WO2015016187A1 - Solution d'électrolyte de batterie secondaire non aqueuse et batterie secondaire non aqueuse - Google Patents

Solution d'électrolyte de batterie secondaire non aqueuse et batterie secondaire non aqueuse Download PDF

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WO2015016187A1
WO2015016187A1 PCT/JP2014/069850 JP2014069850W WO2015016187A1 WO 2015016187 A1 WO2015016187 A1 WO 2015016187A1 JP 2014069850 W JP2014069850 W JP 2014069850W WO 2015016187 A1 WO2015016187 A1 WO 2015016187A1
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group
compound
carbon atoms
secondary battery
atom
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PCT/JP2014/069850
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Japanese (ja)
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児玉　邦彦
郁雄 木下
吉憲 金澤
稔彦 八幡
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富士フイルム株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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 an electrolyte for a non-aqueous secondary battery containing a non-aqueous solvent and a non-aqueous secondary battery using the same.
  • Lithium ion secondary batteries can achieve a large energy density in charge and discharge compared to lead batteries and nickel cadmium batteries. Utilizing this characteristic, application to portable electronic devices such as mobile phones and notebook personal computers is widespread. Accordingly, as a power source for portable electronic devices, development of a secondary battery that is particularly lightweight and capable of obtaining a high energy density is in progress. Furthermore, there is a strong demand for small size, light weight, long life, and reliability. High reliability is essential for applications such as electric vehicles and power storage equipment, which are expected to increase in capacity in the future, and there is a strong demand for both battery performance and reliability.
  • a combination of a carbonate solvent such as propylene carbonate or diethyl carbonate and an electrolyte salt such as lithium hexafluorophosphate is widely used. This is because they have high conductivity and are stable in potential.
  • the present invention provides an electrolyte solution for a non-aqueous secondary battery and a non-aqueous secondary battery that simultaneously satisfy high flame retardancy, durability at high temperature, and maintenance of battery characteristics in large current discharge at low temperature. For the purpose of provision.
  • (I) Compound represented by the following formula (1)
  • (II) At least one compound selected from the following (2-1) to (2-3) (2-1) represented by the following formula (2-1) (2-2) Compound having alkyne structure (2-3) Cyclic ether compound (Wherein R 1 to R 6 each represent a monovalent substituent.
  • At least one of these substituents is —NR A R B , —N ⁇ R C , or an azide group; Is a halogen atom, n represents an integer of 1 or more, and R A and R B are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, silyl group, or A substituent represented by the following formula (1A), (1B), (1C), or (1D) R C represents a substituent represented by any of the following formulas (C1) to (C6) .) (In the formula, R 1A1 , R 1C1 , R 1D1 and R 1D2 represent an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a halogen atom, or an amino group.
  • X A1 represents an oxygen atom or a sulfur atom.
  • X D1 represents an oxygen atom, a sulfur atom, or a nitrogen atom
  • X D1 is an oxygen atom, a sulfur atom
  • R 1D3 is not a substituent .
  • X D1 is a nitrogen atom
  • R 1D3 is an alkyl group, an aryl group
  • R 1B1 and R 1B2 each represents an alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a phosphonyl group, or a silyl group
  • * represents a bond.
  • R X1 , R X2 and R X3 represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a heterocyclic group, a halogen atom, or a silyl group.
  • R Y1 and R Y2 Represents a halogen atom, and * represents a bond.
  • Ra 1 to Ra 3 are independently an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, or — (CH 2 ) n C ( ⁇ O) — (O) m Rb 4 (n is 0 or 1, m represents 0 or 1, and Rb 4 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, and X represents an oxygen atom, a sulfur atom, or N (Ra 12 ), and Ra 12 represents a hydrogen atom.
  • a nonaqueous secondary battery comprising the electrolyte for a nonaqueous secondary battery according to any one of [1] to [5], a positive electrode, and a negative electrode.
  • the positive electrode active material is made of a material containing nickel and / or manganese.
  • the active material of the negative electrode is made of a material containing at least one selected from carbon, silicon, titanium, and tin.
  • substituents and the like may be the same as or different from each other. Further, when a plurality of substituents and the like are close to each other, they may be bonded to each other or condensed to form a ring. At this time, the hetero linking group described later may be incorporated in the ring.
  • the non-aqueous electrolyte of the present invention achieves durability under high temperature conditions in a secondary battery equipped with the non-aqueous electrolyte, and can exhibit high flame retardancy while suppressing capacity deterioration in low temperature / large current discharge. Excellent effects such as. Furthermore, if necessary, the battery is adapted to a battery using a positive electrode material that can be used up to a high potential containing Ni and / or Mn, and exhibits the above-described excellent performance.
  • the nonaqueous electrolytic solution of the present invention contains a nonaqueous solvent, an electrolyte, the following compound (I), and the following compound (II).
  • (I) Compound represented by the following formula (1)
  • (II) At least one compound selected from the following (2-1) to (2-3) (2-1) represented by the following formula (2-1) (2-2) Compound having alkyne structure (2-3) Cyclic ether compound
  • R 1 to R 6 each represent a monovalent substituent. At least one of the substituents for R 1 to R 6 is —NR A R B , —N ⁇ R C , or an azide group, and at least one other is a halogen atom. Among them, all of R 1 to R 6 are a group selected from —NR A R B , —N ⁇ R C , and an azide group or a combination thereof (hereinafter, this may be referred to as a “specific nitrogen-containing group”). , And preferably in combination with a halogen atom. As the halogen atom, fluorine is preferred.
  • the number of the specific nitrogen-containing group is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3, particularly preferably 1 to 2, and still more preferably 1. .
  • As a substitution position it is preferable that one specific nitrogen-containing group is substituted on one phosphorus atom.
  • R 1 to R 6 may be adjacent to each other to form a ring containing a phosphorus atom.
  • R 1 to R 6 may be different from each other or the same. In particular, when a ring is formed, it is preferable that R 1 and R 2 , R 3 and R 4 , R 5 and R 6 form a ring.
  • the substituents R 1 to R 6 are preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, the specific nitrogen-containing group, or a halogen atom.
  • an alkyl group having 1 to 6 carbon atoms an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, An arylthio group having 6 to 12 carbon atoms, a halogen atom (preferably chlorine or fluorine), and the specific nitrogen-containing group, and particularly preferably the specific nitrogen-containing group, fluorine atom, an alkyl group having 1 to 6 carbon atoms, or An alkoxy group having 1 to 6 carbon atoms.
  • the alkyl group and aryl group may be substituted.
  • the alkyl group may be linear or branched.
  • ⁇ N n represents an integer of 1 or more, preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.
  • R A , R B R A and R B are a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, a cyano group, a silyl group, or the following formula (1A), (1B), (1C), or (1D) It is a substituent represented by these.
  • an alkyl group, an aryl group, a substituent represented by the formula (1A) or the formula (1D) is preferable, and an alkyl group having 1 to 8 carbon atoms or a carbon group having 1 to 8 carbon atoms is particularly preferable.
  • the total number of carbon atoms is particularly preferably 4 or less.
  • R A and R B may be bonded to each other or condensed to form a ring containing a nitrogen atom.
  • the alkyl group may be linear or branched.
  • R A, R B may be the same or different from each other.
  • R 1A1 , R 1C1 , R 1D1 , R 1D2 each represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a halogen atom, or an amino group.
  • substituents include the following examples. That is, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, a chlorine group, and a fluorine atom are preferable. More preferred are an alkyl group having ⁇ 6, an alkoxy group having 1 to 6 carbon atoms, a chlorine group and a fluorine atom. These substituents may be further substituted. * Represents a bond.
  • R 1B1 , R 1B2 R 1B1 and R 1B2 each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a silyl group, or a phosphonyl group (—P ( ⁇ O) (OR N ) 2 ) ( RN is as defined below).
  • Preferred examples of these substituents include the following examples.
  • Particularly preferred are alkylsulfonyl groups having 1 to 6 carbon atoms, silyl groups having 1 to 6 carbon atoms, and phosphonyl groups having 1 to 12 carbon atoms.
  • X A1 represents an oxygen atom or a sulfur atom.
  • X D1 represents an oxygen atom, a sulfur atom, or a nitrogen atom.
  • R 1D3 is not a substituent.
  • R 1D3 is an alkyl group (preferably having 1 to 4 carbon atoms), an aryl group (preferably having 6 to 12 carbon atoms), a silyl group (preferably having 1 to 6 carbon atoms), or a phosphonyl group. (Preferably having 1 to 12 carbon atoms).
  • R c represents a substituent represented by any one of formulas (C1) to (C6).
  • R X1 , R X2 and R X3 are alkyl groups (preferably having 1 to 6 carbon atoms), aryl groups (preferably having 6 to 24 carbon atoms), alkoxy groups (preferably having 1 to 6 carbon atoms), aryloxy groups (preferably Has 6 to 24 carbon atoms, an alkylthio group (preferably 1 to 6 carbon atoms), an arylthio group (preferably 6 to 24 carbon atoms), a heterocyclic group (preferably 1 to 12 carbon atoms), a halogen atom, or silyl Represents a group (preferably having 1 to 6 carbon atoms).
  • R Y1 and R Y2 represent a halogen atom.
  • R X1 , R X2 and R X3 are each an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, a chlorine atom, a fluorine atom, or 1 to 6 carbon atoms.
  • R 1 to R 6 are composed of a halogen atom (preferably a fluorine atom) and the specific nitrogen-containing group (more preferably —NR A R B ).
  • a halogen atom preferably a fluorine atom
  • the specific nitrogen-containing group more preferably —NR A R B .
  • 1 to 3 of them are the specific nitrogen-containing group, more preferably the specific nitrogen-containing group is 1 or 2, and still more preferably when the specific nitrogen-containing group is 1. is there.
  • the compound represented by the above formula (1) can be synthesized by a conventional method, but for example, the method described in German Patent Publication No. 2139691 can be referred to. Further, after introducing the same amino group as the target product into hexachlorocyclotriphosphazene, the target product can also be obtained by fluorination with a fluorinating agent such as sodium fluorinated, potassium fluorinated, or antimony fluorinated. .
  • amination of chlorocyclotriphosphazene and fluorocyclotriphosphazene in the above method can be used as an acid remover that produces the same amine as the target product, but the same amine, inorganic base and organic as the target product.
  • the inorganic base is preferably an inorganic base composed of an anion and a metal cation, particularly preferably an anion as a hydroxide, carbonate, bicarbonate, or fluoride, and a metal cation as an alkali metal, A combination selected from alkaline earth metals is preferred.
  • the metal cation is preferably selected from sodium, potassium, magnesium, and calcium.
  • Preferable examples include hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as potassium carbonate, sodium carbonate and sodium hydrogen carbonate, fluorides such as sodium fluorinated and potassium fluorinated, and triethylamine as the organic base.
  • Examples thereof include trialkylamines such as diisopropylethylamine, methylmorpholine and diazabicycloundecene, and aromatic bases such as pyridine and lutidine.
  • the solvent used at the time of synthesis is a commonly used solvent, and can be used without any problem.
  • Preferred examples include ester solvents, ether solvents, nitrile solvents, aliphatic solvents, and organic solvent-water two-layer solvents. .
  • ester solvents such as ethyl acetate and butyl acetate
  • ether solvents such as diethyl ether, tert-butyl methyl ether and cyclopentyl methyl ether
  • nitrile solvents such as acetonitrile
  • aliphatic solvents such as hexane and decane
  • a two-layer solvent such as toluene-water and ethyl acetate-water.
  • ether solvents and nitrile solvents are preferable.
  • an amine-metal bond can be formed and reacted with chlorocyclotriphosphazene or fluorocyclotriphosphazene.
  • amine-metal bonds include bonds with alkali metals such as amine-lithium and amine-sodium bonds, bonds with alkaline earth metals such as amine-calcium bonds, and bonds with silicon such as amine-trimethylsilyl bonds.
  • the concentration of the compound represented by the formula (1) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more with respect to the total electrolyte solution (including the electrolyte). .
  • the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.
  • Ra 1 to Ra 3 are independently an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms), an alkoxy group (preferably 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms). More preferably, 1 to 3 is particularly preferable), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 and particularly preferably 6 to 10), a halogen atom, an amino group (having 0 to 6 carbon atoms). Preferably 0 to 3), or — (CH 2 ) n C ( ⁇ O) — (O) m Rb 4 .
  • Rb 4 represents an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 4 carbon atoms), an aryl group (C6-C22 is preferable, C6-C14 is more preferable, and C6-C10 is particularly preferable), or aralkyl groups (C7-C23 is preferable, C7-15 is more preferable, C7-11 is particularly preferable) It is.
  • X represents an oxygen atom, a sulfur atom, or N (Ra 12 ).
  • Ra 12 represents a hydrogen atom or a monovalent substituent.
  • the alkyl group in Ra 1 to Ra 3 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.
  • the alkoxy group preferably has 1 to 8 carbon atoms, and is an unsubstituted alkoxy group such as a methoxy group, an ethoxy group, or a butoxy group, 2,2,2-trifluoroethoxy group, 1,1,1,3,3,3- Examples include fluorine-substituted alkoxy groups such as hexafluoroisopropoxy group and perfluorobutylethyl group, methoxy group, 2,2,2-trifluoroethoxy group, 1,1,1,3,3,3-hexa A fluoroisopropoxy group is preferred.
  • Ra 1 to Ra 3 may be an aralkyloxy group having 7 to 20 carbon atoms (-O-Alk-Ar: Alk is an alkylene group having 1 to 6 carbon atoms, Ar is an aryl group having 6 to 14 carbon atoms). preferable.
  • the aryloxy group is preferably a phenoxy group or a fluorine-substituted phenoxy group.
  • a halogen atom a chlorine atom and a fluorine atom are preferable, and a fluorine atom is more preferable.
  • the amino group is preferably a dialkylamino group, and a dialkylamino group having 2 to 8 carbon atoms in total, such as a dimethylamino group, a diethylamino group, or a dibutylamino group.
  • the monovalent substituent in Ra 12 is preferably an alkyl group (preferably having 1 to 6 carbon atoms), —S ( ⁇ O) 2 Ra 13 (Ra 13 is an alkyl group (preferably having 1 to 6 carbon atoms), an aryl group.
  • Ra 1 to Ra 3 and Ra 12 may further have a substituent T, and among them, a halogen atom (fluorine atom), a cyano group, and the like can be given.
  • the concentration of the compound represented by the formula (2-1) is preferably 0.01% by mass or more, and more preferably 0.5% by mass or more with respect to the total electrolytic solution.
  • the upper limit is preferably 10% by mass or less, and more preferably 7% by mass or less.
  • the compound having an alkyne structure is not particularly limited, but has an alkyne bond (carbon-carbon triple bond) in the molecule. Further, in the molecule, —C ( ⁇ O) O— bond, —O—C ( ⁇ O) O— bond, —S ( ⁇ O) 2 O— bond, —O—S ( ⁇ O) 2 O— bond, It preferably has an aromatic ring structure. It is preferable that 1 to 3 alkyne structures are contained in the molecule.
  • the compound having an alkyne structure is a compound represented by any of the following formulas (2-2a) to (2-2g).
  • Rc 1 to Rc 14 represent a hydrogen atom or a monovalent group. At least one of Rc 1 and Rc 2 has an alkyne structure (carbon-carbon triple bond). At least one of Rc 3 and Rc 4 has an alkyne structure. At least one of Rc 5 and Rc 6 has an alkyne structure. At least one of Rc 7 and Rc 8 has an alkyne structure. At least one of Rc 9 and Rc 10 has an alkyne structure. At least one of Rc 11 and Rc 12 has an alkyne structure. At least one of Rc 13 and Rc 14 has an alkyne structure.
  • Lc represents a hydrocarbon linking group described later, and is preferably an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and particularly preferably 1 to 3).
  • Rc 1 to Rc 14 are monovalent groups, examples of the substituent T described below are given except for groups having an alkyne structure.
  • an alkyl group preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms
  • an alkenyl group having 2 to 2 carbon atoms.
  • 12 is preferable, 2 to 6 are more preferable), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 and particularly preferably 6 to 10), and an aralkyl group (preferably having 7 to 23 carbon atoms, 7 To 15 are more preferable, and 7 to 11 are particularly preferable, and a silyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and particularly preferably 1 to 3) is preferable.
  • These groups may further have a substituent T described later, and examples of the further substituent include a halogen atom (fluorine atom) and a cyano group.
  • Examples of the group having an alkyne structure include the following structure (A1).
  • L 1 has the same meaning as a single bond or a linking group L (a hydrocarbon linking group, a hetero linking group, or a linking group obtained by combining these), and an alkylene group (preferably having 1 to 12 carbon atoms, preferably having 1 to 6 carbon atoms). More preferably, 1 to 3 is particularly preferable, and an alkenylene group (2 to 12 carbon atoms is preferable, and 2 to 6 are more preferable), or a single bond is preferable.
  • L 2 has the same meaning as the linking group L (a hydrocarbon linking group, a hetero linking group, or a linking group obtained by combining these), and is preferably a hetero linking group.
  • nl is an integer of 0 to 10, preferably 0 to 4, more preferably 0 to 2, and particularly preferably 1.
  • R 21 examples include a substituent T, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, 6 To 14 are more preferable, and 6 to 10 are particularly preferable), aralkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 15 carbon atoms, particularly preferably 7 to 11 carbon atoms), amino groups (preferably 0 to 6 carbon atoms are preferable). 0 to 3 are more preferable), a silyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and particularly preferably 1 to 3), or a hydrogen atom is preferable.
  • an alkyl group preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms
  • an aryl group preferably having 6 to 22 carbon atoms, 6 To 14 are more preferable, and 6 to 10
  • the compound having an alkyne structure may have two or more structures of 2-2a to 2-2g in one molecule.
  • Rc 1 to Rc 14 may be bonded to each other to form a ring structure. When there are a plurality of Rc 1 to Rc 10 in one molecule, they may be different from each other.
  • the above ring may interpose a hetero linking group described later.
  • the concentration of the compound having an alkyne structure is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.2% by mass or more with respect to the total electrolyte solution.
  • the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less.
  • Cyclic ether compound a 5- or 6-membered ring ether compound is preferable, and a compound having 1 or 2 oxygen atoms in the ring is preferable.
  • the cyclic ether compound is preferably represented by any of the following formulas (B1) to (B5).
  • R 31 to R 36 are each independently an arbitrary substituent T, and among them, an alkyl group, an alkenyl group, and an aryl group are preferable. These groups may be substituted via a hetero linking group described later, and a hetero linking group may be interposed in the substituent.
  • the substituent the following (A2) is preferable. * -L 1- (O) na- (CO) nb- (O) nc -R 37 (A2) L 1 is synonymous with the formula (A1).
  • na and nc are 0 or 1.
  • nb is an integer of 0-2.
  • na + nb + nc is 1 or more.
  • R 37 includes a hydrogen atom or an arbitrary substituent T, and examples thereof include a group having the structure of the above cyclic ethers (B1) to (B5), an alkyl group, and a heterocyclic group (tetrahydrofuran, tetrahydropyran, etc.). Two or more adjacent R 31 to R 36 may be bonded or condensed to form a ring. At this time, a hetero linking group described later may be incorporated.
  • n1 represents an integer of 0 to 8.
  • n2 represents an integer of 0 to 6.
  • n3 represents an integer of 0 to 10.
  • n4 represents an integer of 0 to 8.
  • n5 and n6 each represents an integer of 0 to 5.
  • Formulas (B1) to (B5) may each have a dimer structure linked to each other.
  • Preferred are aliphatic cyclic ether compounds such as tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 1,3-dioxolane or derivatives thereof, and cyclic ether compounds in which an aromatic ring such as benzofuran or dibenzofuran is substituted or condensed.
  • Two or more cyclic ether structures may be bonded via a single bond or a linking group L described later.
  • the concentration of the cyclic ether compound is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.5% by mass or more with respect to the total electrolytic solution.
  • the upper limit is preferably 10% by mass or less, more preferably 7% by mass or less, and particularly preferably 5% by mass or less.
  • compound (II) compound defined by any one of (2-1) to (2-3)
  • its concentration is preferably 0.01% by mass or more, more preferably 0.1% by mass. It is at least 0.5% by mass, more preferably at least 0.5% by mass.
  • the upper limit is preferably 10% by mass or less, more preferably 7% by mass or less, and particularly preferably 5% by mass or less.
  • the compound (II) is preferably used in an amount of 1 part by mass or more with respect to 100 parts by mass of the compound (I), and preferably 5 parts by mass or more. More preferably, it is 10 parts by mass or more. As an upper limit, it is preferable that it is 200 mass parts or less, It is more preferable that it is 150 mass parts or less, It is especially preferable that it is 100 mass parts or less. It is considered that the compound (II) has a function of suppressing the influence on the battery performance while maintaining the effect of improving the flame retardancy of the compound (I).
  • the decomposition product of the compound (II) formed a specific film on the positive electrode, thereby suppressing the decomposition of the compound (I) and the resulting deterioration of the positive electrode. From that point of view, as described above, the compound (II) does not need to be excessive with respect to the compounding amount of the compound (I), and a desired effect can be obtained by applying an equal amount or a small amount. .
  • the electrolyte used in the electrolytic solution of the present invention is preferably a salt of a metal ion belonging to Group 1 or Group 2 of the Periodic Table.
  • the material is appropriately selected depending on the intended use of the electrolytic solution.
  • lithium salt, potassium salt, sodium salt, calcium salt, magnesium salt and the like can be mentioned.
  • lithium salt is preferable from the viewpoint of output.
  • a lithium salt may be selected as a metal ion salt.
  • the lithium salt normally used for the electrolyte of the nonaqueous electrolyte solution for lithium secondary batteries is preferable, For example, what is described below is preferable.
  • Inorganic lithium salts inorganic fluoride salts such as LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 ; perhalogenates such as LiClO 4 , LiBrO 4 , LiIO 4 ; inorganic chloride salts such as LiAlCl 4 etc.
  • (L-3) Oxalatoborate salt lithium bis (oxalato) borate, lithium difluorooxalatoborate and the like.
  • imide salts More preferred are imide salts.
  • Rf 1 and Rf 2 each represent a perfluoroalkyl group.
  • the electrolyte used for electrolyte solution may be used individually by 1 type, or may combine 2 or more types arbitrarily.
  • the electrolyte in the electrolytic solution (preferably a metal ion belonging to Group 1 or Group 2 of the periodic table or a metal salt thereof) is added in an amount so as to obtain a preferable salt concentration described in the method for preparing the electrolytic solution below. It is preferable.
  • the salt concentration is appropriately selected depending on the intended use of the electrolytic solution, but is generally 10% to 50% by mass, more preferably 15% to 30% by mass, based on the total mass of the electrolytic solution.
  • the molar concentration is preferably 0.5M to 1.5M.
  • concentration when evaluating as an ion density
  • the non-aqueous solvent used in the present invention is preferably an aprotic organic solvent, and more preferably an aprotic organic solvent having 2 to 10 carbon atoms.
  • the non-aqueous solvent is preferably a compound having an ether group, a carbonyl group, an ester group, or a carbonate group.
  • the said compound may have a substituent and the postscript substituent T is mentioned as the example.
  • non-aqueous solvent examples include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2 -Methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, butyric acid Methyl, methyl isobutyrate, methyl trimethylacetate, ethyl trimethylacetate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-
  • ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, and ⁇ -butyrolactone is preferable.
  • a high viscosity (high dielectric constant) solvent such as ethylene carbonate or propylene carbonate.
  • a combination of (for example, relative dielectric constant ⁇ ⁇ 30) and a low viscosity solvent (for example, viscosity ⁇ 1 mPa ⁇ s) such as dimethyl carbonate, ethyl methyl carbonate, or diethyl carbonate is more preferable. This is because the dissociation property of the electrolyte salt and the ion mobility are improved.
  • the non-aqueous solvent used in the present invention is not limited by the above examples.
  • the electrolytic solution of the present invention preferably contains various functional additives.
  • Examples of the function manifested by this additive include improved flame retardancy, improved cycle characteristics, and improved capacity characteristics.
  • Examples of functional additives that are preferably applied to the electrolyte of the present invention are shown below.
  • aromatic compounds include biphenyl compounds and alkyl-substituted benzene compounds.
  • the biphenyl compound has a partial structure in which two benzene rings are bonded by a single bond, and the benzene ring may have a substituent.
  • Preferred substituents are alkyl groups having 1 to 4 carbon atoms (for example, Methyl, ethyl, propyl, t-butyl, etc.) and aryl groups having 6 to 10 carbon atoms (eg, phenyl, naphthyl, etc.).
  • the biphenyl compound examples include biphenyl, o-terphenyl, m-terphenyl, p-terphenyl, 4-methylbiphenyl, 4-ethylbiphenyl, and 4-tert-butylbiphenyl.
  • the alkyl-substituted benzene compound is preferably a benzene compound substituted with an alkyl group having 1 to 10 carbon atoms, and specifically includes ethylbenzene, isopropylbenzene, cyclohexylbenzene, t-amylbenzene, t-butylbenzene, and tetrahydrohydronaphthalene. Can be mentioned.
  • the halogen atom contained in the halogen-containing compound is preferably a fluorine atom, a chlorine atom, or a bromine atom, and more preferably a fluorine atom.
  • the number of halogen atoms is preferably 1 to 6, more preferably 1 to 3.
  • the halogen-containing compound is preferably a carbonate compound substituted with a fluorine atom, a polyether compound having a fluorine atom, or a fluorine-substituted aromatic compound.
  • the halogen-substituted carbonate compound may be either linear or cyclic.
  • a cyclic carbonate compound having a high coordination property of an electrolyte salt for example, lithium ion
  • a 5-membered cyclic carbonate compound is particularly preferable.
  • Preferred specific examples of the halogen-substituted carbonate compound are shown below. Among these, compounds of Bex1 to Bex4 are particularly preferable, and Bex1 is particularly preferable.
  • the polymerizable compound is preferably a compound having a carbon-carbon double bond, and is selected from carbonate compounds having a double bond such as vinylene carbonate and vinyl ethylene carbonate, acrylate groups, methacrylate groups, cyanoacrylate groups, and ⁇ CF 3 acrylate groups.
  • a compound having a group and a compound having a styryl group are preferable, and a carbonate compound having a double bond or a compound having two or more polymerizable groups in the molecule is more preferable.
  • the phosphorus-containing compound is a phosphorus-containing compound other than (1) and (2-1), and a phosphazene compound is preferable.
  • a compound represented by the following formula (D2) or (D3) is also preferable.
  • R D4 to R D11 each represent a monovalent substituent.
  • the monovalent substituents preferred are alkyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms such as fluorine, chlorine, bromine and the like.
  • At least one of the substituents of R D4 to R D11 is preferably a fluorine atom, more preferably an alkoxy group or a substituent composed of a fluorine atom.
  • a compound having —SO 2 —, —SO 3 —, —OS ( ⁇ O) O— bond is preferable, and cyclic sulfur-containing compounds such as propane sultone, propene sultone, ethylene sulfite, and sulfonic acid Esters are preferred.
  • sulfur-containing cyclic compound compounds represented by the following formulas (E1) and (E2) are preferable.
  • X 1 and X 2 each independently represent —O— or —C (Ra) (Rb) —.
  • Ra and Rb each independently represent a hydrogen atom or a substituent.
  • the substituent is preferably an alkyl group having 1 to 8 carbon atoms, a fluorine atom, or an aryl group having 6 to 12 carbon atoms.
  • ⁇ represents an atomic group necessary for forming a 5- to 6-membered ring.
  • the skeleton of ⁇ may contain a sulfur atom, an oxygen atom, etc. in addition to a carbon atom.
  • ⁇ may be substituted, and examples of the substituent include a substituent T, preferably an alkyl group, a fluorine atom, and an aryl group.
  • ⁇ Silicon-containing compound (F)> As the silicon-containing compound, a compound represented by the following formula (F1) or (F2) is preferable.
  • R F1 represents an alkyl group, an alkenyl group, an acyl group, an acyloxy group, or an alkoxycarbonyl group.
  • R F2 represents an alkyl group, an alkenyl group, an alkynyl group, or an alkoxy group.
  • a plurality of R F1 and R F2 in one formula may be different or the same.
  • nitrile compound (G) As the nitrile compound, a compound represented by the following formula (G) is preferable.
  • R G1 to R G3 each independently represent a hydrogen atom, an alkyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a carbamoyl group, a sulfonyl group, a halogen atom, or a phosphonyl group.
  • examples of the substituent T can be referred to, and among them, a compound in which any one of R G1 to R G3 has a plurality of nitrile groups containing a cyano group is preferable.
  • -Ng represents an integer of 1-8.
  • Specific examples of the compound represented by the formula (G) include acetonitrile, propionitrile, isobutyronitrile, succinonitrile, malononitrile, glutaronitrile, adiponitrile, 2-methylglutanonitrile, hexanetricarbonitrile, propane. Tetracarbonitrile and the like are preferable. Particularly preferred are succinonitrile, malononitrile, glutaronitrile, adiponitrile, 2-methylglutanonitrile, hexanetricarbonitrile, and propanetetracarbonitrile.
  • Metal complex compound (H) As the metal complex compound, a transition metal complex or a rare earth complex is preferable. Of these, complexes represented by any of the following formulas (H-1) to (H-3) are preferred.
  • X H and Y H are a methyl group, an n-butyl group, a bis (trimethylsilyl) amino group, and a thioisocyanate group, respectively, and X H and Y H are condensed to form a cyclic alkenyl group (butadiene group).
  • MH represents a transition element or a rare earth element. Specifically, MH is preferably Fe, Ru, Cr, V, Ta, Mo, Ti, Zr, Hf, Y, La, Ce, Sw, Nd, Lu, Er, Yb, and Gd.
  • n H and n H are integers satisfying 0 ⁇ m H + n H ⁇ 3.
  • n H + m H is preferably 1 or more.
  • the 2 or more groups defined therein may be different from each other.
  • the metal complex compound is also preferably a compound having a partial structure represented by the following formula (H-4).
  • MH represents a transition element or a rare earth element and is synonymous with formulas (H-1) to (H-3).
  • R 1H and R 2H are hydrogen, an alkyl group (preferably having a carbon number of 1 to 6), an alkenyl group (preferably having a carbon number of 2 to 6), an alkynyl group (preferably having a carbon number of 2 to 6), and an aryl group (preferably having a carbon number). Represents a heteroaryl group (preferably having a carbon number of 3 to 6), an alkylsilyl group (preferably having a carbon number of 1 to 6), or a halogen.
  • R 1H and R 2H may be linked to each other.
  • R 1H and R 2H may each be connected to form a ring.
  • Preferable examples of R 1H and R 2H include examples of the substituent T described later.
  • a methyl group, an ethyl group, and a trimethylsilyl group are preferable.
  • q H represents an integer of 1 to 4, preferably an integer of 2 to 4. More preferably, it is 2 or 4. When q H is 2 or more, where a plurality of groups as defined may be the same or different from each other.
  • the metal complex compound is also preferably a compound represented by any of the following formulas.
  • the central metal M h is, Ti, Zr, ZrO, Hf , V, Cr, Fe, Ce is particularly preferred, Ti, Zr, Hf, V , Cr is the most preferred.
  • R 3h , R 5h , R 7h to R 10h represent substituents.
  • an alkyl group, an alkoxy group, an aryl group, an alkenyl group, and a halogen atom are preferable.
  • R 33h , R 55h R 33h and R 55h represent a hydrogen atom or a substituent of R 3h .
  • Y h is preferably an alkyl group having 1 to 6 carbon atoms or a bis (trialkylsilyl) amino group, and more preferably a methyl group or a bis (trimethylsilyl) amino group.
  • ⁇ L h, m h, o h l h , m h , and o h represent an integer of 0 to 3, and an integer of 0 to 2 is preferable.
  • the plurality of structural portions defined therein may be the same as or different from each other.
  • L h is preferably an alkylene group or an arylene group, more preferably a cycloalkylene group having 3 to 6 carbon atoms or an arylene group having 6 to 14 carbon atoms, and further preferably cyclohexylene or phenylene.
  • ⁇ Imide compound (I)> As the imide compound, a sulfonimide compound having a perfluoro group is preferable from the viewpoint of oxidation resistance, and specifically, a perfluorosulfoimide lithium compound may be mentioned. Specific examples of the imide compound include the following structures, and Cex1 and Cex2 are more preferable.
  • the electrolytic solution of the present invention may contain at least one selected from the above, a negative electrode film forming agent, a flame retardant, an overcharge preventing agent and the like.
  • the content ratio of these functional additives in the nonaqueous electrolytic solution is not particularly limited, but is preferably 0.001% by mass to 10% by mass with respect to the entire nonaqueous electrolytic solution (including the electrolyte).
  • alkyl group preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • alkenyl A group preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl and the like
  • an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl and the like
  • a cycloalkyl group preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.
  • each of the groups listed as the substituent T may be further substituted with the substituent T described above.
  • a compound or a substituent / linking group includes an alkyl group / alkylene group, an alkenyl group / alkenylene group, an alkynyl group / alkynylene group, etc., these may be cyclic or linear, and may be linear or branched These may be substituted as described above or may be unsubstituted.
  • Linking group L Each substituent defined in the present specification may be substituted via the following linking group L within a range that exhibits the effects of the present invention.
  • the alkyl group / alkylene group, alkenyl group / alkenylene group and the like may further have the following hetero-linking group interposed in the structure.
  • the linking group L includes a hydrocarbon linking group [an alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), an alkenylene group having 2 to 10 carbon atoms (more preferably carbon atoms).
  • the said hydrocarbon coupling group may form the double bond and the triple bond suitably, and may connect.
  • the ring to be formed is preferably a 5-membered ring or a 6-membered ring.
  • a nitrogen-containing five-membered ring is preferable, and examples of the compound forming the ring include pyrrole, imidazole, pyrazole, indazole, indole, benzimidazole, pyrrolidine, imidazolidine, pyrazolidine, indoline, carbazole, or these And derivatives thereof.
  • 6-membered ring examples include piperidine, morpholine, piperazine, and derivatives thereof. Moreover, when an aryl group, a heterocyclic group, etc. are included, they may be monocyclic or condensed and may be similarly substituted or unsubstituted.
  • RN is a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), and an alkenyl group (preferably having 2 to 24 carbon atoms and 2 carbon atoms).
  • To 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is particularly preferable, and an alkynyl group (2 to 24 carbon atoms is preferable, 2 to 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is Particularly preferred), an aralkyl group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, 6 to 14 carbon atoms). 10 is particularly preferred).
  • RP is a hydrogen atom, a hydroxyl group, or a substituent.
  • substituents examples include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), and an alkenyl group (preferably having 2 to 24 carbon atoms and 2 carbon atoms).
  • To 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is particularly preferable, and an alkynyl group (2 to 24 carbon atoms is preferable, 2 to 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is Particularly preferred), an aralkyl group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, 6 to 14 carbon atoms).
  • an alkoxy group preferably having 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 1 to 6 and particularly preferably 1 to 3
  • an alkenyloxy group having carbon number
  • More preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 to 3, and an alkynyloxy group preferably having 2 to 24 carbon atoms, more preferably 2 to 12 and more preferably 2 to 6.
  • More preferably, 2 to 3 are particularly preferred
  • an aralkyloxy group preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms
  • an aryloxy group preferably 6 to 22 carbon atoms, 6 to 14 are more preferable, and 6 to 10 are particularly preferable.
  • the number of atoms constituting the linking group is preferably from 1 to 36, more preferably from 1 to 24, still more preferably from 1 to 12, and from 1 to 6 Is particularly preferred.
  • the number of linking atoms in the linking group is preferably 10 or less, and more preferably 8 or less.
  • the lower limit is 1 or more.
  • the number of connected atoms refers to the minimum number of atoms that are located in a path connecting predetermined structural portions and are involved in the connection. For example, in the case of —CH 2 —C ( ⁇ O) —O—, the number of atoms constituting the linking group is 6, but the number of linking atoms is 3. Specific examples of combinations of linking groups include the following.
  • x is an integer of 1 or more, preferably 1 to 500, more preferably 1 to 100.
  • Lr is preferably an alkylene group, an alkenylene group or an alkynylene group.
  • the carbon number of Lr is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3.
  • a plurality of Lr, R N , R P , x, etc. need not be the same.
  • the direction of the linking group is not limited by the above description, and may be understood as appropriate according to a predetermined chemical formula.
  • the nonaqueous electrolytic solution of the present invention is prepared by a conventional method by dissolving each of the above components in the nonaqueous electrolytic solution solvent, including an example in which a lithium salt is used as a metal ion salt.
  • non-water means substantially not containing water, and may contain a small amount of water as long as the effect of the invention is not hindered.
  • the concentration of water is preferably 200 ppm (mass basis) or less, more preferably 100 ppm or less, and still more preferably 20 ppm or less. Although there is no lower limit in particular, it is practical that it is 1 ppm or more considering inevitable mixing.
  • the viscosity of the electrolytic solution of the present invention is not particularly limited, but it is preferably 10 to 0.1 mPa ⁇ s, more preferably 5 to 0.5 mPa ⁇ s at 25 ° C.
  • the viscosity is a value measured by the following method. 1 mL of a sample is put into a rheometer (CLS 500) and measured using a Steel Cone (both manufactured by TA Instruments) having a diameter of 4 cm / 2 °. The sample is kept warm in advance until the temperature becomes constant at the measurement start temperature, and the measurement starts thereafter. The measurement temperature is 25 ° C.
  • the lithium ion secondary battery 10 of this embodiment includes the electrolyte solution 5 for a non-aqueous secondary battery of the present invention and a positive electrode C capable of inserting and releasing lithium ions (a positive electrode current collector 1 and a positive electrode active material layer 2). And a negative electrode A (negative electrode current collector 3, negative electrode active material layer 4) capable of inserting and releasing lithium ions or dissolving and depositing lithium ions.
  • a separator 9 disposed between the positive electrode and the negative electrode, a current collecting terminal (not shown), an outer case, etc. (Not shown).
  • a protective element may be attached to at least one of the inside of the battery and the outside of the battery.
  • the battery shape to which the lithium secondary battery of the present embodiment is applied is not particularly limited, and examples thereof include a bottomed cylindrical shape, a bottomed square shape, a thin shape, a sheet shape, and a paper shape. Any of these may be used. Further, it may be of a different shape such as a horseshoe shape or a comb shape considering the shape of the system or device to be incorporated. Among them, from the viewpoint of efficiently releasing the heat inside the battery to the outside, a square shape such as a bottomed square shape or a thin shape having at least one surface that is relatively flat and has a large area is preferable.
  • FIG. 2 is an example of a bottomed cylindrical lithium secondary battery 100.
  • This battery is a bottomed cylindrical lithium secondary battery 100 in which a positive electrode sheet 14 and a negative electrode sheet 16 overlapped with a separator 12 are wound and accommodated in an outer can 18.
  • the 2S / T value is preferably 100 or more, and more preferably 200 or more.
  • the lithium secondary battery according to the present embodiment is configured to include the electrolytic solution 5, the positive electrode and negative electrode electrode mixtures C and A, and the separator basic member 9, based on FIG. 1.
  • the electrode mixture is obtained by applying a dispersion of an active material and a conductive agent, a binder, a filler, etc. on a current collector (electrode substrate).
  • the active material is a positive electrode active material. It is preferable to use a negative electrode mixture in which the positive electrode mixture and the active material are a negative electrode active material.
  • each component in the dispersion (electrode composition) constituting the electrode mixture will be described.
  • a transition metal oxide for the positive electrode active material, and in particular, it has a transition element M a (one or more elements selected from Co, Ni, Fe, Mn, Cu, V). Is preferred. Further, mixed element M b (elements of the first (Ia) group of the metal periodic table other than lithium, elements of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si , P, B, etc.) may be mixed. Examples of the transition metal oxide include specific transition metal oxides including those represented by any of the following formulas (MA) to (MC), or other transition metal oxides such as V 2 O 5 and MnO 2. Is mentioned. As the positive electrode active material, a particulate positive electrode active material may be used. Specifically, a transition metal oxide capable of reversibly inserting and releasing lithium ions can be used, but the specific transition metal oxide is preferably used.
  • the transition metal oxides, oxides containing the above transition element M a is preferably exemplified.
  • a mixed element M b (preferably Al) or the like may be mixed.
  • the mixing amount is preferably 0 to 30 mol% with respect to the amount of the transition metal. That the molar ratio of li / M a was synthesized were mixed so that 0.3 to 2.2, more preferably.
  • M 1 is as defined above Ma.
  • a represents 0 to 1.2, preferably 0.1 to 1.15, and more preferably 0.6 to 1.1.
  • b represents 1 to 3 and is preferably 2.
  • a part of M 1 may be substituted with the mixed element M b .
  • the transition metal oxide represented by the above formula (MA) typically has a layered rock salt structure.
  • the transition metal oxide is more preferably one represented by the following formulas.
  • g has the same meaning as a.
  • j represents 0.1 to 0.9.
  • i represents 0 to 1; However, 1-ji is 0 or more.
  • k has the same meaning as b above.
  • Specific examples of the transition metal compound include LiCoO 2 (lithium cobaltate [LCO]), LiNi 2 O 2 (lithium nickelate) LiNi 0.85 Co 0.01 Al 0.05 O 2 (nickel cobalt aluminum acid Lithium [NCA]), LiNi 0.33 Co 0.33 Mn 0.33 O 2 (lithium nickel manganese cobaltate [NMC]), LiNi 0.5 Mn 0.5 O 2 (lithium manganese nickelate).
  • the transition metal oxide represented by the formula (MA) partially overlaps, but when represented by changing the notation, those represented by the following are also preferable examples.
  • (I) Li g Ni x Mn y Co z O 2 (x> 0.2, y> 0.2, z ⁇ 0, x + y + z 1) Representative: Li g Ni 1/3 Mn 1/3 Co 1/3 O 2 Li g Ni 1/2 Mn 1/2 O 2
  • (Ii) Li g Ni x Co y Al z O 2 (x> 0.7, y>0.1,0.1> z ⁇ 0.05, x + y + z 1) Representative: Li g Ni 0.8 Co 0.15 Al 0.05 O 2
  • M 2 is as defined above Ma.
  • c represents 0 to 2, preferably 0.1 to 1.15, and more preferably 0.6 to 1.5.
  • d represents 3 to 5 and is preferably 4.
  • the transition metal oxide represented by the formula (MB) is more preferably one represented by the following formulas.
  • (MB-1) Li m Mn 2 O n
  • (MB-2) Li m Mn p Al 2-p O n
  • (MB-3) Li m Mn p Ni 2-p O n
  • m is synonymous with c.
  • n is synonymous with d.
  • p represents 0-2.
  • Specific examples of the transition metal compound are LiMn 2 O 4 and LiMn 1.5 Ni 0.5 O 4 .
  • Preferred examples of the transition metal oxide represented by the formula (MB) include those represented by the following.
  • an electrode containing Ni is more preferable from the viewpoint of high capacity and high output.
  • Transition metal oxide represented by formula (MC) As the lithium-containing transition metal oxide, it is also preferable to use a lithium-containing transition metal phosphor oxide, and among them, one represented by the following formula (MC) is also preferable. Li e M 3 (PO 4 ) f ... (MC)
  • e 0 to 2, preferably 0.1 to 1.15, and more preferably 0.5 to 1.5.
  • f represents 1 to 5, and preferably 0.5 to 2.
  • the M 3 represents one or more elements selected from V, Ti, Cr, Mn, Fe, Co, Ni, and Cu.
  • the M 3 are, in addition to the mixing element M b above, Ti, Cr, Zn, Zr, may be substituted by other metals such as Nb.
  • Specific examples include, for example, olivine-type iron phosphates such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , cobalt phosphates such as LiCoPO 4 , and Li 3.
  • Monoclinic Nasicon type vanadium phosphate salts such as V 2 (PO 4 ) 3 (lithium vanadium phosphate) can be mentioned.
  • the a, c, g, m, and e values representing the composition of Li are values that change due to charge and discharge, and are typically evaluated as values in a stable state when Li is contained.
  • the composition of Li is shown as a specific value, but this also varies depending on the operation of the battery.
  • a positive electrode active material containing nickel and / or manganese atoms is preferably used, and a positive electrode active material containing both nickel and manganese atoms is more preferably used.
  • particularly preferable positive electrode active materials include the following.
  • LiNi 0.33 Co 0.33 Mn 0.33 O 2 LiNi 0.6 Co 0.2 Mn 0.2 O 2 LiNi 0.8 Co 0.1 Mn 0.1 O 2 LiNi 0.5 Co 0.3 Mn 0.2 O 2 LiNi 0.5 Mn 0.5 O 2 LiNi 0.5 Mn 1.5 O 4 Since these can be used at a high potential, the battery capacity can be increased, and even when used at a high potential, the capacity retention rate is high, which is particularly preferable.
  • the positive electrode active material is preferably a material that can maintain normal use at a positive electrode potential (Li / Li + standard) of 3.5 V or higher, more preferably 3.8 V or higher, and more preferably 4 V or higher. More preferably, it is more preferably 4.25V or more, and further preferably 4.3V or more. Although there is no upper limit in particular, it is practical that it is 5V or less. By setting it as the above range, cycle characteristics and high rate discharge characteristics can be improved.
  • being able to maintain normal use means that even when charging is performed at that voltage, the electrode material does not deteriorate and cannot be used, and this potential is also referred to as a normal usable potential.
  • positive electrode potential (negative electrode potential) + (battery voltage).
  • the negative electrode potential is 1.55V.
  • graphite is used as the negative electrode, the negative electrode potential is 0.1V. The battery voltage is observed during charging and the positive electrode potential is calculated.
  • the non-aqueous electrolyte of the present invention is particularly preferably used in combination with a positive electrode that can be used up to a high potential.
  • a positive electrode having a high potential When a positive electrode having a high potential is used, the cycle characteristics tend to be greatly deteriorated.
  • the nonaqueous electrolytic solution of the present invention can maintain good performance with this decrease suppressed. This is also an advantage and feature of the preferred embodiment of the present invention.
  • the average particle size of the positive electrode active material used is not particularly limited, but is preferably 0.1 ⁇ m to 50 ⁇ m.
  • the specific surface area is not particularly limited, but is preferably 0.01 m 2 / g to 50 m 2 / g by the BET method.
  • the pH of the supernatant when 5 g of the positive electrode active material is dissolved in 100 ml of distilled water is preferably 7 or more and 12 or less.
  • the positive electrode active material In order to make the positive electrode active material have a predetermined particle size, a well-known grinder or classifier is used. For example, a mortar, a ball mill, a vibration ball mill, a vibration mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill, a sieve, or the like is used.
  • the positive electrode active material obtained by the above firing method may be used after washing with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
  • the blending amount of the positive electrode active material is not particularly limited, but is preferably 60 to 98% by mass, and 70 to 95% by mass in 100% by mass of the solid component in the dispersion (mixture) for constituting the active material layer. % Is more preferable.
  • Negative electrode active material As the negative electrode active material, those capable of reversibly inserting and releasing lithium ions are preferable, and there is no particular limitation. Carbonaceous materials, metal oxides such as tin oxide and silicon oxide, metal composite oxides, lithium Examples thereof include a single alloy and a lithium alloy such as a lithium aluminum alloy and a metal capable of forming an alloy with lithium such as Sn or Si.
  • carbonaceous materials or lithium composite oxides are preferably used from the viewpoint of reliability.
  • the metal composite oxide is preferably capable of occluding and releasing lithium, and preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
  • the carbonaceous material used as the negative electrode active material is a material substantially made of carbon.
  • Examples thereof include carbonaceous materials obtained by baking various synthetic resins such as artificial pitches such as petroleum pitch, natural graphite, and vapor-grown graphite, and PAN-based resins and furfuryl alcohol resins.
  • various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA-based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber, mesophase micro
  • Examples thereof include spheres, graphite whiskers, and flat graphite.
  • carbonaceous materials can be divided into non-graphitizable carbon materials and graphite-based carbon materials depending on the degree of graphitization.
  • the carbonaceous material preferably has a face spacing, density, and crystallite size described in JP-A-62-222066, JP-A-2-6856, and 3-45473.
  • the carbonaceous material does not have to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, or the like is used. You can also.
  • the metal oxide and the metal composite oxide which are the negative electrode active materials used in the nonaqueous secondary battery of the present invention, contain at least one of them.
  • amorphous oxide is particularly preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used.
  • chalcogenite which is a reaction product of a metal element and an element of Group 16 of the periodic table.
  • amorphous as used herein means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering band having a peak in the region of 20 ° to 40 ° in terms of 2 ⁇ , and is a crystalline diffraction line. You may have.
  • the strongest intensity of crystalline diffraction lines seen from 2 ° to 40 ° to 70 ° is 100 times the diffraction line intensity at the peak of the broad scattering band seen from 2 ° to 20 °. It is preferable that it is 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.
  • amorphous metal oxides and chalcogenides are more preferable, and elements in groups 13 (IIIB) to 15 (VB) of the periodic table are preferable.
  • oxides and chalcogenides composed of one kind of Al, Ga, Si, Sn, Ge, Pb, Sb, Bi or a combination of two or more kinds thereof.
  • preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , SiO, GeO, SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , Bi 2 O 3 , Bi 2 O 4 , SnSiO 3 , GeS, SnS, SnS 2 , PbS, PbS 2 , Sb 2 S 3 , Sb 2 S 5 , such as SnSiS 3 may preferably be mentioned. Moreover, these may be a complex oxide with lithium oxide, for example, Li 2 SnO 2 .
  • the average particle size of the negative electrode active material used is preferably 0.1 ⁇ m to 60 ⁇ m.
  • a well-known pulverizer or classifier is used.
  • a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill or a sieve is preferably used.
  • wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary.
  • classification is preferably performed.
  • the classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be used both dry and wet.
  • the chemical formula of the compound obtained by the above firing method can be calculated from an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method, and from a mass difference between powders before and after firing as a simple method.
  • ICP inductively coupled plasma
  • the negative electrode active material that can be used in combination with the amorphous oxide negative electrode active material centering on Sn, Si, Ge, a carbon material capable of inserting and extracting lithium ions or lithium metal, lithium
  • Preferred examples include lithium alloys and metals that can be alloyed with lithium.
  • the electrolyte of the present invention is preferably combined with a high potential negative electrode (preferably lithium / titanium oxide, a potential of 1.55 V vs. Li metal) and a low potential negative electrode (preferably a carbon material, a silicon-containing material, a potential of about 0). Excellent properties are exhibited in any combination with .1V vs. Li metal.
  • a high potential negative electrode preferably lithium / titanium oxide, a potential of 1.55 V vs. Li metal
  • a low potential negative electrode preferably a carbon material, a silicon-containing material, a potential of about 0. Excellent properties are exhibited in any combination with .1V vs. Li metal.
  • metal or metal oxide negative electrodes preferably Si, Si oxide, Si / Si oxide, Sn, Sn oxide, SnB x P y O z , Cu, which can be alloyed with lithium, which are being developed for higher capacity
  • metal or metal oxide negative electrodes preferably Si, Si oxide, Si / Si oxide, Sn, Sn oxide, SnB x P y O z , Cu, which can be alloyed with lithium, which are being developed for higher capacity
  • a battery using a composite of these metals or metal oxides and a carbon material as a negative electrode it is particularly preferable to use a negative electrode active material containing at least one selected from carbon, silicon, titanium, and tin.
  • the nonaqueous electrolytic solution of the present invention is particularly preferably used in combination with a high potential negative electrode.
  • the high potential negative electrode is often used in combination with the above high potential positive electrode, and can be suitably adapted to large-capacity charging / discharging. Under such conditions, the above conditions (I) to (III) It is the same as that described in the section of the positive electrode active material that exhibits the advantages according to the preferred embodiment of the present invention having the specific composition set in the above.
  • the conductive material is preferably an electron conductive material that does not cause a chemical change in the configured secondary battery, and a known conductive material can be arbitrarily used.
  • natural graphite scale-like graphite, scale-like graphite, earth-like graphite, etc.
  • artificial graphite carbon black, acetylene black, ketjen black, carbon fiber and metal powder (copper, nickel, aluminum, silver (Japanese Patent Laid-Open No. Sho 63-63)) 10148,554), etc.
  • metal fibers or polyphenylene derivatives (described in JP-A-59-20971) can be contained as one kind or a mixture thereof.
  • the addition amount of the conductive agent is preferably 11 to 50% by mass, and more preferably 2 to 30% by mass. In the case of carbon or graphite, 2 to 15% by mass is particularly preferable.
  • binders include polysaccharides, thermoplastic resins, and polymers having rubber elasticity. Among them, for example, starch, carboxymethyl cellulose, cellulose, diacetyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose.
  • Water-soluble such as sodium alginate, polyacrylic acid, sodium polyacrylate, polyvinylphenol, polyvinyl methyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, polyacrylamide, polyhydroxy (meth) acrylate, styrene-maleic acid copolymer
  • Polymer polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, vinyl (Meta) such as redene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated EPDM, polyvinyl acetal resin, methyl methacrylate, 2-ethylhexyl acrylate (Meth) acrylic acid ester copolymer containing acrylic acid ester, (
  • Binders can be used alone or in combination of two or more.
  • the amount of the binder added is small, the holding power and cohesive force of the electrode mixture are weakened. If the amount is too large, the electrode volume increases and the capacity per electrode unit volume or unit mass decreases. For this reason, the addition amount of the binder is preferably 1 to 30% by mass, and more preferably 2 to 10% by mass.
  • the electrode compound material may contain the filler.
  • the material forming the filler is preferably a fibrous material that does not cause a chemical change in the secondary battery of the present invention.
  • fibrous fillers made of materials such as olefin polymers such as polypropylene and polyethylene, glass, and carbon are used.
  • the addition amount of the filler is not particularly limited, but is preferably 0 to 30% by mass in the dispersion.
  • the positive / negative electrode current collector an electron conductor that does not cause a chemical change in the nonaqueous electrolyte secondary battery of the present invention is used.
  • the current collector of the positive electrode in addition to aluminum, stainless steel, nickel, titanium, etc., the surface of aluminum or stainless steel is preferably treated with carbon, nickel, titanium, or silver. Among them, aluminum and aluminum alloys are preferable. More preferred.
  • the negative electrode current collector aluminum, copper, stainless steel, nickel and titanium are preferable, and aluminum, copper and copper alloy are more preferable.
  • a film sheet shape is usually used, but a net, a punched material, a lath body, a porous body, a foamed body, a molded body of a fiber group, and the like can also be used.
  • the thickness of the current collector is not particularly limited, but is preferably 1 ⁇ m to 500 ⁇ m.
  • the current collector surface is roughened by surface treatment.
  • An electrode mixture of the lithium secondary battery is formed by a member appropriately selected from these materials.
  • the separator used in the non-aqueous secondary battery of the present invention is made of a material that mechanically insulates the positive electrode and the negative electrode, has ion permeability, and has oxidation / reduction resistance at the contact surface between the positive electrode and the negative electrode.
  • a material a porous polymer material, an inorganic material, an organic-inorganic hybrid material, glass fiber, or the like is used.
  • These separators preferably have a shutdown function for ensuring reliability, that is, a function of closing a gap at 80 ° C. or higher to increase resistance and blocking current, and a closing temperature is 90 ° C. or higher and 180 ° C. or lower. It is preferable.
  • the shape of the holes of the separator is usually circular or elliptical, and the size is 0.05 ⁇ m to 30 ⁇ m, preferably 0.1 ⁇ m to 20 ⁇ m. Furthermore, it may be a rod-like or irregular-shaped hole as in the case of making by a stretching method or a phase separation method.
  • the ratio of these gaps, that is, the porosity, is 20% to 90%, preferably 35% to 80%.
  • the polymer material may be a single material such as a cellulose nonwoven fabric, polyethylene, or polypropylene, or may be a material using two or more composite materials. What laminated
  • oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate are used, and those having a particle shape or fiber shape are used.
  • a thin film shape such as a non-woven fabric, a woven fabric, or a microporous film is used.
  • the thin film shape those having a pore diameter of 0.01 ⁇ m to 1 ⁇ m and a thickness of 5 ⁇ m to 50 ⁇ m are preferably used.
  • a separator formed by forming a composite porous layer containing the inorganic particles on the surface layer of the positive electrode and / or the negative electrode using a resin binder can be used.
  • alumina particles having a 90% particle diameter of less than 1 ⁇ m are formed on both surfaces of the positive electrode as a porous layer using a fluororesin binder.
  • the shape of the nonaqueous secondary battery of the present invention can be applied to any shape such as a sheet shape, a square shape, and a cylinder shape.
  • a positive electrode active material or a mixture of negative electrode active materials is mainly used after being applied (coated), dried and compressed on a current collector.
  • FIG. 2 shows an example of a bottomed cylindrical lithium secondary battery 100.
  • This battery is a bottomed cylindrical lithium secondary battery 100 in which a positive electrode sheet 14 and a negative electrode sheet 16 overlapped with a separator 12 are wound and accommodated in an outer can 18.
  • 20 is an insulating plate
  • 22 is a sealing plate
  • 24 is a positive electrode current collector
  • 26 is a gasket
  • 28 is a pressure sensitive valve body
  • 30 is a current interruption element.
  • each member corresponds to the whole drawing by reference numerals.
  • a negative electrode active material is mixed with a binder or filler used as desired in an organic solvent to prepare a slurry or paste negative electrode mixture.
  • the obtained negative electrode mixture is uniformly applied over the entire surface of both surfaces of the metal core as a current collector, and then the organic solvent is removed to form a negative electrode mixture layer.
  • the laminate of the current collector and the negative electrode composite material layer is rolled with a roll press or the like to prepare a predetermined thickness to obtain a negative electrode sheet (electrode sheet).
  • the coating method of each agent, the drying of the coated material, and the method of forming the positive and negative electrodes may be in accordance with conventional methods.
  • a cylindrical battery is taken as an example, but the present invention is not limited to this, for example, after the positive and negative electrode sheets produced by the above method are overlapped via a separator, After processing into a sheet battery as it is, or inserting it into a rectangular can after being folded and electrically connecting the can and the sheet, injecting an electrolyte and sealing the opening using a sealing plate A square battery may be formed.
  • the safety valve can be used as a sealing plate for sealing the opening.
  • the sealing member may be provided with various conventionally known safety elements.
  • a fuse, bimetal, PTC element, or the like is preferably used as the overcurrent prevention element.
  • a method of cutting the battery can a method of cracking the gasket, a method of cracking the sealing plate, or a method of cutting the lead plate can be used.
  • the charger may be provided with a protection circuit incorporating measures against overcharge and overdischarge, or may be connected independently.
  • a metal or alloy having electrical conductivity can be used.
  • metals such as iron, nickel, titanium, chromium, molybdenum, copper, and aluminum, or alloys thereof are preferably used.
  • a known method eg, direct current or alternating current electric welding, laser welding, ultrasonic welding
  • a welding method for the cap, can, sheet, and lead plate can be used as a welding method for the cap, can, sheet, and lead plate.
  • the sealing agent for sealing a conventionally known compound or mixture such as asphalt can be used.
  • Secondary batteries called lithium batteries are secondary batteries that use the insertion and extraction of lithium for charge / discharge reactions (lithium ion secondary batteries), and secondary batteries that use precipitation and dissolution of lithium (lithium metal secondary batteries). ).
  • lithium ion secondary batteries secondary batteries that use the insertion and extraction of lithium for charge / discharge reactions
  • lithium metal secondary batteries secondary batteries that use precipitation and dissolution of lithium
  • application as a lithium ion secondary battery is preferable. Since the nonaqueous secondary battery of the present invention can produce a secondary battery with good cycle performance, it is applied to various applications.
  • a notebook computer when installed in an electronic device, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a mobile phone, a cordless phone, a pager, a handy terminal, a mobile fax machine, a mobile phone Copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, minidisc, electric shaver, transceiver, electronic notebook, calculator, memory card, portable tape recorder, radio, backup power supply, memory card, etc. It is done.
  • Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military use and space use. Moreover, it can also combine with a solar cell.
  • Example 1 and Comparative Example 1 Preparation of Electrolytic Solution Compounds (1) and (2) are added to the solvents S1 to S3 of the electrolytic solution shown in Table 1 so as to have the amounts shown in the table, and vinylene carbonate becomes 1% by mass with respect to the total electrolytic solution. Thus, an electrolytic solution for each test was prepared. All the prepared electrolyte solutions had a viscosity at 25 ° C. of 5 mPa ⁇ s or less, and the moisture content measured by the Karl Fischer method (JISK0113) was 20 ppm (mass basis) or less.
  • the flame retardancy of the prepared electrolyte was evaluated as follows at 25 ° C. in the atmosphere. The following test system was used for evaluation with reference to the UL-94HB horizontal combustion test. A glass filter paper (ADVANTEC GA-100) having a width of 13 mm and a length of 110 mm was cut out, and 1.5 ml of the prepared electrolyte was evenly dropped onto the glass filter paper. After the electrolyte solution was sufficiently infiltrated into the glass filter paper, the excess electrolyte solution was wiped and hung so as to be horizontal. The butane gas burner adjusted to a total flame length of 2 cm ignites for 3 seconds from the position where it touches the tip of the glass filter paper.
  • the arrival time was evaluated as follows. The time for the flame to reach from the ignition point to the other end of the electrolyte solution to which no additive was added was less than 5 seconds. 5 ... Ignition was not seen and it was nonflammable. 4 ... I ignited but immediately extinguished 3 . I ignited but extinguished before the flame reached from the ignition point to the other end 2 ... Time to reach the flame from the ignition point to the other end 10 seconds In the above, the combustion suppression effect is seen, but the level which does not lead to non-flammability and flame extinguishing 1... The flame reaches from the ignition point to the other end in less than 10 seconds and there is no combustion suppression effect.
  • the positive electrode is made of active material: LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC) 85% by mass, conductive auxiliary agent: carbon black 7.5% by mass, binder: PVDF 7.5% by mass,
  • the negative electrode was made of active material: 85% by mass of graphite, conductive auxiliary agent: 7.5% by mass of carbon black, and binder: 7.5% by mass of PVDF.
  • the separator is a polypropylene porous membrane having a thickness of 24 ⁇ m.
  • 1C represents a current value for discharging or charging the battery capacity in one hour
  • 0.2C represents 0.2 times
  • 0.5C represents 0.5 times
  • 2C represents twice the current value.
  • the capacity tends to deteriorate.
  • the capacity is likely to deteriorate, and a low temperature large current discharge combining the two becomes a more severe condition.
  • the temperature in the cycle test is also important. When charging and discharging are repeated at a high temperature, the oxidation-reduction decomposition of the electrolytic solution component is accelerated and the resistance is likely to increase.
  • the upper limit of the time was 2 hours.
  • a cycle of performing 0.5C constant current discharge of this battery in a thermostat at 45 ° C. until the battery voltage reached 2.75 V was repeated 300 times.
  • the battery after the high-temperature cycle test was charged and discharged under the same conditions as the initial discharge capacity measurement, and the discharge capacity (II) after the cycle test was measured.
  • the battery after the high-temperature cycle test was charged at a constant current of 0.7 C in a thermostat bath at 30 ° C. until the battery voltage reached 4.3 V, and then charged until the current value reached 0.12 mA at a constant voltage of 4.3 V. Went.
  • the upper limit of the time was 2 hours.
  • the battery was subjected to 2C constant current discharge in a 10 ° C constant temperature bath until the battery voltage reached 2.75 V, and the 10 ° C / 2C discharge capacity (III) after the cycle test was measured.
  • Discharge capacity maintenance ratio after cycle test (II) / (I)
  • Low-temperature, large-current discharge capacity retention rate after cycle test (III) / (I)
  • the obtained discharge capacity retention rate was evaluated as follows. The larger the value, the higher the capacity is maintained even under severe test conditions.
  • Solvent EC Ethylene carbonate
  • EMC Ethyl methyl carbonate
  • DMC Dimethyl carbonate
  • GBL ⁇ -Butyrolactone
  • PC Propylene carbonate
  • Example 2 The same operation as in Example 1 was performed except that the positive electrode active material was lithium manganate (LiMn 2 O 4 ) and the voltage at the cycle test charge was 4.2 V.
  • the electrolytic solution of the present application obtained excellent results with a high capacity retention rate at low temperature / large current discharge even after the high temperature cycle test, whereas the electrolyte of the comparative example had a low temperature / high capacity at the time of cycle test charging.
  • the capacity retention rate in current discharge was inferior.
  • the voltage at the time of cycle test charging was set to 4.3 V, the capacity retention rate at low temperature / large current discharge after the cycle test was lowered by using any of the electrolyte solutions of the examples and comparative examples. It was enough to meet practical requirements.
  • Example 3 The same operation as in Example 2 was performed except that the positive electrode active material was lithium cobalt oxide (LiCoO 2 ) and the voltage at the cycle test charge was 4.0 V or 4.1 V.
  • the electrolytic solution of the present application had an excellent result that the capacity retention ratio at low temperature / large current discharge was high even after the high temperature cycle test at any voltage of 4.0V and 4.1V.
  • the electrolytic solution of the comparative example was equivalent to the electrolytic solution of the present application at the voltage 4.0 V during the cycle test charge, but the capacity at the low temperature / large current discharge after the cycle test at the voltage 4.1 V during the charge. The maintenance rate was inferior.
  • the voltage at the time of the cycle test was set to 4.2 V, the capacity retention rate at low temperature / high current discharge after the cycle test was lowered by using any of the electrolyte solutions of the example and the comparative example. It was enough to meet practical requirements.
  • Electrolytic solutions for each test were prepared by adding 1% by mass to the electrolytic solution and 2% by mass of t-amylbenzene with respect to the total electrolytic solution. All the prepared electrolyte solutions had a viscosity at 25 ° C. of 5 mPa ⁇ s or less, and the water content measured by the Karl Fischer method (JIS K0113) was 20 ppm or less.
  • the prepared electrolyte solution was evaluated for flame retardancy using the method of Example 1.
  • the positive electrode is made of active material: nickel manganese lithium cobaltate (LiNi 1/3 Mn 1/3 Co 1/3 O 2 ) 85% by mass, conductive auxiliary agent: carbon black 7% by mass, binder: PVDF 8% by mass,
  • the negative electrode was prepared with 94% by mass of active material: lithium titanate (Li 4 Ti 5 O 12 ), conductive auxiliary agent: 3% by mass of carbon black, and binder: 3% by mass of PVDF.
  • the separator is made of polypropylene and has a thickness of 25 ⁇ m. Using the positive and negative electrodes and the separator, a 2032 type coin battery (2) was produced.
  • ⁇ Battery initialization> Charged at a constant current of 0.2 C until the battery voltage reaches 2.85 V (positive electrode potential 4.4 V) in a constant temperature bath at 30 ° C., and then charged until the battery voltage reaches a current value of 0.12 mA at a constant voltage of 2.85 V. Went. However, the upper limit of the time was 2 hours. Next, 0.2 C constant current discharge was performed in a thermostat at 30 ° C. until the battery voltage reached 1.2 V (positive electrode potential (2.75 V). This operation was repeated twice. The following items were evaluated using a 2032 type battery, and the results are shown in Table 2. (First discharge capacity) The battery was charged at a constant current of 1 C in a thermostat at 30 ° C.
  • a cycle in which 1C constant current discharge was performed on this battery in a 45 ° C. thermostat until the battery voltage reached 2.75 V was repeated 300 times.
  • discharge capacity after cycle test The battery after the high-temperature cycle test was charged and discharged under the same conditions as the initial discharge capacity measurement, and the discharge capacity (V) after the cycle test was measured.
  • Low temperature, large current discharge capacity after cycle test The battery after the high-temperature cycle test was charged at a constant current of 1 C in a thermostatic chamber at 30 ° C. until the battery voltage reached 2.85 V, and then charged until the current value reached 0.12 mA at a constant voltage of the battery voltage of 2.85 V. It was. However, the upper limit of the time was 2 hours.
  • This battery was subjected to 4C constant current discharge in a 10 ° C constant temperature bath until the battery voltage became 1.2V, and the 10 ° C / 4C discharge capacity (VI) after the cycle test was measured.
  • the obtained discharge capacity retention rate was evaluated as follows. The larger the value, the higher the capacity is maintained even under severe test conditions.
  • the electrolytic solution of the present invention By using the electrolytic solution of the present invention, it is possible to suppress the capacity deterioration even under severe conditions such as low-temperature and large-current discharge, and to obtain an excellent effect of achieving both a combustion suppression effect.
  • the secondary battery in which LTO suitable for large current discharge is applied to the negative electrode active material also shows good performance.
  • the battery of the present invention exhibits excellent characteristics in combination with a lithium / titanium oxide negative electrode as a negative electrode, a carbon negative electrode, and nickel manganese lithium cobaltate, lithium manganate, lithium cobaltate as a positive electrode. Showed that. If the present invention is used, the same applies to a positive electrode used at a potential of 4.5 V or more, such as lithium nickel manganate, or a battery using a Si-containing negative electrode or a tin-containing negative electrode expected to have a higher capacity than a carbon negative electrode. It can be assumed that an excellent effect is exhibited.
  • PN1 of Test 101 was converted to the above exemplified compounds (1-6), (1-10), (1-14), (1-22), (1-25), (1-30), (1-46) , (1-62), and (1-67), each test was conducted in the same manner except that each was replaced. As a result, it was confirmed that good performance was exhibited with respect to flame retardancy, durability at high temperatures and low temperature discharge properties.
  • Tests were conducted in the same manner except that the compound 2-2-1 in Test 104 was replaced with the exemplified compounds b7, b9, b10, and b18, respectively. As a result, it was confirmed that good performance was exhibited with respect to flame retardancy, durability at high temperatures and low temperature discharge properties.

Abstract

Solution d'électrolyte de batterie secondaire non aqueuse, contenant un solvant non aqueux, un électrolyte, un composé de phosphazène spécifique, et un composé contenant du phosphore, un composé alcyne, ou un composé d'éther cyclique.
PCT/JP2014/069850 2013-07-29 2014-07-28 Solution d'électrolyte de batterie secondaire non aqueuse et batterie secondaire non aqueuse WO2015016187A1 (fr)

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