity is decreased due to an increase in viscosity, and the non-aqueous electrolyte using the non-aqueous electrolyte of the present invention is reduced. It suppresses the deterioration of the performance of the secondary battery.
  • Non-aqueous solvent contained in the non-aqueous electrolyte ⁇ of the present invention can be appropriately selected from conventionally known solvents for non-aqueous electrolytes.
  • Examples of commonly used non-aqueous solvents include cyclic carbonates, chain carbonates, chain and cyclic carboxylic acid esters, chain and cyclic ethers, phosphorus-containing organic solvents, sulfur-containing organic solvents, and aromatic fluorine-containing solvents. Can be mentioned.
  • cyclic carbonate examples include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and the carbon number of the cyclic carbonate is usually 3 or more and 6 or less.
  • ethylene carbonate and propylene carbonate are preferable in that the electrolyte is easily dissolved because of a high dielectric constant, and the cycle characteristics are good when a non-aqueous electrolyte secondary battery is obtained.
  • the cyclic carbonate which substituted some hydrogen of these compounds with the fluorine is also mentioned.
  • Examples of the cyclic carbonate substituted with fluorine include fluoroethylene carbonate, 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2-trifluoroethylene carbonate, tetrafluoroethylene carbonate, 1-fluoro-2 Fluorine such as methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1,2-difluoro-1-methylethylene carbonate, 1,1,2-trifluoro-2-methylethylene carbonate, trifluoromethylethylene carbonate, etc.
  • cyclic carbonates of 3 to 5 carbon atoms substituted with Fluoroethylene carbonate, 1,2-difluoroethylene carbonate, and trifluoromethylethylene carbonate are preferred among these. There.
  • chain carbonate examples include chain carbonates such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate, and di-n-propyl carbonate.
  • the number of carbon atoms is preferably 1 or more and 5 or less, and particularly preferably 1 or more and 4 or less.
  • dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate are preferable from the viewpoint of improving battery characteristics.
  • chain carbonates in which a part of hydrogen of the alkyl group is substituted with fluorine are also included.
  • Chain carbonates substituted with fluorine include bis (fluoromethyl) carbonate, bis (difluoromethyl) carbonate, bis (trifluoromethyl) carbonate, bis (2-fluoroethyl) carbonate, bis (2,2-difluoroethyl) Examples include carbonate, bis (2,2,2-trifluoroethyl) carbonate, 2-fluoroethyl methyl carbonate, 2,2-difluoroethyl methyl carbonate, 2,2,2-trifluoroethyl methyl carbonate, and the like.
  • chain carboxylic acid esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, sec-butyl acetate, isobutyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, and propionic acid Isopropyl, methyl butyrate, ethyl butyrate, propyl butyrate, methyl isobutyrate, ethyl isobutyrate, methyl valerate, ethyl valerate, methyl pivalate, ethyl pivalate, etc.
  • Carboxylic acid esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, sec-butyl acetate, isobutyl acetate, t-butyl
  • Examples of the chain carboxylic acid ester substituted with fluorine include methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, butyl trifluoroacetate, 2,2,2-trifluoroethyl trifluoroacetate and the like.
  • batteries are methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, methyl valerate, methyl isobutyrate, ethyl isobutyrate, and methyl pivalate. It is preferable from the viewpoint of improving characteristics.
  • cyclic carboxylic acid ester examples include ⁇ -butyrolactone, ⁇ -valerolactone, and the like, and cyclic carboxylic acid esters in which part of hydrogen of these compounds is substituted with fluorine. Among these, ⁇ -butyrolactone is more preferable.
  • chain ethers examples include dimethoxymethane, 1,1-dimethoxyethane, 1,2-dimethoxyethane, diethoxymethane, 1,1-diethoxyethane, 1,2-diethoxyethane, ethoxymethoxymethane, 1,1 -Ethoxymethoxyethane, 1,2-ethoxymethoxyethane and the like, and chain ethers obtained by substituting a part of hydrogen of these compounds with fluorine.
  • chain ether substituted with fluorine bis (trifluoroethoxy) ethane, ethoxytrifluoroethoxyethane, methoxytrifluoroethoxyethane, 1,1,1,2,2,3,4,5,5,5-deca Fluoro-3-methoxy-4-trifluoromethyl-pentane, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-ethoxy-4-trifluoromethyl-pentane, 1 , 1,1,2,2,3,4,5,5,5-decafluoro-3-propoxy-4-trifluoromethyl-pentane, 1,1,2,2-tetrafluoroethyl-2,2, Examples include 3,3-tetrafluoropropyl ether and 2,2-difluoroethyl-2,2,3,3-tetrafluoropropyl ether. Among these, 1,2-dimethoxyethane and 1,2-diethoxyethane are more preferable.
  • Examples of the cyclic ether include tetrahydrofuran, 2-methyltetrahydrofuran and the like, and cyclic ethers obtained by substituting a part of hydrogen of these compounds with fluorine.
  • Examples of the phosphorus-containing organic solvent include trimethyl phosphate, triethyl phosphate, dimethyl ethyl phosphate, methyl diethyl phosphate, ethylene methyl phosphate, ethylene ethyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, Examples thereof include triphenyl phosphite, trimethylphosphine oxide, triethylphosphine oxide, triphenylphosphine oxide and the like, and phosphorus-containing organic solvents in which part of hydrogen of these compounds is substituted with fluorine.
  • Examples of the phosphorus-containing organic solvent substituted with fluorine include tris phosphate (2,2,2-trifluor
  • sulfur-containing organic solvents examples include sulfolane, 2-methyl sulfolane, 3-methyl sulfolane, dimethyl sulfone, diethyl sulfone, ethyl methyl sulfone, methyl propyl sulfone, dimethyl sulfoxide, methyl methanesulfonate, ethyl methanesulfonate, and methyl ethanesulfonate. , Ethyl ethanesulfonate, dimethyl sulfate, diethyl sulfate, dibutyl sulfate and the like, and sulfur-containing organic solvents in which part of hydrogen of these compounds is substituted with fluorine.
  • non-aqueous solvents it is preferable to use ethylene carbonate and / or propylene carbonate, which are cyclic carbonates, and the combined use of these with chain carbonate can achieve both high conductivity and low viscosity of the electrolytic solution.
  • a non-aqueous solvent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
  • the suitable content of the chain carbonate in the non-aqueous solvent is usually 20% by volume or more, preferably 40% by volume or more, Moreover, it is 95 volume% or less normally, Preferably it is 90 volume% or less.
  • the suitable content of the cyclic carbonate in the non-aqueous solvent is usually 5% by volume or more, preferably 10% by volume or more, and usually 80% by volume or less, preferably 60% by volume or less.
  • the ratio of the chain carbonate is in the above range, an increase in the viscosity of the non-aqueous electrolyte is suppressed, and a decrease in the electrical conductivity of the non-aqueous electrolyte due to a decrease in the degree of dissociation of the lithium salt that is the electrolyte is suppressed.
  • fluoroethylene carbonate may be used as a solvent or an additive, and in that case, the content is not limited to the above.
  • the volume of the non-aqueous solvent is a measured value at 25 ° C., but the measured value at the melting point is used for a solid at 25 ° C. such as ethylene carbonate.
  • the nonaqueous electrolytic solution ⁇ of the present invention may contain various additives as long as the effects of the present invention are not significantly impaired.
  • a conventionally well-known thing can be arbitrarily used as an additive.
  • an additive may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
  • overcharge inhibitor examples include alkylbiphenyls such as 2-methylbiphenyl and 2-ethylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclopentylbenzene, cis-1-propyl-4-phenylcyclohexane, trans -1-propyl-4-phenylcyclohexane, cis-1-butyl-4-phenylcyclohexane, trans-1-butyl-4-phenylcyclohexane, diphenyl ether, dibenzofuran, ethylphenyl carbonate, tris (2-t-amylphenyl) phosphate , Tris (3-t-amylphenyl) phosphate, tris (4-t-amylphenyl) phosphate, tris (2-cyclohexylphenyl) phosphate, tris (3-cyclohexylphenyl) phosphate, tris (3-cycl
  • the content of these overcharge inhibitors in the non-aqueous electrolyte ⁇ is usually 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.00%. 5 mass% or more, and usually 5 mass% or less, preferably 3 mass% or less, more preferably 2 mass% or less.
  • concentration is in the above range, the desired effect of the overcharge inhibitor is easily exhibited, and a decrease in battery characteristics such as high-temperature storage characteristics is suppressed.
  • an overcharge inhibitor in the non-aqueous electrolyte, it is possible to suppress the rupture / ignition of the non-aqueous electrolyte secondary battery due to overcharging, and the safety of the non-aqueous electrolyte secondary battery is improved. preferable.
  • auxiliaries include carbonate compounds such as erythritan carbonate, spiro-bis-dimethylene carbonate, methoxyethyl-methyl carbonate, methoxyethyl-ethyl carbonate, ethoxyethyl-methyl carbonate, ethoxyethyl-ethyl carbonate; dimethyl succinate , Diethyl succinate, diallyl succinate, dimethyl maleate, diethyl maleate, diallyl maleate, dipropyl maleate, dibutyl maleate, bis (trifluoromethyl) maleate, bis (pentafluoroethyl) maleate, bis maleate Dicarboxylic acid diester compounds such as (2,2,2-trifluoroethyl); 2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-divinyl-2,4,8,10- Tetrao Spiro compounds such as saspiro [5.5] undecane
  • ethylene sulfite, 1,3-propane sultone, 1,4-butane sultone, 1,3-propene sultone, 1,4-butene sultone, busulfan, 1,4 are used for improving battery characteristics after high-temperature storage.
  • Sulfur-containing compounds such as butanediol bis (2,2,2-trifluoroethanesulfonate) are preferred. Two or more of these may be used in combination.
  • the content of these auxiliaries in the non-aqueous electrolyte ⁇ is not particularly limited, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more.
  • the amount is usually 8% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 2% by mass or less.
  • the addition of these auxiliaries is preferable in terms of improving capacity maintenance characteristics and cycle characteristics after high-temperature storage. When this concentration is in the above range, the effect of the auxiliary agent is easily exhibited, and the deterioration of battery characteristics such as high load discharge characteristics is suppressed.
  • Non-aqueous electrolyte ⁇ contains an electrolyte and a non-aqueous solvent that dissolves the electrolyte, as well as a general non-aqueous electrolyte, and contains a compound represented by the following general formula (1) and a carboxylic acid. And content of the said carboxylic acid is 0.00001 mass% or more and less than 0.01 mass% with respect to the said whole non-aqueous electrolyte solution, It is characterized by the above-mentioned.
  • R 1 to R 6 each independently represents a hydrogen atom, a fluorine atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group.
  • R 1 to R 6 in the general formula (1) each independently represent a hydrogen atom, a fluorine atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group.
  • R 1 to R 6 are an alkyl group, an alkenyl group, an alkynyl group or an aryl group, some or all of the hydrogen atoms contained therein may be substituted with fluorine atoms.
  • alkyl group, alkenyl group, alkynyl group, and aryl group described above are as described in [1-1. Examples thereof include the same groups as those exemplified in the compound represented by the general formula (1). Further, specific examples of the compound (1) include [1-1.
  • Compounds represented by general formula (1)] are exemplified. Compounds A to D shown below are relatively easy to produce, have moderate reactivity, and have an effect of improving battery characteristics. It is preferably used because of its large size.
  • the nonaqueous electrolytic solution ⁇ of the present invention is characterized by containing the compound (1), but the compound (1) to be contained is not limited to one type, and a plurality of types may be used in combination. Moreover, preferable content of a compound (1) is the same as content of the compound (1) in the non-aqueous electrolyte solution (alpha).
  • carboxylic acid Although there is no restriction
  • R 1 to R 3 each independently represents a hydrogen atom, a fluorine atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group.
  • R 1 ⁇ R 3 in the formula (2) preferably represent those same respectively R 1 ⁇ R 3 in the formula (1).
  • Specific examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, isobutyric acid, benzoic acid, acrylic acid, methacrylic acid, crotonic acid, angelic acid, cinnamic acid, succinic acid, malonic acid, and succinic acid. Can be mentioned.
  • the carboxylic acid is contained in the nonaqueous electrolytic solution ⁇
  • acrylic acid, methacrylic acid, crotonic acid, angelic acid, and cinnamic acid are preferable among the above.
  • These carboxylic acids may be contained as impurities or hydrolysates in the compound (1) in the present invention, and are preferable because they do not need to be separately added to the non-aqueous electrolyte solution, and have little adverse effect on battery characteristics.
  • the non-aqueous electrolyte solution ⁇ of the present invention contains a carboxylic acid
  • the carboxylic acid is not limited to one type, and a plurality of types may be used in combination.
  • the content of carboxylic acid with respect to the total amount of the non-aqueous electrolyte ⁇ is 0.00001% by mass or more and less than 0.01% by mass, which is preferable as the lower limit value.
  • Electrolytes There is no restriction
  • a lithium salt is usually used as an electrolyte.
  • electrolytes include [1-3. Examples similar to the specific examples described in [Electrolyte] can be mentioned, and preferable electrolytes, preferable usage forms, contents, lithium salt concentrations and the like are also described in [1-3. It is the same as described in [Electrolyte].
  • the non-aqueous solvent contained in the non-aqueous electrolyte solution ⁇ of the present invention is appropriately selected from those conventionally known as non-aqueous electrolyte solutions as well as the non-aqueous solvent contained in the non-aqueous electrolyte solution ⁇ .
  • Examples of commonly used non-aqueous solvents include cyclic carbonates, chain carbonates, chain and cyclic carboxylic acid esters, chain and cyclic ethers, phosphorus-containing organic solvents, sulfur-containing organic solvents, and aromatic fluorine-containing solvents. Can be mentioned.
  • non-aqueous solvent contained in the non-aqueous electrolyte ⁇ [1-4.
  • nonaqueous solvent examples similar to the specific examples described in [Nonaqueous solvent] can be given, and preferred nonaqueous solvents, preferred use forms, contents, and the like are also the same.
  • aromatic fluorine-containing solvent examples include fluorobenzene, difluorobenzene, trifluorobenzene, tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene, benzotrifluoride and the like.
  • the nonaqueous electrolytic solution ⁇ of the present invention may contain various additives as long as the effects of the present invention are not significantly impaired.
  • a conventionally well-known thing can be arbitrarily used as an additive.
  • an additive may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
  • Non-aqueous electrolyte ⁇ has other additives such as cyclic carbonate compound having unsaturated bond, cyclic carbonate compound having fluorine atom, acid anhydride, isocyanate compound, nitrile compound, monofluorophosphate, difluorophosphoric acid Examples include salts.
  • an overcharge preventing agent and other auxiliary agents are listed.
  • Cyclic carbonate compound having an unsaturated bond examples of the cyclic carbonate compound having an unsaturated bond are [1-2. Cyclic carbonate compounds having unsaturated bonds, cyclic carbonate compounds having fluorine atoms, nitrile compounds, isocyanate compounds, aromatic hydrocarbons, fluorinated benzene compounds, Si-Si without aliphatic substituents having unsaturated bonds Compounds having a bond, compounds having an S ⁇ O group, compounds represented by formula (6), monofluorophosphates, difluorophosphates] (cyclic carbonate compounds having an unsaturated bond) The same thing is mentioned.
  • vinylene carbonate, vinyl ethylene carbonate, and ethynyl ethylene carbonate are preferable from the viewpoint of improving cycle characteristics and capacity maintenance characteristics after high-temperature storage, and vinylene carbonate or vinyl ethylene carbonate is more preferable, and vinylene carbonate is particularly preferable. These may be used alone or in combination of two or more. When using 2 or more types together, it is preferable to use together vinylene carbonate and vinyl ethylene carbonate.
  • the content of the cyclic carbonate compound having an unsaturated bond in the nonaqueous electrolytic solution ⁇ is the same as the content of the cyclic carbonate compound having an unsaturated bond in the nonaqueous electrolytic solution ⁇ described above.
  • Cyclic carbonate compound having a fluorine atom examples include [1-2. Cyclic carbonate compounds with unsaturated bonds, cyclic carbonate compounds with fluorine atoms, nitrile compounds, isocyanate compounds, aromatic hydrocarbons, fluorinated benzene compounds, Si-Si without aliphatic substituents with unsaturated bonds A compound having a bond, a compound having an S ⁇ O group, a compound represented by the general formula (6), a monofluorophosphate, a difluorophosphate] (a cyclic carbonate compound having a fluorine atom) and The same thing is mentioned.
  • the content of the cyclic carbonate compound having a fluorine atom in the nonaqueous electrolytic solution ⁇ is the same as the content of the cyclic carbonate compound having a fluorine atom in the nonaqueous electrolytic solution ⁇ .
  • acid anhydride examples include succinic anhydride, methyl succinic anhydride, 4,4-dimethyl succinic anhydride, 4,5-dimethyl succinic anhydride, maleic anhydride, citraconic anhydride, dimethyl maleic anhydride, and phenyl anhydride.
  • succinic anhydride, maleic anhydride, and citraconic anhydride are preferable from the viewpoint of improving cycle characteristics and high-temperature storage characteristics. These may be used alone or in combination of two or more.
  • the content in the non-aqueous electrolyte ⁇ is usually 0.001% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass. More preferably, it is 0.3% by mass or more, usually 10% by mass or less, preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.
  • the content of the acid anhydride is within the above range, the effect of improving the cycle characteristics of the battery and the capacity maintenance characteristics after high-temperature storage is sufficiently exhibited, and an increase in internal resistance is suppressed.
  • Isocyanate compound is not limited as long as it has an isocyanato group (NCO group).
  • NCO group isocyanato group
  • Examples include 1,2-bis (isocyanatomethyl) cyclohexane 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, allyl isocyanate, and the like.
  • tetramethylene diisocyanate pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-bis (isocyanatomethyl) cyclohexane 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane Is preferable from the viewpoint of improving cycle characteristics and high-temperature storage characteristics. These may be used alone or in combination of two or more.
  • the content and preferred content in the non-aqueous electrolyte solution ⁇ are the same as the content of the isocyanate compound in the non-aqueous electrolyte solution ⁇ described above.
  • the nitrile compound is not limited as long as it has a nitrile group (CN group). Specifically, acetonitrile, propionitrile, butyronitrile, valeronitrile, hexanenitrile, heptanenitrile, octanenitrile, Nonane nitrile, decane nitrile, dodecane nitrile (lauronitrile), tridecane nitrile, tetradecane nitrile (myristonitrile), hexadecane nitrile, pentadecane nitrile, heptadecane nitrile, octadecane nitrile (stearonitrile), nonadecane nitrile, icosonitrile Mononitriles such as: malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, icosonitrile Mon
  • the content in the non-aqueous electrolyte ⁇ is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more. More preferably, it is 0.2% by mass or more, usually 10% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.8% by mass. It is as follows. When the content of the nitrile compound is within the above range, the effect of the auxiliary agent is manifested, which is preferable in terms of suppressing gas generation and improving capacity retention characteristics after high-temperature storage.
  • the total content of monofluorophosphate and difluorophosphate in the non-aqueous electrolyte ⁇ is the same as the total content of monofluorophosphate and difluorophosphate in the non-aqueous electrolyte ⁇ . It is.
  • overcharge inhibitor examples include [1-5. The same as the specific examples described above in (Overcharge preventive agent) of [Other additives].
  • aromatic hydrocarbons such as biphenyl, cyclohexylbenzene, t-butylbenzene, and t-amylbenzene may also be contained.
  • alkylbiphenyl such as biphenyl and 2-methylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclopentylbenzene, cyclohexylbenzene, cis-1-propyl-4-phenylcyclohexane, trans-1-propyl-4- Phenylcyclohexane, cis-1-butyl-4-phenylcyclohexane, trans-1-butyl-4-phenylcyclohexane, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran, methylphenyl carbonate, diphenyl carbonate, triphenyl phosphate, Aromatic compounds such as tris (4-t-butylphenyl) phosphate, tris (4-cyclohexylphenyl) phosphate; 2-fluorobiphenyl, 3-fluorobiphenyl Preferred are partially
  • terphenyl a combination of cyclohexylbenzene and t-butylbenzene or t-amylbenzene
  • a partially hydrogenated biphenyl alkylbiphenyl, terphenyl or terphenyl.
  • the content of these overcharge inhibitors in the non-aqueous electrolyte ⁇ is [1-5. This is the same as the content of the overcharge inhibitor in the nonaqueous electrolytic solution ⁇ described in (Overcharge inhibitor) in “Other additives”.
  • ethylene sulfite, 1,3-propane sultone, 1,4-butane sultone, 1,3-propene sultone, 1,4-butene sultone, busulfan, 1,4 are used for improving battery characteristics after high-temperature storage.
  • Sulfur-containing compounds such as butanediol bis (2,2,2-trifluoroethanesulfonate) are preferred. Two or more of these may be used in combination.
  • the content of these auxiliaries in the non-aqueous electrolyte ⁇ is [1-5. It is the same as the content of the other auxiliary agent in the non-aqueous electrolyte ⁇ described in (Other auxiliary agent) in “Other additives”. It should be noted that the time until the evaluation test after the preparation of the electrolytic solution or after the preparation of the electrolytic solution is allowed even without intentionally adding the carboxylic acid compound to the electrolytic solution, such as the non-aqueous electrolytic solution ⁇ described above. Depending on the time to be kept and the surrounding environment, it may be considered that the carboxylic acid is contained in the range of 0.00001 wt% to 0.01 wt%.
  • the compound which may be contained in the non-aqueous electrolyte (alpha) and the non-aqueous electrolyte (beta) may play a some role.
  • the compound represented by the general formula (6) in the non-aqueous electrolyte ⁇ is a compound that functions indispensably to solve the problems of the present invention, it also functions as an electrolyte. Examples include a case where an aromatic hydrocarbon acts as a solvent while it is a compound that functions indispensably to solve the problems of the present invention.
  • the subject of the present invention is not required to add “other compounds” such as a cyclic carbonate compound having an unsaturated bond to the non-aqueous electrolyte ⁇ .
  • “other compounds” such as a cyclic carbonate compound having an unsaturated bond
  • the content of the compound represented by the general formula (6) is included in both the content as the “other compound” and the content as the “electrolyte”.
  • the non-aqueous electrolyte secondary battery in which the non-aqueous electrolyte ⁇ or ⁇ according to the present invention (hereinafter sometimes simply referred to as “the non-aqueous electrolyte according to the present invention”) is used is a metal ion occlusion.
  • -It has the negative electrode which has the negative electrode active material which can be discharge
  • the negative electrode includes a binder, a solvent, and, if necessary, a thickener, a conductive material, a filler, and the like.
  • the negative electrode active material used for the negative electrode is described below.
  • the negative electrode active material is not particularly limited as long as it can electrochemically occlude and release metal ions, and more preferably, it can occlude and release lithium ions.
  • Specific examples include carbonaceous materials, alloy materials, lithium-containing metal composite oxide materials, and the like. These may be used individually by 1 type, and may be used together combining 2 or more types arbitrarily.
  • Carbonaceous material examples include (1) natural graphite, (2) artificial graphite, (3) amorphous carbon, (4) carbon-coated graphite, (5) graphite-coated graphite, and (6) resin-coated graphite. .
  • Examples of natural graphite include scaly graphite, scaly graphite, soil graphite, and / or graphite particles obtained by subjecting these graphites to spheroidization and densification.
  • spherical or ellipsoidal graphite subjected to spheroidizing treatment is particularly preferable from the viewpoints of particle filling properties and charge / discharge rate characteristics.
  • an apparatus used for the spheroidization treatment for example, an apparatus that repeatedly gives mechanical action such as compression, friction, shearing force, etc. including the interaction of particles mainly to the impact force to the particles can be used.
  • it has a rotor with a large number of blades installed inside the casing, and mechanical action such as impact compression, friction, shearing force, etc. on the carbon material introduced inside the rotor by rotating at high speed.
  • a device for performing the spheroidizing treatment is preferable.
  • the peripheral speed of the rotating rotor is preferably 30 to 100 m / second, more preferably 40 to 100 m / second, and more preferably 50 to 100 m / second. More preferably.
  • the treatment can be performed by simply passing a carbonaceous material, but it is preferable to circulate or stay in the apparatus for 30 seconds or longer, and it is preferable to circulate or stay in the apparatus for 1 minute or longer. More preferred.
  • Artificial graphite includes coal tar pitch, coal heavy oil, atmospheric residue, petroleum heavy oil, aromatic hydrocarbon, nitrogen-containing cyclic compound, sulfur-containing cyclic compound, polyphenylene, polyvinyl chloride,
  • An organic compound such as polyvinyl alcohol, polyacrylonitrile, polyvinyl butyral, natural polymer, polyphenylene sulfide, polyphenylene oxide, furfuryl alcohol resin, phenol-formaldehyde resin, imide resin is usually in a range of 2500 ° C. or more and usually 3200 ° C. or less. Examples thereof include those produced by graphitization at a temperature and, if necessary, pulverized and / or classified. At this time, a silicon-containing compound or a boron-containing compound can also be used as a graphitization catalyst.
  • artificial graphite obtained by graphitizing mesocarbon microbeads separated in the heat treatment process of pitch, and artificial graphite of granulated particles composed of primary particles are also included.
  • graphitized catalyst with graphitizable binder such as mesocarbon microbeads or graphitizable carbonaceous material powder such as coke and tar, pitch, etc., graphitized, and pulverized as necessary.
  • amorphous carbon an amorphous carbon that has been heat-treated at least once in a temperature range (400 to 2200 ° C.) in which no graphitizable carbon precursor such as tar or pitch is used as a raw material.
  • amorphous carbon particles that are heat-treated using particles or a non-graphitizable carbon precursor such as a resin as a raw material.
  • Carbon-coated graphite is obtained by mixing natural graphite and / or artificial graphite with a carbon precursor that is an organic compound such as tar, pitch, or resin, and heat-treating it at least once in the range of 400 to 2300 ° C.
  • a carbon precursor that is an organic compound such as tar, pitch, or resin
  • Examples thereof include carbon graphite composites in which natural graphite and / or artificial graphite is used as nuclear graphite, and amorphous carbon coats the nuclear graphite.
  • the composite form may cover the entire surface or a part thereof, or may be a composite of a plurality of primary particles using carbon originating from the carbon precursor as a binder.
  • Carbon can also be deposited (CVD) by reacting natural graphite and / or artificial graphite with hydrocarbon gases such as benzene, toluene, methane, propane, and aromatic volatiles at high temperatures, and depositing carbon on the graphite surface (CVD).
  • hydrocarbon gases such as benzene, toluene, methane, propane, and aromatic volatiles at high temperatures, and depositing carbon on the graphite surface (CVD).
  • a graphite composite can also be obtained.
  • graphite-coated graphite natural graphite and / or artificial graphite and a carbon precursor of an easily graphitizable organic compound such as tar, pitch or resin are mixed and once in the range of about 2400 to 3200 ° C.
  • examples thereof include graphite-coated graphite in which natural graphite and / or artificial graphite obtained by heat treatment as described above is used as nuclear graphite, and graphitized material covers the whole or part of the surface of nuclear graphite.
  • the carbonaceous materials (1) to (6) may be used alone or in combination of two or more in any combination and ratio.
  • organic compounds such as tar, pitch and resin used in the carbonaceous materials (2) to (5) above include heavy coal-based oils, direct-current heavy oils, cracked heavy petroleum oils, and aromatic hydrocarbons.
  • the raw material organic compound may be used after being dissolved in a low molecular organic solvent in order to adjust the viscosity at the time of mixing.
  • natural graphite and / or artificial graphite used as a raw material of nuclear graphite natural graphite subjected to spheroidization treatment is preferable.
  • the alloy material used as the negative electrode active material is not particularly limited as long as it can occlude / release metal ions, particularly lithium ions. Specific examples include simple lithium, simple metals and alloys that form lithium alloys, and compounds such as oxides, carbides, nitrides, silicides, sulfides, and phosphides thereof.
  • the single metal and alloy forming the lithium alloy are preferably materials containing group 13 and group 14 metal / metalloid elements (that is, excluding carbon), and more preferably single metals of aluminum, silicon and tin. And alloys or compounds containing these atoms. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
  • the lithium-containing metal composite oxide material used as the negative electrode active material is not particularly limited as long as lithium can be occluded / released, but titanium and lithium-containing materials are preferable from the viewpoint of high current density charge / discharge characteristics. More preferred is a lithium-containing composite metal oxide material containing lithium, and even more preferred is a composite oxide of lithium and titanium (hereinafter sometimes abbreviated as “lithium-titanium composite oxide”). That is, it is particularly preferable to use a lithium titanium composite oxide having a spinel structure in a negative electrode active material for a non-aqueous electrolyte secondary battery because the output resistance is greatly reduced.
  • lithium or titanium of the lithium titanium composite oxide is at least selected from the group consisting of other metal elements such as Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb.
  • a metal oxide substituted with one element is also preferably used.
  • the metal oxide is a lithium titanium composite oxide represented by the following general formula (C). In the general formula (C), 0.7 ⁇ x ⁇ 1.5, 1.5 ⁇ y ⁇ 2.3. And a compound satisfying 0 ⁇ z ⁇ 1.6 is more preferable because the structure upon doping and dedoping of lithium ions is stable.
  • M represents at least one element selected from the group consisting of Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb.
  • the particularly preferred representative composition of the compound represented by the general formula (C) is Li 4/3 Ti 5/3 O 4 in the above (i), Li 1 Ti 2 O 4 in the above (ii), (iii) ) Li 4/5 Ti 11/5 O 4 .
  • the structure of z ⁇ 0, for example, Li 4/3 Ti 4/3 Al 1/3 O 4 is preferable.
  • a general method is used as a manufacturing method of an inorganic compound.
  • a titanium raw material such as titanium oxide, a raw material of another element as necessary, and a Li source such as LiOH, Li 2 CO 3 , LiNO 3 are uniformly mixed and fired at a high temperature to obtain an active material.
  • the method of obtaining is mentioned.
  • a titanium precursor material such as titanium oxide and, if necessary, a raw material of another element are dissolved or pulverized and dispersed in a solvent such as water, and the pH is adjusted while stirring to form a spherical precursor.
  • a titanium raw material such as titanium oxide and, if necessary, a raw material of another element are dissolved or pulverized and dispersed in a solvent such as water.
  • a method of obtaining an active material by adding a Li source such as LiOH, Li 2 CO 3 , LiNO 3 and the like to an elliptical spherical precursor and baking at a high temperature can be mentioned.
  • a titanium raw material such as titanium oxide, a Li source such as LiOH, Li 2 CO 3 and LiNO 3 and a raw material of another element as necessary are dissolved or pulverized in a solvent such as water.
  • elements other than Ti such as Al, Mn, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, C, Si, Sn
  • elements obtained from the group consisting of Ag may be present in the metal oxide structure containing titanium and / or in contact with the oxide containing titanium. By containing these elements, the operating voltage and capacity of the battery can be controlled.
  • the d-value (interlayer distance) of the lattice plane (002 plane) determined by X-ray diffraction by the Gakushin method of carbonaceous materials is usually 0.335 nm or more, usually 0.360 nm or less, and 0.350 nm. The following is preferable, and 0.345 nm or less is more preferable.
  • the crystallite size (Lc) of the carbonaceous material obtained by X-ray diffraction by the Gakushin method is preferably 1.0 nm or more, and more preferably 1.5 nm or more.
  • the volume-based average particle diameter of the carbonaceous material is a volume-based average particle diameter (median diameter) obtained by a laser diffraction / scattering method, and is usually 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and 7 ⁇ m.
  • the above is particularly preferable, and is usually 100 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, further preferably 30 ⁇ m or less, and particularly preferably 25 ⁇ m or less.
  • the volume-based average particle size is measured by dispersing carbon powder in a 0.2% by weight aqueous solution (about 10 mL) of polyoxyethylene (20) sorbitan monolaurate, which is a surfactant, and laser diffraction / scattering particle size distribution. The measurement is performed using a meter (for example, LA-700 manufactured by Horiba, Ltd.). The median diameter determined by the measurement is defined as the volume-based average particle diameter of the carbonaceous material of the present invention.
  • the Raman R value of the carbonaceous material is a value measured using a laser Raman spectrum method, and is usually 0.01 or more, preferably 0.03 or more, more preferably 0.1 or more, and usually 1. 5 or less, preferably 1.2 or less, more preferably 1 or less, and particularly preferably 0.5 or less.
  • the crystallinity of the particle surface becomes too high, and there are cases where the number of sites where Li enters between layers decreases with charge / discharge. That is, charge acceptance may be reduced. Further, when the density of the negative electrode is increased by applying it to the current collector and then pressing it, the crystals are likely to be oriented in a direction parallel to the electrode plate, which may lead to a decrease in load characteristics. On the other hand, if it exceeds the above range, the crystallinity of the particle surface is lowered, the reactivity with the non-aqueous electrolyte is increased, and the efficiency may be lowered and the gas generation may be increased.
  • the Raman spectrum is measured by using a Raman spectrometer (for example, a Raman spectrometer manufactured by JASCO Corporation) to drop the sample naturally into the measurement cell and filling the sample cell with argon ion laser light (or a semiconductor). While irradiating a laser beam, the cell is rotated in a plane perpendicular to the laser beam.
  • the resulting Raman spectrum, the intensity I A of the peak P A in the vicinity of 1580 cm -1, and measuring the intensity I B of a peak P B in the vicinity of 1360 cm -1, the intensity ratio R (R I B / I A) Is calculated.
  • the Raman R value calculated by the measurement is defined as the Raman R value of the carbonaceous material of the present invention.
  • said Raman measurement conditions are as follows. ⁇ Laser wavelength: Ar ion laser 514.5 nm (semiconductor laser 532 nm) Measurement range: 1100 cm ⁇ 1 to 1730 cm ⁇ 1 ⁇ Raman R value: Background processing ⁇ Smoothing processing: Simple average, 5 points of convolution
  • BET specific surface area of the carbonaceous material is a value of the measured specific surface area using the BET method is usually 0.1 m 2 ⁇ g -1 or more, 0.7 m 2 ⁇ g -1 or more, 1. 0 m 2 ⁇ g -1 or more, and particularly preferably 1.5 m 2 ⁇ g -1 or more, generally not more than 100 m 2 ⁇ g -1, preferably 25 m 2 ⁇ g -1 or less, 15 m 2 ⁇ g ⁇ 1 or less is more preferable, and 10 m 2 ⁇ g ⁇ 1 or less is particularly preferable.
  • the value of the BET specific surface area is less than this range, the acceptability of lithium is likely to deteriorate during charging when it is used as a negative electrode material, and lithium is likely to precipitate on the electrode surface, which may reduce the stability.
  • it exceeds this range when used as a negative electrode material, the reactivity with the non-aqueous electrolyte increases, gas generation tends to increase, and a preferable battery may be difficult to obtain.
  • the specific surface area is measured by the BET method using a surface area meter (for example, a fully automated surface area measuring device manufactured by Okura Riken), preliminarily drying the sample at 350 ° C. for 15 minutes under nitrogen flow, Using a nitrogen helium mixed gas that is accurately adjusted so that the relative pressure value of nitrogen is 0.3, the nitrogen adsorption BET one-point method is performed by a gas flow method.
  • a surface area meter for example, a fully automated surface area measuring device manufactured by Okura Riken
  • the circularity is measured as the degree of the sphere of the carbonaceous material, it is preferably within the following range.
  • the circularity of particles having a carbonaceous material particle size in the range of 3 to 40 ⁇ m is preferably 0.1 or more, more preferably 0.5 or more, more preferably 0.8 or more, and even more preferably 0.85 or more, 0.9 or more is particularly preferable, and the closer to 1, the more preferable.
  • High current density charge / discharge characteristics improve as the degree of circularity increases. Therefore, when the circularity is less than the above range, the filling property of the negative electrode active material is lowered, the resistance between particles is increased, and the high current density charge / discharge characteristics may be lowered for a short time.
  • the circularity is measured using a flow type particle image analyzer (for example, FPIA manufactured by Sysmex Corporation). About 0.2 g of a sample was dispersed in a 0.2% by mass aqueous solution (about 50 mL) of polyoxyethylene (20) sorbitan monolaurate as a surfactant, and irradiated with 28 kHz ultrasonic waves at an output of 60 W for 1 minute.
  • the detection range is specified as 0.6 to 400 ⁇ m, and the particle size is measured in the range of 3 to 40 ⁇ m.
  • the method for improving the circularity is not particularly limited, but a sphere-shaped sphere is preferable because the shape of the interparticle void when the electrode body is formed is preferable.
  • spheroidizing treatment include a method of mechanically approaching a sphere by applying a shearing force and a compressive force, a mechanical / physical processing method of granulating a plurality of fine particles by the binder or the adhesive force of the particles themselves, etc. Is mentioned.
  • the tap density of the carbonaceous material is usually 0.1 g ⁇ cm ⁇ 3 or more, preferably 0.5 g ⁇ cm ⁇ 3 or more, more preferably 0.7 g ⁇ cm ⁇ 3 or more, and 1 g ⁇ cm ⁇ 3 or more. particularly preferred, and is preferably 2 g ⁇ cm -3 or less, more preferably 1.8 g ⁇ cm -3 or less, 1.6 g ⁇ cm -3 or less are particularly preferred.
  • the tap density is below the above range, the packing density is difficult to increase when used as a negative electrode, and a high-capacity battery may not be obtained.
  • the above range is exceeded, there are too few voids between particles in the electrode, it is difficult to ensure conductivity between the particles, and it may be difficult to obtain preferable battery characteristics.
  • the tap density is measured by passing through a sieve having an opening of 300 ⁇ m, dropping the sample onto a 20 cm 3 tapping cell and filling the sample to the upper end surface of the cell, and then measuring a powder density measuring device (for example, manufactured by Seishin Enterprise Co., Ltd.). Using a tap denser, tapping with a stroke length of 10 mm is performed 1000 times, and the tap density is calculated from the volume at that time and the mass of the sample.
  • a powder density measuring device for example, manufactured by Seishin Enterprise Co., Ltd.
  • the orientation ratio of the carbonaceous material is usually 0.005 or more, preferably 0.01 or more, more preferably 0.015 or more, and usually 0.67 or less. When the orientation ratio is below the above range, the high-density charge / discharge characteristics may deteriorate.
  • the upper limit of the above range is the theoretical upper limit value of the orientation ratio of the carbonaceous material.
  • the orientation ratio is measured by X-ray diffraction after pressure-molding the sample.
  • Set the molding obtained by filling 0.47g of the sample into a molding machine with a diameter of 17mm and compressing it with 58.8MN ⁇ m -2 so that it is flush with the surface of the sample holder for measurement.
  • X-ray diffraction is measured.
  • From the (110) diffraction and (004) diffraction peak intensities of the obtained carbon, a ratio represented by (110) diffraction peak intensity / (004) diffraction peak intensity is calculated.
  • the X-ray diffraction measurement conditions are as follows. “2 ⁇ ” indicates a diffraction angle.
  • ⁇ Target Cu (K ⁇ ray) graphite monochromator
  • Light receiving slit 0.15
  • Scattering slit 0.5 degree / measurement range and step angle / measurement time: (110) plane: 75 degrees ⁇ 2 ⁇ ⁇ 80 degrees 1 degree / 60 seconds (004) plane; 52 degrees ⁇ 2 ⁇ ⁇ 57 degrees 1 degree / 60 seconds
  • the aspect ratio of the carbonaceous material is usually 1 or more and usually 10 or less, preferably 8 or less, and more preferably 5 or less. If the aspect ratio exceeds the above range, streaking or a uniform coated surface cannot be obtained when forming an electrode plate, and the high current density charge / discharge characteristics may deteriorate.
  • the lower limit of the above range is the theoretical lower limit value of the aspect ratio of the carbonaceous material.
  • Carbonaceous material particles when three-dimensional observation is performed by selecting arbitrary 50 graphite particles fixed to the end face of a metal having a thickness of 50 ⁇ m or less and rotating and tilting the stage on which the sample is fixed.
  • the aspect ratio is measured by measuring the longest diameter A and the shortest diameter B orthogonal thereto and obtaining the average value of A / B.
  • the binder (binder) for binding the negative electrode active material is not particularly limited as long as it is a material that is stable with respect to the non-aqueous electrolyte solution and the solvent used during electrode production.
  • resin-based polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, polyimide, cellulose, and nitrocellulose; SBR (styrene-butadiene rubber), isoprene rubber, butadiene rubber, fluorine rubber, Rubber polymers such as NBR (acrylonitrile / butadiene rubber) and ethylene / propylene rubber; styrene / butadiene / styrene block copolymer or hydrogenated product thereof; EPDM (ethylene / propylene / diene terpolymer), styrene / Thermoplastic elastomeric polymers such as ethylene / butadiene / st
  • the ratio of the binder to the negative electrode active material is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 0.6% by mass or more, and preferably 20% by mass or less, 15% by mass. The following is more preferable, 10% by mass or less is further preferable, and 8% by mass or less is particularly preferable.
  • the ratio of the binder with respect to a negative electrode active material exceeds the said range, the ratio of the binder which does not contribute to battery capacity may increase, and the fall of battery capacity may be caused.
  • the strength of the negative electrode may be reduced.
  • the ratio of the binder to the negative electrode active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, 0 .6% by mass or more is more preferable, usually 5% by mass or less, preferably 3% by mass or less, and more preferably 2% by mass or less.
  • the ratio to the negative electrode active material is usually 1% by mass or more, preferably 2% by mass or more, and more preferably 3% by mass or more. It is preferably 15% by mass or less, preferably 10% by mass or less, and more preferably 8% by mass or less.
  • solvent As a solvent for forming the slurry used for the production of the negative electrode, as long as it is a solvent capable of dissolving or dispersing the negative electrode active material, the binder, and the thickener and conductive material used as necessary, The type is not particularly limited, and either an aqueous solvent or an organic solvent may be used. Examples of the aqueous solvent include water and alcohol.
  • organic solvent examples include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N, N- Examples include dimethylaminopropylamine, tetrahydrofuran (THF), toluene, acetone, diethyl ether, dimethylacetamide, hexamethylphosphalamide, dimethyl sulfoxide, benzene, xylene, quinoline, pyridine, methylnaphthalene, hexane, and the like.
  • NMP N-methylpyrrolidone
  • dimethylformamide dimethylacetamide
  • methyl ethyl ketone cyclohexanone
  • methyl acetate methyl acrylate
  • diethyltriamine N
  • N- Examples include dimethylaminopropylamine, tetrahydr
  • aqueous solvent when used, it is preferable to add a dispersant or the like in addition to the thickener and make a slurry using a latex such as SBR (styrene butadiene rubber).
  • a dispersant or the like in addition to the thickener and make a slurry using a latex such as SBR (styrene butadiene rubber).
  • these solvents may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and a ratio.
  • a thickener is usually used to adjust the viscosity of the slurry.
  • the thickener is not particularly limited, and specific examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios.
  • the ratio of the thickener to the negative electrode active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.6% by mass or more, Usually, it is 5 mass% or less, 3 mass% or less is preferable, and 2 mass% or less is more preferable.
  • the ratio of the thickener to the negative electrode active material is within the above range, it is possible to suppress a decrease in battery capacity and an increase in resistance, and it is possible to ensure appropriate applicability.
  • the conductive material used for the negative electrode examples include metal materials such as copper and nickel; carbon materials such as graphite and carbon black. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. In particular, it is preferable to use a carbon material as the conductive material because the carbon material acts as an active material.
  • the content of the conductive material in the whole negative electrode material is usually 3% by mass or more, particularly 5% by mass or more, and usually 30% by mass or less, particularly 25% by mass or less.
  • the content of the conductive material is too small, the conductivity tends to be insufficient.
  • the content of the negative electrode active material or the like is relatively insufficient, which tends to decrease the battery capacity and strength.
  • the current collector for holding the negative electrode active material As the current collector for holding the negative electrode active material, a known material can be arbitrarily used. Examples of the current collector for the negative electrode include metal materials such as aluminum, copper, nickel, stainless steel, and nickel-plated steel. Copper is particularly preferable from the viewpoint of ease of processing and cost. Further, the current collector of the negative electrode may be roughened in advance.
  • the shape of the current collector includes, for example, a metal foil, a metal cylinder, a metal coil, a metal plate, a metal thin film, an expanded metal, a punch metal, and a foam metal when the current collector is a metal material.
  • a metal thin film is preferable, a copper foil is more preferable, and a rolled copper foil by a rolling method and an electrolytic copper foil by an electrolytic method are more preferable, and both can be used as a current collector.
  • the thickness of the current collector is usually 1 ⁇ m or more, preferably 5 ⁇ m or more, and usually 100 ⁇ m or less, preferably 50 ⁇ m or less, from the viewpoint of securing battery capacity and handling properties.
  • the ratio of the thickness of the current collector to the negative electrode active material layer is not particularly limited, but the value of “(the thickness of the negative electrode active material layer on one side immediately before the nonaqueous electrolyte injection) / (thickness of the current collector)”
  • 150 or less is preferable, 20 or less is more preferable, 10 or less is particularly preferable, 0.1 or more is preferable, 0.4 or more is more preferable, and 1 or more is particularly preferable.
  • the ratio of the thickness of the current collector to the negative electrode active material layer is in the above range, battery capacity can be secured and heat generation of the current collector during high current density charge / discharge can be suppressed.
  • Surface adhering substances include 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 and carbonates such as lithium carbonate, calcium carbonate and magnesium carbonate.
  • any known method can be used for the production of the electrode as long as the effects of the present invention are not significantly impaired. For example, it is formed by adding a binder, a solvent, and, if necessary, a thickener, a conductive material, a filler, etc. to a negative electrode active material to form a slurry, which is applied to a current collector, dried and then pressed. Can do.
  • a method of forming a thin film layer (negative electrode active material layer) containing the above negative electrode active material by a method such as vapor deposition, sputtering, or plating is also used. It is done.
  • the electrode structure when the negative electrode active material is made into an electrode is not particularly limited, but the density of the negative electrode active material present on the current collector is preferably 1 g ⁇ cm ⁇ 3 or more, and 1.2 g ⁇ cm ⁇ 3 or more. but more preferably, particularly preferably 1.3 g ⁇ cm -3 or more, preferably 2.2 g ⁇ cm -3 or less, more preferably 2.1 g ⁇ cm -3 or less, 2.0 g ⁇ cm -3 or less More preferred is 1.9 g ⁇ cm ⁇ 3 or less.
  • the density of the negative electrode active material existing on the current collector exceeds the above range, the negative electrode active material particles are destroyed, and the initial irreversible capacity increases or non-aqueous system near the current collector / negative electrode active material interface. There is a case where high current density charge / discharge characteristics are deteriorated due to a decrease in permeability of the electrolytic solution.
  • the amount is less than the above range, the conductivity between the negative electrode active materials decreases, the battery resistance increases, and the capacity per unit volume may decrease.
  • the thickness of the negative electrode plate is designed according to the positive electrode plate to be used, and is not particularly limited.
  • the thickness of the composite layer obtained by subtracting the thickness of the metal foil of the core is usually 15 ⁇ m or more, preferably 20 ⁇ m or more. More preferably, it is 30 ⁇ m or more, and usually 300 ⁇ m or less, preferably 280 ⁇ m or less, more preferably 250 ⁇ m or less.
  • the area of the negative electrode plate is not particularly limited, but it is preferably designed to be slightly larger than an opposing positive electrode plate, which will be described later, so that the positive electrode plate does not protrude from the negative electrode plate. Further, from the viewpoint of suppressing the life of a cycle in which charge and discharge are repeated and deterioration due to high temperature storage, it is preferable that the area be as close to the positive electrode as possible, because the ratio of electrodes that work more uniformly and effectively is increased and the characteristics are improved. In particular, when used with a large current, the design of the area of the negative electrode plate is important.
  • the area of the electrode plate represents an apparent geometric area, not a specific surface area per unit weight.
  • the non-aqueous electrolyte secondary battery in which the non-aqueous electrolyte according to the present invention is used includes a positive electrode having a positive electrode active material capable of occluding and releasing metal ions.
  • the positive electrode includes a binder, a solvent, and, if necessary, a thickener, a conductive material, a filler, and the like.
  • the positive electrode active material used for the positive electrode is described below.
  • the positive electrode active material is not particularly limited as long as it can electrochemically occlude / release metal ions, and more preferably, it can occlude / release lithium ions.
  • lithium transition metal compounds are preferably used. These may be used individually by 1 type, and may be used together combining 2 or more types arbitrarily.
  • a lithium transition metal compound is a compound having a structure capable of desorbing and inserting Li ions, and examples thereof include sulfides, phosphate compounds, and lithium transition metal composite oxides.
  • the sulfide is represented by a compound having a two-dimensional layered structure such as TiS 2 or MoS 2 or a general formula Me x Mo 6 S 8 (Me represents various transition metals including Pb, Ag, and Cu). And the like, such as a chevrille compound having a strong three-dimensional skeleton structure. Where x is 0-4 Represents.
  • Examples of the phosphate compound include those belonging to the olivine structure, and are generally represented by LiMePO 4 (Me represents at least one transition metal), specifically, LiFePO 4 , LiCoPO 4 , Examples thereof include LiNiPO 4 and LiMnPO 4 .
  • Examples of the lithium transition metal composite oxide include spinel structures capable of three-dimensional diffusion and those belonging to a layered structure capable of two-dimensional diffusion of lithium ions. Those having a spinel structure are generally expressed as LiMe 2 O 4 (Me represents at least one transition metal), specifically, LiMn 2 O 4 , LiCoMnO 4 , LiNi 0.5 Mn 1. .5 O 4 , LiCoVO 4 and the like.
  • LiMeO 2 Those having a layered structure are generally expressed as LiMeO 2 (Me represents at least one transition metal).
  • LiCoO 2 Specifically, LiNiO 2, LiNi 1-x Co x O 2, LiNi 1-x-y Co x Mn y O 2, LiNi 0.5 Mn 0.5 O 2, Li 1.2 Cr 0. 4 Mn 0.4 O 2, Li 1.2 Cr 0.4 Ti 0.4 O 2, such as LiMnO 2 and the like.
  • composition examples of the lithium-containing transition metal compound include a lithium transition metal compound represented by the following composition formula (A) or (B).
  • x is usually 0 or more and 0.5 or less.
  • M represents a transition metal and is composed of Ni and Mn or Ni, Mn and Co.
  • Mn / Ni molar ratio is usually 0.1 or more and 5 or less, Ni / M molar ratio is usually 0 or more and 0.5 or less, and Co / M molar ratio is usually 0 or more and 0.5 or less.
  • the rich portion of Li represented by x may be replaced with the transition metal site M.
  • composition formula (A) the atomic ratio of the oxygen amount is described as 2 for convenience, but there may be some non-stoichiometry.
  • x in the said compositional formula is the preparation composition in the manufacture stage of a lithium transition metal type compound.
  • batteries on the market are aged after the batteries are assembled.
  • the Li amount of the positive electrode may be deficient with charge / discharge.
  • x may be measured to be ⁇ 0.65 or more and 1 or less when discharged to 3 V in composition analysis.
  • the lithium transition metal compound is excellent in battery characteristics when fired at a high temperature in an oxygen-containing gas atmosphere in order to enhance the crystallinity of the positive electrode active material.
  • the lithium transition metal compound represented by the composition formula (A) may be a solid solution with Li 2 MO 3 called a 213 layer, as represented by the following general formula (A ′).
  • ⁇ is a number that satisfies 0 ⁇ ⁇ 1.
  • M is at least one metal element having an average oxidation number of 4 +
  • M ′ is at least one metal element having an average oxidation number of 3 + .
  • M is at least one metal element selected from the group consisting of Mn, Zr, Ti, Ru, Re, and Pt.
  • M ′ is preferably at least one metal element selected from the group consisting of V, Mn, Fe, Co and Ni, more preferably at least one selected from the group consisting of Mn, Co and Ni. It is a metal element.
  • M is an element composed of at least one of transition metals selected from Ni, Cr, Fe, Co, Cu, Zr, Al and Mg, and the value of a is usually 0. As described above, it is 0.3 or less, the value of b is usually 0.4 or more and 0.6 or less, and the value of ⁇ is usually in the range of ⁇ 0.5.
  • a in the composition formula (B) is a charged composition in the production stage of the lithium transition metal compound.
  • batteries on the market are aged after the batteries are assembled.
  • the Li amount of the positive electrode may be deficient with charge / discharge.
  • a may be measured to be ⁇ 0.65 or more and 1 or less when discharged to 3 V in composition analysis. When the value of a is within this range, the energy density per unit weight in the lithium transition metal compound is not significantly impaired, and good load characteristics can be obtained.
  • ⁇ is within this range, the stability as a crystal structure is high, and the cycle characteristics and high-temperature storage of a battery having an electrode produced using this lithium transition metal compound are good.
  • each transition metal and lithium are analyzed by an inductively coupled plasma emission spectrometer (ICP-AES) to obtain a Li / Ni / Mn ratio. It is calculated by the thing.
  • ICP-AES inductively coupled plasma emission spectrometer
  • lithium related to a is substituted for the same transition metal site.
  • the average valence of M and manganese becomes larger than 3.5 due to the principle of charge neutrality.
  • the lithium transition metal-based compound may be fluorine-substituted and is expressed as LiMn 2 O 4-x F 2x .
  • lithium transition metal compound having the above composition examples include, for example, Li 1 + x Ni 0.5 Mn 0.5 O 2 , Li 1 + x Ni 0.85 Co 0.10 Al 0.05 O 2 , Li 1 + x Ni 0.33 Mn 0.33 Co 0.33 O 2 , Li 1 + x Ni 0.45 Mn 0.45 Co 0.1 O 2 , Li 1 + x Mn 1.8 Al 0.2 O 4 , Li 1 + x Mn 1.5 Ni 0.5 O 4 and the like. These lithium transition metal compounds may be used alone or in a blend of two or more.
  • a different element may be introduce
  • Different elements include B, Na, Mg, Al, K, Ca, Ti, V, Cr, Fe, Cu, Zn, Sr, Y, Zr, Nb, Ru, Rh, Pd, Ag, In, Sb, Te. Ba, Ta, Mo, W, Re, Os, Ir, Pt, Au, Pb, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Bi , N, F, S, Cl, Br, I, As, Ge, P, Pb, Sb, Si, and Sn.
  • These foreign elements may be incorporated into the crystal structure of the lithium transition metal compound, or may not be incorporated into the crystal structure of the lithium transition metal compound, and may be a single element or compound on the particle surface or grain boundary. May be unevenly distributed.
  • the binder (binder) used for the positive electrode in the present invention is not particularly limited, and in the case of a coating method, any material that is stable with respect to the liquid medium used at the time of electrode production may be used.
  • resin-based polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, cellulose, and nitrocellulose; SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), fluororubber, Rubber polymers such as isoprene rubber, butadiene rubber, ethylene / propylene rubber; styrene / butadiene / styrene block copolymer and its hydrogenated product, EPDM (ethylene / propylene / diene terpolymer), styrene / ethylene / Thermoplastic elastomeric polymers such as butadiene / ethylene copoly
  • the ratio of the binder in the positive electrode active material layer is usually 0.1% by mass or more and 80% by mass or less. If the proportion of the binder is too low, the positive electrode active material cannot be sufficiently retained and the positive electrode has insufficient mechanical strength, which may deteriorate battery performance such as cycle characteristics. Battery capacity and conductivity may be reduced.
  • solvent used for the positive electrode in the present invention is [3-3.
  • the same solvents as those used for the negative electrode described in [Solvent] can be used.
  • the positive electrode active material layer in the present invention usually contains a conductive material in order to increase conductivity.
  • a conductive material there are no particular restrictions on the type, but specific examples include metal materials such as copper and nickel, graphite such as natural graphite and artificial graphite, carbon black such as acetylene black, and amorphous carbon such as needle coke. And carbon materials.
  • these substances may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
  • the proportion of the conductive material in the positive electrode active material layer is usually 0.01% by mass or more and 50% by mass or less. If the proportion of the conductive material is too low, the conductivity may be insufficient, and conversely if it is too high, the battery capacity may be reduced.
  • Liquid medium As a liquid medium for forming a slurry, it is possible to dissolve or disperse a lithium transition metal compound powder as a positive electrode material, a binder, and a conductive material and a thickener used as necessary. If it is a solvent, there is no restriction
  • organic solvents examples include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N, N-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran (THF) Toluene, acetone, dimethyl ether, dimethylacetamide, hexamethylphosphalamide, dimethyl sulfoxide, benzene, xylene, quinoline, pyridine, methylnaphthalene, hexane, and the like.
  • NMP N-methylpyrrolidone
  • dimethylformamide dimethylacetamide
  • methyl ethyl ketone cyclohexanone
  • methyl acetate methyl acrylate
  • diethyltriamine N, N-dimethylaminopropylamine
  • THF t
  • a dispersant is added together with the thickener, and a slurry such as SBR is slurried.
  • these solvents may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
  • the current collector used for the positive electrode in the present invention is usually a metal material such as aluminum, stainless steel, nickel plating, titanium, or tantalum, or a carbon material such as carbon cloth or carbon paper.
  • a metal material such as aluminum, stainless steel, nickel plating, titanium, or tantalum
  • a carbon material such as carbon cloth or carbon paper.
  • a metal material a metal foil, a metal cylinder, a metal coil, a metal plate, a metal thin film, an expanded metal, a punch metal, a foam metal, etc. are mentioned.
  • a carbon material a carbon plate, a carbon thin film, A carbon cylinder etc. are mentioned.
  • the positive electrode current collector When a thin film is used as the positive electrode current collector, its thickness is arbitrary, but a range of usually 1 ⁇ m or more and 100 mm or less is suitable. If it is thinner than the above range, the strength required for the current collector may be insufficient. On the other hand, if it is thicker than the above range, the handleability may be impaired.
  • a positive electrode for a lithium secondary battery will be described as an example as a configuration and a manufacturing method of the positive electrode.
  • the positive electrode for a lithium secondary battery is formed by forming a positive electrode active material layer containing the above-described lithium transition metal compound powder and a binder (binder) on a current collector.
  • the positive electrode active material layer is usually formed by mixing a positive electrode material, a binder, and a conductive material and a thickener, which are used if necessary, in a dry form into a sheet shape, and then pressing the positive electrode current collector on the positive electrode current collector.
  • these materials are dissolved or dispersed in a liquid medium to form a slurry, which is applied to the positive electrode current collector and dried.
  • the content ratio of the lithium transition metal-based compound powder as the positive electrode material in the positive electrode active material layer is usually 10% by mass or more and 99.9% by mass or less. If the proportion of the lithium transition metal compound powder in the positive electrode active material layer is too large, the strength of the positive electrode tends to be insufficient, and if it is too small, the capacity may be insufficient.
  • the thickness of the positive electrode active material layer is usually about 10 to 200 ⁇ m.
  • the electrode density after pressing the positive electrode is usually 2.2 g / cm 3 or more and 4.2 g / cm 3 or less.
  • the positive electrode active material layer obtained by coating and drying is preferably consolidated by a roller press or the like in order to increase the packing density of the positive electrode active material.
  • a separator is interposed between the positive electrode and the negative electrode in order to prevent a short circuit.
  • the nonaqueous electrolytic solution of the present invention is usually used by impregnating the separator.
  • the material and shape of the separator are not particularly limited, and known ones can be arbitrarily adopted as long as the effects of the present invention are not significantly impaired.
  • a resin, glass fiber, inorganic material or the like formed of a material that is stable with respect to the non-aqueous electrolyte solution according to the present invention is used, and a porous sheet or a nonwoven fabric-like material having excellent liquid retention properties is used.
  • materials for the resin and glass fiber separator for example, polyolefins such as polyethylene and polypropylene, aromatic polyamides, polytetrafluoroethylene, polyethersulfone, glass filters and the like can be used. Of these, glass filters and polyolefins are preferred, and polyolefins are more preferred. These materials may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
  • the thickness of the separator is arbitrary, but is usually 1 ⁇ m or more, preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and usually 50 ⁇ m or less, preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less. If the separator is too thin than the above range, the insulating properties and mechanical strength may decrease. On the other hand, if it is thicker than the above range, not only the battery performance such as the rate characteristic may be lowered, but also the energy density of the whole non-aqueous electrolyte secondary battery may be lowered.
  • the porosity of the separator is arbitrary, but is usually 20% or more, preferably 35% or more, more preferably 45% or more, Further, it is usually 90% or less, preferably 85% or less, and more preferably 75% or less. If the porosity is too smaller than the above range, the membrane resistance tends to increase and the rate characteristics tend to deteriorate. Moreover, when larger than the said range, it exists in the tendency for the mechanical strength of a separator to fall and for insulation to fall.
  • the average pore diameter of the separator is also arbitrary, but is usually 0.5 ⁇ m or less, preferably 0.2 ⁇ m or less, and usually 0.05 ⁇ m or more. If the average pore diameter exceeds the above range, a short circuit tends to occur. On the other hand, below the above range, the film resistance may increase and the rate characteristics may deteriorate.
  • oxides such as alumina and silicon dioxide
  • nitrides such as aluminum nitride and silicon nitride
  • sulfates such as barium sulfate and calcium sulfate are used. Used.
  • a thin film shape such as a non-woven fabric, a woven fabric, or a microporous film is used.
  • the thin film shape those having a pore diameter of 0.01 to 1 ⁇ m and a thickness of 5 to 50 ⁇ m are preferably used.
  • a separator formed by forming a composite porous layer containing the inorganic particles on the surface layer of the positive electrode and / or the negative electrode using a resin binder can be used.
  • the characteristic of the separator in the non-aqueous electrolyte secondary battery can be grasped by the Gurley value.
  • Gurley value indicates the difficulty of air passage in the film thickness direction, and is represented by the number of seconds required for 100 ml of air to pass through the film. Therefore, it means that the smaller the numerical value is, the easier it is to pass through, and the higher numerical value is, the more difficult it is to pass. That is, a smaller value means better communication in the thickness direction of the film, and a larger value means lower communication in the thickness direction of the film. Communication is the degree of connection of holes in the film thickness direction. If the Gurley value of the separator of the present invention is low, it can be used for various purposes. For example, when used as a separator for a non-aqueous lithium secondary battery, a low Gurley value means that lithium ions can be easily transferred and is preferable because of excellent battery performance.
  • the Gurley value of the separator is arbitrary, but is preferably 10 to 1000 seconds / 100 ml, more preferably 15 to 800 seconds / 100 ml, and still more preferably 20 to 500 seconds / 100 ml. If the Gurley value is 1000 seconds / 100 ml or less, the electrical resistance is substantially low, which is preferable as a separator.
  • the non-aqueous electrolyte secondary battery of the present invention includes a positive electrode having a positive electrode active material capable of occluding and releasing metal ions and a negative electrode having a negative electrode active material capable of occluding and releasing metal ions, and the non-aqueous electrolyte described above.
  • Electrolytic solution ⁇ or ⁇ is provided.
  • the negative electrode active material preferably contains carbon.
  • the electrode group has a laminated structure in which the positive electrode plate and the negative electrode plate are interposed through the separator, and a structure in which the positive electrode plate and the negative electrode plate are wound in a spiral shape through the separator. Either is acceptable.
  • the ratio of the volume of the electrode group to the internal volume of the battery (hereinafter referred to as “electrode group occupation ratio”) is usually 40% or more, preferably 50% or more, and usually 90% or less, 80% The following is preferred. If the electrode group occupancy is below the above range, a desired battery capacity may not be obtained. Also, if the above range is exceeded, the void space is small, the battery expands, and the member expands or the vapor pressure of the electrolyte liquid component increases and the internal pressure rises. In some cases, the gas release valve that lowers various characteristics such as storage at high temperature and the like, or releases the internal pressure to the outside is activated.
  • the material of the outer case is not particularly limited as long as it is a substance that is stable with respect to the non-aqueous electrolyte used. Specifically, a nickel-plated steel plate, stainless steel, aluminum, an aluminum alloy, a metal such as a magnesium alloy, or a laminated film (laminate film) of a resin and an aluminum foil is used. From the viewpoint of weight reduction, an aluminum or aluminum alloy metal or a laminate film is preferably used.
  • the metal is welded together by laser welding, resistance welding, or ultrasonic welding to form a sealed sealed structure, or a caulking structure using the above metals via a resin gasket. Things.
  • the outer case using the laminate film include a case where a resin-sealed structure is formed by heat-sealing resin layers.
  • a resin different from the resin used for the laminate film may be interposed between the resin layers.
  • a modification having a polar group or a polar group introduced as the intervening resin Resins are preferably used.
  • Protection elements such as PTC (Positive Temperature Coefficient), thermal fuse, thermistor, which increases resistance when abnormal heat is generated or excessive current flows, shuts off current flowing through the circuit due to sudden increase in battery internal pressure or internal temperature during abnormal heat generation
  • a valve current cutoff valve or the like can be used. It is preferable to select a protective element that does not operate under normal use at a high current, and it is more preferable that the protective element is designed so as not to cause abnormal heat generation or thermal runaway even without the protective element.
  • the non-aqueous electrolyte secondary battery of the present invention is usually configured by housing the non-aqueous electrolyte, the negative electrode, the positive electrode, the separator, and the like according to the present invention in an exterior body.
  • This exterior body is not particularly limited, and any known one can be arbitrarily adopted as long as the effects of the present invention are not significantly impaired.
  • the material of the exterior body is arbitrary, but usually, for example, nickel-plated iron, stainless steel, aluminum or an alloy thereof, nickel, titanium, or the like is used.
  • the shape of the exterior body is also arbitrary, and may be any of a cylindrical shape, a square shape, a laminate shape, a coin shape, a large size, and the like.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • a reference electrolyte solution was prepared in the same manner as Example 1A-1, and each non-aqueous electrolyte solution was prepared by adding the compounds shown in Table 1 below in proportion to the total reference electrolyte solution obtained.
  • Comparative Example 1A-1 is the reference electrolyte itself.
  • ⁇ Production of negative electrode> Add 98 parts by weight of graphite powder as a negative electrode active material, 1 part by weight of an aqueous dispersion of sodium carboxymethylcellulose and 1 part by weight of an aqueous dispersion of styrene-butadiene rubber as a thickener and binder, respectively, and mix with a disperser. To make a slurry. The obtained slurry was applied to one side of a copper foil, dried and pressed, and this negative electrode was cut into a circle having a diameter of 12.5 mm and used. The produced negative electrode was used after drying under reduced pressure at 60 ° C. for 12 hours.
  • Comparative Example 1A-2 using only methacrylic anhydride as the compound (1) and vinylene carbonate, fluoroethylene carbonate, t-pentylbenzene or t-butyl as compared with Comparative Example 1A-1 using the reference electrolyte
  • Comparative Examples 1A-3, 1A-4, 1A-6, and 1A-7 using only benzene the cycle capacity retention rate was improved, but the effect was small.
  • Comparative Examples 1A-5 and 1A-8 using adiponitrile and hexamethylene diisocyanate, the cycle capacity retention rate was lowered.
  • Reference Example 1A-9 using only isobutyric anhydride as an acid anhydride not corresponding to Compound (1) improves the cycle capacity retention rate over Comparative Example 1A-1 using only the reference electrolyte.
  • Reference Example 1A-10 in which isobutyric anhydride and vinylene carbonate, which are acid anhydrides not corresponding to compound (1), were used at the same time the methacrylic anhydride and vinylene carbonate that were compound (1) were used simultaneously. Compared with Example 1A-1, the synergistic effect of compound (1) and vinylene carbonate was small.
  • Reference Example 1A-11 which uses isobutyric anhydride and hexamethylene diisocyanate, which are acid anhydrides not corresponding to compound (1), used isobutyric anhydride as an acid anhydride not corresponding to compound (1).
  • the cycle capacity retention rate was lower than in Reference Example 1A-9.
  • a reference electrolyte solution was prepared in the same manner as in Example 1A-1, and each non-aqueous electrolyte solution was prepared by adding the compounds shown in Table 2 below in proportion to the total reference electrolyte solution obtained.
  • a coin-type battery was produced.
  • Table 2 shows the results of initial charge / discharge efficiency (%) obtained by (initial discharge capacity / initial charge capacity) ⁇ 100.
  • the examples, comparative examples, and reference examples described in Table 2 all use the same reference electrolyte as in Table 1.
  • Comparative Example 2A-2 using methacrylic anhydride which is a compound represented by Formula (1), had a lower initial charge / discharge efficiency.
  • Comparative Examples 2A-3 to 2A-7 using only vinylene carbonate, fluoroethylene carbonate, cyclohexylbenzene, and hexamethylene diisocyanate vinylene carbonate, fluoroethylene simultaneously with methacrylic anhydride as compound (1)
  • the initial charge / discharge efficiency was clearly improved, and the compounds represented by the formula (1) It can be seen that the characteristics are specifically improved by combining the compounds described in the present invention.
  • succinic anhydride and isobutyric anhydride which do not correspond to a compound (1) were used, as shown in the reference example, such a specific
  • An electrolyte solution was prepared by adding 0.5% by mass of methacrylic anhydride and 2% by mass of vinylene carbonate with respect to the entire reference electrolyte solution 2.
  • Comparative Examples 3A-1, 3A-2 An electrolyte solution was prepared by adding the compounds shown in Table 3 to the entire reference electrolyte solution 2 at the ratio shown in Table 3 below. However, Comparative Example 3A-1 is the reference electrolyte 2 itself. These electrolytes were examined in the same manner using the same battery as used in Example 1A-1. The initial charge / discharge efficiency is also defined in the same manner as in Example 2A-1.
  • Comparative Example 3A-2 using vinylene carbonate although the initial charge and discharge efficiency was improved, Example 3A-1 using methacrylic anhydride and vinylene carbonate as the compound (1) at the same time was improved. The effect of improving the discharge efficiency was great.
  • the present invention is also effective in suppressing the decomposition of PC on graphite.
  • An electrolyte solution was prepared by adding 0.5% by mass of methacrylic anhydride, 1% by mass of vinylene carbonate, and 1% by mass of fluoroethylene carbonate with respect to the entire reference electrolyte solution 3, respectively.
  • ⁇ Production of negative electrode> 98 parts by weight of graphite powder as the negative electrode active material, 1 part by weight of aqueous dispersion of sodium carboxymethylcellulose (concentration of 1% by weight of sodium carboxymethylcellulose) as the thickener and binder, respectively, and aqueous dispersion of styrene-butadiene rubber 1 part by mass (concentration of styrene-butadiene rubber 50% by mass) was added and mixed with a disperser to form a slurry. The obtained slurry was applied to both sides of the copper foil, dried, and rolled to a thickness of 75 ⁇ m with a press. This was cut out so that the active material had a width of 30 mm and a length of 40 mm to form a negative electrode. The produced negative electrode was dried under reduced pressure for 12 hours at 60 degrees Celsius.
  • PVdF polyvinylidene fluoride
  • the obtained slurry was applied to both sides of an aluminum foil, dried, and rolled to a thickness of 60 ⁇ m with a press machine, and cut into an active material having a width of 30 mm and a length of 40 mm to form a positive electrode.
  • the positive electrode, the negative electrode, and the polyethylene separator were laminated in the order of the positive electrode, the separator, the negative electrode, the separator, and the positive electrode to produce a battery element.
  • This battery element was inserted into a bag made of a laminate film in which both surfaces of aluminum (thickness: 40 ⁇ m) were coated with a resin layer while projecting positive and negative terminals, and then 0.4 mL of non-aqueous electrolyte was put into the bag. This was injected and vacuum sealed to produce a sheet battery. Furthermore, in order to improve the adhesion between the electrodes, the sheet-like battery was sandwiched between glass plates and pressurized.
  • succinic anhydride, which is an acid anhydride that is not compound (1) was used, even when vinylene carbonate and fluoroethylene carbonate were used at the same time, the gas generation inhibiting effect was small (Reference Example 4A-1).
  • Example 1A-1 A coating film of a negative electrode active material produced in the same manner as in Example 1A-1 was cut out so that the active material had a width of 30 mm and a length of 40 mm, thereby forming a negative electrode.
  • the produced negative electrode was dried under reduced pressure for 12 hours at 60 degrees Celsius.
  • Example 1A-1 A coating film of the positive electrode active material produced in the same manner as in Example 1A-1 was cut out to make a positive electrode so that the active material had a width of 30 mm and a length of 40 mm.
  • the produced positive electrode was used after drying under reduced pressure for 12 hours at 80 degrees Celsius.
  • An electrolyte solution was prepared by adding 0.5% by mass of methacrylic anhydride and 2% by mass of vinylene carbonate with respect to the entire reference electrolyte solution 5.
  • Example 6A-2 Comparative Examples 6A-1 to 6A-3
  • a compound was added to the entire reference electrolyte solution 5 at a ratio shown in Table 6 below to prepare an electrolyte solution.
  • Example 1A-1 A coating film of a negative electrode active material produced in the same manner as in Example 1A-1 was cut out so that the active material had a width of 30 mm and a length of 40 mm, thereby forming a negative electrode.
  • the produced negative electrode was dried under reduced pressure for 12 hours at 60 degrees Celsius.
  • Example 1A-1 A coating film of the positive electrode active material produced in the same manner as in Example 1A-1 was cut out to make a positive electrode so that the active material had a width of 30 mm and a length of 40 mm.
  • the produced positive electrode was used after drying under reduced pressure for 12 hours at 80 degrees Celsius.
  • Comparative Example 6A-2 using vinylene carbonate alone improved the cycle capacity retention rate, but increased the amount of gas generated after high-temperature storage.
  • Comparative Example 6A-3 in which methacrylic anhydride, which is a compound represented by the formula (1), was used alone, the cycle capacity retention rate was improved, and the amount of gas generated after high-temperature storage was also suppressed.
  • the methacrylic acid anhydride (Example 6A-1) and the crotonic acid anhydride (Example 6A-2), which are compounds represented by the formula (1) are used in combination with vinylene carbonate, the cycle capacity is maintained.
  • Example 7A-1 An electrolyte solution was prepared by adding 0.5% by mass of methacrylic anhydride and 2% by mass of vinylene carbonate with respect to the entire reference electrolyte solution 1.
  • Example 7A-2 Comparative Example 7A-1, Examples 8A-1 to 8A-3, Comparative Examples 8A-1 to 8A-3
  • a compound was added to the entire reference electrolyte solution 1 at a ratio shown in Table 7 below to prepare an electrolyte solution.
  • Example 1A-1 A coating film of a negative electrode active material produced in the same manner as in Example 1A-1 was cut out so that the active material had a width of 30 mm and a length of 40 mm, thereby forming a negative electrode.
  • the produced negative electrode was dried under reduced pressure for 12 hours at 60 degrees Celsius.
  • Example 1A-1 A coating film of the positive electrode active material produced in the same manner as in Example 1A-1 was cut out to make a positive electrode so that the active material had a width of 30 mm and a length of 40 mm.
  • the produced positive electrode was used after being dried under reduced pressure at 80 degrees Celsius for 12 hours.
  • Examples 7A-1 and 7A-2 the battery produced as described above was charged to 4.2 V at 25 ° C., then discharged to 3 V, and conditioned until the capacity was stabilized. Thereafter, a high-temperature storage test was performed in which the battery was charged at 4.2 V under a condition of 80 ° C. for 3 days. The amount of gas generated after the high-temperature storage test was measured, and the amount of gas generated when Comparative Example 7A-1 was taken as 100 is shown in Table 7.
  • Examples 8A-1 to 8A-3 the battery produced as described above was charged to 4.35 V at 25 ° C., then discharged to 3 V, and conditioned until the capacity was stabilized.
  • Example 8A-3 was found to have a very large gas generation suppressing effect. Thus, it has been clarified that the present invention has an effect that cannot be achieved even if the amount of fluorobenzene is increased.
  • Example 9A-1 An electrolyte solution was prepared by adding 0.5% by mass of methacrylic anhydride and 2% by mass of vinylene carbonate with respect to the entire reference electrolyte solution 1.
  • Example 9A-2, 9A-3, Comparative Examples 9A-1 to 9A-3 An electrolyte solution was prepared by adding the compounds shown in Table 9 to the entire reference electrolyte solution 1 at the ratio shown in Table 9 below.
  • Example 1A-1 A coating film of a negative electrode active material produced in the same manner as in Example 1A-1 was cut out so that the active material had a width of 30 mm and a length of 40 mm, thereby forming a negative electrode.
  • the produced negative electrode was dried under reduced pressure for 12 hours at 60 degrees Celsius.
  • Example 1A-1 A coating film of the positive electrode active material produced in the same manner as in Example 1A-1 was cut out to make a positive electrode so that the active material had a width of 30 mm and a length of 40 mm.
  • the produced positive electrode was used after being dried under reduced pressure at 80 degrees Celsius for 12 hours.
  • Example 9A-1 using methacrylic anhydride and vinylene carbonate, which are compounds represented by the formula (1) the cycle capacity retention rate was improved as compared with Comparative Example 9A-1, and the effect of the present invention was improved. Indicated.
  • Example 10A-1 An electrolyte solution was prepared by adding 0.5% by mass of methacrylic anhydride, 2% by mass of vinylene carbonate, and 5% by mass of fluorobenzene to the entire reference electrolyte solution 1, respectively.
  • Example 10A-1 using methacrylic anhydride, vinylene carbonate and fluorobenzene, which are compounds represented by the formula (1) it was found that the amount of gas generated after high-temperature storage decreased.
  • Example 11A-1 An electrolyte solution was prepared by adding 0.5% by mass of methacrylic anhydride and 2% by mass of vinylene carbonate with respect to the entire reference electrolyte solution 1.
  • Example 11A-2 and 11A-3, Comparative Examples 11A-1 to 11A-4 A compound was added to the entire reference electrolyte solution 1 at a ratio shown in Table 11 below to prepare an electrolyte solution.
  • Example 1A-1 A coating film of a negative electrode active material produced in the same manner as in Example 1A-1 was cut out so that the active material had a width of 30 mm and a length of 40 mm, thereby forming a negative electrode.
  • the produced negative electrode was dried under reduced pressure for 12 hours at 60 degrees Celsius.
  • ⁇ Preparation of positive electrode> A coating film of the positive electrode active material prepared in the same manner as in Example 1 was cut out to obtain a positive electrode so that the active material had a width of 30 mm and a length of 40 mm. The prepared positive electrode was used after being dried under reduced pressure at 80 degrees Celsius for 12 hours.
  • Example 11A-1 using both methacrylic anhydride and vinylene carbonate which are compounds represented by the formula (1), is the amount of gas generated after high-temperature storage. Was suppressed.
  • Example 11A-2 in which methacrylic anhydride and vinylene carbonate and hexamethyldisilane were used simultaneously, the gas generation suppressing effect was greater.
  • Comparative Example 11A-4 in which fluorobenzene was further added to Comparative Example 11A-3 although the amount of gas generated was certainly suppressed, methacrylic anhydride and vinylene carbonate, which are compounds represented by the formula (1),
  • Example 11A-3 in which fluoroethylene carbonate and fluorobenzene were used simultaneously the effect of suppressing the amount of gas generation was greater. As described above, it was shown that by using the electrolytic solution of the present invention, the amount of gas generated after storage was effectively suppressed even at a high temperature state of 85 ° C.
  • Example 12A-1 An electrolyte solution was prepared by adding 0.3% by mass of methacrylic anhydride, 1% by mass of vinylene carbonate, fluoroethylene carbonate, and adiponitrile to the total amount of the reference electrolyte solution 1.
  • Example 12A-2 Comparative Examples 12A-1 to 12A-3
  • a compound was added to the entire reference electrolyte solution 1 at a ratio shown in Table 12 below to prepare an electrolyte solution.
  • Example 12A-2 when methacrylic anhydride, vinylene carbonate, fluoroethylene carbonate, adiponitrile, and propane sultone, which are compounds represented by the formula (1), were used at the same time, the cycle was compared with Comparative Example 12A-2. The improvement of capacity maintenance rate was confirmed. This is a result that cannot be achieved by increasing the amount of propane sultone, and can be said to be a specific effect of the present invention.
  • Example 13A-1 An electrolytic solution was prepared by adding 0.4% by mass of methacrylic anhydride, 1% by mass of vinylene carbonate, fluoroethylene carbonate, and adiponitrile to the entire reference electrolytic solution 1 respectively.
  • a negative electrode was produced in the same manner as in Example 11A-1.
  • a positive electrode was produced in the same manner as in Example 11A-1.
  • Example 14A-2, 14A-3, Comparative Examples 14A-1 to 14A-4 A compound was added to the entire reference electrolyte solution 6 at a ratio shown in Table 14 below to prepare an electrolyte solution.
  • the obtained slurry was applied to both sides of an aluminum foil, dried, and rolled with a press to cut out the active material to have a width of 30 mm and a length of 40 mm to obtain a positive electrode.
  • the positive electrode, the negative electrode, and the polyethylene separator were laminated in the order of the positive electrode, the separator, and the negative electrode to produce a battery element.
  • This battery element was inserted into a bag made of a laminate film in which both surfaces of aluminum (thickness: 40 ⁇ m) were coated with a resin layer while projecting positive and negative terminals, and then 0.2 mL of nonaqueous electrolyte solution was put into the bag. This was injected and vacuum sealed to produce a sheet battery. Furthermore, in order to improve the adhesion between the electrodes, the sheet-like battery was sandwiched between glass plates and pressurized.
  • Comparative Example 14A-2 using vinylene carbonate alone has improved cycle characteristics, but methacrylic anhydride, which is a compound represented by the formula (1), is improved.
  • Example 14A-1 in which the product and vinylene carbonate were used at the same time the cycle capacity retention rate was further improved.
  • methacrylic anhydride and fluoroethylene carbonate, which are compounds represented by the formula (1), and methacrylic anhydride and vinylene, which are compounds represented by the formula (1) By using carbonate and fluoroethylene carbonate at the same time, a good cycle capacity retention rate could be obtained.
  • Example 15A-1 An electrolyte solution was prepared by adding 0.5% by mass of methacrylic anhydride and 0.3% by mass of lithium bis (oxalatoborate) with respect to the entire reference electrolyte solution 1, respectively.
  • Comparative Examples 15A-1 to 15A-3, Reference Examples 15A-1 and 15A-2 A compound was added to the entire reference electrolyte solution 1 at a ratio shown in Table 15 below to prepare an electrolyte solution. However, Comparative Example 15A-1 used the reference electrolyte 1 itself.
  • a negative electrode was produced in the same manner as in Example 1A-1.
  • a positive electrode was produced in the same manner as in Example 1A-1.
  • Rate characteristic (%) (capacity when discharging from 4.2 V charge state to 3 V at a current of 1.74 mA / capacity when discharging from 4.2 V charge state to 3 V at a current of 0.7 mA) ⁇ 100
  • Comparative Example 15A-2 using methacrylic acid anhydride, which is a compound represented by Formula (1), and lithium bis (oxalato) borate were used in comparison with Comparative Example 15A-1 using the reference electrolyte 1 as it was.
  • the electrolytic solution of the present invention that is, methacrylic anhydride and lithium bis (oxalato) borate, which are compounds represented by the formula (1), were used at the same time.
  • Example 15A-1 was confirmed to have an even greater improvement in rate characteristics.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • Examples 2B to 3B, Comparative Examples 1B to 4B The content of methacrylic acid used in Example 1B is 0.001% by mass in Example 2B, 0.008% by mass in Example 3B, and no methacrylic acid in Comparative Example 1B with respect to the entire non-aqueous electrolyte. (Below the analysis limit), 0.01% by mass in Comparative Example 2B, 0.012% by mass in Comparative Example 3B, 0.03% by mass in Comparative Example 4B, and 0.1% by mass in Comparative Example 5B Were prepared in the same manner as Example 1B, respectively.
  • ⁇ Production of negative electrode> Add 98 parts by weight of graphite powder as a negative electrode active material, 1 part by weight of an aqueous dispersion of sodium carboxymethylcellulose and 1 part by weight of an aqueous dispersion of styrene-butadiene rubber as a thickener and binder, respectively, and mix with a disperser. To make a slurry. The obtained slurry was applied to one side of a copper foil, dried and pressed, and this negative electrode was cut into a circle having a diameter of 12.5 mm and used. The produced negative electrode was used after drying under reduced pressure at 60 ° C. for 12 hours.
  • the electrolyte solution containing no compound (1) has a carboxylic acid content of less than 0.01% by mass (Reference Example 1B) or 0.01% by mass or more (Example 2B). There was no difference in the cycle capacity retention rate, which was worse than that of Reference Example 3B.
  • the decomposition of the electrolyte solution of the non-aqueous electrolyte secondary battery is suppressed, and when the battery is used in a high temperature environment, gas generation and deterioration of the battery are suppressed and a high energy density.
  • the non-aqueous electrolyte secondary battery can be manufactured. Therefore, it can be suitably used in various fields such as an electronic device in which a non-aqueous electrolyte secondary battery is used.
  • the application of the non-aqueous electrolyte secondary battery of the present invention is not particularly limited, and can be used for various known applications.
  • Specific examples include notebook computers, pen input computers, mobile computers, electronic book players, mobile phones, mobile faxes, mobile copy, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, minidiscs, and transceivers.
  • Electronic notebook, calculator, memory card, portable tape recorder, radio, backup power supply, motor, automobile, motorcycle, motorbike, bicycle, lighting equipment, toy, game equipment, clock, electric tool, strobe, camera, home-use large A storage battery etc. can be mentioned.

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Abstract

L'objectif de la présente invention est de fournir : une solution électrolytique non aqueuse qui améliore des caractéristiques de cycle et des caractéristiques de charge, tout en supprimant la génération d'un gaz ; et une batterie secondaire électrolytique non aqueuse qui utilise cette solution électrolytique non aqueuse. La présente invention porte sur une solution électrolytique non aqueuse qui est utilisée dans une batterie secondaire électrolytique non aqueuse qui comporte une électrode positive et une électrode négative qui ont des matériaux actifs aptes à absorber et à désorber des ions métalliques. Cette solution électrolytique non aqueuse contient un composé représenté par une formule générale (1), et contient de plus une quantité spécifique d'acide carboxylique ou au moins un composé qui est sélectionné parmi le groupe de composés spécifiques tels qu'un composé de carbonate cyclique ayant une liaison insaturée.
PCT/JP2013/071547 2012-08-09 2013-08-08 Solution électrolytique non aqueuse et batterie secondaire électrolytique non aqueuse l'utilisant WO2014024990A1 (fr)

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CN201380041629.4A CN104584309B (zh) 2012-08-09 2013-08-08 非水系电解液和使用该非水系电解液的非水系电解液二次电池

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