WO2015045386A1 - Nonaqueous secondary battery - Google Patents

Nonaqueous secondary battery

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Publication number
WO2015045386A1
WO2015045386A1 PCT/JP2014/004910 JP2014004910W WO2015045386A1 WO 2015045386 A1 WO2015045386 A1 WO 2015045386A1 JP 2014004910 W JP2014004910 W JP 2014004910W WO 2015045386 A1 WO2015045386 A1 WO 2015045386A1
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substituted
group
substituent
electrolyte
battery
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PCT/JP2014/004910
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French (fr)
Japanese (ja)
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山田 淳夫
裕貴 山田
智之 河合
佳浩 中垣
浩平 間瀬
雄紀 長谷川
合田 信弘
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国立大学法人東京大学
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0568Liquid materials characterised by the solutes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0569Liquid materials characterised by the solvents
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/60Other road transportation technologies with climate change mitigation effect
    • Y02T10/70Energy storage for electromobility
    • Y02T10/7005Batteries
    • Y02T10/7011Lithium ion battery

Abstract

The positive electrode of this nonaqueous secondary battery comprises a positive electrode active material that contains at least one material selected from among lithium metal composite oxides having a layered rock salt structure, lithium metal composite oxides having a spinel structure and polyanion-based materials. The electrolyte solution of this nonaqueous secondary battery contains a metal salt, wherein an alkali metal, an alkaline earth metal or aluminum serves as cations, and an organic solvent having a hetero element. With respect to the peak intensity ascribed to the organic solvent in a vibrational spectrum of the electrolyte solution, if Io is the original peak intensity of the organic solvent and Is is the intensity of a shifted peak of the organic solvent, Io and Is satisfy Is > Io. The highest working potential of the positive electrode of this nonaqueous secondary battery may be 4.5 V or more relative to Li/Li+.

Description

Non-aqueous secondary battery

The present invention relates to a nonaqueous secondary battery such as a lithium ion secondary battery.

Nonaqueous secondary battery such as a lithium ion secondary battery has a high energy density in a small, widely used as a power source for portable electronic devices. As the positive electrode active material of the lithium ion secondary battery mainly lithium metal composite oxide with LiCoO 2, LiNiO 2, Li ( Ni x Co y Mn z) O 2 (x + y + z = 1) layered rock salt structure, such as objects are used (Patent Document 1). Electrolyte solution is prepared by dissolving a lithium salt in an organic solvent containing ethylene carbonate.

In general, in the charged state, the above-mentioned lithium-metal composite oxide has the structure compared to the discharge state becomes unstable. With the collapse of the crystal structure applying energy such as heat, to release oxygen (O), in the released oxygen is believed to combustion heat by the reaction with the electrolyte.

High Li (Ni x Co y Mn z ) O 2 otherwise LiNiO 2, Ni ratio among the lithium metal composite oxide having a layered rock salt structure, material cost is low and the current capacity that can be extracted is larger than that, such as LiCoO 2 there is an advantage in that. On the other hand, with the increase of Ni content, increased reactivity with the electrolyte in a charged state, the heat generation initiation temperature by reaction of the electrolytic solution and the positive electrode at the time of overheating has been reported to be reduced (Non-Patent Document 1). With these lithium-metal composite oxide with a volatile electrolyte solution, when the damage has occurred in the battery, there is a possibility that liquid is superheated electrolyte is discharged to the outside instantaneously.

For example, a mixed organic solvent containing a wide ethylene carbonate used in the electrolytic solution has a low viscosity and melting point of the electrolyte, while the electrolyte solution having a high ionic conductivity, easily volatilized. Unlikely event that a case or damage where there is a gap occurs in the battery, it may be released as a gas instantaneously out battery system.

The use of low volatile liquids such as ionic liquids as the electrolyte, it is conceivable to suppress the volatilization of the electrolyte solution when the damage has occurred in the battery. However, ionic liquids are less as compared with conventional electrolyte high ion conductivity viscosity. Therefore, deteriorating the output characteristics of the battery.

The present inventor has intensively explored for the electrolyte solution, has developed a new low volatility of the electrolyte solution. The present inventor has this new electrolyte, when combined with the positive electrode of the lithium-metal composite oxide as an active material, it has been found that excellent non-aqueous secondary battery of the input-output characteristics can be obtained.

As the positive electrode active material of a lithium ion secondary battery, there is the lithium metal composite oxide mainly having the spinel structure such as LiMn 2 O 4 is used. Electrolytic solution, the lithium salt, by dissolving in a solvent containing ethylene carbonate (Patent Documents 1 and 2).
In such a secondary battery, the negative electrode, it is necessary to reversibly charge and discharge reaction is performed Seikyokutomo.

As the positive electrode active material of a lithium ion secondary battery, it may polyanionic material having an olivine structure such as LiFePO 4 is used. Battery using an olivine-based active material safety, excellent cycle property, has a feature that it is inexpensive. Electrolytic solution, a metal salt, by dissolving in a solvent containing ethylene carbonate (Patent Documents 3 and 4).

In such a secondary battery, the negative electrode, it is necessary to reversibly charge and discharge reaction is performed Seikyokutomo. Further, a high rate capacity characteristics are desired.

As the positive electrode active material of a lithium ion secondary battery, lithium metal mainly with LiCoO 2, LiNiO 2, Li ( Ni x Co y Mn z) O 2 (x + y + z = 1) layered rock salt structure, such as composite oxide, spinel oxides such as LiMn 2 O 4, may be polyanionic compound, such as LiFePO 4, Li 2 MnSiO 4 is used. Electrolytic solution, the lithium salt, by dissolving in a solvent containing ethylene carbonate (Patent Documents 1 and 2).

Generally the lithium ion secondary battery reversibly charged and discharged reaction. For this purpose, a high reduction resistance to the electrolyte, oxidation resistance is required. Particularly, the case of obtaining a high capacity in a nonaqueous secondary battery, in the case of using an active material for the reversible charge and discharge reaction in the vicinity of 5V (vs Li + / Li) in the positive electrode, the use of cell body it is necessary to increase the possible upper limit potential. In this case, the electrolyte is desired to have a high oxidative decomposition potential of greater than highest potential use of the positive electrode.

Therefore, in Patent Document 5, it is proposed to add a compound having a high reaction potential in the electrolyte.

The present inventors have made intensive quest result, have developed an electrolytic solution having a high oxidation resistance at different approaches to the prior art.

WO 2011/111364 JP 2013-82581 JP JP 2013-65575 JP JP 2009-123474 JP JP-T 2008-501220 JP

Netsu Sokutei 30 (1) 3-8

The present invention has been made in view of such circumstances, the first object is to provide a nonaqueous secondary battery having excellent output characteristics.

The second problem is to provide improved safety and a nonaqueous secondary battery which both are possible reversible charge and discharge reactions.

A third object is to provide a nonaqueous secondary battery having a combination of novel electrolyte and cathode to improve reversible charge and discharge reactions possible rate capacity characteristics.

The fourth object is to provide a nonaqueous secondary battery which can be used at a high potential.

Non-aqueous secondary battery according to a first aspect of the present invention, there is provided a nonaqueous secondary battery having a positive electrode and the negative electrode and the electrolyte,
The positive electrode has a positive active material having a lithium metal composite oxide having a layered rock-salt structure,
The electrolyte may include a metal salt with an alkali metal, an alkaline earth metal or aluminum cation, an organic solvent having a hetero element,
Per peak intensity derived from the organic solvent in the vibration spectrum of the electrolyte, in that the strength of the organic solvent inherent peak and Io, if the intensity of a peak the peak is shifted to the Is, it is Is> Io and features.
A first aspect of the present invention, the present inventors have conducted intensive quest result, the nonaqueous secondary battery comprising a positive electrode having a lithium metal composite oxide having a layered rock salt structure, can be reversibly charge and discharge reaction , due to the fact that we have developed a novel electrolyte having excellent input and output characteristics.

Non-aqueous secondary battery according to the second aspect of the present invention, there is provided a nonaqueous secondary battery having a positive electrode and the negative electrode and the electrolyte, wherein the positive electrode includes a positive electrode having a lithium metal composite oxide having a spinel structure has an active material, the electrolyte is a metal salt of an alkali metal, an alkaline earth metal or aluminum cation, and a organic solvent having a hetero element, the derived organic solvent in the vibration spectrum of the electrolyte per peak intensity, the the intensity of the organic solvent original peak and Io, if the intensity of a peak the peak is shifted to the is, characterized in that it is a is> Io.

A second aspect of the present invention, the present inventors have conducted intensive quest result, the nonaqueous secondary battery comprising a positive electrode having a lithium metal composite oxide having a spinel structure, reversibly capable charge and discharge reaction new due to the fact that developed the Do electrolyte.

The third non-aqueous secondary battery according to aspects of the present invention, there is provided a nonaqueous secondary battery having a positive electrode and the negative electrode and the electrolyte, wherein the cathode has a cathode active material having a polyanionic material, the electrolytic solution, an alkali metal, a metal salt and an alkaline earth metal or aluminum cation, wherein an organic solvent having a hetero element, per peak intensity derived from the organic solvent in the vibration spectrum of the electrolyte solution, the organic the strength of the solvent inherent peak and Io, if the intensity of a peak the peak is shifted to the is, characterized in that it is a is> Io.

A third aspect of the present invention, novel present inventors have conducted intensive quest result, to improve the non-aqueous secondary battery comprising a positive electrode having a polyanionic material, is reversibly capable of charge and discharge reactions rate capacity characteristics due to the fact that we have developed a combination of Do the electrolyte solution and the positive electrode.

The fourth non-aqueous secondary battery according to aspects of the present invention includes a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, a nonaqueous secondary battery having an electrolyte solution,
The electrolyte may include a metal salt with an alkali metal, an alkaline earth metal or aluminum cation, an organic solvent having a hetero element,
The electrolyte peak intensity derived from the organic solvent in the vibration spectrum of every said organic solvent strength of the original peak and Io, when the peak has an intensity of peak shifted Is, a Is> Io,
The nonaqueous secondary battery, the highest potential use of the positive electrode when the reference potential of Li / Li + is equal to or is 4.5V or more.

According to a first aspect of the present invention, the use of the above electrolyte solution, it is possible to provide a nonaqueous secondary battery having excellent output characteristics.

According to a second aspect of the present invention, the use of a novel electrolyte solution described above, provide improved safety and a nonaqueous secondary battery which both are possible reversible charge and discharge reaction can do.

According to a third aspect of the present invention, the use of a novel electrolyte of the nonaqueous with novel combinations of electrolyte and cathode to improve reversibly charge and discharge reaction can be rate capacity characteristics it is possible to provide a secondary battery.

According to a non-aqueous secondary battery of the fourth aspect of the present invention, because of its above-mentioned electrolyte solution, it can be used at a high potential, the average voltage and the battery capacity increases.

It is an IR spectrum of the electrolyte E3. It is an IR spectrum of the electrolyte solution E4. It is an IR spectrum of the electrolyte E7. It is an IR spectrum of the electrolyte E8. It is an IR spectrum of the electrolyte E10. It is an IR spectrum of the electrolyte solution C2. It is an IR spectrum of the electrolyte solution C4. It is an IR spectrum of acetonitrile. (CF 3 SO 2) is an IR spectrum of 2 NLi. (FSO 2) is an IR spectrum of 2 NLi (2100 ~ 2400cm -1) . It is an IR spectrum of the electrolyte of the electrolyte solution E11. It is an IR spectrum of the electrolyte of the electrolyte solution E12. It is an IR spectrum of the electrolyte of the electrolyte solution E13. It is an IR spectrum of the electrolyte of the electrolyte solution E14. It is an IR spectrum of the electrolyte of the electrolyte solution E15. It is an IR spectrum of the electrolyte of the electrolyte solution C6. It is an IR spectrum of the dimethyl carbonate. It is an IR spectrum of the electrolyte of the electrolyte solution E16. It is an IR spectrum of the electrolyte of the electrolyte solution E17. It is an IR spectrum of the electrolyte of the electrolyte solution E18. It is an IR spectrum of the electrolyte of the electrolyte solution C7. It is an IR spectrum of the ethyl methyl carbonate. It is an IR spectrum of the electrolyte of the electrolyte solution E19. It is an IR spectrum of the electrolyte of the electrolyte solution E20. It is an IR spectrum of the electrolyte of the electrolyte solution E21. It is an IR spectrum of the electrolyte of the electrolyte solution C8. It is an IR spectrum of diethyl carbonate. (FSO 2) is an IR spectrum of 2 NLi (1900 ~ 1600cm -1) . It is a Raman spectrum of the electrolyte E8. It is a Raman spectrum of the electrolyte E9. It is a Raman spectrum of the electrolyte solution C4. It is a Raman spectrum of the electrolyte E11. It is a Raman spectrum of the electrolyte E13. It is a Raman spectrum of the electrolyte E15. It is a Raman spectrum of the electrolyte C6. It shows a DSC curve of Comparative Example A-1 Example A-1. It shows a DSC curve of Comparative Example A-1 Example A-2. Example A-5, the lithium ion secondary battery of Comparative Example A-3, is a graph showing the relationship between the square root of the number of cycles at the time of cycle test and the discharge capacity retention ratio. In Evaluation Example A-15, the complex impedance plane plots of the battery. In Evaluation Example A-16, cell A-8, is an XPS analysis result for the negative electrode S, the carbon element of the O-containing coating of the battery A-9 and the battery A-C3. In Evaluation Example A-16, cell A-8, is an XPS analysis result for the negative electrode S, the fluorine element of O-containing coating of the battery A-9 and the battery A-C3. In Evaluation Example A-16, cell A-8, is an XPS analysis result for the negative electrode S, the nitrogen element O-containing coating of the battery A-9 and the battery A-C3. In Evaluation Example A-16, cell A-8, is an XPS analysis result for the negative electrode S, oxygen elements O containing coating of the battery A-9 and the battery A-C3. In Evaluation Example A-16, cell A-8, is an XPS analysis result for the negative electrode S, elemental sulfur O-containing coating of the battery A-9 and the battery A-C3. Negative electrode S of the battery A-8 in Evaluation Example A-16, an XPS analysis result of the O-containing coating. Negative electrode S of the battery A-9 in Evaluation Example A-19, an XPS analysis result of the O-containing coating. Negative electrode S of the battery A-8 in Evaluation Example A-19, a BF-STEM image of O-containing coating. In Evaluation Example A-19, a STEM analysis for C of the negative electrode S, O containing coatings of the battery A-8. In Evaluation Example A-19, a STEM analysis results for O negative electrode S, O containing coatings of the battery A-8. In Evaluation Example A-19, a STEM analysis results for the S of the negative electrode S, O containing coatings of the battery A-8. In Evaluation Example A-19, an XPS analysis result for positive S, the O-containing coating O of the battery A-8. In Evaluation Example A-19, an XPS analysis result for positive S, the O-containing coating S of the battery A-8. In Evaluation Example A-19, an XPS analysis result for positive S, the O-containing coating S of the battery A-11. In Evaluation Example A-19, an XPS analysis result for positive S, the O-containing coating O of the battery A-11. In Evaluation Example A-19, cell A-11, an XPS analysis result for positive S, the O-containing coating S of the battery A-12 and battery A-C4. In Evaluation Example A-19, cell A-13, an XPS analysis result for positive S, the O-containing coating S of the battery A-14 and battery A-C5. In Evaluation Example A-19, cell A-11, an XPS analysis result for positive S, the O-containing coating O of the battery A-12 and battery A-C4. In Evaluation Example A-19, cell A-13, the analysis results for the positive electrode S, the O-containing coating O of the battery A-14 and battery A-C5. In Evaluation Example A-19, cell A-11, the analysis results for the S of the negative electrode S, O containing coatings of the battery A-12 and battery A-C4. In Evaluation Example A-19, cell A-13, the analysis results for the S of the negative electrode S, O containing coatings of the battery A-14 and battery A-C5. In Evaluation Example A-19, cell A-11, the analysis result for O negative electrode S, O containing coatings of the battery A-12 and battery A-C4. In Evaluation Example A-19, cell A-13, the analysis result for O negative electrode S, O containing coatings of the battery A-14 and battery A-C5. In Evaluation Example A-21, a surface analysis of the aluminum foil after charging and discharging of the lithium ion secondary battery of the battery A-8. In Evaluation Example A-21, a surface analysis of the aluminum foil after charging and discharging of the lithium ion secondary battery of the battery A-9. It is a graph showing the relationship between the response current potential (3.1 ~ 4.6V) for half cell of the battery A1. It is a graph showing the relationship between the response current potential (3.1 ~ 5.1V) for half cell of the battery A1. It is a graph showing the relationship between the response current potential (3.1 ~ 4.6V) for half cell of the battery A2. It is a graph showing the relationship between the response current potential (3.1 ~ 5.1V) for half cell of the battery A2. It is a graph showing the relationship between the response current potential (3.1 ~ 4.6V) for half cell of the battery A3. It is a graph showing the relationship between the response current potential (3.1 ~ 5.1V) for half cell of the battery A3. It is a graph showing the relationship between the response current potential (3.1 ~ 4.6V) for half cell of the battery A4. It is a graph showing the relationship between the response current potential (3.1 ~ 5.1V) for half cell of the battery A4. It is a graph showing the relationship between the response current potential (3.1 ~ 4.6V) for half cell battery AC1. It is a graph showing the relationship between the response current potential (3.0 ~ 4.5V) for half cell of the battery A2. It is a graph showing the relationship between the response current potential (3.0 ~ 5.0V) for half cell of the battery A2. It is a graph showing the relationship between the response current potential (3.0 ~ 4.5V) for half cell of the battery A5. It is a graph showing the relationship between the response current potential (3.0 ~ 5.0V) for half cell of the battery A5. It is a graph showing the relationship between the response current potential (3.0 ~ 4.5V) for half cell battery AC2. It is a graph showing the relationship between the response current potential (3.0 ~ 5.0V) for half cell battery AC2. Is a diagram showing the results of CV measurement half cell. It shows the charge-discharge curve of the half-cell. It is a diagram showing a discharge curve of half cell of Example C-1. Shows the discharge curve of Comparative Example C-1 of the half-cell. It is a diagram showing a charge-discharge curve of half cell of Example C-2. Is a graph showing changes in discharge rate capacity due to charge-discharge cycles of half cell of Example C-2, C-3 and Comparative Example C-1, C-2. Is a diagram showing charge-discharge curves at each rate of half cell of Example C-1. Is a diagram showing charge-discharge curves at each rate of Comparative Example C-1 of the half-cell. Potential by LSV measurement of battery D-1 and the battery D-C1, D-C2 - shows the current curve. Potential by LSV measurement of battery D-2 - shows the current curve. It shows a charge-discharge curve of the half-cell batteries D-3. It shows a charge-discharge curve of the half-cell batteries D-4. It shows a model illustration of the charge curve of the lithium-metal composite oxide. A charge-discharge curve of the half-cell batteries D-5. A charge-discharge curve of the half-cell batteries D-6. A charge-discharge curve of the half-cell batteries D-7. A charge-discharge curve of the half-cell batteries D-8. A charge-discharge curve of the half-cell batteries D-C3.

For non-aqueous secondary battery according to the first to fourth aspect of the present invention will be described in detail. Unless otherwise specified, the numerical ranges described herein, "a ~ b" includes the lower a and an upper limit b within its scope. Then, it may constitute these upper and lower values, and numerical ranges by combining them arbitrarily, including numerical values ​​listed in the examples. The selected number to the arbitrary upper, can be a number of lower limit from further within the numerical range.

(Electrolyte)
Electrolytic solution, an alkali metal, alkaline earth metal or aluminum salt of a cation (hereinafter "metal salts" or simply referred to as "salt".), And an electrolytic solution containing an organic solvent having a hetero element there are, per peak intensity derived from the organic solvent in the vibration spectrum of the electrolyte solution, if the intensity of the peak in the original peak wavenumber organic solvent and Io, and the intensity of a peak inherent peak organic solvent was wavenumber shifts as is, characterized in that it is a is> Io.
Incidentally, conventional electrolytic solution, the relationship between Is and Io is Is <Io.
Hereinafter, a salt of an alkali metal, an alkaline earth metal or aluminum cation, an electrolytic solution containing an organic solvent having a hetero element, per peak intensity derived from the organic solvent in the vibration spectrum of the electrolyte solution, an organic solvent the strength of the original peak and Io, when the intensity of a peak peak shifted with is, that the electrolyte is is> Io, may be referred to as "electrolytic solution of the present invention".

Metal salt, usually, LiClO 4 contained in the electrolyte of the battery, LiAsF 6, LiPF 6, LiBF 4, LiAlCl 4, may be any compound used as an electrolyte, such as. As the cation of the metal salt include lithium, sodium, alkali metals such as potassium, beryllium, magnesium, calcium, strontium, alkaline earth metals such as barium, and aluminum. Cations of the metal salt is preferably the same metal ions and charge carriers of a battery using the electrolytic solution. For example, if you are using the electrolytic solution of the present invention as an electrolyte for a lithium ion secondary battery, cations of the metal salt is lithium are preferred.

The chemical structure of the anion of the salt may include halogen, boron, nitrogen, oxygen and at least one element selected from oxygen, sulfur or carbon. Specific examples of the chemical structure of anions containing halogen or boron, ClO 4, PF 6, AsF 6, SbF 6, TaF 6, BF 4, SiF 6, B (C 6 H 5) 4, B (oxalate) 2, Cl, Br, may be mentioned I.

Nitrogen, oxygen, the chemical structure of anions containing sulfur or carbon, will be specifically described below.

The chemical structure of the anion of the salt is represented by the following general formula (1), the chemical structure is preferably represented by the general formula (2) or general formula (3).
(R 1 X 1) (R 2 X 2) N Formula (1)
(R 1 is hydrogen, halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, optionally substituted with a substituent unsaturated alkyl group, a substituted group in optionally substituted unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, it may be substituted by optionally substituted heterocyclic group, optionally substituted with a substituent alkoxy group , selection may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent unsaturated thioalkoxy group, CN, SCN, from OCN It is.
R 2 is hydrogen, halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, optionally substituted with a substituent unsaturated alkyl group, a substituted group optionally substituted unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, may be substituted by optionally substituted heterocyclic group, optionally substituted with a substituent alkoxy group, may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent unsaturated thioalkoxy group, CN, SCN, selected from OCN that.
Alternatively, R 1 and R 2 may be bonded to each other to form a ring.
X 1 is, SO 2, C = O, C = S, R a P = O, R b P = S, S = O, is selected from Si = O.
X 2 is, SO 2, C = O, C = S, R c P = O, R d P = S, S = O, is selected from Si = O.
R a, R b, R c , R d represents a substituted independently hydrogen, halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, a substituted group which may be unsaturated alkyl group, which may be substituted with a substituent unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, it may be substituted by optionally substituted heterocyclic group , which may be substituted with a substituent alkoxy group, may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent not saturated thioalkoxy group, OH, SH, CN, SCN, is selected from the OCN.
Furthermore, R a, R b, R c, R d is combined with R 1 or R 2 may form a ring. )
R 3 X 3 Y Formula (2)
(R 3 is hydrogen, halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, which may be unsaturated alkyl group substituted with a substituent, in optionally substituted unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, it may be substituted by optionally substituted heterocyclic group, optionally substituted with a substituent alkoxy group , selection may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent unsaturated thioalkoxy group, CN, SCN, from OCN It is.
X 3 is, SO 2, C = O, C = S, R e P = O, R f P = S, S = O, is selected from Si = O.
R e, R f are, each independently, hydrogen, Good halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, optionally substituted with a substituent not saturated alkyl group, which may be substituted with a substituent unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, may be substituted by optionally substituted heterocyclic group, it is substituted with a substituent even though alkoxy group, may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent unsaturated thioalkoxy group, OH , SH, CN, SCN, is selected from the OCN.
Also, R e, is R f, may form a ring with R 3.
Y is, O, is selected from S. )
(R 4 X 4) (R 5 X 5) (R 6 X 6) C Formula (3)
(R 4 is hydrogen, halogen, optionally substituted with a substituent alkyl group, substituted with a substituent which may have a cycloalkyl group, substituents which may be substituted unsaturated alkyl group, a substituted group in optionally substituted unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, it may be substituted by optionally substituted heterocyclic group, optionally substituted with a substituent alkoxy group , selection may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent unsaturated thioalkoxy group, CN, SCN, from OCN It is.
R 5 is hydrogen, halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, optionally substituted with a substituent unsaturated alkyl group, a substituted group optionally substituted unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, may be substituted by optionally substituted heterocyclic group, optionally substituted with a substituent alkoxy group, may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent unsaturated thioalkoxy group, CN, SCN, selected from OCN that.
R 6 is hydrogen, halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, optionally substituted with a substituent unsaturated alkyl group, a substituted group optionally substituted unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, may be substituted by optionally substituted heterocyclic group, optionally substituted with a substituent alkoxy group, may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent unsaturated thioalkoxy group, CN, SCN, selected from OCN that.
Further, R 4, R 5, of R 6, any two or three may be combined with each other to form a ring.
X 4 is, SO 2, C = O, C = S, R g P = O, R h P = S, S = O, is selected from Si = O.
X 5 is, SO 2, C = O, C = S, R i P = O, R j P = S, S = O, is selected from Si = O.
X 6 is, SO 2, C = O, C = S, R k P = O, R l P = S, S = O, is selected from Si = O.
R g, R h, R i , R j, R k, R l are each independently hydrogen, halogen, optionally substituted with a substituent an alkyl group, cycloalkyl which may be substituted with a substituent group, may be substituted with a substituent unsaturated alkyl group, which may be substituted with a substituent unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, substituted with a substituent be heterocyclic group, may be substituted with a substituent alkoxy group, may be substituted with a substituent unsaturated alkoxy group, may be substituted with a substituent thioalkoxy group, substituted with a substituent which may be unsaturated thioalkoxy group, OH, SH, CN, SCN, is selected from the OCN.
Also, R g, R h, R i, R j, R k, R l is, R 4, R 5 or may be R 6 combine with other to form a ring. )
In the chemical structure represented by the above general formula (1) to (3) will be described wording as "may be substituted with a substituent." For example, if the "may be substituted with a substituent alkyl group", the alkyl group one or more is replaced with a substituent of hydrogen alkyl group, or an alkyl group having no particular substituent It means.
The substituent in the wording of the "may be substituted with a substituent" include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an unsaturated cycloalkyl group, an aromatic group, a heterocyclic group, halogen, OH , SH, CN, SCN, OCN, a nitro group, an alkoxy group, an unsaturated alkoxy group, an amino group, an alkylamino group, a dialkylamino group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an aryloxycarbonyl group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, a ureido group, a phosphoric acid amido group, a sulfo group, a carboxyl group, hydroxamic acid group, Rufino group, a hydrazino group, an imino group, and a silyl group. These substituents may be further substituted. Further, when the substituents are two or more, the substituents may be the same or different.

The chemical structure of the anion of the salt is represented by the following general formula (4), the general formula (5) or chemical structure represented by the general formula (6) is more preferable.
(R 7 X 7) (R 8 X 8) N Formula (4)
(R 7, R 8 are each independently C n H a F b Cl c Br d I e (CN) f (SCN) g (OCN) h.
n, a, b, c, d, e, f, g, h are each independently an integer of 0 or more satisfying the 2n + 1 = a + b + c + d + e + f + g + h.
Further, R 7 and R 8 may be bonded to each other to form a ring, in that case, satisfy 2n = a + b + c + d + e + f + g + h.
X 7 is, SO 2, C = O, C = S, R m P = O, R n P = S, S = O, is selected from Si = O.
X 8 is, SO 2, C = O, C = S, R o P = O, R p P = S, S = O, is selected from Si = O.
R m, R n, R o , R p is substituted independently hydrogen, halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, a substituted group which may be unsaturated alkyl group, which may be substituted with a substituent unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, it may be substituted by optionally substituted heterocyclic group , which may be substituted with a substituent alkoxy group, may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent not saturated thioalkoxy group, OH, SH, CN, SCN, is selected from the OCN.
Also, R m, R n, R o, R p may be bonded to R 7 or R 8 to form a ring. )
R 9 X 9 Y Formula (5)
(R 9 is a C n H a F b Cl c Br d I e (CN) f (SCN) g (OCN) h.
n, a, b, c, d, e, f, g, h are each independently an integer of 0 or more satisfying the 2n + 1 = a + b + c + d + e + f + g + h.
X 9 is, SO 2, C = O, C = S, R q P = O, R r P = S, S = O, is selected from Si = O.
R q, R r are each independently hydrogen, halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, optionally substituted with a substituent not saturated alkyl group, which may be substituted with a substituent unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, may be substituted by optionally substituted heterocyclic group, it is substituted with a substituent even though alkoxy group, may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent unsaturated thioalkoxy group, OH , SH, CN, SCN, is selected from the OCN.
Also, R q, R r may be bonded together to form a ring with R 9.
Y is, O, is selected from S. )
(R 10 X 10) (R 11 X 11) (R 12 X 12) C Formula (6)
(R 10, R 11, R 12 are each independently C n H a F b Cl c Br d I e (CN) f (SCN) g (OCN) h.
n, a, b, c, d, e, f, g, h are each independently an integer of 0 or more satisfying the 2n + 1 = a + b + c + d + e + f + g + h.
R 10, R 11, any two of R 12 is bonded, it may form a ring, in which case the group to form a ring satisfies 2n = a + b + c + d + e + f + g + h.Also, R 10, R 11, may be R 12 3 is coupled to the other to form a ring, in that case, the two groups of three satisfies 2n = a + b + c + d + e + f + g + h, 1 single group 2n-1 = a + b + c + d + e + f + g + h Fulfill.
X 10 is, SO 2, C = O, C = S, R s P = O, R t P = S, S = O, is selected from Si = O.
X 11 is, SO 2, C = O, C = S, R u P = O, R v P = S, S = O, is selected from Si = O.
X 12 is, SO 2, C = O, C = S, R w P = O, R x P = S, S = O, is selected from Si = O.
R s, R t, R u , R v, R w, R x is independently hydrogen, halogen, optionally substituted with a substituent an alkyl group, cycloalkyl which may be substituted with a substituent group, may be substituted with a substituent unsaturated alkyl group, which may be substituted with a substituent unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, substituted with a substituent be heterocyclic group, may be substituted with a substituent alkoxy group, may be substituted with a substituent unsaturated alkoxy group, may be substituted with a substituent thioalkoxy group, substituted with a substituent which may be unsaturated thioalkoxy group, OH, SH, CN, SCN, is selected from the OCN.
Further, R s, R t, R u, R v, R w, R x may be bonded to R 10, R 11 or R 12 form a ring. )
In the chemical structure represented by the general formula (4) to (6), the meaning of the wording of "may be substituted with a substituent" has been explained above general formula (1) to (3) as synonymous.
In the chemical structure represented by the general formula (4) ~ (6), n is preferably 0-6 integer, more preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 2. Incidentally, the chemical structure represented by the general formula (4) ~ (6), R 7 and R 8 bond, or, when R 10, R 11, R 12 are joined to form a ring , n is preferably an integer of from 1 to 8, more preferably an integer of 1-7, an integer of 1 to 3 are particularly preferred.

The chemical structure of the anion of the salt is represented by the following general formula (7), the general formula (8) or those represented by the general formula (9) is more preferred.
(R 13 SO 2) (R 14 SO 2) N Formula (7)
(R 13, R 14 are each independently C n H a F b Cl c Br d I e.
n, a, b, c, d, e are each independently an integer of 0 or more satisfying the 2n + 1 = a + b + c + d + e.
Also, R 13 and R 14 may be bonded to each other to form a ring, in that case, satisfy 2n = a + b + c + d + e. )
R 15 SO 3 Formula (8)
(R 15 is a C n H a F b Cl c Br d I e.
n, a, b, c, d, e are each independently an integer of 0 or more satisfying the 2n + 1 = a + b + c + d + e. )
(R 16 SO 2) (R 17 SO 2) (R 18 SO 2) C Formula (9)
(R 16, R 17, R 18 are each independently C n H a F b Cl c Br d I e.
n, a, b, c, d, e are each independently an integer of 0 or more satisfying the 2n + 1 = a + b + c + d + e.
R 16, R 17, any two of R 18 is bonded, it may form a ring, in which case the group to form a ring satisfies 2n = a + b + c + d + e.Also, may be three are bonded to the R 16, R 17, R 18 form a ring, in that case, the two groups of three satisfies 2n = a + b + c + d + e, 1 single group 2n-1 = a + b + c + d + e Fulfill. )

In the chemical structure represented by the above general formula (7) ~ (9), n is preferably 0-6 integer, more preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 2. Incidentally, the chemical structure represented by the general formula (7) to (9), binding R 13 and R 14, or, if R 16, R 17, R 18 combine together to form a ring , n is preferably an integer of from 1 to 8, more preferably an integer of 1-7, an integer of 1 to 3 are particularly preferred.

Further, in the chemical structure represented by the above general formula (7) ~ (9), a, c, d, e is preferably that of 0.

Metal salts, (CF 3 SO 2) 2 NLi ( hereinafter sometimes referred to as "LiTFSA".), (FSO 2) 2 NLi ( hereinafter sometimes referred to as "LiFSA".), (C 2 F 5 SO 2) 2 NLi, FSO 2 ( CF 3 SO 2) NLi, (SO 2 CF 2 CF 2 SO 2) NLi, (SO 2 CF 2 CF 2 CF 2 SO 2) NLi, FSO 2 (CH 3 SO 2) NLi , FSO 2 (C 2 F 5 SO 2) NLi, or FSO 2 (C 2 H 5 SO 2) NLi are particularly preferred.

Metal salts of the present invention may be employed a combination in respective appropriate number cations and anion described above. Metal salt in the electrolytic solution of the present invention may be employed one kind or as a combination of plural kinds.

The organic solvent having a hetero element, nitrogen hetero element, oxygen, sulfur, an organic solvent is preferably at least one selected from halogen, at least is one organic solvent hetero atom is selected from nitrogen or oxygen It is more preferable. As the organic solvent having a hetero element, NH group, NH 2 group, OH group, no proton-donating group such as SH group, aprotic solvents are preferred.

The organic solvent (hereinafter, simply there. Referred to as "organic solvent") having a hetero element Specific examples of the acetonitrile, propionitrile, acrylonitrile, nitriles such as malononitrile, 1,2-dimethoxyethane, 1, 2-diethoxyethane, tetrahydrofuran, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, 2,2-dimethyl-1,3-dioxolane, 2-methyl-tetrahydropyran, 2-methyltetrahydrofuran, crown ethers such as ether, ethylene carbonate, propylene carbonate, dimethyl carbonate, carbonates such as diethyl carbonate, ethyl methyl carbonate, formamide, N, N- dimethylformamide, N, N- dimethylacetamide, N- methylpyrrolidone Amides, isopropyl isocyanate, n- propyl isocyanate, isocyanates chloromethyl isocyanate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, methyl formate, ethyl formate, vinyl acetate, methyl acrylate, esters such as methyl methacrylate s, glycidyl methyl ether, epoxy such as epoxy butane, 2-ethyl oxirane, oxazole, 2-ethyl-oxazole, oxazoline, oxazole and 2-methyl-2-oxazoline, acetone, methyl ethyl ketone, ketones such as methyl isobutyl ketone , acetic anhydride, acid anhydrides such as propionic anhydride, dimethyl sulfone, sulfones such as sulfolane, sulfoxides such as dimethyl sulfoxide, 1-nitropropane, 2-nitro Nitro such as propane, furan, furan such as furfural, .gamma.-butyrolactone, .gamma.-valerolactone, cyclic esters such as δ- valerolactone, thiophene, such as pyridine, tetrahydro-4-pyrone, 1-methylpyrrolidine, heterocyclic compounds such as N- methylmorpholine, trimethyl phosphate, can be mentioned phosphoric acid esters such as triethyl phosphate.

As organic solvents, mention may be made of chain carbonates represented by the following general formula (10).
R 19 OCOOR 20 formula (10)
(R 19, R 20 are each independently a linear alkyl C n H a F b Cl c Br d I e, or, C m H f F g Cl h Br i I contains a cyclic alkyl in the chemical structure .n selected from any of j, a, b, c, d, e, m, f, g, h, i, j are each independently an integer of 0 or more, 2n + 1 = a + b + c + d + e, 2m = f + g + h + i + j meet.)

In the linear carbonate represented by the general formula (10), n is preferably an integer of 1 to 6, more preferably an integer of 1 to 4, an integer of 1 or 2 it is particularly preferred. m is preferably an integer of 3 to 8, more preferably an integer of 4-7, particularly preferably an integer of 5-6. Also, among the chain carbonates represented by the above general formula (10), dimethyl carbonate (hereinafter sometimes referred to as "DMC".), Diethyl carbonate (hereinafter sometimes referred to as "DEC".), Ethylmethyl carbonate (hereinafter sometimes referred to as "EMC".) is particularly preferred.

As the organic solvent, the dielectric constant is preferably a solvent having 20 or more or a donor of the ether oxygen, as such an organic solvent, acetonitrile, propionitrile, acrylonitrile, nitriles such as malononitrile, 1,2-dimethoxyethane , 1,2-diethoxyethane, tetrahydrofuran, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, 2,2-dimethyl-1,3-dioxolane, 2-methyl-tetrahydropyran, 2-methyl ethers such as tetrahydrofuran, crown ethers, N, N- dimethylformamide, may be mentioned acetone, dimethyl sulfoxide, sulfolane, especially acetonitrile (hereinafter, sometimes referred to as "aN".), 1,2-dimethoxyethane (hereinafter sometimes referred to as "DME" ) Is preferable.
It These organic solvents may be used alone in the electrolytic solution may be used in combination of two or more.

Electrolytic solution of the present invention, in the vibration spectrum, per peak intensity derived from the organic solvent contained in the electrolytic solution, the intensity of the original peak organic solvent and Io, peak inherent peak organic solvent is shifted (hereinafter, " when the strength of it is that the shift peak ".) and is, characterized in that it is a is> Io. That is, in the vibration spectrum chart obtained is subjected to an electrolytic solution of the present invention the vibration spectrometry, relationship of the two peak intensities becomes Is> Io.

Here, "organic solvent inherent peak", the peak position in the case where only the organic solvent vibrates spectrometry (wavenumber) means a peak observed. The value of the intensity Io of the organic solvent the original peak value of the intensity of the shift peak Is is the height or area from each peak of the baseline in the vibration spectrum.

In the vibration spectrum of the electrolyte solution of the present invention, when a peak inherent peak organic solvent is shifted there are a plurality, it may determine the relationship based on the peak and easy determination of the relation between the most Is and Io. Further, when an organic solvent having a hetero element in the electrolytic solution of the present invention using multiple species, most Is and Io of the relationship easily determined (most difference Is and Io is marked) organic solvent is selected, it may determine the relationship between Is and Io on the basis of the peak intensity. Also, small amount of shift of the peak, if the overlap peak shift back and forth look like a gentle mountain performs peak separation using known means may determine the relationship between Is and Io.

In the vibrational spectrum of the electrolyte solution using plural kinds of organic solvent having a hetero element, apt organic solvent most coordinated with the cation peak (hereinafter, sometimes referred to as "Priority coordinating solvent".) Other to shift in preference to. In the electrolytic solution using plural kinds of organic solvent having a hetero element, by mass% of the priority coordinating solvent to the total organic solvent having a hetero element is preferably at least 40%, more preferably at least 50%, further 60% or more preferably, and particularly preferably 80% or more. Further, in the electrolytic solution using plural kinds of organic solvent having a hetero element, vol% of priority coordinating solvent to the total organic solvent having a hetero element is preferably at least 40%, more preferably at least 50%, 60% and still more preferably 80% or more.

Relationship of the two peak intensities in the vibration spectrum of the electrolyte solution of the present invention, Is> satisfy it is preferable for 2 × Io, Is> satisfies more preferably the 3 × Io, Is> 5 × satisfy still more preferably from Io, is> 7 × satisfy the Io is particularly preferred. Most preferably, in the vibration spectrum of the electrolyte solution of the present invention, the intensity Io of the original peak organic solvent is not observed, an electrolytic solution strength of the shift peak Is is observed. In the electrolyte solution, which means that all the molecules of the organic solvent contained in the electrolytic solution is completely solvated metal salt. Electrolytic solution of the present invention, with all molecules of the organic solvent contained in the electrolytic solution is completely solvated metal salt (state of Io = 0) is most preferred.

In the electrolytic solution of the present invention, a metal salt, an organic solvent having a hetero element (or priority coordinating solvent) It is estimated that interact each other. Specifically, a metal salt, a hetero atom of an organic solvent (or priority coordinating solvent) having a hetero element forms a coordinate bond, an organic solvent having a metal salt and a hetero element (or priority coordinating solvent stable clusters of) is estimated to form. This cluster, as viewed from the results of evaluation example described later, generally, with respect to the metal salt per molecule, is estimated as an organic solvent (or priority coordinating solvent) 2 molecule having a hetero element is formed by coordination that. In view of this, in the electrolytic solution of the present invention, the molar range of organic solvents (or priority coordinating solvent) having a hetero element to the metal salt 1 mole, preferably less than 3.5 mol 1.4 mol or more, 1 more preferably .5 mol 3.1 mol, further preferably 1.6 mol or more 3 mol.

Because in the electrolyte solution of the present invention, generally, with respect to the metal salt per molecule, an organic solvent (or priority coordinating solvent) having a hetero element 2 molecules is estimated to be clustered by coordination, the the concentration of the electrolytic solution of the present invention (mol / L) is dependent on the molecular weight of each metal salt and an organic solvent, the density in the case of the solution. Therefore, it is not appropriate to define the concentration of the electrolytic solution of the present invention indiscriminately.

The concentration of the electrolytic solution of the present invention c an (mol / L) illustrated separately in Table 1.

Figure JPOXMLDOC01-appb-T000001

And an organic solvent that forms a cluster, and the organic solvent which is not involved in the formation of clusters, different each occurrence environment. Therefore, in the vibration spectroscopy, a peak derived from the organic solvent forming the clusters, from the observed wave number of the peak of the organic solvent from not involved in the formation of clusters (the original peak organic solvents), high frequency side or is observed is shifted to a lower wave number side. That is, the shift peak corresponds to the peak of an organic solvent to form a cluster.

The vibration spectrum can include IR spectrum or Raman spectrum. As a measuring method of IR measurement, mention may be made nujol, transmission measurement method, such as liquid membrane method, a reflection measurement method, such as ATR method. About one to select the IR spectrum or the Raman spectrum, the vibrational spectrum of the electrolyte solution of the present invention may be selected towards the spectrum tends to determine the relationship between Is and Io. Incidentally, vibrational spectroscopy measurements may be carried out under conditions that can reduce or ignoring the effect of atmospheric moisture. For example, dry room, to perform the IR measurement at low humidity or no humidity conditions, such as a glove box, or, may be carried out Raman measurements in a state containing the electrolytic solution in a sealed container.

Here, LiTFSA metal salt, per peak in the electrolytic solution of the present invention containing acetonitrile as the organic solvent, specifically described.

If only it was IR measurement acetonitrile, peak derived from stretching vibration triple bond between C and N is observed in the vicinity of the normal 2100 ~ 2400 cm -1.

Here, according to conventional technical common sense, it is assumed that the electrolyte is dissolved at a concentration of 1 mol / L of LiTFSA to acetonitrile solvent. Since acetonitrile 1L corresponds to about 19 mol, in the conventional electrolytic solution 1L, there is acetonitrile 1mol of LiTFSA and 19 mol. Then, in the conventional electrolytic solution, simultaneously with acetonitrile (a coordinating to Li) that LiTFSA solvated, not LiTFSA solvated (not coordinated to Li) there are many acetonitrile . Now, acetonitrile molecules that LiTFSA solvated, and acetonitrile molecules that do not LiTFSA solvated, since the environment where the acetonitrile molecules different, in the IR spectrum observed acetonitrile peaks of both distinguish It is. More specifically, the peak of acetonitrile which is not LiTFSA and solvated, is observed only acetonitrile at the same position as when the IR measurement (wavenumber), while the peak of acetonitrile are LiTFSA solvated the peak position (wave number) is observed to shift to the high wave number side.

Then, in the concentration of the conventional electrolytic solution because acetonitrile is not LiTFSA solvated is to present a large number, in the vibration spectrum of a conventional electrolytic solution, the intensity Io of the original peak of acetonitrile, the original peak acetonitrile but the relationship between the intensity of the peak shifted is becomes the is <Io.

On the other hand, the electrolytic solution of the present invention has high concentrations of LiTFSA compared with conventional electrolytic solution, and the number of (to form a cluster are) that LiTFSA are solvated acetonitrile molecules in the electrolytic solution, and LiTFSA more than the number of acetonitrile molecule that is not solvated. Then, in the vibration spectrum of the electrolyte solution of the present invention, the relationship between the intensity Io of the original peak of acetonitrile, the original peak acetonitrile and intensity Is of the peak shifted becomes Is> Io.

Table 2, in the vibration spectrum of the electrolyte solution of the present invention are illustrated and the wave number of organic solvents that may be useful in calculating the Io and Is, the attribution. The measurement apparatus of the vibration spectrum, measurement environment, and due to the measurement conditions, the wave number of peaks observed which are made by those that may be different than the wave number.

Figure JPOXMLDOC01-appb-T000002

Wave number of the organic solvent and for its attribution may reference a known data. As a reference, JASCO Society measurement method Series 17 Raman spectroscopy, Hiroo Hamaguchi, Akiko Hirakawa, Japan Scientific Societies Press, cited pp. 231-249. Further, it is possible to predict by calculation using a computer, and the wave number of organic solvents that may be useful in calculating the Io and Is, the wave number shift of the case where the organic solvent and the metal salt is coordinated. For example, Gaussian 09 (registered trademark, Gaussian, Inc.) was used, may be calculated density functional B3LYP, as a basis function 6-311G ++ (d, p). Those skilled in the art can forth in Table 2, the known data, the calculation results of the computer with reference to select the peak of an organic solvent, to calculate the Io and Is.

Electrolytic solution of the present invention, as compared with the conventional electrolytic solution, unlike the present environment of the metal salt and an organic solvent, and, because of the high metal salt concentrations, improved metal ion transport rate in the electrolyte (particularly, metal If is lithium, improvement of lithium transference number), improvement in the reaction rate of the electrode and the electrolyte interface, alleviation of uneven distribution of the salt concentration of the electrolyte solution which occurs during high-rate charge and discharge of the battery, an electric double layer capacity increase can be expected . Furthermore, in the electrolytic solution of the present invention, since the majority of the organic solvent having a hetero element forms a metal salt and clusters, the vapor pressure of the organic solvent contained in the electrolytic solution is lowered. As a result, it volatilization reduction of organic solvent from the electrolytic solution of the present invention.

Electrolytic solution of the present invention, as compared to the electrolyte of the conventional battery, the high viscosity. Therefore, if the battery using the electrolyte of the present invention, even if the battery is damaged, electrolyte leakage is prevented. Further, the lithium ion secondary battery using a conventional electrolyte, volume reduction is remarkable in high-speed charge-discharge cycle. One of the reasons rapidly due to the Li concentration unevenness occurs in the electrolytic solution at the time of repeated charge and discharge, the electrolyte a sufficient amount of Li to the reaction interface between the electrode can no longer be supplied, i.e. , it can be considered uneven distribution of the Li concentration of the electrolyte solution. However, the secondary battery electrolyte using the present invention, it was revealed that the capacity at the time of high-speed charge and discharge can be suitably maintained. The physical properties of the high viscosity of the electrolyte of the present invention, it is believed that the reason for it is possible to suppress the uneven distribution of Li concentration in the electrolyte. Also, the physical properties of the high viscosity of the electrolyte of the present invention, improved liquid retention of the electrolytic solution in the electrode interface, also the electrolyte at the electrode interface can be inhibited state be insufficient (so-called liquid withered state), high speed considered a cause of capacity reduction during charge and discharge cycles it was suppressed.

Stated the viscosity of the electrolyte of the present invention η (mPa · s), 10 <η <500 is preferably in the range of, 12 <eta <more preferably in the range of 400, 15 <η <more preferably in the range of 300, 18 <eta <particularly preferably in the range of 150, 20 <η <most preferred range of 140.

The higher ionic conductivity of the electrolyte solution σ (mS / cm) is higher, ions move easily in the electrolytic solution. Therefore, such electrolyte can be a electrolyte of excellent battery. Describing the ionic conductivity of the electrolyte solution of the present invention σ (mS / cm), it is preferably 1 ≦ sigma. Per electrolyte ion conductivity of the present invention σ (mS / cm), dare and shows a preferred range including the upper limit, 2 <σ <200 is preferably in the range of, 3 <sigma <more preferably in the range of 100 , 4 <sigma <more preferably in the range of 50, 5 <sigma range of <35 are particularly preferred.

Incidentally, the electrolytic solution of the present invention contains a high concentration of cations of the metal salt. Therefore, in the electrolytic solution of the present invention, the distance between adjacent cationic is very close. Then, cations such as lithium ions during charge and discharge of the secondary battery when moving between the positive electrode and the negative electrode, the most recent cation destination electrode is first supplied to the electrode. Then, in the place where there is supplied the cation, other cations adjacent to the cation moves. That is, in the electrolytic solution of the present invention, the adjacent cation of changing one by one position in order toward the electrode to be supplied subject is expected to domino-like phenomenon occurs. Therefore, the moving distance of the charging and discharging time of the cation is short, the moving speed of the cations is correspondingly considered to be high. Then, due to this fact, the reaction rate of the secondary battery having an electrolyte of the present invention is considered high.

Density in the electrolytic solution of the present invention d (g / cm 3) is preferably a d ≧ 1.2 or d ≦ 2.2, more preferably in a range of 1.2 ≦ d ≦ 2.2, 1. more preferably in the range of 24 ≦ d ≦ 2.0, more preferably in the range of 1.26 ≦ d ≦ 1.8, particularly preferably in the range of 1.27 ≦ d ≦ 1.6. The density in the electrolytic solution of the present invention d (g / cm 3) means a density at 20 ° C..

D / c obtained by dividing the concentration c of the electrolyte (mol / L) of the electrolyte density d (g / cm 3) in the electrolytic solution of the present invention is in the range of 0.15 ≦ d / c ≦ 0.71 preferably, 0.15 preferably in the range of ≦ d / c ≦ 0.56, more preferably in a range of 0.25 ≦ d / c ≦ 0.56, a 0.26 ≦ d / c ≦ 0.50 more preferably in the range, particularly preferably in the range of 0.27 ≦ d / c ≦ 0.47.

d / c in the electrolytic solution of the present invention can be defined even if the specified metal salt and an organic solvent. For example, LiTFSA metal salt, if you choose the DME as organic solvents, d / c is preferably in the range of 0.42 ≦ d / c ≦ 0.56, 0.44 ≦ d / c ≦ 0.52 within the scope of the more preferred. LiTFSA metal salt, if you choose the AN as the organic solvent, d / c is preferably in the range of 0.35 ≦ d / c ≦ 0.41, a range of 0.36 ≦ d / c ≦ 0.39 inside it is more preferable. LiFSA metal salt, if you choose the DME as organic solvents, d / c is preferably in the range of 0.32 ≦ d / c ≦ 0.46, a range of 0.34 ≦ d / c ≦ 0.42 inside it is more preferable. LiFSA metal salt, if you choose the AN as the organic solvent, d / c is preferably in the range of 0.25 ≦ d / c ≦ 0.31, a range of 0.26 ≦ d / c ≦ 0.29 inside it is more preferable. LiFSA metal salt, if you choose the DMC as organic solvents, d / c is preferably in the range of 0.32 ≦ d / c ≦ 0.48, a range of 0.32 ≦ d / c ≦ 0.46 preferably the inner, more preferably in the range of 0.34 ≦ d / c ≦ 0.42. LiFSA metal salt, if you choose the EMC as the organic solvent, d / c is preferably in the range of 0.34 ≦ d / c ≦ 0.50, a range of 0.37 ≦ d / c ≦ 0.45 inside it is more preferable. LiFSA metal salt, if you select DEC as the organic solvent, d / c is preferably in the range of 0.36 ≦ d / c ≦ 0.54, a range of 0.39 ≦ d / c ≦ 0.48 inside it is more preferable.

Illustrating a method of manufacturing the electrolytic solution of the present invention. For the electrolytic solution of the present invention contains a high amount of the metal salt as compared to the conventional electrolyte, the solid in the manufacturing method of adding an organic solvent to a metal salt (powder) will be aggregates is obtained, the solution state it is difficult to manufacture an electrolyte solution. Therefore, in the method of manufacturing the electrolytic solution of the present invention, gradually added a metal salt to the organic solvent, and is preferably produced while maintaining the solution state of the electrolyte.

Due to the type of metal salt and an organic solvent, the electrolytic solution of the present invention includes a liquid metal salt is dissolved in the organic solvent exceeds the saturation solubility has been considered conventionally. Method of manufacturing an electrolytic solution of such invention, by mixing the organic solvent and metal salts having a hetero element, by dissolving the metal salt, a first dissolution step of preparing the first electrolyte solution, stirring and / or warming conditions, the metal salt is added to the first electrolytic solution, to dissolve the metal salt, and a second dissolution step of preparing a second electrolyte supersaturated, stirring and / or heating conditions, a second electrolyte the metal salt added to the solution to dissolve the metal salt, a third dissolution step of preparing a third electrolyte solution.

Here, The "supersaturated" when releasing the stirring and / or heating conditions, or, when given the nucleation energy of the vibrations, to the situation where the metal salt crystals precipitate from the electrolyte It means. The second electrolyte solution is "supersaturated" first electrolyte and the third electrolyte not "supersaturated".

In other words, the method of manufacturing an electrolytic solution of the present invention, through a thermodynamically stable a liquid state first electrolyte comprises a conventional metal salt concentration, the thermodynamically unstable liquid state via 2 electrolyte, and, thermodynamically third electrolyte stable fresh liquid state, that is, the electrolytic solution of the present invention.

From keeping the liquid state in the third electrolyte stable liquid state normal conditions, in the third electrolyte solution, for example, it is composed of an organic solvent 2 molecules to the lithium salt 1 molecule strong between these molecules distribution clusters stabilized is estimated to inhibit the crystallization of the lithium salt by-position bonds.

The first dissolution step, mixing the organic solvent and metal salts having a hetero atom, by dissolving the metal salt is a step of preparing the first electrolyte solution.

To mix the organic solvent and metal salts having a heteroatom, to to the organic solvent having a hetero atom may be added a metal salt may be added an organic solvent having a hetero atom to a metal salt.

The first dissolution step is preferably carried out in a stirred and / or heated conditions. It may be set as appropriate for the stirring speed. The heating conditions, preferably controlled appropriately in a constant temperature bath, such as a water bath or oil bath. Since dissolution heat is generated at the time of dissolution of the metal salts, in the case of using unstable metal salt to heat, it is preferable to strictly control the temperature conditions. Also, in advance, may be previously organic solvent is cooled, the first dissolution step may be carried out in cold conditions.

The first dissolution step and the second dissolution step may be carried out continuously, leave temporarily store a first electrolytic solution obtained in the first dissolution step (left), after a certain time, the second the dissolution step may be performed.

The second dissolution step, stirring and / or heating conditions, a metal salt added to the first electrolytic solution, to dissolve the metal salt is a step of preparing a second electrolyte supersaturated.

The second dissolution step is to prepare the second electrolyte of thermodynamically unstable supersaturation, it is essential to carry out stirring and / or heating conditions. By performing the second dissolution process in a stirred apparatus with a stirrer such as a mixer, may be stirred conditions, performing the second dissolution process using a device for operating the stirrer and stir bar (stirrer) by, it may be stirring conditions. The heating conditions, preferably controlled appropriately in a constant temperature bath, such as a water bath or oil bath. Of course, it is particularly preferred to carry out the second dissolution step using a device or system combines the stirring function and a heating function. Incidentally, warming called the manufacturing method of the electrolyte refers to warm the object normal temperature (25 ° C.) to a temperature above. More preferably heating temperature is 30 ° C. or higher, more preferably at 35 ° C. or higher. Further, heating temperature, and even better at temperatures lower than the boiling point of the organic solvent.

In the second dissolution process, if the added metal salt is not sufficiently dissolved is carried out an increase in stirring rate and / or additional heating. In this case, it may be added a small amount of organic solvent having a hetero atom in the electrolytic solution of the second dissolution process.

Since Once standing second electrolyte solution obtained in the second dissolution step is crystal of the metal salt thus precipitated, preferably the second dissolution step and the third dissolution step is performed continuously.

The third dissolution process, stirring and / or heating conditions, a metal salt added to the second electrolyte solution by dissolving the metal salt is a step of preparing a third electrolyte solution. In the third dissolution process, the metal salt is added to the second electrolyte supersaturated, it is necessary to dissolve, it is essential to carry out the second dissolution step as well as stirring and / or heating conditions. Specific agitation and / or warming conditions are similar to the second dissolution process.

First dissolution process, second dissolution step and the third dissolution molar ratio of the organic solvent and a metal salt is added through steps substantially 2: if the order of 1, the production of the third electrolyte (electrolytic solution of the present invention) to the end. When you break a stirred and / or heated conditions, metal salt crystals from the electrolyte of the present invention will not precipitate. Viewed from these circumstances, the electrolytic solution of the present invention, for example, made of an organic solvent 2 molecules to the lithium salt 1 molecule, it is estimated to form stabilized clusters by a strong coordination bonds between these molecules It is.

Incidentally, in manufacturing the electrolytic solution of the present invention, due to the type of metal salt and an organic solvent, at a treatment temperature in each dissolution step, even when not passing through the supersaturated, the first to third dissolution step in the specific lysis means mentioned electrolytic solution of the present invention can be appropriately prepared using.

In the method of manufacturing the electrolytic solution of the present invention preferably has a vibration spectrometry step of vibrational spectroscopy measure the electrolytic solution in the process of production. The method Specific vibrational spectroscopy measurement step, for example, may be a method of subjecting to vibration spectrometry by sampling a portion of each electrolyte in the process of production, that vibrational spectroscopy measure each electrolyte solution in situ (in situ) But good. The method for vibrational spectroscopy measures the electrolyte solution in situ, a method of vibrating spectrometry by introducing an electrolytic solution in the process of production to a transparent flow cell, or a method of Raman measurements from the vessel outside of a transparent manufacturing vessel it can be mentioned. The inclusion of vibrational spectroscopy measurement step to the manufacturing method of the electrolytic solution of the present invention, it is possible to confirm the relationship between Is and Io in the electrolytic solution in the course of manufacturing, or a process of producing the electrolyte solution reaches the electrolytic solution of the present invention it can determine whether, also know whether the electrolyte in the process of production reaches the electrolyte when not reach the electrolyte extent of the amount of the present invention by adding a metal salt of the present invention can do.

The electrolyte of the present invention, in addition to an organic solvent having the hetero element, a low polarity (low dielectric constant) or low donor number, solvent showing no special interaction with the metal salt, i.e., the present invention it can be added a solvent which does not affect the formation and maintenance of the cluster in the electrolytic solution. By adding such a solvent for the electrolytic solution of the present invention, while retaining the form of the cluster of the electrolytic solution of the present invention, it can be expected to lower the viscosity of the electrolyte.

The solvent that does not exhibit metal salt and otherwise interacting specifically benzene, toluene, ethylbenzene, o- xylene, m- xylene, p- xylene, 1-methylnaphthalene, hexane, heptane, be exemplified cyclohexane it can.

Further, the electrolytic solution of the present invention, in addition to an organic solvent having the hetero element may be added to the solvent of the flame retardant. By adding a solvent of flame retardancy to the electrolyte of the present invention, it is possible to further enhance the safety of the electrolyte of the present invention. The solvent for the flame retardancy, can be exemplified carbon tetrachloride, tetrachloroethane, halogenated solvents such as hydrofluoroether, trimethyl phosphate, phosphoric acid derivatives such as triethyl phosphate.

Further, when the electrolytic solution was mixed with the polymer and the inorganic filler mixtures of the present invention, the mixture contained an electrolytic solution, a pseudo solid electrolyte. By using a pseudo-solid electrolyte as an electrolyte of the battery, it is possible to suppress the leakage of the electrolytic solution in the battery.

As the polymer, it may be employed polymers polymers and general chemical crosslinking for use in batteries such as lithium ion secondary batteries. In particular, the polymer or capable of gelation by absorbing the electrolytic solution, such as polyvinylidene fluoride and polyhexafluoropropylene, those obtained by introducing ion-conducting groups into the polymer, such as polyethylene oxide are preferred.

Specific polymers, polymethyl acrylate, polymethyl methacrylate, polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride, polyethylene glycol dimethacrylate, polyethylene glycol acrylate, polyglycidol, polytetrafluoroethylene, polyhexafluoropropylene, polysiloxanes, polyvinyl acetate, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyitaconic acid, polyfumaric acid, polycrotonic acid, poly angelic acid, polycarboxylic acids, such as carboxymethyl cellulose, styrene - butadiene rubbers, nitrile - butadiene rubbers, polystyrene , polycarbonates, unsaturated polyesters obtained by copolymerizing maleic anhydride and glycols, substituted It can be exemplified polyethylene oxide derivative, a copolymer of vinylidene fluoride and hexafluoropropylene having. Further, as the polymer may be selected copolymers obtained by copolymerizing two or more monomers constituting the specific polymer.

As the polymer, polysaccharides are also suitable. Specific polysaccharides, glycogen, cellulose, chitin, agarose, carrageenan, heparin, hyaluronic acid, pectin, amylopectin, xyloglucan, the amylose can be exemplified. Also, it may be employed a material containing these polysaccharides as the polymer, as the material can be exemplified agar containing polysaccharides such as agarose.

As the inorganic filler, inorganic ceramics are preferred, such as oxides or nitrides.

Inorganic ceramic has a hydrophilic and hydrophobic functional groups on the surface thereof. Therefore, the functional groups by attracting electrolyte, conductive pathway within the inorganic ceramic can be formed. Further, the dispersed inorganic ceramics electrolyte wherein the functional group to form a network among inorganic ceramics, may play a role to contain the electrolyte. These features of inorganic ceramics, it is possible to more suitably suppress the leakage of the electrolytic solution in the battery. To suitably exhibit the above function of inorganic ceramics, inorganic ceramics preferably have particle shape, in particular those particle diameter thereof is nano level preferred.

The type of inorganic ceramic can include general alumina, silica, titania, zirconia, and lithium phosphate. It is also possible but the inorganic ceramic itself has lithium conductivity, specifically, Li 3 N, LiI, LiI -Li 3 N-LiOH, LiI-Li 2 S-P 2 O 5, LiI-Li 2 S -P 2 S 5, LiI-Li 2 S-B 2 S 3, Li 2 O-B 2 S 3, Li 2 O-V 2 O 3 -SiO 2, Li 2 O-B 2 O 3 -P 2 O 5, Li 2 O-B 2 O 3 -ZnO, Li 2 O-Al 2 O 3 -TiO 2 -SiO 2 -P 2 O 5, LiTi 2 (PO 4) 3, Li-βAl 2 O 3, LiTaO 3 it can be exemplified.

The glass ceramic may be employed as inorganic fillers. Since glass-ceramics may contain the ionic liquid can be expected a similar effect on the electrolyte of the present invention. The glass ceramic, xLi 2 S- (1-x ) P 2 S 5 in compounds represented, and those obtained by substituting a part of S of the compound with other elements, and one of P of the compound part can be exemplified those obtained by replacing the germanium.

Electrolytic solution of the present invention described above, exhibits excellent ion conductivity, is suitably used as the electrolyte of a battery, such as the power storage device. In particular, it is preferred for use as the electrolyte of the secondary battery, preferably used among them as the electrolyte of lithium ion secondary battery.

Meanwhile, the negative electrode and / or the surface of the positive electrode of the non-aqueous electrolyte secondary battery of the present invention is S, O-containing coating is formed. As described below, the coating comprises S and O, at least S = O structure. Then, the S, O-containing coating, since it has a S = O structure, believed to be derived from the electrolyte. In the electrolytic solution of the present invention, as compared with conventional electrolyte is believed that the Li cations and anions are present in the vicinity. Therefore anion is preferentially reduced and decomposed by receiving strong electrostatic effect from Li cations. In a typical non-aqueous electrolyte secondary battery using a general electrolyte, an organic solvent (e.g., EC: ethylene carbonate, etc.) contained in the electrolytic solution is reduced and decomposed, SEI film by decomposition products of the organic solvent but composed. However, in the electrolytic solution of the present invention contained in the non-aqueous electrolyte secondary battery of the present invention as described above anion is preferentially reduced and decomposed. Thus, SEI film in the non-aqueous electrolyte secondary battery of the present invention, i.e. S, the O-containing coatings, believed to S = O structure derived from anions contained many. That is, in the conventional non-aqueous electrolyte secondary battery using a conventional electrolyte, SEI film derived from the degradation of the organic solvent EC or the like is fixed on the electrode surface. On the other hand, in the non-aqueous electrolyte secondary battery of the present invention using the electrolytic solution of the present invention, SEI film mainly from the anion of the metal salt is fixed on the electrode surface.

Moreover, the reason is not clear, non-aqueous S in electrolyte secondary battery, O-containing coating of the present invention changes state in response to the charge-discharge operations. For example, as described below, depending on the state of the charge-discharge sometimes S, thickness and S the O-containing coating, the proportion of the elements O, etc. changes. Therefore, S in the non-aqueous electrolyte secondary battery of the present invention, the O-containing coating, a portion for fixing in the coating derived from the decomposition product of the above-mentioned anions (hereinafter, referred to as a fixing unit if necessary), portion increases or decreases reversibly with the charge and discharge (hereinafter, a suction portion is referred as necessary) is considered and there. The suction unit is presumed to have a structure such as S = O derived from the anion of the same metal salt and fixing unit.

Incidentally, S, O-containing coating consists of decomposition products of the electrolyte, since it is considered to include other adsorbate, S, most (or all) of the O-containing coatings initial charge and discharge of a nonaqueous electrolyte secondary battery It is considered to be generated in later time. In other words, the non-aqueous electrolyte secondary battery of the present invention, in use, with S, the O-containing film on the surface and / or the surface of the positive electrode of the negative electrode. S, other constituents of the O-containing coatings, components and other than sulfur and oxygen contained in the electrolytic solution, various different depending on the composition of the negative electrode. Also, the S, O containing coatings may need only include S = O structure, its content is not particularly limited. Furthermore, S, ingredients and amounts except for S = O structure included in the O-containing coating is not particularly limited. Then, S, to O-containing coatings may be formed only on the negative electrode surface, it may be formed only on the surface of the positive electrode. However, S as described above, it is considered that the O-containing coating is derived from the anion of the metal salt contained in the electrolytic solution of the present invention, the components derived from the anion of the metal salt that contains more than the other components preferable. Also, S, O-containing coating is preferably formed on both the surface of the negative electrode and the positive electrode surface. Hereinafter, if necessary, S formed on the surface of the negative electrode, referred to O containing coating negative electrode S, and O containing coatings, called S formed on the surface of the positive electrode, the O-containing coating positive electrode S, and O containing coatings .

As described above, it can be preferably used an imide salt as the metal salt in the electrolytic solution of the present invention. Conventionally, a technique of adding an imide salt in the electrolytic solution are known, in the non-aqueous electrolyte secondary battery using this type of electrolyte, the positive electrode and / or negative electrode coating, an organic solvent of the electrolyte solution in addition to the compound derived from the decomposition product, compounds derived from imide salt, i.e. it is known to include compounds containing S. For example, JP 2013-145732, the components derived from the imide salt contained partially in the film, to improve the durability of the non-aqueous electrolyte secondary battery while suppressing an increase in internal resistance of the nonaqueous electrolyte secondary battery it has been introduced to obtain.

However, in the prior art described above, it was not possible to enrich imide salt derived components in the film for the following reasons. First, the case of using graphite as the negative electrode active material, graphite reversibly react to charge carriers, in order to reversibly charging and discharging the nonaqueous electrolyte secondary battery, SEI film is formed on the surface of the anode It is necessary and it is believed that there is. Conventionally, in order to form the SEI film, it has been used a cyclic carbonate compound typified by EC as an organic solvent for the electrolytic solution. Then, to form an SEI film by the decomposition product of the cyclic carbonate compound. That is, the conventional electrolyte containing an imide salt, with a high content of cyclic carbonate EC such as organic solvents contained imide salt as an additive. However, in this case, the main component of the SEI film becomes a component derived from an organic solvent, it has been difficult to increase the content of the imide salt of SEI film. Also, if is to be used as a metal salt rather than as an additive an imide salt (i.e. an electrolyte salt, supporting salt), it is necessary to consider the combination of a positive electrode collector. That is, the imide salts are known to corrode aluminum current collector is generally used as the current collector for the positive electrode. Therefore, in the case of using a positive electrode in particular operating at about 4V potential, there electrolyte was LiPF 6 or the like and an electrolyte salt to form an aluminum and unmoving body needs to coexist with the aluminum current collector. The total concentration of the electrolyte salt consisting of LiPF 6 and imide salts such as a conventional electrolytic solution, from the viewpoint of the ionic conductivity and viscosity, about 1mol / L ~ 2mol / L is optimum (JP 2013-145732 ). Thus the addition of a sufficient amount of LiPF 6, since the amount of inevitably imide salt reduces, the imide salt has a problem that it is difficult to use a large amount of the metal salt for the electrolytic solution. Hereinafter, if necessary, sometimes simply abbreviated as metal salts imide salt.

In contrast, the electrolytic solution of the present invention includes a metal salt in a high concentration. Then, as described later, the electrolytic solution of the present invention, the metal salt is considered to be present at all from the conventional in different states. Therefore, in the electrolytic solution of the present invention, unlike the conventional electrolytic solution, the problem is less likely to occur resulting from that the metal salt is highly concentrated. For example, according to the electrolytic solution of the present invention, it is also possible to a reduction in the output performance of the nonaqueous electrolyte secondary battery according to increase in the viscosity of the electrolyte can be suppressed, inhibiting the corrosion of aluminum current collector. The metal salt contained in high concentrations in the electrolyte solution is preferentially reduced and decomposed on the negative electrode. As a result, even without using a cyclic carbonate compound of EC such as organic solvents, SEI film special structure derived from a metal salt, that is S, O-containing film is formed on the negative electrode. The non-aqueous electrolyte secondary battery of this for the present invention, even when using the graphite as the anode active material, a reversible charging and discharging possible without using a cyclic carbonate compound in an organic solvent.

The non-aqueous electrolyte secondary battery of this for the present invention, in the case of using an aluminum collector as using graphite and the positive electrode current collector as an anode active material also, LiPF metal salt or with a cyclic carbonate compound as an organic solvent without or with 6, a reversibly chargeable and dischargeable. Furthermore, it is possible to constitute the majority of the SEI film on the anode and / or cathode surfaces anion derived components. As described later, S containing anion derived components may improve battery characteristics due the non-aqueous electrolyte secondary battery O containing coating.

Note that the film of the negative electrode in the nonaqueous electrolyte secondary battery using a common electrolyte containing EC solvent, carbon derived from the EC solvent include many polymerized polymer structure. Structure contrast, the negative electrode S, O-containing coating in the non-aqueous electrolyte secondary battery of the present invention, the polymer structure such carbon is polymerized is not included little (or no), derived from the anion of the metal salt the rich. The same applies to the positive electrode film.

Incidentally, the electrolytic solution of the present invention contains a high concentration of cations of the metal salt. Therefore, in the electrolytic solution of the present invention, the distance between adjacent cationic is very close. Then, when the cations of lithium ions during charge and discharge of a nonaqueous electrolyte secondary battery is moved between the positive electrode and the negative electrode, the most recent cation destination electrode is first supplied to the electrode. Then, in the place where there is supplied the cation, other cations adjacent to the cation moves. That is, in the electrolytic solution of the present invention, the adjacent cation of changing one by one position in order toward the electrode to be supplied subject is expected to domino-like phenomenon occurs. Therefore, the moving distance of the charging and discharging time of the cation is short, the moving speed of the cations is correspondingly considered to be high. Then, due to this fact, the reaction rate of the non-aqueous electrolyte secondary battery of the present invention with the electrolytic solution of the present invention is considered to be high. The non-aqueous electrolyte secondary battery of the present invention have S the electrode (i.e. the negative electrode and / or positive electrode), the O-containing film, the S, O containing coating contains many cationic and has a S = O structure considered. The S, cations contained in the O-containing coating is believed to be supplied preferentially to the electrode. Thus, in the non-aqueous electrolyte secondary battery of the present invention, the transport speed of the cation is considered to be further improved by having abundant cation sources in the vicinity of the electrode (that is S, O-containing coating). Thus, in the non-aqueous electrolyte secondary battery of the present invention, electrolyte and S of the present invention, by cooperation of the O-containing coatings, believed to be exerted excellent battery characteristics.

For reference, SEI film of the negative electrode is thought to be composed by the electrolytic solution at a predetermined voltage less than the reduction decomposition, deposition of the electrolyte solution generated at that time. In other words, in order to efficiently generate the above-mentioned S, O-containing film on the surface of the negative electrode, a nonaqueous electrolyte secondary battery of the present invention, it is preferable to make the minimum value of the negative electrode potential becomes less than a predetermined . Specifically, the non-aqueous electrolyte secondary battery of the present invention is suitable as a battery for use in conditions where the minimum value of the negative electrode potential when the counter electrode lithium becomes 1.3V or less.

Highest potential use of non-aqueous secondary battery according to a fourth aspect of the present invention is 4.5V or more when the reference potential Li / Li +. Here, "the maximum operating voltage" means a positive electrode potential (Li / Li + reference potential) at the time of end of charge of a battery is controlled within a range not to cause disintegration of the positive electrode active material, electrolyte is used in the present invention liquid is less likely to be decomposed even at a high potential.

The reason for this is considered to be as follows. The above electrolyte solution, the peak intensity derived from the organic solvent in the vibration spectrum of the electrolyte solution, if the strength of the original peak organic solvent and I 0, and the intensity of a peak inherent peak organic solvent has shifted Is, is> is set to Io. This electrolyte solution, almost all organic solvents and Li ions and anions reciprocally cited by electrostatic attraction in the metal salt, is extremely small solvent-free state. Many organic solvents, to form a metal salt and clusters, it is energetically stable. Therefore, improvement in oxidation resistance can be expected with respect to conventional electrolytic solution. Therefore, it considered unlikely to be decomposed by 4.5V or more high potential. Therefore, the maximum potential use of the positive electrode of the battery, can be as high as 4.5V or higher.

Therefore, it is possible to use a lithium-metal composite oxide or polyanionic material charging reaction at a high potential as a positive electrode active material. For example, the average reaction potential can be used lithium-metal composite oxide of the above 4.5V as the positive electrode active material.

Further, even in the lithium-metal composite oxide having an average reaction potential is less than 4.5V, it is also possible to use charged to a potential higher than 4.5V.

From the above, according to the non-aqueous secondary battery which is a combination of lithium metal composite oxide or polyanionic material and the electrolytic solution, the maximum potential use of the positive electrode can have high 4.5V higher than the conventional . Stated upper limit of maximum potential use of the positive electrode, can be exemplified 6.0V or 5.7 V.

Oxidative decomposition potential of the electrolytic solution is preferably 4.5V or more Li + / Li electrode reference. In this case, it is possible to suppress the oxidative decomposition of the electrolyte solution even when the battery is used in the above 4.5V high positive electrode potential. Stated limit oxidative decomposition potential of the electrolyte solution, can be exemplified 6.0V or 5.7 V.

The above electrolytic solution, and platinum as a working electrode, the battery including a lithium metal as a counter electrode was measured in the linear sweep voltammetry (LSV), the current formed by the measurement - potential curve, Li + / Li electrode reference potential and the potential 4.5V or more, more above 5.0V, preferred to exhibit a rising portion. Electrolyte having such characteristics are considered not to oxidative decomposition to at least potential 4.5V. LSV is an evaluation method which measures the current flowing when the potential of the electrode is continuously changed. Current curve is created - the potential of the non-aqueous secondary battery by measuring the LSV for nonaqueous secondary batteries. Potential - in current curve, the ratio of the increase in current value with respect to increase in potential, the current increase rate. This growth rate is low immediately after voltage application. Electrolyte is decomposed oxidized upon application of a voltage to a predetermined high potential, the current increase rate rapidly increases, current begins to flow.

In other words, the current was formed by performing LSV evaluation - in potential curve, between immediately after the voltage application until the potential 4.5V (vs Li + / Li) higher than a predetermined potential has a flat portion. When the potential is in the flat portion, the electrolyte is stable.

Current - in potential curve, when it exceeds a predetermined potential, showing a rising portion of the current increase rate sharply increases. Here, "rising portion", a current - in potential curve refers to a moiety current increase rate is larger than the flat portion. The rising portion, and the electrolytic solution is decomposed oxidation, current flows.

The following describes a non-aqueous secondary battery using the electrolyte according to the first to fourth aspect of the present invention.

The nonaqueous secondary battery of the present invention, a negative electrode having a positive electrode having a positive electrode active material a metal ion capable of occluding and releasing lithium ions, a negative electrode active material a metal ion such as lithium ion can occlude and release, and a electrolytic solution having a metal salt.

The positive electrode used in the nonaqueous secondary battery has a positive electrode active material capable of occluding and releasing metal ions. The positive electrode includes a current collector and a positive electrode active material layer formed by binding to the surface of the current collector.

In a first aspect of the present invention, the positive electrode active material has a lithium metal composite oxide having a layered rock-salt structure. Lithium-metal composite oxide having a layered rock salt structure is also referred to as layered compound. Lithium-metal composite oxide having a layered rock salt structure represented by the general formula: Li a Ni b Co c Mn d D e O f (0.2 ≦ a ≦ 1.2, b + c + d + e = 1,0 ≦ e <1, D is selected li, Fe, Cr, Cu, Zn, Ca, Mg, S, Si, Na, K, Al, Zr, Ti, P, Ga, Ge, V, Mo, Nb, W, La, Ni, Co, at least one element, 1.7 ≦ f ≦ 2.1), can be mentioned Li 2 MnO 3.

b in the formula: c: a ratio of d is 0.5: 0.2: 0.3, 1/3: 1/3: 1 / 3,0.75: 0.10: 0.15 , 0: 0: 1, 1: 0: 0, and 0: 1: it is good at least one selected from 0.

That is, specific examples of the lithium-metal composite oxide having a layered rock salt structure, LiNi 0.5 Co 0.2 Mn 0.3 O 2, LiNi 1/3 Co 1/3 Mn 1/3 O 2, LiNi 0 .5 Mn 0.5 O 2, LiNi 0.75 Co 0.1 Mn 0.15 O 2, LiMnO 2, LiNiO 2, and may be at least one selected from LiCoO 2.

Further, the cathode active material may comprise lithium metal composite oxide having a layered rock salt structure, a solid solution composed of a mixture of spinel such as LiMn 2 O 4, Li 2 Mn 2 O 4, for example, there is a Li 2 MnO 3 -LiCoO 2.

Any of the metal oxide used as the positive electrode active material also may be a basic composition of the above composition formula, also to be used those with substitution of metal element contained in the basic composition with other metallic elements, such as Mg it may be a metal oxide in addition to those of the basic composition of another metal element.

In a second aspect of the present invention, the positive electrode active material has a lithium metal composite oxide having a spinel structure. Lithium-metal composite oxide having a spinel structure of the general formula: the general formula: Li x (A y Mn 2 -y) O 4 (A is, Ca, Mg, S, Si , Na, K, Al, P, Ga , at least one metal element selected from at least one element, and a transition metal element selected from Ge, 0 <x ≦ 2.2,0 may be represented by <y ≦ 1). Transition metal elements capable of constituting the A in the general formula, for example, Fe, Cr, Cu, Zn, Zr, Ti, V, Mo, Nb, W, La, Ni, at least one element selected from Co may there.

Specific examples of the lithium-metal composite oxide may be at least one selected from LiMn 2 O 4, LiNi 0.5 Mn 1.5 O 4.

Lithium metal composite oxide used as the positive electrode active material may be a basic composition of the above composition formula, also to be used those with substitution of metal element contained in the basic composition with another metal element, Mg, etc. other metal elements may be in addition to those of the basic composition metal oxides.

In a third aspect of the present invention, the positive electrode active material has a polyanionic material. Polyanionic materials are, for example, may be a polyanionic material containing lithium. Polyanionic material containing lithium, LiMPO 4, LiMVO 4 or Li 2 MSiO 4 (M in the formula is Co, Ni, Mn, at least one selected from among Fe) polyanionic compound represented by like it can be mentioned.

Specific examples of the polyanionic material, LiFePO 4 having an olivine structure, Li 2 FeSiO 4, LiCoPO 4 , Li 2 CoPO 4, Li 2 MnPO 4, Li may be at least one selected from 2 MnSiO 4.

Polyanionic material used as the positive electrode active material may be a basic composition of the above composition formula, also to be used those with substitution of metal element contained in the basic composition with other metal elements, other such as Mg metallic elements may be in addition to those of the basic composition metal oxides.

In a fourth aspect of the present invention, the positive electrode active material, lithium metal composite oxide, and / or it may have a polyanionic material.

The lithium-metal composite oxide may have a spinel structure. Lithium-metal composite oxide having a spinel structure represented by the general formula: Li x (A y Mn 2 -y) is O 4 (A, transition metal elements, Ca, Mg, S, Si , Na, K, Al, P, Ga, and at least one element selected from Ge, 0 <x ≦ 2.2,0 <may be expressed by y ≦ 1). Transition metal elements capable of constituting the A in the general formula, for example, Fe, Cr, Cu, Zn, Zr, Ti, V, Mo, Nb, W, La, Ni, at least one element selected from Co may there. Specific examples of the lithium-metal composite oxide may be at least one selected from the group consisting of LiMn 2 O 4 and LiNi 0.5 Mn 1.5 O 4.

Lithium metal composite oxide, with those having a spinel structure, or in place of those having a spinel structure may be one having a layered rock-salt structure. Lithium-metal composite oxide having a layered rock salt structure is also referred to as layered compound. Lithium-metal composite oxide having a layered rock salt structure represented by the general formula: Li a Ni b Co c Mn d D e O f (0.2 ≦ a ≦ 1.2, b + c + d + e = 1,0 ≦ e <1, D is selected li, Fe, Cr, Cu, Zn, Ca, Mg, S, Si, Na, K, Al, Zr, Ti, P, Ga, Ge, V, Mo, Nb, W, La, Ni, Co, at least one element, 1.7 ≦ f ≦ 2.1), can be mentioned Li 2 MnO 3.

Further, the lithium metal composite oxide, and those with a layered rock-salt structure, may contain a solid solution composed of a mixture of spinel such as LiMn 2 O 4, LiNi 0.5 Mn 1.5 O 4.

Polyanionic materials are, for example, may be a polyanionic material containing lithium. Polyanionic material containing lithium, LiMPO 4, LiMVO 4 or Li 2 MSiO 4 (M in the formula is Co, Ni, Mn, at least one selected from among Fe) polyanionic compound represented by like it can be mentioned.

Among these positive electrode active material, lithium metal composite oxide and / or polyanionic material is preferably having a reaction potential of 4.5V or more at Li + / Li electrode reference. Here, the "reaction potential of the positive electrode active material", refers to the potential of the positive electrode active material results in a reduction reaction by charging. The reaction potential, and Li + / Li electrode reference. The reaction potential, there may have some width, "reaction potential" as used herein refers to the average value in the reaction potential is wide. When the reaction potential have multiple stages, it refers to the average value in the reaction potential of the plurality of stages. Lithium-metal composite oxide and polyanionic material reaction potential is 4.5V or more Li + / Li electrode standard, for example, LiNi 0.5 Mn 1.5 O 4 (spinel), LiCoPO 4 (polyanion), Li 2 CoPO 4 F (polyanion), Li 2 MnO 3 -LiMO 2 (M in the formula Co, Ni, Mn, are selected from at least one of Fe) (solid solution system having a layered rock-salt structure), Li 2 such MnSiO 4 (polyanion) include, but are not limited thereto.

Further, the lithium metal composite oxide and polyanionic material may have a reaction potential of less than 4.5V at Li + / Li electrode reference. Examples of such a lithium metal composite oxide, for example, among those having a layered rock salt structure, LiNi 0.5 Co 0.2 Mn 0.3 O 2, LiNi 1/3 Co 1/3 Mn 1/3 O 2, LiNi 0.5 Mn 0.5 O 2 , LiNi 0.75 Co 0.1 Mn 0.15 O 2, LiMnO 2, LiNiO 2, and at least one can be cited selected from LiCoO 2. Among the polyanionic material, LiFePO 4 having an olivine structure, and Li 2 least but one are mentioned selected from FeSiO 4, but is not limited thereto.

The positive electrode active material and a battery using thereof will be described the features are classified into the type shown in Table 3.

Figure 92 shows a model diagram of a charging curve of the lithium-metal composite oxide and polyanionic materials. As shown in FIG. 92, the lithium metal composite oxide, there is a solid solution type and two-phase coexisting type. Solid solution type, in the case where the reaction of the active material through the solid solution, the positive electrode potential with the discharge progresses gradually decreases, the potential gradually increases with the charging progresses. Biphasic coexistence type, the active material is discharged appear the second phase two phases coexist, it has an area that also discharge progressed positive electrode potential does not decrease, a region where the potential even when the charge has proceeded does not rise is there.

In batteries using solid solution of 4V Kyukatsu substances (such as LiCoO 2), when the maximum operating potential to 5V, the average cell voltage and capacity is improved slightly. However, in general it may degrade by which also the active material itself to a high potential.

In batteries using a two-phase coexisting type 4V Kyukatsu substances (such as LMn 2 O 4), when the maximum operating potential to 5V, the average cell voltage and the capacity hardly changes. However, the high potential resistance generally active material itself is so high, it is possible to increase the maximum operating potential to 5V.

In the battery using the two-phase coexistence type 5V Kyukatsu substances (such as LiNi 0.5 Mn 1.5 O 4), but not the capacity when the maximum operating potential to 4V, capacity appears when to 5V.

In consideration of these properties may be any combination of the electrolyte of the positive electrode and the present invention.

Figure JPOXMLDOC01-appb-T000003

Lithium metal composite oxide used as the positive electrode active material may be a basic composition of the above composition formula, also to be used those with substitution of metal element contained in the basic composition with another metal element, Mg, etc. other metal elements may be in addition to those of the basic composition metal oxides.

Considering the above, the nonaqueous secondary battery of the present invention includes a positive electrode having the lithium metal composite oxide or the polyanionic material as a cathode active material, a negative electrode having a negative electrode active material, a nonaqueous having an electrolyte a secondary battery, the electrolyte solution may include a metal salt with an alkali metal, an alkaline earth metal or aluminum cation, an organic solvent having a hetero element, the organic solvent in the vibration spectrum of the electrolyte per peak intensity derived from the the strength of the organic solvent the original peak Io, the peak when the intensity of a peak shifted with is, to grasp a nonaqueous secondary battery, which is a is> Io be able to.

In the first to fourth aspect of the present invention, the current collector of the positive electrode is not particularly limited as long as the metal capable of withstanding the voltage suitable for the active material to be used. The current collector during discharge or charge of the nonaqueous secondary battery refers to a chemically inert electron height conductors for continuing to flow the current to the electrodes. As the current collector, silver, copper, gold, aluminum, tungsten, cobalt, zinc, nickel, iron, platinum, tin, indium, titanium, ruthenium, tantalum, chromium, such as at least one, and stainless steel selected from molybdenum it can be exemplified metallic materials.

Specifically, as the positive electrode current collector, to use one made of aluminum or an aluminum alloy. Here the aluminum refers to pure aluminum, called a purity 99.0% or more aluminum and pure aluminum. A material obtained by an alloy with the addition of various elements to pure aluminum is referred to as an aluminum alloy. As the aluminum alloy, Al-Cu-based, Al-Mn-based, Al-Fe-based, Al-Si-based, Al-Mg-based, AL-Mg-Si-based, Al-Zn-Mg systems.

Further, as an aluminum or aluminum alloy, specifically, for example JIS A1085, A1000 alloy (pure aluminum-based), such A1N30, JIS A3003, A3000 alloy such as A3004 (Al-Mn based), JIS A8079, A8021, etc. A8000 alloy of (Al-Fe system) and the like.

When the positive electrode potential 4V or higher based on lithium, it is preferable to employ aluminum as a current collector. The current collector may be coated by known protective layer. A material obtained by treating the surface of the current collector by a known method may be used as a current collector.

The current collector may take the foil, sheet, film, wire, rod, such forms as mesh. Therefore, as the current collector, for example, a copper foil, nickel foil, aluminum foil, metal foil such as stainless steel foil can be preferably used. Foil current collector, sheet, in the case of film form, it is preferred that the thickness is in the range of 1 [mu] m ~ 100 [mu] m.

The positive electrode active material layer including a positive active material, and a binder and / or conductive auxiliary agent, if necessary.

Binder plays a role of anchoring the active material and conductive auxiliary agent to the surface of the current collector.

As the binder, for example polyvinylidene fluoride, polytetrafluoroethylene, fluorinated resin such as fluorine rubber, polypropylene, thermoplastic resins such as polyethylene, polyimide, imide resin and polyamide-imide, an alkoxysilyl group-containing resin be able to.

Further, as a binder, it may be employed a polymer having a hydrophilic group. The hydrophilic group of the polymer having a hydrophilic group, a carboxyl group, a sulfo group, a silanol group, an amino group, a hydroxyl group, a phosphoric acid group such as phosphoric acid group are exemplified. Among them, polyacrylic acid (PAA), carboxymethyl cellulose (CMC), such as polymethacrylic acid, polymers containing carboxyl groups in the molecule, or polymers containing sulfo groups, such as poly (p- styrene sulfonate) are preferred.

Polyacrylic acid, or a copolymer of acrylic acid and vinylsulfonic acid, a polymer containing many carboxyl groups and / or sulfo group is water-soluble. Thus polymers having a hydrophilic group is preferably a water-soluble polymer, preferably a polymer containing a plurality of carboxyl groups and / or sulfo groups in one molecule.

Polymers containing carboxyl groups in the molecule, for example, to polymerize the acid monomer, or to impart carboxyl groups in the polymer can be produced by a method such as. The acid monomers include acrylic acid, methacrylic acid, vinyl benzoic acid, crotonic acid, pentenoic acid, angelica acid, acid monomer having one carboxyl group in the molecule, such as tiglic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid , maleic acid, 2-pentene diacid, methylene succinic acid, allylmalonic acid, isopropylidene succinic acid, 2,4-hexadiene diacid, such acid monomer is exemplified with two or more carboxyl groups in the molecule, such as acetylene dicarboxylic acid It is. It may be used copolymer obtained by polymerizing two or more monomers selected from these.

For example, in Japanese Patent as described in 2013-065493 JP-polymer comprising consist copolymer of acrylic acid and itaconic acid, an acid anhydride group each other carboxyl groups are formed by condensation in the molecule it is also preferable to use as a binder. The presence of the structure derived from highly acidic monomer having two or more carboxyl groups in one molecule, are believed more likely to trap metal ions such as lithium ions before the electrolyte decomposition reaction during charging occurs. Furthermore, the carboxyl group more acidity than the polyacrylic acid or polymethacrylic acid is increased, a predetermined amount of the carboxyl group because it changes the acid anhydride group, nor that the acidity is too increased. Therefore, a secondary battery having a negative electrode formed by using the binder, improved initial efficiency, input-output characteristics are improved.

The mixing ratio of the binder in the positive electrode active material layer is in a mass ratio, a positive electrode active material: binder = 1: 0.005 to 1: 0.5 at which the well is further a positive electrode active material: binding Chakuzai = 1: 0.005 to 1: it is preferred that 0.3. If the binder is too small moldability of the electrode is reduced, also, it is because if the binder is too large energy density of the electrode becomes low.

Conductive auxiliary agent is added to increase the conductivity of the electrode. Therefore, the conductive additive may be added optionally to be insufficient conductivity of the electrode is, if the conductive electrode is good enough may not added. The conductive additive chemically well so long as it is inert electron height conductors, carbon black is carbonaceous fine particles, graphite, acetylene black, ketjen black (registered trademark), vapor grown carbon fiber (Vapor Grown Carbon Fiber: VGCF), and various metal particles are exemplified. These conductive additive singly or two or more can be added to the active material layer.

The mixing ratio of the binder in the positive electrode active material layer is in a mass ratio, a positive electrode active material: binder = 1: 0.05 to 1: is preferably 0.5. If the binder is too small moldability of the electrode is reduced, also, it is because if the binder is too large energy density of the electrode becomes low.

The negative electrode used in the nonaqueous secondary battery of the present invention includes a current collector and a negative electrode active material layer formed by binding to the surface of the current collector. Negative electrode active material layer includes a negative active material, and a binder and / or conductive auxiliary agent, if necessary. Binder and conductive auxiliaries which may be contained in the negative electrode active material layer may be the same components and composition ratio and binder and conductive additive may be included in the positive electrode active material layer.

As the negative electrode active material, the material can be used, which may the metal ions to occlude and release lithium ions. Therefore, it not particularly limited as long as it is alone, an alloy or a compound capable of occluding and releasing metal ions such as lithium ions. For example, Li or as the anode active material, carbon, silicon, germanium, Group 14 elements such as tin, aluminum, Group 13 elements such as indium, zinc, Group 12 elements such as cadmium, antimony, Group 15 elements such as bismuth, magnesium alkaline earth metals such as calcium metal, silver, may be employed group 11 elements such as gold alone, respectively. By employing silicon and the negative electrode active material, since the silicon 1 atom is reacted with a plurality of lithium, but the active material of the high capacity, the expansion and contraction of volume caused by the insertion and extraction of lithium becomes significant problems because it may occur, for the relief of the fear, also suitable to employ an alloy or compound in combination with other elements such as transition metal simple substance such as silicon as an anode active material. Examples of alloys or compounds, Ag-Sn alloy, Cu-Sn alloy, Co-Sn tin based materials such as alloys, carbon-based materials such as various graphite, SiO x to disproportionation to silicon simple substance and silicon dioxide ( 0.3 ≦ x ≦ 1.6) silicon-based materials such as composites that combine silicon simple substance or a silicon material and a carbon-based material. Further, the anode active material, Nb 2 O 5, TiO 2 , Li 4 Ti 5 O 12, WO 2, MoO 2, Fe oxides, such as 2 O 3, or, Li 3-x M x N (M = Co, Ni, may be employed nitride represented by Cu). As an anode active material, it is possible to use one or more of these things. In this specification, the non-aqueous secondary battery using the material of the lithium ion may occluding and releasing as a negative electrode active material and positive electrode active material, that lithium ion secondary battery.

Current collector of the negative electrode, as long as the metal capable of withstanding the voltage suitable for the active material to be used is not particularly limited, for example, it can be employed those described in the current collector of the positive electrode. Binder and conductive auxiliaries of the negative electrode can be employed those described in the positive electrode.

The method of forming an active material layer on the surface of the current collector, a roll coating method, a die coating method, dip coating method, a doctor blade method, spray coating method, a conventionally known method such as a curtain coating method, collecting the active material may be applied to the surface of the collector. Specifically, active material, and an active material layer-forming composition comprising a binder and conductive additive was prepared as desired, into a paste by adding a suitable solvent to the composition, collecting after coating the surface of the collector, and dried. The solvent can be exemplified by N- methyl-2-pyrrolidone, methanol, methyl isobutyl ketone, and water. Order to increase the electrode density, may be compressed ones after drying.

The separator is used as required in the nonaqueous secondary battery. The separator separates the positive electrode and the negative electrode, prevents current short circuit due to contact of both electrodes, and lets through the metal ions such as lithium ions. As the separator, polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamide, polyaramide (Aromatic Polyamide), polyester, synthetic resins such as polyacrylonitrile, cellulose, polysaccharides amylose, etc., fibroin, keratin, lignin, natural, such as suberic mention may be made of a polymer, one or more used porous body electrically insulating material such as ceramics, non-woven fabric, woven fabric or the like. The separator may be a multilayer structure. Because electrolytic solution is higher slightly higher polarity viscosity, a polar solvent is immersion see write easy film such as water is preferred. Specifically, a film polar solvent Komu penetrates such 90% of water present gap is more preferable.

It is not an electrode member sandwiched separator as necessary to the positive electrode and the negative electrode. Electrode assembly includes a positive electrode, a separator and a laminated type of repeated negative or positive electrode, it may be any type of wound in which seeded the separator and the negative electrode. Between the collector and the anode current collector of the positive electrode to the positive and negative terminals leading to the outside, after connecting with a current collecting lead or the like, a non-aqueous secondary battery by adding an electrolyte to the electrode body or equal to. The non-aqueous secondary battery of the present invention, it is sufficient in a voltage range suitable for the type of active material contained in the electrode perform the charge and discharge.

Nonaqueous secondary battery of the shape of the present invention is not limited in particular, cylindrical, square, coin, laminated or the like, it is possible to adopt various shapes.

The nonaqueous secondary battery of the present invention may be mounted on a vehicle. Vehicle may be any vehicle that uses electrical energy according to a non-aqueous secondary battery in all or part of the power source, for example, an electric vehicle, may the hybrid vehicle is like. When mounting the non-aqueous secondary battery in a vehicle, or equal to the battery pack by connecting the nonaqueous secondary battery in a plurality in series. Nonaqueous secondary battery, in addition to the vehicle is also a personal computer, such as a portable communication equipment, various home electric appliances driven by a battery, office equipment, industrial equipment and the like. Further, the nonaqueous secondary battery of the present invention, wind power, solar power generation, power storage device and power smoothing apparatus hydropower other power systems, power and / or power supply of auxiliary machinery such as ships, aircraft, power and / or power supply of auxiliaries, such as spacecraft, electric power for auxiliary vehicle that does not use a power source, the power source of mobile home robots, power supply system backup, uninterruptible power supply, it may be used to power storage device temporarily storing electric power required for charging the like charging station for electric vehicles.

Having described the embodiments of the electrolytic solution, the present invention is not limited to the above embodiment. Without departing from the scope of the present invention, modifications that those skilled in the art can perform, can be carried out in various forms subjected to improvements like.

The following Examples and Comparative Examples, the present invention will be described specifically. The following examples, Evaluation Examples for evaluating the comparative examples and the battery and they are first case in accordance with aspects of the of the present invention "Example A- number", "Comparative Examples A- number", "battery A- No. ", shown in" evaluation examples A- number ", if according to the second aspect of the present invention" example B- number "," Comparative example B- number "," battery B- number "," evaluation example B - indicated by numbers ", if according to the third aspect of the present invention is shown in" example C- number "," Comparative examples C- number "," battery C- number "," evaluation example C- number ", If according to the fourth aspect of the present invention "example D- number", "Comparative example D- number", "battery D- number" shown in "evaluation examples D- number". Incidentally, A-, B-, C-, electrolyte does not bear the D-, batteries, evaluation example is common to the first to fourth embodiments.
The present invention is not limited to these examples. In the following, unless otherwise stated, it refers to parts by weight and "parts" means mass% as "%".
(Electrolyte E1)
The electrolytic solution used in the present invention were prepared as follows.

1,2-dimethoxyethane about 5mL with an organic solvent, were placed in a flask equipped with a stirrer and a thermometer. A stirrer conditions, to 1,2-dimethoxyethane in the flask, a lithium salt (CF 3 SO 2) 2 NLi the solution temperature was slowly added so as to keep the 40 ° C. or less, and dissolved. Since at the time of (CF 3 SO 2) were added 2 NLi about 13g (CF 3 SO 2) dissolved in 2 NLi stagnated temporarily put the flask in a thermostatic bath, the temperature of the solution in the flask and 50 ° C. so as heated, it was dissolved (CF 3 sO 2) 2 NLi . Since about 15g of (CF 3 SO 2) 2 NLi when added (CF 3 SO 2) dissolved in 2 NLi stagnated again, was added one drop of 1,2-dimethoxyethane pipetted, (CF 3 SO 2) 2 NLi were dissolved. Further (CF 3 SO 2) 2 NLi added slowly, plus the total amount of predetermined (CF 3 SO 2) 2 NLi. The resulting electrolytic solution was transferred to 20mL volumetric flask, and the volume was added 1,2-dimethoxyethane until 20mL. This was an electrolytic solution E1. The obtained electrolyte is the volume 20 mL, this is contained in the electrolytic solution (CF 3 SO 2) 2 NLi was 18.38 g.(CF 3 SO 2) of 2 NLi concentration in the electrolytic solution E1 was 3.2 mol / L. In the electrolytic solution E1, are included (CF 3 SO 2) to 2 NLi1 molecule 1,2-dimethoxyethane 1.6 molecules. The above preparation was performed in a glove box under an inert gas atmosphere.

(Electrolytic solution E2)
With (CF 3 SO 2) 2 NLi in 16.08G, in a similar manner to the electrolyte E1, was prepared (CF 3 SO 2) 2 electrolyte E2 is the concentration of NLi is 2.8 mol / L. In the electrolytic solution E2, are included (CF 3 SO 2) to 2 NLi1 molecule 1,2-dimethoxyethane 2.1 molecules.

(Electrolyte E3)
Acetonitrile approximately 5mL an organic solvent, were placed in a flask equipped with a stir bar. A stirrer conditions, to acetonitrile in the flask, a lithium salt (CF 3 SO 2) 2 NLi added slowly and dissolved.(CF 3 SO 2) was stirred overnight at was added 19.52g of 2 NLi in total amount. The resulting electrolytic solution was transferred to 20mL volumetric flask, was added acetonitrile to a volume of 20mL. This was an electrolytic solution E3. The above preparation was performed in a glove box under an inert gas atmosphere.

(CF 3 SO 2) of 2 NLi concentration in the electrolytic solution E3 was 3.4 mol / L. In the electrolyte solution E3, are included acetonitrile 3 molecules to (CF 3 SO 2) 2 NLi1 molecule.

(Electrolytic solution E4)
With (CF 3 SO 2) 2 NLi of 24.11 g, in the same manner as the electrolyte solution E3, was produced (CF 3 SO 2) 2 electrolyte E4 at a concentration of NLi is 4.2 mol / L. In the electrolytic solution E4, it contains 1.9 molecules acetonitrile to (CF 3 SO 2) 2 NLi1 molecule.

(Electrolyte E5)
Using (FSO 2) 2 NLi of 13.47g lithium salt, except for using 1,2-dimethoxyethane as the organic solvent, in the same manner as the electrolyte solution E3, (FSO 2) concentration of 2 NLi 3 to produce an electrolyte solution E5 is a .6mol / L. In the electrolyte solution E5, it contains (FSO 2) to 2 NLi1 molecule 1,2-dimethoxyethane 1.9 molecules.

(Electrolyte E6)
Using (FSO 2) 2 NLi of 14.97 g, in the same manner as the electrolyte solution E5, was prepared electrolyte E6 is (FSO 2) concentration of 2 NLi is 4.0 mol / L. In the electrolyte solution E6, it contains (FSO 2) to 2 NLi1 molecule 1,2-dimethoxyethane 1.5 molecules.

(Electrolyte E7)
Except for using (FSO 2) 2 NLi of 15.72g as lithium salt, in a similar manner to the electrolyte E3, to produce an electrolyte E7 is (FSO 2) concentration of 2 NLi is 4.2 mol / L . In the electrolyte solution E7, are included acetonitrile 3 molecules to (FSO 2) 2 NLi1 molecule.

(Electrolyte E8)
Using (FSO 2) 2 NLi of 16.83 g, in the same manner as the electrolyte solution E7, was prepared electrolyte E8 is (FSO 2) concentration of 2 NLi is 4.5 mol / L. In the electrolyte solution E8, it contains acetonitrile 2.4 molecules relative (FSO 2) 2 NLi1 molecule.

(Electrolyte E9)
Using (FSO 2) 2 NLi in 18.71G, in the same manner as the electrolyte solution E7, was prepared electrolyte E9 is (FSO 2) concentration of 2 NLi is 5.0 mol / L. In the electrolyte solution E9, it contains acetonitrile 2.1 molecules relative (FSO 2) 2 NLi1 molecule.

(Electrolyte E10)
Using (FSO 2) 2 NLi of 20.21 g, in the same manner as the electrolyte solution E7, was prepared electrolyte E10 is (FSO 2) concentration of 2 NLi is 5.4 mol / L. In the electrolyte solution E10, it contains (FSO 2) 2 molecule acetonitrile to 2 NLi1 molecule.

(Electrolyte E11)
Dimethyl carbonate about 5mL an organic solvent, were placed in a flask equipped with a stir bar. A stirrer conditions, to dimethyl carbonate in the flask, a lithium salt (FSO 2) 2 NLi added slowly and dissolved.(FSO 2) was stirred overnight at was added 14.64g of 2 NLi in total amount. The resulting electrolytic solution was transferred to 20mL volumetric flask, and the volume was added dimethyl carbonate until 20mL. This was an electrolytic solution E11. The above preparation was performed in a glove box under an inert gas atmosphere.

(FSO 2) of 2 NLi concentration in the electrolytic solution E11 was 3.9 mol / L. In the electrolyte solution E11, it contains (FSO 2) dimethyl carbonate 2 molecules to 2 NLi1 molecule.

(Electrolyte E12)
It was diluted with dimethyl carbonate in the electrolytic solution E11, (FSO 2) concentration of 2 NLi was an electrolytic solution E12 of 3.4 mol / L. In the electrolyte solution E12, it contains dimethyl carbonate 2.5 molecules relative (FSO 2) 2 NLi1 molecule.

(Electrolyte E13)
It was diluted with dimethyl carbonate in the electrolytic solution E11, (FSO 2) concentration of 2 NLi was an electrolytic solution E13 of 2.9 mol / L. In the electrolyte solution E13, it contains (FSO 2) 2 NLi1 dimethyl carbonate 3 molecule to molecule.

(Electrolyte E14)
It was diluted with dimethyl carbonate in the electrolytic solution E11, (FSO 2) concentration of 2 NLi was an electrolytic solution E14 of 2.6 mol / L. In the electrolyte solution E14, it contains dimethyl carbonate 3.5 molecules relative (FSO 2) 2 NLi1 molecule.

(Electrolyte E15)
It was diluted with dimethyl carbonate in the electrolytic solution E11, (FSO 2) concentration of 2 NLi was an electrolytic solution E15 of 2.0 mol / L. In the electrolyte solution E15, it contains (FSO 2) 2 NLi1 dimethyl carbonate 5 molecule to molecule.

(Electrolyte E16)
Ethyl methyl carbonate about 5mL an organic solvent, were placed in a flask equipped with a stir bar. A stirrer conditions, to ethyl methyl carbonate in the flask, a lithium salt (FSO 2) 2 NLi added slowly and dissolved.(FSO 2) was stirred overnight at was added 12.81g of 2 NLi in total amount. The resulting electrolytic solution was transferred to 20mL volumetric flask, and the volume was added ethyl methyl carbonate until 20mL. This was an electrolytic solution E16. The above preparation was performed in a glove box under an inert gas atmosphere.

(FSO 2) of 2 NLi concentration in the electrolytic solution E16 was 3.4 mol / L. In the electrolyte solution E16, it contains ethyl methyl carbonate 2 molecules to (FSO 2) 2 NLi1 molecule.

(Electrolyte E17)
It was diluted by adding ethyl methyl carbonate in the electrolytic solution E16, (FSO 2) concentration of 2 NLi was an electrolytic solution E17 of 2.9 mol / L. In the electrolyte solution E17, it contains ethyl methyl carbonate 2.5 molecules relative (FSO 2) 2 NLi1 molecule.

(Electrolyte E18)
It was diluted by adding ethyl methyl carbonate in the electrolytic solution E16, (FSO 2) concentration of 2 NLi was an electrolytic solution E18 of 2.2 mol / L. In the electrolyte solution E18, it contains ethyl methyl carbonate 3.5 molecules relative (FSO 2) 2 NLi1 molecule.

(Electrolyte E19)
Diethyl carbonate about 5mL an organic solvent, were placed in a flask equipped with a stir bar. A stirrer conditions, to diethyl carbonate in the flask, a lithium salt (FSO 2) 2 NLi added slowly and dissolved.(FSO 2) was stirred overnight at was added 11.37g of 2 NLi in total amount. The resulting electrolytic solution was transferred to 20mL volumetric flask, and the volume was added diethyl carbonate until 20mL. This was an electrolytic solution E19. The above preparation was performed in a glove box under an inert gas atmosphere.

(FSO 2) of 2 NLi concentration in the electrolytic solution E19 was 3.0 mol / L. In the electrolyte solution E19, it contains diethyl carbonate 2 molecules to (FSO 2) 2 NLi1 molecule.

(Electrolyte E20)
The electrolyte E19 was diluted with diethyl carbonate, (FSO 2) concentration of 2 NLi was an electrolytic solution E20 of 2.6 mol / L. In the electrolyte solution E20, it contains diethyl carbonate 2.5 molecules relative (FSO 2) 2 NLi1 molecule.

(Electrolyte E21)
The electrolyte E19 was diluted with diethyl carbonate, (FSO 2) concentration of 2 NLi was an electrolytic solution E21 of 2.0 mol / L. In the electrolyte solution E21, it contains diethyl carbonate 3.5 molecules relative (FSO 2) 2 NLi1 molecule.

(Electrolyte C1)
Using (CF 3 SO 2) 2 NLi of 5.74 g, as except for using 1,2-dimethoxyethane organic solvents, in the same manner as the electrolyte solution E3, is (CF 3 SO 2) concentration of 2 NLi the electrolyte C1 is 1.0 mol / L was prepared. In the electrolytic solution C1 is included (CF 3 SO 2) to 2 NLi1 molecule 1,2-dimethoxyethane 8.3 molecules.

(Electrolytic solution C2)
With (CF 3 SO 2) 2 NLi of 5.74 g, in a similar manner to the electrolyte E3, was produced (CF 3 SO 2) 2 electrolyte C2 is the concentration of NLi is 1.0 mol / L. In the electrolyte solution C2, it is included (CF 3 SO 2) 16 molecules acetonitrile to 2 NLi1 molecule.

(Electrolyte C3)
Using (FSO 2) 2 NLi of 3.74 g, in a similar manner to the electrolyte E5, were prepared (FSO 2) 2 electrolyte C3 concentration NLi is 1.0 mol / L. In the electrolytic solution C3 is included (FSO 2) to 2 NLi1 molecule 1,2-dimethoxyethane 8.8 molecules.

(Electrolyte C4)
Using (FSO 2) 2 NLi of 3.74 g, in a similar manner to the electrolyte E7, was prepared electrolyte C4 is (FSO 2) concentration of 2 NLi is 1.0 mol / L. In the electrolyte solution C4, it contains (FSO 2) 2 NLi1 acetonitrile 17 molecule to molecule.

(Electrolyte C5)
A mixed solvent of ethylene carbonate and diethyl carbonate as an organic solvent (volume ratio 3:. 7, hereinafter, which may be referred to as "EC / DEC") used, except that LiPF 6 was used in 3.04g as lithium salt, the electrolyte in the same manner as liquid E3, the concentration of LiPF 6 was prepared an electrolyte C5 is 1.0 mol / L.

(Electrolyte C6)
It was diluted with dimethyl carbonate in the electrolytic solution E11, (FSO 2) concentration of 2 NLi was the electrolyte C6 of 1.1 mol / L. In the electrolyte solution C6, it contains (FSO 2) dimethyl carbonate 10 molecules to 2 NLi1 molecule.

(Electrolyte C7)
It was diluted by adding ethyl methyl carbonate in the electrolytic solution E16, (FSO 2) concentration of 2 NLi was an electrolytic solution C7 of 1.1 mol / L. In the electrolyte solution C7, it contains (FSO 2) ethylmethyl carbonate 8 molecules to 2 NLi1 molecule.

(Electrolyte C8)
The electrolyte E19 was diluted with diethyl carbonate, (FSO 2) concentration of 2 NLi was the electrolyte C8 of 1.1 mol / L. In the electrolyte solution C8, it contains diethyl carbonate 7 molecules to (FSO 2) 2 NLi1 molecule.

Table 4 shows the list of the electrolyte E1 ~ E21 and electrolyte C1 ~ C8.

Figure JPOXMLDOC01-appb-T000004

(Evaluation Example 1: IR measurement)
Electrolyte E3, electrolyte E4, electrolyte E7, electrolyte E8, electrolyte E10, electrolyte C2, electrolyte C4, as well as acetonitrile, (CF 3 SO 2) 2 NLi, per (FSO 2) 2 NLi, or less It was IR measurement in the conditions. It shows 2100 cm -1 of ~ 2400 cm -1 range of IR spectra in FIGS. 1 to FIG. Furthermore, the electrolyte E11 ~ E15, C6, dimethyl carbonate, E16-E18, C7, ethyl methyl carbonate, E19-E21, C8, per diethyl carbonate were IR measurement under the following conditions. The IR spectrum in the range of 1900 - 1600 cm -1 respectively shown in FIGS. 11 to 27.Also, it is shown in (FSO 2) per 2 NLi, 28 the IR spectrum in the range of 1900 ~ 1600 cm -1. In the figure, the horizontal axis is the wave number (cm -1), and a vertical axis indicates absorbance (reflection absorbance).

IR measurement conditions apparatus: FT-IR (Bruker Optics Co., Ltd.)
Measurement conditions: ATR method (diamond used)
Measurement atmosphere: inert gas atmosphere

The 2250cm around -1 of the IR spectrum of acetonitrile shown in Figure 8, the characteristic peak derived from stretching vibration triple bond between C and N of acetonitrile was observed. Incidentally, as shown in FIG. 9 (CF 3 SO 2) represented by the IR spectrum and Figure 10 the 2 NLi (FSO 2) in the vicinity of 2250 cm -1 of the IR spectrum of 2 NLi, particular peaks were not observed.

The IR spectrum of the electrolyte E3 shown in Figure 1, the characteristic peak derived from stretching vibration triple bond between C and N acetonitrile around 2250 cm -1 is slightly (Io = 0.00699) observed It was. More IR spectrum of FIG. 1, 2250 cm characteristic peaks peak intensity derived from the stretching vibration of the triple bond between the vicinity of -1 acetonitrile near 2280 cm -1 shifted to the high frequency side C and N Is = 0 It was observed at .05828. Relationship of the peak intensity of Is and Io is the Is> Io, was Is = 8 × Io.

The IR spectrum of the electrolyte E4 shown in FIG. 2, 2250 cm -1 peak derived from acetonitrile was not observed in the vicinity, between 2250 cm from the vicinity -1 acetonitrile near 2280 cm -1 shifted to the high frequency side C and N characteristic peak derived from stretching vibration of the triple bond was observed at a peak intensity is = .05234 in. Relationship between the peak intensity of the Is and Io was Is> Io.

The IR spectrum of the electrolyte E7 shown in FIG. 3, the characteristic peak derived from stretching vibration triple bond between C and N acetonitrile around 2250 cm -1 is slightly (Io = 0.00997) observed It was. More IR spectrum of FIG. 3, 2250 cm characteristic peaks peak intensity derived from the stretching vibration of the triple bond between the vicinity of -1 acetonitrile near 2280 cm -1 shifted to the high frequency side C and N Is = 0 It was observed at .08288. Relationship of the peak intensity of Is and Io is the Is> Io, was Is = 8 × Io. For even IR spectrum of the electrolyte E8 shown in FIG. 4, the peak of the same intensity and IR chart of FIG. 3 was observed in the same manner of the wave number. Relationship of the peak intensity of Is and Io is the Is> Io, was Is = 11 × Io.

FIG The IR spectrum of the electrolyte E10 represented by 5, is not a peak derived from acetonitrile observed around 2250 cm -1, inter 2250 cm from the vicinity -1 shifted acetonitrile 2280cm around -1 to the high frequency side C and N characteristic peak derived from stretching vibration of the triple bond was observed at a peak intensity is = 0.07350 in. Relationship between the peak intensity of the Is and Io was Is> Io.

The IR spectrum of the electrolyte C2 shown in Figure 6, similarly to FIG. 8, the characteristic peaks peak intensity Io to be derived from the stretching vibration of the triple bond between C and N acetonitrile around 2250 cm -1 = 0. It was observed at 04,441. More IR spectrum of FIG. 6, 2250 cm characteristic peaks peak intensity derived from the stretching vibration of the triple bond between the vicinity of -1 acetonitrile near 2280 cm -1 shifted to the high frequency side C and N Is = 0 It was observed at .03018. Relationship between the peak intensity of the Is and Io was Is <Io.

The IR spectrum of the electrolyte C4 shown in FIG. 7, similarly to FIG. 8, the characteristic peaks peak intensity Io to be derived from the stretching vibration of the triple bond between C and N acetonitrile around 2250 cm -1 = 0. It was observed at 04,975. More IR spectrum of Figure 7, 2250 cm characteristic peaks peak intensity derived from the stretching vibration of the triple bond between the vicinity of -1 acetonitrile near 2280 cm -1 shifted to the high frequency side C and N Is = 0 It was observed at .03804. Relationship between the peak intensity of the Is and Io was Is <Io.

In the vicinity of 1750 cm -1 of the IR spectrum of dimethyl carbonate shown in Figure 17, the characteristic peak derived from stretching vibration of double bonds between C and O of dimethyl carbonate was observed. Incidentally, represented by (FSO 2) in FIG. 28 in the vicinity of 1750 cm -1 of the IR spectrum of 2 NLi, particular peaks were not observed.

The IR spectrum of the electrolyte E11 shown in FIG. 11, the characteristic peaks is slightly derived from stretching vibration of double bonds between C and O of dimethyl carbonate in the vicinity of 1750cm -1 (Io = 0.16628) It was observed. More IR spectrum of Figure 11, characteristic peaks peak intensity Is derived from stretching vibration of double bonds between C and O of dimethyl carbonate in the vicinity of 1717 cm -1 shifted from the vicinity of 1750 cm -1 to a lower wavenumber side = was observed at 0.48032. Relationship between the peak intensity of the Is and Io is the Is> Io, was Is = 2.89 × Io.

FIG The IR spectrum of the electrolyte E12 indicated by 12, characteristic peaks slightly derived from stretching vibration of double bonds between C and O of dimethyl carbonate in the vicinity of 1750cm -1 (Io = 0.18129) It was observed. More IR spectrum of Figure 12, characteristic peaks peak intensity Is derived from stretching vibration of double bonds between C and O of dimethyl carbonate in the vicinity of 1717 cm -1 shifted from the vicinity of 1750 cm -1 to a lower wavenumber side = was observed at 0.52005. Relationship between the peak intensity of the Is and Io is the Is> Io, was Is = 2.87 × Io.

The IR spectrum of the electrolyte E13 shown in FIG. 13, the characteristic peaks is slightly derived from stretching vibration of double bonds between C and O of dimethyl carbonate in the vicinity of 1750cm -1 (Io = 0.20293) It was observed. More IR spectrum of Figure 13, characteristic peaks peak intensity Is derived from stretching vibration of double bonds between C and O of dimethyl carbonate in the vicinity of 1717 cm -1 shifted from the vicinity of 1750 cm -1 to a lower wavenumber side = was observed at 0.53091. Relationship between the peak intensity of the Is and Io is the Is> Io, was Is = 2.62 × Io.

The IR spectrum of the electrolyte E14 shown in FIG. 14, the characteristic peaks is slightly derived from stretching vibration of double bonds between C and O of dimethyl carbonate in the vicinity of 1750cm -1 (Io = 0.23891) It was observed. More IR spectrum of Figure 14, characteristic peaks peak intensity Is derived from stretching vibration of double bonds between C and O of dimethyl carbonate in the vicinity of 1717 cm -1 shifted from the vicinity of 1750 cm -1 to a lower wavenumber side = was observed at 0.53098. Relationship between the peak intensity of the Is and Io is the Is> Io, was Is = 2.22 × Io.

The IR spectrum of the electrolyte E15 shown in FIG. 15, the characteristic peaks is slightly derived from stretching vibration of double bonds between C and O of dimethyl carbonate in the vicinity of 1750cm -1 (Io = 0.30514) It was observed. More IR spectrum of Figure 15, characteristic peaks peak intensity Is derived from stretching vibration of double bonds between C and O of dimethyl carbonate in the vicinity of 1717 cm -1 shifted from the vicinity of 1750 cm -1 to a lower wavenumber side = was observed at 0.50223. Relationship between the peak intensity of the Is and Io is the Is> Io, was Is = 1.65 × Io.

The IR spectrum of the electrolyte C6 shown in Figure 16, the characteristic peaks (Io = 0.48204) derived from the stretching vibration of double bonds between C and O of dimethyl carbonate in the vicinity of 1750 cm -1 is observed It was. More IR spectrum of Figure 16, characteristic peaks peak intensity Is derived from stretching vibration of double bonds between C and O of dimethyl carbonate in the vicinity of 1717 cm -1 shifted from the vicinity of 1750 cm -1 to a lower wavenumber side = was observed at 0.39244. Relationship between the peak intensity of the Is and Io was Is <Io.

In the vicinity of 1745 cm -1 of the IR spectrum of the ethyl methyl carbonate represented by Figure 22, the characteristic peak derived from stretching vibration of double bonds between C and O of ethylmethyl carbonate was observed.

The IR spectrum of the electrolyte E16 shown in FIG. 18, slightly distinctive peak derived from stretching vibration of double bonds between C and O ethyl methyl carbonate in the vicinity of 1745cm -1 (Io = 0.13582 ) it was observed. More IR spectrum of Figure 18, characteristic peaks peak intensity derived from the stretching vibration of double bonds between C and O ethyl methyl carbonate in the vicinity of 1711cm -1 shifted from the vicinity of 1745 cm -1 to a lower wavenumber side It was observed at is = 0.45888. Relationship between the peak intensity of the Is and Io is the Is> Io, was Is = 3.38 × Io.

The IR spectrum of the electrolyte E17 shown in FIG. 19, slightly distinctive peak derived from stretching vibration of double bonds between C and O ethyl methyl carbonate in the vicinity of 1745cm -1 (Io = 0.15151 ) it was observed. More IR spectrum of Figure 19, characteristic peaks peak intensity derived from the stretching vibration of double bonds between C and O ethyl methyl carbonate in the vicinity of 1711cm -1 shifted from the vicinity of 1745 cm -1 to a lower wavenumber side It was observed at is = 0.48779. Relationship between the peak intensity of the Is and Io is the Is> Io, was Is = 3.22 × Io.

The IR spectrum of the electrolyte E18 shown in FIG. 20, slightly distinctive peak derived from stretching vibration of double bonds between C and O ethyl methyl carbonate in the vicinity of 1745cm -1 (Io = 0.20191 ) it was observed. More IR spectrum of Figure 20, characteristic peaks peak intensity derived from the stretching vibration of double bonds between C and O ethyl methyl carbonate in the vicinity of 1711cm -1 shifted from the vicinity of 1745 cm -1 to a lower wavenumber side It was observed at is = 0.48407. Relationship between the peak intensity of the Is and Io is the Is> Io, was Is = 2.40 × Io.

The IR spectrum of the electrolyte C7 shown in Figure 21, the characteristic peak derived from stretching vibration of double bonds between C and O ethyl methyl carbonate in the vicinity of 1745 cm -1 is (Io = 0.41907) observed It has been. More IR spectrum of Figure 21, characteristic peaks peak intensity derived from the stretching vibration of double bonds between C and O ethyl methyl carbonate in the vicinity of 1711cm -1 shifted from the vicinity of 1745 cm -1 to a lower wavenumber side It was observed at is = 0.33929. Relationship between the peak intensity of the Is and Io was Is <Io.

In the vicinity of 1742 cm -1 of the IR spectrum of diethyl carbonate shown in Figure 27, the characteristic peak derived from stretching vibration of double bonds between C and O in diethyl carbonate was observed.

The IR spectrum of the electrolyte E19 shown in FIG. 23, the characteristic peaks is slightly derived from stretching vibration of double bonds between C and O in diethyl carbonate in the vicinity of 1742cm -1 (Io = 0.11202) It was observed. More IR spectrum of Figure 23, characteristic peaks peak intensity Is derived from stretching vibration of double bonds between C and O in diethyl carbonate in the vicinity of 1706 cm -1 shifted from the vicinity of 1742 cm -1 to a lower wavenumber side = was observed at 0.42925. Relationship between the peak intensity of the Is and Io is the Is> Io, was Is = 3.83 × Io.

The IR spectrum of the electrolyte E20 shown in FIG. 24, the characteristic peaks is slightly derived from stretching vibration of double bonds between C and O in diethyl carbonate in the vicinity of 1742cm -1 (Io = 0.15231) It was observed. More IR spectrum of Figure 24, characteristic peaks peak intensity Is derived from stretching vibration of double bonds between C and O in diethyl carbonate in the vicinity of 1706 cm -1 shifted from the vicinity of 1742 cm -1 to a lower wavenumber side = was observed at 0.45679. Relationship between the peak intensity of the Is and Io is the Is> Io, was Is = 3.00 × Io.

The IR spectrum of the electrolyte E21 shown in FIG. 25, the characteristic peaks is slightly derived from stretching vibration of double bonds between C and O in diethyl carbonate in the vicinity of 1742cm -1 (Io = 0.20337) It was observed. More IR spectrum of Figure 25, characteristic peaks peak intensity Is derived from stretching vibration of double bonds between C and O in diethyl carbonate in the vicinity of 1706 cm -1 shifted from the vicinity of 1742 cm -1 to a lower wavenumber side = was observed at 0.43841. Relationship between the peak intensity of the Is and Io is the Is> Io, was Is = 2.16 × Io.

The IR spectrum of the electrolyte C8 shown in Figure 26, the characteristic peaks (Io = 0.39636) derived from the stretching vibration of double bonds between C and O in diethyl carbonate in the vicinity of 1742 cm -1 is observed It was. More IR spectrum of Figure 26, characteristic peaks peak intensity Is derived from stretching vibration of double bonds between C and O in diethyl carbonate in the vicinity of 1709 cm -1 shifted from the vicinity of 1742 cm -1 to a lower wavenumber side = was observed at 0.31129. Relationship between the peak intensity of the Is and Io was Is <Io.

(Evaluation Example 2: Ion conductivity)
Electrolyte E1, E2, electrolyte E4 ~ E6, electrolyte E8, electrolyte E9, electrolyte E11, electrolyte E13, electrolyte E16, and the ionic conductivity of the electrolyte E19 was measured under the following conditions. The results are shown in Table 5.

Under ionic conductivity measurement condition Ar atmosphere, the cell constant known glass cell with a platinum electrode, and enclosing the electrolyte solution, 30 ° C., was measured impedance at 1 kHz. From the measurement results of the impedance, ionic conductivities were determined. Measurement instrument was used Solartron 147055BEC (Solartron).

Figure JPOXMLDOC01-appb-T000005

Electrolyte E1, electrolytic solution E2, electrolyte E4 ~ E6, electrolyte E8, electrolyte E9, electrolyte E11, electrolyte E13, electrolyte E16, electrolyte E19 all showed ionic conductivity. Thus, the electrolytic solution of the present invention, any can understand and can function as an electrolyte for various batteries.

(Evaluation Example 3: viscosity)
Electrolyte E1, electrolytic solution E2, electrolyte E4 ~ E6, electrolyte E8, electrolyte E9, electrolyte E11, electrolyte E13, electrolyte E16, electrolyte E19 and electrolyte C1 ~ C4, electrolyte C6 ~ C8 the viscosity was measured under the following conditions. The results are shown in Table 6.

Using the viscosity measurement conditions falling ball viscometer (AntonPaar GmbH (Anton Paar) manufactured by Lovis 2000 M), under Ar atmosphere, an electrolytic solution is sealed in the test cell, the viscosity was measured under the conditions of 30 ° C..

Figure JPOXMLDOC01-appb-T000006

Electrolyte E1, electrolytic solution E2, electrolyte E4 ~ E6, electrolyte E8, electrolyte E9, electrolyte E11, electrolyte E13, electrolyte E16, viscosity of the electrolyte E19 is electrolyte C1 ~ C4, electrolyte C6 compared to the viscosity of ~ C8, it was significantly higher. Therefore, if the battery using the electrolyte of the present invention, even if the battery is damaged, electrolyte leakage is prevented.

(Evaluation Example 4: volatile)
Electrolyte E2, E4, E8, E11, E13, and the volatile electrolytic solution C1, C2, C4, C6 measured by the following methods.

The electrolytic solution of about 10mg placed in an aluminum pan, thermogravimetric measuring apparatus (TA Instruments, Inc., SDT600) arranged to measure the weight change of the electrolyte at room temperature. It was calculated evaporation rate by differentiating weight change (% by mass) at the time. Select the largest of the volatilization rate, shown in Table 7.

Figure JPOXMLDOC01-appb-T000007

Maximum rate of volatilization of the electrolyte solution E2, E4, E8, E11, E13, as compared to the maximum rate of volatilization of the electrolyte solution C1, C2, C4, C6, was significantly less. Therefore, battery electrolyte using the present invention, even damaged if, for volatilization rate of the electrolyte is small, the rapid volatilization of the organic solvent to the outside of the battery is suppressed.

(Evaluation Example 5: flammability)
Electrolyte E4, and the flammability of the electrolyte solution C2 was tested in the following manner.

It defeated 3 dropwise pipetted an electrolytic solution in a glass filter, an electrolytic solution is held by the glass filter. Gripping the glass filter with tweezers and allowed to Se'en to the glass filter.

Electrolyte E4 did not ignite even by 15 seconds indirect flame. On the other hand, the electrolyte solution C2 was burned out at more than 5 seconds.

Electrolytic solution of the present invention was confirmed that the hard burning.

(Evaluation Example 6: Li transference number)
The Li transport number of the electrolyte E2, E8 and electrolyte C4, C5 was measured under the following conditions. The results are shown in Table 8.

<Li transport number measurement conditions>
Electrolyte E2, E8 or electrolyte C4, C5 PFG-NMR device NMR tube containing a (ECA-500, JEOL) were subjected to, as target 7 Li, 19 F, using a spin echo method, magnetic field pulse width while changing to measure the diffusion coefficient of Li ions and anions of the electrolyte. Li transference number was calculated by the following formula.
Li transference number = (Li ion diffusion coefficient) / (Li ion diffusion coefficient + anion diffusion coefficient)

Figure JPOXMLDOC01-appb-T000008

Li transport number of the electrolyte E2, E8, compared to Li transference number of the electrolyte C4, C5, were significantly higher. Here, Li ion conductivity of the electrolyte solution can be calculated by multiplying the Li transport number in the ion conductivity contained in the electrolytic solution (total ionic conductivity). Then, the electrolytic solution of the present invention, as compared with the conventional electrolytic solutions shows an ion conductivity comparable, it can be said that the transport speed of the lithium ions (cations) is higher.

Also, every electrolyte of the electrolytic solution E8, the Li transport number in the case of changing the temperature, measured according to the Li transport number measurement conditions. The results are shown in Table 9.

Figure JPOXMLDOC01-appb-T000009

The results in Table 9, the electrolytic solution of the present invention, regardless of the temperature, it can be seen that maintain suitable Li transference number. Electrolytic solution of the present invention can be said to maintain a liquid state even at low temperatures.

(Evaluation Example 7: low temperature test)
Electrolyte E11, electrolyte E13, electrolyte E16, placed electrolyte E19 in the container, respectively, and sealed filled with an inert gas. These were stored for two days at -30 ℃ freezer. It was observed each of the electrolyte solution after storage. Maintains a liquid state without solidification any of the electrolyte solution was not observed the precipitation of salts.

(Evaluation Example 8: Raman spectrum measurement)
With regard to the electrolyte solution E8, E9, C4, E11, E13, E15, C6, was subjected to Raman spectra measured under the following conditions. A Raman spectrum peak derived from the anionic portion was observed in the metal salt of the electrolytic solution shown in FIGS 29 to 35. In the figure, the horizontal axis is the wave number (cm -1), and the vertical axis represents the scattering intensity.

Raman spectral measurement conditions Apparatus: laser Raman spectrophotometer (JASCO Corporation NRS series)
Laser wavelength: 532nm
The electrolyte was sealed in a quartz cell in an inert gas atmosphere, and subjected to measurement.

Electrolyte E8 shown in FIGS. 29 to 31, the electrolytic solution E9, the 700 ~ 800 cm -1 in the Raman spectrum of the electrolyte C4, characteristic peaks derived from (FSO 2) 2 N of LiFSA in acetonitrile There was observed. Here, from 29 to 35, with increasing concentrations of LiFSA, the said peak is shifted to a higher wave number side is seen. Electrolyte according to enrichment, corresponds to the anion of the salt (FSO 2) 2 N is presumed to be a state that interacts with more Li. Then, it considered that such a state was observed as a peak shift of a Raman spectrum.

In FIGS. 32 to 35 in an electrolytic solution represented E11, E13, E15, 700 ~ 800cm -1 in a Raman spectrum of C6 is, (FSO 2) of LiFSA dissolved in dimethyl carbonate characteristic peaks derived from the 2 N It was observed. Here, FIGS. 32 to 35, with increasing concentrations of LiFSA, the said peak is shifted to a higher wave number side is seen. This phenomenon is similar to that discussed in the preceding paragraph, that the electrolyte is high concentration, the spectral state corresponding to the anion of the salt (FSO 2) 2 N is interacting with a plurality of Li which is a result of the reflected, in other words if the concentration is low Li and anions are primarily form SSIP (Solvent-separeted ion pairs) state, with high concentrations of CIP (contact ion pairs) state and AGG ( It is presumed that the aggregate) state is mainly formed. Then, it considered that a change in such a state was observed as a peak shift of a Raman spectrum.

(Example A-1)
The lithium ion secondary battery of Example A-1 has a positive electrode and the negative electrode and the electrolytic solution and a separator.

The positive electrode is composed of a positive electrode active material layer, a current collector coated with the positive electrode active material layer. The positive electrode active material layer includes a positive active material, a binder, and a conductive additive. The positive electrode active material, a lithium-containing metal oxide of a layered rock salt structure represented by LiNi 0.5 Co 0.2 Mn 0.3 O 2 . Binder consists of polyvinylidene fluoride (PVDF). Conductive additive consists of acetylene black (AB). The current collector made of an aluminum foil having a thickness of 20 [mu] m. When the positive electrode active material layer is 100 parts by mass, the content weight ratio of the positive electrode active material, a binder and a conductive aid, 94: 3: 3.

To produce a positive electrode, a mixture of LiNi 0.5 Co 0.2 Mn 0.3 O 2 , PVDF and AB to be the mass ratio of the solvent as the N- methyl-2-pyrrolidone (NMP) the added to a paste-like positive electrode material. A paste-like positive electrode material is coated with a doctor blade on the surface of the current collector, to form a positive electrode active material layer. The positive electrode active material layer, and dried at 80 ° C. 20 minutes was removed by volatilizing the NMP. The aluminum foil to form a positive electrode active material layer on the surface, b - Rupuresu machine compressed using, was strongly adhered bond the aluminum foil and the positive electrode active material layer. 6 hours conjugate at 120 ° C., by heating in a vacuum drier, cut into a predetermined shape to obtain a positive electrode. Hereinafter, if necessary, LiNi 5/10 Co 2/10 Mn 3/10 lithium-containing metal oxide of a layered rock salt structure represented by O 2 and abbreviated as NCM523, short acetylene black and AB, polyvinylidene fluoride abbreviated as PVdF.

The negative electrode is composed of a negative electrode active material layer, a current collector coated with the negative electrode active material layer. Negative electrode active material layer includes a negative active material, a binder. To prepare a negative electrode, graphite 98 parts by weight, as a binder of styrene as a negative electrode active material - a mixture of a butadiene rubber (SBR) 1 part by weight and carboxymethylcellulose (CMC) 1 part by mass. The mixture is dispersed in an appropriate amount of ion-exchanged water to prepare a slurry of negative electrode material. It was then coated so that the film-like by using a doctor blade to form the anode active material layer on a copper foil of this slurry thickness 20μm is a negative electrode material negative electrode current collector. A current collector to form a negative electrode active material layer was pressed after drying, 6 hours conjugate at 100 ° C., by heating in a vacuum drier, cut into a predetermined shape to obtain a negative electrode.

As the electrolytic solution in Example A-1, using the above electrolyte E8.

The above positive electrode, the negative electrode and electrolyte solution was fabricated laminated lithium ion secondary battery. Specifically, between the positive electrode and the negative electrode, and an electrode plate group was sandwiched a cellulose nonwoven fabric (Toyo Roshi Co. filter paper (cellulose, 260 .mu.m thickness)) as a separator. The electrode plate assembly was covered with two pair of laminate films, after sealing the three sides, was injected the electrolytic solution to the laminate film becomes a bag shape. Then, by sealing the remaining side, four sides are hermetically sealed, the electrode plate group and the electrolyte solution was obtained sealed laminate type lithium ion secondary battery. Note that positive and negative electrodes comprising an outer electrically connectable tabs, part of the tab extends outwardly of the laminated lithium ion secondary battery.

(Example A-2)
Lithium ion secondary batteries of Example A-2, except using the above electrolytic solution E4 as the electrolytic solution is similar to Example A-1.

(Example A-3)
Lithium ion secondary batteries of Example A-3, except using the electrolytic solution E1 as the electrolytic solution is similar to Example A-1.

(Example A-4)
Lithium ion secondary batteries of Example A-4 were prepared as follows.

The positive electrode was prepared similarly to the positive electrode of a lithium ion secondary battery of Example A-1.

Natural graphite 90 parts by weight of the negative electrode active material, and were mixed 10 parts by weight of polyvinylidene fluoride as a binder. The mixture is dispersed in an appropriate amount of ion-exchanged water to prepare a slurry. It was prepared copper foil having a thickness of 20μm as a negative electrode current collector. The surface of the copper foil, using a doctor blade and coating the slurry in a film form. The copper foil slurry is coated and dried to remove water, after which the copper foil was pressed to obtain a conjugate. The resulting conjugate 120 ° C. in a vacuum dryer, and dried by heating for 6 hours to obtain a copper foil negative electrode active material layer was formed. This was used as a negative electrode.

As the separator, it was prepared with a thickness of 20μm cellulose non-woven fabric.

Sandwiching the separator between the positive electrode and the negative electrode, and an electrode plate group. The electrode plate assembly was covered with two pair of laminate films, after sealing the three sides, an electrolytic solution was injected E8 used in laminated film in which a bag-shaped in Example A-1. Then, by sealing the remaining side, four sides are hermetically sealed, the electrode plate group and the electrolyte solution was obtained sealed lithium ion secondary battery. This battery was a lithium ion secondary battery of Example A-4.

(Comparative Example A-1)
The lithium ion secondary battery of Comparative Example A-1, except using the above electrolyte C5 as the electrolytic solution is similar to Example A-1.

(Comparative Example A-2)
The lithium ion secondary battery of Comparative Example A-2, except using the electrolytic solution C5 was used in Comparative Example A-1 are the same as in Example A-4.

Table 10 shows a list of example A-1, A-2, A-3, A-4 and the electrolyte of Comparative Example A-1, A-2.

Figure JPOXMLDOC01-appb-T000010

(Evaluation Example A-9: input-output characteristics)
(1) 0 ℃, and evaluating the output characteristic of the output characteristic evaluation described above in Example A-1 and Comparative Example A-1 in the lithium ion secondary battery in SOC 20%. Basis weight of the positive electrode of the test was Example A-1 and Comparative Example A-1 of the lithium-ion secondary battery for evaluation was 11 mg / cm 2, weight per unit area of the negative electrode is 8 mg / cm 2. Evaluation conditions, state of charge (SOC) 20%, 0 ℃, voltage range 3V-4.2 V, a capacity 13.5MAh. SOC 20%, 0 ° C., for example, a region not easily emitted output characteristics as in the case of using in such refrigerating compartment. Example Evaluation of A-1 and Comparative Example A-1 of the output characteristics were carried out three times each for each 2 seconds output and 5 seconds output. The evaluation results of output characteristics are shown in Table 11. "2 seconds Output" in the table 11 refers to the output at two seconds after the discharge start, "5 seconds Output" means the output at 5 seconds after the discharge initiation.

As shown in Table 11, 0 ° C. of the battery in Example A-1, the output of the SOC 20%, as compared to the output of the battery of Comparative Example A-1, was higher 1.2-1.3 times.

(2) 25 ℃, the output characteristic of the output characteristic evaluation described above in Example A-1 and Comparative Example A-1 of the battery at SOC 20%, state of charge (SOC) 20%, 25 ℃, voltage range 3V-4 .2V, it was evaluated in terms of capacity 13.5mAh. Example Evaluation of A-1 and Comparative Example A-1 of the output characteristics were carried out three times each for each 2 seconds output and 5 seconds output. The evaluation results are shown in Table 11.

As shown in Table 11, 25 ° C. of the battery in Example A-1, the output of the SOC 20%, as compared to the output of the battery of Comparative Example A-1, was higher 1.2-1.3 times.

(3) for the output characteristics of the lithium ion secondary batteries according to the temperature effects the relative output characteristic example A-1 and Comparative Example A-1, was examined the influence of temperature at the time of measurement. Measured at 0 ℃ and 25 ° C., even in the measurement under any temperature, evaluation conditions, state of charge (SOC) 20%, working voltage range 3V-4.2 V, and a capacitor 13.5MAh. It was determined the ratio of the output at 0 ℃ for output at 25 ° C. (0 ℃ Output / 25 ° C. Output). The results are shown in Table 11.

As shown in Table 11, the electrolytic solution of Example A-1 it was found to be suppressed output reduction at low temperatures to the same extent as the electrolyte solution of Comparative Example A-1.

Further, in the electrolytic solution in Example A-1, since the majority of the organic solvents acetonitrile with a hetero element forms a lithium salt LIFSA and clusters, the vapor pressure of the organic solvent contained in the electrolytic solution is lowered. As a result, it is possible to reduce the volatilization of the organic solvent from the electrolyte solution.

In contrast, in Comparative Example A-1, is used EC solvents. EC are mixed to lower the viscosity and melting point of the electrolyte. The solvent in Comparative Example A-1, also includes DEC is a chain carbonate. Chain carbonate is volatilized easily, by any chance, if a case or damage a gap there occurs in the battery, there is a possibility that a large amount of organic solvent instantaneously out of the system is released as a gas.

As the solvent of the electrolytic solution, by using a low-volatile liquid such as ionic liquids, it is possible to solve the problem of electrolyte solution of Comparative Example A-1. However, ionic liquids, high viscosity, ionic conductivity for low compared to conventional electrolytic solution is expected that input-output characteristic is deteriorated. This tendency is remarkable at low temperature such as 0 ° C., 0 ° C. Output / 25 ° C. output is expected to be 0.2 or less.

Figure JPOXMLDOC01-appb-T000011

(4) 0 ° C. or 25 ° C., were evaluated input characteristics of the input characterization lithium ion secondary battery in SOC 80%. Battery used in this evaluation, except for using the thickness 20μm of the cellulose nonwoven fabric as the separator, Example A-1, Example A-4, Comparative Example A-1, the lithium ion secondary of Comparative Example A-2 is the same as the next battery. Example A-1, A-4, the battery corresponding to Comparative Example A-1, A-2, carried out in order cell A-1, exemplary cell A-4, the comparative batteries A-1, Comparative Battery A-2 did. Evaluation conditions, state of charge (SOC) 80%, 0 ℃ or 25 ° C., voltage range 3V-4.2 V, and a capacitor 13.5MAh. Evaluation of the input characteristics were carried out three times each for each cell for 2 seconds inputs and 5 seconds input.

Further, based on the volume of each cell, 25 ° C., it was calculated battery output density at 2 seconds Input (W / L). Table 12 shows evaluation results of the input characteristic.

As shown in Table 12, regardless of the difference in temperature, the input of the batteries in the battery A-1, as compared to the input of the cell of Comparative Battery A-1, was significantly higher. Similarly, the input of the batteries in the battery A-4, as compared to the input of the cell of Comparative Battery A-2, was significantly higher.

The battery input density exemplary cell A-1, as compared to the battery input density of Comparative Battery A-1, was significantly higher. Similarly, battery input density exemplary cell A-4, as compared to the battery input density of Comparative Battery A-2, was significantly higher.

(5) 0 ° C. or 25 ° C., output characteristic evaluation conducted Battery A-1 at SOC 20%, exemplary cell A-4, the comparative batteries A-1, was evaluated under the following conditions the output characteristics of the comparative battery A-2. Evaluation conditions, state of charge (SOC) 20%, 0 ℃ or 25 ° C., voltage range 3V-4.2 V, and a capacitor 13.5MAh. SOC 20%, 0 ° C., for example, a region not easily emitted output characteristics as in the case of using in such refrigerating compartment. Evaluation of the output characteristics were carried out three times each for each cell for 2 seconds output and 5 seconds output.

Further, based on the volume of each cell, 25 ° C., it was calculated battery output density at 2 seconds the output (W / L). The evaluation results of output characteristics shown in Table 12.

As shown in Table 12, regardless of the difference in temperature, the output of the exemplary cell A-1, as compared with the output of the comparison battery A-1, was significantly higher. Similarly, the output of the exemplary cell A-4, as compared with the output of the comparison battery A-2, was significantly higher.

The battery power density of exemplary cell A-1, as compared to the cell output densities of Comparative Battery A-1, was significantly higher. Similarly, cell output density exemplary cell A-4, as compared to the cell output densities of Comparative Battery A-2, was significantly higher.

Figure JPOXMLDOC01-appb-T000012

(Evaluation Example A-10: DSC test)
Example A-1, was subjected to a thermal physical property tests of the positive electrode and the electrolyte in the batteries of Examples A-2 and Comparative Example A-1.

For each cell, the charge throughout voltage 4.2 V, was fully charged at a constant current constant voltage. Dismantled full lithium ion secondary battery after charging was removed cathode. Put the positive 3mg and the electrolyte 1.8μL into a stainless steel pan and sealed the pan. By using a closed pan under a nitrogen atmosphere, heating rate 20 ° C. / min. Performs differential scanning calorimetry at conditions were observed DSC curve. Using Rigaku DSC8230 as differential scanning calorimeter. The measurement results of Comparative Example A-1 Example A-1 shown in FIG. 36, showing the measurement results of Comparative Example A-1 Example A-2 in FIG. 37.

Figure 36, as shown in FIG. 37, although the heat generation in the vicinity of Example A-1 at 300 ° C. did not occur in Comparative Example A-1, heat generation occurred at around 300 ° C.. In the battery in Example A-1, low reactivity with the electrolytic solution and the positive electrode active material in a charged, was found to have excellent thermal properties.

In the electrolytic solution in Example A-1, since the majority of the organic solvents acetonitrile with a hetero element forms a lithium salt LIFSA and clusters, the vapor pressure of the organic solvent contained in the electrolytic solution is lowered. As a result, it is possible to reduce the volatilization of the organic solvent from the electrolyte solution. Further, since the solvent amount is smaller than normal, less potential amount of heat when burned. Furthermore, because of poor reactivity with oxygen electrolyte itself is released from the positive electrode is considered to have excellent thermal properties.

Heating at around 300 ° C. Comparative Example A-1 is the reaction between the electrolytic solution and the positive electrode, in particular considered to be a reaction of the oxygen generated from the positive electrode and the electrolyte.

As shown in FIG. 37, the electrolytic solution of Example A-2, as compared to the electrolyte of Comparative Example A-1, the amount of heat generated was extremely small. Electrolytic solution of Example A-2 also, since the Li ions and solvent molecules LiTFSA are attracted to the mutual electrostatic attraction, there is no free solvent molecules, which is not easily volatilized. In addition, it is difficult to react with the positive electrode active material at the time of charging. Therefore, the battery of Example A-2 is considered to have excellent thermal properties.

(Evaluation Example A-11: Evaluation of rate capacity characteristics)
It was evaluated rate capacity characteristics of Example A-1 and Comparative Example A-1. Capacity of each cell was adjusted to be 160 mAh / g. Evaluation conditions, 0.1 C, 0.2 C, was discharged 0.5 C, 1C, after the charging at a 2C rate of was measured capacity of the positive electrode (discharge capacity) at the respective speeds. 1C shows a current value required to fully charge or discharge the battery in 1 hour at a constant current. The discharge capacity after 0.1C discharge after and 1C discharge shown in Table 13. Discharge capacity shown in Table 13 is the calculated value of capacitance per positive electrode weight.

As shown in Table 13, 0.1 C discharge capacity was not great difference in Comparative Example A-1 Example A-1, 1C discharge capacity is more of Example A-1 from Comparative Example A-1 It was also large.

Figure JPOXMLDOC01-appb-T000013

(Example A-5)
Electrolyte of lithium ion secondary battery of Example A-5 was used an electrolytic solution E11. Example A-5 of the lithium ion secondary battery positive electrode, negative electrode and separator were the same as in the battery A-1 (separator thickness 20 [mu] m).

(Comparative Example A-3)
Comparative Example A-3 of the lithium ion secondary battery positive electrode, negative electrode, separator and the electrolyte are the same as those of the comparative battery A-1.

(Evaluation Example A-12: Capacity retention rate)
Example A-5, the lithium secondary battery of Comparative Example A-3, respectively temperature 25 ° C., charged to 4.1V under the conditions of CC charging 1C, after resting for one minute, at CC discharging 1C discharged to 3.0 V, the cycle test to repeat 500 cycles of the rest 1 minute. The discharge capacity retention ratio at each cycle was measured and the results are shown in Figure 38. The discharge capacity retention ratio at the 500th cycle are shown in Table 14. Discharge capacity retention ratio is a value determined as a percentage of value obtained by dividing the discharge capacity of each cycle in the initial discharge capacity ((discharge capacity of each cycle) / (discharge capacity Initial) × 100).

As shown in Table 14 and Figure 38, the use of DMC as a solvent for the electrolyte solution as in Example A-5, was improved cycle life.

Figure JPOXMLDOC01-appb-T000014

In the initial and 200th cycle, temperature 25 ° C., was adjusted to the voltage 3.5V in CCCV of 0.5 C, and the voltage change amount (pre-discharge voltage and the discharge 10 seconds after voltage produced by the CC discharge 10 seconds 3C It was measured DC resistance (discharge) by the difference) and Ohm's law from the current value.

Further the initial and 200th cycle, temperature 25 ° C., was adjusted to the voltage 3.5V in CCCV of 0.5 C, and the voltage change amount (precharge voltage and charging 10 seconds after voltage produced by the CC charging 10 seconds 3C It was measured DC resistance (charge) by the difference) and Ohm's law from the current value. The respective results are shown in Table 15.

Figure JPOXMLDOC01-appb-T000015

Lithium secondary batteries of Examples A-5 is found to be the resistance after the cycle is small. The lithium secondary battery of Example A-5 has a high capacity retention ratio, it can be said that withstands.

(Evaluation Example A-13: Ni, Mn, elution confirmation Co)
The lithium ion secondary battery of Example A-5 and Comparative Example A-3, the voltage range 3V ~ 4.1 V, charging and discharging are repeated 500 times at a rate 1C. Dismantling the battery after the charge and discharge 500 times, it was taken out anode. Eluted from the positive electrode to the electrolyte, Ni was deposited to the negative electrode surface, Mn, the amount of Co was determined by ICP (inductively coupled plasma) emission spectrometer. The measurement results are shown in Table 16. Ni in Table 16, Mn, Co content (wt%) shows a Ni per negative electrode active material layer 1 g, Mn, the weight of the Co%, Ni, Mn, Co amount ([mu] g / sheets) are It represents the negative electrode active material per one layer Ni, Mn, Co of mass (μg), Ni, Mn, Co content (mass%) ÷ 100 × the negative electrode active material layer one mass = Ni, Mn, Co amount It was exposed by (μg / sheets) of the formula.

Figure JPOXMLDOC01-appb-T000016

As shown in Table 16, the negative electrode of Example A-5, as compared to the negative electrode of Comparative Example A-3, Ni, Mn, Co content (mass%) and Ni, Mn, Co amount ([mu] g / sheet) both It was lower. The results shown in Table 16 when combined with the results shown in Table 15, Example A-5, as compared with Comparative Example A-3, less metal elution from the positive electrode, precipitation from the positive electrode to the negative electrode of the eluted metal less, also, it was found that the higher capacity retention rate.

(Evaluation Example A-14: basis weight and the output characteristics of the electrode)
The Evaluation Example A-14 Evaluation Example A-6 which is the target of Comparative Example A-4, respectively in Example A-1 and Comparative Example A-1 of the battery and the positive electrode of the basis weight is different. Example A-6, Comparative Example A-4 are both the basis weight of the positive electrode and 5.5 mg / cm 2, the basis weight of the negative electrode was 4 mg / cm 2. Basis weight of the electrode, Evaluation Example (1) of A-18 ~ (5) of the input characteristics and half the basis weight of the cell electrodes used in the evaluation of the output characteristic, that is, half of the battery capacity. This each battery was measured input-output characteristics under the following three conditions. The measurement results are shown in Table 17.
<Measurement conditions>
- state of charge (SOC) 30%, - 30 ℃, voltage range 3V-4.2V, 2 seconds Output-charged state (SOC) 30%, - 10 ℃, voltage range 3V-4.2V, 2 seconds Output - state of charge (SOC) 80%, 25 ℃, voltage range 3V-4.2V, 5 seconds input

Figure JPOXMLDOC01-appb-T000017

As shown in Table 17, even when the half of the battery was evaluated for the basis weight of the electrode (1) to (5), in the case of using the electrolytic solution of Example A-6, the Comparative Example A input-output characteristic is improved as compared with the electrolytic solution of -4.

(Battery A-1)
Lithium ion secondary batteries of the battery A-1 has the same configuration as the lithium ion secondary battery of Example A-1.

That is, the electrolyte used in the battery A-1 is an electrolytic solution E8. Configuration of the positive electrode, LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM253) 90 parts by mass as a positive electrode active material, acetylene black as a conductive aid (AB) 8 parts by weight, and a binder a positive electrode active material layer formed from one of polyvinylidene fluoride (PVdF) 2 parts by mass, consisting of an aluminum foil having a thickness of 20μm consisting of positive electrode collector (JIS A1000 No. system).

The negative electrode used in the battery A-1 is 98 parts by weight of natural graphite as a negative electrode active material, and a negative electrode active material layer made of SBR1 parts by and CMC1 parts by a binder, the thickness of 20μm as a negative electrode current collector consisting of a copper foil.

The separator used in the battery A-1 is a cellulosic nonwoven thickness 20 [mu] m.

(Battery A-2)
Lithium ion secondary batteries of the battery A-2 is obtained by using an electrolytic solution E11.
Lithium ion secondary batteries of the battery A-2, the mixing ratio of the positive electrode active material, the conductive auxiliary agent and a binder, the mixing ratio of the negative electrode active material and a binder, and a lithium battery A-1 except the separator is the same as the ion secondary battery. For the positive electrode, NCM523: AB: PVdF = 90: 8: was 2. The negative electrode, natural graphite: SBR: CMC = 98: 1: was 1. As the separator using the cellulose nonwoven fabric having a thickness of 20 [mu] m.

(Battery A-3)
Lithium ion secondary batteries of the battery A-3 is obtained by using an electrolytic solution E13. Lithium ion secondary batteries of the battery A-3, the mixing ratio of the positive electrode active material, the conductive auxiliary agent and a binder, the mixing ratio of the negative electrode active material and a binder, and a lithium battery A-1 except the separator is the same as the ion secondary battery. For the positive electrode, NCM523: AB: PVdF = 90: 8: was 2. The negative electrode, natural graphite: SBR: CMC = 98: 1: was 1. As the separator using the cellulose nonwoven fabric having a thickness of 20 [mu] m.

(Battery A-C1)
Lithium ion secondary batteries of the battery A-C1 are those using an electrolytic solution C5. Lithium ion secondary batteries of the battery A-C1, the type of electrolyte, the mixing ratio of the positive electrode active material, the conductive auxiliary agent and a binder, the mixing ratio of the negative electrode active material and the binder, and other separators battery is the same as the lithium ion secondary battery a-1. For the positive electrode, NCM523: AB: PVdF = 90: 8: was 2. The negative electrode, natural graphite: SBR: CMC = 98: 1: was 1. As the separator using the cellulose nonwoven fabric having a thickness of 20 [mu] m.

(Evaluation Example A-15: the internal resistance of the battery)
Prepare the lithium ion secondary battery of the battery A-1 ~ cell A-3 and the battery A-C1, to evaluate the internal resistance of the battery.

For each of the lithium ion secondary battery of the battery A-1 ~ cell A-3 and the battery A-C1, RT, CC discharge at a range of 3.0V ~ 4.1V (vs.Li reference) (i.e. a constant current charge and discharge ) was repeated. Then, AC impedance after the initial charge and discharge, and was measured AC impedance after 100 cycles passed. Based on the resulting complex impedance plane plots, electrolyte was analyzed each reaction resistance of the negative electrode and the positive electrode. As shown in FIG. 39, in the complex impedance plane plots, two arc was observed. An arc left side in the drawing (i.e. the real part is smaller side of the complex impedance) is called a first arc. The right side of the arc in the drawing is referred to as a second circular arc. Analyzing the reaction resistance of the negative electrode based on the magnitude of the first arc, the reaction was analyzed resistance of the positive electrode based on the size of the second arc. It was analyzed resistance of the electrolytic solution on the basis of the leftmost plot in Figure 39 continuous to the first arc. The analysis results are shown in Table 18 and Table 19. Incidentally, Table 18, first the resistance of the charge and discharge after the electrolyte (so-called solution resistance), reaction resistance of the negative electrode, reaction resistance of the cathode, and shows a diffusion resistance, Table 19 shows the respective resistance after 100 cycles.

Figure JPOXMLDOC01-appb-T000018

Figure JPOXMLDOC01-appb-T000019

As shown in Table 18 and Table 19, in each of the lithium ion secondary battery, the negative electrode reaction resistance and the positive electrode reaction resistance after 100 cycles elapsed, it tends to decrease as compared with the resistance after the initial charge and discharge. Then, after the 100 cycles elapse shown in Table 19, the negative electrode reaction resistance and the positive electrode reaction resistance of the lithium ion secondary battery of the battery A-1 ~ cell A-3 is a negative electrode of lithium ion secondary battery of the battery A-C1 lower than the resistance and the positive electrode reaction resistance.

As described above, the battery A-1, a lithium ion secondary battery of the battery A-2 are those using the electrolytic solution of the present invention, the negative electrode and the surface of the positive electrode from the electrolyte of the present invention S, O-containing film is formed. In contrast, in the electrolytic solution does not use a battery A-C1 lithium ion secondary battery of the present invention, the S, O-containing coating is not formed on the negative electrode and the surface of the positive electrode. Then, the battery A-1, the negative electrode reaction resistance and the positive electrode reaction resistance of the battery A-2 is lower than the lithium ion secondary battery of the battery A-C1. Therefore, in the battery A-1 ~ cell A-3, S derived from the electrolytic solution, the anode reaction resistance and the positive electrode reaction resistance due to the presence of O-containing film is presumed to have reduced the present invention.

Incidentally, the solution resistance of the electrolyte in the lithium ion secondary battery of the battery A-2 and cell A-C1 is substantially the same, solution resistance of the electrolyte in the lithium ion secondary battery of the battery A-1, the battery A- higher than the 2 and battery a-C1. Further, solution resistance of the electrolyte in each of the lithium ion secondary battery is the same after 100 cycles elapsed after the initial charge and discharge. Therefore, deterioration in durability of each of the electrolyte solution is considered not to occur, the difference of the negative electrode reaction resistance and the positive electrode reaction resistance caused in the battery A-C1 and battery A-1 ~ cell A-3 described above, the electrolytic solution believed to be caused in the electrode itself not relate to deterioration of durability.

The internal resistance of the lithium ion secondary battery, solution resistance of the electrolyte solution, can be comprehensively judged from the reaction resistance and the positive electrode of the reaction resistance of the negative electrode. On the basis of the results of Tables 18 and 19, from the viewpoint of suppressing the internal resistance increase of the lithium ion secondary battery excellent in most durable lithium ion secondary battery of the battery A-1, then cell A-2 lithium ion secondary battery is said to be excellent in durability.

(Evaluation Example A-16: cycle durability of the battery)
Battery A-1 ~ cell A-3, for each of the lithium ion secondary battery of the battery A-C1, repeated CC discharge at a range of room temperature, 3.0V ~ 4.1V (vs.Li reference), initial charge and discharge discharge capacity of time, 100 cycles when the discharge capacity, and the discharge capacity at 500 cycles was measured. Then, the capacity of each lithium ion secondary battery at the time of initial charge-discharge was 100%, was calculated 100 cycles and at 500 the capacity retention rate of each of the lithium ion secondary battery at the time of cycles (%). The results are shown in Table 20.

Figure JPOXMLDOC01-appb-T000020

As shown in Table 20, cell A-1, a lithium ion secondary battery of the battery A-2, despite not containing EC as a SEI of the material, the lithium ion secondary battery A-C1 containing EC order of a battery equivalent capacitance retention rate. This cell A-1, the positive and negative electrodes in a lithium ion secondary battery of the battery A-2, S derived from the electrolytic solution of the present invention is believed to be because the O-containing coating is present. Then, the lithium ion secondary battery of the battery A-2, in particular showed very high capacity retention rate at 500 cycles elapsed, was particularly excellent in durability. From this result, when selecting a DMC as organic solvents, as compared with the case of selecting the AN, it can be said that the more durable is improved.

(Battery A-4)
The half cell using the electrolytic solution E8 was prepared as follows.

Graphite 90 parts by weight of the average particle size of 10μm as an active material, and were mixed 10 parts by weight of polyvinylidene fluoride as a binder. The mixture is dispersed in an appropriate amount of N- methyl-2-pyrrolidone to prepare a slurry. I was preparing a copper foil with a thickness of 20μm as the current collector. The surface of the copper foil, using a doctor blade and coating the slurry in a film form. The slurry is dried copper foil coated N- methyl-2-pyrrolidone was removed, after which the copper foil was pressed to obtain a conjugate. The resulting conjugate 120 ° C. in a vacuum dryer, and dried by heating for 6 hours to obtain copper foil in which an active material layer was formed. This was a working electrode. The mass of the active material per copper foil 1 cm 2 was 1.48 mg. The density of the press before the graphite and polyvinylidene fluoride is 0.68 g / cm 3, the density of the active material layer after pressing was 1.025 g / cm 3.

The counter electrode was a metal Li.

Working electrode, counter electrode, and an electrolyte E8, housed in a battery case of size 13.82Mm (Hohsen CR2032 type coin cell case, Ltd.) to constitute a half cell. This was a half-cell of the battery A-4.

(Battery A-5)
Except for using the electrolyte E11, in the same manner as the battery A-4, were prepared half cell battery A-5.

(Battery A-6)
Except for using the electrolyte E16, in the same manner as the battery A-4, were prepared half cell battery A-6.

(Battery A-7)
Except for using the electrolyte solution of the electrolyte E19, in the same manner as the battery A-4, were prepared half cell battery A-7.

(Battery A-C2)
Except for using the electrolytic solution C5, in the same manner as the battery A-4, were prepared half cell battery A-C2.

(Evaluation Example A-17: Rate Characteristics)
Battery A-4 ~ Battery A-7, was tested in the following manner rate characteristics of half-cell of the battery A-C2.
To half cell, 0.1C, 0.2C, 0.5C, 1C, charging at 2C rate (the 1C means the current value required to fully charge or discharge the battery in 1 hour at a constant current.) performing was discharged after a was measured volume of the working electrode at each speed (discharge capacity). The description given here is regarded counter anode, a working electrode and a positive electrode. To volume of the working electrode at 0.1C rate was calculated the ratio of the capacity at other rates (rate characteristics). The results are shown in Table 21.

Figure JPOXMLDOC01-appb-T000021

Comparative Battery A-4 ~ Battery A-7 is a half-cell 0.2 C, 0.5 C, in 1C rate, further, the battery A-4, cell A-5 is a half-cell of the battery A-C1 even 2C rate to, and capacity reduction can be suppressed, backed to exhibit excellent rate characteristics.

(Evaluation Example A-18: Capacity retention rate)
Battery A-4 ~ Battery A-7, was tested in the following manner and the capacity retention ratio of the half-cell batteries A-C2.

For each half-cell, 25 ° C., and CC charged to a voltage 2.0 V (constant current charging), the charge-discharge cycle of 2.0 V-0.01 V to perform CC discharge (constant current discharge) to the voltage 0.01 V, charging discharge rate 0.1C in three cycles, then, 0.2 C, 0.5 C, 1C, 2C, 5C, performs the charge and discharge rate per 3 cycles each charge and discharge in the order of 10C, finally with 0.1C 3 were cycles of charge and discharge. Capacity maintenance ratio of each half-cell (%) was calculated by the following equation.

Capacity retention ratio (%) = B / A × 100
A: the discharge capacity of the second working electrode in the first 0.1C charge and discharge cycles B: shown in Table 22, the discharge capacity results in the second working electrode in the charge-discharge cycle of the last 0.1C. The description given here is regarded counter anode, a working electrode and a positive electrode.

Figure JPOXMLDOC01-appb-T000022
Either half cell also performs better charge and discharge reaction, it showed a suitable capacity retention rate. In particular, cell A-5, battery A-6, the capacity retention rate of half-cell of the battery A-7 was significantly better.

(Battery A-8)
Lithium ion secondary batteries of the battery A-8 using the electrolyte E8 is similar to the lithium ion secondary battery of the battery A-1. The ingredients ratio in the positive electrode active material layer, NCM523: AB: PVDF = 94: 3: 3, and as the separator, using a laboratory filter paper (Toyo Roshi Co., cellulosic, 260 .mu.m thickness). Electrolyte E8 in the lithium ion secondary battery of the battery A-8 is, (FSO 2) the concentration of 2 NLi a 4.5 mol / L. In the electrolyte solution E8, it contains acetonitrile 2.4 molecules relative (FSO 2) 2 NLi1 molecule.

(Battery A-9)
Lithium ion secondary batteries of the battery A-9, except for using an electrolytic solution E4 as the electrolytic solution is the same as the lithium ion secondary battery of the battery A-8. The electrolytic solution in the lithium ion secondary battery of the battery A-9 is acetonitrile as solvent, by dissolving as a supporting salt (SO 2 CF 3) 2 NLi (LiTFSA). The concentration of the lithium salt contained in 1 liter of the electrolyte solution is a 4.2 mol / L. Electrolyte, the lithium salt 1 molecule, including acetonitrile 2 molecule.

(Battery A-10)
Lithium ion secondary batteries of the battery A-10, except for using an electrolytic solution E11 as the electrolytic solution is the same as the lithium ion secondary battery of the battery A-8. The electrolytic solution in the lithium ion secondary battery of the battery A-10 is the DMC as a solvent, by dissolving the LiFSA as a supporting salt. The concentration of the lithium salt contained in 1 liter of the electrolyte solution is a 3.9 mol / L. Electrolyte, the lithium salt 1 molecule, including DMC two molecules.

(Battery A-11)
Lithium ion secondary batteries of the battery A-11 is obtained by using an electrolytic solution E11. Lithium ion secondary batteries of the battery A-11, the type of electrolyte, the mixing ratio of the positive electrode active material, the conductive auxiliary agent and a binder, the mixing ratio of the negative electrode active material and the binder, and other separators battery is the same as the lithium ion secondary battery a-8. For the positive electrode, using NCM523 as the positive electrode active material, using AB as a conductive additive for the positive electrode, as the binder using PVdF. This is the same as the battery A-8. The mixing ratios, NCM523: AB: PVdF = 90: 8: was 2. Basis weight of the active material layer in the positive electrode is 5.5 mg / cm 2, the density was 2.5 g / cm 3. This also applies to the following cell A-12 ~ cell A-15 and the battery A-C3 ~ cell A-C5.

The negative electrode, natural graphite used as a negative electrode active material, using SBR and CMC as a binder for the negative electrode. This is also the same as the battery A-8. The mixing ratios, natural graphite: SBR: CMC = 98: 1: 1. Basis weight of the active material layer in the negative electrode is 3.8 mg / cm 2, the density was 1.1 g / cm 3. This also applies to the following cell A-12 ~ cell A-15 and the battery A-C3 ~ cell A-C5.

As the separator using the cellulose nonwoven fabric having a thickness of 20 [mu] m.

The electrolytic solution in the lithium ion secondary battery of the battery A-11 is the DMC as a solvent, by dissolving the LiFSA as a supporting salt. The concentration of the lithium salt contained in 1 liter of the electrolyte solution is a 3.9 mol / L. Electrolyte, the lithium salt 1 molecule, including DMC two molecules.

(Battery A-12)
Lithium ion secondary batteries of the battery A-12 are those using an electrolytic solution E8. Lithium ion secondary batteries of the battery A-12, the mixing ratio of the positive electrode active material, the conductive auxiliary agent and a binder, the mixing ratio of the negative electrode active material and a binder, and a lithium non-separator battery A-8 is the same as the ion secondary battery. For the positive electrode, NCM523: AB: PVdF = 90: 8: was 2. The negative electrode, natural graphite: SBR: CMC = 98: 1: was 1. As the separator using the cellulose nonwoven fabric having a thickness of 20 [mu] m.

(Battery A-13)
Lithium ion secondary batteries of the battery A-13 is one using an electrolyte E11. Lithium ion secondary batteries of the battery A-13, the type of electrolyte, the mixing ratio of the positive electrode active material, the conductive auxiliary agent and a binder, the type of binder for the negative electrode, the negative electrode active material and a binder mixing ratio, and other separators is the same as the lithium ion secondary battery of the battery a-8. For the positive electrode, NCM523: AB: PVdF = 90: 8: was 2. The negative electrode, natural graphite used as a negative electrode active material, using polyacrylic acid (PAA) as a binder for the negative electrode. The mixing ratios, natural graphite: PAA = 90: was 10. As the separator using the cellulose nonwoven fabric having a thickness of 20 [mu] m.

(Battery A-14)
Lithium ion secondary batteries of the battery A-14 are those using an electrolytic solution E8. Lithium ion secondary batteries of the battery A-14, the mixing ratio of the positive electrode active material, the conductive auxiliary agent and a binder, the type of binder for the negative electrode, the mixing ratio of the negative electrode active material and a binder, and except the separator is the same as the lithium ion secondary battery of the battery a-8. For the positive electrode, NCM523: AB: PVdF = 90: 8: was 2. The negative electrode, natural graphite: PAA = 90: was 10. As the separator using the cellulose nonwoven fabric having a thickness of 20 [mu] m.

(Battery A-15)
Lithium ion secondary batteries of the battery A-15 is obtained by using an electrolytic solution E13. Lithium ion secondary batteries of the battery A-15, the mixing ratio of the positive electrode active material, the conductive auxiliary agent, the type of binder for the negative electrode, the mixing ratio of the negative electrode active material and the binder, and other separators battery is the same as the lithium ion secondary battery a-1. For the positive electrode, NCM523: AB: PVdF = 90: 8: was 2. The negative electrode, natural graphite: SBR: CMC = 98: 1: was 1. As the separator using the cellulose nonwoven fabric having a thickness of 20 [mu] m.

(Battery A-C3)
Lithium ion secondary batteries of the battery A-C3, except using an electrolytic solution C5, is similar to cell A-1.

(Battery A-C4)
Lithium ion secondary batteries of the battery A-C4 is obtained using an electrolytic solution C5. Lithium ion secondary batteries of the battery A-C4, the type of electrolyte, the mixing ratio of the positive electrode active material, the conductive auxiliary agent and a binder, the mixing ratio of the negative electrode active material and the binder, and other separators battery is the same as the lithium ion secondary battery a-1. For the positive electrode, NCM523: AB: PVdF = 90: 8: was 2. The negative electrode, natural graphite: SBR: CMC = 98: 1: was 1. As the separator using the cellulose nonwoven fabric having a thickness of 20 [mu] m.

(Battery A-C5)
Lithium ion secondary batteries of the battery A-C5 is obtained by using an electrolytic solution C5. Lithium ion secondary batteries of the battery A-C5, the type of electrolyte, the mixing ratio of the positive electrode active material, the conductive auxiliary agent and a binder, the type of binder for the negative electrode, the negative electrode active material and a binder mixing ratio, and other separators is the same as the lithium ion secondary battery of the battery a-1. For the positive electrode, NCM523: AB: PVdF = 90: 8: was 2. The negative electrode, natural graphite: PAA = 90: was 10. As the separator using the cellulose nonwoven fabric having a thickness of 20 [mu] m.
The battery structure of the battery are shown in Table 23.

Figure JPOXMLDOC01-appb-T000023

(Evaluation Example A-19: S, Analysis of O-containing coating)
Hereinafter, abbreviated as needed, S formed on the surface of the negative electrode in a lithium ion secondary battery of the battery A-8 ~ A-15, the negative electrode S of the O-containing coating each cell, the O-containing film, batteries A the film formed on the surface of the negative electrode in -C3 ~ a-C5 lithium ion secondary battery is substantially the negative electrode coating of each battery.

If necessary, each of the batteries A-8 ~ A-15 each battery the film formed on the surface of the positive electrode in the lithium ion secondary battery A-8 ~ A-15 positive S of the O-containing coating short, substantially the positive electrode film of each battery a-C3 ~ a-C5 each cell a film formed on the surface of the positive electrode in the lithium ion secondary battery a-C3 ~ a-C5.

(Negative electrode S, the analysis of O-containing coating and the anode coating)
Battery A-8, the lithium ion secondary battery of the battery A-9 and the battery A-C3, after repeated 100 cycles of charge and discharge, X-rays photoelectron spectroscopy in a discharged state voltage 3.0V (X-ray Photoelectron Spectroscopy , S, the analysis of O-containing coating or film surface was carried out by XPS). As a pre-treatment was subjected to the following processing. First, take out the negative electrode was disassembled, a lithium ion secondary battery, and washing and drying the negative electrode, to obtain a negative electrode to be analyzed. Washing was performed 3 times with DMC (dimethyl carbonate). Moreover, all the steps required to transport the dismantling of the cell to the negative electrode as analyzed in the analyzer, in Ar gas atmosphere, a negative electrode was carried out without exposure to the air. Following pretreatment battery A-8 to perform with the lithium ion secondary battery of the battery A-9 and the battery A-C3, the anode specimens obtained XPS analysis. As a device, using a ULVAC-PHI, Inc. PHI5000 VersaProbeII. X-ray source was monochromatic AlKα line (15kV, 10mA). Battery A-8 was measured by XPS, the negative electrode S of the battery A-9, the analysis result of the negative electrode coating O-containing coatings and battery A-C3 shown in FIGS. 40 to 44. Specifically, FIG. 40 is a result of analysis of the carbon element, Figure 41 is an analysis result of elemental fluorine, FIG 42 is an analysis result of the nitrogen element, Figure 43 is the analysis results for oxygen element , and the FIG. 44 is an analytical result for elemental sulfur.

The electrolytic solution in the lithium ion secondary battery of the battery A-8, and an electrolyte in a lithium ion secondary battery of the battery A-9 include elemental sulfur (S), oxygen element and nitrogen element (N) into a salt. This electrolytic solution in the lithium ion secondary battery of the battery A-C3 respect does not include these salts. Further, the electrolytic solution in the battery A-8, the lithium ion secondary battery of the battery A-9 and the battery A-C3 are both containing fluorine element (F) carbon element (C) and oxygen element (O) in the salt .

As shown in FIGS. 40 to 44, the negative electrode S of the battery A-8, O-containing coating and the negative electrode S of the battery A-9, the result of analysis of the O-containing coating, a peak indicating the presence of S (FIG. 44) and N peak indicating the presence of a (FIG. 42) was observed. In other words, the negative electrode S, a negative electrode S, O-containing film of O-containing coatings and battery A-9 of the battery A-8 contained S and N. However, these peaks in the analysis result of the negative electrode coating of the battery A-C3 was not confirmed. In other words, the negative electrode coating of the battery A-C3 for both S and N, did not include the amount of more than the detection limit. The peak indicated F, C, and the presence of O, the battery A-8, was observed in the analysis results of all of the negative electrode S, O-containing coating and the negative electrode film of the battery A-C3 batteries A-9. That is, the battery A-8, the negative electrode S of the battery A-9, both the negative electrode film of O-containing coatings and battery A-C3 contained F, C, and O.

Each of these elements is also a component derived from the electrolyte. In particular S, O and F is a component contained in the metal salt of the electrolyte, in particular a component contained in the chemical structure of the anion of the metal salt. Therefore, from these results, each negative electrode S, the O-containing coating and a negative electrode coating it can be seen that contain components derived from the chemical structure of the anion of the metal salt (i.e. supporting salt).

The analysis results of elemental sulfur (S) as shown in FIG. 44, were analyzed in more detail. For analysis of cell A-8 and the battery A-9, were peak separation using a Gaussian / Lorentzian mixed function. The analysis results of the batteries A-8 shown in FIG. 45 shows the analysis results of the batteries A-9 in FIG. 46.

As shown in FIGS. 45 and 46, the negative electrode S of the battery A-8 and the battery A-9, the result of analysis of the O-containing coating, a relatively large peak (wave) was observed in the vicinity of 165 ~ 175 eV. Then, as shown in FIGS. 45 and 46, the peak near the 170 eV (waveform) were separated into four peaks. One of which is a peak near 170eV indicating the presence of SO 2 (S = O structure). This result, S, O-containing film formed on the negative electrode surface in a lithium ion secondary battery of the present invention can be said to have a S = O structure. Then, considering the results the results and the above XPS analysis, S, S contained in S = O structure of O-containing coating is presumed that it is S contained in the chemical structure of the anion of the metal salt or support salt.

(Negative electrode S, S element ratio O containing coating)
Anode above S, based on XPS analysis results of the O-containing coating, calculates the ratio of S elements during discharge of the negative electrode S, O-containing coating and the negative electrode film of the battery A-C3 battery A-8 and the battery A-9 did. Specifically, each of the negative electrode S, per O containing coatings and the negative electrode film were calculated S, N, F, C, the element ratio S when the sum of the peak intensities of O to 100%. The results are shown in Table 24.

Figure JPOXMLDOC01-appb-T000024

Negative film batteries A-C3 as described above did not contain S above the detection limit, the negative electrode S of the battery A-8, the negative electrode S of O-containing coatings and battery A-9, the O-containing coating S has been detected. Moreover, the negative electrode S, O containing coatings of the battery A-8 contained many S compared to the negative electrode S, O containing coatings of the battery A-9. The negative electrode S, O since S is not detected from the containing coating, a negative electrode S, S unavoidable impurities and other additives contained in the positive electrode active material contained in the O-containing coating of each battery cell A-C3 not derived from, it can be said that is derived from the metal salt in the electrolyte solution.

It battery negative electrode S of A-8, S elemental ratio in O-containing coating is 10.4 atomic%, a negative electrode S, S elemental ratio in O-containing film is 3.7 atomic% of the battery A-9 from the non-aqueous electrolyte secondary battery of the present invention, the negative electrode S, S elemental ratio in O-containing coating is 2.0 atom% or more, preferably 2.5 atomic% or more, more preferably 3.0 and at atomic% or more, further preferably 3.5 atomic% or more. Note that the element ratio of S (atomic%), refers to S, as described above, N, F, C, and peak intensity ratio of S when the sum of the peak intensities of O is 100%. The upper limit of the element ratio of S is not particularly defined, if say by force, it is equal to or less than 25 atomic%.

(Negative electrode S, the thickness of the O-containing coating)
For lithium-ion secondary battery of the battery A-8, which was discharged state voltage 3.0V after repeated 100 cycles of charge and discharge, and were the charge state of the voltage 4.1V after repeated 100 cycles of charge and discharge prepare things, to obtain a negative electrode specimen to be analyzed before processing the same method as the above XPS analysis. The resulting negative electrode specimen FIB (focused ion beam: Focused Ion Beam) by processing, to obtain a STEM analytical specimen thickness of about 100 nm. Incidentally, as a pretreatment for FIB processing, a negative electrode was deposited Pt. The above process was carried out without exposing the negative electrode to the atmosphere.

Each STEM analytical sample EDX (energy dispersive X-ray analysis: Energy Dispersive X-ray spectroscopy) device is included STEM (scanning transmission electron microscope: Scanning Transmission Electron Microscope) were analyzed by. The results are shown in FIGS. 47 to 50. These, FIG. 47 BF (bright field: Bright-field) is -STEM images, FIGS. 48 to 50 is an element distribution image by SETM-EDX of the same observation area as Figure 47. Furthermore, Figure 48 is an analysis result of the C, Figure 49 is an analysis result of O, FIG. 50 is an analytical result for S. Incidentally, FIGS. 48 to 50 is an analysis result of the negative electrode in a lithium ion secondary battery in the discharged state.

As shown in FIG. 47, the upper left portion of the STEM image is present the black parts. Portions of the black is derived from Pt deposited by pretreatment FIB processing. In each STEM image, portion of the upper side than the portion derived from the Pt (referred to as Pt unit) may be considered contaminated portion after Pt deposition. Thus, in FIGS. 48 to 50 were examined only portions located below the Pt unit.

As shown in FIG. 48, the lower side of the Pt unit, C is had a layered. This is considered that it is a layered structure of the negative electrode active material serving as graphite. In Figure 49, O is the portion corresponding to the outer periphery and the interlayer of the graphite. Also, S is located in a portion corresponding to the outer periphery and the interlayer of the graphite in FIG. 50. These results, the negative electrode S, O-containing coating containing S and O, such as S = O structure is presumed to have been formed on the surface and between layers of the graphite.

Negative S formed on the surface of the graphite, randomly selected 10 sites of O-containing coating, a negative electrode S, the thickness of the O-containing coating was measured to calculate the average value of the measured values. Also analyzed in the same manner for the negative electrode in a lithium ion secondary battery in a charged state, based on each analysis result, the negative electrode S are formed on the surface of graphite was calculated an average value of the thickness of the O-containing coating. The results are shown in Table 25.

Figure JPOXMLDOC01-appb-T000025

As shown in Table 25, the negative electrode S, the thickness of the O-containing coating is increased after the charging. From this result, the negative electrode S, a fixing portion to O-containing coating present stable for charging and discharging, presumably adsorbed portion to increase or decrease along with the charging and discharging are present. Then, the presence of suction portion, the negative electrode S, O-containing coating is estimated to have a thickness upon charging and discharging increases or decreases.

(Analysis of the positive electrode coating)
For lithium-ion secondary battery of the battery A-8, which was discharged state voltage 3.0V after repeated 3 cycles of charge and discharge, which was the state of charge of voltage 4.1V after repeated 3 cycles of charge and discharge, those in discharge state voltage 3.0V after repeated 100 cycles of charge and discharge, which was the state of charge of voltage 4.1V after repeated 100 cycles of charge and discharge were prepared four. For four lithium-ion secondary battery of the battery A-8, using the same method as respectively described above, to obtain a positive electrode to be analyzed. And the resulting each positive electrode of XPS analysis. The results are shown in FIGS. 51 and 52. Note that FIG. 51 is an analysis result of the oxygen element, FIG. 52 is an analytical result for elemental sulfur.

As shown in FIGS. 51 and 52, the positive electrode S of the battery A-8, O-containing coating also seen to contain S and O. Further, since the observed peak near 170eV in FIG. 52, from the positive electrode S of the battery A-8, the negative electrode S of O-containing coating also battery A-8, the electrolytic solution of the invention, as O-containing coating found to have a S = O structure.

Meanwhile, as shown in FIG. 51, the height of the peaks present in the vicinity of 529eV is reduced after cycles elapse. This peak is considered to indicate the presence of O derived from the positive electrode active material, specifically, detecting photoelectrons excited by O atoms of the positive electrode active material in the XPS analysis through S, the O-containing coating It is considered to have been. Since this peak is reduced after the lapse of the cycle, S formed on the surface of the positive electrode, the thickness of the O-containing coating is considered to have increased with cycles elapse.

Further, as shown in FIGS. 51 and 52, the positive electrode S, O and S in the O-containing coating was reduced during charging increases during discharge. This result, O and S are considered positive S, and out of the O-containing coating in accordance with the charging and discharging. And this reason, charge and discharge time of the positive electrode S, or the concentration of S and O in the O-containing coating is increased or decreased, or the presence of the suction unit is also negative S, O-containing coating as well as positive S, the O-containing coating thickness is presumed to increase or decrease by.

Further, the battery A-11 positive S also lithium ion secondary battery, O-containing coating and the anode S, O-containing coatings XPS analysis.

The lithium ion secondary battery of the battery A-11, 25 ℃, the voltage range 3.0 V ~ 4.1 V, the CC charge and discharge was repeated 500 cycles at a rate 1C. After 500 cycles, the discharge state of 3.0 V, and a positive electrode S in the charged state of 4.0V, was measured XPS spectra of O-containing coating. The negative electrode S of the discharge state of 3.0V before the cycle test (i.e. after the initial charge and discharge), O-containing coating, and the negative electrode S of the discharge state of 3.0V after 500 cycles, the O-containing coating, by XPS perform elemental analysis was calculated the negative electrode S, S element ratio included in the O-containing coating. The positive electrode S of the battery A-11 as measured by XPS, the results of an analysis of O-containing coating is shown in FIGS. 53 and 54. Specifically, FIG. 53 is an analysis result of the elemental sulfur, FIG. 54 is an analytical result for oxygen element. Also shows S element ratio of the negative electrode coating as measured by XPS (atomic%) in Table 26. Incidentally, S elemental ratio was calculated similarly to the "negative S, S element ratio O containing coating" above.

As shown in FIGS. 53 and 54, the positive electrode S in the lithium ion secondary battery of the battery A-11, also from O containing coating, a peak indicating the existence of a peak and O indicates the presence of S is detected. Moreover, both the peak of the peak and O of S was reduced when increasing during the discharge charging. From this result, the positive electrode S, O-containing coating has an S = O structure, the positive electrode S, O and S in the O-containing coating is supported to be out of the positive electrode S, O-containing coating in accordance with the charge and discharge .

Figure JPOXMLDOC01-appb-T000026

Further, as shown in Table 26, the negative electrode S of the battery A-11, O-containing coatings, even after the initial charge and discharge, even after 500 cycles passed, contained 2.0 atomic% or more S. This result, the negative electrode S, O-containing coating in the non-aqueous electrolyte secondary battery of the present invention, even after the cycle has elapsed even before cycle elapses seen to contain 2.0 atomic percent or more of S.

Battery A-11 ~ cell A-14 and battery A-C4, the lithium ion secondary battery of the battery A-C5, performs high-temperature storage test of storage for one week at 60 ° C., each battery after the high temperature storage test A- 11 positive electrode S of ~ a-14, O-containing coating and the anode S, O-containing coating, and were analyzed positive film and negative electrode film of each of the batteries a-C4, a-C5. Before starting the high temperature storage test, CC-CV was charged at a rate 0.33C from 3.0V down to 4.1 V. The charging capacity at this time as a reference (SOC 100), after a 20% fraction with respect to the reference was adjusted to SOC80 by CC discharge was initiated high temperature storage test. And CC-CV discharge to 3.0V at 1C after high-temperature storage test. Then, the positive electrode S after discharge, O-containing coating and the anode S, the XPS spectrum of the O-containing coating as well as the positive electrode film and negative electrode film were measured. Positive S, O containing coatings of the battery A-11 - Battery A-14 as measured by XPS, and shows the result of analysis of the positive electrode coating battery A-C4 and battery A-C5 in FIG. 55 to FIG 58. Moreover, the negative electrode S, O containing coatings of the battery A-11 - Battery A-14 as measured by XPS, and shows the result of analysis of the negative electrode coating of the battery A-C4 and battery A-C5 in FIG. 59 to FIG 62.

Specifically, FIG. 55 is an analytical result for elemental sulfur of the positive electrode coating of the battery A-11, the positive electrode S of the battery A-12, O-containing coatings and battery A-C4. Figure 56 is an analytical result for elemental sulfur of the positive electrode coating cell A-13, the positive electrode S, O containing coatings and battery A-C5 battery A-14. Figure 57 is an analytical result for the oxygen element of the positive electrode coating of the battery A-11, the positive electrode S of the battery A-12, O-containing coatings and battery A-C4. Figure 58 is an analytical result for the oxygen element of the positive electrode coating cell A-13, the positive electrode S, O containing coatings and battery A-C5 battery A-14. Further, FIG. 59 is an analytical result for the sulfur element of the anode coating of the battery A-11, the negative electrode S of the battery A-12, O-containing coatings and battery A-C4. Figure 60 is an analytical result for the sulfur element of the anode coating of the battery A-13, the negative electrode S of the battery A-14, O-containing coatings and battery A-C5. Figure 61 is an analytical result for the oxygen element of the anode coating of the battery A-11, the negative electrode S of the battery A-12, O-containing coatings and battery A-C4. Figure 62 is an analytical result for the oxygen element of the anode coating of the battery A-13, the negative electrode S of the battery A-14, O-containing coatings and battery A-C5.

As shown in FIGS. 55 and 56, a lithium ion secondary battery of the battery A-C4 and battery A-C5 using conventional electrolytic solution for free of S in the positive electrode film, the electrolytic solution of the present invention battery a-11 ~ lithium ion secondary battery of the battery a-14 with contained S positive S, the O-containing coating. Further, as shown in FIGS. 57 and 58, a lithium ion secondary battery of the battery A-11 ~ cell A-14 are all contained O positive S, the O-containing coating. Furthermore, as shown in FIGS. 55 and 56, the presence of the positive electrode S in the lithium ion secondary battery of the battery A-11 ~ cell A-14, from the O-containing coating, either, SO 2 (S = O structure) peak near 170eV showing a has been detected. These results, in a lithium ion secondary battery of the present invention, when using AN as the organic solvent for the electrolytic solution also, even when using a DMC, stable positive S containing the S and O, it can be seen that O-containing film is formed. Further, this positive electrode S, O-containing coatings since it is not affected by the type of the negative electrode binder, a positive electrode S, O in O-containing coating is considered not intended to be derived from CMC. Furthermore, as shown in FIGS. 57 and 58, in the case of using DMC as the organic solvent for the electrolytic solution, in the vicinity of 530 eV, O peak derived from the positive electrode active material was detected. Therefore, in the case of using DMC as the organic solvent for the electrolytic solution, positive electrode S, the thickness of the O-containing coating is considered to be thinner than the case of using the AN.

Similarly, from FIG. 59 to FIG. 62, a lithium ion secondary battery of the battery A-11 - Battery A-14 contains S and O in the negative electrode S, O-containing coating, form a S = O structure and the electrolyte it can be seen that derived from the liquid. And this negative electrode S, O-containing coating is found to be formed in the case of using a DMC even when using AN as the organic solvent for the electrolytic solution.

Battery A-11, the lithium ion secondary battery of the battery A-12 and battery A-C4, each negative electrode S after the high temperature storage test and discharge described above, the XPS spectrum of the O-containing coating as well as the negative film is measured, the battery A -11 was calculated the ratio of S elements during discharge of the negative electrode coating of the negative electrode S, O containing coatings and battery a-C4 battery a-12. Specifically, each of the negative electrode S, per O containing coatings or the negative electrode coating was calculated S, N, F, C, the element ratio S when the sum of the peak intensities of O to 100%. The results are shown in Table 27.

Figure JPOXMLDOC01-appb-T000027

As shown in Table 27, although the negative film batteries A-C4 did not contain S above the detection limit, S is detected from the negative electrode S, O containing coatings of the battery A-11 and battery A-12 It was. Moreover, the negative electrode S, O containing coatings of the battery A-12 contained the negative electrode S, a number of S compared to O-containing coating of the battery A-11. Further, from these results, it can be seen that the S element ratio also in the negative electrode S, O containing coatings after high-temperature storage is 2.0 atomic percent or more.

(Evaluation Example A-20: cycle durability of the battery)
Battery A-11, cell A-12, for each of the lithium ion secondary battery of the battery A-15 and the battery A-C4, room temperature, the CC charge and discharge in a range of 3.0V ~ 4.1V (vs.Li reference) repeated, the discharge capacity at the time of initial charge-discharge was 100 cycles when the discharge capacity, and the discharge capacity at 500 cycles was measured. Then, the capacity of each lithium ion secondary battery at the time of initial charge-discharge was 100%, was calculated 100 cycles and at 500 the capacity retention rate of each of the lithium ion secondary battery at the time of cycles (%). The results are shown in Table 28.

Figure JPOXMLDOC01-appb-T000028

As shown in Table 28, the battery A-11, a lithium ion secondary battery of the battery A-12 and battery A-15, despite not containing EC as a SEI of the material, cell A-C4 including EC It showed a lithium ion secondary battery equivalent capacitance retention rate. This is the positive and negative electrodes in a lithium ion secondary battery of the respective batteries, S derived from the electrolytic solution of the present invention is believed to be because the O-containing coating is present. Then, the lithium ion secondary battery of the battery A-11, in particular shows a very high capacity retention rate at 500 cycles elapsed, was particularly excellent in durability. From this result, when selecting a DMC as organic solvents, as compared with the case of selecting the AN, it can be said that the more durable is improved.

Battery A-11, the lithium ion secondary battery of the battery A-12 and battery A-C4, were subjected to a high-temperature storage test of storage for one week at 60 ° C.. Before starting the high temperature storage test, CC-CV (constant-current constant voltage) was charged to 4.1V from 3.0 V. The charging capacity at this time as a reference (SOC 100), after a 20% fraction with respect to the reference was adjusted to SOC80 by CC discharge was initiated high temperature storage test. And CC-CV discharge to 3.0V at 1C after high-temperature storage test. From the ratio of the SOC80 capacity before the discharge capacity and the storage of this time, was calculated remaining capacity by the following equation. The results are shown in Table 29.

SOC = 100 × (CC-CV discharge capacity after storage) / (SOC 80 capacity before storage)

Figure JPOXMLDOC01-appb-T000029

Remaining capacity of the nonaqueous electrolyte secondary battery of the battery A-11 and battery A-12 is larger than the remaining capacity of the nonaqueous electrolyte secondary battery of the battery A-C4. The results, S formed from to the positive electrode and the negative electrode to the electrolytic solution of the present invention, O-containing coating, it can be said that contributes to the remaining capacity increase.

(Evaluation Example A-21: Surface analysis of Al current collector)
The lithium ion secondary battery of the battery A-8 and the battery A-9, a voltage range 3V ~ 4.2 V, the charging and discharging repeatedly 100 times at a rate 1C, disassembled after charging and discharging 100 times, the positive electrode current collector removed aluminum foil each is to wash the surface of the aluminum foil with dimethyl carbonate.

The surface of the aluminum foil of the lithium ion secondary battery of the battery after washing A-8 and the battery A-9, was subjected to a surface analysis by while etching with Ar sputtering X-ray photoelectron spectroscopy (XPS). Surface analysis of aluminum foil after the charge and discharge of the lithium ion secondary battery of the battery A-8 and the battery A-9 are shown in FIGS. 63 and 64.

Comparing FIGS. 63 and 64, is substantially the same both surface analysis results of the aluminum foil is positive electrode current collector after the charge and discharge of the lithium ion secondary battery of the battery A-8 and the battery A-9, the following can be said. The surface of the aluminum foil, the chemical state of Al in the outermost surface was AlF 3. When the aluminum foil in the depth direction gradually etched, Al, O, F peak was detected. In the portion where the aluminum foil began to etch once to three times from the surface, it was found that the chemical state of the Al is a composite state of Al-F bonds and Al-O bonds. Further etched to continue the four etching O from where it (about 25nm Depth in terms of SiO 2), the peak of F disappears, the peak of Al alone was observed. Incidentally, in the XPS measurement data, AlF 3 is observed in the Al peak position 76.3EV, pure Al is observed on Al peak position 73EV, the composite state of AlF bond and Al-O bond, Al peak position It is observed to 74eV ~ 76.3eV. Dashed line shown in FIG. 63 and FIG. 64, AlF 3, Al, shows a Al 2 O 3 each representative peak position.

From the above results, the surface of the aluminum foil of the lithium ion secondary battery after the charge and discharge of the present invention is about 25nm thick in the depth direction, a layer of AlF binding (presumably AlF 3) , it was confirmed that the mixed layers of AlF binding (presumably Al 2 O 3) and Al-O bonds (AlF 3 is is presumed) is formed.

That is, in the lithium ion secondary battery of the present invention using the aluminum foil on the cathode current collector, the outermost surface of the aluminum foil even after charge and discharge with the electrolyte present invention and AlF bond (AlF 3 is it has been found that passivation film made deduced) is formed.

From the results of evaluation Example A-21, an electrolytic solution of the present invention, in the lithium ion secondary battery that combines the positive electrode collector made of aluminum or an aluminum alloy, the surface of the positive electrode current collector by charging and discharging the non kinetics film is formed, yet, Al elution from even the positive electrode current collector in a high potential state was found to be inhibited.

(Evaluation Example A-22: positive electrode S, O containing coatings analysis)
TOF-SIMS: using (Time-of-Flight Secondary Ion Mass Spectrometry time-of-flight secondary ion mass spectrometry), and analyzed the structure information of each molecule included positive S of the battery A-11, the O-containing coating .

After 3 cycles of charge and discharge at 25 ° C. The non-aqueous electrolyte secondary battery of the battery A-11, was taken out of the positive electrode was disassembled at 3V discharge state. Apart from this, after 500 cycles of charge and discharge at 25 ° C. The non-aqueous electrolyte secondary battery of the battery A-11, was taken out of the positive electrode was disassembled at 3V discharge state. Further alternatively, after 3 cycles of charge and discharge at 25 ° C. The non-aqueous electrolyte secondary battery of the battery A-11, and left one month at 60 ° C., was taken out of the positive electrode was disassembled at 3V discharge state. Each positive electrode was washed three times with DMC, it was obtained a positive electrode for analysis. Incidentally, the positive electrode S is in the positive, O-containing film is formed, structural information of the molecule that contains the positive electrode S, the O-containing film has been analyzed in the following analysis.

Each positive electrode for analysis were analyzed by TOF-SIMS. The time-of-flight secondary ion mass spectrometer as the mass spectrometer to measure the positive secondary ions and negative secondary ions. Using Bi as a primary ion source, a primary acceleration voltage was 25 kV. The sputter ion source with Ar-GCIB (Ar1500). The measurement results are shown in Table 30 through Table 32. Here, the positive ion intensity of each fragment in Table 31 (relative value) is a relative value to 100% the sum of the positive ion intensities of all of the fragments that have been detected. Similarly, the negative ionic strength of each fragment as described in Table 32 (relative value) is a relative value taken as 100% of the sum of negative ionic strength of all fragments detected.

Figure JPOXMLDOC01-appb-T000030

Figure JPOXMLDOC01-appb-T000031

Figure JPOXMLDOC01-appb-T000032

Fragment is estimated to solvent from the electrolytic solution as shown in Table 30 was only C 3 H 3, and C 4 H 3 was detected as positive secondary ions. Also, fragments presumed from salt electrolyte is detected primarily as a negative secondary ions, the ionic strength is larger than the fragments from the solvent mentioned above. Further, a fragment containing Li is mainly detected as a positive secondary ion, the ionic strength of the fragment containing Li is a significant percentage among the positive secondary ions and negative secondary ions.

From the above, S, the main component of the O-containing coating of the present invention is a component derived from a metal salt contained in the electrolytic solution, and speculated that S of the present invention, the O-containing coating contains many Li It is.

Furthermore, as shown in Table 30, the fragment is estimated to be derived from the salt has also been detected SNO 2, SFO 2, S 2 F 2 NO 4 like. We both have S = O structure, and N and F is a structure binding to S. That, S of the present invention, the O-containing coating, S is O and not only double bond, SNO 2, SFO 2, as such S 2 F 2 NO 4, combined with other elements structures a can take also. Therefore, S, O-containing coating of the present invention may have at least S = O structure, it can be said that S contained in the S = O structure may be bonded to other element. Incidentally, of course notwithstanding et, S of the present invention, O-containing coatings may contain S and O do not take the S = O structure.

Incidentally, for example, an electrolytic solution of a conventional type which is introduced in the above-mentioned JP 2013-145732, that is, in the conventional electrolytic solution containing a LiFSA as LiPF 6 and an additive as EC and metal salts of organic solvents, S is taken into decomposition products of the organic solvent. Therefore S is, C p H q S at the negative electrode coating and / or positive film in considered (p, q are each independently integers) exist as such ions. In contrast, as shown in Table 30 to Table 32, the fragment containing the S to S, is detected from the O-containing coating of the present invention, C p H q S principal fragments reflecting the anion structure rather than a fragment it is. This also, S of the present invention, O-containing coatings are different, it is apparent to fundamentally the film formed on the conventional non-aqueous electrolyte secondary battery.

(Battery A1)
The half cell using the electrolytic solution E8 was prepared as follows.
Diameter 13.82Mm, area 1.5 cm 2, and a working electrode of aluminum foil with a thickness of 20 [mu] m (JIS A1000 No. system), the counter electrode was a metal Li. Separator thickness 400μm of Whatman glass filter nonwoven fabric: Using part 1825-055.
Working electrode, counter electrode, accommodated to constitute a half cell the separator and the electrolyte of the battery case (Hohsen CR2032 type coin cell case, Ltd.). This was a half-cell of the battery A1.

(Battery A2)
Except for using the electrolyte E11, in the same manner as the half cell battery A1, to prepare a half cell of the battery A2.

(Battery A3)
Except for using the electrolyte E16, in the same manner as the half cell battery A1, to prepare a half cell of the battery A3.

(Battery A4)
Except for using the electrolyte E19, in the same manner as the half cell battery A1, to prepare a half cell of the battery A4.

(Battery A5)
Except for using the electrolyte E13, in the same manner as the half cell battery A1, to prepare a half cell of the battery A5.

(Battery AC1)
Except for using the electrolytic solution C5, in the same manner as the half cell battery A1, to prepare a half cell battery AC1.

(Battery AC2)
Except for using the batteries C6, as in the half-cell of the battery A1, to prepare a half cell battery AC2.

(Evaluation Example 23: cyclic voltammetry evaluation at the working electrode Al)
For the half-cell of the battery A1 ~ battery A4 and battery AC1, performs a 3.1V ~ 4.6V, cyclic voltammetry evaluation of 5 cycles under the conditions of 1mV / s, then, 3.1V ~ 5.1V, 1mV / cyclic voltammetry evaluation of 5 cycles were carried out under the conditions of s. A graph showing the relationship between potential and current response for half-cell batteries A1-cell A4 and cell AC1 shown in FIG. 65 to FIG 73.

In addition, the battery A2, for the half-cell of the battery A5 and battery AC2, 3.0V ~ 4.5V, under the conditions of 1mV / s, performs a cyclic voltammetry evaluation of the 10 cycles, then, 3.0V ~ 5.0V , under the conditions of 1mV / s, it was subjected to cyclic voltammetry evaluation of 10 cycles. Cell A2, the graph showing the relationship between potential and current response for half-cell of the battery A5 and battery AC2 shown in FIG. 74 to FIG 79.

From Figure 73, the half-cell batteries AC1, 2 even later cycles current flows toward 4.6V from 3.1 V, it can be seen that the current in accordance becomes a high potential is increased. Further, from FIGS. 78 and 79, also in the half-cell batteries AC2, 2 cycles after the current also flows toward 4.5V from 3.0 V, the current is increased in accordance becomes a high potential. This current is estimated to oxidation current of Al due to the aluminum working electrode was corroded.

On the other hand, from FIG. 65 to FIG. 72, two cycles after the half-cell batteries A1-cell A4 is seen that almost no current flows toward 4.6V from 3.1 V. Although in 4.3V or increase slightly the current due to the potential rise is observed, in accordance with repeated cycles, the amount of current decreases, towards the steady state. In particular, half-cell batteries A1 ~ cell A4 is a significant increase in current up to 5.1V which is a high potential is not observed, moreover, decrease the amount of current due to the repeated cycles was observed.

Further, from FIG. 74 to FIG. 77, also in the half-cell batteries A2 and cell A5, the second cycle or later it can be seen that almost no current flows toward 4.5V from 3.0 V. No particular almost the increase in current up to 4.5V in 3 subsequent cycles. Then, the half cell battery A5 is increased current since 4.5V to a high potential is observed, which is a small value much compared to the current value of the subsequent 4.5V in half cell battery AC2. The half-cell of the battery A2, substantially without the increase in current up to and beyond 4.5V leading to 5.0V, reduction in the amount of current due to the repeated cycles was observed.

From the results of cyclic voltammetry evaluated, even at a high potential condition exceeding 5V, electrolyte E8, corrosive to aluminum the electrolyte of the electrolytic solution E11, electrolyte E16 and the electrolyte E19 it can be said to be low. That is, the electrolyte solution of the electrolyte solution E8, electrolyte E11, electrolyte E16 and the electrolyte E19, compared batteries using aluminum or the like current collector, it can be said that a suitable electrolyte.

As the electrolytic solution of the present invention, specifically include the following electrolyte. Note that the following electrolyte, is also included as described above.

(Electrolytic solution A)
The electrolytic solution of the present invention were prepared as follows.
1,2-dimethoxyethane about 5mL with an organic solvent, were placed in a flask equipped with a stirrer and a thermometer. A stirrer conditions, to 1,2-dimethoxyethane in the flask, a lithium salt (CF 3 SO 2) 2 NLi the solution temperature was slowly added so as to keep the 40 ° C. or less, and dissolved. Since at the time of (CF 3 SO 2) were added 2 NLi about 13g (CF 3 SO 2) dissolved in 2 NLi stagnated temporarily put the flask in a thermostatic bath, the temperature of the solution in the flask and 50 ° C. so as heated, it was dissolved (CF 3 sO 2) 2 NLi . Since about 15g of (CF 3 SO 2) 2 NLi when added (CF 3 SO 2) dissolved in 2 NLi stagnated again, was added one drop of 1,2-dimethoxyethane pipetted, (CF 3 SO 2) 2 NLi were dissolved. Further (CF 3 SO 2) 2 NLi added slowly, plus the total amount of predetermined (CF 3 SO 2) 2 NLi. The resulting electrolytic solution was transferred to 20mL volumetric flask, and the volume was added 1,2-dimethoxyethane until 20mL. The obtained electrolyte is the volume 20 mL, this is contained in the electrolytic solution (CF 3 SO 2) 2 NLi was 18.38 g. This was an electrolytic solution A.(CF 3 SO 2) of 2 NLi concentration in the electrolytic solution A was 3.2 mol / L, density was 1.39 g / cm 3. Density was measured at 20 ° C..
The above preparation was performed in a glove box under an inert gas atmosphere.

(Electrolytic solution B)
In the electrolytic solution A and the same method, (CF 3 SO 2) concentration of 2 NLi is 2.8 mol / L, density of 1.36 g / cm 3, to produce an electrolyte B.

(Electrolyte C)
Acetonitrile approximately 5mL an organic solvent, were placed in a flask equipped with a stir bar. A stirrer conditions, to acetonitrile in the flask, a lithium salt (CF 3 SO 2) 2 NLi added slowly and dissolved. It was stirred overnight at plus predetermined (CF 3 SO 2) 2 NLi . The resulting electrolytic solution was transferred to 20mL volumetric flask, was added acetonitrile to a volume of 20mL. This was the electrolyte C. The above preparation was performed in a glove box under an inert gas atmosphere.

Electrolyte C is, (CF 3 SO 2) concentration of 2 NLi is 4.2 mol / L, a density of 1.52 g / cm 3.

(Electrolyte D)
In the electrolytic solution C and the same method, (CF 3 SO 2) concentration of 2 NLi is 3.0 mol / L, density of 1.31 g / cm 3, to produce an electrolyte solution D.

(Electrolyte E)
Except for using sulfolane as an organic solvent, the electrolytic solution C and the same method, (CF 3 SO 2) concentration of 2 NLi is 3.0 mol / L, density of 1.57 g / cm 3, electrolyte to produce a liquid E.

(Electrolyte F)
Except that dimethylsulfoxide was used as the organic solvent, the electrolytic solution C and the same method, (CF 3 SO 2) concentration of 2 NLi is 3.2 mol / L, density of 1.49 g / cm 3, to produce an electrolyte solution F.

(Electrolyte G)
As the lithium salt using (FSO 2) 2 NLi, except for using 1,2-dimethoxyethane as the organic solvent, the electrolytic solution C and the same method, (FSO 2) concentration of 2 NLi is 4.0 mol / L , and the density of 1.33 g / cm 3, to produce an electrolyte solution G.

(Electrolyte H)
In the same manner as the electrolyte solution G, (FSO 2) the concentration of 2 NLi was 3.6 mol / L, density of 1.29 g / cm 3, to produce an electrolyte H.

(Electrolyte I)
In the same manner as the electrolyte solution G, (FSO 2) the concentration of 2 NLi was 2.4 mol / L, density of 1.18 g / cm 3, to produce an electrolyte solution I.

(Electrolytic solution J)
Except that acetonitrile was used as the organic solvent, in the same manner as the electrolyte solution G, (FSO 2) concentration of 2 NLi is 5.0 mol / L, density of 1.40 g / cm 3, electrolyte J It was prepared.

(Electrolyte K)
In the electrolytic solution J the same way, (FSO 2) the concentration of 2 NLi was 4.5 mol / L, density of 1.34 g / cm 3, to produce an electrolyte solution K.

(Electrolytic solution L)
Dimethyl carbonate about 5mL an organic solvent, were placed in a flask equipped with a stir bar. A stirrer conditions, to dimethyl carbonate in the flask, a lithium salt (FSO 2) 2 NLi added slowly and dissolved.(FSO 2) was stirred overnight at was added 14.64g of 2 NLi in total amount. The resulting electrolytic solution was transferred to 20mL volumetric flask, and the volume was added dimethyl carbonate until 20mL. This was an electrolytic solution L. The above preparation was performed in a glove box under an inert gas atmosphere.
The concentration of (FSO 2) 2 NLi in the electrolytic solution L is 3.9 mol / L, the density of the electrolytic solution L was 1.44 g / cm 3.

(Electrolyte M)
In the electrolytic solution L and the same method, (FSO 2) the concentration of 2 NLi was 2.9 mol / L, density of 1.36 g / cm 3, to produce an electrolyte M.

(Electrolyte N)
Ethyl methyl carbonate about 5mL an organic solvent, were placed in a flask equipped with a stir bar. A stirrer conditions, to ethyl methyl carbonate in the flask, a lithium salt (FSO 2) 2 NLi added slowly and dissolved.(FSO 2) was stirred overnight at was added 12.81g of 2 NLi in total amount. The resulting electrolytic solution was transferred to 20mL volumetric flask, and the volume was added ethyl methyl carbonate until 20mL. This was an electrolytic solution N. The above preparation was performed in a glove box under an inert gas atmosphere.
The concentration of (FSO 2) 2 NLi in the electrolytic solution N is 3.4 mol / L, the density of the electrolyte solution N was 1.35 g / cm 3.

(Electrolyte O)
Diethyl carbonate about 5mL an organic solvent, were placed in a flask equipped with a stir bar. A stirrer conditions, to diethyl carbonate in the flask, a lithium salt (FSO 2) 2 NLi added slowly and dissolved.(FSO 2) was stirred overnight at was added 11.37g of 2 NLi in total amount. The resulting electrolytic solution was transferred to 20mL volumetric flask, and the volume was added diethyl carbonate until 20mL. This was an electrolytic solution O. The above preparation was performed in a glove box under an inert gas atmosphere.
The concentration of (FSO 2) 2 NLi in the electrolytic solution O is 3.0 mol / L, the density of the electrolyte solution O was 1.29 g / cm 3.

Table 33 shows a list of the electrolytic solution.

Figure JPOXMLDOC01-appb-T000033

(Example B-1)
To prepare a half cell having a positive electrode (working electrode) and the electrolyte solution, it was carried out cyclic voltammetry (CV) evaluated for this.

The positive electrode is composed of a positive electrode active material layer, a current collector coated with the positive electrode active material layer. The positive electrode active material layer includes a positive active material, a binder, and a conductive additive. The positive electrode active material is composed of LiMn 2 O 4. Binder consists of polyvinylidene fluoride (PVDF). Conductive additive consists of acetylene black (AB). The current collector made of an aluminum foil having a thickness of 20 [mu] m. When the positive electrode active material layer is 100 parts by mass, the content weight ratio of the positive electrode active material, a binder and a conductive aid, 94: 3: 3.

To produce a positive electrode, a LiMn 2 O 4, PVDF and AB were mixed so that the mass ratio described above, and a solvent as the N- methyl-2-pyrrolidone (NMP) was added a paste-like positive electrode material to. A paste-like positive electrode material is coated with a doctor blade on the surface of the current collector, to form a positive electrode active material layer. The positive electrode active material layer, and dried at 80 ° C. 20 minutes was removed by volatilizing the NMP. The aluminum foil to form a positive electrode active material layer on the surface, b - Rupuresu machine compressed using, was strongly adhered bond the aluminum foil and the positive electrode active material layer. 6 hours conjugate at 120 ° C., by heating in a vacuum drier, cut into a predetermined shape to obtain a positive electrode.

As the electrolytic solution in Example B-1, using the above electrolyte E8.

Using the above positive electrode (working electrode) and the electrolyte was fabricated half cell. A counter electrode is made of a metal lithium. The separator consists of a glass filter nonwoven.

(Example B-2)
As the electrolytic solution of Example B-2, using the above electrolytic solution E4. Other points of half cell of Example B-2, the same as in Example B-1.

(Example B-3)
As the electrolytic solution of Example B-3, using the above electrolyte E11. Other points of half cell of Example B-3, the same as in Example B-1.

(Comparative Example B-1)
As the electrolytic solution of Comparative Example B-1, using the above electrolyte solution C5. Other points of half cell of Example B-3, the same as in Example B-1.

(Evaluation Example B-1: CV evaluation)
About half cell in Example B-1, cyclic voltammetry - was (CV) evaluation test. The evaluation conditions, sweep rate 0.1mV / s, and the sweep range 3.1V ~ 4.6V (vs Li), charging, was repeated two cycles of discharge.

The results of CV measurements are shown in FIG. 80. The horizontal axis represents the potential of the working electrode (vs.Li/Li +), the vertical axis represents the current generated by oxidation-reduction. As shown in FIG. 80, the oxidation peak near 4.4 V, to check the reduction peak near 3.8 V, it was found that has occurred reversible electrochemical reactions. Therefore, in the nonaqueous secondary battery including the above positive electrode and the electrolyte solution was found to reversibly electrochemical reaction takes place.

(Evaluation Example B-2: charge-discharge characteristics)
Example B-1, Example B-2, the half cell of Example B-3 and Comparative Example B-1, 3V ~ 4.4V, 0.1C (1C is fully charged the battery in one hour at a constant current , or an electric current value necessary to discharge.) at performs CC discharge, creating the charge-discharge curve. The measurement results are shown in Figure 81.

Therefore, half cell of Example B-1, B-2 using the electrolytic solution of the present invention, found that the comparative Example using a general electrolyte B-1 and not inferior charge-discharge capacity can be obtained It was. Furthermore, Example B-3 is Example B-1, the charge capacity and the discharge capacity is larger than that in Example B-2 and Comparative Example B-1. Therefore, the embodiment B-3, the reversible capacity was increased. The reason is not clear, the linear carbonate-based high-concentration electrolyte is estimated that increasing available capacity by reducing the initial irreversible capacity.

(Example C-1)
Example C-1 is a half-cell comprising a working electrode and (positive electrode) and counter electrode (negative electrode) and an electrolytic solution.

The positive electrode as working electrode consists of a cathode active material layer, a current collector coated with the positive electrode active material layer. The positive electrode active material layer includes a positive active material, a binder, and a conductive additive. The positive electrode active material is a conductive carbon from LiFePO 4 with 10% and olivine structure. Binder consists of polyvinylidene fluoride (PVDF). Conductive additive consists of acetylene black (AB). The current collector made of an aluminum foil having a thickness of 20 [mu] m. When the positive electrode active material layer is 100 parts by mass, the content weight ratio of the positive electrode active material, a binder and a conductive aid, 90: 5: 5.

To produce a positive electrode, a mixture of LiFePO 4, PVDF and AB to be the mass ratio described above, a paste-like positive electrode material by adding a solvent as the N- methyl-2-pyrrolidone (NMP). A paste-like positive electrode material is coated with a doctor blade on the surface of the current collector, to form a positive electrode active material layer. The positive electrode active material layer, and dried at 80 ° C. 20 minutes was removed by volatilizing the NMP. The aluminum foil to form a positive electrode active material layer on the surface, b - Rupuresu machine compressed using, was strongly adhered bond the aluminum foil and the positive electrode active material layer. 6 hours conjugate at 120 ° C., by heating in a vacuum drier, cut into a predetermined shape to obtain a positive electrode.

As the electrolytic solution of Example C-1, using the above electrolyte E8.

Using the above positive electrode (working electrode) and the electrolyte was fabricated half cell. A counter electrode is made of a metal lithium. The separator consists of a glass filter (GE Healthcare Japan Corporation, thickness 400μm).

(Example C-2)
Half cell of Example C-2 as an electrolytic solution, and using the above electrolyte E11. Other configurations are the same as in Example C-1.

(Example C-3)
Half cell of Example C-3 as an electrolyte, and using the above electrolyte E13. Other configurations are the same as in Example C-1.

(Comparative Example C-1)
Half cell of Comparative Example C-1, as the electrolytic solution, and using the above electrolyte solution C5. Other configurations are the same as in Example C-1.

(Comparative Example C-2)
Half cell of Comparative Example C-2 as an electrolytic solution, and using the above electrolyte C6. Other configurations are the same as in Example C-1.

(Evaluation Example C-1: Rate Capacity Evaluation 1)
Example respect C-1 and Comparative Example C-1 of the half-cell, 4 at a rate (. Represents a current value required for the 1C to completely charge, or discharge of the battery in one hour at a constant current) 0.1 C. after constant current charge was performed until 2V (vs Li), carried 0.1C, 1C, 5C, the discharge at 10C rate to 2V, to measure the capacity (discharge capacity) at the respective rate. For Example C-1 and Comparative Example C-1, shows discharge curves at each rate Figure 82, Figure 83. And calculating a ratio of the discharge capacity at 5C and 10C for 0.1C discharge capacity (rate capacity characteristics). The results are shown in Table 34.

Figure JPOXMLDOC01-appb-T000034

Figure 82, as shown in FIG. 83, and Table 34, half cell of Example C-1 of the present invention, comparative example compared to C-1 of the half-cell, and decrease in capacity when a higher rate is suppressed cage, showed excellent rate capacity characteristics. Secondary battery using the electrolytic solution of the present invention have been found to exhibit excellent rate capacity characteristics.

(Evaluation Example C-2: Charge and Discharge Test)
A charge-discharge test was performed on half cell of Example C-2. Charge and discharge conditions, 0.1 C, a constant current, 2.5V-4.0V (vs Li). Charging and discharging was repeated 5 times. The charge-discharge curves shown in FIG. 84.
As shown in FIG. 84, in the half cell of Example C-2, it was confirmed that reversible charge and discharge are repeated.

(Evaluation Example C-3: Rate Capacity Evaluation 2)
To half cell of Example C-2, were repeated charging and discharging at a constant current in the range of 2.5 ~ 4.0V. To measure the discharge capacity in each cycle of charging and discharging. The rate of charging and discharging every three cycles was varied as follows.
0.1 C, 3 cycles → 0.2 C, 3 cycles → 0.5 C, 3 cycles → 1C, 3 cycles → 2C, 3 cycles → 5C, 3 cycles → 0.1 C, discharge rate capacity of each 3 Cycles measured, as shown in FIG. 85. Further, in the room temperature rate capacity test, 0.1 C, of ​​the three cycles in 5C, showing the discharge capacity of each 2 cycle in Table 35.

Figure JPOXMLDOC01-appb-T000035

As shown in Figure 85 and Table 35, Example C-2, C-3, compared to Comparative Example C-1, C-2, the discharge rate capacity was high. Especially for the discharge rate capacity upon 0.5 C ~ 5C rate, Example C-2, C-3, compared to Comparative Example C-1, C-2, was significantly higher. In Example C-2, C-3, the Example C-2 was higher rate capacity as compared with Example C-3.

(Evaluation Example C-4: Rate Capacity Evaluation at low temperatures)
To half cell of Example C-1 and Comparative Example C-1, under -20 ° C. environment after the constant current charging until 4.2 V (vs Li) at 0.1C rate, 0.05 C, 0 It was discharged to 2V at .5C rate, to measure the discharge capacity and charge capacity at each rate. The charge and discharge curves at each rate of half cell of Example C-1 shown in FIG. 86, showing a charge-discharge curve for each rate of half-cell of Comparative Example C-1 in Figure 87. In Examples C-1 and Comparative Example C-1 of the half-cell of 0.05 C, a discharge capacity at 0.5C rate, and the ratio of discharge capacity at 0.5C to the discharge capacity at 0.05 C (rate capacity characteristics) shown in Table 36. The proportion of the charge capacity at 0.5C to the charge capacity of Example C-1 and Comparative Example C-1 of the half-cell of 0.05 C, the charge capacity at 0.5C rate, and at 0.05 C (rate capacity characteristics) It is shown in Table 37.

Figure JPOXMLDOC01-appb-T000036

Figure JPOXMLDOC01-appb-T000037

Table 36, as shown in Table 37, Example C-1 as compared with Comparative Example C-1, the charging, discharging both rate capacity characteristics (0.5 C / 0.05 C capacity) is high. Figure 86, as shown in FIG. 87, as compared with Comparative Example C-1 Example C-1, Comparative Example C-1, for example, the charging curve in 50 mAh / g point potential and (closed circuit voltage) Discharge large difference between the curve of the potential (closed circuit voltage), this difference is particularly become noticeable during the high-rate tests, such as 1 / 2C. In contrast, in Example C-1, as compared with Comparative Example C-1, a potential difference is very small. That is, Example C-1 is said to polarization to Comparative Example C-1 is small.

(Battery D-1)
The working electrode is platinum (Pt), the counter electrode was lithium metal (Li). The separator was a glass filter non-woven fabric.
The above electrolytic solution E1, the working electrode, using an electrolytic solution and the separator was fabricated half-cell of the battery D-1.

(Battery D-2)
Except for using an electrolytic solution E4 as an electrolytic solution, in the same manner as in the battery D-1, to produce a half cell of the battery D-2.

(Battery D-3)
To prepare a half cell of the battery D-3 in the following manner.
Working electrode, was prepared as follows.
LiNi 0.5 Mn 1.5 O 4 89 parts by weight of an active material, and were mixed polyvinylidene fluoride 11 parts by weight as a binder. The mixture is dispersed in an appropriate amount of N- methyl-2-pyrrolidone to prepare a slurry. I was preparing a copper foil with a thickness of 20μm as the current collector. The surface of the copper foil, using a doctor blade and coating the slurry in a film form. The slurry is dried copper foil coated N- methyl-2-pyrrolidone was removed, after which the copper foil was pressed to obtain a conjugate. The resulting conjugate 120 ° C. in a vacuum dryer, and dried by heating for 6 hours to obtain copper foil in which an active material layer was formed. This was a working electrode. Here, the mass of the active material per copper foil 1 cm 2 was 6.3 mg.
The counter electrode was lithium metal. Working electrode, counter electrode, a separator and an electrolyte E4 made of glass filter nonwoven, accommodated to constitute a half cell battery case of size 13.82Mm (Hohsen CR2032 type coin cell case, Ltd.). This was a half-cell of the battery D-3.

(Battery D-4)
Except for using the electrolyte E11, in the same manner as the battery D-3, to prepare a half cell of the battery D-4.

(Battery D-C1)
Except for using the electrolytic solution C1 as an electrolytic solution, in the same manner as in the battery D-1, to produce a half cell of the battery D-C1.

(Battery D-C2)
As the electrolytic solution, an organic solvent is DME (CF 3 SO 2) except that the concentration of 2 NLi was used an electrolyte C9 is 0.1 mol / L, as in the battery D-1, a battery D-C2 to produce a half-cell. The electrolyte C9 batteries D-C2, are included (CF 3 SO 2) to 2 NLi1 molecule 1,2-dimethoxyethane 93 molecules.

Table 38 shows the list of the electrolytic solution used in each cell.

Figure JPOXMLDOC01-appb-T000038

(Evaluation Example D-1: LSV measurement)
Battery D-1, battery D-2 and the battery D-C1, the half-cell batteries D-C2, was measured linear sweep voltammetry (LSV). The measurement conditions, the battery D-1 and the battery D-C1, for battery D-C2, sweep rate 0.1 mV / s, for battery D-2 was sweep rate 1 mV / s. Figure 88, Figure 89, the potential formed by LSV measurement - showed current curve. Figure 88 is a battery D-1 and the battery D-C1, the potential of the battery D-C2 - indicates current curve, Figure 89 is a potential battery D-2 - shows the current curve. The horizontal axis of FIG. 88, Li + / Li electrode shows a potential (V) which is a reference potential, and the vertical axis represents the current value (mAcm -2). The horizontal axis of FIG. 89, Li + / Li electrode shows a potential (V) which is a reference potential, and the vertical axis represents current value (.mu.A).

As shown in Figure 88, the potential battery D-1 - rising portion of the current curve, was located on the side of higher potential than the rising portion of the comparative examples 1 and 2. In the battery D-1, the starting point of the rising portion is located in the potential 4.7V when the reference potential of Li / Li + electrode, the rising part at higher potential from the starting point potential 4.7V shows It had been.

In the battery D-2, the start point of the rising portion is located in the potential 5.7V when the reference potential of Li / Li + electrode, the rising part at higher potential from the starting point potential 5.7V shows It had been. From the above, the electrolyte of the battery D-1, the oxidation decomposition potential of the oxidation reaction occurs is at 4.5V or higher, was found to be cell D-2 at 5V or more.

Battery D-1, in the battery D-2, and the battery D-C1, when the second-order differential value with increasing amounts of increase the potential of the current is B, the current - rising part immediately after the voltage application in the potential curve in the region between the up, we had a relationship of B ≧ 0.

In the battery D-C1, the starting point of the rising portion was 4.2 V. It was 4.2V in the battery D-C2. In the battery D-C2, we had a relationship of potentials 4.5 ~ 4.6V (vs Li + / Li) B near <0. Typical secondary battery includes detection means for detecting a rapid drop in voltage that occurs when fully charged, the stop means for stopping charging when the sudden voltage drop has occurred. Lithium ion secondary battery electrolyte prepared by using a C9 battery D-C2, at the time of charging from the voltage application start until the rising portion, it is misidentified as sudden voltage drop seen overcharging detection unit, termination there is a possibility that the charging by the means is stopped.

(Evaluation Example D-2: charge-discharge characteristics)
The half-cell of the battery D-3, 3V ~ 4.8V, 0.1C (1C are. Indicating a current value required to fully charge or discharge the battery in 1 hour at a constant current) performs CC discharge at , it was to create a charge-discharge curve. The measurement results of the batteries D-3 shown in FIG. 90. In addition, the half-cell of the battery D-4, 3.0V ~ 4.9V, performs a CC charge and discharge at 0.1C, you create a charge-discharge curve. The measurement results of the batteries D-4 shown in FIG. 91.

As shown in FIG. 90, the half-cell batteries D-3 were able to perform reversible charge and discharge at 4.8 V. Further, as shown in FIG. 91, the half-cell batteries D-4 could be performed reversibly charged and discharged at 4.9 V. Half-cell of the capacity of the battery D-4 was about 120 mAh / g.

(Battery D-5)
The half cell using the electrolytic solution E8 was prepared as follows.

Graphite 90 parts by weight of the average particle size of 10μm as an active material, and were mixed 10 parts by weight of polyvinylidene fluoride as a binder. The mixture is dispersed in an appropriate amount of N- methyl-2-pyrrolidone to prepare a slurry. I was preparing a copper foil with a thickness of 20μm as the current collector. The surface of the copper foil, using a doctor blade and coating the slurry in a film form. The slurry is dried copper foil coated N- methyl-2-pyrrolidone was removed, after which the copper foil was pressed to obtain a conjugate. The resulting conjugate 120 ° C. in a vacuum dryer, and dried by heating for 6 hours to obtain copper foil in which an active material layer was formed. This was a working electrode. The mass of the active material per copper foil 1 cm 2 was 1.48 mg. The density of the press before the graphite and polyvinylidene fluoride is 0.68 g / cm 3, the density of the active material layer after pressing was 1.025 g / cm 3.

The counter electrode was a metal Li.

The working electrode, containing a counter electrode, a Whatman glass fiber filter paper and the electrolyte E8 thickness 400μm as separators sandwiched therebetween, in a battery case of size 13.82Mm (Hohsen CR2032 type coin cell case, Ltd.) to constitute a half-cell. This was a half-cell of the battery D-5.

(Battery D-6)
Except for using the electrolyte E11, in the same manner as in the battery D-5, was prepared half cell battery D-6.

(Battery D-7)
Except for using the electrolyte E16, in the same manner as in the battery D-5, was prepared half cell battery D-7.

(Battery D-8)
Except for using the electrolyte E19, in the same manner as in the battery D-5, was prepared half cell battery D-8.

(Battery D-C3)
Except for using the electrolyte solution of the electrolyte solution C5, in the same manner as in the battery D-5, was prepared half cell battery D-C3.

(Evaluation Example D-3: reversibility of charge and discharge)
Battery D-5 ~ batteries D-8, relative to the half-cell batteries D-C3, 25 ° C., and CC charged to a voltage 2.0 V (constant current charging), and CC discharge (constant current discharge) to a voltage 0.01V the charge-discharge cycle of 2.0 V-0.01 V, was carried out three cycles with charge and discharge rate 0.1 C. The charge-discharge curve of each half cell is shown in FIG. 93 to FIG 97.

Figure 93 As shown in to FIG. 97, the half-cell batteries D-5 - battery D-8, like the half-cell of the battery D-C3 with common electrolytes, be reversibly charge and discharge reaction It is seen.

Claims (21)

  1. A nonaqueous secondary battery having a positive electrode and the negative electrode and the electrolyte,
    The positive electrode has a positive active material having a lithium metal composite oxide having a layered rock-salt structure,
    The electrolyte may include a metal salt with an alkali metal, an alkaline earth metal or aluminum cation, an organic solvent having a hetero element,
    Per peak intensity derived from the organic solvent in the vibration spectrum of the electrolyte, in that the strength of the organic solvent inherent peak and Io, if the intensity of a peak the peak is shifted to the Is, it is Is> Io non-aqueous secondary battery, wherein.
  2. A nonaqueous secondary battery having a positive electrode and the negative electrode and the electrolyte,
    The positive electrode has a positive active material having a lithium metal composite oxide having a spinel structure,
    The electrolyte may include a metal salt with an alkali metal, an alkaline earth metal or aluminum cation, an organic solvent having a hetero element,
    Per peak intensity derived from the organic solvent in the vibration spectrum of the electrolyte, in that the strength of the organic solvent inherent peak and Io, if the intensity of a peak the peak is shifted to the Is, it is Is> Io non-aqueous secondary battery, wherein.
  3. A nonaqueous secondary battery having a positive electrode and the negative electrode and the electrolyte,
    The positive electrode has a positive active material having a polyanionic material,
    The electrolyte may include a metal salt with an alkali metal, an alkaline earth metal or aluminum cation, an organic solvent having a hetero element,
    Per peak intensity derived from the organic solvent in the vibration spectrum of the electrolyte, in that the strength of the organic solvent inherent peak and Io, if the intensity of a peak the peak is shifted to the Is, it is Is> Io nonaqueous secondary battery comprising.
  4. A positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, a nonaqueous secondary battery having an electrolyte solution,
    The electrolyte may include a metal salt with an alkali metal, an alkaline earth metal or aluminum cation, an organic solvent having a hetero element,
    The electrolyte peak intensity derived from the organic solvent in the vibration spectrum of every said organic solvent strength of the original peak and Io, when the peak has an intensity of peak shifted Is, a Is> Io,
    The nonaqueous secondary battery, nonaqueous secondary battery, wherein the maximum potential use of the positive electrode when the reference potential of Li / Li + is 4.5V or more.
  5. Nonaqueous secondary battery according to any one of claims 1 to 4, the cation of said metal salt is lithium.
  6. The chemical structure of the anion of the metal salt, halogen, boron, nitrogen, oxygen, non-aqueous secondary battery according to any one of claims 1 to 5 containing at least one element selected from oxygen, sulfur or carbon.
  7. The chemical structure of the anion is represented by the following general formula of the metal salt (1), the general formula (2) or a non-aqueous secondary battery according to any one of the general formula (3) according to claim 1 to 6 represented by.
    (R 1 X 1) (R 2 X 2) N Formula (1)
    (R 1 is hydrogen, halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, optionally substituted with a substituent unsaturated alkyl group, a substituted group in optionally substituted unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, it may be substituted by optionally substituted heterocyclic group, optionally substituted with a substituent alkoxy group , selection may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent unsaturated thioalkoxy group, CN, SCN, from OCN It is.
    R 2 is hydrogen, halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, optionally substituted with a substituent unsaturated alkyl group, a substituted group optionally substituted unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, may be substituted by optionally substituted heterocyclic group, optionally substituted with a substituent alkoxy group, may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent unsaturated thioalkoxy group, CN, SCN, selected from OCN that.
    Alternatively, R 1 and R 2 may be bonded to each other to form a ring.
    X 1 is, SO 2, C = O, C = S, R a P = O, R b P = S, S = O, is selected from Si = O.
    X 2 is, SO 2, C = O, C = S, R c P = O, R d P = S, S = O, is selected from Si = O.
    R a, R b, R c , R d represents a substituted independently hydrogen, halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, a substituted group which may be unsaturated alkyl group, which may be substituted with a substituent unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, it may be substituted by optionally substituted heterocyclic group , which may be substituted with a substituent alkoxy group, may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent not saturated thioalkoxy group, OH, SH, CN, SCN, is selected from the OCN.
    Furthermore, R a, R b, R c, R d is combined with R 1 or R 2 may form a ring. )
    R 3 X 3 Y Formula (2)
    (R 3 is hydrogen, halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, which may be unsaturated alkyl group substituted with a substituent, in optionally substituted unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, it may be substituted by optionally substituted heterocyclic group, optionally substituted with a substituent alkoxy group , selection may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent unsaturated thioalkoxy group, CN, SCN, from OCN It is.
    X 3 is, SO 2, C = O, C = S, R e P = O, R f P = S, S = O, is selected from Si = O.
    R e, R f are, each independently, hydrogen, Good halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, optionally substituted with a substituent not saturated alkyl group, which may be substituted with a substituent unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, may be substituted by optionally substituted heterocyclic group, it is substituted with a substituent even though alkoxy group, may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent unsaturated thioalkoxy group, OH , SH, CN, SCN, is selected from the OCN.
    Also, R e, is R f, may form a ring with R 3.
    Y is, O, is selected from S. )
    (R 4 X 4) (R 5 X 5) (R 6 X 6) C Formula (3)
    (R 4 is hydrogen, halogen, optionally substituted with a substituent alkyl group, substituted with a substituent which may have a cycloalkyl group, substituents which may be substituted unsaturated alkyl group, a substituted group in optionally substituted unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, it may be substituted by optionally substituted heterocyclic group, optionally substituted with a substituent alkoxy group , selection may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent unsaturated thioalkoxy group, CN, SCN, from OCN It is.
    R 5 is hydrogen, halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, optionally substituted with a substituent unsaturated alkyl group, a substituted group optionally substituted unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, may be substituted by optionally substituted heterocyclic group, optionally substituted with a substituent alkoxy group, may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent unsaturated thioalkoxy group, CN, SCN, selected from OCN that.
    R 6 is hydrogen, halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, optionally substituted with a substituent unsaturated alkyl group, a substituted group optionally substituted unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, may be substituted by optionally substituted heterocyclic group, optionally substituted with a substituent alkoxy group, may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent unsaturated thioalkoxy group, CN, SCN, selected from OCN that.
    Further, R 4, R 5, of R 6, any two or three may be combined with each other to form a ring.
    X 4 is, SO 2, C = O, C = S, R g P = O, R h P = S, S = O, is selected from Si = O.
    X 5 is, SO 2, C = O, C = S, R i P = O, R j P = S, S = O, is selected from Si = O.
    X 6 is, SO 2, C = O, C = S, R k P = O, R l P = S, S = O, is selected from Si = O.
    R g, R h, R i , R j, R k, R l are each independently hydrogen, halogen, optionally substituted with a substituent an alkyl group, cycloalkyl which may be substituted with a substituent group, may be substituted with a substituent unsaturated alkyl group, which may be substituted with a substituent unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, substituted with a substituent be heterocyclic group, may be substituted with a substituent alkoxy group, may be substituted with a substituent unsaturated alkoxy group, may be substituted with a substituent thioalkoxy group, substituted with a substituent which may be unsaturated thioalkoxy group, OH, SH, CN, SCN, is selected from the OCN.
    Also, R g, R h, R i, R j, R k, R l is, R 4, R 5 or may be R 6 combine with other to form a ring. )
  8. Nonaqueous secondary battery according to any one of the chemical structure of the anion of the metal salt is represented by the following general formula (4), the general formula (5) or claims 1 to 7, represented by the general formula (6).
    (R 7 X 7) (R 8 X 8) N Formula (4)
    (R 7, R 8 are each independently C n H a F b Cl c Br d I e (CN) f (SCN) g (OCN) h.
    n, a, b, c, d, e, f, g, h are each independently an integer of 0 or more satisfying the 2n + 1 = a + b + c + d + e + f + g + h.
    Further, R 7 and R 8 may be bonded to each other to form a ring, in that case, satisfy 2n = a + b + c + d + e + f + g + h.
    X 7 is, SO 2, C = O, C = S, R m P = O, R n P = S, S = O, is selected from Si = O.
    X 8 is, SO 2, C = O, C = S, R o P = O, R p P = S, S = O, is selected from Si = O.
    R m, R n, R o , R p is substituted independently hydrogen, halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, a substituted group which may be unsaturated alkyl group, which may be substituted with a substituent unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, it may be substituted by optionally substituted heterocyclic group , which may be substituted with a substituent alkoxy group, may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent not saturated thioalkoxy group, OH, SH, CN, SCN, is selected from the OCN.
    Also, R m, R n, R o, R p may be bonded to R 7 or R 8 to form a ring. )
    R 9 X 9 Y Formula (5)
    (R 9 is a C n H a F b Cl c Br d I e (CN) f (SCN) g (OCN) h.
    n, a, b, c, d, e, f, g, h are each independently an integer of 0 or more satisfying the 2n + 1 = a + b + c + d + e + f + g + h.
    X 9 is, SO 2, C = O, C = S, R q P = O, R r P = S, S = O, is selected from Si = O.
    R q, R r are each independently hydrogen, halogen, optionally substituted with a substituent alkyl group may be substituted with a substituted cycloalkyl group, optionally substituted with a substituent not saturated alkyl group, which may be substituted with a substituent unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, may be substituted by optionally substituted heterocyclic group, it is substituted with a substituent even though alkoxy group, may be substituted with a substituent unsaturated alkoxy group, it may be substituted with a substituent thioalkoxy group, may be substituted with a substituent unsaturated thioalkoxy group, OH , SH, CN, SCN, is selected from the OCN.
    Also, R q, R r may be bonded together to form a ring with R 9.
    Y is, O, is selected from S. )
    (R 10 X 10) (R 11 X 11) (R 12 X 12) C Formula (6)
    (R 10, R 11, R 12 are each independently C n H a F b Cl c Br d I e (CN) f (SCN) g (OCN) h.
    n, a, b, c, d, e, f, g, h are each independently an integer of 0 or more satisfying the 2n + 1 = a + b + c + d + e + f + g + h.
    R 10, R 11, any two of R 12 is bonded, it may form a ring, in which case the group to form a ring satisfies 2n = a + b + c + d + e + f + g + h.Also, R 10, R 11, may be R 12 3 is coupled to the other to form a ring, in that case, the two groups of three satisfies 2n = a + b + c + d + e + f + g + h, 1 single group 2n-1 = a + b + c + d + e + f + g + h Fulfill.
    X 10 is, SO 2, C = O, C = S, R s P = O, R t P = S, S = O, is selected from Si = O.
    X 11 is, SO 2, C = O, C = S, R u P = O, R v P = S, S = O, is selected from Si = O.
    X 12 is, SO 2, C = O, C = S, R w P = O, R x P = S, S = O, is selected from Si = O.
    R s, R t, R u , R v, R w, R x is independently hydrogen, halogen, optionally substituted with a substituent an alkyl group, cycloalkyl which may be substituted with a substituent group, may be substituted with a substituent unsaturated alkyl group, which may be substituted with a substituent unsaturated cycloalkyl group, which may be substituted with a substituent an aromatic group, substituted with a substituent be heterocyclic group, may be substituted with a substituent alkoxy group, may be substituted with a substituent unsaturated alkoxy group, may be substituted with a substituent thioalkoxy group, substituted with a substituent which may be unsaturated thioalkoxy group, OH, SH, CN, SCN, is selected from the OCN.
    Further, R s, R t, R u, R v, R w, R x may be bonded to R 10, R 11 or R 12 form a ring. )
  9. Nonaqueous secondary battery according to any one of the chemical structure of the anion of the metal salt is represented by the following general formula (7), the general formula (8) or claim represented by the general formula (9) 1-8.
    (R 13 SO 2) (R 14 SO 2) N Formula (7)
    (R 13, R 14 are each independently C n H a F b Cl c Br d I e.
    n, a, b, c, d, e are each independently an integer of 0 or more satisfying the 2n + 1 = a + b + c + d + e.
    Also, R 13 and R 14 may be bonded to each other to form a ring, in that case, satisfy 2n = a + b + c + d + e. )
    R 15 SO 3 Formula (8)
    (R 15 is a C n H a F b Cl c Br d I e.
    n, a, b, c, d, e are each independently an integer of 0 or more satisfying the 2n + 1 = a + b + c + d + e. )
    (R 16 SO 2) (R 17 SO 2) (R 18 SO 2) C Formula (9)
    (R 16, R 17, R 18 are each independently C n H a F b Cl c Br d I e.
    n, a, b, c, d, e are each independently an integer of 0 or more satisfying the 2n + 1 = a + b + c + d + e.
    R 16, R 17, any two of R 18 is bonded, it may form a ring, in which case the group to form a ring satisfies 2n = a + b + c + d + e.Also, may be three are bonded to the R 16, R 17, R 18 form a ring, in that case, the two groups of three satisfies 2n = a + b + c + d + e, 1 single group 2n-1 = a + b + c + d + e Fulfill. )
  10. Wherein the metal salt is (CF 3 SO 2) 2 NLi , (FSO 2) 2 NLi, (C 2 F 5 SO 2) 2 NLi, FSO 2 (CF 3 SO 2) NLi, (SO 2 CF 2 CF 2 SO 2 ) NLi, or (non-aqueous secondary battery according to any one of the SO 2 CF 2 CF 2 CF 2 SO 2) according to claim 1 to 9 is NLi.
  11. Hetero element a nitrogen of the organic solvent, oxygen, sulfur, non-aqueous secondary battery according to any one of claims 1 to 10 is at least one selected from halogen.
  12. Nonaqueous secondary battery according to any one of claims 1 to 11 wherein the organic solvent is an aprotic solvent.
  13. Nonaqueous secondary battery according to any one of claims 1 to 12, wherein the organic solvent is selected from acetonitrile or 1,2-dimethoxyethane.
  14. Nonaqueous secondary battery according to any one of claims 1 to 13, wherein said organic solvent is selected from linear carbonates represented by the following general formula (10).
    R 19 OCOOR 20 formula (10)
    (R 19, R 20 are each independently a linear alkyl C n H a F b Cl c Br d I e or, C m H f F g Cl h Br i I j including cyclic alkyl in the chemical structure .n selected from any of, a, b, c, d, e, m, f, g, h, i, j are each independently an integer of 0 or more, 2n + 1 = a + b + c + d + e, the 2m = f + g + h + i + j Fulfill.)
  15. Nonaqueous secondary battery according to any one of the preceding claims wherein the organic solvent is dimethyl carbonate, is selected from ethyl methyl carbonate or diethyl carbonate 1-12, and 14.
  16. The lithium metal composite oxide is represented by the general formula: Li a Ni b Co c Mn d D e O f (0.2 ≦ a ≦ 1.2, b + c + d + e = 1,0 ≦ e <1, D is Li, Fe, cr, Cu, Zn, Ca, Mg, S, Si, Na, K, Al, Zr least one element, Ti, P, Ga, Ge, V, Mo, Nb, W, is selected from La, 1.7 ≦ f ≦ 2.1), and non-aqueous secondary battery according to any one of claims 1, and 5-15 consists of one selected from the group consisting of Li 2 MnO 3.
  17. b in the formula: c: a ratio of d is 0.5: 0.2: 0.3, 1/3: 1/3: 1 / 3,0.75: 0.10: 0.15 , 0: 0: 1, 1: 0: 0, and 0: 1: 0 at least one non-aqueous secondary battery according to claim 16, wherein selected from.
  18. The lithium metal composite oxide is represented by the general formula: Li x (A y Mn 2 -y) O 4 (A is a transition metal elements, Ca, Mg, S, Si , Na, K, Al, P, Ga, and at least one metal element selected from Ge, 0 <x ≦ 1.2,0 <nonaqueous secondary battery according to any one of claims 2, and 5 to 15 represented by the y ≦ 1) .
  19. The polyanionic material, according to claim consisting of LiMPO 4, LiMVO 4 or Li 2 MSiO 4 polyanionic compound (the M in the formula Co, Ni, Mn, are selected from at least one of Fe) represented by like nonaqueous secondary battery according to any one of 3, or 5-15.
  20. The oxidative decomposition potential of the electrolytic solution, a nonaqueous secondary battery according to any one of claims 4-15 is 4.5V or more when the reference potential Li / Li +.
  21. The positive active material is non-aqueous secondary battery according to any one of claims 4 to 15 and 20, having a spinel structure containing Li and Mn.
PCT/JP2014/004910 2013-09-25 2014-09-25 Nonaqueous secondary battery WO2015045386A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017051470A1 (en) * 2015-09-25 2017-03-30 株式会社東芝 Electrode for non-aqueous electrolyte battery, non-aqueous electrolyte battery, and battery pack

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001507043A (en) * 1997-07-25 2001-05-29 アセップ・インク Ionic compounds having delocalized anionic charge, and their use as ion-conducting component or catalyst
JP2002523879A (en) * 1998-08-25 2002-07-30 スリーエム イノベイティブ プロパティズ カンパニー Cyano-substituted methide salts and amides salts
JP2006073434A (en) * 2004-09-03 2006-03-16 Gs Yuasa Corporation:Kk Nonaqueous electrolyte secondary battery
JP2007091573A (en) * 2005-06-10 2007-04-12 Tosoh Corp Lithium-nickel-manganese-cobalt multiple oxide, method for producing the same, and application of the multiple oxide
JP2013178885A (en) * 2012-02-28 2013-09-09 Toyota Industries Corp Positive electrode active material, production method of positive electrode active material, nonaqueous electrolyte secondary battery and vehicle mounting the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001507043A (en) * 1997-07-25 2001-05-29 アセップ・インク Ionic compounds having delocalized anionic charge, and their use as ion-conducting component or catalyst
JP2002523879A (en) * 1998-08-25 2002-07-30 スリーエム イノベイティブ プロパティズ カンパニー Cyano-substituted methide salts and amides salts
JP2006073434A (en) * 2004-09-03 2006-03-16 Gs Yuasa Corporation:Kk Nonaqueous electrolyte secondary battery
JP2007091573A (en) * 2005-06-10 2007-04-12 Tosoh Corp Lithium-nickel-manganese-cobalt multiple oxide, method for producing the same, and application of the multiple oxide
JP2013178885A (en) * 2012-02-28 2013-09-09 Toyota Industries Corp Positive electrode active material, production method of positive electrode active material, nonaqueous electrolyte secondary battery and vehicle mounting the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MAKOTO YAEGASHI: "Yobai Bunshi no Haii Jotai Seigyo ni yoru Yuki Yoeki no Shin Kino Hatsugen", DAI 53 KAI ABSTRACTS, BATTERY SYMPOSIUM IN JAPAN, 13 November 2012 (2012-11-13), pages 507 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017051470A1 (en) * 2015-09-25 2017-03-30 株式会社東芝 Electrode for non-aqueous electrolyte battery, non-aqueous electrolyte battery, and battery pack
JPWO2017051470A1 (en) * 2015-09-25 2017-10-26 株式会社東芝 A non-aqueous electrolyte battery electrode, a nonaqueous electrolyte battery and a battery pack

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