WO2017006977A1 - Non-aqueous electrolyte solution for secondary battery, method for producing same, and secondary battery provided with same - Google Patents

Non-aqueous electrolyte solution for secondary battery, method for producing same, and secondary battery provided with same Download PDF

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WO2017006977A1
WO2017006977A1 PCT/JP2016/070077 JP2016070077W WO2017006977A1 WO 2017006977 A1 WO2017006977 A1 WO 2017006977A1 JP 2016070077 W JP2016070077 W JP 2016070077W WO 2017006977 A1 WO2017006977 A1 WO 2017006977A1
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group
carbon atoms
halogen atom
unsaturated bond
atom
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PCT/JP2016/070077
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French (fr)
Japanese (ja)
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紀敬 坂口
壮二郎 近
静郁 桂
雅士 山本
西田　哲郎
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ステラケミファ株式会社
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Priority to KR1020187001782A priority Critical patent/KR20180026462A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous electrolyte for a secondary battery that can suppress the generation of bubbles, a manufacturing method thereof, and a secondary battery including the same.
  • a conventional general lithium secondary battery uses a material capable of reversibly inserting Li ions into a positive electrode active material and a negative electrode active material.
  • a compound such as LiNiO 2 , LiCoO 2 , LiMn 2 O 4 , or LiFePO 4 is used for the positive electrode active material.
  • the negative electrode active material lithium metal, an alloy thereof, a carbon material, a graphite material, or the like is used.
  • an electrolytic solution used for a lithium secondary battery a solution obtained by dissolving an electrolyte such as LiPF 6 or LiBF 4 in a mixed solvent such as ethylene carbonate, diethyl carbonate, or propylene carbonate is used.
  • lithium-ion secondary batteries used for in-vehicle applications have high performance such as improved output density and energy density, reduced capacity deterioration at high / low temperatures, improved cycle life, and improved safety. Is required.
  • Patent Document 1 discloses a nonaqueous storage device containing a nonaqueous solvent, a first lithium salt having a boron atom, a second lithium salt not having a boron atom, and a phosphate ester.
  • An electrolyte is disclosed. According to the electrolyte for a non-aqueous storage device, it is possible to realize a lithium ion secondary battery having a high cycle life even when a positive electrode active material that operates at a high potential of 4 or 4 V or higher is used. .
  • the non-aqueous electrolyte for a secondary battery of the present invention is a non-aqueous electrolyte for a secondary battery used for a secondary battery in order to solve the above-described problems, and includes the following components (A) and (B): It is characterized by including.
  • M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion.
  • R 1 and R 2 do not have a halogen atom, and each independently represents the number of carbon atoms.
  • M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion or an onium ion.
  • X 1 to X 4 are independent of each other, and one or two combinations selected arbitrarily) Forms a cyclic structure of —OOC—Y—COO—, —O—Y—O— or —OOC—Y—O—, wherein Y is a hydrocarbon having 0 to 20 carbon atoms Or a hydrocarbon group having 0 to 20 carbon atoms and having a hetero atom, an unsaturated bond, or a cyclic structure, or X 1 to X 4 are each independently a halogen atom, An alkyl group having 0 to 20 carbon atoms, an alkoxy group having 0 to 20 carbon atoms, an alkyl group having 0 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond A group
  • R 3 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, or a carbon group having 1 to 20 carbon atoms and having a halogen atom, a hetero atom or an unsaturated bond. Represents a hydrogen group.
  • M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion.
  • a 1 and A 2 are each independently an oxygen atom, a sulfur atom, or selenium.
  • X 5 and X 6 each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a range having 1 to 20 carbon atoms, and may be a halogen atom, heteroatom or And represents an alkyl group having at least one of a saturated bond, or X 5 and X 6 are each an alkyl group having 1 to 20 carbon atoms, or a range of 1 to 20 carbon atoms, Any of an alkyl group having at least one of an atom, a hetero atom, and an unsaturated bond, and bonded to each other to form a cyclic structure, where n represents a valence.)
  • M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion.
  • X 7 to X 12 each independently represent a halogen atom or a carbon number of 1;
  • a 3 represents an oxygen atom, a sulfur atom or a selenium atom.
  • X 13 to X 15 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number of 1).
  • An alkoxy group having at least one of a halogen atom, a heteroatom and an unsaturated bond, or a carbon atom having a range of 1 to 20 and being a halogen atom, heteroatom or unsaturated Represents an alkylthio group having at least one of the bonds, or at least one combination selected from X 13 to X 15 is a group having 1 to 20 alkyl groups, alkoxy groups having 1 to 20 carbon atoms, alkylthio groups having 1 to 20 carbon atoms, at least one of halogen atoms, heteroatoms and unsaturated bonds in the range of 1 to 20 carbon atoms
  • X 16 to X 18 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, An alkyl group having at least one of a halogen atom, a heteroatom or an unsaturated bond in the range of 1 to 20, a carbon number in the range of 1 to 20 and a halogen atom, a heteroatom or an unsaturated bond Or an alkylthio group having at least one of a halogen atom, a heteroatom, and an unsaturated bond having 1 to 20 carbon atoms, or at least one of the above, or X 16 ⁇ X at least one combination selected at any one of 18, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, 1 or 2 carbon atoms An alkylthio group having a carbon number in the range of 1 to 20 and having at least at least
  • the amount of the component (A) added is 0.05% by mass to 5% by mass with respect to the total mass of the non-aqueous electrolyte for secondary battery, and the amount of the component (B) added Is preferably 0.05% by mass to 5% by mass with respect to the total mass of the non-aqueous electrolyte for secondary battery.
  • the component (A) is preferably lithium diethyl phosphate.
  • the boron complex salt represented by the general formula (2) of the component (B) is lithium bisoxalatoborate, triethylmethylammonium bisoxalatoborate, lithium bissalicylate borate or lithium bis [ 1,2′-Benziolate (2) —O, O ′] borate is preferred.
  • the borate ester is preferably trimethyl borate.
  • the acid anhydride is preferably maleic anhydride.
  • the cyclic carbonate having an unsaturated bond is preferably vinylene carbonate.
  • the cyclic carbonate having a halogen atom is preferably fluoroethylene carbonate.
  • the cyclic sulfonate ester is preferably 1,3-propane sultone.
  • the amine having an acetoacetyl group represented by the general formula (3) is preferably N, N-dimethylacetoacetamide.
  • the phosphorus compound represented by the general formula (4) is lithium difluorophosphate.
  • the phosphorus compound represented by the general formula (5) is preferably lithium difluorobisoxalate phosphate.
  • the phosphorus compound represented by the general formula (6) is trimethyl phosphate, tris (2,2,2-trifluoroethyl phosphate) or bis (2,2,2-trifluoroethyl). ) Preference is given to phosphonic acid.
  • the phosphorus compound represented by the general formula (7) is preferably trimethylphosphine or methyldiphenylphosphine.
  • the method for producing a non-aqueous electrolyte for a secondary battery according to the present invention is a method for producing a non-aqueous electrolyte for a secondary battery used in a secondary battery in order to solve the above-mentioned problems, and the electrolyte is an organic solvent.
  • a first step of adding a salt of the second a second step of adding the following component (A) to the organic solvent after the addition of the electrolyte salt, and the addition of the electrolyte salt and the component (A)
  • M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion.
  • R 1 and R 2 do not have a halogen atom, and each independently represents the number of carbon atoms.
  • M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion or an onium ion.
  • X 1 to X 4 are independent of each other, and one or two combinations selected arbitrarily) Forms a cyclic structure of —OOC—Y—COO—, —O—Y—O— or —OOC—Y—O—, wherein Y is a hydrocarbon having 0 to 20 carbon atoms Or a hydrocarbon group having 0 to 20 carbon atoms and having a hetero atom, an unsaturated bond, or a cyclic structure, or X 1 to X 4 are each independently a halogen atom, An alkyl group having 0 to 20 carbon atoms, an alkoxy group having 0 to 20 carbon atoms, an alkyl group having 0 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond A group
  • R 3 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, or a carbon group having 1 to 20 carbon atoms and having a halogen atom, a hetero atom or an unsaturated bond. Represents a hydrogen group.
  • M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion.
  • a 1 and A 2 are each independently an oxygen atom, a sulfur atom, or selenium.
  • X 5 and X 6 each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a range having 1 to 20 carbon atoms, and may be a halogen atom, heteroatom or And represents an alkyl group having at least one of a saturated bond, or X 5 and X 6 are each an alkyl group having 1 to 20 carbon atoms, or a range of 1 to 20 carbon atoms, Any of an alkyl group having at least one of an atom, a hetero atom, and an unsaturated bond, and bonded to each other to form a cyclic structure, where n represents a valence.)
  • M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion.
  • X 7 to X 12 each independently represent a halogen atom or a carbon number of 1;
  • a 3 represents an oxygen atom, a sulfur atom or a selenium atom.
  • X 13 to X 15 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number of 1).
  • An alkoxy group having at least one of a halogen atom, a heteroatom and an unsaturated bond, or a carbon atom having a range of 1 to 20 and being a halogen atom, heteroatom or unsaturated Represents an alkylthio group having at least one of the bonds, or at least one combination selected from X 13 to X 15 is a group having 1 to 20 alkyl groups, alkoxy groups having 1 to 20 carbon atoms, alkylthio groups having 1 to 20 carbon atoms, at least one of halogen atoms, heteroatoms and unsaturated bonds in the range of 1 to 20 carbon atoms
  • X 16 to X 18 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, An alkyl group having at least one of a halogen atom, a heteroatom or an unsaturated bond in the range of 1 to 20, a carbon number in the range of 1 to 20 and a halogen atom, a heteroatom or an unsaturated bond Or an alkylthio group having at least one of a halogen atom, a heteroatom, and an unsaturated bond having 1 to 20 carbon atoms, or at least one of the above, or X 16 ⁇ X at least one combination selected at any one of 18, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, 1 or 2 carbon atoms An alkylthio group having a carbon number in the range of 1 to 20 and having at least at least
  • the amount of the component (A) added in the second step is 0.05% by mass to 5% by mass with respect to the total mass of the non-aqueous electrolyte for secondary battery
  • the amount of component (B) added in the third step is preferably 0.05% by mass to 5% by mass with respect to the total mass of the non-aqueous electrolyte for secondary battery.
  • the secondary battery of the present invention is a secondary battery comprising at least the non-aqueous electrolyte for a secondary battery, a positive electrode, and a negative electrode in order to solve the above-described problems, and the non-aqueous battery for the secondary battery.
  • the electrolytic solution includes the following component (A) and component (B).
  • M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion.
  • R 1 and R 2 do not have a halogen atom, and each independently represents the number of carbon atoms.
  • M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion or an onium ion.
  • X 1 to X 4 are independent of each other, and one or two combinations selected arbitrarily) Forms a cyclic structure of —OOC—Y—COO—, —O—Y—O— or —OOC—Y—O—, wherein Y is a hydrocarbon having 0 to 20 carbon atoms Or a hydrocarbon group having 0 to 20 carbon atoms and having a hetero atom, an unsaturated bond, or a cyclic structure, or X 1 to X 4 are each independently a halogen atom, An alkyl group having 0 to 20 carbon atoms, an alkoxy group having 0 to 20 carbon atoms, an alkyl group having 0 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond A group
  • R 3 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, or a carbon group having 1 to 20 carbon atoms and having a halogen atom, a hetero atom or an unsaturated bond. Represents a hydrogen group.
  • M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion.
  • a 1 and A 2 are each independently an oxygen atom, a sulfur atom, or selenium.
  • X 5 and X 6 each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a range having 1 to 20 carbon atoms, and may be a halogen atom, heteroatom or And represents an alkyl group having at least one of a saturated bond, or X 5 and X 6 are each an alkyl group having 1 to 20 carbon atoms, or a range of 1 to 20 carbon atoms, Any of an alkyl group having at least one of an atom, a hetero atom, and an unsaturated bond, and bonded to each other to form a cyclic structure, where n represents a valence.)
  • M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion.
  • X 7 to X 12 each independently represent a halogen atom or a carbon number of 1;
  • a 3 represents an oxygen atom, a sulfur atom or a selenium atom.
  • X 13 to X 15 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number of 1).
  • An alkoxy group having at least one of a halogen atom, a heteroatom and an unsaturated bond, or a carbon atom having a range of 1 to 20 and being a halogen atom, heteroatom or unsaturated Represents an alkylthio group having at least one of the bonds, or at least one combination selected from X 13 to X 15 is a group having 1 to 20 alkyl groups, alkoxy groups having 1 to 20 carbon atoms, alkylthio groups having 1 to 20 carbon atoms, at least one of halogen atoms, heteroatoms and unsaturated bonds in the range of 1 to 20 carbon atoms
  • X 16 to X 18 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, An alkyl group having at least one of a halogen atom, a heteroatom or an unsaturated bond in the range of 1 to 20, a carbon number in the range of 1 to 20 and a halogen atom, a heteroatom or an unsaturated bond Or an alkylthio group having at least one of a halogen atom, a heteroatom, and an unsaturated bond having 1 to 20 carbon atoms, or at least one of the above, or X 16 ⁇ X at least one combination selected at any one of 18, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, 1 or 2 carbon atoms An alkylthio group having a carbon number in the range of 1 to 20 and having at least at least
  • a halogen atom such as a fluorine atom has a chemical structure. Since it is not contained, bubbles can be prevented from being generated when the electrolytic solution is used in a secondary battery. As a result, battery defects can be reduced.
  • the following components (A) are added to the first step of adding an electrolyte salt to the organic solvent, and the organic solvent after the addition of the electrolyte salt.
  • a second step of adding the following component (B) to the organic solvent after the addition of the electrolyte salt and the component (A) to produce a non-aqueous electrolyte for a secondary battery In the phosphoric acid diester salt of the component (A), halogen atoms such as fluorine atoms are not included in the chemical structure.
  • the second step of adding the following component (A) to the organic solvent after the addition of the electrolyte salt and the component (B) are added to the organic solvent after the addition of the electrolyte salt and the component (A).
  • the generation of bubbles is suppressed, or even if bubbles are generated, they disappear immediately. Therefore, the step for defoaming the bubbles can be omitted.
  • the production efficiency can be improved as compared with the conventional method for producing an electrolyte.
  • non-aqueous electrolyte for secondary battery includes at least one of the following components (A ) And the following component (B).
  • the non-aqueous electrolyte of the present embodiment uses a component that does not contain a halogen atom as the component (A). Therefore, the reason is unknown, but bubbles are generated when used in a secondary battery. Can be suppressed. As a result, battery defects can be reduced.
  • the component (A) does not contain a halogen atom and consists of at least one phosphoric diester salt represented by the following general formula (1).
  • the halogen atom represents iodine, bromine, chlorine, or fluorine.
  • M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion.
  • the alkali metal ion is not particularly limited and includes lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion and the like. These can be used alone or in combination of two or more.
  • alkaline earth metal ions examples include magnesium ions, calcium ions, strontium ions, barium ions and the like. These can be used alone or in combination of two or more.
  • the transition metal ions are not particularly limited, and examples thereof include manganese ions, cobalt ions, nickel ions, chromium ions, copper ions, molybdenum ions, tungsten ions, vanadium ions, and the like. These can be used alone or in combination of two or more.
  • onium ions examples include ammonium ions (NH 4+ ), primary ammonium ions, secondary ammonium ions, tertiary ammonium ions, quaternary ammonium ions, quaternary phosphonium ions, sulfonium ions, and the like.
  • the primary ammonium ion is not particularly limited, and examples thereof include methylammonium ion, ethylammonium ion, propylammonium ion, and isopropylammonium ion. These can be used alone or in combination of two or more.
  • the secondary ammonium ion is not particularly limited, and for example, dimethylammonium ion, diethylammonium ion, dipropylammonium ion, dibutylammonium ion, ethylmethylammonium ion, methylpropylammonium ion, methylbutylammonium ion, propylbutylammonium Ion, diisopropylammonium ion and the like. These can be used alone or in combination of two or more.
  • the tertiary ammonium ion is not particularly limited, and examples thereof include trimethylammonium ion, triethylammonium ion, tripropylammonium ammonium ion, tributylammonium ion, ethyldimethylammonium ion, diethylmethylammonium ion, triisopropylammonium ion, dimethylisopropyl.
  • the quaternary ammonium forming the quaternary ammonium ion is not particularly limited, and examples thereof include aliphatic quaternary ammoniums, imidazoliums, pyridiniums, pyrazoliums, and pyridaziniums. These can be used alone or in combination of two or more.
  • the aliphatic quaternary ammoniums are not particularly limited, and examples thereof include tetraethylammonium, tetrapropylammonium, tetraisopropylammonium, trimethylethylammonium, dimethyldiethylammonium, methyltriethylammonium, trimethylpropylammonium, trimethylisopropylammonium, tetra Butylammonium, trimethylbutylammonium, trimethylpentylammonium, trimethylhexylammonium, 1-ethyl-1-methyl-pyrrolidinium, 1-butyl-1-methylpyrrolidinium, 1-ethyl-1-methyl-piperidinium, 1-butyl- Examples include 1-methylpiperidinium. These can be used alone or in combination of two or more.
  • the imidazoliums are not particularly limited. For example, 1,3 dimethyl-imidazolium, 1-ethyl-3-methylimidazolium, 1-n-propyl-3-methylimidazolium, 1-n-butyl-3 -Methylimidazolium, 1-n-hexyl-3-methylimidazolium and the like. These can be used alone or in combination of two or more.
  • the pyridiniums are not particularly limited, and examples thereof include 1-methylpyridinium, 1-ethylpyridinium, 1-n-propylpyridinium and the like. These can be used alone or in combination of two or more.
  • the pyrazoliums are not particularly limited. For example, 1,2-dimethylpyrazolium, 1-methyl-2-ethylpyrazolium, 1-propyl-2-methylpyrazolium, 1-methyl-2-butyl Pyrazolium, 1-methylpyrazolium, 3-methylpyrazolium, 4-methylpyrazolium, 4-iodopyrazolium, 4-bromopyrazolium, 4-iodo3-methylpyrazolium, 4 -Bromo-3-methylpyrazolium, 3-trifluoromethylpyrazolium. These can be used alone or in combination of two or more.
  • the pyridaziniums are not particularly limited, and for example, 1-methylpyridazinium, 1-ethylpyridazinium, 1-propylpyridazinium, 1-butylpyridazinium, 3-methylpyridazinium Ni, 4-methylpyridazinium, 3-methoxypyridazinium, 3,6-dichloropyridazinium, 3,6-dichloro-4-methylpyridazinium, 3-chloro-6-methylpyri Examples include dazinium and 3-chloro-6-methoxypyridazinium. These can be used alone or in combination of two or more.
  • the quaternary phosphonium forming the quaternary phosphonium ion is not particularly limited, and examples thereof include benzyltriphenylphosphonium, tetraethylphosphonium, and tetraphenylphosphonium. These can be used alone or in combination of two or more.
  • the sulfonium ion is not particularly limited, and examples thereof include trimethylsulfonium, triphenylsulfonium, triethylsulfonium, and the like. These can be used alone or in combination of two or more.
  • lithium ion, sodium ion, and tetraalkylammonium ion are preferable from the viewpoint of availability.
  • R 1 and R 2 have no halogen atom in the chemical structure.
  • R 1 and R 2 are each independently a hydrocarbon group or a hydrocarbon group having at least one of a hetero atom or an unsaturated bond (hereinafter referred to as “hydrocarbon group having a hetero atom, etc.”). ").
  • the hydrocarbon group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • the hydrocarbon group having a hetero atom or the like has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the heteroatom means an atom such as oxygen, nitrogen or sulfur.
  • the number of unsaturated bonds is preferably in the range of 1 to 10, more preferably in the range of 1 to 5, and particularly preferably in the range of 1 to 3.
  • hydrocarbon group or the hydrocarbon group having a hetero atom include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
  • a cyclic alkyl group such as cyclopentyl group, cyclohexyl group, 2-iodoethyl group, 2-bromoethyl group, 2-chloroethyl group, 2-fluoroethyl group, 1,2-diiodoethyl group, 1,2-dibromo Ethyl group, 1,2-dichloroethyl group, 1,2-difluoroethyl group, 2,2-diiodoethyl group, 2,2-dibromoethyl group, 2,2-dichloroethyl group, 2,2-difluoroethyl group, 2,2,2-tribromoethyl group, 2,2,2-trichloroethyl group, 2,2,2-trifluoroethyl group, hexafluoro- Chain-containing halogen-containing alkyl groups such as propyl groups, 2-iodocyclohe
  • Examples thereof include a naphthyl group such as a halogenphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 3-amino-2-naphthyl group.
  • a naphthyl group such as a halogenphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 3-amino-2-naphthyl group.
  • each of R 1 and R 2 does not have a halogen atom, and is any one of the hydrocarbon group or the hydrocarbon group having the heteroatom, and is bonded to each other to form a cyclic structure. It may be formed.
  • the hydrocarbon group or the hydrocarbon group having a hetero atom or the like specifically includes, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, Non-ylene groups such as linear alkylene groups, cyclohexylene groups, phenylene groups, benzylene groups, naphthylene groups, anthracylene groups, naphthacylene groups, pentasilene groups, and some or all of them are replaced with heteroatoms, etc. And the like.
  • the R 1 and R 2 may be the same or different from each other in the functional group group exemplified above. Moreover, the functional group group illustrated above is only an illustration, and is not limited to these.
  • n a valence.
  • M is a monovalent cation
  • n 1, when it is a divalent cation
  • n 2
  • n 3
  • Specific examples of the compound represented by the general formula (1) include, for example, lithium dimethyl phosphate, lithium diethyl phosphate, lithium dipropyl phosphate, lithium dibutyl phosphate, lithium dipentyl phosphate, lithium ethylene phosphate, and binaphthyl phosphate.
  • the compound represented by the general formula (1) is preferably lithium diethyl phosphate from the viewpoint of availability.
  • the amount of the component (A) added is preferably in the range of 0.05 to 5% by mass, more preferably in the range of 0.1 to 3% by mass with respect to the total mass of the non-aqueous electrolyte. Preferably, it is in the range of 0.5 to 2% by mass.
  • the addition amount 0.05% by mass or more, cycle characteristics of the secondary battery in a high temperature environment can be further improved.
  • the said addition amount 5 mass% or less it can suppress that the solubility with respect to the nonaqueous electrolyte solvent of the electrolyte in a nonaqueous electrolyte solution falls.
  • At least one component (A) may be contained in the non-aqueous electrolyte, but the number of types of component (A) to be contained is preferably five. Or less, more preferably 3 or less, and particularly preferably 2 or less. By reducing the type of the component (A), it is possible to suppress complication of the process in the production of the nonaqueous electrolytic solution.
  • the component (B) includes at least one boron complex salt represented by the following general formula (2), boric acid ester, acid anhydride, cyclic carbonate having an unsaturated bond, cyclic carbonate having a halogen atom, and cyclic sulfone. At least one selected from the group consisting of acid esters, amines having an acetoacetyl group represented by the following general formula (3), and phosphorus compounds represented by any of the following general formulas (4) to (7) A compound.
  • boron complex salt represented by the following general formula (2), boric acid ester, acid anhydride, cyclic carbonate having an unsaturated bond, cyclic carbonate having a halogen atom, and cyclic sulfone.
  • boron complex salt As described above, the boron complex salt is specifically represented by the following general formula (2).
  • M n + is as described above and represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. Therefore, detailed description thereof will be omitted.
  • X 1 to X 4 are independent of each other, and one or two arbitrarily selected combinations can be represented by —OOC—Y—COO—, —O—Y—O— or — This represents an OOC-Y—O— cyclic structure.
  • Y is a hydrocarbon group having 0 to 20, preferably 0 to 10, more preferably 0 to 10 carbon atoms, or 0 to 20, preferably 0 to 10, more preferably 0 to 10 carbon atoms.
  • 5 represents a hydrocarbon group having a hetero atom, an unsaturated bond, or a cyclic structure.
  • each Y is different It may be.
  • the hetero atom means an oxygen atom, a nitrogen atom or a sulfur atom.
  • Y include, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and other linear alkylene groups, iodomethylene, di Iodomethylene, bromomethylene, dibromomethylene, fluoromethylene, difluoromethylene, iodoethylene, 1,1-diiodoethylene, 1,2-diiodoethylene, triiodoethylene, tetraiodoethylene Group, chloroethylene group, 1,1-dichloroethylene group, 1,2-dichloroethylene group, trichloroethylene group, tetrachloroethylene group, fluoroethylene group, 1,1-difluoroethylene group, 1,2-difluoroethylene group, trifluoroethylene group , Tetrafluoroethylene group, etc.
  • Halogen straight chain alkylene group cyclohexylene group, phenylene group, benzylene group, naphthylene group, anthracylene group, naphthacylene group, pentasilene group, etc. It is done.
  • —OOC—Y—COO— is —OOC—COO—, which represents an oxalate group.
  • Y is a 1,2-phenylene group
  • —O—Y—O— represents a benzenediolate group
  • —O—Y—COO— represents a salicylate group.
  • X 1 to X 4 are each independently a halogen atom, an alkyl group having 0 to 20 carbon atoms, preferably 0 to 10, more preferably 0 to 5 carbon atoms, and 0 to 20 carbon atoms, preferably 0 to 0 carbon atoms.
  • halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • a hetero atom means an oxygen atom, a nitrogen atom, or a sulfur atom.
  • X 1 to X 4 include a chain alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and a cyclopentyl group.
  • Cycloalkyl group such as cyclohexyl group, iodomethyl group, bromomethyl group, chloromethyl group, fluoromethyl group, diiodomethyl group, dibromomethyl group, dichloromethyl group, difluoromethyl group, triiodomethyl group, tribromomethyl group, trichloromethyl Group, trifluoromethyl group, 2-iodoethyl group, 2-bromoethyl group, 2-chloroethyl group, 2-fluoroethyl group, 1,2-diiodoethyl group, 1,2-dibromoethyl group, 1,2-dichloroethyl group 1,2-difluoroethyl group, 2,2-diiodoethyl group, 2,2-dibu Moethyl group, 2,2-dichloroethyl group, 2,2-difluoroethyl group, 2,2,2-tribromoethyl
  • Cyclic alkoxy groups such as xy group, cyclopentoxy group, cyclohexoxy group, 2-iodoethoxy group, 2-bromoethoxy group, 2-chloroethoxy group, 2-fluoroethoxy group, 1,2-diiodoethoxy group, 1,2-dibromoethoxy group, 1,2-dichloroethoxy group, 1,2-difluoroethoxy group, 2,2-diiodoethoxy group, 2,2-dibromoethoxy group, 2,2-dichloroethoxy group, 2 , 2-difluoroethoxy group, 2,2,2-tribromoethoxy group, 2,2,2-trichloroethoxy group, 2,2,2-trifluoroethoxy group, hexafluoro-2-propoxy group, etc.
  • the boron complex salt is lithium bisoxalatoborate, triethylmethylammonium bisoxalatoborate, lithium bissalicylate borate or lithium bis [1,2'-benziolate (2). -O, O '] borate is preferred.
  • n in the said General formula (2) represents a valence similarly to the case of the said General formula (1).
  • the borate ester is not particularly limited as long as it does not impair the characteristics of the nonaqueous electrolytic solution of the present embodiment and the secondary battery using the boric acid ester, and various types can be selected. .
  • Examples include tris (4-iodophenyl) acid, tris (4-bromophenyl) borate, tris (4-chlorophenyl) borate, tris (4-fluorophenyl) borate, die
  • the acid anhydride is not particularly limited as long as it does not impair the characteristics of the nonaqueous electrolytic solution of the present embodiment and the secondary battery using the acid anhydride, and various types can be selected. . Specifically, for example, acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride, octanoic anhydride, nonanoic anhydride, decanoic anhydride Eicosanoic anhydride, docosanoic anhydride, benzoic anhydride, 4-methoxybenzoic anhydride, diphenylacetic anhydride, crotonic anhydride, cyclohexanecarboxylic anhydride, elaidic anhydride, isobutyric anhydride, Isovaleric anhydride, lauric anhydride, linoleic anhydride, myr
  • the cyclic carbonate having an unsaturated bond is not particularly limited as long as the characteristics of the nonaqueous electrolytic solution of the present embodiment and the secondary battery using the cyclic carbonate are not impaired, and various types are selected. can do.
  • the number of unsaturated bonds is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.
  • Specific examples of the cyclic carbonate having an unsaturated bond include vinylene carbonate, iodovinylene carbonate, bromovinylene carbonate, chlorovinylene carbonate, fluorovinylene carbonate, 1,2-diiodovinylene carbonate, 1,2-dibromo.
  • the cyclic carbonate having a halogen atom is not particularly limited as long as it does not impair the characteristics of the nonaqueous electrolytic solution of the present embodiment and the secondary battery using the same, and various types are selected. be able to.
  • the halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • cyclic carbonate having a halogen atom examples include iodoethylene carbonate, bromoethylene carbonate, chloroethylene carbonate, fluoroethylene carbonate, 1,2-diiodoethylene carbonate, 1,2-dibromoethylene carbonate, 1 2,2-dichloroethylene carbonate, 1,2-difluoroethylene carbonate, and the like.
  • the cyclic sulfonic acid ester is not particularly limited as long as it does not impair the characteristics of the nonaqueous electrolytic solution of the present embodiment and the secondary battery using the same, and various types can be selected. it can. Specific examples of the cyclic sulfonic acid ester include 1,3-propane sultone, 2,4-butane sultone, 1,4-butane sultone, ethylene sulfite, and the like.
  • R 3 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, or 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. More preferably, it is in the range of 1 to 5 and represents a halogen atom, a hetero atom or a hydrocarbon group having an unsaturated bond.
  • the halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • a hetero atom means an oxygen atom, a nitrogen atom, or a sulfur atom.
  • R 3 and R 4 specifically, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a pentyl group, a hexyl group, a heptyl group, a chain alkyl group such as octyl, cyclopentyl Group, cyclic alkyl group such as cyclohexyl group, 2-iodoethyl group, 2-bromoethyl group, 2-chloroethyl group, 2-fluoroethyl group, 1,2-diiodoethyl group, 1,2-dibromoethyl group, 1,2- Dichloroethyl group, 1,2-difluoroethyl group, 2,2-diiodoethyl group, 2,2-dibromoethyl group, 2,2-dichloroethyl group, 2,2-difluoroe
  • R 3 and R 4 may be the same or different from each other.
  • the functional group group illustrated above is only a mere illustration, and this Embodiment is not limited to these.
  • Specific examples of the compound represented by the general formula (3) include, for example, N, N-dimethylacetoacetamide, N, N-diethylacetoacetamide, N, N-dipropylacetoacetamide, N, N-dibutylacetamide.
  • Examples include acetamide, N, N-ethylmethylacetoacetamide, N, N-methylpropylacetoacetamide, N, N-butylmethylacetoacetamide and the like.
  • these compounds are merely examples, and the present embodiment is not limited to these.
  • M n + is as described above and represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion or an onium ion. Therefore, detailed description thereof will be omitted.
  • a 1 and A 2 each independently represent an oxygen atom, a sulfur atom or a selenium atom.
  • each of X 5 and X 6 independently represents a halogen atom, an alkyl group, or an alkyl group having at least one of a halogen atom, a hetero atom and an unsaturated bond ( Hereinafter, it is referred to as an “alkyl group having a halogen atom”.
  • the carbon number of the alkyl group and the alkyl group having a halogen atom or the like is in the range of 1 to 20, preferably 1 to 10, and more preferably 1 to 4.
  • the number of unsaturated bonds is preferably in the range of 1 to 10, more preferably in the range of 1 to 5, and particularly preferably in the range of 1 to 3.
  • the halogen atom represents iodine, bromine, chlorine, or fluorine.
  • alkyl group or the alkyl group having a halogen atom include chains such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
  • Examples thereof include a naphthyl group such as a halogenphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 3-amino-2-naphthyl group.
  • a naphthyl group such as a halogenphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 3-amino-2-naphthyl group.
  • the halogen atom means a fluorine, chlorine, bromine or iodine atom.
  • the said hetero atom means atoms, such as oxygen, nitrogen, or sulfur.
  • part or all of the hydrogen in the alkyl group may be substituted with any of these halogen atoms and / or heteroatoms.
  • X 5 and X 6 may be a group in which either the alkyl group or an alkyl group having a halogen atom is bonded to each other to form a cyclic structure.
  • the alkyl group or the alkyl group having a halogen atom or the like in X 1 and X 2 is, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, or a nonylene group.
  • Linear alkylene group such as iodomethylene group, diiodomethylene group, bromomethylene group, dibromomethylene group, fluoromethylene group, difluoromethylene group, iodoethylene group, 1,1-diiodoethylene group, 1,2-di Iodoethylene group, triiodoethylene group, tetraiodoethylene group, chloroethylene group, 1,1-dichloroethylene group, 1,2-dichloroethylene group, trichloroethylene group, tetrachloroethylene group, fluoroethylene group, 1,1-difluoroethylene group, 1,2-difluoroethylene group Halogen-containing linear alkylene groups such as trifluoroethylene group and tetrafluoroethylene group, cyclic hydrocarbon groups such as cyclohexylene group, phenylene group, benzylene group, naphthylene group, anthracylene group, naphthacylene group, pentasilene group and
  • X 5 and X 6 may be the same or different from each other in the functional group group exemplified above.
  • the functional group group illustrated above is only an illustration, and is not limited to these.
  • Specific examples of the phosphorus compound represented by the general formula (4) include, for example, lithium difluorophosphate and sodium difluorophosphate which are easily available.
  • the M n + and the valence n are the same as those described in the general formula (4).
  • X 7 to X 12 are each independently at least one of a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a halogen atom, a hetero atom, or an unsaturated bond.
  • An alkyl group having at least one of a halogen atom, a hetero atom or an unsaturated bond hereinafter referred to as an “alkoxy group having a halogen atom”).
  • an alkylthio group having at least one of a halogen atom, a heteroatom or an unsaturated bond hereinafter referred to as “alkylthio group having a halogen atom”).
  • the alkyl group, alkoxy group, alkylthio group, alkyl group having a halogen atom and the like, the alkoxy group having a halogen atom and the like, and the alkylthio group having a halogen atom and the like have a carbon number in the range of 1 to 20, preferably 1 to 10 More preferably, it is 1 to 4. Further, the number of unsaturated bonds is preferably in the range of 1 to 10, more preferably in the range of 1 to 5, and particularly preferably in the range of 1 to 3.
  • the halogen atom and the hetero atom are the same as described in the general formula (4).
  • the alkyl group having a halogen atom or the like, the alkoxy group having a halogen atom or the like, and the alkylthio group having a halogen atom or the like the halogen atom or the heteroatom is such that a part or all of hydrogen in these functional groups It may be substituted with any of the halogen atoms and / or heteroatoms.
  • X 7 to X 12 are, for example, a chain alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, or a cyclopentyl group.
  • Cycloalkyl group such as cyclohexyl group, iodomethyl group, bromomethyl group, chloromethyl group, fluoromethyl group, diiodomethyl group, dibromomethyl group, dichloromethyl group, difluoromethyl group, triiodomethyl group, tribromomethyl group, trichloromethyl Group, trifluoromethyl group, 2-iodoethyl group, 2-bromoethyl group, 2-chloroethyl group, 2-fluoroethyl group, 1,2-diiodoethyl group, 1,2-dibromoethyl group, 1,2-dichloroethyl group 1,2-difluoroethyl group, 2,2-diiodoethyl group, 2,2-di Lomoethyl group, 2,2-dichloroethyl group, 2,2-difluoroethyl group, 2,2,2-tribromoethy
  • Cyclic alkoxy groups such as a coxy group, a cyclopentoxy group, a cyclohexoxy group, a 2-iodoethoxy group, a 2-bromoethoxy group, a 2-chloroethoxy group, a 2-fluoroethoxy group, a 1,2-diiodoethoxy group, 1,2-dibromoethoxy group, 1,2-dichloroethoxy group, 1,2-difluoroethoxy group, 2,2-diiodoethoxy group, 2,2-dibromoethoxy group, 2,2-dichloroethoxy group, 2 , 2-difluoroethoxy group, 2,2,2-tribromoethoxy group, 2,2,2-trichloroethoxy group, 2,2,2-trifluoroethoxy group, hexafluoro-2-propoxy group, etc.
  • Halogen-containing alkoxy group 2-iodocyclohexoxy group, 2-bromocyclohexoxy group, 2-chlorocyclohexoxy group, 2-fluorocyclohex Cyclic halogen-containing alkoxy groups such as oxy group, 2-propenoxy group, isopropenoxy group, 2-butenoxy group, chain alkenyl alkoxy groups such as 3-butenoxy group, 2-cyclopentenoxy group, 2-cyclohexenoxy group, Cyclic alkenylalkoxy groups such as 3-cyclohexenoxy group, 2-propynoxy group, 1-butynoxy group, 2-butynoxy group, 3-butynoxy group, 1-pentynoxy group, 2-pentynoxy group, 3-pentynoxy group, 4- Chain alkynylalkoxy groups such as pentynoxy group, phenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, phenoxy group such as 3,5-dimethylphenoxy group, 2-iodophenoxy group,
  • X 7 to X 12 are any combination of any one of the cyclic structures of —OOC—Z—COO—, —OOC—Z—O—, and —O—Z—O—. May be formed.
  • the cyclic structures may be the same or different from each other.
  • Z is a hydrocarbon group having 0 to 20 carbon atoms or a range of 0 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom, an unsaturated bond, or a cyclic structure. Represents a hydrocarbon group.
  • the number of unsaturated bonds is preferably in the range of 1 to 10, more preferably in the range of 1 to 5, and particularly preferably in the range of 1 to 3.
  • the Z is not particularly limited, and specific examples include, for example, a linear alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, and a nonylene group; Methylene group, diiodomethylene group, bromomethylene group, dibromomethylene group, fluoromethylene group, difluoromethylene group, iodoethylene group, 1,1-diiodoethylene group, 1,2-diiodoethylene group, triiodoethylene group Tetraiodoethylene group, chloroethylene group, 1,1-dichloroethylene group, 1,2-dichloroethylene group, trichloroethylene group, tetrachloroethylene group, fluoroethylene group, 1,1-difluoroethylene group, 1,2-difluoroethylene group, Trifluoroethylene group
  • -OOC-Z-COO- is -OOC-COO- and represents an oxalate group.
  • Z is a 1,2-phenylene group
  • —O—Z—O— represents a benzenediolate group
  • —O—Z—COO— represents a salicylate group.
  • Examples of the phosphorus compound represented by the general formula (5) include lithium difluorobisoxalate phosphate, sodium difluorobisoxalate phosphate, lithium tetrafluorooxalate phosphate, and sodium tetrafluorooxalate phosphate, which are easily available. Etc.
  • a 3 represents an oxygen atom, a sulfur atom or a selenium atom.
  • X 13 to X 15 each independently represents an alkyl group having at least one of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a halogen atom, a hetero atom, or an unsaturated bond (hereinafter, "Alkyl group having a halogen atom”), an alkoxy group having at least one of a halogen atom, a hetero atom or an unsaturated bond (hereinafter referred to as "an alkoxy group having a halogen atom”), or a halogen
  • Alkylthio group having at least one of an atom, a heteroatom and an unsaturated bond hereinafter referred to as “alkylthio group having a halogen atom” is represented.
  • the alkyl group, alkoxy group, alkylthio group, alkyl group having a halogen atom and the like, the alkoxy group having a halogen atom and the like, and the alkylthio group having a halogen atom and the like have a carbon number in the range of 1 to 20, preferably 1 to 10 More preferably, it is 1 to 4. Further, the number of unsaturated bonds is preferably in the range of 1 to 10, more preferably in the range of 1 to 5, and particularly preferably in the range of 1 to 3.
  • X 13 to X 15 are not particularly limited. Specifically, for example, chain alkyl such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, pentyl group, hexyl group, heptyl group, octyl group, etc.
  • cyclic alkyl group such as cyclopentyl group, cyclohexyl group, iodomethyl group, bromomethyl group, chloromethyl group, fluoromethyl group, diiodomethyl group, dibromomethyl group, dichloromethyl group, difluoromethyl group, triiodomethyl group, tribromomethyl Group, trichloromethyl group, trifluoromethyl group, 2-iodoethyl group, 2-bromoethyl group, 2-chloroethyl group, 2-fluoroethyl group, 1,2-diiodoethyl group, 1,2-dibromoethyl group, 1,2 -Dichloroethyl group, 1,2-difluoroethyl group, 2,2-diiodoethyl Group, 2,2-dibromoethyl group, 2,2-dichloroethyl group, 2,2-difluoroethyl
  • Halogen-containing phenyl group methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexoxy Chain alkoxy groups such as thio group, cyclic alkoxy groups such as cyclopentoxy group, cyclohexoxy group, 2-iodoethoxy group, 2-bromoethoxy group, 2-chloroethoxy group, 2-fluoroethoxy group, 1,2 -Diiodoethoxy group, 1,2-dibromoethoxy group, 1,2-dichloroethoxy group, 1,2-difluoroethoxy group, 2,2-diiodoethoxy group, 2,2-dibromoethoxy group, 2,2 -Dichloroethoxy group, 2,2-difluoroethoxy group, 2,2,2-tribromoethoxy group, 2,2,2-trifluoroethoxy group, hexafluoro-2
  • X 13 to X 15 may be an alkyl group, an alkoxy group, an alkylthio group, an alkyl group having a halogen atom, an alkoxy group having a halogen atom or the like, a halogen atom, etc. Any of the alkylthio groups having the above may be bonded to each other to form a cyclic structure.
  • the alkyl group in X 9 to X 11 is, for example, a linear alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, and a nonylene group.
  • a linear alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, and a nonylene group.
  • Iodomethylene group diiodomethylene group, bromomethylene group, dibromomethylene group, fluoromethylene group, difluoromethylene group, iodoethylene group, 1,1-diiodoethylene group, 1,2-diiodoethylene group, triiodo Ethylene group, tetraiodoethylene group, chloroethylene group, 1,1-dichloroethylene group, 1,2-dichloroethylene group, trichloroethylene group, tetrachloroethylene group, fluoroethylene group, 1,1-difluoroethylene group, 1,2-difluoroethylene Group, trifluoroethylene group, Halogen-containing linear alkylene groups such as lafluoroethylene groups, cyclic hydrocarbon groups such as cyclohexylene groups, phenylene groups, benzylene groups, naphthylene groups, anthracylene groups, naphthacylene groups, pentasilene groups, and some or all of them It
  • the halogen atom and the hetero atom are the same as described in the general formula (4). Further, in the alkyl group having a halogen atom or the like, the alkoxy group having a halogen atom or the like, and the alkylthio group having a halogen atom or the like, the halogen atom or the heteroatom is such that a part or all of hydrogens in these functional groups are these. It may be substituted with any of the halogen atoms and / or heteroatoms.
  • phosphorus compound represented by the general formula (6) include, for example, trimethyl phosphate, triethyl phosphate, tris (2,2,2-trifluoroethyl) phosphate, bis (2 , 2,2-trifluoroethyl) phosphonic acid and the like.
  • X 16 to X 18 are each independently an alkyl group having at least one of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a halogen atom, a hetero atom, or an unsaturated bond (hereinafter referred to as the following).
  • Alkyl group having a halogen atom or the like an alkoxy group having at least one of a halogen atom, a hetero atom or an unsaturated bond (hereinafter referred to as “an alkoxy group having a halogen atom”), or a halogen
  • an alkoxy group having a halogen atom an alkoxy group having a halogen atom
  • an alkoxy group having a halogen atom an alkoxy group having a halogen atom
  • alkylthio group having a halogen atom an alkylthio group having at least one of an atom, a heteroatom and an unsaturated bond
  • the alkyl group, alkoxy group, alkylthio group, alkyl group having a halogen atom and the like, the alkoxy group having a halogen atom and the like, and the alkylthio group having a halogen atom and the like have a carbon number in the range of 1 to 20, preferably 1 to 10 More preferably, it is 1 to 4. Further, the number of unsaturated bonds is preferably in the range of 1 to 10, more preferably in the range of 1 to 5, and particularly preferably in the range of 1 to 3.
  • X 16 to X 18 are not particularly limited. Specifically, for example, chain alkyl such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, pentyl group, hexyl group, heptyl group, octyl group, etc.
  • cyclic alkyl group such as cyclopentyl group, cyclohexyl group, iodomethyl group, bromomethyl group, chloromethyl group, fluoromethyl group, diiodomethyl group, dibromomethyl group, dichloromethyl group, difluoromethyl group, triiodomethyl group, tribromomethyl Group, trichloromethyl group, trifluoromethyl group, 2-iodoethyl group, 2-bromoethyl group, 2-chloroethyl group, 2-fluoroethyl group, 1,2-diiodoethyl group, 1,2-dibromoethyl group, 1,2 -Dichloroethyl group, 1,2-difluoroethyl group, 2,2-diiodoethyl Group, 2,2-dibromoethyl group, 2,2-dichloroethyl group, 2,2-difluoroethyl
  • Halogen-containing phenyl group methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexoxy Chain alkoxy groups such as thio group, cyclic alkoxy groups such as cyclopentoxy group, cyclohexoxy group, 2-iodoethoxy group, 2-bromoethoxy group, 2-chloroethoxy group, 2-fluoroethoxy group, 1,2 -Diiodoethoxy group, 1,2-dibromoethoxy group, 1,2-dichloroethoxy group, 1,2-difluoroethoxy group, 2,2-diiodoethoxy group, 2,2-dibromoethoxy group, 2,2 -Dichloroethoxy group, 2,2-difluoroethoxy group, 2,2,2-tribromoethoxy group, 2,2,2-trifluoroethoxy group, hexafluoro-2
  • X 16 to X 18 may be an alkyl group, an alkoxy group, an alkylthio group, an alkyl group having a halogen atom, an alkoxy group having a halogen atom, or a halogen atom, etc. Any of the alkylthio groups possessed may be bonded to each other to form a cyclic structure.
  • the alkyl group in X 16 to X 18 is, for example, a linear alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, or a nonylene group.
  • phosphorus compound represented by the general formula (7) examples include trimethylphosphine and methyldiphenylphosphine that are easily available.
  • the amount of component (B) added is preferably in the range of 0.05% by mass to 5% by mass, and in the range of 0.1% by mass to 3% by mass with respect to the total mass of the non-aqueous electrolyte. More preferably, it is particularly preferably in the range of 0.5% by mass to 2% by mass.
  • At least one kind of the component (B) may be contained in the nonaqueous electrolytic solution, but the number of kinds of the component (B) to be contained is preferably 5 The number is not more than one, more preferably not more than three, and particularly preferably not more than two.
  • ⁇ Electrolyte> A conventionally well-known thing can be employ
  • a lithium salt is used for a lithium ion battery
  • a sodium salt is used for a sodium ion battery. Therefore, what is necessary is just to select the kind of electrolyte suitably according to the kind of secondary battery.
  • fluorine-containing anions include, for example, BF 4 ⁇ , PF 6 ⁇ , BF 3 CF 3 ⁇ , BF 3 C 2 F 5 ⁇ , CF 3 SO 3 ⁇ , C 2 F 5 SO 3 ⁇ , C 3 F 7 SO 3 ⁇ , C 4 F 9 SO 3 ⁇ , N (SO 2 F) 2 ⁇ , N (CF 3 SO 2 ) 2 ⁇ , N (C 2 F 5 SO 2 ) 2 ⁇ , N (CF 3 SO 2 ) (CF 3 CO) ⁇ , N (CF 3 SO 2 ) (C 2 F 5 SO 2 ) ⁇ , C (CF 3 SO 2 ) 3 — and the like.
  • BF 4 ⁇ , PF 6 ⁇ , and N (CF 3 SO 2 ) 2 ⁇ are preferable from the viewpoint of improving the safety and stability of the non-aqueous electrolyte, electrical conductivity, and cycle characteristics.
  • BF 4 ⁇ and PF 6 ⁇ are particularly preferable.
  • the concentration of the electrolyte with respect to the organic solvent is not particularly limited, and is usually 0.1 to 2M, preferably 0.15 to 1.8M, more preferably 0.2 to 1.5M, particularly preferably 0.3 to. 1.2M.
  • concentration 0.1 M or more it is possible to prevent the electrical conductivity of the non-aqueous electrolyte from becoming insufficient.
  • concentration 2M or less it is possible to suppress a decrease in electrical conductivity due to an increase in the viscosity of the non-aqueous electrolyte and to prevent a secondary battery performance from being deteriorated.
  • the organic solvent (nonaqueous solvent) used in the nonaqueous electrolytic solution is not particularly limited.
  • a cyclic carbonate, a chain carbonate, a phosphate ester, a cyclic ether, a chain ether, a lactone compound, a chain examples thereof include esters, nitrile compounds, amide compounds, and sulfone compounds.
  • these organic solvents they are generally used as organic solvents for lithium secondary batteries, and carbonates are preferred from the viewpoint of availability and performance.
  • the cyclic carbonate is not particularly limited, and examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate, and the like. Among these, cyclic carbonates such as ethylene carbonate and propylene carbonate are preferable from the viewpoint of improving the charging efficiency of the lithium secondary battery.
  • the chain carbonate is not particularly limited, and examples thereof include dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate. Among these, dimethyl carbonate and ethyl methyl carbonate are preferable from the viewpoint of improving the charging efficiency of the lithium secondary battery.
  • the phosphate ester is not particularly limited, and examples thereof include trimethyl phosphate, triethyl phosphate, ethyldimethyl phosphate, and diethylmethyl phosphate.
  • the cyclic ether is not particularly limited, and examples thereof include tetrahydrofuran and 2-methyltetrahydrofuran.
  • the chain ether is not particularly limited, and examples thereof include dimethoxyethane.
  • the lactone compound is not particularly limited, and examples thereof include ⁇ -butyrolactone.
  • the chain ester is not particularly limited, and examples thereof include methyl propionate, methyl acetate, ethyl acetate, and methyl formate.
  • the nitrile compound is not particularly limited, and examples thereof include acetonitrile.
  • the amide compound is not particularly limited, and examples thereof include dimethylformamide.
  • the sulfone compound is not particularly limited, and examples thereof include sulfolane and methyl sulfolane.
  • numerator with the fluorine can be used suitably.
  • These organic solvents may be used alone or in combination of two or more.
  • the component (A) is added to the first step of adding the electrolyte salt to the organic solvent and the organic solvent after the addition of the electrolyte salt.
  • a step for defoaming bubbles is not performed.
  • the method of adding an electrolyte salt to the organic solvent is not particularly limited, and a conventionally known method can be employed.
  • the temperature condition at the time of addition is not particularly limited, but it is usually 10 ° C. to 40 ° C., preferably 15 ° C. to 35 ° C., more preferably 20 ° C. to 30 ° C.
  • the component (A) is further added to the organic solvent to which the electrolyte salt is added.
  • the addition method of component (A) is not particularly limited, and a conventionally known method can be employed. When a plurality of types of components (A) are added, the order of their addition can be appropriately set as necessary. In addition, when the component (A) is added, in the present embodiment, since the generation of bubbles is suppressed, the defoaming step can be omitted. As a result, in this embodiment, the production efficiency is improved.
  • the temperature condition at the time of addition of the component (A) is not particularly limited, and is usually 10 ° C. to 40 ° C., preferably 15 ° C. to 35 ° C., more preferably 20 ° C. to 30 ° C. .
  • the component (B) is further added to the organic solvent after the addition of the electrolyte salt and the component (A).
  • the addition method of component (B) is not particularly limited, and a conventionally known method can be employed. When adding multiple types of component (B), the order of those additions can be suitably set as needed.
  • the component (B) is added, in the present embodiment, the generation of bubbles is suppressed, so that the defoaming step can be omitted. As a result, the production efficiency can be further improved.
  • the organic solvent the electrolyte salt, the component (A) and the component (B)
  • FIG. 1 is a schematic cross-sectional view showing an outline of a lithium ion secondary battery provided with the non-aqueous electrolyte.
  • the lithium ion secondary battery according to the present embodiment has a positive electrode 1, a separator 3, a negative electrode 2, an internal space formed by a positive electrode can 4 and a negative electrode can 5, from the positive electrode can 4 side. It has a structure in which a laminated body laminated in the order of the spacers 7 is accommodated. By interposing a spring 8 between the negative electrode can 5 and the spacer 7, the positive electrode 1 and the negative electrode 2 are appropriately pressed and fixed.
  • the nonaqueous electrolytic solution containing the component (A) and the component (B) compound of the present embodiment is impregnated between the positive electrode 1, the separator 3 and the negative electrode 2. In a state where the gasket 6 is interposed between the positive electrode can 4 and the negative electrode can 5, the positive electrode can 4 and the negative electrode can 5 are sandwiched to bond them together, and the laminate is sealed.
  • the material of the positive electrode active material layer in the positive electrode 1 is not particularly limited, and examples thereof include a transition metal compound having a structure capable of diffusing lithium ions, or an oxide of the transition metal compound and lithium.
  • a transition metal compound having a structure capable of diffusing lithium ions or an oxide of the transition metal compound and lithium.
  • LiCoO 2, LiNiO 2, LiMn 2 O 4, Li 2 MnO 3 + LiMeO 2 (Me Mn, Co, Ni) solid solution
  • oxides such as LiFeF
  • the positive electrode 1 is formed by press molding the positive electrode active materials listed above together with known conductive aids and binders, or the positive electrode active material together with known conductive aids and binders and organic solvents such as pyrrolidone. It can be obtained by applying a paste obtained by mixing to a current collector such as an aluminum foil and then drying.
  • the material of the negative electrode active material layer in the negative electrode 2 is not particularly limited as long as it is a material capable of occluding and releasing lithium.
  • the metal composite oxide is not particularly limited.
  • the not particularly restricted but includes metal oxides, for example SnO, SnO 2, SiO x ( 0 ⁇ x ⁇ 2), PbO, PbO 2, Pb 2 O 3, Pb 3 O 4, Sb 2 O 3, Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , Bi 2 O 5 and the like.
  • metal oxides for example SnO, SnO 2, SiO x ( 0 ⁇ x ⁇ 2), PbO, PbO 2, Pb 2 O 3, Pb 3 O 4, Sb 2 O 3, Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , Bi 2 O 5 and the like.
  • the carbon material is not particularly limited, and examples thereof include natural graphite, artificial graphite, borated graphite, fluorinated graphite, mesocarbon microbeads, pitch-based carbon fiber graphitized material, carbon nanotube, hard carbon, fullerene and the like.
  • the negative electrode 2 may be a foil or powder of the electrode material.
  • copper paste is formed by pressure molding with a known conductive aid and binder, or mixed with pyrrolidone and other organic solvents together with a known conductive aid and binder. It can be obtained by coating a current collector such as a foil and then drying.
  • a separator 3 is usually interposed between the positive electrode 1 and the negative electrode 2 in order to prevent a short circuit.
  • the material and shape of the separator 3 are not particularly limited, it is preferable that the above-described non-aqueous electrolyte is easy to pass through, is an insulator, and is a chemically stable material. Examples thereof include microporous films and sheets made of various polymer materials. Specific examples of the polymer material include polyolefin polymers such as nylon (registered trademark), nitrocellulose, polyacrylonitrile, polyvinylidene fluoride, polyethylene, and polypropylene. From the viewpoints of electrochemical stability and chemical stability, polyolefin polymers are preferred.
  • the optimum working voltage of the lithium ion secondary battery of the present embodiment varies depending on the combination of the positive electrode 1 and the negative electrode 2, and can usually be used within the range of 2.4 to 4.6V.
  • the shape of the lithium ion secondary battery of the present embodiment is not particularly limited, but examples thereof include a cylindrical type, a square type, and a laminated type in addition to the coin type cell shown in FIG.
  • the nonaqueous electrolytic solution according to the present embodiment can suppress the generation of bubbles in the nonaqueous electrolytic solution, it is possible to reduce the need for a battery, and is preferably used for, for example, a lithium ion secondary battery. be able to.
  • the lithium ion secondary battery shown in FIG. 1 is an example of one embodiment of the secondary battery of the present invention, and the secondary battery of the present invention is not limited to this.
  • the PFA container was cooled to room temperature and stirred for 3 hours. Further, filtration under reduced pressure was performed to separate a white precipitate and an ethanol solution. By distilling off ethanol from the filtrate under reduced pressure, 5.1 g of a white solid was obtained.
  • the obtained white solid was subjected to anion analysis using ion chromatography (trade name; IC-850, manufactured by Metrohm), and it was confirmed that the obtained white solid was lithium diethyl phosphate.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • lithium diethyl phosphate as the component (A) was added to this mixed solution so that the addition concentration was 0.5% by mass with respect to the total mass of the non-aqueous electrolyte as the final product.
  • the height of the liquid level during the addition was 2.7 cm.
  • the sample tube was shaken 30 times and the height of the liquid level was measured again. As a result of the generation of bubbles, the height of the liquid level became 2.9 cm, and the liquid level rose by 0.2 cm.
  • the sample tube was allowed to stand and the disappearance time of the bubbles was confirmed. As a result, it was confirmed that the bubbles almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • lithium bisoxalate borate as the component (B) was added to the mixed solution so that the addition concentration was 0.5% by mass with respect to the total mass of the non-aqueous electrolyte as the final product. .
  • the height (reference value) of the liquid level during the addition was 2.7 cm.
  • the sample tube was shaken 30 times and the height of the liquid level was measured again.
  • the height of the liquid level was 3.0 cm, and the liquid level rose by 0.3 cm.
  • the sample tube was allowed to stand and the disappearance time of the bubbles was confirmed. As a result, it was confirmed that the bubbles almost disappeared after 10 seconds, and the bubbles disappeared completely after 32 seconds.
  • Table 1 The results are shown in Table 1 below.
  • the nonaqueous electrolytic solution according to this example was produced.
  • Example 2 lithium bisoxalate borate as component (B) of Example 1 was changed to triethylmethylammonium bisoxalatoborate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • Example 3 In this example, the lithium bisoxalate borate as the component (B) in Example 1 was changed to lithium bissalicylate borate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • Example 4 the lithium bisoxalate borate as the component (B) in Example 1 was changed to lithium bis [1,2′-benzdiolate (2) —O, O ′] borate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • Example 5 lithium bisoxalate borate as component (B) of Example 1 was changed to trimethyl borate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • Example 6 lithium bisoxalate borate as component (B) of Example 1 was changed to maleic anhydride. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • the liquid level after adding maleic anhydride as component (B) to the mixed solution after addition of component (A) is 2.7 cm, and the liquid after shaking the sample tube 30 times The height of the surface was 3.0 cm. Further, the bubbles generated at this time completely disappeared after 25 seconds.
  • Table 1 The results are shown in Table 1 below.
  • Example 7 lithium bisoxalate borate as component (B) of Example 1 was changed to vinylene carbonate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • the liquid level after adding vinylene carbonate as the component (B) to the mixed solution after the addition of the component (A) is 2.7 cm, and the liquid level after the sample tube is shaken 30 times. The height was 3.1 cm. Further, the bubbles generated at this time disappeared completely after 15 seconds.
  • Table 1 The results are shown in Table 1 below.
  • Example 8 lithium bisoxalate borate as component (B) of Example 1 was changed to fluoroethylene carbonate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • the liquid level after adding fluoroethylene carbonate as the component (B) to the mixed solution after the addition of the component (A) is 2.7 cm, and the liquid level after the sample tube is shaken 30 times. The height was 3.1 cm. The bubbles generated at this time completely disappeared after 21 seconds.
  • Table 1 The results are shown in Table 1 below.
  • Example 9 lithium bisoxalate borate as component (B) in Example 1 was changed to 1,3-propane sultone. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • Example 10 lithium bisoxalate borate as component (B) in Example 1 was changed to N, N-dimethylacetoacetamide. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • Example 11 lithium bisoxalate borate as the component (B) in Example 1 was changed to lithium difluorophosphate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • the liquid level after adding lithium difluorophosphate as the component (B) to the mixed solution after the addition of the component (A) is 2.7 cm, and the liquid after the sample tube is shaken 30 times The height of the surface was 3.0 cm. Further, the bubbles generated at this time completely disappeared after 30 seconds.
  • Table 1 The results are shown in Table 1 below.
  • Example 12 In this example, the lithium bisoxalate borate as the component (B) in Example 1 was changed to lithium difluorobisoxalate phosphate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • the liquid level after adding lithium difluorobisoxalate phosphate as component (B) to the mixed solution after addition of component (A) is 2.7 cm, and the sample tube is shaken 30 times. The height of the liquid surface was 3.2 cm. The bubbles generated at this time disappeared completely after 52 seconds.
  • Table 1 The results are shown in Table 1 below.
  • Example 13 lithium bisoxalate borate as component (B) of Example 1 was changed to trimethyl phosphate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • Example 14 lithium bisoxalate borate as component (B) in Example 1 was changed to tris (2,2,2-trifluoroethyl) phosphate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • Example 15 a non-aqueous electrolyte was prepared in the same manner as in Example 1 except that the lithium bisoxalate borate of Example 1 was changed to bis (2,2,2-trifluoroethyl) phosphonic acid. did.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • Example 16 In this example, a nonaqueous electrolytic solution was prepared in the same manner as in Example 1 except that the lithium bisoxalate borate in Example 1 was changed to trimethylphosphine.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • the liquid level after adding trimethylphosphine as the component (B) to the mixed solution after the addition of the component (A) is 2.7 cm, and the liquid level after the sample tube is shaken 30 times. The height was 3.0 cm. The bubbles generated at this time completely disappeared after 33 seconds.
  • Table 1 The results are shown in Table 1 below.
  • Example 17 a nonaqueous electrolytic solution was prepared in the same manner as in Example 1 except that the lithium bisoxalate borate in Example 1 was changed to methyldiphenylphosphine.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • the liquid level after adding methyldiphenylphosphine as component (B) to the mixed solution after addition of component (A) is 2.7 cm, and the liquid level after shaking the sample tube 30 times The height of was 3.2 cm. The bubbles generated at this time disappeared completely after 43 seconds.
  • Table 1 The results are shown in Table 1 below.
  • Example 18 In this example, the concentration of vinylene carbonate in Example 7 was changed from 0.5% by mass to 0.05% by mass. Other than that was carried out similarly to Example 7, and prepared the non-aqueous electrolyte which concerns on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • the liquid level after adding vinylene carbonate as the component (B) to the mixed solution after the addition of the component (A) is 2.7 cm, and the liquid level after the sample tube is shaken 30 times. The height was 3.1 cm. Also, the bubbles generated at this time completely disappeared after 20 seconds. The results are shown in Table 1 below.
  • Example 19 In this example, the concentration of vinylene carbonate in Example 7 was changed from 0.5% by mass to 5% by mass. Other than that was carried out similarly to Example 7, and prepared the non-aqueous electrolyte which concerns on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • the liquid level after adding vinylene carbonate as the component (B) to the mixed solution after the addition of the component (A) is 2.7 cm, and the liquid level after the sample tube is shaken 30 times. The height was 3.1 cm. The bubbles generated at this time completely disappeared after 18 seconds.
  • Table 1 The results are shown in Table 1 below.
  • Example 20 In this example, the concentration of lithium diethyl phosphate in Example 7 was changed from 0.5% by mass to 5% by mass, and the concentration of vinylene carbonate was changed from 0.5% by mass to 5% by mass. Other than that was carried out similarly to Example 7, and prepared the non-aqueous electrolyte which concerns on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • the liquid level after adding vinylene carbonate as the component (B) to the mixed solution after the addition of the component (A) is 2.7 cm, and the liquid level after the sample tube is shaken 30 times. The height was 2.9 cm. The bubbles generated at this time disappeared completely after 35 seconds.
  • Table 1 The results are shown in Table 1 below.
  • Example 21 In this example, the concentration of lithium phosphate in Example 7 was changed from 0.5% by mass to 0.05% by mass, and the concentration of vinylene carbonate was changed from 0.5% by mass to 0.05% by mass. did. Other than that was carried out similarly to Example 7, and prepared the non-aqueous electrolyte which concerns on a present Example.
  • the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube was 30 times and the liquid level was 2.9 cm.
  • the bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
  • the liquid level after adding vinylene carbonate as the component (B) to the mixed solution after the addition of the component (A) is 2.7 cm, and the liquid level after the sample tube is shaken 30 times. The height was 2.8 cm. Further, the bubbles generated at this time completely disappeared after 12 seconds.
  • Table 1 The results are shown in Table 1 below.
  • Comparative Example 2 lithium bisoxalate borate as component (B) was further added to the electrolytic solution prepared in comparative example 1 so that the concentration was 0.5 mass%. Other than that was carried out similarly to the comparative example 1, and prepared the non-aqueous electrolyte which concerns on this comparative example.
  • the liquid level height after adding lithium bis (2,2,2trifluoroethyl) phosphate to a mixed solution obtained by adding LiPF 6 to a mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm.
  • the height of the liquid surface after shaking the sample tube 30 times was 3.4 cm. The bubbles did not disappear even after 120 seconds.

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Abstract

The purpose of the present invention is to provide: a non-aqueous electrolyte solution for a secondary battery, which can suppress the occurrence of bubbles; a secondary battery that includes same; and a method for producing a non-aqueous electrolyte solution for a secondary battery, in which a bubble degassing step is omitted and which exhibits improved production efficiency. This non-aqueous electrolyte solution for a secondary battery contains: component (A) which is at least one type of phosphoric acid diester salt represented by general formula (1), and which does not contain a halogen atom; and component (B) which is at least one type of compound selected from among the group consisting of a boron complex salt represented by general formula (2) and/or a boric acid ester, an acid anhydride, a cyclic carbonate having an unsaturated bond, a cyclic carbonate having a halogen atom, a cyclic sulfonic acid ester, an amine compound having an acetoacetyl group represented by general formula (3), and a phosphorus compound represented by any one of general formulae (4) to (7).

Description

二次電池用非水電解液、その製造方法及びそれを備えた二次電池Non-aqueous electrolyte for secondary battery, method for producing the same, and secondary battery equipped with the same
　本発明は、気泡の発生を抑制可能にした二次電池用非水電解液、その製造方法及びそれを備えた二次電池に関するものである。 The present invention relates to a non-aqueous electrolyte for a secondary battery that can suppress the generation of bubbles, a manufacturing method thereof, and a secondary battery including the same.
　近年、リチウム二次電池を始めとする二次電池の応用分野は、携帯電話やパソコン、デジタルカメラ等の電子機器から車載への用途拡大に伴い、出力密度やエネルギー密度の向上ならびに容量損失の抑制等、さらなる高性能化が進められている。車載用途では使用環境温度が高温側、低温側ともに従来以上の耐久性が求められている。特に高温環境については、セルが大型化されるため、使用環境のみならず自己発熱によって定常的に比較的高い温度にさらされることになり、高温耐久性の向上は非常に重要である。さらに、高温環境下で保存すると、電極や電解液、電解質の劣化に伴いセルの内部抵抗が上昇し、低温環境下での内部抵抗に起因するエネルギーロスが著しくなる。 In recent years, the application field of secondary batteries, including lithium secondary batteries, has increased output density and energy density and reduced capacity loss as the use of electronic devices such as mobile phones, personal computers, and digital cameras has increased from in-vehicle use. Etc., higher performance is being promoted. For in-vehicle use, durability higher than conventional is required on both the high temperature side and low temperature side of the use environment temperature. Particularly in a high temperature environment, since the cell is increased in size, the cell is constantly exposed to a relatively high temperature not only by the use environment but also by self-heating, and improvement of the high temperature durability is very important. Furthermore, when stored in a high temperature environment, the internal resistance of the cell increases with deterioration of the electrode, electrolyte, and electrolyte, and energy loss due to the internal resistance in a low temperature environment becomes significant.
　従来の一般的なリチウム二次電池には、正極活物質及び負極活物質にＬｉイオンを可逆的に挿入できる材料が用いられている。例えば、正極活物質には、ＬｉＮｉＯ２、ＬｉＣｏＯ２、ＬｉＭｎ２Ｏ４、又はＬｉＦｅＰＯ４等の化合物が使用されている。また、負極活物質には、リチウム金属、その合金、炭素材料、又は黒鉛材料等が使用されている。更に、リチウム二次電池に用いられる電解液には、エチレンカーボネート、ジエチルカーボネート、プロピレンカーボネート等の混合溶媒にＬｉＰＦ６、ＬｉＢＦ４等の電解質を溶解させたものが使用されている。 A conventional general lithium secondary battery uses a material capable of reversibly inserting Li ions into a positive electrode active material and a negative electrode active material. For example, a compound such as LiNiO 2 , LiCoO 2 , LiMn 2 O 4 , or LiFePO 4 is used for the positive electrode active material. As the negative electrode active material, lithium metal, an alloy thereof, a carbon material, a graphite material, or the like is used. Furthermore, as an electrolytic solution used for a lithium secondary battery, a solution obtained by dissolving an electrolyte such as LiPF 6 or LiBF 4 in a mixed solvent such as ethylene carbonate, diethyl carbonate, or propylene carbonate is used.
　また、車載用途などに用いられる大型のリチウムイオン二次電池では、出力密度やエネルギー密度の向上、高温時／低温時の容量劣化の抑制、サイクル寿命の向上、安全性の向上など、高性能化が求められている。 In addition, large lithium-ion secondary batteries used for in-vehicle applications have high performance such as improved output density and energy density, reduced capacity deterioration at high / low temperatures, improved cycle life, and improved safety. Is required.
　これらの課題を解決するため、従来、リチウム二次電池における正極材料、負極材料及び電解液などの構成部材の最適化が検討されてきた。例えば、電解液の場合、使用される各種溶媒（具体的には、例えば、環状のエチレンカーボネート、プロピレンカーボネート、鎖状のジメチルカーボネート、ジエチルカーボネート等）、電解質（具体的には、例えば、ヘキサフルオロリン酸リチウム、四フッ化ホウ酸リチウム、過塩素酸リチウム等）、及び上記特性を改善するための添加剤（具体的には、例えば、フルオロエチレンカーボネート、ｔｒａｎｓ-ジフルオロエチレンカ－ボネート等）の種類やこれらの最適な組み合わせが提案されている。 In order to solve these problems, conventionally, optimization of components such as a positive electrode material, a negative electrode material, and an electrolytic solution in a lithium secondary battery has been studied. For example, in the case of an electrolytic solution, various solvents used (specifically, for example, cyclic ethylene carbonate, propylene carbonate, chain dimethyl carbonate, diethyl carbonate, etc.), electrolyte (specifically, for example, hexafluoro Lithium phosphate, lithium tetrafluoroborate, lithium perchlorate, etc.) and additives for improving the above properties (specifically, for example, fluoroethylene carbonate, trans-difluoroethylene carbonate, etc.) Types and optimal combinations of these have been proposed.
　例えば、下記特許文献１には、非水溶媒と、ホウ素原子を有する第一のリチウム塩と、ホウ素原子を有さない第二のリチウム塩と、リン酸エステルとを含有する非水蓄電デバイス用電解液が開示されている。この非水蓄電デバイス用電解液によれば、４，４Ｖ以上の高電位で作動する正極活物質を用いた場合にも、高いサイクル寿命を有するリチウムイオン二次電池の実現が可能とされている。 For example, the following Patent Document 1 discloses a nonaqueous storage device containing a nonaqueous solvent, a first lithium salt having a boron atom, a second lithium salt not having a boron atom, and a phosphate ester. An electrolyte is disclosed. According to the electrolyte for a non-aqueous storage device, it is possible to realize a lithium ion secondary battery having a high cycle life even when a positive electrode active material that operates at a high potential of 4 or 4 V or higher is used. .
　しかしながら、特許文献１に記載の非水蓄電デバイス用電解液の場合、実施例に記載されているように、化学構造内にフッ素原子を有するリン酸ジエステル塩が含まれていると、当該非水蓄電デバイス用電解液の各製造段階において気泡が発生することから、当該気泡を消失させるための脱泡工程が必要になり、生産効率の低下を招来するという問題がある。また、最終製品であるリチウムイオン二次電池においても、電池不良の原因になり得るという問題がある。 However, in the case of the electrolyte for a non-aqueous electricity storage device described in Patent Document 1, if a phosphoric diester salt having a fluorine atom is contained in the chemical structure as described in the examples, the non-aqueous Since bubbles are generated at each stage of manufacturing the electrolytic solution for an electricity storage device, a defoaming step for eliminating the bubbles is required, which causes a problem of reducing production efficiency. In addition, the lithium ion secondary battery, which is the final product, has a problem that it can cause battery failure.
特開２０１４－２２３３２号公報JP 2014-22332 A
　本発明は前記問題点に鑑みなされたものであり、気泡の発生を抑制可能にした二次電池用非水電解液、及びそれを含む二次電池を提供することを目的とする。また、本発明は、気泡の脱泡工程を省略し、生産効率を向上させた二次電池用非水電解液の製造方法を提供することを他の目的とする。 The present invention has been made in view of the above problems, and an object thereof is to provide a non-aqueous electrolyte for a secondary battery that can suppress the generation of bubbles, and a secondary battery including the same. Another object of the present invention is to provide a method for producing a non-aqueous electrolyte for a secondary battery in which the bubble defoaming step is omitted and the production efficiency is improved.
　本発明の二次電池用非水電解液は、前記の課題を解決する為に、二次電池に用いられる二次電池用非水電解液であって、下記成分（Ａ）及び成分（Ｂ）を含むことを特徴とする。
　成分（Ａ）：ハロゲン原子を含まず、かつ、下記一般式（１）で表される少なくとも１種のリン酸ジエステル塩；
　成分（Ｂ）：下記一般式（２）で表される少なくとも１種のホウ素錯体塩、ホウ酸エステル、酸無水物、不飽和結合を有する環状カーボネート、ハロゲン原子を有する環状カーボネート、環状スルホン酸エステル、下記一般式（３）で表されるアセトアセチル基を有するアミン類及び下記一般式（４）～（７）の何れかで表されるリン化合物からなる群より選ばれる少なくとも１種 The non-aqueous electrolyte for a secondary battery of the present invention is a non-aqueous electrolyte for a secondary battery used for a secondary battery in order to solve the above-described problems, and includes the following components (A) and (B): It is characterized by including.
Component (A): at least one phosphoric diester salt that does not contain a halogen atom and is represented by the following general formula (1);
Component (B): at least one boron complex salt represented by the following general formula (2), boric acid ester, acid anhydride, cyclic carbonate having an unsaturated bond, cyclic carbonate having a halogen atom, cyclic sulfonic acid ester At least one selected from the group consisting of amines having an acetoacetyl group represented by the following general formula (3) and phosphorus compounds represented by any of the following general formulas (4) to (7)
Figure JPOXMLDOC01-appb-C000022
 （前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｒ１及びＲ２はハロゲン原子を有しておらず、それぞれ独立して、炭素数が１～２０の炭化水素基、又は炭素数が１～２０の範囲であって、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有する炭化水素基を表す。あるいは、前記Ｒ１とＲ２はハロゲン原子を有しておらず、前記炭素数が１～２０の炭化水素基、又は前記炭素数が１～２０の範囲であり、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有する炭化水素基の何れかであって、相互に結合して環状構造を形成する。前記ｎは価数を表す。）
Figure JPOXMLDOC01-appb-C000022
 (M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. R 1 and R 2 do not have a halogen atom, and each independently represents the number of carbon atoms. Represents a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and having at least one of a heteroatom and an unsaturated bond, or the above R 1 and R 2 Has no halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, or the carbon number in the range of 1 to 20 carbon atoms and having at least one of heteroatoms and unsaturated bonds Any of hydrogen groups, which are bonded to each other to form a cyclic structure, where n represents a valence.)
Figure JPOXMLDOC01-appb-C000023
 （前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｘ１～Ｘ４はそれぞれ独立しており、任意に選択される１又は２つの組合せが、－ＯＯＣ－Ｙ－ＣＯＯ－、－Ｏ－Ｙ－Ｏ－又は－ＯＯＣ－Ｙ－Ｏ－の環状構造を形成しており、その場合の前記Ｙは、炭素数が０～２０の炭化水素基、又は炭素数が０～２０の範囲であって、ヘテロ原子、不飽和結合若しくは環状構造を有する炭化水素基を表す。あるいは、前記Ｘ１～Ｘ４は、それぞれ独立して、ハロゲン原子、炭素数０～２０のアルキル基、炭素数０～２０のアルコキシ基、炭素数が０～２０の範囲内であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有するアルキル基、又は炭素数が０～２０の範囲内であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有するアルコキシ基を表す。前記ｎは価数を表す。）
Figure JPOXMLDOC01-appb-C000023
 (Wherein M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion or an onium ion. X 1 to X 4 are independent of each other, and one or two combinations selected arbitrarily) Forms a cyclic structure of —OOC—Y—COO—, —O—Y—O— or —OOC—Y—O—, wherein Y is a hydrocarbon having 0 to 20 carbon atoms Or a hydrocarbon group having 0 to 20 carbon atoms and having a hetero atom, an unsaturated bond, or a cyclic structure, or X 1 to X 4 are each independently a halogen atom, An alkyl group having 0 to 20 carbon atoms, an alkoxy group having 0 to 20 carbon atoms, an alkyl group having 0 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond A group, or an alkoxy group having 0 to 20 carbon atoms and having at least one of a halogen atom, a heteroatom and an unsaturated bond, wherein n represents a valence.)
Figure JPOXMLDOC01-appb-C000024
 （前記Ｒ３及びＲ４は、それぞれ独立して、炭素数が１～２０の炭化水素基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合を有する炭化水素基を表す。）
Figure JPOXMLDOC01-appb-C000024
 (R 3 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, or a carbon group having 1 to 20 carbon atoms and having a halogen atom, a hetero atom or an unsaturated bond. Represents a hydrogen group.)
Figure JPOXMLDOC01-appb-C000025
 （式中、前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ａ１及びＡ２は、それぞれ独立して、酸素原子、硫黄原子又はセレン原子を表す。前記Ｘ５とＸ６は、それぞれ独立して、ハロゲン原子、炭素数が１～２０のアルキル基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基を表す。あるいは、前記Ｘ５とＸ６は、前記炭素数が１～２０のアルキル基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基の何れかであって、相互に結合して環状構造を形成する。前記ｎは価数を表す。）
Figure JPOXMLDOC01-appb-C000025
 (In the formula, M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. A 1 and A 2 are each independently an oxygen atom, a sulfur atom, or selenium. X 5 and X 6 each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a range having 1 to 20 carbon atoms, and may be a halogen atom, heteroatom or And represents an alkyl group having at least one of a saturated bond, or X 5 and X 6 are each an alkyl group having 1 to 20 carbon atoms, or a range of 1 to 20 carbon atoms, Any of an alkyl group having at least one of an atom, a hetero atom, and an unsaturated bond, and bonded to each other to form a cyclic structure, where n represents a valence.)
Figure JPOXMLDOC01-appb-C000026
 （式中、前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｘ７～Ｘ１２は、それぞれ独立して、ハロゲン原子、炭素数が１～２０のアルキル基、炭素数が１～２０のアルコキシ基、炭素数が１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、炭素数が１～２０のアルキルチオ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ７～Ｘ１２は、任意に選択される少なくとも１つの組合せが、－ＯＯＣ－Ｚ－ＣＯＯ－、－ＯＯＣ－Ｚ－Ｏ－又は－Ｏ－Ｚ－Ｏ－の環状構造を形成しており、その場合の前記Ｚは、炭素数が０～２０の炭化水素基、又は炭素数が０～２０の範囲であって、ハロゲン原子、ヘテロ原子、不飽和結合若しくは環状構造の少なくとも何れか１つを有する炭化水素基を表す。前記ｎは価数を表す。）
Figure JPOXMLDOC01-appb-C000026
 (In the formula, M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. X 7 to X 12 each independently represent a halogen atom or a carbon number of 1; An alkyl group having ˜20, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a range of 1 to 20 carbon atoms, and at least any one of a halogen atom, a hetero atom and an unsaturated bond An alkyl group having 1 or 2 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond, An alkylthio group having 1 to 20 carbon atoms, or a range having 1 to 20 carbon atoms, and at least a halogen atom, a hetero atom or an unsaturated bond; Or an alkylthio group having any one of X 7 to X 12 , wherein at least one combination selected arbitrarily is —OOC—Z—COO—, —OOC—Z—O— or —O; In which case Z represents a hydrocarbon group having 0 to 20 carbon atoms, or a carbon group having 0 to 20 carbon atoms, a halogen atom, a hetero atom Represents a hydrocarbon group having at least one of an unsaturated bond or a cyclic structure, wherein n represents a valence.)
Figure JPOXMLDOC01-appb-C000027
 （式中、前記Ａ３は酸素原子、硫黄原子又はセレン原子を表す。前記Ｘ１３～Ｘ１５は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ１３～Ｘ１５のうち任意に選択される少なくとも１つの組合せが、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基の何れかであって、相互に結合して環状構造を形成する。）
Figure JPOXMLDOC01-appb-C000027
 (In the formula, A 3 represents an oxygen atom, a sulfur atom or a selenium atom. X 13 to X 15 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number of 1). An alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond, An alkoxy group having at least one of a halogen atom, a heteroatom and an unsaturated bond, or a carbon atom having a range of 1 to 20 and being a halogen atom, heteroatom or unsaturated Represents an alkylthio group having at least one of the bonds, or at least one combination selected from X 13 to X 15 is a group having 1 to 20 alkyl groups, alkoxy groups having 1 to 20 carbon atoms, alkylthio groups having 1 to 20 carbon atoms, at least one of halogen atoms, heteroatoms and unsaturated bonds in the range of 1 to 20 carbon atoms An alkyl group having a carbon number in the range of 1-20, an alkoxy group having at least one of a halogen atom, a heteroatom or an unsaturated bond, or a carbon number in the range of 1-20, Any of a halogen atom, a hetero atom and an alkylthio group having at least one of an unsaturated bond, which are bonded to each other to form a cyclic structure.)
Figure JPOXMLDOC01-appb-C000028
 （式中、前記Ｘ１６～Ｘ１８は、それぞれ独立して、ハロゲン原子、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ１６～Ｘ１８のうち任意に選択される少なくとも１つの組合せが、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基の何れかであって、相互に結合して環状構造を形成する。）
Figure JPOXMLDOC01-appb-C000028
 (Wherein X 16 to X 18 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, An alkyl group having at least one of a halogen atom, a heteroatom or an unsaturated bond in the range of 1 to 20, a carbon number in the range of 1 to 20 and a halogen atom, a heteroatom or an unsaturated bond Or an alkylthio group having at least one of a halogen atom, a heteroatom, and an unsaturated bond having 1 to 20 carbon atoms, or at least one of the above, or X 16 ~ X at least one combination selected at any one of 18, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, 1 or 2 carbon atoms An alkylthio group having a carbon number in the range of 1 to 20 and having at least one of a halogen atom, a heteroatom or an unsaturated bond, a carbon number in the range of 1 to 20 and a halogen atom , An alkoxy group having at least one of a heteroatom or an unsaturated bond, or an alkylthio group having 1 to 20 carbon atoms and having at least one of a halogen atom, a heteroatom or an unsaturated bond And bonded to each other to form a cyclic structure.)
　前記の構成において、前記成分（Ａ）の添加量は、前記二次電池用非水電解液の全質量に対し、０．０５質量％～５質量％であり、前記成分（Ｂ）の添加量は、前記二次電池用非水電解液の全質量に対し、０．０５質量％～５質量％であることが好ましい。 In the above configuration, the amount of the component (A) added is 0.05% by mass to 5% by mass with respect to the total mass of the non-aqueous electrolyte for secondary battery, and the amount of the component (B) added Is preferably 0.05% by mass to 5% by mass with respect to the total mass of the non-aqueous electrolyte for secondary battery.
　前記の構成においては、前記成分（Ａ）がジエチルリン酸リチウムであることが好ましい。 In the above configuration, the component (A) is preferably lithium diethyl phosphate.
　前記の構成においては、前記成分（Ｂ）の前記一般式（２）で表されるホウ素錯体塩がリチウムビスオキサラトボレート、トリエチルメチルアンモニウムビスオキサラトボレート、リチウムビスサリチラートボレート又はリチウムビス［１，２’－ベンジオラート（２）－Ｏ，Ｏ’］ボレートであることが好ましい。 In the above structure, the boron complex salt represented by the general formula (2) of the component (B) is lithium bisoxalatoborate, triethylmethylammonium bisoxalatoborate, lithium bissalicylate borate or lithium bis [ 1,2′-Benziolate (2) —O, O ′] borate is preferred.
　前記の構成においては、前記ホウ酸エステルがホウ酸トリメチルであることが好ましい。 In the above configuration, the borate ester is preferably trimethyl borate.
　前記の構成においては、前記酸無水物がマレイン酸無水物であることが好ましい。 In the above configuration, the acid anhydride is preferably maleic anhydride.
　前記の構成においては、前記不飽和結合を有する環状カーボネートがビニレンカーボネートであることが好ましい。 In the above configuration, the cyclic carbonate having an unsaturated bond is preferably vinylene carbonate.
　前記の構成においては、前記ハロゲン原子を有する環状カーボネートがフルオロエチレンカーボネートであることが好ましい。 In the above configuration, the cyclic carbonate having a halogen atom is preferably fluoroethylene carbonate.
　前記の構成においては、前記環状スルホン酸エステルが１，３－プロパンスルトンであることが好ましい。 In the above configuration, the cyclic sulfonate ester is preferably 1,3-propane sultone.
　前記の構成においては、前記一般式（３）で表されるアセトアセチル基を有するアミン類がＮ，Ｎ－ジメチルアセトアセトアミドであることが好ましい。 In the above configuration, the amine having an acetoacetyl group represented by the general formula (3) is preferably N, N-dimethylacetoacetamide.
　前記の構成においては、前記一般式（４）で表されるリン化合物がジフルオロリン酸リチウムであることが好ましい。 In the above configuration, it is preferable that the phosphorus compound represented by the general formula (4) is lithium difluorophosphate.
　前記の構成においては、前記一般式（５）で表されるリン化合物がリチウムジフルオロビスオキサレートホスフェートであることが好ましい。 In the above configuration, the phosphorus compound represented by the general formula (5) is preferably lithium difluorobisoxalate phosphate.
　前記の構成においては、前記一般式（６）で表されるリン化合物が、リン酸トリメチル、リン酸トリス（２，２，２－トリフルオロエチル）又はビス（２，２，２－トリフルオロエチル）ホスホン酸であることが好ましい。 In the above configuration, the phosphorus compound represented by the general formula (6) is trimethyl phosphate, tris (2,2,2-trifluoroethyl phosphate) or bis (2,2,2-trifluoroethyl). ) Preference is given to phosphonic acid.
　前記の構成においては、前記一般式（７）で表されるリン化合物がトリメチルホスフィン又はメチルジフェニルホスフィンであることが好ましい。 In the above configuration, the phosphorus compound represented by the general formula (7) is preferably trimethylphosphine or methyldiphenylphosphine.
　本発明の二次電池用非水電解液の製造方法は、前記の課題を解決する為に、二次電池に用いられる二次電池用非水電解液の製造方法であって、有機溶媒に電解質の塩を添加する第１工程と、前記電解質の塩の添加後の有機溶媒に、下記成分（Ａ）を添加する第２工程と、前記電解質の塩及び前記成分（Ａ）の添加後の前記有機溶媒に、下記成分（Ｂ）を添加し、二次電池用非水電解液を作製する第３工程とを有し、前記第２工程で作製した前記成分（Ａ）添加後の有機溶媒、及び前記第３工程において作製した二次電池用非水電解液に対し、気泡を脱泡するための工程を行わないことを特徴とする。
　成分（Ａ）：ハロゲン原子を含まず、かつ、下記一般式（１）で表される少なくとも１種のリン酸ジエステル塩；
　成分（Ｂ）：下記一般式（２）で表される少なくとも１種のホウ素錯体塩、ホウ酸エステル、酸無水物、不飽和結合を有する環状カーボネート、ハロゲン原子を有する環状カーボネート、環状スルホン酸エステル、下記一般式（３）で表されるアセトアセチル基を有するアミン類及び下記一般式（４）～（７）の何れかで表されるリン化合物からなる群より選ばれる少なくとも１種 The method for producing a non-aqueous electrolyte for a secondary battery according to the present invention is a method for producing a non-aqueous electrolyte for a secondary battery used in a secondary battery in order to solve the above-mentioned problems, and the electrolyte is an organic solvent. A first step of adding a salt of the second, a second step of adding the following component (A) to the organic solvent after the addition of the electrolyte salt, and the addition of the electrolyte salt and the component (A) A third step of adding the following component (B) to an organic solvent to prepare a non-aqueous electrolyte for a secondary battery, and the organic solvent after the addition of the component (A) prepared in the second step, And the process for defoaming a bubble is not performed with respect to the non-aqueous electrolyte for secondary batteries produced in the said 3rd process.
Component (A): at least one phosphoric diester salt that does not contain a halogen atom and is represented by the following general formula (1);
Component (B): at least one boron complex salt represented by the following general formula (2), boric acid ester, acid anhydride, cyclic carbonate having an unsaturated bond, cyclic carbonate having a halogen atom, cyclic sulfonic acid ester At least one selected from the group consisting of amines having an acetoacetyl group represented by the following general formula (3) and phosphorus compounds represented by any of the following general formulas (4) to (7)
Figure JPOXMLDOC01-appb-C000029
 （前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｒ１及びＲ２はハロゲン原子を有しておらず、それぞれ独立して、炭素数が１～２０の炭化水素基、又は炭素数が１～２０の範囲であって、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有する炭化水素基を表す。あるいは、前記Ｒ１とＲ２はハロゲン原子を有しておらず、前記炭素数が１～２０の炭化水素基、又は前記炭素数が１～２０の範囲であり、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有する炭化水素基の何れかであって、相互に結合して環状構造を形成する。前記ｎは価数を表す。）
Figure JPOXMLDOC01-appb-C000029
 (M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. R 1 and R 2 do not have a halogen atom, and each independently represents the number of carbon atoms. Represents a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and having at least one of a heteroatom and an unsaturated bond, or the above R 1 and R 2 Has no halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, or the carbon number in the range of 1 to 20 carbon atoms and having at least one of heteroatoms and unsaturated bonds Any of hydrogen groups, which are bonded to each other to form a cyclic structure, where n represents a valence.)
Figure JPOXMLDOC01-appb-C000030
 （前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｘ１～Ｘ４はそれぞれ独立しており、任意に選択される１又は２つの組合せが、－ＯＯＣ－Ｙ－ＣＯＯ－、－Ｏ－Ｙ－Ｏ－又は－ＯＯＣ－Ｙ－Ｏ－の環状構造を形成しており、その場合の前記Ｙは、炭素数が０～２０の炭化水素基、又は炭素数が０～２０の範囲であって、ヘテロ原子、不飽和結合若しくは環状構造を有する炭化水素基を表す。あるいは、前記Ｘ１～Ｘ４は、それぞれ独立して、ハロゲン原子、炭素数０～２０のアルキル基、炭素数０～２０のアルコキシ基、炭素数が０～２０の範囲内であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有するアルキル基、又は炭素数が０～２０の範囲内であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有するアルコキシ基を表す。前記ｎは価数を表す。）
Figure JPOXMLDOC01-appb-C000030
 (Wherein M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion or an onium ion. X 1 to X 4 are independent of each other, and one or two combinations selected arbitrarily) Forms a cyclic structure of —OOC—Y—COO—, —O—Y—O— or —OOC—Y—O—, wherein Y is a hydrocarbon having 0 to 20 carbon atoms Or a hydrocarbon group having 0 to 20 carbon atoms and having a hetero atom, an unsaturated bond, or a cyclic structure, or X 1 to X 4 are each independently a halogen atom, An alkyl group having 0 to 20 carbon atoms, an alkoxy group having 0 to 20 carbon atoms, an alkyl group having 0 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond A group, or an alkoxy group having 0 to 20 carbon atoms and having at least one of a halogen atom, a heteroatom and an unsaturated bond, wherein n represents a valence.)
Figure JPOXMLDOC01-appb-C000031
 （前記Ｒ３及びＲ４は、それぞれ独立して、炭素数が１～２０の炭化水素基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合を有する炭化水素基を表す。）
Figure JPOXMLDOC01-appb-C000031
 (R 3 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, or a carbon group having 1 to 20 carbon atoms and having a halogen atom, a hetero atom or an unsaturated bond. Represents a hydrogen group.)
Figure JPOXMLDOC01-appb-C000032
 （式中、前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ａ１及びＡ２は、それぞれ独立して、酸素原子、硫黄原子又はセレン原子を表す。前記Ｘ５とＸ６は、それぞれ独立して、ハロゲン原子、炭素数が１～２０のアルキル基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基を表す。あるいは、前記Ｘ５とＸ６は、前記炭素数が１～２０のアルキル基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基の何れかであって、相互に結合して環状構造を形成する。前記ｎは価数を表す。）
Figure JPOXMLDOC01-appb-C000032
 (In the formula, M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. A 1 and A 2 are each independently an oxygen atom, a sulfur atom, or selenium. X 5 and X 6 each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a range having 1 to 20 carbon atoms, and may be a halogen atom, heteroatom or And represents an alkyl group having at least one of a saturated bond, or X 5 and X 6 are each an alkyl group having 1 to 20 carbon atoms, or a range of 1 to 20 carbon atoms, Any of an alkyl group having at least one of an atom, a hetero atom, and an unsaturated bond, and bonded to each other to form a cyclic structure, where n represents a valence.)
Figure JPOXMLDOC01-appb-C000033
 （式中、前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｘ７～Ｘ１２は、それぞれ独立して、ハロゲン原子、炭素数が１～２０のアルキル基、炭素数が１～２０のアルコキシ基、炭素数が１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、炭素数が１～２０のアルキルチオ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ７～Ｘ１２は、任意に選択される少なくとも１つの組合せが、－ＯＯＣ－Ｚ－ＣＯＯ－、－ＯＯＣ－Ｚ－Ｏ－又は－Ｏ－Ｚ－Ｏ－の環状構造を形成しており、その場合の前記Ｚは、炭素数が０～２０の炭化水素基、又は炭素数が０～２０の範囲であって、ハロゲン原子、ヘテロ原子、不飽和結合若しくは環状構造の少なくとも何れか１つを有する炭化水素基を表す。前記ｎは価数を表す。）
Figure JPOXMLDOC01-appb-C000033
 (In the formula, M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. X 7 to X 12 each independently represent a halogen atom or a carbon number of 1; An alkyl group having ˜20, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a range of 1 to 20 carbon atoms, and at least any one of a halogen atom, a hetero atom and an unsaturated bond An alkyl group having 1 or 2 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond, An alkylthio group having 1 to 20 carbon atoms, or a range having 1 to 20 carbon atoms, and at least a halogen atom, a hetero atom or an unsaturated bond; Or an alkylthio group having any one of X 7 to X 12 , wherein at least one combination selected arbitrarily is —OOC—Z—COO—, —OOC—Z—O— or —O; In which case Z represents a hydrocarbon group having 0 to 20 carbon atoms, or a carbon group having 0 to 20 carbon atoms, a halogen atom, a hetero atom Represents a hydrocarbon group having at least one of an unsaturated bond or a cyclic structure, wherein n represents a valence.)
Figure JPOXMLDOC01-appb-C000034
 （式中、前記Ａ３は酸素原子、硫黄原子又はセレン原子を表す。前記Ｘ１３～Ｘ１５は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ１３～Ｘ１５のうち任意に選択される少なくとも１つの組合せが、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基の何れかであって、相互に結合して環状構造を形成する。）
Figure JPOXMLDOC01-appb-C000034
 (In the formula, A 3 represents an oxygen atom, a sulfur atom or a selenium atom. X 13 to X 15 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number of 1). An alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond, An alkoxy group having at least one of a halogen atom, a heteroatom and an unsaturated bond, or a carbon atom having a range of 1 to 20 and being a halogen atom, heteroatom or unsaturated Represents an alkylthio group having at least one of the bonds, or at least one combination selected from X 13 to X 15 is a group having 1 to 20 alkyl groups, alkoxy groups having 1 to 20 carbon atoms, alkylthio groups having 1 to 20 carbon atoms, at least one of halogen atoms, heteroatoms and unsaturated bonds in the range of 1 to 20 carbon atoms An alkyl group having a carbon number in the range of 1-20, an alkoxy group having at least one of a halogen atom, a heteroatom or an unsaturated bond, or a carbon number in the range of 1-20, Any of a halogen atom, a hetero atom and an alkylthio group having at least one of an unsaturated bond, which are bonded to each other to form a cyclic structure.)
Figure JPOXMLDOC01-appb-C000035
 （式中、前記Ｘ１６～Ｘ１８は、それぞれ独立して、ハロゲン原子、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ１６～Ｘ１８のうち任意に選択される少なくとも１つの組合せが、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基の何れかであって、相互に結合して環状構造を形成する。）
Figure JPOXMLDOC01-appb-C000035
 (Wherein X 16 to X 18 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, An alkyl group having at least one of a halogen atom, a heteroatom or an unsaturated bond in the range of 1 to 20, a carbon number in the range of 1 to 20 and a halogen atom, a heteroatom or an unsaturated bond Or an alkylthio group having at least one of a halogen atom, a heteroatom, and an unsaturated bond having 1 to 20 carbon atoms, or at least one of the above, or X 16 ~ X at least one combination selected at any one of 18, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, 1 or 2 carbon atoms An alkylthio group having a carbon number in the range of 1 to 20 and having at least one of a halogen atom, a heteroatom or an unsaturated bond, a carbon number in the range of 1 to 20 and a halogen atom , An alkoxy group having at least one of a heteroatom or an unsaturated bond, or an alkylthio group having 1 to 20 carbon atoms and having at least one of a halogen atom, a heteroatom or an unsaturated bond And bonded to each other to form a cyclic structure.)
　前記の構成に於いて、前記第２工程における前記成分（Ａ）の添加量は、前記二次電池用非水電解液の全質量に対し、０．０５質量％～５質量％であり、前記第３工程における前記成分（Ｂ）の添加量は、前記二次電池用非水電解液の全質量に対し、０．０５質量％～５質量％であることが好ましい。 In the above configuration, the amount of the component (A) added in the second step is 0.05% by mass to 5% by mass with respect to the total mass of the non-aqueous electrolyte for secondary battery, The amount of component (B) added in the third step is preferably 0.05% by mass to 5% by mass with respect to the total mass of the non-aqueous electrolyte for secondary battery.
　また、本発明の二次電池は、前記の課題を解決する為に、前記二次電池用非水電解液、正極及び負極を少なくとも備えた二次電池であって、前記二次電池用非水電解液は、下記成分（Ａ）及び成分（Ｂ）を含むものであることを特徴とする。
　成分（Ａ）：ハロゲン原子を含まず、かつ、下記一般式（１）で表される少なくとも１種のリン酸ジエステル塩；
　成分（Ｂ）：下記一般式（２）で表される少なくとも１種のホウ素錯体塩、ホウ酸エステル、酸無水物、不飽和結合を有する環状カーボネート、ハロゲン原子を有する環状カーボネート、環状スルホン酸エステル、下記一般式（３）で表されるアセトアセチル基を有するアミン類及び下記一般式（４）～（７）の何れかで表されるリン化合物からなる群より選ばれる少なくとも１種 The secondary battery of the present invention is a secondary battery comprising at least the non-aqueous electrolyte for a secondary battery, a positive electrode, and a negative electrode in order to solve the above-described problems, and the non-aqueous battery for the secondary battery. The electrolytic solution includes the following component (A) and component (B).
Component (A): at least one phosphoric diester salt that does not contain a halogen atom and is represented by the following general formula (1);
Component (B): at least one boron complex salt represented by the following general formula (2), boric acid ester, acid anhydride, cyclic carbonate having an unsaturated bond, cyclic carbonate having a halogen atom, cyclic sulfonic acid ester At least one selected from the group consisting of amines having an acetoacetyl group represented by the following general formula (3) and phosphorus compounds represented by any of the following general formulas (4) to (7)
Figure JPOXMLDOC01-appb-C000036
 （前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｒ１及びＲ２はハロゲン原子を有しておらず、それぞれ独立して、炭素数が１～２０の炭化水素基、又は炭素数が１～２０の範囲であって、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有する炭化水素基を表す。あるいは、前記Ｒ１とＲ２はハロゲン原子を有しておらず、前記炭素数が１～２０の炭化水素基、又は前記炭素数が１～２０の範囲であり、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有する炭化水素基の何れかであって、相互に結合して環状構造を形成する。前記ｎは価数を表す。）
Figure JPOXMLDOC01-appb-C000036
 (M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. R 1 and R 2 do not have a halogen atom, and each independently represents the number of carbon atoms. Represents a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and having at least one of a heteroatom and an unsaturated bond, or the above R 1 and R 2 Has no halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, or the carbon number in the range of 1 to 20 carbon atoms and having at least one of heteroatoms and unsaturated bonds Any of hydrogen groups, which are bonded to each other to form a cyclic structure, where n represents a valence.)
Figure JPOXMLDOC01-appb-C000037
 （前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｘ１～Ｘ４はそれぞれ独立しており、任意に選択される１又は２つの組合せが、－ＯＯＣ－Ｙ－ＣＯＯ－、－Ｏ－Ｙ－Ｏ－又は－ＯＯＣ－Ｙ－Ｏ－の環状構造を形成しており、その場合の前記Ｙは、炭素数が０～２０の炭化水素基、又は炭素数が０～２０の範囲であって、ヘテロ原子、不飽和結合若しくは環状構造を有する炭化水素基を表す。あるいは、前記Ｘ１～Ｘ４は、それぞれ独立して、ハロゲン原子、炭素数０～２０のアルキル基、炭素数０～２０のアルコキシ基、炭素数が０～２０の範囲内であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有するアルキル基、又は炭素数が０～２０の範囲内であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有するアルコキシ基を表す。前記ｎは価数を表す。）
Figure JPOXMLDOC01-appb-C000037
 (Wherein M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion or an onium ion. X 1 to X 4 are independent of each other, and one or two combinations selected arbitrarily) Forms a cyclic structure of —OOC—Y—COO—, —O—Y—O— or —OOC—Y—O—, wherein Y is a hydrocarbon having 0 to 20 carbon atoms Or a hydrocarbon group having 0 to 20 carbon atoms and having a hetero atom, an unsaturated bond, or a cyclic structure, or X 1 to X 4 are each independently a halogen atom, An alkyl group having 0 to 20 carbon atoms, an alkoxy group having 0 to 20 carbon atoms, an alkyl group having 0 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond A group, or an alkoxy group having 0 to 20 carbon atoms and having at least one of a halogen atom, a heteroatom and an unsaturated bond, wherein n represents a valence.)
Figure JPOXMLDOC01-appb-C000038
 （前記Ｒ３及びＲ４は、それぞれ独立して、炭素数が１～２０の炭化水素基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合を有する炭化水素基を表す。）
Figure JPOXMLDOC01-appb-C000038
 (R 3 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, or a carbon group having 1 to 20 carbon atoms and having a halogen atom, a hetero atom or an unsaturated bond. Represents a hydrogen group.)
Figure JPOXMLDOC01-appb-C000039
 （式中、前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ａ１及びＡ２は、それぞれ独立して、酸素原子、硫黄原子又はセレン原子を表す。前記Ｘ５とＸ６は、それぞれ独立して、ハロゲン原子、炭素数が１～２０のアルキル基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基を表す。あるいは、前記Ｘ５とＸ６は、前記炭素数が１～２０のアルキル基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基の何れかであって、相互に結合して環状構造を形成する。前記ｎは価数を表す。）
Figure JPOXMLDOC01-appb-C000039
 (In the formula, M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. A 1 and A 2 are each independently an oxygen atom, a sulfur atom, or selenium. X 5 and X 6 each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a range having 1 to 20 carbon atoms, and may be a halogen atom, heteroatom or And represents an alkyl group having at least one of a saturated bond, or X 5 and X 6 are each an alkyl group having 1 to 20 carbon atoms, or a range of 1 to 20 carbon atoms, Any of an alkyl group having at least one of an atom, a hetero atom, and an unsaturated bond, and bonded to each other to form a cyclic structure, where n represents a valence.)
Figure JPOXMLDOC01-appb-C000040
 （式中、前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｘ７～Ｘ１２は、それぞれ独立して、ハロゲン原子、炭素数が１～２０のアルキル基、炭素数が１～２０のアルコキシ基、炭素数が１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、炭素数が１～２０のアルキルチオ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ７～Ｘ１２は、任意に選択される少なくとも１つの組合せが、－ＯＯＣ－Ｚ－ＣＯＯ－、－ＯＯＣ－Ｚ－Ｏ－又は－Ｏ－Ｚ－Ｏ－の環状構造を形成しており、その場合の前記Ｚは、炭素数が０～２０の炭化水素基、又は炭素数が０～２０の範囲であって、ハロゲン原子、ヘテロ原子、不飽和結合若しくは環状構造の少なくとも何れか１つを有する炭化水素基を表す。前記ｎは価数を表す。）
Figure JPOXMLDOC01-appb-C000040
 (In the formula, M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. X 7 to X 12 each independently represent a halogen atom or a carbon number of 1; An alkyl group having ˜20, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a range of 1 to 20 carbon atoms, and at least any one of a halogen atom, a hetero atom and an unsaturated bond An alkyl group having 1 or 2 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond, An alkylthio group having 1 to 20 carbon atoms, or a range having 1 to 20 carbon atoms, and at least a halogen atom, a hetero atom or an unsaturated bond; Or an alkylthio group having any one of X 7 to X 12 , wherein at least one combination selected arbitrarily is —OOC—Z—COO—, —OOC—Z—O— or —O; In which case Z represents a hydrocarbon group having 0 to 20 carbon atoms, or a carbon group having 0 to 20 carbon atoms, a halogen atom, a hetero atom Represents a hydrocarbon group having at least one of an unsaturated bond or a cyclic structure, wherein n represents a valence.)
Figure JPOXMLDOC01-appb-C000041
 （式中、前記Ａ３は酸素原子、硫黄原子又はセレン原子を表す。前記Ｘ１３～Ｘ１５は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ１３～Ｘ１５のうち任意に選択される少なくとも１つの組合せが、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基の何れかであって、相互に結合して環状構造を形成する。）
Figure JPOXMLDOC01-appb-C000041
 (In the formula, A 3 represents an oxygen atom, a sulfur atom or a selenium atom. X 13 to X 15 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number of 1). An alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond, An alkoxy group having at least one of a halogen atom, a heteroatom and an unsaturated bond, or a carbon atom having a range of 1 to 20 and being a halogen atom, heteroatom or unsaturated Represents an alkylthio group having at least one of the bonds, or at least one combination selected from X 13 to X 15 is a group having 1 to 20 alkyl groups, alkoxy groups having 1 to 20 carbon atoms, alkylthio groups having 1 to 20 carbon atoms, at least one of halogen atoms, heteroatoms and unsaturated bonds in the range of 1 to 20 carbon atoms An alkyl group having a carbon number in the range of 1-20, an alkoxy group having at least one of a halogen atom, a heteroatom or an unsaturated bond, or a carbon number in the range of 1-20, Any of a halogen atom, a hetero atom and an alkylthio group having at least one of an unsaturated bond, which are bonded to each other to form a cyclic structure.)
Figure JPOXMLDOC01-appb-C000042
 （式中、前記Ｘ１６～Ｘ１８は、それぞれ独立して、ハロゲン原子、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ１６～Ｘ１８のうち任意に選択される少なくとも１つの組合せが、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基の何れかであって、相互に結合して環状構造を形成する。）
Figure JPOXMLDOC01-appb-C000042
 (Wherein X 16 to X 18 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, An alkyl group having at least one of a halogen atom, a heteroatom or an unsaturated bond in the range of 1 to 20, a carbon number in the range of 1 to 20 and a halogen atom, a heteroatom or an unsaturated bond Or an alkylthio group having at least one of a halogen atom, a heteroatom, and an unsaturated bond having 1 to 20 carbon atoms, or at least one of the above, or X 16 ~ X at least one combination selected at any one of 18, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, 1 or 2 carbon atoms An alkylthio group having a carbon number in the range of 1 to 20 and having at least one of a halogen atom, a heteroatom or an unsaturated bond, a carbon number in the range of 1 to 20 and a halogen atom , An alkoxy group having at least one of a heteroatom or an unsaturated bond, or an alkylthio group having 1 to 20 carbon atoms and having at least one of a halogen atom, a heteroatom or an unsaturated bond And bonded to each other to form a cyclic structure.)
　本発明の二次電池用非水電解液によれば、当該二次電池用非水電解液中に含まれる前記成分（Ａ）のリン酸ジエステル塩においては、フッ素原子等のハロゲン原子を化学構造中に含まないことから、当該電解液を二次電池に用いる際に気泡が発生するのを抑制することができる。その結果、電池不良の低減が図れる。 According to the non-aqueous electrolyte for a secondary battery of the present invention, in the phosphoric acid diester salt of the component (A) contained in the non-aqueous electrolyte for a secondary battery, a halogen atom such as a fluorine atom has a chemical structure. Since it is not contained, bubbles can be prevented from being generated when the electrolytic solution is used in a secondary battery. As a result, battery defects can be reduced.
　また、本発明の二次電池用非水電解液の製造方法によれば、有機溶媒に電解質の塩を添加する第１工程と、前記電解質の塩の添加後の有機溶媒に、下記成分（Ａ）を添加する第２工程と、前記電解質の塩及び前記成分（Ａ）の添加後の前記有機溶媒に、下記成分（Ｂ）を添加し、二次電池用非水電解液を作製する第３工程とを有しており、当該成分（Ａ）のリン酸ジエステル塩においては、フッ素原子等のハロゲン原子を化学構造中に含まない。そのため、電解質の塩の添加後の有機溶媒に、下記成分（Ａ）を添加する第２工程、及び電解質の塩及び成分（Ａ）の添加後の前記有機溶媒に、成分（Ｂ）を添加する第３工程のそれぞれにおいては、気泡の発生を抑制し、あるいは気泡が発生してもすぐに消失するため、当該気泡を脱泡するための工程を省略することができる。その結果、本発明の二次電池用非水電解液の製造方法によれば、従来の電解液の製造方法と比較して、生産効率の向上が図れる。 In addition, according to the method for producing a non-aqueous electrolyte for a secondary battery of the present invention, the following components (A) are added to the first step of adding an electrolyte salt to the organic solvent, and the organic solvent after the addition of the electrolyte salt. And a second step of adding the following component (B) to the organic solvent after the addition of the electrolyte salt and the component (A) to produce a non-aqueous electrolyte for a secondary battery. In the phosphoric acid diester salt of the component (A), halogen atoms such as fluorine atoms are not included in the chemical structure. Therefore, the second step of adding the following component (A) to the organic solvent after the addition of the electrolyte salt and the component (B) are added to the organic solvent after the addition of the electrolyte salt and the component (A). In each of the third steps, the generation of bubbles is suppressed, or even if bubbles are generated, they disappear immediately. Therefore, the step for defoaming the bubbles can be omitted. As a result, according to the method for producing a non-aqueous electrolyte for a secondary battery of the present invention, the production efficiency can be improved as compared with the conventional method for producing an electrolyte.
本発明の実施の一形態に係る二次電池用非水電解液を備えたリチウムイオン二次電池の概略を示す断面模式図である。It is a cross-sectional schematic diagram which shows the outline of the lithium ion secondary battery provided with the non-aqueous electrolyte for secondary batteries which concerns on one Embodiment of this invention.
（二次電池用非水電解液）
　本実施の形態に係る二次電池用非水電解液（以下、「非水電解液」という。）は、電解質を溶解させた有機溶媒（非水溶媒）に、少なくとも１種の下記成分（Ａ）と、下記成分（Ｂ）とを含むものである。 (Nonaqueous electrolyte for secondary battery)
A non-aqueous electrolyte for a secondary battery according to the present embodiment (hereinafter referred to as “non-aqueous electrolyte”) includes at least one of the following components (A ) And the following component (B).
　本実施の形態の非水電解液は、後述の通り、成分（Ａ）としてハロゲン原子を含まないものを用いているので、理由は不明であるが、二次電池に用いる際に気泡が発生するのを抑制することができる。その結果、電池不良の低減が図れる。 As will be described later, the non-aqueous electrolyte of the present embodiment uses a component that does not contain a halogen atom as the component (A). Therefore, the reason is unknown, but bubbles are generated when used in a secondary battery. Can be suppressed. As a result, battery defects can be reduced.
　＜成分（Ａ）＞
　前記成分（Ａ）は、ハロゲン原子を含まず、かつ、下記一般式（１）で表される少なくとも１種のリン酸ジエステル塩からなる。前記ハロゲン原子としては、ヨウ素、臭素、塩素、フッ素を表す。 <Component (A)>
The component (A) does not contain a halogen atom and consists of at least one phosphoric diester salt represented by the following general formula (1). The halogen atom represents iodine, bromine, chlorine, or fluorine.
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
　前記一般式（１）において、前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。 In the general formula (1), M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion.
　前記アルカリ金属イオンとしては特に限定されず、リチウムイオン、ナトリウムイオン、カリウムイオン、ルビジウムイオン、セシウムイオン等が挙げられる。これらは一種単独で、又は二種以上を併用することができる。 The alkali metal ion is not particularly limited and includes lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion and the like. These can be used alone or in combination of two or more.
　前記アルカリ土類金属イオンとしては、マグネシウムイオン、カルシウムイオン、ストロンチウムイオン、バリウムイオン等が挙げられる。これらは一種単独で、又は二種以上を併用することができる。 Examples of the alkaline earth metal ions include magnesium ions, calcium ions, strontium ions, barium ions and the like. These can be used alone or in combination of two or more.
　前記遷移金属イオンとしては特に限定されず、例えば、マンガンイオン、コバルトイオン、ニッケルイオン、クロムイオン、銅イオン、モリブデンイオン、タングステンイオン、バナジウムイオン等が挙げられる。これらは一種単独で、又は二種以上を併用することができる。 The transition metal ions are not particularly limited, and examples thereof include manganese ions, cobalt ions, nickel ions, chromium ions, copper ions, molybdenum ions, tungsten ions, vanadium ions, and the like. These can be used alone or in combination of two or more.
　前記オニウムイオンとしては、アンモニウムイオン（ＮＨ４＋）、第１級アンモニウムイオン、第２級アンモニウムイオン、第３級アンモニウムイオン、第４級アンモニウムイオン、第４級ホスホニウムイオン、スルホニウムイオン等が挙げられる。 Examples of the onium ions include ammonium ions (NH 4+ ), primary ammonium ions, secondary ammonium ions, tertiary ammonium ions, quaternary ammonium ions, quaternary phosphonium ions, sulfonium ions, and the like.
　前記第１級アンモニウムイオンとしては特に限定されず、例えば、メチルアンモニウムイオン、エチルアンモニウムイオン、プロピルアンモニウムイオン、イソプロピルアンモニウムイオン等が挙げられる。これらは一種単独で、又は二種以上を併用することができる。 The primary ammonium ion is not particularly limited, and examples thereof include methylammonium ion, ethylammonium ion, propylammonium ion, and isopropylammonium ion. These can be used alone or in combination of two or more.
　前記第２級アンモニウムイオンとしては特に限定されず、例えば、ジメチルアンモニウムイオン、ジエチルアンモニウムイオン、ジプロピルアンモニウムイオン、ジブチルアンモニウムイオン、エチルメチルアンモニウムイオン、メチルプロピルアンモニウムイオン、メチルブチルアンモニウムイオン、プロピルブチルアンモニウムイオン、ジイソプロピルアンモニウムイオン等が挙げられる。これらは一種単独で、又は二種以上を併用することができる。 The secondary ammonium ion is not particularly limited, and for example, dimethylammonium ion, diethylammonium ion, dipropylammonium ion, dibutylammonium ion, ethylmethylammonium ion, methylpropylammonium ion, methylbutylammonium ion, propylbutylammonium Ion, diisopropylammonium ion and the like. These can be used alone or in combination of two or more.
　前記第３級アンモニウムイオンとしては特に限定されず、例えば、トリメチルアンモニウムイオン、トリエチルアンモニウムイオン、トリプロピルアンモニウムアンモニウムイオン、トリブチルアンモニウムイオン、エチルジメチルアンモニウムイオン、ジエチルメチルアンモニウムイオン、トリイソプロピルアンモニウムイオン、ジメチルイソプロピルアンモニウムイオン、ジエチルイソプロピルアンモニウムイオン、ジメチルプロピルアンモニウムイオン、ブチルジメチルアンモニウムイオン、１－メチルピロリジニウムイオン、１－エチルピロリジニウムイオン、１－プロピルピロリジニウムイオン、１－ブチルプロピルピロリジニウムイオン、１－メチルイミダゾリウムイオン、１－エチルイミダゾリウムイオン、１－プロピルイミダゾリウムイオン、１－ブチルイミダゾリウムイオン、ピラゾリウムイオン、１－メチルピラゾリウムイオン、１－エチルピラゾリウムイオン、１－プロピルピラゾリウムイオン、１－ブチルピラゾリウムイオン、ピリジニウムイオン等が挙げられる。これらは一種単独で、又は二種以上を併用することができる。 The tertiary ammonium ion is not particularly limited, and examples thereof include trimethylammonium ion, triethylammonium ion, tripropylammonium ammonium ion, tributylammonium ion, ethyldimethylammonium ion, diethylmethylammonium ion, triisopropylammonium ion, dimethylisopropyl. Ammonium ion, diethylisopropylammonium ion, dimethylpropylammonium ion, butyldimethylammonium ion, 1-methylpyrrolidinium ion, 1-ethylpyrrolidinium ion, 1-propylpyrrolidinium ion, 1-butylpropylpyrrolidinium ion, 1-methyl Imidazolium ion, 1-ethylimidazolium ion, 1-propyli Dazo potassium ion, 1-butyl imidazolium ion, pyrazolium ion, 1-methyl pyrazolium ion, 1-ethyl pyrazolium ion, 1-propyl pyrazolium ion, 1-butyl pyrazolium ion, pyridinium ion, and the like. These can be used alone or in combination of two or more.
　前記第４級アンモニウムイオンをなす第４級アンモニウムとしては特に限定されず、例えば、脂肪族４級アンモニウム類、イミダゾリウム類、ピリジニウム類、ピラゾリウム類、ピリダジニウム類等が挙げられる。これらは一種単独で、又は二種以上を併用することができる。 The quaternary ammonium forming the quaternary ammonium ion is not particularly limited, and examples thereof include aliphatic quaternary ammoniums, imidazoliums, pyridiniums, pyrazoliums, and pyridaziniums. These can be used alone or in combination of two or more.
　さらに、前記脂肪族４級アンモニウム類としては特に限定されず、例えば、テトラエチルアンモニウム、テトラプロピルアンモニウム、テトライソプロピルアンモニウム、トリメチルエチルアンモニウム、ジメチルジエチルアンモニウム、メチルトリエチルアンモニウム、トリメチルプロピルアンモニウム、トリメチルイソプロピルアンモニウム、テトラブチルアンモニウム、トリメチルブチルアンモニウム、トリメチルペンチルアンモニウム、トリメチルヘキシルアンモニウム、１－エチル－１－メチル－ピロリジニウム、１－ブチル－１－メチルピロリジニウム、１－エチル－１－メチル－ピペリジニウム、１－ブチル－１－メチルピペリジニウム等が挙げられる。これらは一種単独で、又は二種以上を併用することができる。 Further, the aliphatic quaternary ammoniums are not particularly limited, and examples thereof include tetraethylammonium, tetrapropylammonium, tetraisopropylammonium, trimethylethylammonium, dimethyldiethylammonium, methyltriethylammonium, trimethylpropylammonium, trimethylisopropylammonium, tetra Butylammonium, trimethylbutylammonium, trimethylpentylammonium, trimethylhexylammonium, 1-ethyl-1-methyl-pyrrolidinium, 1-butyl-1-methylpyrrolidinium, 1-ethyl-1-methyl-piperidinium, 1-butyl- Examples include 1-methylpiperidinium. These can be used alone or in combination of two or more.
　前記イミダゾリウム類としては特に限定されず、例えば、１，３ジメチル－イミダゾリウム、１－エチル－３－メチルイミダゾリウム、１－ｎ－プロピル－３－メチルイミダゾリウム、１－ｎ－ブチル－３－メチルイミダゾリウム、１－ｎ－ヘキシル－３－メチルイミダゾリウム等が挙げられる。これらは一種単独で、又は二種以上を併用することができる。 The imidazoliums are not particularly limited. For example, 1,3 dimethyl-imidazolium, 1-ethyl-3-methylimidazolium, 1-n-propyl-3-methylimidazolium, 1-n-butyl-3 -Methylimidazolium, 1-n-hexyl-3-methylimidazolium and the like. These can be used alone or in combination of two or more.
　前記ピリジニウム類としては特に限定されず、例えば、１－メチルピリジニウム、１－エチルピリジニウム、１－ｎ－プロピルピリジニウム等が挙げられる。これらは一種単独で、又は二種以上を併用することができる。 The pyridiniums are not particularly limited, and examples thereof include 1-methylpyridinium, 1-ethylpyridinium, 1-n-propylpyridinium and the like. These can be used alone or in combination of two or more.
　前記ピラゾリウム類としては特に限定されず、例えば、１，２－ジメチルピラゾリウム、１－メチル－２－エチルピラゾリウム、１－プロピル－２－メチルピラゾリウム、１－メチル－２－ブチルピラゾリウム、１－メチルピラゾリウム、３－メチルピラゾリウム、４－メチルピラゾリウム、４－ヨードピラゾリウム、４－ブロモピラゾリウム、４－ヨードー３－メチルピラゾリウム、４－ブロモー３－メチルピラゾリウム、３－トリフルオロメチルピラゾリウムが挙げられる。これらは一種単独で、又は二種以上を併用することができる。 The pyrazoliums are not particularly limited. For example, 1,2-dimethylpyrazolium, 1-methyl-2-ethylpyrazolium, 1-propyl-2-methylpyrazolium, 1-methyl-2-butyl Pyrazolium, 1-methylpyrazolium, 3-methylpyrazolium, 4-methylpyrazolium, 4-iodopyrazolium, 4-bromopyrazolium, 4-iodo3-methylpyrazolium, 4 -Bromo-3-methylpyrazolium, 3-trifluoromethylpyrazolium. These can be used alone or in combination of two or more.
　前記ピリダジニウム類としては特に限定されず、例えば、１－メチルピリダジニウム、１－エチルピリダジニウム、１－プロピルピリダジニウム、１－ブチルピリダジニウム、３－メチルピリダジニウム、４－メチルピリダジニウム、３－メトキシピリダジニウム、３，６－ジクロロピリダジニウム、３，６－ジクロ－４－メチルピリダジニウム、３－クロロ－６－メチルピリダジニウム、３－クロロー６－メトキシピリダジニウムが挙げられる。これらは一種単独で、又は二種以上を併用することができる。 The pyridaziniums are not particularly limited, and for example, 1-methylpyridazinium, 1-ethylpyridazinium, 1-propylpyridazinium, 1-butylpyridazinium, 3-methylpyridazinium Ni, 4-methylpyridazinium, 3-methoxypyridazinium, 3,6-dichloropyridazinium, 3,6-dichloro-4-methylpyridazinium, 3-chloro-6-methylpyri Examples include dazinium and 3-chloro-6-methoxypyridazinium. These can be used alone or in combination of two or more.
　前記第４級ホスホニウムイオンをなす第４級ホスホニウムとしては特に限定されず、例えば、ベンジルトリフェニルホスホニウム、テトラエチルホスホニウム、テトラフェニルホスホニウム等が挙げられる。これらは一種単独で、又は二種以上を併用することができる。 The quaternary phosphonium forming the quaternary phosphonium ion is not particularly limited, and examples thereof include benzyltriphenylphosphonium, tetraethylphosphonium, and tetraphenylphosphonium. These can be used alone or in combination of two or more.
　前記スルホニウムイオンとしては特に限定されず、例えば、トリメチルスルホニウム、トリフェニルスルホニウム、トリエチルスルホニウム等が挙げられる。これらは一種単独で、又は二種以上を併用することができる。 The sulfonium ion is not particularly limited, and examples thereof include trimethylsulfonium, triphenylsulfonium, triethylsulfonium, and the like. These can be used alone or in combination of two or more.
　前記Ｍｎ＋の例示として列挙したもののうち、入手の容易さの観点からは、リチウムイオン、ナトリウムイオン、テトラアルキルアンモニウムイオンが好ましい。 Of those listed as examples of M n + , lithium ion, sodium ion, and tetraalkylammonium ion are preferable from the viewpoint of availability.
　前記一般式（１）において、前記Ｒ１及びＲ２は化学構造中にハロゲン原子を有していない。また、前記Ｒ１及びＲ２は、それぞれ独立して、炭化水素基、又はヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有する炭化水素基（以下、「ヘテロ原子等を有する炭化水素基等」という場合がある。）を表す。前記炭化水素基の炭素数は１～２０であり、好ましくは１～１０、より好ましくは１～４である。また、ヘテロ原子等を有する炭化水素基の炭素数は１～２０であり、好ましくは１～１０、より好ましくは１～４である。前記ヘテロ原子とは、酸素、窒素又は硫黄等の原子を意味する。また、前記不飽和結合の数は１～１０の範囲が好ましく、１～５の範囲がより好ましく１～３の範囲が特に好ましい。 In the general formula (1), R 1 and R 2 have no halogen atom in the chemical structure. R 1 and R 2 are each independently a hydrocarbon group or a hydrocarbon group having at least one of a hetero atom or an unsaturated bond (hereinafter referred to as “hydrocarbon group having a hetero atom, etc.”). "). The hydrocarbon group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The hydrocarbon group having a hetero atom or the like has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The heteroatom means an atom such as oxygen, nitrogen or sulfur. Further, the number of unsaturated bonds is preferably in the range of 1 to 10, more preferably in the range of 1 to 5, and particularly preferably in the range of 1 to 3.
　前記炭化水素基又はヘテロ原子等を有する炭化水素基としては、具体的には、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の鎖状アルキル基、シクロペンチル基、シクロヘキシル基等の環状アルキル基、２－ヨードエチル基、２－ブロモエチル基、２－クロロエチル基、２－フルオロエチル基、１，２－ジヨードエチル基、１，２－ジブロモエチル基、１，２－ジクロロエチル基、１，２－ジフルオロエチル基、２，２－ジヨードエチル基、２，２－ジブロモエチル基、２，２－ジクロロエチル基、２，２－ジフルオロエチル基、２，２，２－トリブロモエチル基、２，２，２－トリクロロエチル基、２，２，２－トリフルオロエチル基、ヘキサフルオロ－２－プロピル基等の鎖状含ハロゲンアルキル基、２－ヨードシクロヘキシル基、２－ブロモシクロヘキシル基、２－クロロシクロヘキシル基、２－フルオロシクロヘキシル基等の環状含ハロゲンアルキル基、２－プロペニル基、イソプロペニル基、２－ブテニル基、３－ブテニル基等の鎖状アルケニル基、２－シクロペンテニル基、２－シクロヘキセニル基、３－シクロヘキセニル基等の環状アルケニル基、２－プロピニル基、１－ブチニル基、２－ブチニル基、３－ブチニル基、１－ペンチニル基、２－ペンチニル基、３－ペンチニル基、４－ペンチニル基等の鎖状アルキニル基、フェニル基、３－メトキシフェニル基、４－メトキシフェニル基、３，５－ジメトキシフェニル基、４－フェノキシフェニル基等のフェニル基、２－ヨードフェニル基、２－ブロモフェニル基、２－クロロフェニル基、２－フルオロフェニル基、３－ヨードフェニル基、３－ブロモフェニル基、３－クロロフェニル基、３－フルオロフェニル基、４－ヨードフェニル基、４－ブロモフェニル基、４－クロロフェニル基、４－フルオロフェニル基、３，５－ジヨードフェニル基、３，５－ジブロモフェニル基、３，５－ジクロロフェニル基、３，５－ジフルオロフェニル基等の含ハロゲンフェニル基、１－ナフチル基、２－ナフチル基、３－アミノ－２－ナフチル基等のナフチル基等が挙げられる。 Specific examples of the hydrocarbon group or the hydrocarbon group having a hetero atom include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. A cyclic alkyl group, a cyclic alkyl group such as cyclopentyl group, cyclohexyl group, 2-iodoethyl group, 2-bromoethyl group, 2-chloroethyl group, 2-fluoroethyl group, 1,2-diiodoethyl group, 1,2-dibromo Ethyl group, 1,2-dichloroethyl group, 1,2-difluoroethyl group, 2,2-diiodoethyl group, 2,2-dibromoethyl group, 2,2-dichloroethyl group, 2,2-difluoroethyl group, 2,2,2-tribromoethyl group, 2,2,2-trichloroethyl group, 2,2,2-trifluoroethyl group, hexafluoro- Chain-containing halogen-containing alkyl groups such as propyl groups, 2-iodocyclohexyl groups, 2-bromocyclohexyl groups, 2-chlorocyclohexyl groups, 2-fluorocyclohexyl groups and other halogen-containing alkyl groups, 2-propenyl groups, isopropenyls Groups, chain alkenyl groups such as 2-butenyl group and 3-butenyl group, cyclic alkenyl groups such as 2-cyclopentenyl group, 2-cyclohexenyl group and 3-cyclohexenyl group, 2-propynyl group, 1-butynyl group Chain alkynyl groups such as 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, phenyl group, 3-methoxyphenyl group, 4-methoxyphenyl Group, phenyl group such as 3,5-dimethoxyphenyl group, 4-phenoxyphenyl group, 2-iodof Nyl group, 2-bromophenyl group, 2-chlorophenyl group, 2-fluorophenyl group, 3-iodophenyl group, 3-bromophenyl group, 3-chlorophenyl group, 3-fluorophenyl group, 4-iodophenyl group, 4 -Including bromophenyl group, 4-chlorophenyl group, 4-fluorophenyl group, 3,5-diiodophenyl group, 3,5-dibromophenyl group, 3,5-dichlorophenyl group, 3,5-difluorophenyl group, etc. Examples thereof include a naphthyl group such as a halogenphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 3-amino-2-naphthyl group.
　さらに、前記Ｒ１とＲ２は何れもハロゲン原子を有しておらず、前記炭化水素基、又は前記ヘテロ原子等を有する炭化水素基の何れかであって、相互に結合して環状構造を形成していてもよい。この場合、前記炭化水素基又はヘテロ原子等を有する炭化水素基としては、具体的には、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、ノニレン基等の直鎖アルキレン基、シクロヘキシレン基、フェニレン基、ベンジレン基、ナフチレン基、アントラシレン基、ナフタシレン基、ペンタシレン基のような環状炭化水素基及びその一部または全部をヘテロ原子等に置き換えたもの等が挙げられる。 Furthermore, each of R 1 and R 2 does not have a halogen atom, and is any one of the hydrocarbon group or the hydrocarbon group having the heteroatom, and is bonded to each other to form a cyclic structure. It may be formed. In this case, the hydrocarbon group or the hydrocarbon group having a hetero atom or the like specifically includes, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, Non-ylene groups such as linear alkylene groups, cyclohexylene groups, phenylene groups, benzylene groups, naphthylene groups, anthracylene groups, naphthacylene groups, pentasilene groups, and some or all of them are replaced with heteroatoms, etc. And the like.
　前記Ｒ１とＲ２は、前記に例示した官能基群において、同種でもよく相互に異なっていてもよい。また前記に例示した官能基群は単なる例示に過ぎず、これらに限定されるものではない。 The R 1 and R 2 may be the same or different from each other in the functional group group exemplified above. Moreover, the functional group group illustrated above is only an illustration, and is not limited to these.
　尚、前記一般式（１）において、前記ｎは価数を表す。例えば、前記Ｍが１価のカチオンである場合はｎ＝１であり、２価のカチオンである場合はｎ＝２であり、３価のカチオンである場合はｎ＝３である。 In the general formula (1), n represents a valence. For example, when M is a monovalent cation, n = 1, when it is a divalent cation, n = 2, and when it is a trivalent cation, n = 3.
　前記一般式（１）で表される化合物の具体例としては、例えば、ジメチルリン酸リチウム、ジエチルリン酸リチウム、ジプロピルリン酸リチウム、ジブチルリン酸リチウム、ジペンチルリン酸リチウム、エチレンリン酸リチウム、ビナフチルリン酸リチウム、ジメチルリン酸ナトリウム、ジエチルリン酸ナトリウム、ジプロピルリン酸ナトリウム、ジブチルリン酸ナトリウム、ジペンチルリン酸ナトリウム、エチレンリン酸マグネシウム、ビナフチルリン酸マグネシウム、ジメチルリン酸マグネシウム、ジエチルリン酸マグネシウム、ジプロピルリン酸マグネシウム、ジブチルリン酸マグネシウム、ジペンチルリン酸マグネシウム、エチレンリン酸マグネシウム、ビナフチルリン酸マグネシウム、トリエチルメチルアンモニウムジメチルリン酸、トリエチルメチルアンモニウムジエチルリン酸、トリエチルメチルアンモニウムジプロピルリン酸、トリエチルメチルアンモニウムジブチルリン酸、トリエチルメチルアンモニウムジペンチルリン酸、トリエチルメチルアンモニウムエチレンリン酸、トリエチルメチルアンモニウムビナフチルリン酸等が挙げられる。但し、これらの化合物は単なる例示に過ぎず、本実施の形態は、これらに限定されるものではない。 Specific examples of the compound represented by the general formula (1) include, for example, lithium dimethyl phosphate, lithium diethyl phosphate, lithium dipropyl phosphate, lithium dibutyl phosphate, lithium dipentyl phosphate, lithium ethylene phosphate, and binaphthyl phosphate. Lithium, sodium dimethyl phosphate, sodium diethyl phosphate, sodium dipropyl phosphate, sodium dibutyl phosphate, sodium dipentyl phosphate, magnesium magnesium phosphate, magnesium binaphthyl phosphate, magnesium dimethyl phosphate, magnesium diethyl phosphate, magnesium dipropyl phosphate, dibutyl phosphorus Magnesium phosphate, magnesium dipentyl phosphate, magnesium magnesium phosphate, magnesium binaphthyl phosphate, triethylmethylammonium dimethyl ester Acid, triethyl methyl ammonium diethyl phosphate, triethyl methyl ammonium dipropyl phosphate, triethyl methyl ammonium dibutyl phosphate, triethyl methyl ammonium dipentyl phosphate, triethyl methyl ammonium ethylene phosphoric acid, and triethylmethylammonium binaphthyl phosphoric acid. However, these compounds are merely examples, and the present embodiment is not limited to these.
　尚、前記一般式（１）で表される化合物としては、入手しやすさの観点からは、ジエチルリン酸リチウムが好ましい。 The compound represented by the general formula (1) is preferably lithium diethyl phosphate from the viewpoint of availability.
　前記成分（Ａ）の添加量は、非水電解液の全質量に対し０．０５～５質量％の範囲内であることが好ましく、０．１～３質量％の範囲内であることがより好ましく、０．５～２質量％の範囲内であることがさらに好ましい。前記添加量を０．０５質量％以上にすることにより、二次電池の高温環境下でのサイクル特性を一層改善することができる。一方、前記添加量を５質量％以下にすることにより、非水電解液中の電解質の非水電解液溶媒に対する溶解性が低下するのを抑制することができる。 The amount of the component (A) added is preferably in the range of 0.05 to 5% by mass, more preferably in the range of 0.1 to 3% by mass with respect to the total mass of the non-aqueous electrolyte. Preferably, it is in the range of 0.5 to 2% by mass. By making the addition amount 0.05% by mass or more, cycle characteristics of the secondary battery in a high temperature environment can be further improved. On the other hand, by making the said addition amount 5 mass% or less, it can suppress that the solubility with respect to the nonaqueous electrolyte solvent of the electrolyte in a nonaqueous electrolyte solution falls.
　また、本実施の形態に於いて、成分（Ａ）は、少なくとも１種類が非水電解液中に含まれていればよいが、含有させる成分（Ａ）の種類の数は、好ましくは５種類以下であり、より好ましくは３種類以下であり、特に好ましくは２種類以下である。成分（Ａ）の種類を低減することにより、非水電解液の製造の際における工程の複雑化を抑制することができる。 In the present embodiment, at least one component (A) may be contained in the non-aqueous electrolyte, but the number of types of component (A) to be contained is preferably five. Or less, more preferably 3 or less, and particularly preferably 2 or less. By reducing the type of the component (A), it is possible to suppress complication of the process in the production of the nonaqueous electrolytic solution.
　＜成分（Ｂ）＞
　前記成分（Ｂ）は、下記一般式（２）で表される少なくとも１種のホウ素錯体塩、ホウ酸エステル、酸無水物、不飽和結合を有する環状カーボネート、ハロゲン原子を有する環状カーボネート、環状スルホン酸エステル、下記一般式（３）で表されるアセトアセチル基を有するアミン類及び下記一般式（４）～（７）の何れかで表されるリン化合物からなる群より選ばれる少なくとも１種の化合物である。 <Component (B)>
The component (B) includes at least one boron complex salt represented by the following general formula (2), boric acid ester, acid anhydride, cyclic carbonate having an unsaturated bond, cyclic carbonate having a halogen atom, and cyclic sulfone. At least one selected from the group consisting of acid esters, amines having an acetoacetyl group represented by the following general formula (3), and phosphorus compounds represented by any of the following general formulas (4) to (7) A compound.
　［ホウ素錯体塩］
　前記ホウ素錯体塩は、前述の通り、具体的には下記一般式（２）で表されるものである。 [Boron complex salt]
As described above, the boron complex salt is specifically represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
　前記一般式（２）において、Ｍｎ＋については、すでに説明した通りであり、アルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。従って、これらの詳細な説明は省略する。 In the general formula (2), M n + is as described above and represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. Therefore, detailed description thereof will be omitted.
　前記一般式（２）において、前記Ｘ１～Ｘ４はそれぞれ独立しており、任意に選択される１又は２つの組合せが、－ＯＯＣ－Ｙ－ＣＯＯ－、－Ｏ－Ｙ－Ｏ－又は－ＯＯＣ－Ｙ－Ｏ－の環状構造を形成したものを表す。その場合の前記Ｙは、炭素数が０～２０、好ましくは０～１０、より好ましくは０～１０の炭化水素基、又は炭素数が０～２０、好ましくは０～１０、より好ましくは０～５の範囲であって、ヘテロ原子、不飽和結合若しくは環状構造を有する炭化水素基を表す。前記Ｘ１～Ｘ４が前記－ＯＯＣ－Ｙ－ＣＯＯ－、－Ｏ－Ｙ－Ｏ－又は－ＯＯＣ－Ｙ－Ｏ－の環状構造の何れか１つを２組有する場合、それぞれのＹは異なっていてもよい。ここで、ヘテロ原子とは、酸素原子、窒素原子又は硫黄原子を意味する。 In the general formula (2), X 1 to X 4 are independent of each other, and one or two arbitrarily selected combinations can be represented by —OOC—Y—COO—, —O—Y—O— or — This represents an OOC-Y—O— cyclic structure. In this case, Y is a hydrocarbon group having 0 to 20, preferably 0 to 10, more preferably 0 to 10 carbon atoms, or 0 to 20, preferably 0 to 10, more preferably 0 to 10 carbon atoms. 5 represents a hydrocarbon group having a hetero atom, an unsaturated bond, or a cyclic structure. When X 1 to X 4 have two sets of any one of the cyclic structures of —OOC—Y—COO—, —O—Y—O—, and —OOC—Y—O—, each Y is different It may be. Here, the hetero atom means an oxygen atom, a nitrogen atom or a sulfur atom.
　前記Ｙとしては、具体的には、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、ノニレン基等の直鎖アルキレン基、ヨードメチレン基、ジヨードメチレン基、ブロモメチレン基、ジブロモメチレン基、フルオロメチレン基、ジフルオロメチレン基、ヨードエチレン基、１，１－ジヨードエチレン基、１，２－ジヨードエチレン基、トリヨードエチレン基、テトラヨードエチレン基、クロロエチレン基、１，１－ジクロロエチレン基、１，２－ジクロロエチレン基、トリクロロエチレン基、テトラクロロエチレン基、フルオロエチレン基、１，１－ジフルオロエチレン基、１，２－ジフルオロエチレン基、トリフルオロエチレン基、テトラフルオロエチレン基等の含ハロゲン直鎖アルキレン基、シクロヘキシレン基、フェニレン基、ベンジレン基、ナフチレン基、アントラシレン基、ナフタシレン基、ペンタシレン基のような環状炭化水素基及びその一部または全部をハロゲンに置き換えたもの等が挙げられる。 Specific examples of Y include, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and other linear alkylene groups, iodomethylene, di Iodomethylene, bromomethylene, dibromomethylene, fluoromethylene, difluoromethylene, iodoethylene, 1,1-diiodoethylene, 1,2-diiodoethylene, triiodoethylene, tetraiodoethylene Group, chloroethylene group, 1,1-dichloroethylene group, 1,2-dichloroethylene group, trichloroethylene group, tetrachloroethylene group, fluoroethylene group, 1,1-difluoroethylene group, 1,2-difluoroethylene group, trifluoroethylene group , Tetrafluoroethylene group, etc. Halogen straight chain alkylene group, cyclohexylene group, phenylene group, benzylene group, naphthylene group, anthracylene group, naphthacylene group, pentasilene group, etc. It is done.
　さらに、前記Ｙの炭素数が０の場合、－ＯＯＣ－Ｙ－ＣＯＯ－は－ＯＯＣ－ＣＯＯ－であり、オキサレート基を表す。また、前記Ｙが１，２－フェニレン基である場合、－Ｏ－Ｙ－Ｏ－はベンゼンジオラート基を表し、－Ｏ－Ｙ－ＣＯＯ－はサリチラート基を表す。 Furthermore, when the carbon number of Y is 0, —OOC—Y—COO— is —OOC—COO—, which represents an oxalate group. When Y is a 1,2-phenylene group, —O—Y—O— represents a benzenediolate group, and —O—Y—COO— represents a salicylate group.
　また、前記Ｘ１～Ｘ４は、それぞれ独立して、ハロゲン原子、炭素数０～２０、好ましくは０～１０、より好ましくは０～５のアルキル基、炭素数０～２０、好ましくは０～１０、より好ましくは０～５のアルコキシ基、炭素数が０～２０、好ましくは０～１０、より好ましくは０～５の範囲内であって、ハロゲン原子、ヘテロ原子、不飽和結合若しくは環状構造の少なくとも何れか１つを有するアルキル基、又は炭素数が０～２０、好ましくは０～１０、より好ましくは０～５の範囲内であって、ハロゲン原子、ヘテロ原子、不飽和結合若しくは環状構造の少なくとも何れか１つを有するアルコキシ基であってもよい。ここで、前記ハロゲン原子とは、フッ素原子、塩素原子、臭素原子又はヨウ素原子を意味する。また、ヘテロ原子とは、酸素原子、窒素原子又は硫黄原子を意味する。 X 1 to X 4 are each independently a halogen atom, an alkyl group having 0 to 20 carbon atoms, preferably 0 to 10, more preferably 0 to 5 carbon atoms, and 0 to 20 carbon atoms, preferably 0 to 0 carbon atoms. 10, more preferably 0-5 alkoxy groups, 0-20, preferably 0-10, more preferably 0-5 carbon atoms, halogen atoms, heteroatoms, unsaturated bonds or cyclic structures An alkyl group having at least one of the above, or a carbon number in the range of 0 to 20, preferably 0 to 10, more preferably 0 to 5, and a halogen atom, hetero atom, unsaturated bond or cyclic structure It may be an alkoxy group having at least one of the following. Here, the halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Moreover, a hetero atom means an oxygen atom, a nitrogen atom, or a sulfur atom.
　前記Ｘ１～Ｘ４は、具体的には、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の鎖状アルキル基、シクロペンチル基、シクロヘキシル基等の環状アルキル基、ヨードメチル基、ブロモメチル基、クロロメチル基、フルオロメチル基、ジヨードメチル基、ジブロモメチル基、ジクロロメチル基、ジフルオロメチル基、トリヨードメチル基、トリブロモメチル基、トリクロロメチル基、トリフルオロメチル基、２－ヨードエチル基、２－ブロモエチル基、２－クロロエチル基、２－フルオロエチル基、１，２－ジヨードエチル基、１，２－ジブロモエチル基、１，２－ジクロロエチル基、１，２－ジフルオロエチル基、２，２－ジヨードエチル基、２，２－ジブロモエチル基、２，２－ジクロロエチル基、２，２－ジフルオロエチル基、２，２，２－トリブロモエチル基、２，２，２－トリクロロエチル基、２，２，２－トリフルオロエチル基、ヘキサフルオロ－２－プロピル基等の鎖状含ハロゲンアルキル基、２－ヨードシクロヘキシル基、２－ブロモシクロヘキシル基、２－クロロシクロヘキシル基、２－フルオロシクロヘキシル基等の環状含ハロゲンアルキル基、２－プロペニル基、イソプロペニル基、２－ブテニル基、３－ブテニル基等の鎖状アルケニル基、２－シクロペンテニル基、２－シクロヘキセニル基、３－シクロヘキセニル基等の環状アルケニル基、２－プロピニル基、１－ブチニル基、２－ブチニル基、３－ブチニル基、１－ペンチニル基、２－ペンチニル基、３－ペンチニル基、４－ペンチニル基等の鎖状アルキニル基、フェニル基、３－メトキシフェニル基、４－メトキシフェニル基、３，５－ジメトキシフェニル基、４－フェノキシフェニル基等のフェニル基、２－ヨードフェニル基、２－ブロモフェニル基、２－クロロフェニル基、２－フルオロフェニル基、３－ヨードフェニル基、３－ブロモフェニル基、３－クロロフェニル基、３－フルオロフェニル基、４－ヨードフェニル基、４－ブロモフェニル基、４－クロロフェニル基、４－フルオロフェニル基、３，５－ジヨードフェニル基、３，５－ジブロモフェニル基、３，５－ジクロロフェニル基、３，５－ジフルオロフェニル基等の含ハロゲンフェニル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペントキシ基、ヘキソキシ基等の鎖状アルコキシ基、シクロペントキシ基、シクロヘキソキシ基等の環状アルコキシ基、２－ヨードエトキシ基、２－ブロモエトキシ基、２－クロロエトキシ基、２－フルオロエトキシ基、１，２－ジヨードエトキシ基、１，２－ジブロモエトキシ基、１，２－ジクロロエトキシ基、１，２－ジフルオロエトキシ基、２，２－ジヨードエトキシ基、２，２－ジブロモエトキシ基、２，２－ジクロロエトキシ基、２，２－ジフルオロエトキシ基、２，２，２－トリブロモエトキシ基、２，２，２－トリクロロエトキシ基、２，２，２－トリフルオロエトキシ基、ヘキサフルオロ－２－プロポキシ基等の鎖状含ハロゲンアルコキシ基、２－ヨードシクロヘキソキシ基、２－ブロモシクロヘキソキシ基、２－クロロシクロヘキソキシ基、２－フルオロシクロヘキソキシ基等の環状含ハロゲンアルコキシ基、２－プロペノキシ基、イソプロペノキシ基、２－ブテノキシ基、３－ブテノキシ基等の鎖状アルケニルアルコキシ基、２－シクロペンテノキシ基、２－シクロヘキセノキシ基、３－シクロヘキセノキシ基等の環状アルケニルアルコキシ基、２－プロピノキシ基、１－ブチノキシ基、２－ブチノキシ基、３－ブチノキシ基、１－ペンチノキシ基、２－ペンチノキシ基、３－ペンチノキシ基、４－ペンチノキシ基等の鎖状アルキニルアルコキシ基、フェノキシ基、３－メチルフェノキシ基、４－メチルフェノキシ基、３，５－ジメチルフェノキシ基等のフェノキシ基、２－ヨードフェノキシ基、２－ブロモフェノキシ基、２－クロロフェノキシ基、２－フルオロフェノキシ基、３－ヨードフェノキシ基、３－ブロモフェノキシ基、３－クロロフェノキシ基、３－フルオロフェノキシ基、４－ヨードフェノキシ基、４－ブロモフェノキシ基、４－クロロフェノキシ基、４－フルオロフェノキシ基、３，５－ジヨードフェノキシ基、３，５－ジブロフェノキシ基、３，５－ジクロロフェノキシ基、３，５－ジフルオロフェノキシ基等の含ハロゲンフェノキシ基等が挙げられる。 Specific examples of X 1 to X 4 include a chain alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and a cyclopentyl group. Cycloalkyl group such as cyclohexyl group, iodomethyl group, bromomethyl group, chloromethyl group, fluoromethyl group, diiodomethyl group, dibromomethyl group, dichloromethyl group, difluoromethyl group, triiodomethyl group, tribromomethyl group, trichloromethyl Group, trifluoromethyl group, 2-iodoethyl group, 2-bromoethyl group, 2-chloroethyl group, 2-fluoroethyl group, 1,2-diiodoethyl group, 1,2-dibromoethyl group, 1,2-dichloroethyl group 1,2-difluoroethyl group, 2,2-diiodoethyl group, 2,2-dibu Moethyl group, 2,2-dichloroethyl group, 2,2-difluoroethyl group, 2,2,2-tribromoethyl group, 2,2,2-trichloroethyl group, 2,2,2-trifluoroethyl group A chain halogen-containing alkyl group such as hexafluoro-2-propyl group, a cyclic halogen-containing alkyl group such as 2-iodocyclohexyl group, 2-bromocyclohexyl group, 2-chlorocyclohexyl group, 2-fluorocyclohexyl group, 2- Chain alkenyl groups such as propenyl group, isopropenyl group, 2-butenyl group and 3-butenyl group, cyclic alkenyl groups such as 2-cyclopentenyl group, 2-cyclohexenyl group and 3-cyclohexenyl group, 2-propynyl group 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group Chain alkynyl group such as 4-pentynyl group, phenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3,5-dimethoxyphenyl group, phenyl group such as 4-phenoxyphenyl group, 2-iodophenyl group, 2-bromophenyl group, 2-chlorophenyl group, 2-fluorophenyl group, 3-iodophenyl group, 3-bromophenyl group, 3-chlorophenyl group, 3-fluorophenyl group, 4-iodophenyl group, 4-bromophenyl , Halogen-containing phenyl groups such as 4-chlorophenyl group, 4-fluorophenyl group, 3,5-diiodophenyl group, 3,5-dibromophenyl group, 3,5-dichlorophenyl group, 3,5-difluorophenyl group Chain alcohol such as methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexoxy group, etc. Cyclic alkoxy groups such as xy group, cyclopentoxy group, cyclohexoxy group, 2-iodoethoxy group, 2-bromoethoxy group, 2-chloroethoxy group, 2-fluoroethoxy group, 1,2-diiodoethoxy group, 1,2-dibromoethoxy group, 1,2-dichloroethoxy group, 1,2-difluoroethoxy group, 2,2-diiodoethoxy group, 2,2-dibromoethoxy group, 2,2-dichloroethoxy group, 2 , 2-difluoroethoxy group, 2,2,2-tribromoethoxy group, 2,2,2-trichloroethoxy group, 2,2,2-trifluoroethoxy group, hexafluoro-2-propoxy group, etc. Halogen-containing alkoxy group, 2-iodocyclohexoxy group, 2-bromocyclohexoxy group, 2-chlorocyclohexoxy group, 2-fluorocyclohex Cyclic halogen-containing alkoxy groups such as xy group, 2-propenoxy group, isopropenoxy group, 2-butenoxy group, chain alkenylalkoxy group such as 3-butenoxy group, 2-cyclopentenoxy group, 2-cyclohexenoxy group, Cyclic alkenylalkoxy groups such as 3-cyclohexenoxy group, 2-propynoxy group, 1-butynoxy group, 2-butynoxy group, 3-butynoxy group, 1-pentynoxy group, 2-pentynoxy group, 3-pentynoxy group, 4- Chain alkynylalkoxy groups such as pentynoxy group, phenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, phenoxy group such as 3,5-dimethylphenoxy group, 2-iodophenoxy group, 2-bromophenoxy group, 2 -Chlorophenoxy group, 2-fluorophenoxy group, 3-iodophenoxy group 3-bromophenoxy group, 3-chlorophenoxy group, 3-fluorophenoxy group, 4-iodophenoxy group, 4-bromophenoxy group, 4-chlorophenoxy group, 4-fluorophenoxy group, 3,5-diiodophenoxy group And halogen-containing phenoxy groups such as 3,5-dibrophenoxy group, 3,5-dichlorophenoxy group, and 3,5-difluorophenoxy group.
　尚、前記ホウ素錯体塩は、入手しやすさの観点からは、リチウムビスオキサラトボレート、トリエチルメチルアンモニウムビスオキサラトボレート、リチウムビスサリチラートボレート又はリチウムビス［１，２’－ベンジオラート（２）－Ｏ，Ｏ’］ボレートが好ましい。 From the viewpoint of easy availability, the boron complex salt is lithium bisoxalatoborate, triethylmethylammonium bisoxalatoborate, lithium bissalicylate borate or lithium bis [1,2'-benziolate (2). -O, O '] borate is preferred.
　尚、前記一般式（２）における前記ｎは、前記一般式（１）の場合と同様、価数を表す。 In addition, the said n in the said General formula (2) represents a valence similarly to the case of the said General formula (1).
　［ホウ酸エステル］
　前記ホウ酸エステルとしては、本実施の形態の非水電解液及びそれを用いた二次電池の特性を損なうものでなければ、その種類に特に制限はなく、種々のものを選択することができる。具体的には、例えば、ホウ酸トリメチル、ホウ酸トリエチル、ホウ酸トリイソプロピル、ホウ酸トリブチル、ホウ酸トリペンチル、ホウ酸トリヘキシル、ホウ酸トリへプチル、ホウ酸トリフェニル、２ホウ酸トリス（２，２，２－ヨードエチル）、ホウ酸トリス（２，２，２－トリブロモエチル）、ホウ酸トリス（２，２，２－トリクロロエチル）ホウ酸トリス（２，２，２－トリフルオロエチル）ホウ酸トリス（４－ヨードフェニル）、ホウ酸トリス（４－ブロモフェニル）、ホウ酸トリス（４－クロロフェニル）、ホウ酸トリス（４－フルオロフェニル）、ホウ酸ジエチルメチル、ホウ酸エチルジメチル等が挙げられる。 [Borate ester]
The borate ester is not particularly limited as long as it does not impair the characteristics of the nonaqueous electrolytic solution of the present embodiment and the secondary battery using the boric acid ester, and various types can be selected. . Specifically, for example, trimethyl borate, triethyl borate, triisopropyl borate, tributyl borate, tripentyl borate, trihexyl borate, triheptyl borate, triphenyl borate, tris borate (2, 2,2-iodoethyl), tris (2,2,2-tribromoethyl) borate, tris (2,2,2-trichloroethyl) borate, tris (2,2,2-trifluoroethyl) borate Examples include tris (4-iodophenyl) acid, tris (4-bromophenyl) borate, tris (4-chlorophenyl) borate, tris (4-fluorophenyl) borate, diethylmethylborate, ethyldimethylborate, and the like. It is done.
　［酸無水物］
　前記酸無水物としては、本実施の形態の非水電解液及びそれを用いた二次電池の特性を損なうものでなければ、その種類に特に制限はなく、種々のものを選択することができる。具体的には、例えば、酢酸無水物、プロピオン酸無水物、酪酸無水物、吉草酸無水物、ヘキサン酸無水物、へプタン酸無水物、オクタン酸無水物、ノナン酸無水物、デカン酸無水物、エイコサン酸無水物、ドコサン酸無水物、安息香酸無水物、４－メトキシ安息香酸無水物、ジフェニル酢酸無水物、クロトン酸無水物、シクロヘキサンカルボン酸無水物、エライジン酸無水物、イソ酪酸無水物、イソ吉草酸無水物、ラウリン酸無水物、リノール酸無水物、ミリスチン酸無水物、アンゲリカ酸無水物、クロロジフルオロ酢酸無水物、トリクロロ酢酸無水物、ジフルオロ酢酸無水物、トリフルオロ酢酸無水物、４－トリフルオロメチル安息香酸無水物などの直鎖カルボン酸無水物、フタル酸無水物、３－アセトアミドフタル酸無水物、４，４’－カルボニルジフタル酸無水物、４，４’－ビフタル酸無水物、３－ヨードフタル酸無水物、３－ブロモフタル酸無水物、３－クロロフタル酸無水物、３－フルオロフタル酸無水物、４－ヨードフタル酸無水物、４－ブロモフタル酸無水物、４－クロロフタル酸無水物、４－クロロフタル酸無水物、４，５－ジヨードフタル酸無水物、４，５－ジブロモフタル酸無水物、４，５－ジクロロフタル酸無水物、４，５－ジフルオロフタル酸無水物、４，４’－スルホニルジフタル酸無水物、３－ニトロフタル酸無水物、４－ニトロフタル酸無水物、ｅｘｏ－３，６－エポキシヘキサヒドロフタル酸無水物、ｅｘｏ－３，６－エポキシ－１，２，３，６－テトラヒドロフタル酸無水物、テトラヨードフタル酸無水物、テトラクロロフタル酸無水物、テトラフルオロフタル酸無水物、４－ｔｅｒｔ－ブチルフタル酸無水物、４－エチニルフタル酸無水物、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物、コハク酸無水物、（Ｒ）－（＋）－２－アセトキシコハク酸無水物、（Ｓ）－（－）－２－アセトキシコハク酸無水物、２－ブテン－１－イルコハク酸無水物、ブチルコハク酸無水物、デシルコハク酸無水物、２，３－ジメチルコハク酸無水物、２－ドデセン－１－イルコハク酸無水物、ドデシルコハク酸無水物、オクタデセニコハク酸無水物、（２，７－オクタジエン－１－イル）コハク酸無水物、ｎ－オクチルコハク酸無水物、ヘキサデシルコハク酸無水物、マレイン酸無水物、２，３－ビス（２，４，５－トリメチル－３－チエニル）マレイン酸無水物、２－（－２－カルボキシエチル）－３－メチル－マレイン酸無水物、２，３－ジメチルマレイン酸無水物、２，３－ジフェニルマレイン酸無水物、フェニルマレイン酸無水物、４－ペンテン－１，２－ジカルボン酸無水物、２，３－アントラセンジカルボン酸無水物、ビシクロ［２，２，２］オクト－５－エン－２，３－ジカルボン酸無水物、４－ブロモ－１，８－ナフタレンジカルボン酸無水物、（±）－ｔｒａｎｓ－１，２－シクロヘキサンジカルボン酸無水物、ｃｉｓ－４－シクロヘキセン－１，２－ジカルボン酸無水物、２，５－ジブロモ－３，４－チオフェンジカルボン酸無水物、５，６－ジヒドロ－１，４－ジチイン－２，３－ジカルボン酸無水物、２，２’－ビフェニルジカルボン酸無水物、４－メチルシクロヘキサン－１，２－ジカルボン酸無水物、３－メチル－４－シクロヘキセン－１，２－ジカルボン酸無水物、４－メチル－４－シクロヘキセン－１，２－ジカルボン酸無水物、２，３－ナフタレンジカルボン酸無水物、３，４－チオフェンジカルボン酸無水物、１，８－ナフタレンジカルボン酸無水物、５－ノルボネン－２，３－ジカルボン酸無水物、１，２－シクロプロパンジカルボン酸無水物、グルタル酸無水物、３，３－ペンタメチレングルタル酸無水物、２，２－ジメチルグルタル酸無水物、３，３－ジメチルグルタル酸無水物、３－メチルグルタル酸無水物、２－フタルイミドグルタル酸無水物、３，３－テトラメチレングルタル酸無水物、Ｎ－メチルイサト酸無水物、４－ヨードイサト酸無水物、４－ブロモイサト酸無水物、４－クロロイサト酸無水物、４－フルオロイサト酸無水物、５－ヨードイサト酸無水物、５－ブロモイサト酸無水物、５－クロロイサト酸無水物、５－フルオロイサト酸無水物、イタコン酸無水物、カロン酸無水物、シトラコン酸無水物、ジグリコール酸無水物、１，２－ナフタル酸無水物、ピロメリット酸無水物、ヘット酸無水物、２，２，３，３，４，４－ヘキサフルオロペンタン二酸無水物などの環状カルボンサン無水物、トリフルオロメタンスルホン酸無水物、ｐ－トルエンスルホン酸無水物などの直鎖スルホン酸無水物、２－スルホ安息香酸無水物、テトラヨード－Ｏ－スルホ安息香酸無水物、テトラブロモ－Ｏ－スルホ安息香酸無水物、テトラクロロ－Ｏ－スルホ安息香酸無水物、テトラフルオロ－Ｏ－スルホ安息香酸無水物などの環状スルホン酸無水物、ジフェニルホスフィン酸などの鎖状ホスフィン酸無水物、１－プロパンホスホン酸無水物などの環状ホスホン酸無水物、３．４－ジヨードフェニルボロン酸無水物、３，４－ジブロモフェニルボロン酸無水物、３，４－ジクロロフェニルボロン酸無水物、３，４－ジフルオロフェニルボロン酸無水物、４－ヨードフェニルボロン酸無水物、４－ブロモフェニルボロン酸無水物、４－クロロフェニルボロン酸無水物、４－フルオロフェニルボロン酸無水物、（ｍ－ターフェニルボロン酸無水物、３，４，５－トリヨードフェニルボロン酸無水物、３，４，５－トリブロモフェニルボロン酸無水物、３，４，５－トリクロロフェニルボロン酸無水物、３，４，５－トリフルオロフェニルボロン酸無水物等が挙げられる。 [Acid anhydride]
The acid anhydride is not particularly limited as long as it does not impair the characteristics of the nonaqueous electrolytic solution of the present embodiment and the secondary battery using the acid anhydride, and various types can be selected. . Specifically, for example, acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride, octanoic anhydride, nonanoic anhydride, decanoic anhydride Eicosanoic anhydride, docosanoic anhydride, benzoic anhydride, 4-methoxybenzoic anhydride, diphenylacetic anhydride, crotonic anhydride, cyclohexanecarboxylic anhydride, elaidic anhydride, isobutyric anhydride, Isovaleric anhydride, lauric anhydride, linoleic anhydride, myristic anhydride, angelic anhydride, chlorodifluoroacetic anhydride, trichloroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, 4- Linear carboxylic anhydride such as trifluoromethylbenzoic anhydride, phthalic anhydride, 3-acetamidophthalic anhydride, 4,4'-ca Rubonyl diphthalic anhydride, 4,4'-biphthalic anhydride, 3-iodophthalic anhydride, 3-bromophthalic anhydride, 3-chlorophthalic anhydride, 3-fluorophthalic anhydride, 4-iodophthalic anhydride 4-bromophthalic anhydride, 4-chlorophthalic anhydride, 4-chlorophthalic anhydride, 4,5-diiodophthalic anhydride, 4,5-dibromophthalic anhydride, 4,5-dichlorophthalic anhydride 4,5-difluorophthalic anhydride, 4,4'-sulfonyldiphthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, exo-3,6-epoxyhexahydrophthalic anhydride Exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, tetraiodophthalic anhydride, tetrachlorophthalic anhydride, tetra Fluorophthalic anhydride, 4-tert-butylphthalic anhydride, 4-ethynylphthalic anhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, succinic anhydride, (R)-(+) -2-acetoxy succinic anhydride, (S)-(-)-2-acetoxy succinic anhydride, 2-buten-1-yl succinic anhydride, butyl succinic anhydride, decyl succinic anhydride, 2,3- Dimethyl succinic anhydride, 2-dodecen-1-yl succinic anhydride, dodecyl succinic anhydride, octadecenic succinic anhydride, (2,7-octadien-1-yl) succinic anhydride, n-octyl Succinic anhydride, hexadecyl succinic anhydride, maleic anhydride, 2,3-bis (2,4,5-trimethyl-3-thienyl) maleic anhydride, 2-(-2-carbon Boxyethyl) -3-methyl-maleic anhydride, 2,3-dimethylmaleic anhydride, 2,3-diphenylmaleic anhydride, phenylmaleic anhydride, 4-pentene-1,2-dicarboxylic anhydride 2,3-anthracene dicarboxylic acid anhydride, bicyclo [2,2,2] oct-5-ene-2,3-dicarboxylic acid anhydride, 4-bromo-1,8-naphthalenedicarboxylic acid anhydride, (± ) -Trans-1,2-cyclohexanedicarboxylic acid anhydride, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride, 2,5-dibromo-3,4-thiophenedicarboxylic acid anhydride, 5,6-dihydro -1,4-dithiin-2,3-dicarboxylic acid anhydride, 2,2′-biphenyldicarboxylic acid anhydride, 4-methylcyclohexane-1,2-dicarboxylic acid Water, 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 3,4 -Thiophene dicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 1,2-cyclopropanedicarboxylic acid anhydride, glutaric acid anhydride, 3,3- Pentamethylene glutaric anhydride, 2,2-dimethyl glutaric anhydride, 3,3-dimethyl glutaric anhydride, 3-methyl glutaric anhydride, 2-phthalimido glutaric anhydride, 3,3-tetramethylene glutar Acid anhydride, N-methyl isatoic anhydride, 4-iodo isatoic anhydride, 4-bromo isatoic anhydride, 4-chloro isatoic anhydride, 4-full Leusatoic anhydride, 5-iodoisatoic anhydride, 5-bromoisatoic anhydride, 5-chloroisatoic anhydride, 5-fluoroisatoic anhydride, itaconic anhydride, caronic anhydride, citraconic anhydride, di Cyclic carboxylic acid anhydrides such as glycolic anhydride, 1,2-naphthalic anhydride, pyromellitic anhydride, het acid anhydride, 2,2,3,3,4,4-hexafluoropentanedioic anhydride , Trifluoromethanesulfonic anhydride, linear sulfonic anhydride such as p-toluenesulfonic anhydride, 2-sulfobenzoic anhydride, tetraiodo-O-sulfobenzoic anhydride, tetrabromo-O-sulfobenzoic acid Cyclic sulfonic anhydrides such as anhydrides, tetrachloro-O-sulfobenzoic anhydride, tetrafluoro-O-sulfobenzoic anhydride, diphenyl Chain phosphinic anhydride such as phosphinic acid, cyclic phosphonic anhydride such as 1-propanephosphonic anhydride, 3.4-diiodophenylboronic anhydride, 3,4-dibromophenylboronic anhydride, 3 , 4-dichlorophenylboronic acid anhydride, 3,4-difluorophenylboronic acid anhydride, 4-iodophenylboronic acid anhydride, 4-bromophenylboronic acid anhydride, 4-chlorophenylboronic acid anhydride, 4-fluorophenyl Boronic anhydride, (m-terphenylboronic anhydride, 3,4,5-triiodophenylboronic anhydride, 3,4,5-tribromophenylboronic anhydride, 3,4,5-tri Examples thereof include chlorophenylboronic acid anhydride and 3,4,5-trifluorophenylboronic acid anhydride.
　［不飽和結合を有する環状カーボネート］
　前記不飽和結合を有する環状カーボネートとしては、本実施の形態の非水電解液及びそれを用いた二次電池の特性を損なうものでなければ、その種類に特に制限はなく、種々のものを選択することができる。前記不飽和結合の数は１～１０が好ましく、１～５がより好ましく、１～３が特に好ましい。不飽和結合を有する環状カーボネートとしては、具体的には、例えば、ビニレンカーボネート、ヨードビニレンカーボネート、ブロモビニレンカーボネート、クロロビニレンカーボネート、フルオロビニレンカーボネート、１，２－ジヨードビニレンカーボネート、１，２－ジブロモビニレンカーボネート、１，２－ジクロロビニレンカーボネート、１，２－ジフルオロビニレンカーボネート、メチルビニレンカーボネート、ヨードメチルビニレンカーボネート、ブロモメチルビニレンカーボネート、クロロメチルビニレンカーボネート、フルオロメチルビニレンカーボネート、ジクロロメチルビニレンカーボネート、ジブロモメチルビニレンカーボネート、ジクロロメチルビニレンカーボネート、ジフルオロメチルビニレンカーボネート、トリヨードメチルビニレンカーボネート、トリブロモメチルビニレンカーボネート、トリクロロメチルビニレンカーボネート、トリフルオロメチルビニレンカーボネート、エチルビニレンカーボネート、プロピルビニレンカーボネート、ブチルビニレンカーボネート、ジメチルビニレンカーボネート、ジエチルビニレンカーボネート、ジプロピルビニレンカーボネート、ビニルエチレンカーボネート等が挙げられる。 [Cyclic carbonate having an unsaturated bond]
The cyclic carbonate having an unsaturated bond is not particularly limited as long as the characteristics of the nonaqueous electrolytic solution of the present embodiment and the secondary battery using the cyclic carbonate are not impaired, and various types are selected. can do. The number of unsaturated bonds is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Specific examples of the cyclic carbonate having an unsaturated bond include vinylene carbonate, iodovinylene carbonate, bromovinylene carbonate, chlorovinylene carbonate, fluorovinylene carbonate, 1,2-diiodovinylene carbonate, 1,2-dibromo. Vinylene carbonate, 1,2-dichlorovinylene carbonate, 1,2-difluorovinylene carbonate, methyl vinylene carbonate, iodomethyl vinylene carbonate, bromomethyl vinylene carbonate, chloromethyl vinylene carbonate, fluoromethyl vinylene carbonate, dichloromethyl vinylene carbonate, dibromomethyl Vinylene carbonate, dichloromethyl vinylene carbonate, difluoromethyl vinylene carbonate, Riodomethyl vinylene carbonate, tribromomethyl vinylene carbonate, trichloromethyl vinylene carbonate, trifluoromethyl vinylene carbonate, ethyl vinylene carbonate, propyl vinylene carbonate, butyl vinylene carbonate, dimethyl vinylene carbonate, diethyl vinylene carbonate, dipropyl vinylene carbonate, vinyl ethylene And carbonate.
　［ハロゲン原子を有する環状カーボネート］
　前記ハロゲン原子を有する環状カーボネートとしては、本実施の形態の非水電解液及びそれを用いた二次電池の特性を損なうものでなければ、その種類に特に制限はなく、種々のものを選択することができる。ここで、ハロゲン原子とは、フッ素原子、塩素原子、臭素原子又はヨウ素原子を意味する。ハロゲン原子を有する環状カーボネートとしては、具体的には、例えば、ヨードエチレンカーボネート、ブロモエチレンカーボネート、クロロエチレンカーボネート、フルオロエチレンカーボネート、１，２－ジヨードエチレンカーボネート、１，２－ジブロモエチレンカーボネート、１，２－ジクロロエチレンカーボネート、１，２－ジフルオロエチレンカーボネート等が挙げられる。 [Cyclic carbonate having a halogen atom]
The cyclic carbonate having a halogen atom is not particularly limited as long as it does not impair the characteristics of the nonaqueous electrolytic solution of the present embodiment and the secondary battery using the same, and various types are selected. be able to. Here, the halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Specific examples of the cyclic carbonate having a halogen atom include iodoethylene carbonate, bromoethylene carbonate, chloroethylene carbonate, fluoroethylene carbonate, 1,2-diiodoethylene carbonate, 1,2-dibromoethylene carbonate, 1 2,2-dichloroethylene carbonate, 1,2-difluoroethylene carbonate, and the like.
　［環状スルホン酸エステル］
　前記環状スルホン酸エステルとしては、本実施の形態の非水電解液及びそれを用いた二次電池の特性を損なうものでなければ、その種類に特に制限はなく、種々のものを選択することができる。環状スルホン酸エステルとしては、具体的には、例えば、１，３－プロパンスルトン、２，４－ブタンスルトン、１，４－ブタンスルトン、エチレンサルファイト等が挙げられる。 [Cyclic sulfonate ester]
The cyclic sulfonic acid ester is not particularly limited as long as it does not impair the characteristics of the nonaqueous electrolytic solution of the present embodiment and the secondary battery using the same, and various types can be selected. it can. Specific examples of the cyclic sulfonic acid ester include 1,3-propane sultone, 2,4-butane sultone, 1,4-butane sultone, ethylene sulfite, and the like.
　［アセトアセチル基を有するアミン類］
　前記アセトアセチル基を有するアミン類は、具体的には、下記一般式（３）で表されるものである。 [Amines having an acetoacetyl group]
The amines having the acetoacetyl group are specifically represented by the following general formula (3).
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
　前記Ｒ３及びＲ４は、それぞれ独立して、炭素数が１～２０、好ましくは１～１０、より好ましくは１～５の炭化水素基、又は炭素数が１～２０、好ましくは１～１０、より好ましくは１～５の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合を有する炭化水素基を表す。ここで、前記ハロゲン原子とは、フッ素原子、塩素原子、臭素原子又はヨウ素原子を意味する。また、ヘテロ原子とは、酸素原子、窒素原子又は硫黄原子を意味する。 R 3 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, or 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. More preferably, it is in the range of 1 to 5 and represents a halogen atom, a hetero atom or a hydrocarbon group having an unsaturated bond. Here, the halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Moreover, a hetero atom means an oxygen atom, a nitrogen atom, or a sulfur atom.
　前記Ｒ３及びＲ４としては、具体的には、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の鎖状アルキル基、シクロペンチル基、シクロヘキシル基等の環状アルキル基、２－ヨードエチル基、２－ブロモエチル基、２－クロロエチル基、２－フルオロエチル基、１，２－ジヨードエチル基、１，２－ジブロモエチル基、１，２－ジクロロエチル基、１，２－ジフルオロエチル基、２，２－ジヨードエチル基、２，２－ジブロモエチル基、２，２－ジクロロエチル基、２，２－ジフルオロエチル基、２，２，２－トリブロモエチル基、２，２，２－トリクロロエチル基、２，２，２－トリフルオロエチル基、ヘキサフルオロ－２－プロピル基等の鎖状含ハロゲンアルキル基、２－ヨードシクロヘキシル基、２－ブロモシクロヘキシル基、２－クロロシクロヘキシル基、２－フルオロシクロヘキシル基等の環状含ハロゲンアルキル基、２－プロペニル基、イソプロペニル基、２－ブテニル基、３－ブテニル基等の鎖状アルケニル基、２－シクロペンテニル基、２－シクロヘキセニル基、３－シクロヘキセニル基等の環状アルケニル基、２－プロピニル基、１－ブチニル基、２－ブチニル基、３－ブチニル基、１－ペンチニル基、２－ペンチニル基、３－ペンチニル基、４－ペンチニル基等の鎖状アルキニル基、フェニル基、３－メトキシフェニル基、４－メトキシフェニル基、３，５－ジメトキシフェニル基、４－フェノキシフェニル基等のフェニル基、２－ヨードフェニル基、２－ブロモフェニル基、２－クロロフェニル基、２－フルオロフェニル基、３－ヨードフェニル基、３－ブロモフェニル基、３－クロロフェニル基、３－フルオロフェニル基、４－ヨードフェニル基、４－ブロモフェニル基、４－クロロフェニル基、４－フルオロフェニル基、３，５－ジヨードフェニル基、３，５－ジブロモフェニル基、３，５－ジクロロフェニル基、３，５－ジフルオロフェニル基等の含ハロゲンフェニル基、１－ナフチル基、２－ナフチル基、３－アミノ－２－ナフチル基等のナフチル基等が挙げられる。 Examples of R 3 and R 4, specifically, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a pentyl group, a hexyl group, a heptyl group, a chain alkyl group such as octyl, cyclopentyl Group, cyclic alkyl group such as cyclohexyl group, 2-iodoethyl group, 2-bromoethyl group, 2-chloroethyl group, 2-fluoroethyl group, 1,2-diiodoethyl group, 1,2-dibromoethyl group, 1,2- Dichloroethyl group, 1,2-difluoroethyl group, 2,2-diiodoethyl group, 2,2-dibromoethyl group, 2,2-dichloroethyl group, 2,2-difluoroethyl group, 2,2,2-tri Chain-containing halogen such as bromoethyl group, 2,2,2-trichloroethyl group, 2,2,2-trifluoroethyl group, hexafluoro-2-propyl group A cyclic halogen-containing alkyl group such as an alkyl group, 2-iodocyclohexyl group, 2-bromocyclohexyl group, 2-chlorocyclohexyl group, 2-fluorocyclohexyl group, 2-propenyl group, isopropenyl group, 2-butenyl group, 3- Chain alkenyl groups such as butenyl group, cyclic alkenyl groups such as 2-cyclopentenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl Groups, chain alkynyl groups such as 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, phenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3,5-dimethoxyphenyl group Phenyl group such as 4-phenoxyphenyl group, 2-iodophenyl group, 2-bromophenyl group, 2 -Chlorophenyl group, 2-fluorophenyl group, 3-iodophenyl group, 3-bromophenyl group, 3-chlorophenyl group, 3-fluorophenyl group, 4-iodophenyl group, 4-bromophenyl group, 4-chlorophenyl group, Halogen-containing phenyl groups such as 4-fluorophenyl group, 3,5-diiodophenyl group, 3,5-dibromophenyl group, 3,5-dichlorophenyl group, 3,5-difluorophenyl group, 1-naphthyl group, 2 A naphthyl group such as a -naphthyl group and a 3-amino-2-naphthyl group;
　前記Ｒ３及びＲ４は、同種でもよく相互に異なっていてもよい。また前記に例示した官能基群は単なる例示に過ぎず、本実施の形態はこれらに限定されるものではない。 R 3 and R 4 may be the same or different from each other. Moreover, the functional group group illustrated above is only a mere illustration, and this Embodiment is not limited to these.
　前記一般式（３）で表される化合物の具体例としては、例えば、Ｎ，Ｎ－ジメチルアセトアセトアミド、Ｎ，Ｎ－ジエチルアセトアセトアミド、Ｎ，Ｎ－ジプロピルアセトアセトアミド、Ｎ，Ｎ－ジブチルアセトアセトアミド、Ｎ，Ｎ－エチルメチルアセトアセトアミド、Ｎ，Ｎ－メチルプルピルアセトアセトアミド、Ｎ，Ｎ－ブチルメチルアセトアセトアミド等が挙げられる。但し、これらの化合物は単なる例示に過ぎず、本実施の形態はこれらに限定されるものではない。 Specific examples of the compound represented by the general formula (3) include, for example, N, N-dimethylacetoacetamide, N, N-diethylacetoacetamide, N, N-dipropylacetoacetamide, N, N-dibutylacetamide. Examples include acetamide, N, N-ethylmethylacetoacetamide, N, N-methylpropylacetoacetamide, N, N-butylmethylacetoacetamide and the like. However, these compounds are merely examples, and the present embodiment is not limited to these.
　［一般式（４）で表されるリン化合物］
　下記一般式（４）において、Ｍｎ＋については、すでに説明した通りであり、アルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。従って、これらの詳細な説明は省略する。 [Phosphorus compound represented by general formula (4)]
In the following general formula (4), M n + is as described above and represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion or an onium ion. Therefore, detailed description thereof will be omitted.
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
　前記Ａ１及びＡ２は、それぞれ独立して、酸素原子、硫黄原子又はセレン原子を表す。 Wherein A 1 and A 2 each independently represent an oxygen atom, a sulfur atom or a selenium atom.
　前記一般式（４）に於いて、前記Ｘ５及びＸ６は、それぞれ独立して、ハロゲン原子、アルキル基、又はハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基（以下、「ハロゲン原子等を有するアルキル基」という。）を表す。アルキル基、及びハロゲン原子等を有するアルキル基の炭素数は１～２０の範囲であり、好ましくは１～１０、より好ましくは１～４である。また、前記不飽和結合の数は１～１０の範囲が好ましく、１～５の範囲がより好ましく、１～３の範囲が特に好ましい。 In the general formula (4), each of X 5 and X 6 independently represents a halogen atom, an alkyl group, or an alkyl group having at least one of a halogen atom, a hetero atom and an unsaturated bond ( Hereinafter, it is referred to as an “alkyl group having a halogen atom”. The carbon number of the alkyl group and the alkyl group having a halogen atom or the like is in the range of 1 to 20, preferably 1 to 10, and more preferably 1 to 4. The number of unsaturated bonds is preferably in the range of 1 to 10, more preferably in the range of 1 to 5, and particularly preferably in the range of 1 to 3.
　前記ハロゲン原子としては、ヨウ素、臭素、塩素、フッ素を表す。 The halogen atom represents iodine, bromine, chlorine, or fluorine.
　前記アルキル基又はハロゲン原子等を有するアルキル基としては、具体的には、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の鎖状アルキル基、シクロペンチル基、シクロヘキシル基等の環状アルキル基、２－ヨードエチル基、２－ブロモエチル基、２－クロロエチル基、２－フルオロエチル基、１，２－ジヨードエチル基、１，２－ジブロモエチル基、１，２－ジクロロエチル基、１，２－ジフルオロエチル基、２，２－ジヨードエチル基、２，２－ジブロモエチル基、２，２－ジクロロエチル基、２，２－ジフルオロエチル基、２，２，２－トリブロモエチル基、２，２，２－トリクロロエチル基、２，２，２－トリフルオロエチル基、ヘキサフルオロー２－プロピル基等の鎖状含ハロゲンアルキル基、２－ヨードシクロヘキシル基、２－ブロモシクロヘキシル基、２－クロロシクロヘキシル基、２－フルオロシクロヘキシル基等の環状含ハロゲンアルキル基、２－プロペニル基、イソプロペニル基、２－ブテニル基、３－ブテニル基等の鎖状アルケニル基、２－シクロペンテニル基、２－シクロヘキセニル基、３－シクロヘキセニル基等の環状アルケニル基、２－プロピニル基、１－ブチニル基、２－ブチニル基、３－ブチニル基、１－ペンチニル基、２－ペンチニル基、３－ペンチニル基、４－ペンチニル基等の鎖状アルキニル基、フェニル基、３－メトキシフェニル基、４－メトキシフェニル基、３，５－ジメトキシフェニル基、４－フェノキシフェニル基等のフェニル基、２－ヨードフェニル基、２－ブロモフェニル基、２－クロロフェニル基、２－フルオロフェニル基、３－ヨードフェニル基、３－ブロモフェニル基、３－クロロフェニル基、３－フルオロフェニル基、４－ヨードフェニル基、４－ブロモフェニル基、４－クロロフェニル基、４－フルオロフェニル基、３，５－ジヨードフェニル基、３，５－ジブロモフェニル基、３，５－ジクロロフェニル基、３，５－ジフルオロフェニル基等の含ハロゲンフェニル基、１－ナフチル基、２－ナフチル基、３－アミノ－２－ナフチル基等のナフチル基等が挙げられる。 Specific examples of the alkyl group or the alkyl group having a halogen atom include chains such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Cyclic alkyl groups, cyclopentyl groups, cyclohexyl groups, etc., 2-iodoethyl groups, 2-bromoethyl groups, 2-chloroethyl groups, 2-fluoroethyl groups, 1,2-diiodoethyl groups, 1,2-dibromoethyl groups 1,2-dichloroethyl group, 1,2-difluoroethyl group, 2,2-diiodoethyl group, 2,2-dibromoethyl group, 2,2-dichloroethyl group, 2,2-difluoroethyl group, 2, 2,2-tribromoethyl group, 2,2,2-trichloroethyl group, 2,2,2-trifluoroethyl group, hexafluoro Chain halogen-containing alkyl groups such as 2-propyl group, cyclic halogen-containing alkyl groups such as 2-iodocyclohexyl group, 2-bromocyclohexyl group, 2-chlorocyclohexyl group, 2-fluorocyclohexyl group, 2-propenyl group, iso Chain alkenyl groups such as propenyl group, 2-butenyl group and 3-butenyl group, cyclic alkenyl groups such as 2-cyclopentenyl group, 2-cyclohexenyl group and 3-cyclohexenyl group, 2-propynyl group and 1-butynyl Group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, chain alkynyl group such as 4-pentynyl group, phenyl group, 3-methoxyphenyl group, 4-methoxy Phenyl group such as phenyl group, 3,5-dimethoxyphenyl group, 4-phenoxyphenyl group, 2-iodo Phenyl group, 2-bromophenyl group, 2-chlorophenyl group, 2-fluorophenyl group, 3-iodophenyl group, 3-bromophenyl group, 3-chlorophenyl group, 3-fluorophenyl group, 4-iodophenyl group, 4 -Including bromophenyl group, 4-chlorophenyl group, 4-fluorophenyl group, 3,5-diiodophenyl group, 3,5-dibromophenyl group, 3,5-dichlorophenyl group, 3,5-difluorophenyl group, etc. Examples thereof include a naphthyl group such as a halogenphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 3-amino-2-naphthyl group.
　尚、前記ハロゲン原子とは、フッ素、塩素、臭素又はヨウ素の原子を意味する。また、前記ヘテロ原子とは、酸素、窒素又は硫黄等の原子を意味する。前記ハロゲン原子等を有するアルキル基において、前記ハロゲン原子及びヘテロ原子は、当該アルキル基中の水素の一部又は全部がこれらのハロゲン原子及び／又はヘテロ原子の何れかで置換されていてもよい。 The halogen atom means a fluorine, chlorine, bromine or iodine atom. Moreover, the said hetero atom means atoms, such as oxygen, nitrogen, or sulfur. In the alkyl group having a halogen atom or the like, in the halogen atom and heteroatom, part or all of the hydrogen in the alkyl group may be substituted with any of these halogen atoms and / or heteroatoms.
　また、前記Ｘ５とＸ６は、前記アルキル基、又はハロゲン原子等を有するアルキル基の何れかが、相互に結合して環状構造を形成するものであってもよい。この場合、前記Ｘ１とＸ２におけるアルキル基又はハロゲン原子等を有するアルキル基は、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、ノニレン基等の直鎖アルキレン基、ヨードメチレン基、ジヨードメチレン基、ブロモメチレン基、ジブロモメチレン基、フルオロメチレン基、ジフルオロメチレン基、ヨードエチレン基、１，１－ジヨードエチレン基、１，２－ジヨードエチレン基、トリヨードエチレン基、テトラヨードエチレン基、クロロエチレン基、１，１－ジクロロエチレン基、１，２－ジクロロエチレン基、トリクロロエチレン基、テトラクロロエチレン基、フルオロエチレン基、１，１－ジフルオロエチレン基、１，２－ジフルオロエチレン基、トリフルオロエチレン基、テトラフルオロエチレン基等の含ハロゲン直鎖アルキレン基、シクロヘキシレン基、フェニレン基、ベンジレン基、ナフチレン基、アントラシレン基、ナフタシレン基、ペンタシレン基のような環状炭化水素基及びその一部又は全部をハロゲン原子等に置き換えたものとなる。 X 5 and X 6 may be a group in which either the alkyl group or an alkyl group having a halogen atom is bonded to each other to form a cyclic structure. In this case, the alkyl group or the alkyl group having a halogen atom or the like in X 1 and X 2 is, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, or a nonylene group. Linear alkylene group such as iodomethylene group, diiodomethylene group, bromomethylene group, dibromomethylene group, fluoromethylene group, difluoromethylene group, iodoethylene group, 1,1-diiodoethylene group, 1,2-di Iodoethylene group, triiodoethylene group, tetraiodoethylene group, chloroethylene group, 1,1-dichloroethylene group, 1,2-dichloroethylene group, trichloroethylene group, tetrachloroethylene group, fluoroethylene group, 1,1-difluoroethylene group, 1,2-difluoroethylene group Halogen-containing linear alkylene groups such as trifluoroethylene group and tetrafluoroethylene group, cyclic hydrocarbon groups such as cyclohexylene group, phenylene group, benzylene group, naphthylene group, anthracylene group, naphthacylene group, pentasilene group and the like Parts or all are replaced with halogen atoms or the like.
　前記Ｘ５とＸ６は、前記に例示した官能基群に於いて、同種でもよく相互に異なっていてもよい。また前記に例示した官能基群は単なる例示に過ぎず、これらに限定されるものではない。 X 5 and X 6 may be the same or different from each other in the functional group group exemplified above. Moreover, the functional group group illustrated above is only an illustration, and is not limited to these.
　前記一般式（４）で表されるリン化合物の具体例としては、例えば、入手が容易なジフルオロリン酸リチウムやジフルオロリン酸ナトリウム等が挙げられる。 Specific examples of the phosphorus compound represented by the general formula (4) include, for example, lithium difluorophosphate and sodium difluorophosphate which are easily available.
　［一般式（５）で表されるリン化合物］
　次に、下記一般式（５）で表されるリン化合物について説明する。但し、前記一般式（４）で表されるリン化合物において説明したものと同一のものについては、その説明を省略する。 [Phosphorus compound represented by general formula (5)]
Next, the phosphorus compound represented by the following general formula (5) will be described. However, the description of the same components as those described in the phosphorus compound represented by the general formula (4) will be omitted.
Figure JPOXMLDOC01-appb-C000047
 　前記一般式（５）に於いて、前記Ｍｎ＋及び価数ｎは、前記一般式（４）で述べたのと同様である。
Figure JPOXMLDOC01-appb-C000047
 In the general formula (5), the M n + and the valence n are the same as those described in the general formula (4).
　前記一般式（５）に於いて、前記Ｘ７～Ｘ１２は、それぞれ独立して、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基（以下、「ハロゲン原子等を有するアルキル基」という。）、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基（以下、「ハロゲン原子等を有するアルコキシ基」という。）、又はハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基（以下、「ハロゲン原子等を有するアルキルチオ基」という。）を表す。前記アルキル基、アルコキシ基、アルキルチオ基、ハロゲン原子等を有するアルキル基、ハロゲン原子等を有するアルコキシ基及びハロゲン原子等を有するアルキルチオ基の炭素数は１～２０の範囲であり、好ましくは１～１０、より好ましくは１～４である。また、不飽和結合の数は１～１０の範囲が好ましく、１～５の範囲がより好ましく、１～３の範囲が特に好ましい。 In the general formula (5), X 7 to X 12 are each independently at least one of a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a halogen atom, a hetero atom, or an unsaturated bond. An alkyl group having at least one of a halogen atom, a hetero atom or an unsaturated bond (hereinafter referred to as an “alkoxy group having a halogen atom”). Or an alkylthio group having at least one of a halogen atom, a heteroatom or an unsaturated bond (hereinafter referred to as “alkylthio group having a halogen atom”). The alkyl group, alkoxy group, alkylthio group, alkyl group having a halogen atom and the like, the alkoxy group having a halogen atom and the like, and the alkylthio group having a halogen atom and the like have a carbon number in the range of 1 to 20, preferably 1 to 10 More preferably, it is 1 to 4. Further, the number of unsaturated bonds is preferably in the range of 1 to 10, more preferably in the range of 1 to 5, and particularly preferably in the range of 1 to 3.
　前記ハロゲン原子及びヘテロ原子は、前記一般式（４）で述べたのと同様である。また、前記ハロゲン原子等を有するアルキル基、ハロゲン原子等を有するアルコキシ基及びハロゲン原子等を有するアルキルチオ基において、前記ハロゲン原子及びヘテロ原子は、これらの官能基中の水素の一部又は全部がこれらのハロゲン原子及び／又はヘテロ原子の何れかで置換されていてもよい。 The halogen atom and the hetero atom are the same as described in the general formula (4). In the alkyl group having a halogen atom or the like, the alkoxy group having a halogen atom or the like, and the alkylthio group having a halogen atom or the like, the halogen atom or the heteroatom is such that a part or all of hydrogen in these functional groups It may be substituted with any of the halogen atoms and / or heteroatoms.
　前記Ｘ７～Ｘ１２は、具体的には、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の鎖状アルキル基、シクロペンチル基、シクロヘキシル基等の環状アルキル基、ヨードメチル基、ブロモメチル基、クロロメチル基、フルオロメチル基、ジヨードメチル基、ジブロモメチル基、ジクロロメチル基、ジフルオロメチル基、トリヨードメチル基、トリブロモメチル基、トリクロロメチル基、トリフルオロメチル基、２－ヨードエチル基、２－ブロモエチル基、２－クロロエチル基、２－フルオロエチル基、１，２－ジヨードエチル基、１，２－ジブロモエチル基、１，２－ジクロロエチル基、１，２－ジフルオロエチル基、２，２－ジヨードエチル基、２，２－ジブロモエチル基、２，２－ジクロロエチル基、２，２－ジフルオロエチル基、２，２，２－トリブロモエチル基、２，２，２－トリクロロエチル基、２，２，２－トリフルオロエチル基、ヘキサフルオロ－２－プロピル基等の鎖状含ハロゲンアルキル基、２－ヨードシクロヘキシル基、２－ブロモシクロヘキシル基、２－クロロシクロヘキシル基、２－フルオロシクロヘキシル基等の環状含ハロゲンアルキル基、２－プロペニル基、イソプロペニル基、２－ブテニル基、３－ブテニル基等の鎖状アルケニル基、２－シクロペンテニル基、２－シクロヘキセニル基、３－シクロヘキセニル基等の環状アルケニル基、２－プロピニル基、１－ブチニル基、２－ブチニル基、３－ブチニル基、１－ペンチニル基、２－ペンチニル基、３－ペンチニル基、４－ペンチニル基等の鎖状アルキニル基、フェニル基、３－メトキシフェニル基、４－メトキシフェニル基、３，５－ジメトキシフェニル基、４－フェノキシフェニル基等のフェニル基、２－ヨードフェニル基、２－ブロモフェニル基、２－クロロフェニル基、２－フルオロフェニル基、３－ヨードフェニル基、３－ブロモフェニル基、３－クロロフェニル基、３－フルオロフェニル基、４－ヨードフェニル基、４－ブロモフェニル基、４－クロロフェニル基、４－フルオロフェニル基、３，５－ジヨードフェニル基、３，５－ジブロモフェニル基、３，５－ジクロロフェニル基、３，５－ジフルオロフェニル基等の含ハロゲンフェニル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペントキシ基、ヘキソキシ基等の鎖状アルコキシ基、シクロペントキシ基、シクロヘキソキシ基等の環状アルコキシ基、２－ヨードエトキシ基、２－ブロモエトキシ基、２－クロロエトキシ基、２－フルオロエトキシ基、１，２－ジヨードエトキシ基、１，２－ジブロモエトキシ基、１，２－ジクロロエトキシ基、１，２－ジフルオロエトキシ基、２，２－ジヨードエトキシ基、２，２－ジブロモエトキシ基、２，２－ジクロロエトキシ基、２，２－ジフルオロエトキシ基、２，２，２－トリブロモエトキシ基、２，２，２－トリクロロエトキシ基、２，２，２－トリフルオロエトキシ基、ヘキサフルオロ－２－プロポキシ基等の鎖状含ハロゲンアルコキシ基、２－ヨードシクロヘキソキシ基、２－ブロモシクロヘキソキシ基、２－クロロシクロヘキソキシ基、２－フルオロシクロヘキソキシ基等の環状含ハロゲンアルコキシ基、２－プロペノキシ基、イソプロペノキシ基、２－ブテノキシ基、３－ブテノキシ基等の鎖状アルケニルアルコキシ基、２－シクロペンテノキシ基、２－シクロヘキセノキシ基、３－シクロヘキセノキシ基等の環状アルケニルアルコキシ基、２－プロピノキシ基、１－ブチノキシ基、２－ブチノキシ基、３－ブチノキシ基、１－ペンチノキシ基、２－ペンチノキシ基、３－ペンチノキシ基、４－ペンチノキシ基等の鎖状アルキニルアルコキシ基、フェノキシ基、３－メチルフェノキシ基、４－メチルフェノキシ基、３，５－ジメチルフェノキシ基等のフェノキシ基、２－ヨードフェノキシ基、２－ブロモフェノキシ基、２－クロロフェノキシ基、２－フルオロフェノキシ基、３－ヨードフェノキシ基、３－ブロモフェノキシ基、３－クロロフェノキシ基、３－フルオロフェノキシ基、４－ヨードフェノキシ基、４－ブロモフェノキシ基、４－クロロフェノキシ基、４－フルオロフェノキシ基、３，５－ジヨードフェノキシ基、３，５－ジブロフェノキシ基、３，５－ジクロロフェノキシ基、３，５－ジフルオロフェノキシ基等の含ハロゲンフェノキシ基、メチルチオ基、エチルチオ基、プロピルチオ基、ブチルチオ基、イオプロピルチオ基、ペンチルチオ基、ヘキシルチオ基等のアルキルチオ基等が挙げられる。 Specifically, X 7 to X 12 are, for example, a chain alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, or a cyclopentyl group. Cycloalkyl group such as cyclohexyl group, iodomethyl group, bromomethyl group, chloromethyl group, fluoromethyl group, diiodomethyl group, dibromomethyl group, dichloromethyl group, difluoromethyl group, triiodomethyl group, tribromomethyl group, trichloromethyl Group, trifluoromethyl group, 2-iodoethyl group, 2-bromoethyl group, 2-chloroethyl group, 2-fluoroethyl group, 1,2-diiodoethyl group, 1,2-dibromoethyl group, 1,2-dichloroethyl group 1,2-difluoroethyl group, 2,2-diiodoethyl group, 2,2-di Lomoethyl group, 2,2-dichloroethyl group, 2,2-difluoroethyl group, 2,2,2-tribromoethyl group, 2,2,2-trichloroethyl group, 2,2,2-trifluoroethyl group A chain halogen-containing alkyl group such as hexafluoro-2-propyl group, a cyclic halogen-containing alkyl group such as 2-iodocyclohexyl group, 2-bromocyclohexyl group, 2-chlorocyclohexyl group, 2-fluorocyclohexyl group, 2- Chain alkenyl groups such as propenyl group, isopropenyl group, 2-butenyl group and 3-butenyl group, cyclic alkenyl groups such as 2-cyclopentenyl group, 2-cyclohexenyl group and 3-cyclohexenyl group, 2-propynyl group 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl Chain alkynyl groups such as 4-pentynyl group, phenyl groups such as phenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3,5-dimethoxyphenyl group, 4-phenoxyphenyl group, 2-iodophenyl group 2-bromophenyl group, 2-chlorophenyl group, 2-fluorophenyl group, 3-iodophenyl group, 3-bromophenyl group, 3-chlorophenyl group, 3-fluorophenyl group, 4-iodophenyl group, 4-bromo Halogen-containing phenyl such as phenyl group, 4-chlorophenyl group, 4-fluorophenyl group, 3,5-diiodophenyl group, 3,5-dibromophenyl group, 3,5-dichlorophenyl group, 3,5-difluorophenyl group Chain, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, etc. Cyclic alkoxy groups such as a coxy group, a cyclopentoxy group, a cyclohexoxy group, a 2-iodoethoxy group, a 2-bromoethoxy group, a 2-chloroethoxy group, a 2-fluoroethoxy group, a 1,2-diiodoethoxy group, 1,2-dibromoethoxy group, 1,2-dichloroethoxy group, 1,2-difluoroethoxy group, 2,2-diiodoethoxy group, 2,2-dibromoethoxy group, 2,2-dichloroethoxy group, 2 , 2-difluoroethoxy group, 2,2,2-tribromoethoxy group, 2,2,2-trichloroethoxy group, 2,2,2-trifluoroethoxy group, hexafluoro-2-propoxy group, etc. Halogen-containing alkoxy group, 2-iodocyclohexoxy group, 2-bromocyclohexoxy group, 2-chlorocyclohexoxy group, 2-fluorocyclohex Cyclic halogen-containing alkoxy groups such as oxy group, 2-propenoxy group, isopropenoxy group, 2-butenoxy group, chain alkenyl alkoxy groups such as 3-butenoxy group, 2-cyclopentenoxy group, 2-cyclohexenoxy group, Cyclic alkenylalkoxy groups such as 3-cyclohexenoxy group, 2-propynoxy group, 1-butynoxy group, 2-butynoxy group, 3-butynoxy group, 1-pentynoxy group, 2-pentynoxy group, 3-pentynoxy group, 4- Chain alkynylalkoxy groups such as pentynoxy group, phenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, phenoxy group such as 3,5-dimethylphenoxy group, 2-iodophenoxy group, 2-bromophenoxy group, 2 -Chlorophenoxy group, 2-fluorophenoxy group, 3-iodophenoxy group 3-bromophenoxy group, 3-chlorophenoxy group, 3-fluorophenoxy group, 4-iodophenoxy group, 4-bromophenoxy group, 4-chlorophenoxy group, 4-fluorophenoxy group, 3,5-diiodophenoxy group Group, 3,5-dibrophenoxy group, halogen-containing phenoxy group such as 3,5-dichlorophenoxy group, 3,5-difluorophenoxy group, methylthio group, ethylthio group, propylthio group, butylthio group, iopropylthio group, Examples thereof include alkylthio groups such as a pentylthio group and a hexylthio group.
　また、前記Ｘ７～Ｘ１２は、任意に選択される少なくとも１つの組合せが、－ＯＯＣ－Ｚ－ＣＯＯ－、－ＯＯＣ－Ｚ－Ｏ－又は－Ｏ－Ｚ－Ｏ－の環状構造の何れかを形成していてもよい。前記Ｘ７～Ｘ１２が２以上の環状構造を形成する場合、当該環状構造は相互に同一でもよく、異なっていてもよい。また、前記Ｚは、炭素数が０～２０の炭化水素基、又は炭素数が０～２０の範囲であって、ハロゲン原子、ヘテロ原子、不飽和結合若しくは環状構造の少なくとも何れか１つを有する炭化水素基を表す。また、不飽和結合の数は１～１０の範囲が好ましく、１～５の範囲がより好ましく、１～３の範囲が特に好ましい。 X 7 to X 12 are any combination of any one of the cyclic structures of —OOC—Z—COO—, —OOC—Z—O—, and —O—Z—O—. May be formed. When X 7 to X 12 form two or more cyclic structures, the cyclic structures may be the same or different from each other. Z is a hydrocarbon group having 0 to 20 carbon atoms or a range of 0 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom, an unsaturated bond, or a cyclic structure. Represents a hydrocarbon group. Further, the number of unsaturated bonds is preferably in the range of 1 to 10, more preferably in the range of 1 to 5, and particularly preferably in the range of 1 to 3.
　前記Ｚとしては特に限定されず、具体的には、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、ノニレン基等の直鎖アルキレン基、ヨードメチレン基、ジヨードメチレン基、ブロモメチレン基、ジブロモメチレン基、フルオロメチレン基、ジフルオロメチレン基、ヨードエチレン基、１，１－ジヨードエチレン基、１，２－ジヨードエチレン基、トリヨードエチレン基、テトラヨードエチレン基、クロロエチレン基、１，１－ジクロロエチレン基、１，２－ジクロロエチレン基、トリクロロエチレン基、テトラクロロエチレン基、フルオロエチレン基、１，１－ジフルオロエチレン基、１，２－ジフルオロエチレン基、トリフルオロエチレン基、テトラフルオロエチレン基等の含ハロゲン直鎖アルキレン基、シクロヘキシレン基、フェニレン基、ベンジレン基、ナフチレン基、アントラシレン基、ナフタシレン基、ペンタシレン基のような環状炭化水素基及びその一部又は全部をハロゲンに置き換えたもの等が挙げられる。 The Z is not particularly limited, and specific examples include, for example, a linear alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, and a nonylene group; Methylene group, diiodomethylene group, bromomethylene group, dibromomethylene group, fluoromethylene group, difluoromethylene group, iodoethylene group, 1,1-diiodoethylene group, 1,2-diiodoethylene group, triiodoethylene group Tetraiodoethylene group, chloroethylene group, 1,1-dichloroethylene group, 1,2-dichloroethylene group, trichloroethylene group, tetrachloroethylene group, fluoroethylene group, 1,1-difluoroethylene group, 1,2-difluoroethylene group, Trifluoroethylene group, tetrafluoro Halogen-containing straight chain alkylene groups such as a tylene group, cyclohexylene groups, phenylene groups, benzylene groups, naphthylene groups, anthracylene groups, naphthacylene groups, and pentasilene groups, and some or all of them are replaced with halogens. And the like.
　例えばＺの炭素数が０の場合、－ＯＯＣ－Ｚ－ＣＯＯ－は－ＯＯＣ－ＣＯＯ－であり、オキサレート基を表す。また、前記Ｚが１，２－フェニレン基である場合、－Ｏ－Ｚ－Ｏ－はベンゼンジオラート基を表し、－Ｏ－Ｚ－ＣＯＯ－はサリチラート基を表す。 For example, when Z has 0 carbon atoms, -OOC-Z-COO- is -OOC-COO- and represents an oxalate group. When Z is a 1,2-phenylene group, —O—Z—O— represents a benzenediolate group, and —O—Z—COO— represents a salicylate group.
　尚、前記一般式（５）で表されるリン化合物としては、例えば、入手が容易なリチウムジフルオロビスオキサレートホスフェート、ナトリウムジフルオロビスオキサレートホスフェート、リチウムテトラフルオロオキサレートホスフェート、ナトリウムテトラフルオロオキサレートホスフェート等が挙げられる。 Examples of the phosphorus compound represented by the general formula (5) include lithium difluorobisoxalate phosphate, sodium difluorobisoxalate phosphate, lithium tetrafluorooxalate phosphate, and sodium tetrafluorooxalate phosphate, which are easily available. Etc.
　［一般式（６）で表されるリン化合物］
　次に、下記一般式（６）で表されるリン化合物について説明する。但し、前記一般式（４）及び（５）で表されるリン化合物において説明したものと同一のものについては、その説明を省略する。 [Phosphorus Compound Represented by General Formula (6)]
Next, the phosphorus compound represented by the following general formula (6) will be described. However, the description of the same compounds described in the phosphorus compounds represented by the general formulas (4) and (5) will be omitted.
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
　前記Ａ３は酸素原子、硫黄原子又はセレン原子を表す。 Wherein A 3 represents an oxygen atom, a sulfur atom or a selenium atom.
　前記Ｘ１３～Ｘ１５は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、ハロゲン原子、ヘテロ原子又は不飽和結合の少なくとも何れか一つを有するアルキル基（以下、「ハロゲン原子等を有するアルキル基」という。）、ハロゲン原子、ヘテロ原子又は不飽和結合の少なくとも何れか一つを有するアルコキシ基（以下、「ハロゲン原子等を有するアルコキシ基」という。）、又はハロゲン原子、ヘテロ原子又は不飽和結合の少なくとも何れか一つを有するアルキルチオ基（以下、「ハロゲン原子等を有するアルキルチオ基」という。）を表す。前記アルキル基、アルコキシ基、アルキルチオ基、ハロゲン原子等を有するアルキル基、ハロゲン原子等を有するアルコキシ基及びハロゲン原子等を有するアルキルチオ基の炭素数は１～２０の範囲であり、好ましくは１～１０、より好ましくは１～４である。また、不飽和結合の数は１～１０の範囲が好ましく、１～５の範囲がより好ましく、１～３の範囲が特に好ましい。 X 13 to X 15 each independently represents an alkyl group having at least one of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a halogen atom, a hetero atom, or an unsaturated bond (hereinafter, "Alkyl group having a halogen atom"), an alkoxy group having at least one of a halogen atom, a hetero atom or an unsaturated bond (hereinafter referred to as "an alkoxy group having a halogen atom"), or a halogen An alkylthio group having at least one of an atom, a heteroatom and an unsaturated bond (hereinafter referred to as “alkylthio group having a halogen atom”) is represented. The alkyl group, alkoxy group, alkylthio group, alkyl group having a halogen atom and the like, the alkoxy group having a halogen atom and the like, and the alkylthio group having a halogen atom and the like have a carbon number in the range of 1 to 20, preferably 1 to 10 More preferably, it is 1 to 4. Further, the number of unsaturated bonds is preferably in the range of 1 to 10, more preferably in the range of 1 to 5, and particularly preferably in the range of 1 to 3.
　前記Ｘ１３～Ｘ１５は特に限定されず、具体的には、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の鎖状アルキル基、シクロペンチル基、シクロヘキシル基等の環状アルキル基、ヨードメチル基、ブロモメチル基、クロロメチル基、フルオロメチル基、ジヨードメチル基、ジブロモメチル基、ジクロロメチル基、ジフルオロメチル基、トリヨードメチル基、トリブロモメチル基、トリクロロメチル基、トリフルオロメチル基、２－ヨードエチル基、２－ブロモエチル基、２－クロロエチル基、２－フルオロエチル基、１，２－ジヨードエチル基、１，２－ジブロモエチル基、１，２－ジクロロエチル基、１，２－ジフルオロエチル基、２，２－ジヨードエチル基、２，２－ジブロモエチル基、２，２－ジクロロエチル基、２，２－ジフルオロエチル基、２，２，２－トリブロモエチル基、２，２，２－トリクロロエチル基、２，２，２－トリフルオロエチル基、ヘキサフルオロ－２－プロピル基等の鎖状含ハロゲンアルキル基、２－ヨードシクロヘキシル基、２－ブロモシクロヘキシル基、２－クロロシクロヘキシル基、２－フルオロシクロヘキシル基等の環状含ハロゲンアルキル基、２－プロペニル基、イソプロペニル基、２－ブテニル基、３－ブテニル基等の鎖状アルケニル基、２－シクロペンテニル基、２－シクロヘキセニル基、３－シクロヘキセニル基等の環状アルケニル基、２－プロピニル基、１－ブチニル基、２－ブチニル基、３－ブチニル基、１－ペンチニル基、２－ペンチニル基、３－ペンチニル基、４－ペンチニル基等の鎖状アルキニル基、フェニル基、３－メトキシフェニル基、４－メトキシフェニル基、３，５－ジメトキシフェニル基、４－フェノキシフェニル基等のフェニル基、２－ヨードフェニル基、２－ブロモフェニル基、２－クロロフェニル基、２－フルオロフェニル基、３－ヨードフェニル基、３－ブロモフェニル基、３－クロロフェニル基、３－フルオロフェニル基、４－ヨードフェニル基、４－ブロモフェニル基、４－クロロフェニル基、４－フルオロフェニル基、３，５－ジヨードフェニル基、３，５－ジブロモフェニル基、３，５－ジクロロフェニル基、３，５－ジフルオロフェニル基等の含ハロゲンフェニル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペントキシ基、ヘキソキシ基等の鎖状アルコキシ基、シクロペントキシ基、シクロヘキソキシ基等の環状アルコキシ基、２－ヨードエトキシ基、２－ブロモエトキシ基、２－クロロエトキシ基、２－フルオロエトキシ基、１，２－ジヨードエトキシ基、１，２－ジブロモエトキシ基、１，２－ジクロロエトキシ基、１，２－ジフルオロエトキシ基、２，２－ジヨードエトキシ基、２，２－ジブロモエトキシ基、２，２－ジクロロエトキシ基、２，２－ジフルオロエトキシ基、２，２，２－トリブロモエトキシ基、２，２，２－トリクロロエトキシ基、２，２，２－トリフルオロエトキシ基、ヘキサフルオロ－２－プロポキシ基等の鎖状含ハロゲンアルコキシ基、２－ヨードシクロヘキソキシ基、２－ブロモシクロヘキソキシ基、２－クロロシクロヘキソキシ基、２－フルオロシクロヘキソキシ基等の環状含ハロゲンアルコキシ基、２－プロペノキシ基、イソプロペノキシ基、２－ブテノキシ基、３－ブテノキシ基等の鎖状アルケニルアルコキシ基、２－シクロペンテノキシ基、２－シクロヘキセノキシ基、３－シクロヘキセノキシ基等の環状アルケニルアルコキシ基、２－プロピノキシ基、１－ブチノキシ基、２－ブチノキシ基、３－ブチノキシ基、１－ペンチノキシ基、２－ペンチノキシ基、３－ペンチノキシ基、４－ペンチノキシ基等の鎖状アルキニルアルコキシ基、フェノキシ基、３－メチルフェノキシ基、４－メチルフェノキシ基、３，５－ジメチルフェノキシ基等のフェノキシ基、２－ヨードフェノキシ基、２－ブロモフェノキシ基、２－クロロフェノキシ基、２－フルオロフェノキシ基、３－ヨードフェノキシ基、３－ブロモフェノキシ基、３－クロロフェノキシ基、３－フルオロフェノキシ基、４－ヨードフェノキシ基、４－ブロモフェノキシ基、４－クロロフェノキシ基、４－フルオロフェノキシ基、３，５－ジヨードフェノキシ基、３，５－ジブロフェノキシ基、３，５－ジクロロフェノキシ基、３，５－ジフルオロフェノキシ基等の含ハロゲンフェノキシ基、メチルチオ基、エチルチオ基、プロピルチオ基、ブチルチオ基、イオプロピルチオ基、ペンチルチオ基、ヘキシルチオ基等のアルキルチオ基等が挙げられる。 X 13 to X 15 are not particularly limited. Specifically, for example, chain alkyl such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, pentyl group, hexyl group, heptyl group, octyl group, etc. Group, cyclic alkyl group such as cyclopentyl group, cyclohexyl group, iodomethyl group, bromomethyl group, chloromethyl group, fluoromethyl group, diiodomethyl group, dibromomethyl group, dichloromethyl group, difluoromethyl group, triiodomethyl group, tribromomethyl Group, trichloromethyl group, trifluoromethyl group, 2-iodoethyl group, 2-bromoethyl group, 2-chloroethyl group, 2-fluoroethyl group, 1,2-diiodoethyl group, 1,2-dibromoethyl group, 1,2 -Dichloroethyl group, 1,2-difluoroethyl group, 2,2-diiodoethyl Group, 2,2-dibromoethyl group, 2,2-dichloroethyl group, 2,2-difluoroethyl group, 2,2,2-tribromoethyl group, 2,2,2-trichloroethyl group, 2,2 , Cyclic halogen-containing alkyl groups such as 2-trifluoroethyl group and hexafluoro-2-propyl group, cyclic groups such as 2-iodocyclohexyl group, 2-bromocyclohexyl group, 2-chlorocyclohexyl group and 2-fluorocyclohexyl group Cyclic alkenyl groups such as halogen-containing alkyl groups, 2-propenyl groups, isopropenyl groups, 2-butenyl groups and 3-butenyl groups, cyclic groups such as 2-cyclopentenyl groups, 2-cyclohexenyl groups and 3-cyclohexenyl groups Alkenyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group Chain alkynyl groups such as 3-pentynyl group and 4-pentynyl group, phenyl groups such as phenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3,5-dimethoxyphenyl group, 4-phenoxyphenyl group, 2 -Iodophenyl group, 2-bromophenyl group, 2-chlorophenyl group, 2-fluorophenyl group, 3-iodophenyl group, 3-bromophenyl group, 3-chlorophenyl group, 3-fluorophenyl group, 4-iodophenyl group 4-bromophenyl group, 4-chlorophenyl group, 4-fluorophenyl group, 3,5-diiodophenyl group, 3,5-dibromophenyl group, 3,5-dichlorophenyl group, 3,5-difluorophenyl group, etc. Halogen-containing phenyl group, methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexoxy Chain alkoxy groups such as thio group, cyclic alkoxy groups such as cyclopentoxy group, cyclohexoxy group, 2-iodoethoxy group, 2-bromoethoxy group, 2-chloroethoxy group, 2-fluoroethoxy group, 1,2 -Diiodoethoxy group, 1,2-dibromoethoxy group, 1,2-dichloroethoxy group, 1,2-difluoroethoxy group, 2,2-diiodoethoxy group, 2,2-dibromoethoxy group, 2,2 -Dichloroethoxy group, 2,2-difluoroethoxy group, 2,2,2-tribromoethoxy group, 2,2,2-trichloroethoxy group, 2,2,2-trifluoroethoxy group, hexafluoro-2- Chain halogen-containing alkoxy groups such as propoxy group, 2-iodocyclohexoxy group, 2-bromocyclohexoxy group, 2-chlorocyclohexoxy group, 2- Cyclic halogen-containing alkoxy groups such as urocyclohexoxy group, chained alkenylalkoxy groups such as 2-propenoxy group, isopropenoxy group, 2-butenoxy group and 3-butenoxy group, 2-cyclopentenoxy group, 2-cyclohexeno Cyclic alkenylalkoxy groups such as xy group, 3-cyclohexenoxy group, 2-propynoxy group, 1-butynoxy group, 2-butynoxy group, 3-butynoxy group, 1-pentynoxy group, 2-pentynoxy group, 3-pentynoxy group Chain alkynylalkoxy groups such as 4-pentynoxy group, phenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 3,5-dimethylphenoxy group and other phenoxy groups, 2-iodophenoxy group, 2-bromophenoxy group Group, 2-chlorophenoxy group, 2-fluorophenoxy group, 3- Dophenoxy group, 3-bromophenoxy group, 3-chlorophenoxy group, 3-fluorophenoxy group, 4-iodophenoxy group, 4-bromophenoxy group, 4-chlorophenoxy group, 4-fluorophenoxy group, 3,5-di Halogen-containing phenoxy groups such as iodophenoxy group, 3,5-dibrophenoxy group, 3,5-dichlorophenoxy group, 3,5-difluorophenoxy group, methylthio group, ethylthio group, propylthio group, butylthio group, iopiothio Groups, alkylthio groups such as a pentylthio group and a hexylthio group.
　また、前記Ｘ１３～Ｘ１５は、任意に選択される少なくとも１つの組合せにより、前記アルキル基、アルコキシ基、アルキルチオ基、ハロゲン原子等を有するアルキル基、ハロゲン原子等を有するアルコキシ基又はハロゲン原子等を有するアルキルチオ基の何れかが、相互に結合して環状構造を形成するものであってもよい。この場合、前記Ｘ９～Ｘ１１における前記アルキル基等が、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、ノニレン基等の直鎖アルキレン基、ヨードメチレン基、ジヨードメチレン基、ブロモメチレン基、ジブロモメチレン基、フルオロメチレン基、ジフルオロメチレン基、ヨードエチレン基、１，１－ジヨードエチレン基、１，２－ジヨードエチレン基、トリヨードエチレン基、テトラヨードエチレン基、クロロエチレン基、１，１－ジクロロエチレン基、１，２－ジクロロエチレン基、トリクロロエチレン基、テトラクロロエチレン基、フルオロエチレン基、１，１－ジフルオロエチレン基、１，２－ジフルオロエチレン基、トリフルオロエチレン基、テトラフルオロエチレン基等の含ハロゲン直鎖アルキレン基、シクロヘキシレン基、フェニレン基、ベンジレン基、ナフチレン基、アントラシレン基、ナフタシレン基、ペンタシレン基のような環状炭化水素基及びその一部又は全部をハロゲン原子等に置き換えたものとなる。 X 13 to X 15 may be an alkyl group, an alkoxy group, an alkylthio group, an alkyl group having a halogen atom, an alkoxy group having a halogen atom or the like, a halogen atom, etc. Any of the alkylthio groups having the above may be bonded to each other to form a cyclic structure. In this case, the alkyl group in X 9 to X 11 is, for example, a linear alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, and a nonylene group. , Iodomethylene group, diiodomethylene group, bromomethylene group, dibromomethylene group, fluoromethylene group, difluoromethylene group, iodoethylene group, 1,1-diiodoethylene group, 1,2-diiodoethylene group, triiodo Ethylene group, tetraiodoethylene group, chloroethylene group, 1,1-dichloroethylene group, 1,2-dichloroethylene group, trichloroethylene group, tetrachloroethylene group, fluoroethylene group, 1,1-difluoroethylene group, 1,2-difluoroethylene Group, trifluoroethylene group, Halogen-containing linear alkylene groups such as lafluoroethylene groups, cyclic hydrocarbon groups such as cyclohexylene groups, phenylene groups, benzylene groups, naphthylene groups, anthracylene groups, naphthacylene groups, pentasilene groups, and some or all of them It will be replaced with atoms.
　前記ハロゲン原子及びヘテロ原子は、前記一般式（４）で述べたのと同様である。また、前記ハロゲン原子等を有するアルキル基、ハロゲン原子等を有するアルコキシ基及びハロゲン原子等を有するアルキルチオ基において、前記ハロゲン原子及びヘテロ原子は、それらの官能基中の水素の一部又は全部がこれらのハロゲン原子及び／又はヘテロ原子の何れかで置換されていてもよい。 The halogen atom and the hetero atom are the same as described in the general formula (4). Further, in the alkyl group having a halogen atom or the like, the alkoxy group having a halogen atom or the like, and the alkylthio group having a halogen atom or the like, the halogen atom or the heteroatom is such that a part or all of hydrogens in these functional groups are these. It may be substituted with any of the halogen atoms and / or heteroatoms.
　前記一般式（６）で表されるリン化合物の具体例としては、例えば、入手が容易なリン酸トリメチル、リン酸トリエチルやリン酸トリス（２，２，２－トリフルオロエチル）、ビス（２，２，２－トリフルオロエチル）ホスホン酸等が挙げられる。 Specific examples of the phosphorus compound represented by the general formula (6) include, for example, trimethyl phosphate, triethyl phosphate, tris (2,2,2-trifluoroethyl) phosphate, bis (2 , 2,2-trifluoroethyl) phosphonic acid and the like.
　［一般式（７）の何れかで表されるリン化合物］
　次に、下記一般式（７）で表されるリン化合物について説明する。但し、前記一般式（４）～（６）で表されるリン化合物において説明したものと同一のものについては、その説明を省略する。 [Phosphorus compound represented by any one of the general formula (7)]
Next, the phosphorus compound represented by the following general formula (7) will be described. However, the description of the same compounds described in the phosphorus compounds represented by the general formulas (4) to (6) will be omitted.
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
　前記Ｘ１６～Ｘ１８は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、ハロゲン原子、ヘテロ原子又は不飽和結合の少なくとも何れか一つを有するアルキル基（以下、「ハロゲン原子等を有するアルキル基」という。）、ハロゲン原子、ヘテロ原子又は不飽和結合の少なくとも何れか一つを有するアルコキシ基（以下、「ハロゲン原子等を有するアルコキシ基」という。）、又はハロゲン原子、ヘテロ原子又は不飽和結合の少なくとも何れか一つを有するアルキルチオ基（以下、「ハロゲン原子等を有するアルキルチオ基」という。）を表す。前記アルキル基、アルコキシ基、アルキルチオ基、ハロゲン原子等を有するアルキル基、ハロゲン原子等を有するアルコキシ基及びハロゲン原子等を有するアルキルチオ基の炭素数は１～２０の範囲であり、好ましくは１～１０、より好ましくは１～４である。また、不飽和結合の数は１～１０の範囲が好ましく、１～５の範囲がより好ましく、１～３の範囲が特に好ましい。 X 16 to X 18 are each independently an alkyl group having at least one of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a halogen atom, a hetero atom, or an unsaturated bond (hereinafter referred to as the following). "Alkyl group having a halogen atom or the like"), an alkoxy group having at least one of a halogen atom, a hetero atom or an unsaturated bond (hereinafter referred to as "an alkoxy group having a halogen atom"), or a halogen An alkylthio group having at least one of an atom, a heteroatom and an unsaturated bond (hereinafter referred to as “alkylthio group having a halogen atom”) is represented. The alkyl group, alkoxy group, alkylthio group, alkyl group having a halogen atom and the like, the alkoxy group having a halogen atom and the like, and the alkylthio group having a halogen atom and the like have a carbon number in the range of 1 to 20, preferably 1 to 10 More preferably, it is 1 to 4. Further, the number of unsaturated bonds is preferably in the range of 1 to 10, more preferably in the range of 1 to 5, and particularly preferably in the range of 1 to 3.
　前記Ｘ１６～Ｘ１８は特に限定されず、具体的には、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の鎖状アルキル基、シクロペンチル基、シクロヘキシル基等の環状アルキル基、ヨードメチル基、ブロモメチル基、クロロメチル基、フルオロメチル基、ジヨードメチル基、ジブロモメチル基、ジクロロメチル基、ジフルオロメチル基、トリヨードメチル基、トリブロモメチル基、トリクロロメチル基、トリフルオロメチル基、２－ヨードエチル基、２－ブロモエチル基、２－クロロエチル基、２－フルオロエチル基、１，２－ジヨードエチル基、１，２－ジブロモエチル基、１，２－ジクロロエチル基、１，２－ジフルオロエチル基、２，２－ジヨードエチル基、２，２－ジブロモエチル基、２，２－ジクロロエチル基、２，２－ジフルオロエチル基、２，２，２－トリブロモエチル基、２，２，２－トリクロロエチル基、２，２，２－トリフルオロエチル基、ヘキサフルオロ－２－プロピル基等の鎖状含ハロゲンアルキル基、２－ヨードシクロヘキシル基、２－ブロモシクロヘキシル基、２－クロロシクロヘキシル基、２－フルオロシクロヘキシル基等の環状含ハロゲンアルキル基、２－プロペニル基、イソプロペニル基、２－ブテニル基、３－ブテニル基等の鎖状アルケニル基、２－シクロペンテニル基、２－シクロヘキセニル基、３－シクロヘキセニル基等の環状アルケニル基、２－プロピニル基、１－ブチニル基、２－ブチニル基、３－ブチニル基、１－ペンチニル基、２－ペンチニル基、３－ペンチニル基、４－ペンチニル基等の鎖状アルキニル基、フェニル基、３－メトキシフェニル基、４－メトキシフェニル基、３，５－ジメトキシフェニル基、４－フェノキシフェニル基等のフェニル基、２－ヨードフェニル基、２－ブロモフェニル基、２－クロロフェニル基、２－フルオロフェニル基、３－ヨードフェニル基、３－ブロモフェニル基、３－クロロフェニル基、３－フルオロフェニル基、４－ヨードフェニル基、４－ブロモフェニル基、４－クロロフェニル基、４－フルオロフェニル基、３，５－ジヨードフェニル基、３，５－ジブロモフェニル基、３，５－ジクロロフェニル基、３，５－ジフルオロフェニル基等の含ハロゲンフェニル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペントキシ基、ヘキソキシ基等の鎖状アルコキシ基、シクロペントキシ基、シクロヘキソキシ基等の環状アルコキシ基、２－ヨードエトキシ基、２－ブロモエトキシ基、２－クロロエトキシ基、２－フルオロエトキシ基、１，２－ジヨードエトキシ基、１，２－ジブロモエトキシ基、１，２－ジクロロエトキシ基、１，２－ジフルオロエトキシ基、２，２－ジヨードエトキシ基、２，２－ジブロモエトキシ基、２，２－ジクロロエトキシ基、２，２－ジフルオロエトキシ基、２，２，２－トリブロモエトキシ基、２，２，２－トリクロロエトキシ基、２，２，２－トリフルオロエトキシ基、ヘキサフルオロ－２－プロポキシ基等の鎖状含ハロゲンアルコキシ基、２－ヨードシクロヘキソキシ基、２－ブロモシクロヘキソキシ基、２－クロロシクロヘキソキシ基、２－フルオロシクロヘキソキシ基等の環状含ハロゲンアルコキシ基、２－プロペノキシ基、イソプロペノキシ基、２－ブテノキシ基、３－ブテノキシ基等の鎖状アルケニルアルコキシ基、２－シクロペンテノキシ基、２－シクロヘキセノキシ基、３－シクロヘキセノキシ基等の環状アルケニルアルコキシ基、２－プロピノキシ基、１－ブチノキシ基、２－ブチノキシ基、３－ブチノキシ基、１－ペンチノキシ基、２－ペンチノキシ基、３－ペンチノキシ基、４－ペンチノキシ基等の鎖状アルキニルアルコキシ基、フェノキシ基、３－メチルフェノキシ基、４－メチルフェノキシ基、３，５－ジメチルフェノキシ基等のフェノキシ基、２－ヨードフェノキシ基、２－ブロモフェノキシ基、２－クロロフェノキシ基、２－フルオロフェノキシ基、３－ヨードフェノキシ基、３－ブロモフェノキシ基、３－クロロフェノキシ基、３－フルオロフェノキシ基、４－ヨードフェノキシ基、４－ブロモフェノキシ基、４－クロロフェノキシ基、４－フルオロフェノキシ基、３，５－ジヨードフェノキシ基、３，５－ジブロフェノキシ基、３，５－ジクロロフェノキシ基、３，５－ジフルオロフェノキシ基等の含ハロゲンフェノキシ基、メチルチオ基、エチルチオ基、プロピルチオ基、ブチルチオ基、イオプロピルチオ基、ペンチルチオ基、ヘキシルチオ基等のアルキルチオ基等が挙げられる。 X 16 to X 18 are not particularly limited. Specifically, for example, chain alkyl such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, pentyl group, hexyl group, heptyl group, octyl group, etc. Group, cyclic alkyl group such as cyclopentyl group, cyclohexyl group, iodomethyl group, bromomethyl group, chloromethyl group, fluoromethyl group, diiodomethyl group, dibromomethyl group, dichloromethyl group, difluoromethyl group, triiodomethyl group, tribromomethyl Group, trichloromethyl group, trifluoromethyl group, 2-iodoethyl group, 2-bromoethyl group, 2-chloroethyl group, 2-fluoroethyl group, 1,2-diiodoethyl group, 1,2-dibromoethyl group, 1,2 -Dichloroethyl group, 1,2-difluoroethyl group, 2,2-diiodoethyl Group, 2,2-dibromoethyl group, 2,2-dichloroethyl group, 2,2-difluoroethyl group, 2,2,2-tribromoethyl group, 2,2,2-trichloroethyl group, 2,2 , Cyclic halogen-containing alkyl groups such as 2-trifluoroethyl group and hexafluoro-2-propyl group, cyclic groups such as 2-iodocyclohexyl group, 2-bromocyclohexyl group, 2-chlorocyclohexyl group and 2-fluorocyclohexyl group Cyclic alkenyl groups such as halogen-containing alkyl groups, 2-propenyl groups, isopropenyl groups, 2-butenyl groups and 3-butenyl groups, cyclic groups such as 2-cyclopentenyl groups, 2-cyclohexenyl groups and 3-cyclohexenyl groups Alkenyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group Chain alkynyl groups such as 3-pentynyl group and 4-pentynyl group, phenyl groups such as phenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3,5-dimethoxyphenyl group, 4-phenoxyphenyl group, 2 -Iodophenyl group, 2-bromophenyl group, 2-chlorophenyl group, 2-fluorophenyl group, 3-iodophenyl group, 3-bromophenyl group, 3-chlorophenyl group, 3-fluorophenyl group, 4-iodophenyl group 4-bromophenyl group, 4-chlorophenyl group, 4-fluorophenyl group, 3,5-diiodophenyl group, 3,5-dibromophenyl group, 3,5-dichlorophenyl group, 3,5-difluorophenyl group, etc. Halogen-containing phenyl group, methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexoxy Chain alkoxy groups such as thio group, cyclic alkoxy groups such as cyclopentoxy group, cyclohexoxy group, 2-iodoethoxy group, 2-bromoethoxy group, 2-chloroethoxy group, 2-fluoroethoxy group, 1,2 -Diiodoethoxy group, 1,2-dibromoethoxy group, 1,2-dichloroethoxy group, 1,2-difluoroethoxy group, 2,2-diiodoethoxy group, 2,2-dibromoethoxy group, 2,2 -Dichloroethoxy group, 2,2-difluoroethoxy group, 2,2,2-tribromoethoxy group, 2,2,2-trichloroethoxy group, 2,2,2-trifluoroethoxy group, hexafluoro-2- Chain halogen-containing alkoxy groups such as propoxy group, 2-iodocyclohexoxy group, 2-bromocyclohexoxy group, 2-chlorocyclohexoxy group, 2- Cyclic halogen-containing alkoxy groups such as urocyclohexoxy group, chained alkenylalkoxy groups such as 2-propenoxy group, isopropenoxy group, 2-butenoxy group and 3-butenoxy group, 2-cyclopentenoxy group, 2-cyclohexeno Cyclic alkenylalkoxy groups such as xy group, 3-cyclohexenoxy group, 2-propynoxy group, 1-butynoxy group, 2-butynoxy group, 3-butynoxy group, 1-pentynoxy group, 2-pentynoxy group, 3-pentynoxy group Chain alkynylalkoxy groups such as 4-pentynoxy group, phenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 3,5-dimethylphenoxy group and other phenoxy groups, 2-iodophenoxy group, 2-bromophenoxy group Group, 2-chlorophenoxy group, 2-fluorophenoxy group, 3- Dophenoxy group, 3-bromophenoxy group, 3-chlorophenoxy group, 3-fluorophenoxy group, 4-iodophenoxy group, 4-bromophenoxy group, 4-chlorophenoxy group, 4-fluorophenoxy group, 3,5-di Halogen-containing phenoxy groups such as iodophenoxy group, 3,5-dibrophenoxy group, 3,5-dichlorophenoxy group, 3,5-difluorophenoxy group, methylthio group, ethylthio group, propylthio group, butylthio group, iopiothio Groups, alkylthio groups such as a pentylthio group and a hexylthio group.
　また、前記Ｘ１６～Ｘ１８は、任意に選択される１つの組合せにより、前記アルキル基、アルコキシ基、アルキルチオ基、ハロゲン原子等を有するアルキル基、ハロゲン原子等を有するアルコキシ基又はハロゲン原子等を有するアルキルチオ基の何れかが、相互に結合して環状構造を形成するものであってもよい。この場合、前記Ｘ１６～Ｘ１８における前記アルキル基等が、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、ノニレン基等の直鎖アルキレン基、ヨードメチレン基、ジヨードメチレン基、ブロモメチレン基、ジブロモメチレン基、フルオロメチレン基、ジフルオロメチレン基、ヨードエチレン基、１，１－ジヨードエチレン基、１，２－ジヨードエチレン基、トリヨードエチレン基、テトラヨードエチレン基、クロロエチレン基、１，１－ジクロロエチレン基、１，２－ジクロロエチレン基、トリクロロエチレン基、テトラクロロエチレン基、フルオロエチレン基、１，１－ジフルオロエチレン基、１，２－ジフルオロエチレン基、トリフルオロエチレン基、テトラフルオロエチレン基等の含ハロゲン直鎖アルキレン基、シクロヘキシレン基、フェニレン基、ベンジレン基、ナフチレン基、アントラシレン基、ナフタシレン基、ペンタシレン基のような環状炭化水素基及びその一部又は全部をハロゲン原子等に置き換えたものとなる。 X 16 to X 18 may be an alkyl group, an alkoxy group, an alkylthio group, an alkyl group having a halogen atom, an alkoxy group having a halogen atom, or a halogen atom, etc. Any of the alkylthio groups possessed may be bonded to each other to form a cyclic structure. In this case, the alkyl group in X 16 to X 18 is, for example, a linear alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, or a nonylene group. , Iodomethylene group, diiodomethylene group, bromomethylene group, dibromomethylene group, fluoromethylene group, difluoromethylene group, iodoethylene group, 1,1-diiodoethylene group, 1,2-diiodoethylene group, triiodo Ethylene group, tetraiodoethylene group, chloroethylene group, 1,1-dichloroethylene group, 1,2-dichloroethylene group, trichloroethylene group, tetrachloroethylene group, fluoroethylene group, 1,1-difluoroethylene group, 1,2-difluoroethylene Group, trifluoroethylene group, Halogen-containing linear alkylene groups such as trifluoroethylene groups, cyclohexylene groups, phenylene groups, benzylene groups, naphthylene groups, anthracylene groups, naphthacylene groups, pentasilene groups, and some or all of them are halogenated It will be replaced with atoms.
　前記一般式（７）で表されるリン化合物の具体例としては、例えば、入手が容易なトリメチルホスフィンやメチルジフェニルホスフィン等が挙げられる Specific examples of the phosphorus compound represented by the general formula (7) include trimethylphosphine and methyldiphenylphosphine that are easily available.
　前記成分（Ｂ）の添加量は、非水電解液の全質量に対し０．０５質量％～５質量％の範囲内であることが好ましく、０．１質量％～３質量％の範囲内であることがより好ましく、０．５質量％～２質量％の範囲あることが特に好ましい。前記添加量を０．０５質量％以上にすることにより、添加剤としての効果、即ち、電極表面に安定した皮膜を形成することができる。一方、前記添加量を５質量％以下にすることにより、非水電解液中の電解質の非水電解液溶媒に対する溶解性が低下するのを抑制することができる。 The amount of component (B) added is preferably in the range of 0.05% by mass to 5% by mass, and in the range of 0.1% by mass to 3% by mass with respect to the total mass of the non-aqueous electrolyte. More preferably, it is particularly preferably in the range of 0.5% by mass to 2% by mass. By making the addition amount 0.05% by mass or more, an effect as an additive, that is, a stable film can be formed on the electrode surface. On the other hand, by making the said addition amount 5 mass% or less, it can suppress that the solubility with respect to the nonaqueous electrolyte solvent of the electrolyte in a nonaqueous electrolyte solution falls.
　また、本実施の形態に於いて、前記成分（Ｂ）は、少なくとも１種類が非水電解液中に含まれていればよいが、含有させる成分（Ｂ）の種類の数は、好ましくは５種類以下であり、より好ましくは３種類以下であり、特に好ましくは２種類以下である。成分（Ｂ）の種類を低減することにより、非水電解液の製造の際における工程の複雑化を抑制することができる。 In the present embodiment, at least one kind of the component (B) may be contained in the nonaqueous electrolytic solution, but the number of kinds of the component (B) to be contained is preferably 5 The number is not more than one, more preferably not more than three, and particularly preferably not more than two. By reducing the type of the component (B), it is possible to suppress complication of the process in the production of the nonaqueous electrolytic solution.
　＜電解質＞
　前記電解質としては、従来公知のものを採用することができる。例えば、リチウムイオン電池用の場合はリチウム塩が用いられ、ナトリウムイオン電池用の場合はナトリウム塩が用いられる。従って、二次電池の種類に応じて電解質の種類は適宜選択すればよい。 <Electrolyte>
A conventionally well-known thing can be employ | adopted as said electrolyte. For example, a lithium salt is used for a lithium ion battery, and a sodium salt is used for a sodium ion battery. Therefore, what is necessary is just to select the kind of electrolyte suitably according to the kind of secondary battery.
　また、前記電解質としては、フッ素を含有するアニオンを含有するものが好ましい。その様なフッ素含有のアニオンの具体例としては、例えばＢＦ４ －、ＰＦ６ －、ＢＦ３ＣＦ３ －、ＢＦ３Ｃ２Ｆ５ －、ＣＦ３ＳＯ３ －、Ｃ２Ｆ５ＳＯ３ －、Ｃ３Ｆ７ＳＯ３ －、Ｃ４Ｆ９ＳＯ３ －、Ｎ（ＳＯ２Ｆ）２ －、Ｎ（ＣＦ３ＳＯ２）２ －、Ｎ（Ｃ２Ｆ５ＳＯ２）２ －、Ｎ（ＣＦ３ＳＯ２）（ＣＦ３ＣＯ）－、Ｎ（ＣＦ３ＳＯ２）（Ｃ２Ｆ５ＳＯ２）－、Ｃ（ＣＦ３ＳＯ２）３ －等が挙げられる。これらは一種単独で、又は二種以上を併用することができる。フッ素含有アニオンのうち、非水電解液の安全性・安定性、電気伝導率やサイクル特性の向上の観点からは、ＢＦ４ －、ＰＦ６ －、Ｎ（ＣＦ３ＳＯ２）２ －が好ましく、ＢＦ４ －、ＰＦ６ －が特に好ましい。 Moreover, as said electrolyte, what contains the anion containing a fluorine is preferable. Specific examples of such fluorine-containing anions include, for example, BF 4 − , PF 6 − , BF 3 CF 3 − , BF 3 C 2 F 5 − , CF 3 SO 3 − , C 2 F 5 SO 3 − , C 3 F 7 SO 3 − , C 4 F 9 SO 3 − , N (SO 2 F) 2 − , N (CF 3 SO 2 ) 2 − , N (C 2 F 5 SO 2 ) 2 − , N (CF 3 SO 2 ) (CF 3 CO) − , N (CF 3 SO 2 ) (C 2 F 5 SO 2 ) − , C (CF 3 SO 2 ) 3 — and the like. These can be used alone or in combination of two or more. Of the fluorine-containing anions, BF 4 − , PF 6 − , and N (CF 3 SO 2 ) 2 − are preferable from the viewpoint of improving the safety and stability of the non-aqueous electrolyte, electrical conductivity, and cycle characteristics. BF 4 − and PF 6 − are particularly preferable.
　前記電解質の前記有機溶媒に対する濃度は特に限定されず、通常は０．１～２Ｍ、好ましくは０．１５～１．８Ｍ、より好ましくは０．２～１．５Ｍ、特に好ましくは０．３～１．２Ｍである。濃度を０．１Ｍ以上にすることにより、非水電解液の電気伝導率が不十分となるのを防止することができる。その一方、濃度を２Ｍ以下にすることにより、非水電解液の粘度上昇により電気伝導率が低下するのを抑制し、二次電池性能が低下するのを防止することができる。 The concentration of the electrolyte with respect to the organic solvent is not particularly limited, and is usually 0.1 to 2M, preferably 0.15 to 1.8M, more preferably 0.2 to 1.5M, particularly preferably 0.3 to. 1.2M. By making the concentration 0.1 M or more, it is possible to prevent the electrical conductivity of the non-aqueous electrolyte from becoming insufficient. On the other hand, by setting the concentration to 2M or less, it is possible to suppress a decrease in electrical conductivity due to an increase in the viscosity of the non-aqueous electrolyte and to prevent a secondary battery performance from being deteriorated.
　＜有機溶媒＞
　前記非水電解液に用いられる前記有機溶媒（非水溶媒）としては特に限定されず、例えば、環状炭酸エステル、鎖状炭酸エステル、リン酸エステル、環状エーテル、鎖状エーテル、ラクトン化合物、鎖状エステル、ニトリル化合物、アミド化合物、スルホン化合物等が挙げられる。これらの有機溶媒のうち、リチウム二次電池用有機溶媒として一般的に使用されており、入手の容易さや性能の観点からは、炭酸エステルが好ましい。 <Organic solvent>
The organic solvent (nonaqueous solvent) used in the nonaqueous electrolytic solution is not particularly limited. For example, a cyclic carbonate, a chain carbonate, a phosphate ester, a cyclic ether, a chain ether, a lactone compound, a chain Examples thereof include esters, nitrile compounds, amide compounds, and sulfone compounds. Of these organic solvents, they are generally used as organic solvents for lithium secondary batteries, and carbonates are preferred from the viewpoint of availability and performance.
　前記環状炭酸エステルとしては特に限定されず、例えば、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート等が挙げられる。これらのうち、リチウム二次電池の充電効率を向上させる点からは、エチレンカーボネート、プロピレンカーボネート等の環状カーボネートが好ましい。前記鎖状炭酸エステルとしては特に限定されず、例えば、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート等が挙げられる。これらのうち、リチウム二次電池の充電効率を向上させる点からは、ジメチルカーボネート、エチルメチルカーボネートが好ましい。前記リン酸エステルとしては特に限定されず、例えば、リン酸トリメチル、リン酸トリエチル、リン酸エチルジメチル、リン酸ジエチルメチル等が挙げられる。前記環状エーテルとしては特に限定されず、例えば、テトラヒドロフラン、２－メチルテトラヒドロフラン等が挙げられる。前記鎖状エーテルとしては特に限定されず、例えば、ジメトキシエタン等が挙げられる。前記ラクトン化合物としては特に限定されず、例えば、γ－ブチロラクトン等が挙げられる。前記鎖状エステルとしては特に限定されず、例えば、メチルプロピオネート、メチルアセテート、エチルアセテート、メチルホルメート等が挙げられる。前記ニトリル化合物としては特に限定されず、例えば、アセトニトリル等が挙げられる。前記アミド化合物としては特に限定されず、例えば、ジメチルホルムアミド等が挙げられる。前記スルホン化合物としては特に限定されず、例えば、スルホラン、メチルスルホラン等が挙げられる。また、前記有機溶媒分子中に含まれる炭化水素基の水素を少なくとも一部フッ素で置換したものも好適に用いることができる。これらの有機溶媒は一種単独で又は二種以上を混合して用いてもよい。 The cyclic carbonate is not particularly limited, and examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate, and the like. Among these, cyclic carbonates such as ethylene carbonate and propylene carbonate are preferable from the viewpoint of improving the charging efficiency of the lithium secondary battery. The chain carbonate is not particularly limited, and examples thereof include dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate. Among these, dimethyl carbonate and ethyl methyl carbonate are preferable from the viewpoint of improving the charging efficiency of the lithium secondary battery. The phosphate ester is not particularly limited, and examples thereof include trimethyl phosphate, triethyl phosphate, ethyldimethyl phosphate, and diethylmethyl phosphate. The cyclic ether is not particularly limited, and examples thereof include tetrahydrofuran and 2-methyltetrahydrofuran. The chain ether is not particularly limited, and examples thereof include dimethoxyethane. The lactone compound is not particularly limited, and examples thereof include γ-butyrolactone. The chain ester is not particularly limited, and examples thereof include methyl propionate, methyl acetate, ethyl acetate, and methyl formate. The nitrile compound is not particularly limited, and examples thereof include acetonitrile. The amide compound is not particularly limited, and examples thereof include dimethylformamide. The sulfone compound is not particularly limited, and examples thereof include sulfolane and methyl sulfolane. Moreover, what substituted at least partially the hydrogen of the hydrocarbon group contained in the said organic-solvent molecule | numerator with the fluorine can be used suitably. These organic solvents may be used alone or in combination of two or more.
　＜非水電解液の製造＞
　本実施の形態の非水電解液の製造方法は、前記有機溶媒に前記電解質の塩を添加する第１工程と、当該電解質の塩の添加後の有機溶媒に、前記成分（Ａ）を添加する第２工程と、当該電解質の塩及び前記成分（Ａ）の添加後の前記有機溶媒に、前記成分（Ｂ）を添加し、二次電池用非水電解液を作製する第３工程とを少なくとも含む。但し、前記第２工程及び第３工程においては、気泡を脱泡するための工程を行わない。 <Manufacture of non-aqueous electrolyte>
In the method for producing a non-aqueous electrolyte according to the present embodiment, the component (A) is added to the first step of adding the electrolyte salt to the organic solvent and the organic solvent after the addition of the electrolyte salt. At least a second step and a third step of adding the component (B) to the organic solvent after the addition of the electrolyte salt and the component (A) to produce a non-aqueous electrolyte for a secondary battery. Including. However, in the second step and the third step, a step for defoaming bubbles is not performed.
　前記第１工程において、有機溶媒に電解質の塩を添加する方法としては特に限定されず、従来公知の方法を採用することができる。また、添加する際の温度条件についても特に限定されないが、通常は１０℃～４０℃、好ましくは１５℃～３５℃、より好ましくは２０℃～３０℃の範囲内で行われる。 In the first step, the method of adding an electrolyte salt to the organic solvent is not particularly limited, and a conventionally known method can be employed. Further, the temperature condition at the time of addition is not particularly limited, but it is usually 10 ° C. to 40 ° C., preferably 15 ° C. to 35 ° C., more preferably 20 ° C. to 30 ° C.
　前記第２工程においては、電解質の塩が添加された有機溶媒に対し、さらに前記成分（Ａ）を添加する。成分（Ａ）の添加方法としては特に限定されず、従来公知の方法を採用することができる。複数種の成分（Ａ）を添加する場合、それらの添加の順序は適宜必要に応じて設定することができる。また、成分（Ａ）の添加の際、本実施の形態に於いては、気泡の発生が抑制されるため、消泡工程の省略が可能になる。その結果、本実施の形態に於いては、生産効率の向上が図られる。尚、成分（Ａ）の添加の際の温度条件についても特に限定されず、通常は１０℃～４０℃、好ましくは１５℃～３５℃、より好ましくは２０℃～３０℃の範囲内で行われる。 In the second step, the component (A) is further added to the organic solvent to which the electrolyte salt is added. The addition method of component (A) is not particularly limited, and a conventionally known method can be employed. When a plurality of types of components (A) are added, the order of their addition can be appropriately set as necessary. In addition, when the component (A) is added, in the present embodiment, since the generation of bubbles is suppressed, the defoaming step can be omitted. As a result, in this embodiment, the production efficiency is improved. The temperature condition at the time of addition of the component (A) is not particularly limited, and is usually 10 ° C. to 40 ° C., preferably 15 ° C. to 35 ° C., more preferably 20 ° C. to 30 ° C. .
　前記第３工程においては、前記電解質の塩及び成分（Ａ）の添加後の有機溶媒に対し、さらに、前記成分（Ｂ）を添加する。成分（Ｂ）の添加方法としては特に限定されず、従来公知の方法を採用することができる。複数種の成分（Ｂ）を添加する場合、それらの添加の順序は適宜必要に応じて設定することができる。また、成分（Ｂ）の添加の際、本実施の形態に於いては、気泡の発生が抑制されるため消泡工程の省略が可能になる。その結果、生産効率の一層の向上が図られる。 In the third step, the component (B) is further added to the organic solvent after the addition of the electrolyte salt and the component (A). The addition method of component (B) is not particularly limited, and a conventionally known method can be employed. When adding multiple types of component (B), the order of those additions can be suitably set as needed. In addition, when the component (B) is added, in the present embodiment, the generation of bubbles is suppressed, so that the defoaming step can be omitted. As a result, the production efficiency can be further improved.
　尚、有機溶媒、電解質の塩、成分（Ａ）及び成分（Ｂ）としては、製造効率を低下させない範囲内で予め精製等して、不純物が極力少ないものを用いることが好ましい。 It should be noted that as the organic solvent, the electrolyte salt, the component (A) and the component (B), it is preferable to use one having as little impurities as possible by purifying in advance within a range not reducing the production efficiency.
　＜その他＞
　本実施の形態に係る非水電解液には、従来公知のその他の添加剤が添加されていてもよい。 <Others>
Other conventionally known additives may be added to the nonaqueous electrolytic solution according to the present embodiment.
（二次電池）
　次に、本発明の二次電池として、リチウムイオン二次電池を例にして以下に説明する。図１は、前記非水電解液を備えたリチウムイオン二次電池の概略を示す断面模式図である。 (Secondary battery)
Next, a lithium ion secondary battery will be described as an example of the secondary battery of the present invention. FIG. 1 is a schematic cross-sectional view showing an outline of a lithium ion secondary battery provided with the non-aqueous electrolyte.
　本実施の形態に係るリチウムイオン二次電池は、図１に示すように、正極缶４と負極缶５とで形成される内部空間に、正極缶４側から正極１、セパレータ３、負極２、スペーサー７の順に積層された積層体が収納された構造を有している。負極缶５とスペーサー７との間にスプリング８を介在させることによって、正極１と負極２を適度に圧着固定している。本実施の形態の成分（Ａ）及び成分（Ｂ）の化合物を含有する非水電解液は、正極１、セパレータ３及び負極２の間に含浸されている。正極缶４及び負極缶５の間にガスケット６を介在させた状態で、正極缶４及び負極缶５を挟持させることによって両者を結合し、前記積層体を密閉状態にしている。 As shown in FIG. 1, the lithium ion secondary battery according to the present embodiment has a positive electrode 1, a separator 3, a negative electrode 2, an internal space formed by a positive electrode can 4 and a negative electrode can 5, from the positive electrode can 4 side. It has a structure in which a laminated body laminated in the order of the spacers 7 is accommodated. By interposing a spring 8 between the negative electrode can 5 and the spacer 7, the positive electrode 1 and the negative electrode 2 are appropriately pressed and fixed. The nonaqueous electrolytic solution containing the component (A) and the component (B) compound of the present embodiment is impregnated between the positive electrode 1, the separator 3 and the negative electrode 2. In a state where the gasket 6 is interposed between the positive electrode can 4 and the negative electrode can 5, the positive electrode can 4 and the negative electrode can 5 are sandwiched to bond them together, and the laminate is sealed.
　前記正極１における正極活物質層の材料としては特に限定されず、例えば、リチウムイオンが拡散可能な構造を持つ遷移金属化合物、又はその遷移金属化合物とリチウムの酸化物が挙げられる。具体的には、ＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＭｎ２Ｏ４、Ｌｉ２ＭｎＯ３＋ＬｉＭｅＯ２（Ｍｅ＝Ｍｎ、Ｃｏ、Ｎｉ）固溶体、ＬｉＦｅＰＯ４、ＬｉＣｏＰＯ４、ＬｉＭｎＰＯ４、Ｌｉ２ＦｅＰＯ４Ｆ、ＬｉＮｉｘＣｏｙＭｎｚＯ２（０≦ｘ≦１、０≦ｙ≦１、０≦ｚ≦１、ｘ＋ｙ＋ｚ＝１）、ＬｉＮｉｘＣｏｙＡｌｚＯ２（０≦ｘ≦１、０≦ｙ≦１、０≦ｚ≦１、ｘ＋ｙ＋ｚ＝１）、ＬｉＦｅＦ３、ＴｉＯ２、Ｖ２Ｏ５、ＭｏＯ３等の酸化物、ＴｉＳ２、ＦｅＳ等の硫化物、又はポリアセチレン、ポリパラフェニレン、ポリアニリン、ポリピロール等の導電性高分子、活性炭、ラジカルを発生するポリマー、カーボン材料等が使用される。 The material of the positive electrode active material layer in the positive electrode 1 is not particularly limited, and examples thereof include a transition metal compound having a structure capable of diffusing lithium ions, or an oxide of the transition metal compound and lithium. Specifically, LiCoO 2, LiNiO 2, LiMn 2 O 4, Li 2 MnO 3 + LiMeO 2 (Me = Mn, Co, Ni) solid solution, LiFePO 4, LiCoPO 4, LiMnPO 4, Li 2 FePO 4 F, LiNi x Co y Mn z O 2 (0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, x + y + z = 1), LiNi x CoyAl z O 2 (0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, x + y + z = 1) , oxides such as LiFeF 3 , TiO 2 , V 2 O 5 , MoO 3 , sulfides such as TiS 2 , FeS, or conductive such as polyacetylene, polyparaphenylene, polyaniline, polypyrrole, etc. Polymers, activated carbon, polymers that generate radicals, carbon materials, and the like are used.
　正極１は、前記に列挙した正極活物質を、公知の導電助剤や結着剤と共に加圧成型することにより、又は正極活物質を公知の導電助剤や結着剤と共にピロリドン等の有機溶剤に混合し、ペースト状にしたものをアルミニウム箔等の集電体に塗工後、乾燥することにより得ることができる。 The positive electrode 1 is formed by press molding the positive electrode active materials listed above together with known conductive aids and binders, or the positive electrode active material together with known conductive aids and binders and organic solvents such as pyrrolidone. It can be obtained by applying a paste obtained by mixing to a current collector such as an aluminum foil and then drying.
　前記負極２における負極活物質層の材料としては、リチウムを吸蔵、放出することが可能な材料であれば特に限定されず、例えば、金属複合酸化物、リチウム金属、リチウム合金、ケイ素、ケイ素系合金、スズ系合金、金属酸化物、ポリアセチレン等の導電性重合体、Ｌｉ－Ｃｏ－Ｎｉ系材料、炭素材料等が挙げられる。 The material of the negative electrode active material layer in the negative electrode 2 is not particularly limited as long as it is a material capable of occluding and releasing lithium. For example, metal composite oxide, lithium metal, lithium alloy, silicon, silicon-based alloy , Tin-based alloys, metal oxides, conductive polymers such as polyacetylene, Li—Co—Ni-based materials, and carbon materials.
　前記金属複合酸化物としては特に限定されず、例えば、ＬｉｘＦｅ２Ｏ３（０≦ｘ≦１）、ＬｉｘＷＯ２（０≦ｘ≦１）、ＳｎｘＭｅ１ １－ｘＭｅ２ ｙＯｚ（Ｍｅ１＝Ｍｎ、Ｆｅ、Ｐｂ、Ｇｅであり、Ｍｅ２＝Ａｌ、Ｂ、Ｐ、Ｓｉ、周期律表の１～３族の元素、ハロゲンであり、０＜ｘ≦１、１≦ｙ≦３、１≦ｚ≦８）等が挙げられる。 The metal composite oxide is not particularly limited. For example, Li x Fe 2 O 3 (0 ≦ x ≦ 1), Li x WO 2 (0 ≦ x ≦ 1), Sn x Me 1 1-x Me 2 y O z (Me 1 = Mn, Fe, Pb, Ge, Me 2 = Al, B, P, Si, Group 1 to 3 elements of the periodic table, halogen, 0 <x ≦ 1, 1 ≦ y ≦ 3, 1 ≦ z ≦ 8) and the like.
　前記金属酸化物としては特に限定されず、例えばＳｎＯ、ＳｎＯ２、ＳｉＯｘ（０＜ｘ＜２）、ＰｂＯ、ＰｂＯ２、Ｐｂ２Ｏ３、Ｐｂ３Ｏ４、Ｓｂ２Ｏ３、Ｓｂ２Ｏ４、Ｓｂ２Ｏ５、ＧｅＯ、ＧｅＯ２、Ｂｉ２Ｏ３、Ｂｉ２Ｏ４、Ｂｉ２Ｏ５等が挙げられる。 The not particularly restricted but includes metal oxides, for example SnO, SnO 2, SiO x ( 0 <x <2), PbO, PbO 2, Pb 2 O 3, Pb 3 O 4, Sb 2 O 3, Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , Bi 2 O 5 and the like.
　前記炭素材料としては特に限定されず、例えば天然黒鉛、人造黒鉛、ホウ素化黒鉛、フッ化黒鉛、メソカーボンマイクロビーズ、ピッチ系炭素繊維黒鉛化物、カーボンナノチューブ、ハードカーボン、フラーレン等が挙げられる。 The carbon material is not particularly limited, and examples thereof include natural graphite, artificial graphite, borated graphite, fluorinated graphite, mesocarbon microbeads, pitch-based carbon fiber graphitized material, carbon nanotube, hard carbon, fullerene and the like.
　負極２は、前記電極材料の箔状のものや粉末状のものを使用できる。粉末状の場合は、公知の導電助剤及び結着剤と共に加圧成型することにより、又は公知の導電助剤及び結着剤と共にピロリドン等の有機溶剤に混合し、ペースト状にしたものを銅箔等の集電体に塗工後、乾燥することにより得ることができる。　 The negative electrode 2 may be a foil or powder of the electrode material. In the case of powder, copper paste is formed by pressure molding with a known conductive aid and binder, or mixed with pyrrolidone and other organic solvents together with a known conductive aid and binder. It can be obtained by coating a current collector such as a foil and then drying. *
　本実施の形態に係るリチウムイオン二次電池には、正極１と負極２の短絡を防止するために、両者の間に通常、セパレータ３が介在される。セパレータ３の材質や形状は特に制限されないが、上述の非水電解液が通過しやすく、絶縁体で、化学的に安定な材質であるものが好ましい。例えば、各種の高分子材料からなる微多孔性のフィルム、シート等が挙げられる。高分子材料の具体例としては、ナイロン（登録商標）、ニトロセルロース、ポリアクリロニトリル、ポリフッ化ビニリデン、ポリエチレン、ポリプロピレン等のポリオレフィン系高分子が用いられる。電気化学的な安定性・化学的安定性の観点からは、ポリオレフィン系高分子が好ましい。 In the lithium ion secondary battery according to the present embodiment, a separator 3 is usually interposed between the positive electrode 1 and the negative electrode 2 in order to prevent a short circuit. Although the material and shape of the separator 3 are not particularly limited, it is preferable that the above-described non-aqueous electrolyte is easy to pass through, is an insulator, and is a chemically stable material. Examples thereof include microporous films and sheets made of various polymer materials. Specific examples of the polymer material include polyolefin polymers such as nylon (registered trademark), nitrocellulose, polyacrylonitrile, polyvinylidene fluoride, polyethylene, and polypropylene. From the viewpoints of electrochemical stability and chemical stability, polyolefin polymers are preferred.
　本実施の形態のリチウムイオン二次電池の最適な使用電圧は、正極１と負極２の組み合わせによって異なり、通常は、２．４～４．６Ｖの範囲内で使用可能である。 The optimum working voltage of the lithium ion secondary battery of the present embodiment varies depending on the combination of the positive electrode 1 and the negative electrode 2, and can usually be used within the range of 2.4 to 4.6V.
　本実施の形態のリチウムイオン二次電池の形状については特に制限はないが、図１に示すコイン型セルの他に、例えば、円筒型、角型、ラミネート型等が挙げられる。 The shape of the lithium ion secondary battery of the present embodiment is not particularly limited, but examples thereof include a cylindrical type, a square type, and a laminated type in addition to the coin type cell shown in FIG.
　本実施の形態に係る非水電解液であると、非水電解液に気泡が発生するのを抑制することができるため、電池不要の低減が図れ、例えばリチウムイオン二次電池等に好適に用いることができる。但し、図１に示すリチウムイオン二次電池は、本発明の二次電池の一態様を例示的に示したものであり、本発明の二次電池はこれに限定されるものではない。 Since the nonaqueous electrolytic solution according to the present embodiment can suppress the generation of bubbles in the nonaqueous electrolytic solution, it is possible to reduce the need for a battery, and is preferably used for, for example, a lithium ion secondary battery. be able to. However, the lithium ion secondary battery shown in FIG. 1 is an example of one embodiment of the secondary battery of the present invention, and the secondary battery of the present invention is not limited to this.
　以下に、この発明の好適な実施例を例示的に詳しく説明する。但し、この実施例に記載されている材料や配合量等は、特に限定的な記載がない限りは、この発明の範囲をそれらのみに限定する趣旨のものではない。 Hereinafter, preferred embodiments of the present invention will be described in detail by way of example. However, the materials, blending amounts, and the like described in the examples are not intended to limit the scope of the present invention only to those unless otherwise specified.
　（成分（Ａ）の合成）
　ジクロロリン酸リチウム５ｇをＰＦＡ容器に投入し、続いてエタノール１６．４ｇを投入した。その後、攪拌しながら、トリエチルアミン８．６ｇを室温（２０℃）下で滴下した。滴下中、少し発熱し、白色沈殿が系内に析出するのが確認された。 (Synthesis of component (A))
5 g of lithium dichlorophosphate was charged into a PFA container, followed by 16.4 g of ethanol. Thereafter, 8.6 g of triethylamine was added dropwise at room temperature (20 ° C.) while stirring. During dripping, a little heat was generated, and it was confirmed that a white precipitate was deposited in the system.
　その後、ＰＦＡ容器を室温まで冷却して戻し、３時間攪拌した。さらに、減圧濾過を行い、白色沈殿物とエタノール溶液とを分離した。減圧下でろ液からエタノールを留去することにより、白色の固体５．１ｇを得た。得られた白色固体について、イオンクロマトグラフィー〈メトローム社製、商品名；ＩＣ－８５０〉を用いてアニオン分析を行ったところ、得られた白色個体はジエチルリン酸リチウムであることが確認された。 Thereafter, the PFA container was cooled to room temperature and stirred for 3 hours. Further, filtration under reduced pressure was performed to separate a white precipitate and an ethanol solution. By distilling off ethanol from the filtrate under reduced pressure, 5.1 g of a white solid was obtained. The obtained white solid was subjected to anion analysis using ion chromatography (trade name; IC-850, manufactured by Metrohm), and it was confirmed that the obtained white solid was lithium diethyl phosphate.
　（実施例１）
　露点が－７０℃以下のアルゴン雰囲気ドライボックス内で、５０ｃｃのサンプル管（ラボラン）にエチレンカーボネート（ＥＣ）及びジメチルカーボネート（ＤＭＣ）からなる混合溶媒（体積比率でＥＣ：ＤＭＣ＝１：１、キシダ化学株式会社製、リチウムバッテリーグレード）２６．４６ｇ投入し、３．５４ｇのＬｉＰＦ６を添加し濃度が１．０モル／リットルとなる様に調製した。 Example 1
In a dry box with an argon atmosphere with a dew point of −70 ° C. or lower, a mixed solvent consisting of ethylene carbonate (EC) and dimethyl carbonate (DMC) in a 50 cc sample tube (laboran) (volume ratio of EC: DMC = 1: 1, Kishida (Chemical Co., Ltd., lithium battery grade) 26.46 g was added, and 3.54 g of LiPF 6 was added to prepare a concentration of 1.0 mol / liter.
　次に、この混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを、最終生成物である非水電解液の全質量に対し、添加濃度が０．５質量％となる様に添加した。添加の際の液面の高さは２．７ｃｍであった。次に、サンプル管を３０回振とうさせ、再び液面の高さを測定したところ、気泡の発生により当該液面の高さは２．９ｃｍになり、液面が０．２ｃｍ上昇した。しかし、その後、サンプル管を静置し、気泡の消失時間を確認したところ３０秒でほぼ気泡が消失し、１分後には気泡が完全に消失していることを確認した。 Next, lithium diethyl phosphate as the component (A) was added to this mixed solution so that the addition concentration was 0.5% by mass with respect to the total mass of the non-aqueous electrolyte as the final product. The height of the liquid level during the addition was 2.7 cm. Next, the sample tube was shaken 30 times and the height of the liquid level was measured again. As a result of the generation of bubbles, the height of the liquid level became 2.9 cm, and the liquid level rose by 0.2 cm. However, after that, the sample tube was allowed to stand and the disappearance time of the bubbles was confirmed. As a result, it was confirmed that the bubbles almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　続いて、成分（Ｂ）としてのリチウムビスオキサレートボレートを、最終生成物である非水電解液の全質量に対し、添加濃度が０．５質量％となる様に、前記混合溶液に添加した。添加の際の液面の高さ（基準値）は２．７ｃｍであった。次に、サンプル管を３０回振とうさせ、再び液面の高さを測定したところ、気泡の発生により当該液面の高さは３．０ｃｍになっており、液面が０．３ｃｍ上昇した。その後、サンプル管を静置し、気泡の消失時間を確認したところ１０秒でほぼ気泡が消失し、３２秒後には気泡が完全に消失していることを確認した。結果を下記表１に示す。 Subsequently, lithium bisoxalate borate as the component (B) was added to the mixed solution so that the addition concentration was 0.5% by mass with respect to the total mass of the non-aqueous electrolyte as the final product. . The height (reference value) of the liquid level during the addition was 2.7 cm. Next, the sample tube was shaken 30 times and the height of the liquid level was measured again. As a result of the generation of bubbles, the height of the liquid level was 3.0 cm, and the liquid level rose by 0.3 cm. . Thereafter, the sample tube was allowed to stand and the disappearance time of the bubbles was confirmed. As a result, it was confirmed that the bubbles almost disappeared after 10 seconds, and the bubbles disappeared completely after 32 seconds. The results are shown in Table 1 below.
　以上により、本実施例に係る非水電解液を作製した。 As described above, the nonaqueous electrolytic solution according to this example was produced.
　（実施例２）
　本実施例においては、実施例１の成分（Ｂ）としてのリチウムビスオキサレートボレートをトリエチルメチルアンモニウムビスオキサラトボレートに変更した。それ以外は、実施例１と同様にして、本実施例に係る非水電解液を調製した。 (Example 2)
In this example, lithium bisoxalate borate as component (B) of Example 1 was changed to triethylmethylammonium bisoxalatoborate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのトリエチルメチルアンモニウムビスオキサラトボレートを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．０ｃｍであった。また、このときに発生した気泡は１９秒後に完全に消失した。結果を下記表１に示す。 The liquid level after adding triethylmethylammonium bisoxalatoborate as component (B) to the mixed solution after addition of component (A) was 2.7 cm, and the sample tube was shaken 30 times. The height of the subsequent liquid level was 3.0 cm. Also, the bubbles generated at this time completely disappeared after 19 seconds. The results are shown in Table 1 below.
　（実施例３）
　本実施例においては、実施例１の成分（Ｂ）としてのリチウムビスオキサレートボレートをリチウムビスサリチラートボレートに変更した。それ以外は、実施例１と同様にして、本実施例に係る非水電解液を調製した。 (Example 3)
In this example, the lithium bisoxalate borate as the component (B) in Example 1 was changed to lithium bissalicylate borate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのリチウムビスサリチラートボレートを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．２ｃｍであった。また、このときに発生した気泡は３２秒後に完全に消失した。結果を下記表１に示す。 The liquid level after adding lithium bis-salicylate borate as component (B) to the mixed solution after addition of component (A) is 2.7 cm, and the sample tube is shaken 30 times. The height of the liquid surface was 3.2 cm. Also, the bubbles generated at this time disappeared completely after 32 seconds. The results are shown in Table 1 below.
　（実施例４）
　本実施例においては、実施例１の成分（Ｂ）としてのリチウムビスオキサレートボレートをリチウムビス［１，２’－ベンジオラート（２）－Ｏ，Ｏ’］ボレートに変更した。それ以外は、実施例１と同様にして、本実施例に係る非水電解液を調製した。 Example 4
In this example, the lithium bisoxalate borate as the component (B) in Example 1 was changed to lithium bis [1,2′-benzdiolate (2) —O, O ′] borate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのリチウムビス［１，２’－ベンジオラート（２）－Ｏ，Ｏ’］ボレートを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．０ｃｍであった。また、このときに発生した気泡は４６秒後に完全に消失した。結果を下記表１に示す。 The liquid surface height after addition of lithium bis [1,2′-benzdiolate (2) -O, O ′] borate as component (B) to the mixed solution after addition of component (A) is 2.7 cm. The height of the liquid level after shaking the sample tube 30 times was 3.0 cm. Further, the bubbles generated at this time disappeared completely after 46 seconds. The results are shown in Table 1 below.
　（実施例５）
　本実施例においては、実施例１の成分（Ｂ）としてのリチウムビスオキサレートボレートをホウ酸トリメチルに変更した。それ以外は、実施例１と同様にして、本実施例に係る非水電解液を調製した。 (Example 5)
In this example, lithium bisoxalate borate as component (B) of Example 1 was changed to trimethyl borate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのホウ酸トリメチルを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．１ｃｍであった。また、このときに発生した気泡は５１秒後に完全に消失した。結果を下記表１に示す。 The liquid level after addition of trimethyl borate as component (B) to the mixed solution after addition of component (A) is 2.7 cm, and the liquid level after shaking the sample tube 30 times The height was 3.1 cm. The bubbles generated at this time completely disappeared after 51 seconds. The results are shown in Table 1 below.
　（実施例６）
　本実施例においては、実施例１の成分（Ｂ）としてのリチウムビスオキサレートボレートをマレイン酸無水物に変更した。それ以外は、実施例１と同様にして、本実施例に係る非水電解液を調製した。 (Example 6)
In this example, lithium bisoxalate borate as component (B) of Example 1 was changed to maleic anhydride. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのマレイン酸無水物を添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．０ｃｍであった。また、このときに発生した気泡は２５秒後に完全に消失した。結果を下記表１に示す。 The liquid level after adding maleic anhydride as component (B) to the mixed solution after addition of component (A) is 2.7 cm, and the liquid after shaking the sample tube 30 times The height of the surface was 3.0 cm. Further, the bubbles generated at this time completely disappeared after 25 seconds. The results are shown in Table 1 below.
　（実施例７）
　本実施例においては、実施例１の成分（Ｂ）としてのリチウムビスオキサレートボレートをビニレンカーボネートに変更した。それ以外は、実施例１と同様にして、本実施例に係る非水電解液を調製した。 (Example 7)
In this example, lithium bisoxalate borate as component (B) of Example 1 was changed to vinylene carbonate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのビニレンカーボネートを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．１ｃｍであった。また、このときに発生した気泡は１５秒後に完全に消失した。結果を下記表１に示す。 The liquid level after adding vinylene carbonate as the component (B) to the mixed solution after the addition of the component (A) is 2.7 cm, and the liquid level after the sample tube is shaken 30 times. The height was 3.1 cm. Further, the bubbles generated at this time disappeared completely after 15 seconds. The results are shown in Table 1 below.
　（実施例８）
　本実施例においては、実施例１の成分（Ｂ）としてのリチウムビスオキサレートボレートをフルオロエチレンカーボネートに変更した。それ以外は、実施例１と同様にして、本実施例に係る非水電解液を調製した。 (Example 8)
In this example, lithium bisoxalate borate as component (B) of Example 1 was changed to fluoroethylene carbonate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのフルオロエチレンカーボネートを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．１ｃｍであった。また、このときに発生した気泡は２１秒後に完全に消失した。結果を下記表１に示す。 The liquid level after adding fluoroethylene carbonate as the component (B) to the mixed solution after the addition of the component (A) is 2.7 cm, and the liquid level after the sample tube is shaken 30 times. The height was 3.1 cm. The bubbles generated at this time completely disappeared after 21 seconds. The results are shown in Table 1 below.
　（実施例９）
　本実施例においては、実施例１の成分（Ｂ）としてのリチウムビスオキサレートボレートを１，３－プロパンスルトンに変更した。それ以外は、実施例１と同様にして、本実施例に係る非水電解液を調製した。 Example 9
In this example, lithium bisoxalate borate as component (B) in Example 1 was changed to 1,3-propane sultone. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としての１，３－プロパンスルトンを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．２ｃｍであった。また、このときに発生した気泡は２８秒後に完全に消失した。結果を下記表１に示す。 The liquid level after adding 1,3-propane sultone as component (B) to the mixed solution after addition of component (A) was 2.7 cm, and the sample tube was shaken 30 times. The height of the liquid surface was 3.2 cm. Also, the bubbles generated at this time completely disappeared after 28 seconds. The results are shown in Table 1 below.
　（実施例１０）
　本実施例においては、実施例１の成分（Ｂ）としてのリチウムビスオキサレートボレートをＮ，Ｎ－ジメチルアセトアセトアミドに変更した。それ以外は、実施例１と同様にして、本実施例に係る非水電解液を調製した。 (Example 10)
In this example, lithium bisoxalate borate as component (B) in Example 1 was changed to N, N-dimethylacetoacetamide. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのＮ，Ｎ－ジメチルアセトアセトアミドを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。また、このときに発生した気泡は２６秒後に完全に消失した。結果を下記表１に示す。 The liquid level after adding N, N-dimethylacetoacetamide as component (B) to the mixed solution after addition of component (A) was 2.7 cm, and the sample tube was shaken 30 times. The height of the subsequent liquid level was 2.9 cm. Further, the bubbles generated at this time completely disappeared after 26 seconds. The results are shown in Table 1 below.
　（実施例１１）
　本実施例においては、実施例１の成分（Ｂ）としてのリチウムビスオキサレートボレートをジフルオロリン酸リチウムに変更した。それ以外は、実施例１と同様にして、本実施例に係る非水電解液を調製した。 (Example 11)
In this example, lithium bisoxalate borate as the component (B) in Example 1 was changed to lithium difluorophosphate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのジフルオロリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．０ｃｍであった。また、このときに発生した気泡は３０秒後に完全に消失した。結果を下記表１に示す。 The liquid level after adding lithium difluorophosphate as the component (B) to the mixed solution after the addition of the component (A) is 2.7 cm, and the liquid after the sample tube is shaken 30 times The height of the surface was 3.0 cm. Further, the bubbles generated at this time completely disappeared after 30 seconds. The results are shown in Table 1 below.
　（実施例１２）
　本実施例においては、実施例１の成分（Ｂ）としてのリチウムビスオキサレートボレートをリチウムジフルオロビスオキサレートホスフェートに変更した。それ以外は、実施例１と同様にして、本実施例に係る非水電解液を調製した。 Example 12
In this example, the lithium bisoxalate borate as the component (B) in Example 1 was changed to lithium difluorobisoxalate phosphate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのリチウムジフルオロビスオキサレートホスフェートを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．２ｃｍであった。また、このときに発生した気泡は５２秒後に完全に消失した。結果を下記表１に示す。 The liquid level after adding lithium difluorobisoxalate phosphate as component (B) to the mixed solution after addition of component (A) is 2.7 cm, and the sample tube is shaken 30 times. The height of the liquid surface was 3.2 cm. The bubbles generated at this time disappeared completely after 52 seconds. The results are shown in Table 1 below.
　（実施例１３）
　本実施例においては、実施例１の成分（Ｂ）としてのリチウムビスオキサレートボレートをリン酸トリメチルに変更した。それ以外は、実施例１と同様にして、本実施例に係る非水電解液を調製した。 (Example 13)
In this example, lithium bisoxalate borate as component (B) of Example 1 was changed to trimethyl phosphate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのリン酸トリメチルを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．１ｃｍであった。また、このときに発生した気泡は１８秒後に完全に消失した。結果を下記表１に示す。 The liquid level after adding trimethyl phosphate as component (B) to the mixed solution after addition of component (A) is 2.7 cm, and the liquid level after shaking the sample tube 30 times The height was 3.1 cm. The bubbles generated at this time completely disappeared after 18 seconds. The results are shown in Table 1 below.
　（実施例１４）
　本実施例においては、実施例１の成分（Ｂ）としてのリチウムビスオキサレートボレートをリン酸トリス（２，２，２－トリフルオロエチル）に変更した。それ以外は、実施例１と同様にして、本実施例に係る非水電解液を調製した。 (Example 14)
In this example, lithium bisoxalate borate as component (B) in Example 1 was changed to tris (2,2,2-trifluoroethyl) phosphate. Other than that was carried out similarly to Example 1, and prepared the non-aqueous electrolyte based on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのリン酸トリス（２，２，２－トリフルオロエチル）を添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．２ｃｍであった。また、このときに発生した気泡は４１秒後に完全に消失した。結果を下記表１に示す。 The liquid surface height after addition of tris phosphate (2,2,2-trifluoroethyl) as component (B) to the mixed solution after addition of component (A) is 2.7 cm, and the sample tube Was 30 times and the liquid level was 3.2 cm. The bubbles generated at this time completely disappeared after 41 seconds. The results are shown in Table 1 below.
　（実施例１５）
　本実施例においては、実施例１のリチウムビスオキサレートボレートをビス（２，２，２－トリフルオロエチル）ホスホン酸に変更したこと以外は、実施例１と同様にして非水電解液を調製した。 (Example 15)
In this example, a non-aqueous electrolyte was prepared in the same manner as in Example 1 except that the lithium bisoxalate borate of Example 1 was changed to bis (2,2,2-trifluoroethyl) phosphonic acid. did.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのビス（２，２，２－トリフルオロエチル）ホスホン酸を添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．１ｃｍであった。また、このときに発生した気泡は２３秒後に完全に消失した。結果を下記表１に示す。 The liquid surface height after addition of bis (2,2,2-trifluoroethyl) phosphonic acid as component (B) to the mixed solution after addition of component (A) is 2.7 cm. The height of the liquid surface after being shaken 30 times was 3.1 cm. The bubbles generated at this time completely disappeared after 23 seconds. The results are shown in Table 1 below.
　（実施例１６）
　本実施例においては、実施例１のリチウムビスオキサレートボレートをトリメチルホスフィンに変更したこと以外は、実施例１と同様にして非水電解液を調製した。 (Example 16)
In this example, a nonaqueous electrolytic solution was prepared in the same manner as in Example 1 except that the lithium bisoxalate borate in Example 1 was changed to trimethylphosphine.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのトリメチルホスフィンを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．０ｃｍであった。また、このときに発生した気泡は３３秒後に完全に消失した。結果を下記表１に示す。 Further, the liquid level after adding trimethylphosphine as the component (B) to the mixed solution after the addition of the component (A) is 2.7 cm, and the liquid level after the sample tube is shaken 30 times. The height was 3.0 cm. The bubbles generated at this time completely disappeared after 33 seconds. The results are shown in Table 1 below.
　（実施例１７）
　本実施例においては、実施例１のリチウムビスオキサレートボレートをメチルジフェニルホスフィンに変更したこと以外は、実施例１と同様にして非水電解液を調製した。 (Example 17)
In this example, a nonaqueous electrolytic solution was prepared in the same manner as in Example 1 except that the lithium bisoxalate borate in Example 1 was changed to methyldiphenylphosphine.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのメチルジフェニルホスフィンを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．２ｃｍであった。また、このときに発生した気泡は４３秒後に完全に消失した。結果を下記表１に示す。 The liquid level after adding methyldiphenylphosphine as component (B) to the mixed solution after addition of component (A) is 2.7 cm, and the liquid level after shaking the sample tube 30 times The height of was 3.2 cm. The bubbles generated at this time disappeared completely after 43 seconds. The results are shown in Table 1 below.
　（実施例１８）
　本実施例においては、実施例７のビニレンカーボネートの濃度を０．５質量％から０．０５質量％に変更した。それ以外は、実施例７と同様にして、本実施例に係る非水電解液を調製した。 (Example 18)
In this example, the concentration of vinylene carbonate in Example 7 was changed from 0.5% by mass to 0.05% by mass. Other than that was carried out similarly to Example 7, and prepared the non-aqueous electrolyte which concerns on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのビニレンカーボネートを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．１ｃｍであった。また、このときに発生した気泡は２０秒後に完全に消失した。結果を下記表１に示す。 The liquid level after adding vinylene carbonate as the component (B) to the mixed solution after the addition of the component (A) is 2.7 cm, and the liquid level after the sample tube is shaken 30 times. The height was 3.1 cm. Also, the bubbles generated at this time completely disappeared after 20 seconds. The results are shown in Table 1 below.
　（実施例１９）
　本実施例においては、実施例７のビニレンカーボネートの濃度を０．５質量％から５質量％に変更した。それ以外は、実施例７と同様にして、本実施例に係る非水電解液を調製した。 (Example 19)
In this example, the concentration of vinylene carbonate in Example 7 was changed from 0.5% by mass to 5% by mass. Other than that was carried out similarly to Example 7, and prepared the non-aqueous electrolyte which concerns on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのビニレンカーボネートを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．１ｃｍであった。また、このときに発生した気泡は１８秒後に完全に消失した。結果を下記表１に示す。 The liquid level after adding vinylene carbonate as the component (B) to the mixed solution after the addition of the component (A) is 2.7 cm, and the liquid level after the sample tube is shaken 30 times. The height was 3.1 cm. The bubbles generated at this time completely disappeared after 18 seconds. The results are shown in Table 1 below.
　（実施例２０）
　本実施例においては、実施例７のジエチルリン酸リチウムの濃度を０．５質量％から５質量％に変更し、ビニレンカーボネートの濃度を０．５質量％から５質量％に変更した。それ以外は、実施例７と同様にして、本実施例に係る非水電解液を調製した。 (Example 20)
In this example, the concentration of lithium diethyl phosphate in Example 7 was changed from 0.5% by mass to 5% by mass, and the concentration of vinylene carbonate was changed from 0.5% by mass to 5% by mass. Other than that was carried out similarly to Example 7, and prepared the non-aqueous electrolyte which concerns on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのビニレンカーボネートを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。また、このときに発生した気泡は３５秒後には完全に消失した。結果を下記表１に示す。 The liquid level after adding vinylene carbonate as the component (B) to the mixed solution after the addition of the component (A) is 2.7 cm, and the liquid level after the sample tube is shaken 30 times. The height was 2.9 cm. The bubbles generated at this time disappeared completely after 35 seconds. The results are shown in Table 1 below.
　（実施例２１）
　本実施例においては、実施例７のジエチルリン酸リチウムの濃度を０．５質量％から０．０５質量％に変更し、ビニレンカーボネートの濃度を０．５質量％から０．０５質量％に変更した。それ以外は、実施例７と同様にして、本実施例に係る非水電解液を調製した。 (Example 21)
In this example, the concentration of lithium phosphate in Example 7 was changed from 0.5% by mass to 0.05% by mass, and the concentration of vinylene carbonate was changed from 0.5% by mass to 0.05% by mass. did. Other than that was carried out similarly to Example 7, and prepared the non-aqueous electrolyte which concerns on a present Example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、成分（Ａ）としてのジエチルリン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．９ｃｍであった。このときに発生した気泡は３０秒でほぼ消失し、１分後には当該気泡が完全に消失した。 Here, the liquid level after adding lithium diethyl phosphate as the component (A) to the mixed solution obtained by adding LiPF 6 to the mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm, and the sample tube Was 30 times and the liquid level was 2.9 cm. The bubbles generated at this time almost disappeared in 30 seconds, and the bubbles disappeared completely after 1 minute.
　また、成分（Ａ）添加後の混合溶液に成分（Ｂ）としてのビニレンカーボネートを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは２．８ｃｍであった。また、このときに発生した気泡は１２秒後に完全に消失した。結果を下記表１に示す。 The liquid level after adding vinylene carbonate as the component (B) to the mixed solution after the addition of the component (A) is 2.7 cm, and the liquid level after the sample tube is shaken 30 times. The height was 2.8 cm. Further, the bubbles generated at this time completely disappeared after 12 seconds. The results are shown in Table 1 below.
　（比較例１）
　先ず、前記実施例１と同様にして、ＥＣ及びＤＭＣからなる混合溶媒（体積比率でＥＣ：ＤＭＣ＝１：１）に、濃度１．０モル／リットルのＬｉＰＦ６を添加した混合溶液を用意した。 (Comparative Example 1)
First, in the same manner as in Example 1, (EC volume ratio: DMC = 1: 1) mixed solvent of EC and DMC in, to prepare a mixed solution prepared by adding LiPF 6 in a concentration of 1.0 mol / liter .
　次に、前記混合溶液に、ビス（２，２，２トリフルオロエチル）リン酸リチウムを、最終生成物である非水電解液の全質量に対し、添加濃度が０．５質量％となる様に添加した。添加の際の液面の高さは２．７ｃｍであった。次に、サンプル管を３０回振とうさせ、再び液面の高さを測定したところ、気泡の発生により当該液面の高さは３．４ｃｍになっており、液面が０．７ｃｍ上昇した。その後、サンプル管を静置し、１２０秒経過後でも気泡は消失しなかった。 Next, bis (2,2,2trifluoroethyl) lithium phosphate is added to the mixed solution so that the addition concentration is 0.5% by mass with respect to the total mass of the non-aqueous electrolyte as the final product. Added to. The height of the liquid level during the addition was 2.7 cm. Next, the sample tube was shaken 30 times, and the height of the liquid level was measured again. As a result of generation of bubbles, the height of the liquid level was 3.4 cm, and the liquid level rose 0.7 cm. . Thereafter, the sample tube was allowed to stand, and bubbles did not disappear even after 120 seconds had elapsed.
　続いて、前記混合溶液に対し、気泡を消失させるため真空ポンプによる吸引脱気を行った。これにより、混合溶液の気泡を消失させた。これにより、本比較例に係る非水電解液を作成した。 Subsequently, the mixed solution was subjected to suction deaeration using a vacuum pump in order to eliminate bubbles. Thereby, bubbles of the mixed solution disappeared. As a result, a nonaqueous electrolytic solution according to this comparative example was prepared.
　（比較例２）
　本比較例においては、比較例１で調製した電解液に対し、さらに成分（Ｂ）としてのリチウムビスオキサレートボレートを濃度が０．５質量％となるように添加した。それ以外は、比較例１と同様にして、本比較例に係る非水電解液を調製した。 (Comparative Example 2)
In this comparative example, lithium bisoxalate borate as component (B) was further added to the electrolytic solution prepared in comparative example 1 so that the concentration was 0.5 mass%. Other than that was carried out similarly to the comparative example 1, and prepared the non-aqueous electrolyte which concerns on this comparative example.
　ここで、エチレンカーボネート及びジメチルカーボネートからなる混合溶媒にＬｉＰＦ６を添加した混合溶液に、ビス（２，２，２トリフルオロエチル）リン酸リチウムを添加した後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．４ｃｍであった。また、気泡は１２０秒経過後でも消失しなかった。 Here, the liquid level height after adding lithium bis (2,2,2trifluoroethyl) phosphate to a mixed solution obtained by adding LiPF 6 to a mixed solvent composed of ethylene carbonate and dimethyl carbonate is 2.7 cm. Yes, the height of the liquid surface after shaking the sample tube 30 times was 3.4 cm. The bubbles did not disappear even after 120 seconds.
　続いて、気泡を消失させるため真空ポンプによる吸引脱気を行った後、成分（Ｂ）としてのリチウムビスオキサレートボレートを添加した。添加後の液面高さは２．７ｃｍであり、サンプル管を３０回振とうさせた後の液面の高さは３．４ｃｍであった。また、気泡は７５秒後に完全に消失した。結果を下記表１に示す。 Subsequently, suction deaeration with a vacuum pump was performed to eliminate bubbles, and then lithium bisoxalate borate as component (B) was added. The liquid level after the addition was 2.7 cm, and the liquid level after the sample tube was shaken 30 times was 3.4 cm. The bubbles disappeared completely after 75 seconds. The results are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000050
１　正極
２　負極
３　セパレータ
４　正極缶
５　負極缶
６　ガスケット
７　スペーサー
 
  DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3 Separator 4 Positive electrode can 5 Negative electrode can 6 Gasket 7 Spacer

Claims (17)

  1. 　二次電池に用いられる二次電池用非水電解液であって、
    　下記成分（Ａ）及び成分（Ｂ）を含む二次電池用非水電解液。
    　成分（Ａ）：ハロゲン原子を含まず、かつ、下記一般式（１）で表される少なくとも１種のリン酸ジエステル塩；
    　成分（Ｂ）：下記一般式（２）で表される少なくとも１種のホウ素錯体塩、ホウ酸エステル、酸無水物、不飽和結合を有する環状カーボネート、ハロゲン原子を有する環状カーボネート、環状スルホン酸エステル、下記一般式（３）で表されるアセトアセチル基を有するアミン類及び下記一般式（４）～（７）の何れかで表されるリン化合物からなる群より選ばれる少なくとも１種
    Figure JPOXMLDOC01-appb-C000001
     （前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｒ１及びＲ２はハロゲン原子を有しておらず、それぞれ独立して、炭素数が１～２０の炭化水素基、又は炭素数が１～２０の範囲であって、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有する炭化水素基を表す。あるいは、前記Ｒ１とＲ２はハロゲン原子を有しておらず、前記炭素数が１～２０の炭化水素基、又は前記炭素数が１～２０の範囲であり、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有する炭化水素基の何れかであって、相互に結合して環状構造を形成する。前記ｎは価数を表す。）
    Figure JPOXMLDOC01-appb-C000002
     （前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｘ１～Ｘ４はそれぞれ独立しており、任意に選択される１又は２つの組合せが、－ＯＯＣ－Ｙ－ＣＯＯ－、－Ｏ－Ｙ－Ｏ－又は－ＯＯＣ－Ｙ－Ｏ－の環状構造を形成しており、その場合の前記Ｙは、炭素数が０～２０の炭化水素基、又は炭素数が０～２０の範囲であって、ヘテロ原子、不飽和結合若しくは環状構造を有する炭化水素基を表す。あるいは、前記Ｘ１～Ｘ４は、それぞれ独立して、ハロゲン原子、炭素数０～２０のアルキル基、炭素数０～２０のアルコキシ基、炭素数が０～２０の範囲内であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有するアルキル基、又は炭素数が０～２０の範囲内であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有するアルコキシ基を表す。前記ｎは価数を表す。）
    Figure JPOXMLDOC01-appb-C000003
     （前記Ｒ３及びＲ４は、それぞれ独立して、炭素数が１～２０の炭化水素基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合を有する炭化水素基を表す。）
    Figure JPOXMLDOC01-appb-C000004
     （式中、前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ａ１及びＡ２は、それぞれ独立して、酸素原子、硫黄原子又はセレン原子を表す。前記Ｘ５とＸ６は、それぞれ独立して、ハロゲン原子、炭素数が１～２０のアルキル基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基を表す。あるいは、前記Ｘ５とＸ６は、前記炭素数が１～２０のアルキル基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基の何れかであって、相互に結合して環状構造を形成する。前記ｎは価数を表す。）
    Figure JPOXMLDOC01-appb-C000005
     （式中、前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｘ７～Ｘ１２は、それぞれ独立して、ハロゲン原子、炭素数が１～２０のアルキル基、炭素数が１～２０のアルコキシ基、炭素数が１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、炭素数が１～２０のアルキルチオ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ７～Ｘ１２は、任意に選択される少なくとも１つの組合せが、－ＯＯＣ－Ｚ－ＣＯＯ－、－ＯＯＣ－Ｚ－Ｏ－又は－Ｏ－Ｚ－Ｏ－の環状構造を形成しており、その場合の前記Ｚは、炭素数が０～２０の炭化水素基、又は炭素数が０～２０の範囲であって、ハロゲン原子、ヘテロ原子、不飽和結合若しくは環状構造の少なくとも何れか１つを有する炭化水素基を表す。前記ｎは価数を表す。）
    Figure JPOXMLDOC01-appb-C000006
     （式中、前記Ａ３は酸素原子、硫黄原子又はセレン原子を表す。前記Ｘ１３～Ｘ１５は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ１３～Ｘ１５のうち任意に選択される少なくとも１つの組合せが、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基の何れかであって、相互に結合して環状構造を形成する。）
    Figure JPOXMLDOC01-appb-C000007
     （式中、前記Ｘ１６～Ｘ１８は、それぞれ独立して、ハロゲン原子、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ１６～Ｘ１８のうち任意に選択される少なくとも１つの組合せが、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基の何れかであって、相互に結合して環状構造を形成する。）     A non-aqueous electrolyte for a secondary battery used in a secondary battery,
    A non-aqueous electrolyte for a secondary battery comprising the following component (A) and component (B).
    Component (A): at least one phosphoric diester salt that does not contain a halogen atom and is represented by the following general formula (1);
    Component (B): at least one boron complex salt represented by the following general formula (2), boric acid ester, acid anhydride, cyclic carbonate having an unsaturated bond, cyclic carbonate having a halogen atom, cyclic sulfonic acid ester At least one selected from the group consisting of amines having an acetoacetyl group represented by the following general formula (3) and phosphorus compounds represented by any of the following general formulas (4) to (7)
    Figure JPOXMLDOC01-appb-C000001
     (M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. R 1 and R 2 do not have a halogen atom, and each independently represents the number of carbon atoms. Represents a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and having at least one of a heteroatom and an unsaturated bond, or the above R 1 and R 2 Has no halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, or the carbon number in the range of 1 to 20 carbon atoms and having at least one of heteroatoms and unsaturated bonds Any of hydrogen groups, which are bonded to each other to form a cyclic structure, where n represents a valence.)
    Figure JPOXMLDOC01-appb-C000002
     (Wherein M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion or an onium ion. X 1 to X 4 are independent of each other, and one or two combinations selected arbitrarily) Forms a cyclic structure of —OOC—Y—COO—, —O—Y—O— or —OOC—Y—O—, wherein Y is a hydrocarbon having 0 to 20 carbon atoms Or a hydrocarbon group having 0 to 20 carbon atoms and having a hetero atom, an unsaturated bond, or a cyclic structure, or X 1 to X 4 are each independently a halogen atom, An alkyl group having 0 to 20 carbon atoms, an alkoxy group having 0 to 20 carbon atoms, an alkyl group having 0 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond A group, or an alkoxy group having 0 to 20 carbon atoms and having at least one of a halogen atom, a heteroatom and an unsaturated bond, wherein n represents a valence.)
    Figure JPOXMLDOC01-appb-C000003
     (R 3 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, or a carbon group having 1 to 20 carbon atoms and having a halogen atom, a hetero atom or an unsaturated bond. Represents a hydrogen group.)
    Figure JPOXMLDOC01-appb-C000004
     (In the formula, M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. A 1 and A 2 are each independently an oxygen atom, a sulfur atom, or selenium. X 5 and X 6 each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a range having 1 to 20 carbon atoms, and may be a halogen atom, heteroatom or And represents an alkyl group having at least one of a saturated bond, or X 5 and X 6 are each an alkyl group having 1 to 20 carbon atoms, or a range of 1 to 20 carbon atoms, Any of an alkyl group having at least one of an atom, a hetero atom, and an unsaturated bond, and bonded to each other to form a cyclic structure, where n represents a valence.)
    Figure JPOXMLDOC01-appb-C000005
     (In the formula, M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. X 7 to X 12 each independently represent a halogen atom or a carbon number of 1; An alkyl group having ˜20, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a range of 1 to 20 carbon atoms, and at least any one of a halogen atom, a hetero atom and an unsaturated bond An alkyl group having 1 or 2 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond, An alkylthio group having 1 to 20 carbon atoms, or a range having 1 to 20 carbon atoms, and at least a halogen atom, a hetero atom or an unsaturated bond; Or an alkylthio group having any one of X 7 to X 12 , wherein at least one combination selected arbitrarily is —OOC—Z—COO—, —OOC—Z—O— or —O; In which case Z represents a hydrocarbon group having 0 to 20 carbon atoms, or a carbon group having 0 to 20 carbon atoms, a halogen atom, a hetero atom Represents a hydrocarbon group having at least one of an unsaturated bond or a cyclic structure, wherein n represents a valence.)
    Figure JPOXMLDOC01-appb-C000006
     (In the formula, A 3 represents an oxygen atom, a sulfur atom or a selenium atom. X 13 to X 15 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number of 1). An alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond, An alkoxy group having at least one of a halogen atom, a heteroatom and an unsaturated bond, or a carbon atom having a range of 1 to 20 and being a halogen atom, heteroatom or unsaturated Represents an alkylthio group having at least one of the bonds, or at least one combination selected from X 13 to X 15 is a group having 1 to 20 alkyl groups, alkoxy groups having 1 to 20 carbon atoms, alkylthio groups having 1 to 20 carbon atoms, at least one of halogen atoms, heteroatoms and unsaturated bonds in the range of 1 to 20 carbon atoms An alkyl group having a carbon number in the range of 1-20, an alkoxy group having at least one of a halogen atom, a heteroatom or an unsaturated bond, or a carbon number in the range of 1-20, Any of a halogen atom, a hetero atom and an alkylthio group having at least one of an unsaturated bond, which are bonded to each other to form a cyclic structure.)
    Figure JPOXMLDOC01-appb-C000007
     (Wherein X 16 to X 18 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, An alkyl group having at least one of a halogen atom, a heteroatom or an unsaturated bond in the range of 1 to 20, a carbon number in the range of 1 to 20 and a halogen atom, a heteroatom or an unsaturated bond Or an alkylthio group having at least one of a halogen atom, a heteroatom, and an unsaturated bond having 1 to 20 carbon atoms, or at least one of the above, or X 16 ~ X at least one combination selected at any one of 18, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, 1 or 2 carbon atoms An alkylthio group having a carbon number in the range of 1 to 20 and having at least one of a halogen atom, a heteroatom or an unsaturated bond, a carbon number in the range of 1 to 20 and a halogen atom , An alkoxy group having at least one of a heteroatom or an unsaturated bond, or an alkylthio group having 1 to 20 carbon atoms and having at least one of a halogen atom, a heteroatom or an unsaturated bond And bonded to each other to form a cyclic structure.)
  2. 　前記成分（Ａ）の添加量は、前記二次電池用非水電解液の全質量に対し、０．０５質量％～５質量％であり、
    　前記成分（Ｂ）の添加量は、前記二次電池用非水電解液の全質量に対し、０．０５質量％～５質量％である請求項１に記載の二次電池用非水電解液。     The amount of the component (A) added is 0.05% by mass to 5% by mass with respect to the total mass of the non-aqueous electrolyte for secondary battery,
    The non-aqueous electrolyte for secondary battery according to claim 1, wherein the amount of the component (B) added is 0.05% by mass to 5% by mass with respect to the total mass of the non-aqueous electrolyte for secondary battery. .
  3. 　前記成分（Ａ）がジエチルリン酸リチウムである請求項２に記載の二次電池用非水電解液。 The non-aqueous electrolyte for a secondary battery according to claim 2, wherein the component (A) is lithium diethyl phosphate.
  4. 　前記一般式（２）で表されるホウ素錯体塩がリチウムビスオキサラトボレート、トリエチルメチルアンモニウムビスオキサラトボレート、リチウムビスサリチラートボレート又はリチウムビス［１，２’－ベンジオラート（２）－Ｏ，Ｏ’］ボレートである請求項２に記載の二次電池用非水電解液。 The boron complex salt represented by the general formula (2) is lithium bisoxalatoborate, triethylmethylammonium bisoxalatoborate, lithium bissalicylate borate or lithium bis [1,2'-benziolate (2) -O, The nonaqueous electrolytic solution for a secondary battery according to claim 2, which is O ′] borate.
  5. 　前記ホウ酸エステルがホウ酸トリメチルである請求項２に記載の二次電池用非水電解液。 The non-aqueous electrolyte for a secondary battery according to claim 2, wherein the borate ester is trimethyl borate.
  6. 　前記酸無水物がマレイン酸無水物である請求項２に記載の二次電池用非水電解液。 The non-aqueous electrolyte for a secondary battery according to claim 2, wherein the acid anhydride is maleic anhydride.
  7. 　前記不飽和結合を有する環状カーボネートがビニレンカーボネートである請求項２に記載の二次電池用非水電解液。 The non-aqueous electrolyte for a secondary battery according to claim 2, wherein the cyclic carbonate having an unsaturated bond is vinylene carbonate.
  8. 　前記ハロゲン原子を有する環状カーボネートがフルオロエチレンカーボネートである請求項２に記載の二次電池用非水電解液。 The non-aqueous electrolyte for a secondary battery according to claim 2, wherein the cyclic carbonate having a halogen atom is fluoroethylene carbonate.
  9. 　前記環状スルホン酸エステルが１，３－プロパンスルトンである請求項２に記載の二次電池用非水電解液。 The non-aqueous electrolyte for a secondary battery according to claim 2, wherein the cyclic sulfonate ester is 1,3-propane sultone.
  10. 　前記一般式（３）で表されるアセトアセチル基を有するアミン類がＮ，Ｎ－ジメチルアセトアセトアミドである請求項２に記載の二次電池用非水電解液。 The non-aqueous electrolyte for a secondary battery according to claim 2, wherein the amine having an acetoacetyl group represented by the general formula (3) is N, N-dimethylacetoacetamide.
  11. 　前記一般式（４）で表されるリン化合物がジフルオロリン酸リチウムである請求項２に記載の二次電池用非水電解液。 The nonaqueous electrolytic solution for a secondary battery according to claim 2, wherein the phosphorus compound represented by the general formula (4) is lithium difluorophosphate.
  12. 　前記一般式（５）で表されるリン化合物がリチウムジフルオロビスオキサレートホスフェートである請求項２に記載の二次電池用非水電解液。 The nonaqueous electrolytic solution for a secondary battery according to claim 2, wherein the phosphorus compound represented by the general formula (5) is lithium difluorobisoxalate phosphate.
  13. 　前記一般式（６）で表されるリン化合物が、リン酸トリメチル、リン酸トリス（２，２，２－トリフルオロエチル）又はビス（２，２，２－トリフルオロエチル）ホスホン酸である請求項２に記載の二次電池用非水電解液。 The phosphorus compound represented by the general formula (6) is trimethyl phosphate, tris (2,2,2-trifluoroethyl phosphate) or bis (2,2,2-trifluoroethyl) phosphonic acid. Item 3. A nonaqueous electrolytic solution for a secondary battery according to Item 2.
  14. 　前記一般式（７）で表されるリン化合物がトリメチルホスフィン又はメチルジフェニルホスフィンである請求項２に記載の二次電池用非水電解液。 The nonaqueous electrolytic solution for a secondary battery according to claim 2, wherein the phosphorus compound represented by the general formula (7) is trimethylphosphine or methyldiphenylphosphine.
  15. 　二次電池に用いられる二次電池用非水電解液の製造方法であって、
    　有機溶媒に電解質の塩を添加する第１工程と、
    　前記電解質の塩の添加後の有機溶媒に、下記成分（Ａ）を添加する第２工程と、
    　前記電解質の塩及び前記成分（Ａ）の添加後の前記有機溶媒に、下記成分（Ｂ）を添加し、二次電池用非水電解液を作製する第３工程とを有し、
    　前記第２工程で作製した前記成分（Ａ）添加後の有機溶媒、及び前記第３工程において作製した二次電池用非水電解液に対し、気泡を脱泡するための工程を行わない二次電池用非水電解液の製造方法。
    　成分（Ａ）：ハロゲン原子を含まず、かつ、下記一般式（１）で表される少なくとも１種のリン酸ジエステル塩；
    　成分（Ｂ）：下記一般式（２）で表される少なくとも１種のホウ素錯体塩、ホウ酸エステル、酸無水物、不飽和結合を有する環状カーボネート、ハロゲン原子を有する環状カーボネート、環状スルホン酸エステル、下記一般式（３）で表されるアセトアセチル基を有するアミン類及び下記一般式（４）～（７）の何れかで表されるリン化合物からなる群より選ばれる少なくとも１種
    Figure JPOXMLDOC01-appb-C000008
     （前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｒ１及びＲ２はハロゲン原子を有しておらず、それぞれ独立して、炭素数が１～２０の炭化水素基、又は炭素数が１～２０の範囲であって、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有する炭化水素基を表す。あるいは、前記Ｒ１とＲ２はハロゲン原子を有しておらず、前記炭素数が１～２０の炭化水素基、又は前記炭素数が１～２０の範囲であり、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有する炭化水素基の何れかであって、相互に結合して環状構造を形成する。前記ｎは価数を表す。）
    Figure JPOXMLDOC01-appb-C000009
     （前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｘ１～Ｘ４はそれぞれ独立しており、任意に選択される１又は２つの組合せが、－ＯＯＣ－Ｙ－ＣＯＯ－、－Ｏ－Ｙ－Ｏ－又は－ＯＯＣ－Ｙ－Ｏ－の環状構造を形成しており、その場合の前記Ｙは、炭素数が０～２０の炭化水素基、又は炭素数が０～２０の範囲であって、ヘテロ原子、不飽和結合若しくは環状構造を有する炭化水素基を表す。あるいは、前記Ｘ１～Ｘ４は、それぞれ独立して、ハロゲン原子、炭素数０～２０のアルキル基、炭素数０～２０のアルコキシ基、炭素数が０～２０の範囲内であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有するアルキル基、又は炭素数が０～２０の範囲内であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有するアルコキシ基を表す。前記ｎは価数を表す。）
    Figure JPOXMLDOC01-appb-C000010
     （前記Ｒ３及びＲ４は、それぞれ独立して、炭素数が１～２０の炭化水素基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合を有する炭化水素基を表す。）
    Figure JPOXMLDOC01-appb-C000011
     （式中、前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ａ１及びＡ２は、それぞれ独立して、酸素原子、硫黄原子又はセレン原子を表す。前記Ｘ５とＸ６は、それぞれ独立して、ハロゲン原子、炭素数が１～２０のアルキル基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基を表す。あるいは、前記Ｘ５とＸ６は、前記炭素数が１～２０のアルキル基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基の何れかであって、相互に結合して環状構造を形成する。前記ｎは価数を表す。）
    Figure JPOXMLDOC01-appb-C000012
     （式中、前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｘ７～Ｘ１２は、それぞれ独立して、ハロゲン原子、炭素数が１～２０のアルキル基、炭素数が１～２０のアルコキシ基、炭素数が１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、炭素数が１～２０のアルキルチオ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ７～Ｘ１２は、任意に選択される少なくとも１つの組合せが、－ＯＯＣ－Ｚ－ＣＯＯ－、－ＯＯＣ－Ｚ－Ｏ－又は－Ｏ－Ｚ－Ｏ－の環状構造を形成しており、その場合の前記Ｚは、炭素数が０～２０の炭化水素基、又は炭素数が０～２０の範囲であって、ハロゲン原子、ヘテロ原子、不飽和結合若しくは環状構造の少なくとも何れか１つを有する炭化水素基を表す。前記ｎは価数を表す。）
    Figure JPOXMLDOC01-appb-C000013
     （式中、前記Ａ３は酸素原子、硫黄原子又はセレン原子を表す。前記Ｘ１３～Ｘ１５は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ１３～Ｘ１５のうち任意に選択される少なくとも１つの組合せが、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基の何れかであって、相互に結合して環状構造を形成する。）
    Figure JPOXMLDOC01-appb-C000014
     （式中、前記Ｘ１６～Ｘ１８は、それぞれ独立して、ハロゲン原子、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ１６～Ｘ１８のうち任意に選択される少なくとも１つの組合せが、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基の何れかであって、相互に結合して環状構造を形成する。）     A method for producing a non-aqueous electrolyte for a secondary battery used in a secondary battery,
    A first step of adding an electrolyte salt to an organic solvent;
    A second step of adding the following component (A) to the organic solvent after the addition of the electrolyte salt;
    A third step of adding the following component (B) to the organic solvent after the addition of the electrolyte salt and the component (A) to produce a non-aqueous electrolyte for a secondary battery;
    A secondary step in which bubbles are not removed from the organic solvent after the addition of the component (A) prepared in the second step and the non-aqueous electrolyte for secondary battery prepared in the third step is not performed. A method for producing a non-aqueous electrolyte for a battery.
    Component (A): at least one phosphoric diester salt that does not contain a halogen atom and is represented by the following general formula (1);
    Component (B): at least one boron complex salt represented by the following general formula (2), boric acid ester, acid anhydride, cyclic carbonate having an unsaturated bond, cyclic carbonate having a halogen atom, cyclic sulfonic acid ester At least one selected from the group consisting of amines having an acetoacetyl group represented by the following general formula (3) and phosphorus compounds represented by any of the following general formulas (4) to (7)
    Figure JPOXMLDOC01-appb-C000008
     (M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. R 1 and R 2 do not have a halogen atom, and each independently represents the number of carbon atoms. Represents a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and having at least one of a heteroatom and an unsaturated bond, or the above R 1 and R 2 Has no halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, or the carbon number in the range of 1 to 20 carbon atoms and having at least one of heteroatoms and unsaturated bonds Any of hydrogen groups, which are bonded to each other to form a cyclic structure, where n represents a valence.)
    Figure JPOXMLDOC01-appb-C000009
     (Wherein M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion or an onium ion. X 1 to X 4 are independent of each other, and one or two combinations selected arbitrarily) Forms a cyclic structure of —OOC—Y—COO—, —O—Y—O— or —OOC—Y—O—, wherein Y is a hydrocarbon having 0 to 20 carbon atoms Or a hydrocarbon group having 0 to 20 carbon atoms and having a hetero atom, an unsaturated bond, or a cyclic structure, or X 1 to X 4 are each independently a halogen atom, An alkyl group having 0 to 20 carbon atoms, an alkoxy group having 0 to 20 carbon atoms, an alkyl group having 0 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond A group, or an alkoxy group having 0 to 20 carbon atoms and having at least one of a halogen atom, a heteroatom and an unsaturated bond, wherein n represents a valence.)
    Figure JPOXMLDOC01-appb-C000010
     (R 3 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, or a carbon group having 1 to 20 carbon atoms and having a halogen atom, a hetero atom or an unsaturated bond. Represents a hydrogen group.)
    Figure JPOXMLDOC01-appb-C000011
     (In the formula, M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. A 1 and A 2 are each independently an oxygen atom, a sulfur atom, or selenium. X 5 and X 6 each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a range having 1 to 20 carbon atoms, and may be a halogen atom, heteroatom or And represents an alkyl group having at least one of a saturated bond, or X 5 and X 6 are each an alkyl group having 1 to 20 carbon atoms, or a range of 1 to 20 carbon atoms, Any of an alkyl group having at least one of an atom, a hetero atom, and an unsaturated bond, and bonded to each other to form a cyclic structure, where n represents a valence.)
    Figure JPOXMLDOC01-appb-C000012
     (In the formula, M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. X 7 to X 12 each independently represent a halogen atom or a carbon number of 1; An alkyl group having ˜20, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a range of 1 to 20 carbon atoms, and at least any one of a halogen atom, a hetero atom and an unsaturated bond An alkyl group having 1 or 2 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond, An alkylthio group having 1 to 20 carbon atoms, or a range having 1 to 20 carbon atoms, and at least a halogen atom, a hetero atom or an unsaturated bond; Or an alkylthio group having any one of X 7 to X 12 , wherein at least one combination selected arbitrarily is —OOC—Z—COO—, —OOC—Z—O— or —O; In which case Z represents a hydrocarbon group having 0 to 20 carbon atoms, or a carbon group having 0 to 20 carbon atoms, a halogen atom, a hetero atom Represents a hydrocarbon group having at least one of an unsaturated bond or a cyclic structure, wherein n represents a valence.)
    Figure JPOXMLDOC01-appb-C000013
     (In the formula, A 3 represents an oxygen atom, a sulfur atom or a selenium atom. X 13 to X 15 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number of 1). An alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond, An alkoxy group having at least one of a halogen atom, a heteroatom and an unsaturated bond, or a carbon atom having a range of 1 to 20 and being a halogen atom, heteroatom or unsaturated Represents an alkylthio group having at least one of the bonds, or at least one combination selected from X 13 to X 15 is a group having 1 to 20 alkyl groups, alkoxy groups having 1 to 20 carbon atoms, alkylthio groups having 1 to 20 carbon atoms, at least one of halogen atoms, heteroatoms and unsaturated bonds in the range of 1 to 20 carbon atoms An alkyl group having a carbon number in the range of 1-20, an alkoxy group having at least one of a halogen atom, a heteroatom or an unsaturated bond, or a carbon number in the range of 1-20, Any of a halogen atom, a hetero atom and an alkylthio group having at least one of an unsaturated bond, which are bonded to each other to form a cyclic structure.)
    Figure JPOXMLDOC01-appb-C000014
     (Wherein X 16 to X 18 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, An alkyl group having at least one of a halogen atom, a heteroatom or an unsaturated bond in the range of 1 to 20, a carbon number in the range of 1 to 20 and a halogen atom, a heteroatom or an unsaturated bond Or an alkylthio group having at least one of a halogen atom, a heteroatom, and an unsaturated bond having 1 to 20 carbon atoms, or at least one of the above, or X 16 ~ X at least one combination selected at any one of 18, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, 1 or 2 carbon atoms An alkylthio group having a carbon number in the range of 1 to 20 and having at least one of a halogen atom, a heteroatom or an unsaturated bond, a carbon number in the range of 1 to 20 and a halogen atom , An alkoxy group having at least one of a heteroatom or an unsaturated bond, or an alkylthio group having 1 to 20 carbon atoms and having at least one of a halogen atom, a heteroatom or an unsaturated bond And bonded to each other to form a cyclic structure.)
  16. 　前記第２工程における前記成分（Ａ）の添加量は、前記二次電池用非水電解液の全質量に対し、０．０５質量％～５質量％であり、
    　前記第３工程における前記成分（Ｂ）の添加量は、前記二次電池用非水電解液の全質量に対し、０．０５質量％～５質量％である請求項１５に記載の二次電池用非水電解液の製造方法。     The amount of the component (A) added in the second step is 0.05% by mass to 5% by mass with respect to the total mass of the non-aqueous electrolyte for secondary battery,
    The secondary battery according to claim 15, wherein the amount of the component (B) added in the third step is 0.05% by mass to 5% by mass with respect to the total mass of the non-aqueous electrolyte for secondary battery. For producing a non-aqueous electrolyte for use.
  17. 　二次電池用非水電解液、正極及び負極を少なくとも備えた二次電池であって、
    　前記二次電池用非水電解液は、下記成分（Ａ）及び成分（Ｂ）を含むものである二次電池。
    　成分（Ａ）：ハロゲン原子を含まず、かつ、下記一般式（１）で表される少なくとも１種のリン酸ジエステル塩；
    　成分（Ｂ）：下記一般式（２）で表される少なくとも１種のホウ素錯体塩、ホウ酸エステル、酸無水物、不飽和結合を有する環状カーボネート、ハロゲン原子を有する環状カーボネート、環状スルホン酸エステル、下記一般式（３）で表されるアセトアセチル基を有するアミン類及び下記一般式（４）～（７）の何れかで表されるリン化合物からなる群より選ばれる少なくとも１種
    Figure JPOXMLDOC01-appb-C000015
     （前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｒ１及びＲ２はハロゲン原子を有しておらず、それぞれ独立して、炭素数が１～２０の炭化水素基、又は炭素数が１～２０の範囲であって、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有する炭化水素基を表す。あるいは、前記Ｒ１とＲ２はハロゲン原子を有しておらず、前記炭素数が１～２０の炭化水素基、又は前記炭素数が１～２０の範囲であり、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有する炭化水素基の何れかであって、相互に結合して環状構造を形成する。前記ｎは価数を表す。）
    Figure JPOXMLDOC01-appb-C000016
     （前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｘ１～Ｘ４はそれぞれ独立しており、任意に選択される１又は２つの組合せが、－ＯＯＣ－Ｙ－ＣＯＯ－、－Ｏ－Ｙ－Ｏ－又は－ＯＯＣ－Ｙ－Ｏ－の環状構造を形成しており、その場合の前記Ｙは、炭素数が０～２０の炭化水素基、又は炭素数が０～２０の範囲であって、ヘテロ原子、不飽和結合若しくは環状構造を有する炭化水素基を表す。あるいは、前記Ｘ１～Ｘ４は、それぞれ独立して、ハロゲン原子、炭素数０～２０のアルキル基、炭素数０～２０のアルコキシ基、炭素数が０～２０の範囲内であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有するアルキル基、又は炭素数が０～２０の範囲内であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか１つを有するアルコキシ基を表す。前記ｎは価数を表す。）
    Figure JPOXMLDOC01-appb-C000017
     （前記Ｒ３及びＲ４は、それぞれ独立して、炭素数が１～２０の炭化水素基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合を有する炭化水素基を表す。）
    Figure JPOXMLDOC01-appb-C000018
     （式中、前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ａ１及びＡ２は、それぞれ独立して、酸素原子、硫黄原子又はセレン原子を表す。前記Ｘ５とＸ６は、それぞれ独立して、ハロゲン原子、炭素数が１～２０のアルキル基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基を表す。あるいは、前記Ｘ５とＸ６は、前記炭素数が１～２０のアルキル基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基の何れかであって、相互に結合して環状構造を形成する。前記ｎは価数を表す。）
    Figure JPOXMLDOC01-appb-C000019
     （式中、前記Ｍｎ＋はアルカリ金属イオン、アルカリ土類金属イオン、アルミニウムイオン、遷移金属イオン又はオニウムイオンを表す。前記Ｘ７～Ｘ１２は、それぞれ独立して、ハロゲン原子、炭素数が１～２０のアルキル基、炭素数が１～２０のアルコキシ基、炭素数が１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、炭素数が１～２０のアルキルチオ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ７～Ｘ１２は、任意に選択される少なくとも１つの組合せが、－ＯＯＣ－Ｚ－ＣＯＯ－、－ＯＯＣ－Ｚ－Ｏ－又は－Ｏ－Ｚ－Ｏ－の環状構造を形成しており、その場合の前記Ｚは、炭素数が０～２０の炭化水素基、又は炭素数が０～２０の範囲であって、ハロゲン原子、ヘテロ原子、不飽和結合若しくは環状構造の少なくとも何れか１つを有する炭化水素基を表す。前記ｎは価数を表す。）
    Figure JPOXMLDOC01-appb-C000020
     （式中、前記Ａ３は酸素原子、硫黄原子又はセレン原子を表す。前記Ｘ１３～Ｘ１５は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ１３～Ｘ１５のうち任意に選択される少なくとも１つの組合せが、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基の何れかであって、相互に結合して環状構造を形成する。）
    Figure JPOXMLDOC01-appb-C000021
     （式中、前記Ｘ１６～Ｘ１８は、それぞれ独立して、ハロゲン原子、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基を表す。あるいは、前記Ｘ１６～Ｘ１８のうち任意に選択される少なくとも１つの組合せが、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数１～２０のアルキルチオ基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキル基、炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルコキシ基、又は炭素数が１～２０の範囲であって、ハロゲン原子、ヘテロ原子若しくは不飽和結合の少なくとも何れか一つを有するアルキルチオ基の何れかであって、相互に結合して環状構造を形成する。）
          A secondary battery comprising at least a non-aqueous electrolyte for a secondary battery, a positive electrode and a negative electrode,
    The non-aqueous electrolyte for a secondary battery is a secondary battery containing the following component (A) and component (B).
    Component (A): at least one phosphoric diester salt that does not contain a halogen atom and is represented by the following general formula (1);
    Component (B): at least one boron complex salt represented by the following general formula (2), boric acid ester, acid anhydride, cyclic carbonate having an unsaturated bond, cyclic carbonate having a halogen atom, cyclic sulfonic acid ester At least one selected from the group consisting of amines having an acetoacetyl group represented by the following general formula (3) and phosphorus compounds represented by any of the following general formulas (4) to (7)
    Figure JPOXMLDOC01-appb-C000015
     (M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. R 1 and R 2 do not have a halogen atom, and each independently represents the number of carbon atoms. Represents a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and having at least one of a heteroatom and an unsaturated bond, or the above R 1 and R 2 Has no halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, or the carbon number in the range of 1 to 20 carbon atoms and having at least one of heteroatoms and unsaturated bonds Any of hydrogen groups, which are bonded to each other to form a cyclic structure, where n represents a valence.)
    Figure JPOXMLDOC01-appb-C000016
     (Wherein M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion or an onium ion. X 1 to X 4 are independent of each other, and one or two combinations selected arbitrarily) Forms a cyclic structure of —OOC—Y—COO—, —O—Y—O— or —OOC—Y—O—, wherein Y is a hydrocarbon having 0 to 20 carbon atoms Or a hydrocarbon group having 0 to 20 carbon atoms and having a hetero atom, an unsaturated bond, or a cyclic structure, or X 1 to X 4 are each independently a halogen atom, An alkyl group having 0 to 20 carbon atoms, an alkoxy group having 0 to 20 carbon atoms, an alkyl group having 0 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond A group, or an alkoxy group having 0 to 20 carbon atoms and having at least one of a halogen atom, a heteroatom and an unsaturated bond, wherein n represents a valence.)
    Figure JPOXMLDOC01-appb-C000017
     (R 3 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, or a carbon group having 1 to 20 carbon atoms and having a halogen atom, a hetero atom or an unsaturated bond. Represents a hydrogen group.)
    Figure JPOXMLDOC01-appb-C000018
     (In the formula, M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. A 1 and A 2 are each independently an oxygen atom, a sulfur atom, or selenium. X 5 and X 6 each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a range having 1 to 20 carbon atoms, and may be a halogen atom, heteroatom or And represents an alkyl group having at least one of a saturated bond, or X 5 and X 6 are each an alkyl group having 1 to 20 carbon atoms, or a range of 1 to 20 carbon atoms, Any of an alkyl group having at least one of an atom, a hetero atom, and an unsaturated bond, and bonded to each other to form a cyclic structure, where n represents a valence.)
    Figure JPOXMLDOC01-appb-C000019
     (In the formula, M n + represents an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion, or an onium ion. X 7 to X 12 each independently represent a halogen atom or a carbon number of 1; An alkyl group having ˜20, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a range of 1 to 20 carbon atoms, and at least any one of a halogen atom, a hetero atom and an unsaturated bond An alkyl group having 1 or 2 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond, An alkylthio group having 1 to 20 carbon atoms, or a range having 1 to 20 carbon atoms, and at least a halogen atom, a hetero atom or an unsaturated bond; Or an alkylthio group having any one of X 7 to X 12 , wherein at least one combination selected arbitrarily is —OOC—Z—COO—, —OOC—Z—O— or —O; In which case Z represents a hydrocarbon group having 0 to 20 carbon atoms, or a carbon group having 0 to 20 carbon atoms, a halogen atom, a hetero atom Represents a hydrocarbon group having at least one of an unsaturated bond or a cyclic structure, wherein n represents a valence.)
    Figure JPOXMLDOC01-appb-C000020
     (In the formula, A 3 represents an oxygen atom, a sulfur atom or a selenium atom. X 13 to X 15 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number of 1). An alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms and having at least one of a halogen atom, a hetero atom and an unsaturated bond, An alkoxy group having at least one of a halogen atom, a heteroatom and an unsaturated bond, or a carbon atom having a range of 1 to 20 and being a halogen atom, heteroatom or unsaturated Represents an alkylthio group having at least one of the bonds, or at least one combination selected from X 13 to X 15 is a group having 1 to 20 alkyl groups, alkoxy groups having 1 to 20 carbon atoms, alkylthio groups having 1 to 20 carbon atoms, at least one of halogen atoms, heteroatoms and unsaturated bonds in the range of 1 to 20 carbon atoms An alkyl group having a carbon number in the range of 1-20, an alkoxy group having at least one of a halogen atom, a heteroatom or an unsaturated bond, or a carbon number in the range of 1-20, Any of a halogen atom, a hetero atom and an alkylthio group having at least one of an unsaturated bond, which are bonded to each other to form a cyclic structure.)
    Figure JPOXMLDOC01-appb-C000021
     (Wherein X 16 to X 18 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, An alkyl group having at least one of a halogen atom, a heteroatom or an unsaturated bond in the range of 1 to 20, a carbon number in the range of 1 to 20 and a halogen atom, a heteroatom or an unsaturated bond Or an alkylthio group having at least one of a halogen atom, a heteroatom, and an unsaturated bond having 1 to 20 carbon atoms, or at least one of the above, or X 16 ~ X at least one combination selected at any one of 18, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, 1 or 2 carbon atoms An alkylthio group having a carbon number in the range of 1 to 20 and having at least one of a halogen atom, a heteroatom or an unsaturated bond, a carbon number in the range of 1 to 20 and a halogen atom , An alkoxy group having at least one of a heteroatom or an unsaturated bond, or an alkylthio group having 1 to 20 carbon atoms and having at least one of a halogen atom, a heteroatom or an unsaturated bond And bonded to each other to form a cyclic structure.)
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