JP6361232B2 - Non-aqueous electrolyte and non-aqueous electrolyte secondary battery using the same - Google Patents

Description

  The present invention relates to a non-aqueous electrolyte and a non-aqueous electrolyte secondary battery using the same.

With the rapid progress of electronic equipment, the demand for higher capacity for secondary batteries is increasing, and non-aqueous systems such as lithium ion secondary batteries with higher energy density than nickel / cadmium batteries and nickel / hydrogen batteries. Electrolyte batteries are widely used and actively researched.
The electrolyte used for a non-aqueous electrolyte battery is usually composed mainly of an electrolyte and a non-aqueous solvent. As an electrolytic solution for a lithium ion secondary battery, an electrolyte such as LiPF ₆ , LiBF ₄ , LiN (CF ₃ SO ₂ ) ₂ , a high dielectric constant solvent such as ethylene carbonate and propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl A non-aqueous electrolyte solution dissolved in a mixed solvent with a low viscosity solvent such as methyl carbonate is used. Moreover, the gel electrolyte which made the matrix polymer contain the above electrolyte solutions and was made into the gel state is also used.

When the lithium ion secondary battery is repeatedly charged and discharged, the electrolytic solution is decomposed on the electrode, the material constituting the battery is deteriorated, and the capacity of the battery is reduced. In some cases, the safety against swelling, ignition, or explosion of the battery may be reduced.
So far, a method for improving battery characteristics of a lithium ion secondary battery by incorporating an isocyanate compound, an unsaturated cyclic carbonate, or the like in a non-aqueous electrolyte has been proposed.

For example, Patent Document 1 discloses a nonaqueous electrolytic solution containing a non-aqueous solvent that is a mixture of a chain carbonate ester, an unsaturated cyclic carbonate ester, and a saturated cyclic carbonate ester, an electrolyte, and a chain isocyanate compound. Electrolytic solution containing 0.01 to 3 wt% of isocyanate compound, 30 to 80 wt% of chain carbonate, 10 to 50 wt% of saturated cyclic carbonate and 0.01 to 5 wt% of unsaturated cyclic carbonate Has been proposed. According to this, the cyclic isocyanate compound and the unsaturated cyclic carbonate have different decomposition potentials on the negative electrode surface, and the cycle characteristics are improved by forming a film layer having a good resistance step by step. is suggesting.
In Patent Document 2, a non-aqueous electrolyte mixed with a low-viscosity solvent such as DMC (dimethyl carbonate) or MP (methyl propionate) and further added with HMDI, which is a diisocyanate compound, is added to the positive electrode potential. Has been proposed as a non-aqueous electrolyte secondary battery system having excellent cycle characteristics in a high-temperature environment even when charged to 4.35 V or higher with respect to lithium.

JP 2006-164759 A International Publication No. 2012/133027

  An object of the present invention is to provide a non-aqueous electrolyte solution that improves high-temperature storage characteristics in a non-aqueous electrolyte solution secondary battery, and a non-aqueous electrolyte solution battery that includes the non-aqueous electrolyte solution.

However, Patent Document 1 and Patent Document 2 do not suggest any specific effect when the specific isocyanate compound and the halogenated isocyanate coexist with a certain content.
As a result of various studies to solve the above problems, the present inventors have included a non-aqueous electrolyte containing a chain diisocyanate compound (compound of formula 1) having a specific structure in the non-aqueous electrolyte. It has been found that the above-mentioned problems can be solved by containing a specific content of the halogenated isocyanate compound (compound of formula 2), and the present invention has been completed.
That is, the gist of the present invention is as follows.
(A) Nonaqueous electrolyte solution used for a nonaqueous electrolyte secondary battery comprising a positive electrode having a positive electrode active material capable of occluding and releasing metal ions and a negative electrode having a negative electrode active material capable of occluding and releasing metal ions Because
It contains a diisocyanate compound represented by the following general formula (1) and a halogenated isocyanate compound, and the content of the halogenated isocyanate compound is 0.000001% by mass or more and 0.06% by mass with respect to the total amount of the non-aqueous electrolyte. A non-aqueous electrolyte characterized by being less than or equal to mass%.

(Y ¹ represents a chain hydrocarbon group having 1 to 20 carbon atoms.)
(B) Content of the said halogenated isocyanate compound is 0.000005 mass% or more and 0.055 mass% or less with respect to nonaqueous electrolyte whole quantity, Nonaqueous electrolyte solution as described in (a) characterized by the above-mentioned .
(C) The non-aqueous electrolyte solution according to (a) or (b), wherein the halogenated isocyanate compound is represented by the following general formula (2).

(Y ² represents a chain hydrocarbon group having 1 to 20 carbon atoms, and X ² represents a halogen atom.)
(D) The diisocyanate compound represented by the general formula (1) is at least one selected from the group consisting of trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate and octamethylene diisocyanate. The non-aqueous electrolyte solution according to any one of (a) to (c),

（Ｙ^１及びＹ^２はそれぞれ独立して炭素数１〜２０の鎖状炭化水素基を表し、Ｘ^２はハロゲン原子を表す。） (E) At least one selected from the group consisting of a cyclic carbonate compound having a carbon-carbon unsaturated bond, a cyclic carbonate compound having a halogen atom, a nitrile compound, cyclohexylbenzene, t-amylbenzene, t-butylbenzene, and a sulfonate ester. The nonaqueous electrolyte solution according to any one of (a) to (d), further comprising:
(F) The nonaqueous electrolytic solution according to any one of (a) to (e), further comprising at least one nitrile compound.
(G) A non-aqueous electrolyte secondary battery comprising a positive electrode having a positive electrode active material capable of occluding and releasing metal ions and a negative electrode having a negative electrode active material capable of occluding and releasing metal ions,
A non-aqueous electrolyte secondary battery comprising the non-aqueous electrolyte solution according to any one of (a) to (f).
(H) a diisocyanate compound represented by the following general formula (1) and a halogenated isocyanate compound represented by the following general formula (2), wherein the content of the halogenated isocyanate compound is the diisocyanate compound and the halogen: The isocyanate composition which is more than 0 and 6 mass% or less in the total mass of the fluorinated isocyanate compound.

(Y ¹ and Y ² each independently represent a chain hydrocarbon group having 1 to 20 carbon atoms, and X ² represents a halogen atom.)

  According to the present invention, in a non-aqueous electrolyte secondary battery, a non-aqueous electrolyte solution that improves load characteristics and cycle high-temperature storage characteristics, and a non-aqueous electrolyte secondary battery including the non-aqueous electrolyte solution are provided. be able to.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the description described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents unless it exceeds the gist of the claims.

[1. Non-aqueous electrolyte)
The non-aqueous electrolyte solution of the present invention contains an electrolyte and a non-aqueous solvent that dissolves the electrolyte in the same manner as a general non-aqueous electrolyte solution, and a diisocyanate compound represented by the following general formula (1): An isocyanate compound is further contained, and the content of the halogenated isocyanate compound is 0.000001% by mass or more and 0.06% by mass or less based on the total amount of the nonaqueous electrolytic solution.

Y ¹ represents a chain hydrocarbon group having 1 to 20 carbon atoms.

[1-1. Diisocyanate compound]
Y ¹ in the general formula (1) is preferably a divalent linear hydrocarbon group having 1 to 20 carbon atoms, more preferably a divalent linear hydrocarbon group having 1 to 10 carbon atoms, A linear saturated hydrocarbon group having 3 to 8 carbon atoms is more preferable, a linear saturated hydrocarbon group having 3 to 6 carbon atoms is particularly preferable, and a linear saturated hydrocarbon group having 6 carbon atoms is most preferable.
The hydrocarbon group represented by Y ¹ may have a substituent. Examples of the substituent include a fluorine atom, a chlorine atom and a bromine atom.

  Specific examples of the diisocyanate compound represented by the general formula (1) (hereinafter also simply referred to as “diisocyanate compound”) include monomethylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene. Diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 1,3-diisocyanatopropene, 1,4-diisocyanato-2-butene, 1,4-diisocyanato-2-fluorobutane, 1, 4-diisocyanato-2,3-difluorobutane, 1,5-diisocyanato-2-pentene, 1,5-diisocyanato-2-methylpentane, 1, - diisocyanato-2-hexene, 1,6-diisocyanato-3-hexene, 1,6-diisocyanato-3-fluoro-hexane, 1,6-diisocyanato-3,4-difluoro-hexane, and the like.

  Among these, from the viewpoint of forming a more stable film, preferably, it is at least one selected from the group consisting of trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate and octamethylene diisocyanate. More preferably, it is at least one selected from the group consisting of trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate and hexamethylene diisocyanate, and most preferably hexamethylene diisocyanate.

Since these diisocyanate compounds are relatively easy to produce and have an appropriate reactivity, the effect of improving battery characteristics is great.
The nonaqueous electrolytic solution of the present invention is characterized by containing the diisocyanate compound represented by the general formula (1). However, the diisocyanate compound to be contained is not limited to one type, and a plurality of types may be used in combination.
Further, the content of the diisocyanate compound (the total amount when a plurality of types are used in combination) is not particularly limited, but is usually 0.01% by mass or more, preferably 0.1% by mass with respect to the total amount of the non-aqueous electrolyte. Above, more preferably 0.2% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 2% by mass or less. Within the above range, not only can a stable film be formed, but also an increase in resistance can be suppressed, so that battery characteristics can be expected to be particularly improved.

  The content of the diisocyanate compound represented by the general formula (1) in the nonaqueous electrolytic solution is measured using gas chromatography or high performance liquid chromatography.

[1-2. Halogenated isocyanate compound]
Although there is no restriction | limiting in particular as a halogenated isocyanate compound whose content in the non-aqueous electrolyte solution of this invention is 0.000001 mass% or more and 0.06 mass% or less, It represents with following General formula (2). It is preferable.

Y ² represents a chain hydrocarbon group having 1 to 20 carbon atoms, and X ² represents a halogen atom.

Y ² is not particularly limited as long as it is a chain hydrocarbon group having 1 to 20 carbon atoms, but a divalent linear hydrocarbon group having 1 to 20 carbon atoms is preferable, and a divalent hydrocarbon having 1 to 10 carbon atoms. Is more preferable, and a C1-C6 bivalent linear saturated hydrocarbon group is particularly preferable.
The hydrocarbon group represented by Y ² may have a substituent. Examples of the substituent include a fluorine atom, a chlorine atom and a bromine atom.
Y ² in the general formula (2) is preferably the same as Y ¹ in the general formula (1).

X ² is not particularly limited as long as it is a halogen atom, but is preferably chlorine or bromine, more preferably chlorine.
Specific examples of the halogenated isocyanate compound include, for example, 1-chloro-1-isocyanatomethane, 1-bromo-1-isocyanatomethane, 1-chloro-2-isocyanatoethane, 1-bromo-2-isocyanate. Natoethane, 1-chloro-3-isocyanatopropane, 1-bromo-3-isocyanatopropane, 1-chloro-4-isocyanatobutane, 1-bromo-4-isocyanatobutane, 1-chloro-5-isocyanate Natopentane, 1-bromo-5-isocyanatopentane, 1-chloro-6-isocyanatohexane, 1-bromo-6-isocyanatohexane, 1-chloro-7-isocyanatoheptane, 1-bromo-7-isocyanate Natoheptane, 1-chloro-8-isocyanatooctane, 1-bromo-8-isocyanatooctane, 1-chloro 9-isocyanatononane, 1-bromo-9-isocyanatononane, 1-chloro-10-isocyanatodecane, 1-bromo-10-isocyanatodecane, 1-chloro-3-isocyanatopropene, 1-bromo- 3-isocyanatopropene, 1-chloro-4-isocyanato-2-butene, 1-bromo-4-isocyanato-2-butene, 1-chloro-4-isocyanato-2-fluorobutane, 1-bromo-4-isocyanato 2-fluorobutane, 1-chloro-4-isocyanato-2,3-difluorobutane, 1-bromo-4-isocyanato-2,3-difluorobutane, 1-chloro-5-isocyanato-2-pentene, 1- Bromo-5-isocyanato-2-pentene, 1-chloro-5-isocyanato-2-methylpentane, 1-bromo-5-i Cyanato-2-methylpentane, 1-chloro-6-isocyanato-2-hexene, 1-bromo-6-isocyanato-2-hexene, 1-chloro-6-isocyanato-3-hexene, 1-bromo-6-isocyanato -3-hexene, 1-chloro-6-isocyanato-3-fluorohexane, 1-bromo-6-isocyanato-3-fluorohexane, 1-chloro-6-isocyanato-3,4-difluorohexane, 1-bromo- Examples include 6-isocyanato-3,4-difluorohexane.

  Of these, 1-chloro-3-isocyanatopropane, 1-bromo-3-isocyanatopropane, 1-chloro-4-isocyanatobutane, 1-bromo are preferable from the viewpoint of forming a more stable film. -4-isocyanatobutane, 1-chloro-5-isocyanatopentane, 1-bromo-5-isocyanatopentane, 1-chloro-6-isocyanatohexane, 1-bromo-6-isocyanatohexane, 1-chloro At least one selected from the group consisting of -7-isocyanatoheptane, 1-bromo-7-isocyanatoheptane, 1-chloro-8-isocyanatooctane and 1-bromo-8-isocyanatooctane, more preferably 1-chloro-3-isocyanatopropane, 1-bromo-3-isocyanatopropane, 1-chloro-4-iso Anatobutane, 1-bromo-4-isocyanatobutane, 1-chloro-5-isocyanatopentane, 1-bromo-5-isocyanatopentane, 1-chloro-6-isocyanatohexane and 1-bromo-6-isocyanato At least one selected from the group consisting of hexane, and more preferably at least one selected from the group consisting of 1-chloro-6-isocyanatohexane and 1-bromo-6-isocyanatohexane. Further, from the viewpoint of improving the effect of the present invention by forming a stable film, preferably 1-chloro-3-isocyanatopropane, 1-chloro-4-isocyanatobutane, 1-chloro-5-isocyanatopentane. 1-chloro-6-isocyanatohexane, 1-chloro-7-isocyanatoheptane and 1-chloro-8-isocyanatooctane, more preferably 1-chloro-3 -At least one selected from the group consisting of isocyanatopropane, 1-chloro-4-isocyanatobutane, 1-chloro-5-isocyanatopentane and 1-chloro-6-isocyanatohexane, most preferably 1- Chloro-6-isocyanatohexane.

The halogenated isocyanate contained in the non-aqueous electrolyte solution of the present invention is not limited to one type, and a plurality of types may be used in combination.
In addition, the content of the halogenated isocyanate compound (the total amount when plural types are used in combination) is 0.000001% by mass or more and 0.06% by mass or less with respect to the total amount of the non-aqueous electrolyte solution. The lower limit is preferably 0.000005% by mass or more, more preferably 0.00001% by mass or more. The upper limit is preferably 0.055% by mass or less, more preferably 0.05% by mass or less, still more preferably 0.03% by mass or less, and particularly preferably 0.01% by mass or less.

  Within the above range, it can be expected that battery characteristics are particularly improved without impairing the effects of the diisocyanate compound represented by the general formula (1). In addition, when the content of the halogenated isocyanate compound is less than 0.000001% by mass relative to the total amount of the non-aqueous electrolyte, there is probably no sufficient amount of halogenated isocyanate to modify the film derived from the diisocyanate compound. The film is not sufficiently modified, and the contribution to improving battery characteristics is reduced. Therefore, it is important that the halogenated isocyanate compound is present to some extent in the non-aqueous electrolyte solution.

The content of the halogenated isocyanate compound in the nonaqueous electrolytic solution can be measured using high performance liquid chromatography, gas chromatography, or the like. For example, the measurement conditions of high performance liquid chromatography are as follows.
HPLC: LC-20AD manufactured by SHIMAZU
Analysis column: CAISEL PAK C18MG 75 mm × 4.6 mm × 3 μm manufactured by SHISEIDO
Mobile phase: Water / acetonitrile (40:60 vol)
Flow rate: 1.0 mL / min
Column temperature: 35 ° C
Detector: UV210nm (detector; SPD-10Avp)
Injection volume: 5 μL

  The content ratio of the halogenated isocyanate compound to the diisocyanate compound in the non-aqueous electrolyte solution (halogenated isocyanate compound / diisocyanate compound) is not particularly limited, and is, for example, more than 0 and 0.12 or less, preferably 0.8. It is 0.0005 or more and 0.1 or less, more preferably 0.00001 or more and 0.006 or less, still more preferably 0.00001 or more and 0.02 or less, and most preferably 0.00001 or more and 0.01 or less. When the content ratio is within the above range, battery characteristics tend to be improved.

[1-3. Electrolytes〕
There is no restriction | limiting in the electrolyte used for the non-aqueous electrolyte of this invention, A well-known thing can be arbitrarily employ | adopted if it is used as an electrolyte for the target non-aqueous electrolyte secondary battery. When the nonaqueous electrolytic solution of the present invention is used for a lithium secondary battery, a lithium salt is usually used as an electrolyte.

Specific examples of the electrolyte include inorganic lithium salts such as LiClO ₄ , LiAsF ₆ , LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiSO ₃ F, and LiN (FSO ₂ ) ₂ ;
LiCF ₃ SO ₃ , LiN (FSO ₂ ) (CF ₃ SO ₂ ), LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , lithium cyclic 1,3-hexafluoropropanedisulfonylimide, Lithium cyclic 1,2-tetrafluoroethanedisulfonylimide, LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ), LiC (CF ₃ SO ₂ ) ₃ , LiPF ₄ (CF ₃ ) ₂ , LiPF ₄ (C ₂ F ₅ ) ₂ , LiPF ₄ (CF ₃ SO ₂ ) ₂ , LiPF ₄ (C ₂ F ₅ SO ₂ ) ₂ , LiBF ₂ (CF ₃ ) ₂ , LiBF ₂ (C ₂ F ₅ ) ₂ , LiBF ₂ (CF ₃ SO ₂ ) ₂ , LiBF ₂ (C ₂ F ₅ SO ₂ ) _{2 and} other fluorine-containing organic lithium salts;
Examples thereof include lithium salts of dicarboxylic acid complexes such as lithium bis (oxalato) borate, lithium difluorooxalatoborate, lithium tris (oxalato) phosphate, lithium difluorobis (oxalato) phosphate, and lithium tetrafluoro (oxalato) phosphate.

Among these, LiPF ₆ , LiBF ₄ , LiSO ₃ F, LiN (FSO ₂ ) ₂ , LiN (FSO ₂ ) (in terms of solubility / dissociation in a non-aqueous solvent, electrical conductivity, and obtained battery characteristics) CF ₃ SO ₂ ), LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , lithium bis (oxalato) borate, lithium difluorooxalatoborate, lithium tris (oxalato) phosphate, lithium difluorobis ( At least one selected from the group consisting of oxalato) phosphate and lithium tetrafluoro (oxalato) phosphate is preferable, and at least one selected from the group consisting of LiPF ₆ and LiBF _{4 is} particularly preferable.

Moreover, electrolyte may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. In particular, when two types of specific inorganic lithium salts are used in combination, or when inorganic lithium salts and fluorine-containing organic lithium salts are used in combination, gas generation during trickle charging is suppressed, and deterioration after high-temperature storage is suppressed. Therefore, it is preferable. In particular, the combination and the LiPF ₆ and LiBF _4, and an inorganic lithium salt such as _{LiPF 6, LiBF 4, LiCF 3} SO 3, LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) _2, etc. It is preferable to use together with a fluorine-containing organic lithium salt.

Furthermore, when LiPF ₆ and LiBF ₄ are used in combination, it is preferable that LiBF ₄ is usually contained at a ratio of 0.01% by mass to 50% by mass with respect to the entire electrolyte. The ratio is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, while preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass or less, Most preferably, it is 3 mass% or less. When the ratio is in the above range, a desired effect can be easily obtained, and the low dissociation degree of LiBF ₄ suppresses increase in resistance of the electrolytic solution.

On the other hand, inorganic lithium salts such as LiPF ₆ and LiBF ₄ and inorganic lithium salts such as LiSO ₃ F and LiN (FSO ₂ ) ₂ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , and LiN (C ₂ F) ₅ SO _{2) 2,} lithium cyclic 1,3-hexafluoropropane disulfonylimide, lithium cyclic 1,2-tetrafluoroethane _{disulfonylimide, LiN (CF 3 SO 2)} (C 4 F 9 SO 2), LiC ( CF ₃ SO ₂ ) ₃ , LiPF ₄ (CF ₃ ) ₂ , LiPF ₄ (C ₂ F ₅ ) ₂ , LiPF ₄ (CF ₃ SO ₂ ) ₂ , LiPF ₄ (C ₂ F ₅ SO ₂ ) ₂ , LiBF ₂ ( _{CF 3) 2, LiBF 2 (} C 2 F 5) 2, LiBF 2 (CF 3 SO 2) 2, LiBF 2 (C 2 F 5 SO 2) ₂ or the like containing Nitrogen organic lithium salt, lithium bis (oxalato) borate, lithium tris (oxalato) phosphate, lithium difluorooxalatoborate, lithium tri (oxalato) phosphate, lithium difluorobis (oxalato) phosphate, lithium tetrafluoro (oxalato) phosphate, etc. When the dicarboxylic acid complex lithium salt is used together, the proportion of the inorganic lithium salt in the entire electrolyte is usually 70% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more, and usually 99%. It is not more than mass%, preferably not more than 95 mass%.

  The concentration of the lithium salt in the non-aqueous electrolyte of the present invention is arbitrary as long as the gist of the present invention is not impaired, but is usually 0.5 mol / L or more, preferably 0.6 mol / L or more, more preferably 0.8. 8 mol / L or more. Moreover, it is 3 mol / L or less normally, Preferably it is 2 mol / L or less, More preferably, it is 1.8 mol / L or less, More preferably, it is the range of 1.6 mol / L or less. When the concentration of the lithium salt is in the above range, the electrical conductivity of the non-aqueous electrolyte is sufficient, the electrical conductivity is decreased due to the increase in viscosity, and the non-aqueous electrolyte secondary containing the non-aqueous electrolyte of the present invention is used. Reduces battery performance degradation.

[1-4. Nonaqueous solvent)
The non-aqueous solvent contained in the non-aqueous electrolyte solution of the present invention can be appropriately selected from conventionally known solvents as non-aqueous electrolyte solutions.
Examples of commonly used non-aqueous solvents include cyclic carbonates, chain carbonates, chain and cyclic carboxylic acid esters, chain and cyclic ethers, phosphorus-containing organic solvents, sulfur-containing organic solvents, and aromatic fluorine-containing solvents. Can be mentioned.

  Examples of the cyclic carbonate include cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate. The carbon number of the cyclic carbonate is usually 3 or more and 6 or less. Among these, ethylene carbonate and propylene carbonate are preferable in that the electrolyte is easily dissolved because of a high dielectric constant, and the cycle characteristics are good when a non-aqueous electrolyte secondary battery is obtained. Moreover, the cyclic carbonate which substituted some hydrogen of these compounds with the fluorine is also mentioned. Examples of the cyclic carbonate substituted with fluorine include fluoroethylene carbonate, 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2-trifluoroethylene carbonate, tetrafluoroethylene carbonate, 1-fluoro-2. -Fluorine such as methyl ethylene carbonate, 1-fluoro-1-methyl ethylene carbonate, 1,2-difluoro-1-methyl ethylene carbonate, 1,1,2-trifluoro-2-methyl ethylene carbonate, trifluoromethyl ethylene carbonate C3-C5 cyclic carbonates substituted with Fluoroethylene carbonate, 1,2-difluoroethylene carbonate, and trifluoromethylethylene carbonate are preferred among these. There.

  Examples of the chain carbonate include chain carbonates such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate, and di-n-propyl carbonate. The number of carbon atoms is preferably 1 or more and 5 or less, and particularly preferably 1 or more and 4 or less. Among these, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate are preferable from the viewpoint of improving battery characteristics. Further, chain carbonates in which a part of hydrogen of the alkyl group is substituted with fluorine are also included. As the chain carbonate substituted with fluorine, bis (fluoromethyl) carbonate, bis (difluoromethyl) carbonate, bis (trifluoromethyl) carbonate, bis (2-fluoroethyl) carbonate, bis (2,2-difluoroethyl) Examples include carbonate, bis (2,2,2-trifluoroethyl) carbonate, 2-fluoroethyl methyl carbonate, 2,2-difluoroethyl methyl carbonate, 2,2,2-trifluoroethyl methyl carbonate, and the like.

  As chain carboxylic acid esters, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, sec-butyl acetate, isobutyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, propionic acid Isopropyl, methyl butyrate, ethyl butyrate, propyl butyrate, methyl isobutyrate, ethyl isobutyrate, methyl valerate, ethyl valerate, methyl pivalate, ethyl pivalate, etc. Carboxylic acid esters. Examples of the chain carboxylate substituted with fluorine include methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, butyl trifluoroacetate, 2,2,2-trifluoroethyl trifluoroacetate and the like. Among these, batteries are methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, methyl valerate, methyl isobutyrate, ethyl isobutyrate, and methyl pivalate. It is preferable from the viewpoint of improving characteristics.

Examples of the cyclic carboxylic acid ester include γ-butyrolactone, δ-valerolactone, and the like, and cyclic carboxylic acid esters in which part of hydrogen of these compounds is substituted with fluorine. Among these, γ-butyrolactone is more preferable.
Examples of chain ethers include dimethoxymethane, 1,1-dimethoxyethane, 1,2-dimethoxyethane, diethoxymethane, 1,1-diethoxyethane, 1,2-diethoxyethane, ethoxymethoxymethane, 1,1 Examples include -ethoxymethoxyethane, 1,2-ethoxymethoxyethane, and the like, and chain ethers obtained by substituting a part of hydrogen of these compounds with fluorine. As chain ether substituted with fluorine, bis (trifluoroethoxy) ethane, ethoxytrifluoroethoxyethane, methoxytrifluoroethoxyethane, 1,1,1,2,2,3,4,5,5,5-deca Fluoro-3-methoxy-4-trifluoromethyl-pentane, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-ethoxy-4-trifluoromethyl-pentane, 1 , 1,1,2,2,3,4,5,5,5-decafluoro-3-propoxy-4-trifluoromethyl-pentane, 1,1,2,2-tetrafluoroethyl-2,2, Examples include 3,3-tetrafluoropropyl ether and 2,2-difluoroethyl-2,2,3,3-tetrafluoropropyl ether. Among these, 1,2-dimethoxyethane and 1,2-diethoxyethane are more preferable.

Examples of the cyclic ether include tetrahydrofuran, 2-methyltetrahydrofuran, and the like, and cyclic ethers obtained by substituting a part of hydrogen of these compounds with fluorine.
Examples of the phosphorus-containing organic solvent include trimethyl phosphate, triethyl phosphate, dimethyl ethyl phosphate, methyl diethyl phosphate, ethylene methyl phosphate, ethylene ethyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, Examples thereof include triphenyl phosphite, trimethylphosphine oxide, triethylphosphine oxide, triphenylphosphine oxide and the like, and phosphorus-containing organic solvents in which part of hydrogen of these compounds is substituted with fluorine. Examples of the phosphorus-containing organic solvent substituted with fluorine include tris phosphate (2,2,2-trifluoroethyl) and tris phosphate (2,2,3,3,3-pentafluoropropyl).

  Examples of sulfur-containing organic solvents include sulfolane, 2-methylsulfolane, 3-methylsulfolane, dimethyl sulfone, diethyl sulfone, ethyl methyl sulfone, methylpropyl sulfone, dimethyl sulfoxide, methyl methanesulfonate, ethyl methanesulfonate, and methyl ethanesulfonate. , Ethyl ethanesulfonate, dimethyl sulfate, diethyl sulfate, dibutyl sulfate and the like, and sulfur-containing organic solvents in which part of hydrogen of these compounds is substituted with fluorine.

Examples of the aromatic fluorine-containing solvent include fluorobenzene, difluorobenzene, trifluorobenzene, tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene, benzotrifluoride and the like.
Among the above non-aqueous solvents, it is preferable to use cyclic carbonates such as ethylene carbonate and / or propylene carbonate, and the combined use of these with chain carbonate can achieve both high conductivity and low viscosity of the electrolyte. To preferred.

A non-aqueous solvent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. When using 2 or more types together, for example, when using a cyclic carbonate and a chain carbonate together, the suitable content of the chain carbonate in the non-aqueous solvent is usually 20% by volume or more, preferably 40% by volume or more, Moreover, it is 95 volume% or less normally, Preferably it is 90 volume% or less. On the other hand, the suitable content of the cyclic carbonate in the non-aqueous solvent is usually 5% by volume or more, preferably 10% by volume or more, and usually 80% by volume or less, preferably 60% by volume or less. When the ratio of the chain carbonate is in the above range, an increase in the viscosity of the non-aqueous electrolyte is suppressed, and a decrease in the electrical conductivity of the non-aqueous electrolyte due to a decrease in the degree of dissociation of the lithium salt that is the electrolyte is suppressed. However, fluoroethylene carbonate may be used as a solvent or an additive, and in that case, the content is not limited to the above.
In this specification, the volume of the non-aqueous solvent is a measured value at 25 ° C., but the measured value at the melting point is used for a solid at 25 ° C. such as ethylene carbonate.

[1-5. Other additives]
The nonaqueous electrolytic solution of the present invention may contain various additives as long as the effects of the present invention are not significantly impaired. A conventionally well-known thing can be arbitrarily used as an additive. In addition, an additive may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

(Cyclic carbonate compound having a carbon-carbon unsaturated bond)
Examples of the cyclic carbonate compound having a carbon-carbon unsaturated bond include vinylene carbonate (VC), methyl vinylene carbonate, ethyl vinylene carbonate, 1,2-dimethyl vinylene carbonate, 1,2-diethyl vinylene carbonate, fluoro vinylene carbonate, Vinylene carbonate compounds such as trifluoromethyl vinylene carbonate; vinyl ethylene carbonate, 1-methyl-2-vinylethylene carbonate, 1-ethyl-2-vinylethylene carbonate, 1-n-propyl-2-vinylethylene carbonate, 1- Vinylethylene carbonate compounds such as methyl-2-vinylethylene carbonate, 1,1-divinylethylene carbonate, 1,2-divinylethylene carbonate; 1,1-di Chill 2-methylene-ethylene carbonate, 1,1-diethyl-2-methylene-ethylene carbonate methylene ethylene carbonate compounds such include ethynyl ethylene carbonate and the like. Among these, vinylene carbonate, vinyl ethylene carbonate, and ethynyl ethylene carbonate are preferable from the viewpoint of improving cycle characteristics and capacity maintenance characteristics after high-temperature storage, and vinylene carbonate or vinyl ethylene carbonate is more preferable, and vinylene carbonate is particularly preferable. These may be used alone or in combination of two or more. When using 2 or more types together, it is preferable to use together vinylene carbonate and vinyl ethylene carbonate.

  When the cyclic carbonate compound having a carbon-carbon unsaturated bond is contained, the content in the non-aqueous electrolyte is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.3% by mass. %, Usually 10% by mass or less, preferably 8% by mass or less, more preferably 6% by mass or less. When the content of the cyclic carbonate compound having a carbon-carbon unsaturated bond is in the above range, the effect of improving the cycle characteristics of the battery and the capacity maintenance characteristics after high-temperature storage is sufficiently exhibited. The increase in the amount of gas generated is suppressed.

(Cyclic carbonate compound having a halogen atom)
Examples of the cyclic carbonate compound having a halogen atom such as a fluorine atom include fluoroethylene carbonate, 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2-trifluoroethylene carbonate, tetrafluoroethylene. Carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1,2-difluoro-1-methylethylene carbonate, 1,1,2-trifluoro-2-methylethylene carbonate, tri Examples include fluoromethylethylene carbonate. Of these, fluoroethylene carbonate, 1,2-difluoroethylene carbonate, and 1-fluoro-2-methylethylene carbonate are preferable from the viewpoint of improving cycle characteristics and high-temperature storage characteristics. These may be used alone or in combination of two or more.

  When the non-aqueous electrolyte contains a cyclic carbonate compound having a halogen atom, the content in the non-aqueous electrolyte is usually 0.001% by mass or more, preferably 0.1% by mass or more, more preferably 0.3%. It is at least 10% by mass, more preferably at least 0.5% by mass, usually at most 10% by mass, preferably at most 5% by mass, more preferably at most 4% by mass, still more preferably at most 3% by mass. However, fluoroethylene carbonate may be used as a solvent, and in that case, the content is not limited to the above.

(Acid anhydride)
Examples of the acid anhydride include succinic anhydride, methyl succinic anhydride, 4,4-dimethyl succinic anhydride, 4,5-dimethyl succinic anhydride, maleic anhydride, citraconic anhydride, dimethyl maleic anhydride, and phenyl anhydride. Examples include maleic acid, diphenyl maleic anhydride, phthalic anhydride, cyclohexane 1,2-dicarboxylic anhydride, acetic anhydride, propionic anhydride, and the like. Of these, succinic anhydride, maleic anhydride, and citraconic anhydride are preferable from the viewpoint of improving cycle characteristics and high-temperature storage characteristics. These may be used alone or in combination of two or more.

  When the non-aqueous electrolyte contains an acid anhydride, the content in the non-aqueous electrolyte is usually 0.001% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, More preferably, it is 0.3% by mass or more, usually 10% by mass or less, preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less. When the content of the acid anhydride is within the above range, the effect of improving the cycle characteristics of the battery and the capacity maintenance characteristics after high-temperature storage is sufficiently exhibited, and an increase in internal resistance is suppressed.

(Other isocyanate compounds)
The non-aqueous electrolyte may contain other isocyanate compounds other than the diisocyanate compound represented by the general formula (1) and the halogenated isocyanate compound. Examples of other isocyanate compounds include monoisocyanate compounds and cyclic diisocyanate compounds.
Examples of monoisocyanate and cyclic diisocyanate include ethyl isocyanate, propyl isocyanate, 1,2-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl). Examples include cyclohexane and allyl isocyanate. Of these, 1,2-bis (isocyanatomethyl) cyclohexane 1,3-bis (isocyanatomethyl) cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane are from the viewpoint of improving cycle characteristics and improving high-temperature storage characteristics. preferable. These may be used alone or in combination of two or more.

  When the non-aqueous electrolyte contains other isocyanate compounds, the content in the non-aqueous electrolyte is usually 0.001% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more. More preferably, it is 0.3% by mass or more, usually 10% by mass or less, preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less. When the isocyanate content is within the above range, the effect of improving the cycle characteristics of the battery and the capacity maintenance characteristics after high-temperature storage is sufficiently exhibited, and an increase in internal resistance is suppressed.

(Nitrile compound)
Examples of nitrile compounds include acetonitrile, propionitrile, butyronitrile, valeronitrile, hexanenitrile, heptanenitrile, octanenitrile, nonanenitrile, decanenitrile, dodecanenitrile (lauronitrile), tridecanenitrile, tetradecanenitrile (myristonitrile), Mononitriles such as hexadecane nitrile, pentadecane nitrile, heptadecane nitrile, octadecane nitrile (steanonitrile), nonadecane nitrile, icosonitrile, etc .; Undecanedinitrile, dodecanedinitrile, methylmalononitrile, ethylmalononitrile, isopropyl Rononitrile, t-butylmalononitrile, methylsuccinonitrile, 2,2-dimethylsuccinonitrile, 2,3-dimethylsuccinonitrile, trimethylsuccinonitrile, tetramethylsuccinonitrile, 3,3'-oxydipropio Nitrile, 3,3′-thiodipropionitrile, 3,3 ′-(ethylenedioxy) dipropionitrile, 3,3 ′-(ethylenedithio) dipropionitrile, 1,2,3-propanetricarbonitrile, Examples include dinitriles such as 1,3,5-pentanetricarbonitrile, 1,2,3-tris (2-cyanoethoxy) propane, tris (2-cyanoethyl) amine, and among these, lauronitrile and succinonitrile. , Glutaronitrile, adiponitrile, pimelonitrile and suberonitrile At least one selected from the preferred.
These may be used alone or in combination of two or more.

  When the non-aqueous electrolyte contains a nitrile compound, the content in the non-aqueous electrolyte is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further Preferably it is 0.2% by mass or more, usually 10% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.8% by mass or less. is there. When the content of the nitrile compound is within the above range, the effect of the auxiliary agent is manifested, which is preferable in terms of suppressing gas generation and improving capacity retention characteristics after high-temperature storage.

(Monofluorophosphate and difluorophosphate)
The counter cation of monofluorophosphate and difluorophosphate is not particularly limited, but lithium, sodium, potassium, magnesium, calcium, and NR ¹ R ² R ³ R ⁴ (wherein R ^{1 to} R ⁴ Are each independently a hydrogen atom or an organic group having 1 to 12 carbon atoms.)

Although there is no particular limitation on the organic group having 1 to 12 carbon atoms represented by R ¹ to R ⁴ of the above ammonium, for example, which may be substituted with a halogen atom an alkyl group, substituted with a halogen atom or an alkyl group Examples thereof include an cycloalkyl group which may be substituted, an aryl group which may be substituted with a halogen atom or an alkyl group, and a nitrogen atom-containing heterocyclic group which may have a substituent. Among these, as R ^{1 to} R ⁴ , a hydrogen atom, an alkyl group, a cycloalkyl group, or a nitrogen atom-containing heterocyclic group is preferable.

  Specific examples of monofluorophosphate and difluorophosphate include lithium monofluorophosphate, sodium monofluorophosphate, potassium monofluorophosphate, tetramethylammonium monofluorophosphate, tetraethylammonium monofluorophosphate, difluoro Examples include lithium phosphate, sodium difluorophosphate, potassium difluorophosphate, tetramethylammonium difluorophosphate, tetraethylammonium difluorophosphate, etc., preferably lithium monofluorophosphate and lithium difluorophosphate, more preferably lithium difluorophosphate. preferable. These may be used alone or in combination of two or more.

  When the non-aqueous electrolyte contains monofluorophosphate and / or difluorophosphate, the content in the non-aqueous electrolyte is usually 0.001% by mass or more, preferably 0.01% by mass or more, more Preferably it is 0.1 mass% or more, More preferably, it is 0.2 mass% or more, and is 5 mass% or less normally, Preferably it is 3 mass% or less, More preferably, it is 2 mass% or less.

(Overcharge prevention agent)
Specific examples of the overcharge inhibitor include alkylbiphenyls such as biphenyl, 2-methylbiphenyl, 2-ethylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclopentylbenzene, cyclohexylbenzene, cis-1-propyl-4 -Phenylcyclohexane, trans-1-propyl-4-phenylcyclohexane, cis-1-butyl-4-phenylcyclohexane, trans-1-butyl-4-phenylcyclohexane, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran Methyl phenyl carbonate, ethyl phenyl carbonate, diphenyl carbonate, triphenyl phosphate, tris (2-t-butylphenyl) phosphate, tris (3-t-butylphenyl) phosphate, triphenyl (4-t-butylphenyl) phosphate, Tris (2-t-amylphenyl) phosphate, Tris (3-t-amylphenyl) phosphate, Tris (4-t-amylphenyl) phosphate, Tris (2-cyclohexylphenyl) Aromatic compounds such as phosphate, tris (3-cyclohexylphenyl) phosphate, tris (4-cyclohexylphenyl) phosphate; 2-fluorobiphenyl, 3-fluorobiphenyl, 4-fluorobiphenyl, 4,4′-difluorobiphenyl, 2 , 4-difluorobiphenyl, o-cyclohexyl fluorobenzene, p-cyclohexyl fluorobenzene and other partially fluorinated products of the above aromatic compounds; 2,4-difluoroanisole, 2,5-difluoroanisole, 2,6-difluoroanisole, 3 , 5-Di Examples thereof include fluorine-containing anisole compounds such as fluoroanisole.

  Among these, alkylbiphenyl such as biphenyl and 2-methylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclopentylbenzene, cyclohexylbenzene, cis-1-propyl-4-phenylcyclohexane, trans-1-propyl-4- Phenylcyclohexane, cis-1-butyl-4-phenylcyclohexane, trans-1-butyl-4-phenylcyclohexane, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran, methylphenyl carbonate, diphenyl carbonate, triphenyl phosphate, Aromatic compounds such as tris (4-t-butylphenyl) phosphate and tris (4-cyclohexylphenyl) phosphate; 2-fluorobiphenyl, 3-fluorobiphenyl, 4 -Partially fluorinated products of the above aromatic compounds such as -fluorobiphenyl, 4,4'-difluorobiphenyl, o-cyclohexylfluorobenzene, p-cyclohexylfluorobenzene, etc. are preferred. Partially hydrogenated terphenyl, cyclopentylbenzene, cyclohexylbenzene, Cis-1-propyl-4-phenylcyclohexane, trans-1-propyl-4-phenylcyclohexane, cis-1-butyl-4-phenylcyclohexane, trans-1-butyl-4-phenylcyclohexane, t-butylbenzene, t -Amylbenzene, methylphenyl carbonate, diphenyl carbonate, triphenyl phosphate, tris (4-tert-butylphenyl) phosphate, tris (4-cyclohexylphenyl) phosphate, o-cyclohex At least one, more preferably selected from the group consisting of Le fluorobenzene and p- cyclohexyl fluorobenzene, cyclohexylbenzene, at least one selected from the group consisting of t- butyl benzene and t- amylbenzene particularly preferred.

  Two or more of these may be used in combination. When two or more types are used in combination, in particular, a partially hydrogenated terphenyl, a combination of cyclohexylbenzene and t-butylbenzene or t-amylbenzene, or a partially hydrogenated biphenyl, alkylbiphenyl, terphenyl or terphenyl. It is overcharged to use together those selected from oxygen-free aromatic compounds such as cyclohexylbenzene, t-butylbenzene, t-amylbenzene and those selected from oxygen-containing aromatic compounds such as diphenyl ether and dibenzofuran. This is preferable from the viewpoint of the balance between prevention characteristics and high-temperature storage characteristics.

  The content of these overcharge inhibitors in the non-aqueous electrolyte is usually 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass. It is usually 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less. When the concentration is in the above range, the desired effect of the overcharge inhibitor is easily exhibited, and a decrease in battery characteristics such as high-temperature storage characteristics is suppressed. By including an overcharge inhibitor in the non-aqueous electrolyte, it is possible to suppress the rupture / ignition of the non-aqueous electrolyte secondary battery due to overcharging, and the safety of the non-aqueous electrolyte secondary battery is improved. preferable.

  Other auxiliaries include carbonate compounds such as erythritan carbonate, spiro-bis-dimethylene carbonate, methoxyethyl-methyl carbonate, methoxyethyl-ethyl carbonate, ethoxyethyl-methyl carbonate, ethoxyethyl-ethyl carbonate; dimethyl succinate Diethyl succinate, diallyl succinate, dimethyl maleate, diethyl maleate, diallyl maleate, dipropyl maleate, dibutyl maleate, bis (trifluoromethyl) maleate, bis (pentafluoroethyl) maleate, bis maleate Dicarboxylic acid diester compounds such as (2,2,2-trifluoroethyl); 2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-divinyl-2,4,8,10- Tetraoxaspir [5.5] Spiro compounds such as undecane; ethylene sulfite, propylene sulfite, 1,3-propane sultone, 1,4-butane sultone, 1,3-propene sultone, 1,4-butene sultone, methyl methanesulfonate, ethyl Methanesulfonate, methyl-methoxymethanesulfonate, methyl-2-methoxyethanesulfonate, busulfan, diethylene glycol dimethanesulfonate, 1,2-ethanediol bis (2,2,2-trifluoroethanesulfonate), 1,4-butanediol Bis (2,2,2-trifluoroethanesulfonate), sulfolane, 3-sulfolene, 2-sulfolene, dimethylsulfone, diethylsulfone, divinylsulfone, diphenylsulfone, bis (methylsulfonyl) methane Sulfur-containing compounds such as bis (methylsulfonyl) ethane, bis (ethylsulfonyl) methane, bis (ethylsulfonyl) ethane, bis (vinylsulfonyl) methane, bis (vinylsulfonyl) ethane; 1-methyl-2-pyrrolidinone, 1 -Nitrogen-containing compounds such as methyl-2-piperidone, 3-methyl-2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone and N-methylsuccinimide; heptane, octane, nonane, decane, cycloheptane, Hydrocarbon compounds such as methylcyclohexane, ethylcyclohexane, propylcyclohexane, n-butylcyclohexane, t-butylcyclohexane, dicyclohexyl; fluorinated benzenes such as fluorobenzene, difluorobenzene, pentafluorobenzene, hexafluorobenzene; 2 Fluorinated toluene such as fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, benzotrifluoride; methyl dimethyl phosphinate, ethyl dimethyl phosphinate, ethyl diethyl phosphinate, trimethyl phosphonoformate, triethyl phosphonoformate, Examples thereof include phosphorus-containing compounds such as trimethylphosphonoacetate, triethylphosphonoacetate, trimethyl-3-phosphonopropionate, and triethyl-3-phosphonopropionate. Among these, ethylene sulfite, 1,3-propane sultone, 1,4-butane sultone, 1,3-propene sultone, 1,4-butene sultone, busulfan, 1,4 in terms of improving battery characteristics after high-temperature storage Sulfur-containing compounds that are sulfonate esters such as butanediol bis (2,2,2-trifluoroethanesulfonate) are preferred. These may be used alone or in combination of two or more.

  The content of these auxiliaries in the non-aqueous electrolyte solution is not particularly limited, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, Usually, it is 8 mass% or less, Preferably it is 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 2 mass% or less. The addition of these auxiliaries is preferable in terms of improving capacity maintenance characteristics and cycle characteristics after high-temperature storage. When this concentration is in the above range, the effect of the auxiliary agent is easily exhibited, and the deterioration of battery characteristics such as high load discharge characteristics is suppressed.

  The non-aqueous electrolyte is a cyclic carbonate compound having a carbon-carbon unsaturated bond, a cyclic carbonate compound having a halogen atom, a nitrile compound, cyclohexylbenzene, t-, from the viewpoint of safety and life of the non-aqueous electrolyte secondary battery. It is preferable to further contain at least one selected from the group consisting of amylbenzene, t-butylbenzene and sulfonic acid ester, and it is more preferable to further contain at least one nitrile compound.

[2. Nonaqueous electrolyte secondary battery)
A non-aqueous electrolyte secondary battery of the present invention includes a positive electrode having a positive electrode active material capable of occluding and releasing metal ions and a negative electrode having a negative electrode active material capable of occluding and releasing metal ions. A secondary battery comprising the non-aqueous electrolyte of the present invention.

[2-1. Negative electrode)
The negative electrode active material used for the negative electrode is described below. The negative electrode active material is not particularly limited as long as it can electrochemically occlude and release lithium ions. Specific examples include carbonaceous materials, alloy materials, lithium-containing metal composite oxide materials, and the like. These may be used individually by 1 type, and may be used together combining 2 or more types arbitrarily.

<Negative electrode active material>
Examples of the negative electrode active material include carbonaceous materials, alloy-based materials, lithium-containing metal composite oxide materials, and the like.
Examples of the carbonaceous material include (1) natural graphite, (2) artificial graphite, (3) amorphous carbon, (4) carbon-coated graphite, (5) graphite-coated graphite, and (6) resin-coated graphite. .

(1) Examples of natural graphite include scaly graphite, scaly graphite, soil graphite, and / or graphite particles obtained by subjecting these graphites to spheroidization or densification. Among these, spherical or ellipsoidal graphite subjected to spheroidizing treatment is particularly preferable from the viewpoints of particle filling properties and charge / discharge rate characteristics.
As an apparatus used for the spheroidization treatment, for example, an apparatus that repeatedly gives mechanical action such as compression, friction, shearing force, etc. including the interaction of particles mainly with impact force to the particles can be used. Specifically, it has a rotor with a large number of blades installed inside the casing, and mechanical action such as impact compression, friction, shearing force, etc. on the carbon material introduced inside the rotor by rotating at high speed. And a device for performing the spheroidizing treatment is preferable. Moreover, it is preferable to have a mechanism that repeatedly gives mechanical action by circulating the carbon material.

  For example, when the spheroidizing treatment is performed using the above-described apparatus, the peripheral speed of the rotating rotor is preferably 30 to 100 m / second, more preferably 40 to 100 m / second, and 50 to 100 m / second. More preferably. The treatment can be performed by simply passing a carbonaceous material, but it is preferable to circulate or stay in the apparatus for 30 seconds or longer, and it is preferable to circulate or stay in the apparatus for 1 minute or longer. More preferred.

  (2) Artificial graphite includes coal tar pitch, coal heavy oil, atmospheric residue, petroleum heavy oil, aromatic hydrocarbon, nitrogen-containing cyclic compound, sulfur-containing cyclic compound, polyphenylene, polyvinyl chloride, Organic compounds such as polyvinyl alcohol, polyacrylonitrile, polyvinyl butyral, natural polymer, polyphenylene sulfide, polyphenylene oxide, furfuryl alcohol resin, phenol-formaldehyde resin, imide resin are usually in the range of 2500 ° C. or higher and usually 3200 ° C. or lower. Examples thereof include those produced by graphitization at a temperature and, if necessary, pulverized and / or classified. At this time, a silicon-containing compound or a boron-containing compound can also be used as a graphitization catalyst. In addition, artificial graphite obtained by graphitizing mesocarbon microbeads separated in the heat treatment process of pitch can be mentioned. Furthermore, the artificial graphite of the granulated particle which consists of primary particles is also mentioned. For example, by mixing mesocarbon microbeads or graphitizable carbonaceous material powders such as coke with a graphitizable binder such as tar and pitch and a graphitization catalyst, graphitizing, and grinding as necessary Examples of the resulting graphite particles include a plurality of flat particles and aggregated or bonded so that the orientation planes are non-parallel.

(3) As amorphous carbon, amorphous carbon that has been heat-treated at least once in a temperature range (400 to 2200 ° C.) in which no graphitizable carbon precursor such as tar or pitch is used as a raw material. Examples thereof include amorphous carbon particles that are heat-treated using particles or a non-graphitizable carbon precursor such as a resin as a raw material.
(4) Carbon-coated graphite can be obtained by mixing natural graphite and / or artificial graphite with a carbon precursor that is an organic compound such as tar, pitch, or resin, and heat-treating it at least once in the range of 400 to 2300 ° C. Examples thereof include a carbon graphite composite in which natural graphite and / or artificial graphite is used as nuclear graphite, and amorphous carbon coats the nuclear graphite. The composite form may cover the entire surface or a part thereof, or may be a composite of a plurality of primary particles using carbon originating from the carbon precursor as a binder. Carbon can also be deposited (CVD) by reacting natural graphite and / or artificial graphite with hydrocarbon gases such as benzene, toluene, methane, propane, and aromatic volatiles at a high temperature to deposit carbon on the graphite surface. A graphite composite can also be obtained.

(5) As graphite-coated graphite, natural graphite and / or artificial graphite and a carbon precursor of an easily graphitizable organic compound such as tar, pitch or resin are mixed and once in a range of about 2400 to 3200 ° C. Examples thereof include graphite-coated graphite in which natural graphite and / or artificial graphite obtained by heat treatment is used as nuclear graphite, and graphitized material covers the whole or part of the surface of nuclear graphite.
(6) As the resin-coated graphite, natural graphite and / or artificial graphite obtained by mixing natural graphite and / or artificial graphite with a resin and drying at a temperature of less than 400 ° C. is used as nuclear graphite, and the resin is nuclear graphite. And resin-coated graphite covering the surface.

Moreover, the carbonaceous material of (1)-(6) may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
Examples of organic compounds such as tar, pitch and resin used in the above (2) to (5) include coal-based heavy oil, direct-current heavy oil, cracked heavy petroleum oil, aromatic hydrocarbon, N-ring compound. , S ring compound, polyphenylene, organic synthetic polymer, natural polymer, thermoplastic resin and carbonizable organic compound selected from the group consisting of thermosetting resins. The raw material organic compound may be used after being dissolved in a low molecular organic solvent in order to adjust the viscosity at the time of mixing.

Moreover, as natural graphite and / or artificial graphite used as a raw material of nuclear graphite, natural graphite subjected to spheroidization treatment is preferable.
As an alloy material used as the negative electrode active material, as long as lithium can be occluded / released, lithium alone, simple metals and alloys forming lithium alloys, or oxides, carbides, nitrides, silicides, sulfides thereof Any of compounds such as products or phosphides may be used and is not particularly limited. The single metal and alloy forming the lithium alloy are preferably materials containing group 13 and group 14 metal / metalloid elements (that is, excluding carbon), more preferably aluminum, silicon and tin single metals and An alloy or compound containing these atoms. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

<Physical properties of carbonaceous materials>
When using a carbonaceous material as a negative electrode active material, it is desirable to have the following physical properties.
(X-ray parameters)
The d-value (interlayer distance) of the lattice plane (002 plane) obtained by X-ray diffraction by the Gakushin method of carbonaceous materials is usually 0.335 nm or more, usually 0.360 nm or less, and 0.350 nm. The following is preferable, and 0.345 nm or less is more preferable. Further, the crystallite size (Lc) of the carbonaceous material obtained by X-ray diffraction by the Gakushin method is preferably 1.0 nm or more, and more preferably 1.5 nm or more.

(Volume-based average particle size)
The volume-based average particle diameter of the carbonaceous material is a volume-based average particle diameter (median diameter) obtained by a laser diffraction / scattering method, and is usually 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, and 7 μm. The above is particularly preferable, and is usually 100 μm or less, preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and particularly preferably 25 μm or less.

If the volume-based average particle size is below the above range, the irreversible capacity may increase, leading to loss of initial battery capacity. On the other hand, when the above range is exceeded, when an electrode is produced by coating, an uneven coating surface tends to be formed, which may be undesirable in the battery production process.
The volume-based average particle size is measured by dispersing carbon powder in a 0.2% by weight aqueous solution (about 10 mL) of polyoxyethylene (20) sorbitan monolaurate, which is a surfactant, and laser diffraction / scattering particle size distribution. This is performed using a meter (for example, LA-700 manufactured by Horiba, Ltd.). The median diameter determined by the measurement is defined as the volume-based average particle diameter of the carbonaceous material of the present invention.

(Raman R value)
The Raman R value of the carbonaceous material is a value measured using a laser Raman spectrum method, and is usually 0.01 or more, preferably 0.03 or more, more preferably 0.1 or more, and usually 1. 5 or less, preferably 1.2 or less, more preferably 1 or less, and particularly preferably 0.5 or less.

When the Raman R value is below the above range, the crystallinity of the particle surface becomes too high, and there are cases where the number of sites where Li enters between layers decreases with charge / discharge. That is, charge acceptance may be reduced. In addition, when the negative electrode is densified by applying it to the current collector and then pressing it, the crystals are likely to be oriented in a direction parallel to the electrode plate, which may lead to a decrease in load characteristics.
On the other hand, if it exceeds the above range, the crystallinity of the particle surface is lowered, the reactivity with the non-aqueous electrolyte is increased, and the efficiency may be lowered and the gas generation may be increased.

The Raman spectrum is measured by using a Raman spectrometer (for example, a Raman spectrometer manufactured by JASCO Corporation) to drop the sample naturally into the measurement cell and filling the sample cell with argon ion laser light (or a semiconductor). While irradiating a laser beam, the cell is rotated in a plane perpendicular to the laser beam. The resulting Raman spectrum, the intensity _{I A} of the peak _{P A} in the vicinity of 1580 cm ^-1, and measuring the intensity _{I B} of a peak _{P B} in the vicinity of 1360 cm ^-1, the intensity ratio _{R (R = I B / I} A) Is calculated. The Raman R value calculated by the measurement is defined as the Raman R value of the carbonaceous material of the present invention.

Moreover, said Raman measurement conditions are as follows.
・ Laser wavelength: Ar ion laser 514.5 nm (semiconductor laser 532 nm)
Measurement range: 1100 cm ^{−1 to} 1730 cm ⁻¹
-Raman R value: background processing,
-Smoothing processing: simple average, convolution 5 points

(BET specific surface area)
BET specific surface area of the carbonaceous material is a value of the measured specific surface area using the BET method is usually 0.1 m ² · ^{g -1} or more, 0.7 m ² · ^{g -1} or more, 1. 0 m ² · ^{g -1} or more, and particularly preferably 1.5 m ² · ^{g -1} or more, generally not more than 100 m ² · ^{g -1,} preferably ^{25 m} 2 · ^{g -1} or less, 15 m ² · g ^-1 more preferably less, ^{10 m} 2 · ^{g -1} or less are especially preferred.

  When the value of the BET specific surface area is less than this range, the acceptability of lithium is likely to deteriorate during charging when used as a negative electrode material, lithium is likely to precipitate on the electrode surface, and stability may be reduced. On the other hand, if it exceeds this range, when used as a negative electrode material, the reactivity with the non-aqueous electrolyte increases, gas generation tends to increase, and a preferable battery may be difficult to obtain.

  The specific surface area is measured by the BET method using a surface area meter (for example, a fully automated surface area measuring device manufactured by Okura Riken), preliminarily drying the sample at 350 ° C. for 15 minutes under nitrogen flow, Using a nitrogen helium mixed gas that is accurately adjusted so that the relative pressure value of nitrogen is 0.3, the nitrogen adsorption BET one-point method is performed by a gas flow method.

(Roundness)
When the circularity is measured as the degree of the sphere of the carbonaceous material, it is preferably within the following range. The circularity is defined as “circularity = (peripheral length of an equivalent circle having the same area as the particle projection shape) / (actual perimeter of the particle projection shape)”, and is theoretical when the circularity is 1. Become a true sphere.
The circularity of the particles having a particle size of 3 to 40 μm in the range of the carbonaceous material is desirably closer to 1, and is preferably 0.1 or more, more preferably 0.5 or more, and more preferably 0.8 or more, 0.85 or more is more preferable, and 0.9 or more is particularly preferable. High current density charge / discharge characteristics improve as the degree of circularity increases. Therefore, when the circularity is less than the above range, the filling property of the negative electrode active material is lowered, the resistance between particles is increased, and the high current density charge / discharge characteristics may be lowered for a short time.

  The circularity is measured using a flow type particle image analyzer (for example, FPIA manufactured by Sysmex Corporation). About 0.2 g of a sample was dispersed in a 0.2% by mass aqueous solution (about 50 mL) of polyoxyethylene (20) sorbitan monolaurate as a surfactant, and irradiated with 28 kHz ultrasonic waves at an output of 60 W for 1 minute. The detection range is specified as 0.6 to 400 μm, and the particle size is measured in the range of 3 to 40 μm.

  The method for improving the circularity is not particularly limited, but a sphere-shaped sphere is preferable because the shape of the interparticle void when the electrode body is formed is preferable. Examples of spheroidizing treatment include a method of mechanically approaching a sphere by applying a shearing force and a compressive force, a mechanical / physical processing method of granulating a plurality of fine particles by the binder or the adhesive force of the particles themselves, etc. Is mentioned.

(Tap density)
The tap density of the carbonaceous material is usually 0.1 g · cm ⁻³ or more, preferably 0.5 g · cm ⁻³ or more, more preferably 0.7 g · cm ⁻³ or more, and 1 g · cm ⁻³ or more. Particularly preferable, 2 g · cm ⁻³ or less is preferable, 1.8 g · cm ⁻³ or less is more preferable, and 1.6 g · cm ⁻³ or less is particularly preferable. When the tap density is below the above range, the packing density is difficult to increase when used as a negative electrode, and a high-capacity battery may not be obtained. On the other hand, when the above range is exceeded, there are too few voids between particles in the electrode, it is difficult to ensure conductivity between the particles, and it may be difficult to obtain preferable battery characteristics.

The tap density is measured by passing through a sieve having an opening of 300 μm, dropping the sample onto a 20 cm ³ tapping cell and filling the sample to the upper end surface of the cell, and then measuring a powder density measuring device (for example, manufactured by Seishin Enterprise Co., Ltd.). Using a tap denser, tapping with a stroke length of 10 mm is performed 1000 times, and the tap density is calculated from the volume at that time and the mass of the sample.

(Orientation ratio)
The orientation ratio of the carbonaceous material is usually 0.005 or more, preferably 0.01 or more, more preferably 0.015 or more, and usually 0.67 or less. When the orientation ratio is below the above range, the high-density charge / discharge characteristics may deteriorate. The upper limit of the above range is the theoretical upper limit value of the orientation ratio of the carbonaceous material.
The orientation ratio is measured by X-ray diffraction after pressure-molding the sample. Set the molding obtained by filling 0.47 g of the sample into a molding machine with a diameter of 17 mm and compressing it with 58.8 MN · m ^{-2 so} that it is flush with the surface of the sample holder for measurement. X-ray diffraction is measured. From the (110) diffraction and (004) diffraction peak intensities of the obtained carbon, a ratio represented by (110) diffraction peak intensity / (004) diffraction peak intensity is calculated.

The X-ray diffraction measurement conditions are as follows. “2θ” indicates a diffraction angle.
・ Target: Cu (Kα ray) graphite monochromator ・ Slit:
Divergence slit = 0.5 degree Light receiving slit = 0.15 mm
Scattering slit = 0.5 degree / measurement range and step angle / measurement time:
(110) plane: 75 degrees ≦ 2θ ≦ 80 degrees 1 degree / 60 seconds (004) plane: 52 degrees ≦ 2θ ≦ 57 degrees 1 degree / 60 seconds

(Aspect ratio (powder))
The aspect ratio of the carbonaceous material is usually 1 or more and usually 10 or less, preferably 8 or less, and more preferably 5 or less. If the aspect ratio exceeds the above range, streaking or a uniform coated surface cannot be obtained when forming an electrode plate, and the high current density charge / discharge characteristics may deteriorate. The lower limit of the above range is the theoretical lower limit value of the aspect ratio of the carbonaceous material.

  The aspect ratio is measured by magnifying and observing the carbonaceous material particles with a scanning electron microscope. Carbonaceous material particles when three-dimensional observation is performed by selecting arbitrary 50 graphite particles fixed to the end face of a metal having a thickness of 50 μm or less and rotating and tilting the stage on which the sample is fixed. The longest diameter A and the shortest diameter B orthogonal thereto are measured, and the average value of A / B is obtained.

<Configuration and production method of negative electrode>
Any known method can be used for producing the electrode as long as the effects of the present invention are not significantly impaired. For example, it is formed by adding a binder, a solvent, and, if necessary, a thickener, a conductive material, a filler, etc. to the negative electrode active material to form a slurry, which is applied to a current collector, dried and then pressed. Can do.
In the case of using an alloy-based material, a method of forming a thin film layer (negative electrode active material layer) containing the above-described negative electrode active material by a technique such as vapor deposition, sputtering, or plating is also used.

(Electrode density)
The electrode structure when the negative electrode active material is made into an electrode is not particularly limited, but the density of the negative electrode active material present on the current collector is preferably 1 g · cm ⁻³ or more, and 1.2 g · cm ⁻³ or more. but more preferably, particularly preferably 1.3 g · ^{cm -3} or more, preferably 2.2 g · ^{cm -3} or less, more preferably 2.1 g · ^{cm -3} or less, 2.0 g · ^{cm -3} or less Further preferred is 1.9 g · cm ⁻³ or less. When the density of the negative electrode active material existing on the current collector exceeds the above range, the negative electrode active material particles are destroyed, and the initial irreversible capacity increases or non-aqueous system near the current collector / negative electrode active material interface. There is a case where high current density charge / discharge characteristics are deteriorated due to a decrease in permeability of the electrolytic solution. On the other hand, if the amount is less than the above range, the conductivity between the negative electrode active materials decreases, the battery resistance increases, and the capacity per unit volume may decrease.

[2-2. (Positive electrode)
<Positive electrode active material>
The positive electrode active material (lithium transition metal compound) used for the positive electrode is described below.
<Lithium transition metal compound>
A lithium transition metal compound is a compound having a structure capable of desorbing and inserting Li ions, and examples thereof include sulfides, phosphate compounds, and lithium transition metal composite oxides. Examples of sulfides include compounds having a two-dimensional layered structure such as TiS ₂ and MoS ₂ , and strong compounds represented by the general formula Me _x Mo ₆ S ₈ (Me is various transition metals including Pb, Ag, and Cu). Examples thereof include a sugar compound having a three-dimensional skeleton structure. Examples of the phosphate compound include those belonging to the olivine structure, and are generally represented by LiMePO ₄ (Me is at least one transition metal), specifically, LiFePO ₄ , LiCoPO ₄ , LiNiPO ₄ , Examples include LiMnPO ₄ . Examples of the lithium transition metal composite oxide include spinel structures capable of three-dimensional diffusion and those belonging to a layered structure capable of two-dimensional diffusion of lithium ions. Those having a spinel structure are generally expressed as LiMe ₂ O ₄ (Me is at least one transition metal), specifically, LiMn ₂ O ₄ , LiCoMnO ₄ , LiNi _0.5 Mn _1.5 O. ₄ , LiCoVO _{4 and the} like. Those having a layered structure are generally expressed as LiMeO ₂ (Me is at least one transition metal). LiCoO _{2 Specifically, LiNiO 2, LiNi 1-x} Co x O 2, LiNi 1-x-y Co x Mn y O 2, LiNi 0.5 Mn 0.5 O 2, Li 1.2 Cr 0. _{4 Mn 0.4 O 2, Li 1.2} Cr 0.4 Ti 0.4 O 2, such as LiMnO ₂ and the like.

(composition)
The lithium-containing transition metal compound is, for example, a lithium transition metal compound represented by the following composition formula (A) or (B).
1) In the case of a lithium transition metal compound represented by the following composition formula (A)

Li _{1 + x} MO ₂ (A)
However, x is usually 0 or more and 0.5 or less. M is an element composed of Ni and Mn or Ni, Mn and Co, and the Mn / Ni molar ratio is usually 0.1 or more and 5 or less. The Ni / M molar ratio is usually 0 or more and 0.5 or less. The Co / M molar ratio is usually 0 or more and 0.5 or less. In addition, the rich portion of Li represented by x may be replaced with the transition metal site M.

  In the composition formula (A), the atomic ratio of the oxygen amount is described as 2 for convenience, but there may be some non-stoichiometry. Moreover, x in the said compositional formula is the preparation composition in the manufacture stage of a lithium transition metal type compound. Usually, batteries on the market are aged after the batteries are assembled. For this reason, the Li amount of the positive electrode may be deficient with charge / discharge. In this case, x may be measured to be −0.65 or more and 1 or less when discharged to 3 V in composition analysis.

A lithium transition metal-based compound is excellent in battery characteristics when fired at a high temperature in an oxygen-containing gas atmosphere in order to enhance the crystallinity of the positive electrode active material. Further, the lithium transition metal-based compound represented by the composition formula (A) may be a solid solution with Li ₂ MO ₃ called a 213 layer, as shown in the general formula (A ′) below.

αLi ₂ MO ₃ · (1-α) LiM′O ₂ (A ′)
In the general formula, α is a number satisfying 0 <α <1.
M is at least one metallic element average oxidation number of 4 ^+, specifically, at least one metal element Mn, Zr, Ti, Ru, selected from the group consisting of Re and Pt.

M 'is at least one metallic element average oxidation number of 3 ^+, preferably, V, Mn, Fe, at least one metallic element selected from the group consisting of Co and Ni, more preferably , At least one metal element selected from the group consisting of Mn, Co and Ni.
2) A lithium transition metal compound represented by the following general formula (B).

_{Li [Li a M b Mn 2} -b-a] O 4 + δ ··· (B)
However, M is an element comprised from at least 1 sort (s) of the transition metals chosen from Ni, Cr, Fe, Co, Cu, Zr, Al, and Mg.
The value of b is usually 0.4 or more and 0.6 or less.
If the value of b is this range, the energy density per unit weight in a lithium transition metal type compound will be high.

  The value of a is usually 0 or more and 0.3 or less. Moreover, a in the above composition formula is a charged composition in the production stage of the lithium transition metal compound. Usually, batteries on the market are aged after the batteries are assembled. For this reason, the Li amount of the positive electrode may be deficient with charge / discharge. In this case, a may be measured to be −0.65 or more and 1 or less when discharged to 3 V in composition analysis. When the value of a is within this range, the energy density per unit weight in the lithium transition metal compound is not significantly impaired, and good load characteristics can be obtained.

Furthermore, the value of δ is usually in the range of ± 0.5.
If the value of δ is within this range, the stability as a crystal structure is high, and the cycle characteristics and high-temperature storage of a battery having an electrode produced using this lithium transition metal compound are good.
Here, the chemical meaning of the lithium composition in the lithium nickel manganese composite oxide, which is the composition of the lithium transition metal compound, will be described in more detail below.

In order to obtain a and b in the composition formula of the lithium transition metal compound, each transition metal and lithium are analyzed with an inductively coupled plasma emission spectrometer (ICP-AES) to obtain a ratio of Li / Ni / Mn. It is calculated by the thing.
From a structural point of view, it is considered that lithium related to a is substituted for the same transition metal site. Here, due to the lithium according to a, the average valence of M and manganese becomes larger than 3.5 due to the principle of charge neutrality.
Further, the lithium transition metal based compound may be substituted with fluorine, it is expressed as _{LiMn 2 O 4-x F 2x} .

(blend)
Specific examples of the lithium transition metal compound having the above composition include, for example, Li _{1 + x} Ni _0.5 Mn _0.5 O ₂ , Li _{1 + x} Ni _0.85 Co _0.10 Al _0.05 O ₂ , Li _{1 + x} Ni _0.33 Mn _0.33 Co _0.33 O ₂ , Li _{1 + x} Ni _0.45 Mn _0.45 Co _0.1 O ₂ , Li _{1 + x} Mn _1.8 Al _0.2 O ₄ , Li _{1 + x} Mn _1.5 Ni _0.5 O ₄ and the like. These lithium transition metal compounds may be used alone or in a blend of two or more.

(Introducing foreign elements)
Moreover, a different element may be introduce | transduced into a lithium transition metal type compound. As the different elements, B, Na, Mg, Al, K, Ca, Ti, V, Cr, Fe, Cu, Zn, Sr, Y, Zr, Nb, Ru, Rh, Pd, Ag, In, Sb, Te , Ba, Ta, Mo, W, Re, Os, Ir, Pt, Au, Pb, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Bi , N, F, S, Cl, Br, I, As, Ge, P, Pb, Sb, Si, and Sn. These foreign elements may be incorporated into the crystal structure of the lithium transition metal compound, or may not be incorporated into the crystal structure of the lithium transition metal compound, and may be a single element or compound on the particle surface or grain boundary. May be unevenly distributed.

<Configuration and production method of positive electrode for lithium secondary battery>
The positive electrode for a lithium secondary battery is formed by forming a positive electrode active material layer containing the above-described lithium transition metal compound powder for a lithium secondary battery positive electrode material and a binder on a current collector.
The positive electrode active material layer is usually formed by mixing a positive electrode material, a binder, and a conductive material and a thickener, which are used as necessary, in a dry form into a sheet shape, and then pressing the positive electrode current collector on the positive electrode current collector. Alternatively, these materials are dissolved or dispersed in a liquid medium to form a slurry, which is applied to the positive electrode current collector and dried.

As the material for the positive electrode current collector, metal materials such as aluminum, stainless steel, nickel plating, titanium, and tantalum, and carbon materials such as carbon cloth and carbon paper are usually used. As for the shape, in the case of a metal material, a metal foil, a metal cylinder, a metal coil, a metal plate, a metal thin film, an expanded metal, a punch metal, a foam metal, etc., and in the case of a carbon material, a carbon plate, a carbon thin film, a carbon cylinder Etc. In addition, you may form a thin film suitably in mesh shape.
When a thin film is used as the positive electrode current collector, its thickness is arbitrary, but a range of usually 1 μm or more and 100 mm or less is suitable. If it is thinner than the above range, the strength required for the current collector may be insufficient. On the other hand, if it is thicker than the above range, the handleability may be impaired.

  The binder used in the production of the positive electrode active material layer is not particularly limited, and in the case of a coating method, any material that is stable with respect to the liquid medium used during electrode production may be used. Specific examples include polyethylene, Resin polymers such as polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, cellulose, nitrocellulose, SBR (styrene butadiene rubber), NBR (acrylonitrile butadiene rubber), fluorine rubber, isoprene rubber, butadiene rubber, ethylene・ Rubber polymers such as propylene rubber, styrene / butadiene / styrene block copolymers and hydrogenated products thereof, EPDM (ethylene / propylene / diene terpolymers), styrene / ethylene / butadiene / ethylene copolymers, Styrene / isoprene styrene bromide Copolymer and its hydrogenated thermoplastic elastomeric polymer, syndiotactic-1,2-polybutadiene, polyvinyl acetate, ethylene / vinyl acetate copolymer, propylene / α-olefin copolymer, etc. Fluorine polymers such as soft resinous polymers, polyvinylidene fluoride, polytetrafluoroethylene, fluorinated polyvinylidene fluoride, polytetrafluoroethylene / ethylene copolymers, ion conductivity of alkali metal ions (especially lithium ions) And a polymer composition having the same. In addition, these substances may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

The ratio of the binder in the positive electrode active material layer is usually 0.1% by mass or more and 80% by mass or less. If the proportion of the binder is too low, the positive electrode active material cannot be sufficiently retained and the positive electrode has insufficient mechanical strength, which may deteriorate battery performance such as cycle characteristics. Battery capacity and conductivity may be reduced.
The positive electrode active material layer usually contains a conductive material in order to increase conductivity. There are no particular restrictions on the type, but specific examples include metal materials such as copper and nickel, graphite such as natural graphite and artificial graphite, carbon black such as acetylene black, and amorphous carbon such as needle coke. And carbon materials. In addition, these substances may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. The proportion of the conductive material in the positive electrode active material layer is usually 0.01% by mass or more and 50% by mass or less. If the proportion of the conductive material is too low, the conductivity may be insufficient, and conversely if it is too high, the battery capacity may be reduced.

  As a liquid medium for forming a slurry, it is possible to dissolve or disperse a lithium transition metal compound powder as a positive electrode material, a binder, and a conductive material and a thickener used as necessary. If it is a solvent, there is no restriction | limiting in particular in the kind, You may use either an aqueous solvent or an organic solvent. Examples of the aqueous solvent include water and alcohol. Examples of the organic solvent include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N , N-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran (THF), toluene, acetone, dimethyl ether, dimethylacetamide, hexamethylphosphalamide, dimethyl sulfoxide, benzene, xylene, quinoline, pyridine, methylnaphthalene, hexane, etc. be able to. In particular, when an aqueous solvent is used, a dispersant is added together with the thickener, and a slurry such as SBR is slurried. In addition, these solvents may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

The content ratio of the lithium transition metal-based compound powder as the positive electrode material in the positive electrode active material layer is usually 10% by mass or more and 99.9% by mass or less. If the proportion of the lithium transition metal compound powder in the positive electrode active material layer is too large, the strength of the positive electrode tends to be insufficient, and if it is too small, the capacity may be insufficient.
The thickness of the positive electrode active material layer is usually about 10 to 200 μm.
The electrode density after pressing the positive electrode is usually 2.2 g / cm ³ or more and 4.2 g / cm ³ or less.
The positive electrode active material layer obtained by coating and drying is preferably consolidated by a roller press or the like in order to increase the packing density of the positive electrode active material.

[2-3. (Separator)
Usually, a separator is interposed between the positive electrode and the negative electrode in order to prevent a short circuit. In this case, the nonaqueous electrolytic solution of the present invention is usually used by impregnating the separator.
The material and shape of the separator are not particularly limited, and known ones can be arbitrarily adopted as long as the effects of the present invention are not significantly impaired. Among them, a resin, glass fiber, inorganic material, etc. formed of a material that is stable with respect to the non-aqueous electrolyte solution of the present invention is used, and a porous sheet or a nonwoven fabric-like material having excellent liquid retention properties is used. Is preferred.
As materials for the resin and glass fiber separator, for example, polyolefins such as polyethylene and polypropylene, aromatic polyamides, polytetrafluoroethylene, polyethersulfone, glass filters and the like can be used. Of these, glass filters and polyolefins are preferred, and polyolefins are more preferred. These materials may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The thickness of the separator is arbitrary, but is usually 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more, and usually 50 μm or less, preferably 40 μm or less, more preferably 30 μm or less. If the separator is too thin than the above range, the insulating properties and mechanical strength may decrease. On the other hand, if it is thicker than the above range, not only the battery performance such as the rate characteristic may be lowered, but also the energy density of the whole non-aqueous electrolyte secondary battery may be lowered.

  Furthermore, when using a porous material such as a porous sheet or nonwoven fabric as the separator, the porosity of the separator is arbitrary, but is usually 20% or more, preferably 35% or more, more preferably 45% or more, Further, it is usually 90% or less, preferably 85% or less, and more preferably 75% or less. If the porosity is too smaller than the above range, the membrane resistance tends to increase and the rate characteristics tend to deteriorate. Moreover, when larger than the said range, it exists in the tendency for the mechanical strength of a separator to fall and for insulation to fall.

Moreover, although the average pore diameter of a separator is also arbitrary, it is 0.5 micrometer or less normally, 0.2 micrometer or less is preferable, and it is 0.05 micrometer or more normally. If the average pore diameter exceeds the above range, a short circuit tends to occur. On the other hand, below the above range, the film resistance may increase and the rate characteristics may deteriorate.
On the other hand, as the inorganic material, for example, oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate are used. Used.

  As the form, a thin film shape such as a non-woven fabric, a woven fabric, or a microporous film is used. In the thin film shape, those having a pore diameter of 0.01 to 1 μm and a thickness of 5 to 50 μm are preferably used. In addition to the above-described independent thin film shape, a separator formed by forming a composite porous layer containing the inorganic particles on the surface layer of the positive electrode and / or the negative electrode using a resin binder can be used. For example, a porous layer may be formed by using alumina particles having a 90% particle size of less than 1 μm on both surfaces of the positive electrode and using a fluororesin as a binder.

  The characteristics of the separator in the non-electrolyte secondary battery can be grasped by the Gurley value. The Gurley value indicates the difficulty of air passage in the film thickness direction, and is expressed as the number of seconds required for 100 ml of air to pass through the film. It means that it is harder to go through. That is, a smaller value means better communication in the thickness direction of the film, and a larger value means lower communication in the thickness direction of the film. Communication is the degree of connection of holes in the film thickness direction. If the Gurley value of the separator of the present invention is low, it can be used for various purposes. For example, when used as a separator for a non-aqueous lithium secondary battery, a low Gurley value means that lithium ions can be easily transferred and is preferable because of excellent battery performance. Although the Gurley value of a separator is arbitrary, Preferably it is 10-1000 second / 100ml, More preferably, it is 15-800 second / 100ml, More preferably, it is 20-500 second / 100ml. If the Gurley value is 1000 seconds / 100 ml or less, the electrical resistance is substantially low, which is preferable as a separator.

[2-4. Battery design)
<Electrode group>
The electrode group has a laminated structure in which the positive electrode plate and the negative electrode plate are interposed through the separator, and a structure in which the positive electrode plate and the negative electrode plate are wound in a spiral shape through the separator. Either is acceptable. The ratio of the volume of the electrode group to the internal volume of the battery (hereinafter referred to as electrode group occupancy) is usually 40% or more, preferably 50% or more, and usually 90% or less, preferably 80% or less. .

  When the electrode group occupancy is below the above range, the battery capacity decreases. Also, if the above range is exceeded, there are few void spaces, the battery expands, and the member expands or the vapor pressure of the liquid component of the electrolytic solution increases and the internal pressure rises, and charging and discharging as a battery is repeated. In some cases, the gas release valve that lowers various characteristics such as performance and high-temperature storage or operates to release the internal pressure to the outside may operate.

<Exterior case>
The material of the outer case is not particularly limited as long as it is a substance that is stable with respect to the non-aqueous electrolyte used. Specifically, a nickel-plated steel plate, stainless steel, aluminum, an aluminum alloy, a metal such as a magnesium alloy, or a laminated film (laminate film) of a resin and an aluminum foil is used. From the viewpoint of weight reduction, an aluminum or aluminum alloy metal or a laminate film is preferably used.

  In an exterior case using metals, the metal is welded together by laser welding, resistance welding, or ultrasonic welding to form a sealed sealed structure, or a caulking structure using the above metals via a resin gasket. Things. Examples of the outer case using the laminate film include a case where a resin-sealed structure is formed by heat-sealing resin layers. In order to improve sealing performance, a resin different from the resin used for the laminate film may be interposed between the resin layers. In particular, when a resin layer is heat-sealed through a current collecting terminal to form a sealed structure, a metal and a resin are joined, so that a resin having a polar group or a modified group having a polar group introduced as an intervening resin is used. Resins are preferably used.

<Protective element>
Protection elements such as PTC (Positive Temperature Coefficient), thermal fuse, thermistor, whose resistance increases when abnormal heat is generated or excessive current flows, cut off the current flowing through the circuit due to sudden increase in battery internal pressure or internal temperature during abnormal heat generation A valve (current cutoff valve) or the like can be used. It is preferable to select a protective element that does not operate under normal use at a high current, and it is more preferable that the protective element is designed so as not to cause abnormal heat generation or thermal runaway even without the protective element.

<Exterior body>
The non-aqueous electrolyte secondary battery of the present invention is usually configured by housing the non-aqueous electrolyte, the negative electrode, the positive electrode, the separator, and the like in an exterior body. This exterior body is not particularly limited, and any known one can be arbitrarily adopted as long as the effects of the present invention are not significantly impaired. Specifically, the material of the exterior body is arbitrary, but usually, for example, nickel-plated iron, stainless steel, aluminum or an alloy thereof, nickel, titanium, or the like is used.
The shape of the exterior body is also arbitrary, and may be any of a cylindrical shape, a square shape, a laminate shape, a coin shape, a large size, and the like.

[3. Isocyanate composition]
The isocyanate composition of the present invention includes a diisocyanate compound represented by the following general formula (1) and a halogenated isocyanate compound represented by the following general formula (2), and the content of the halogenated isocyanate compound is the above The total amount of the diisocyanate compound and the halogenated isocyanate compound is more than 0 and 6% by mass or less.

（Ｙ^１及びＹ^２はそれぞれ独立して炭素数１〜２０の鎖状炭化水素基を表し、Ｘ^２はハロゲン原子を表す。）

(Y ¹ and Y ² each independently represent a chain hydrocarbon group having 1 to 20 carbon atoms, and X ² represents a halogen atom.)

  The preferred embodiment of the diisocyanate compound represented by the general formula (1) and the preferred embodiment of the halogenated isocyanate compound represented by the general formula (2) in the isocyanate composition are as described above.

  The content of the halogenated isocyanate compound in the isocyanate composition is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more as a lower limit value in the total mass of the diisocyanate compound and the halogenated isocyanate compound. . The upper limit is preferably 5.5% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, still more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, and most preferably It is 0.1 mass% or less.

The content of the halogenated isocyanate compound in the isocyanate composition can be measured by gas chromatography. The measurement conditions for gas chromatography are, for example, as follows.
Equipment; Shimadzu GC-2010
Detector; FID
Column; DB-5 60m * 0.25mm * 1.0μm
Carrier gas; He 150KPa (pressure mode)
Inlet temperature: 180 ° C
Detector temperature: 250 ° C
Column temperature: 100 ° C. (0 min) → 10 ° C./min→240° C. (45 min)
Split ratio: 20
Injection volume: 0.5 μl

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these Examples, unless the summary is exceeded.
The compounds used in this example are shown below.

(A) Hexamethylene diisocyanate (1,6-diisocyanatohexane; DIH)
(B) 1-chloro-6-isocyanatohexane (CIH)

<Examples 1-1 to 1-3, Comparative Examples 1-1 to 1-4>
[Preparation of non-aqueous electrolyte]
Under a dry argon atmosphere, 1 mol / L of LiPF ₆ sufficiently dried in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (volume-volume ratio 3: 7) (concentration in non-aqueous electrolyte) And then, 1.0 mass% of a diisocyanate compound (DIH) was added (this is referred to as a reference electrolyte solution 1). An electrolyte solution was prepared by adding a halogenated isocyanate compound (CIH) at a ratio shown in Table 1 below with respect to the entire reference electrolyte solution 1. However, Comparative Example 1-1 is the reference electrolyte 1 itself.

[Production of positive electrode]
97% by mass of lithium cobaltate (LiCoO ₂ ) as a positive electrode active material, 1.5% by mass of acetylene black as a conductive material, and 1.5% by mass of polyvinylidene fluoride (PVdF) as a binder, N-methylpyrrolidone In a solvent, the mixture was slurried by mixing with a disperser. This was uniformly applied to one side of an aluminum foil having a thickness of 21 μm, dried, and then pressed to obtain a positive electrode.

[Production of negative electrode]
100 parts by weight of graphite powder as the negative electrode active material, 1 part by weight of aqueous dispersion of sodium carboxymethyl cellulose (concentration of 1% by weight of sodium carboxymethyl cellulose) as the thickener and binder, respectively, and aqueous dispersion of styrene-butadiene rubber 1 part by mass (concentration of styrene-butadiene rubber 50% by mass) was added and mixed with a disperser to form a slurry. This slurry was uniformly applied to one side of a 12 μm thick copper foil, dried, and then pressed to obtain a negative electrode.

[Manufacture of non-aqueous electrolyte batteries (coin type)]
Using the above positive electrode and negative electrode and the non-aqueous electrolyte prepared in each Example and Comparative Example, a coin-type cell was produced by the following procedure. That is, the negative electrode was placed through a polyethylene separator impregnated with an electrolytic solution on a positive electrode accommodated in a stainless steel can body also serving as a positive electrode conductor. The can body and a sealing plate serving also as a negative electrode conductor were caulked and sealed via an insulating gasket to produce a coin-type cell.

[Battery evaluation]
In a constant temperature bath at 25 ° C., a non-aqueous electrolyte secondary battery of a coin-type cell was charged at a constant current for 6 hours at a current corresponding to 0.05 C (hereinafter referred to as “CC charging” as appropriate), and then 3 at 0.2 C The value obtained by discharging to 0.000 V and [discharge capacity] / [charge capacity] of the obtained capacity was defined as the initial efficiency. Constant current-constant voltage charging (hereinafter, referred to as “CC-CV charging” as appropriate) was performed at 0.2 C up to 4.1 V. Then, it discharged to 3.00V at 0.2C, and stabilized the non-aqueous electrolyte secondary battery. Then, after performing CC-CV charge to 4.35V at 0.2C, the operation which discharges to 3.00V at 0.2C was performed 3 times, and the initial conditioning was performed.
Here, 1C represents a current value for discharging the reference capacity of the battery in one hour, and for example, 0.2C represents a current value of 1/5 thereof.

[High temperature storage characteristics evaluation]
After the initial conditioning, the non-aqueous electrolyte battery was subjected to CC-CV charge (0.05C cut) up to 4.35V at 0.2C at 25 ° C, and then the battery open circuit voltage (OCV; initial OCV) was measured. Thereafter, high-temperature storage was performed at 85 ° C. for 24 hours. After the battery was sufficiently cooled, the OCV of the battery after storage (OCV after storage) was measured, and the difference between the initial OCV and the OCV after storage was defined as “ΔOCV”.
After storage at high temperature, the capacity after storage at high temperature was determined by discharging to 25 ° C. and 3.0C at 0.2C. The remaining capacity after high-temperature storage was normalized by the remaining capacity of Comparative Example 1-1, and the relative remaining capacity was evaluated based on Comparative Example 1-1 as the standard (1.00).

  As apparent from Table 1, in Examples 1-1 to 1-3, good high-temperature storage characteristics were obtained. On the other hand, in Comparative Example 1-1 (not containing a halogenated isocyanate compound (below the analysis limit)) and Comparative Examples 1-2 to 1-4 (content of the halogenated isocyanate compound is 0.01% by mass or more) Compared with Examples 1-1 to 1-3, the high-temperature storage characteristics deteriorated. Moreover, even if it is a case where a halogenated isocyanate compound is not included like the comparative example 1-1, it turns out that a high temperature storage characteristic falls. In Comparative Example 1-4, although ΔOCV was good, the relative residual capacity was insufficient, and the high-temperature storage characteristics were insufficient as a comprehensive evaluation.

<Example 2>
[Preparation of isocyanate composition]
Literature; Organic Synthesis, Coll. Vol. 4, p. 521 (1963); Vol. 31, p. 62 (1951), hexamethylene diisocyanate was synthesized as a diisocyanate compound (DIH) from hexamethylenediamine and phosgene. To the obtained diisocyanate compound, 1-chloro-6-isocyanatohexane was added as a halogenated isocyanate compound to prepare an isocyanate composition.
When the content of the halogenated isocyanate compound was analyzed for the obtained isocyanate composition using gas chromatography, it was 0.1 mass%.

[Preparation of non-aqueous electrolyte]
Under a dry argon atmosphere, 1 mol / L of LiPF ₆ sufficiently dried in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (volume-volume ratio 3: 7) (concentration in non-aqueous electrolyte) And a non-aqueous electrolyte solution was prepared by adding 1.0% by mass of the diisocyanate composition obtained above.

When the content of the halogenated isocyanate compound (CIH) was analyzed using the high performance liquid chromatography about the obtained non-aqueous electrolyte, it was in the range of 0.000001 mass% or more and 0.06 mass% or less.
Moreover, when this non-aqueous electrolyte solution was used and a non-aqueous electrolyte battery was produced in the same manner as described above and the high-temperature storage characteristics were evaluated, good results were obtained.

According to the non-aqueous electrolyte solution of the present invention, the decomposition of the electrolyte solution of the non-aqueous electrolyte secondary battery is suppressed, and when the battery is used in a high temperature environment, gas generation and deterioration of the battery are suppressed and a high energy density. The non-aqueous electrolyte secondary battery can be manufactured. Therefore, it can be suitably used in various fields such as an electronic device in which a non-aqueous electrolyte secondary battery is used.
The application of the non-aqueous electrolyte secondary battery of the present invention is not particularly limited, and can be used for various known applications. Specific examples include notebook computers, pen input computers, mobile computers, electronic book players, mobile phones, mobile faxes, mobile copy, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, minidiscs, and transceivers. , Electronic notebook, calculator, memory card, portable tape recorder, radio, backup power supply, motor, automobile, motorcycle, motorbike, bicycle, lighting equipment, toy, game equipment, clock, electric tool, strobe, camera, home-use large A storage battery etc. can be mentioned.

Claims (7)

A non-aqueous electrolyte solution included in a non-aqueous electrolyte secondary battery comprising a positive electrode having a positive electrode active material capable of occluding and releasing metal ions and a negative electrode having a negative electrode active material capable of occluding and releasing metal ions. ,
It contains a diisocyanate compound represented by the following general formula (1) and a halogenated isocyanate compound, and the content of the halogenated isocyanate compound is 0.000001% by mass or more, based on the total amount of the non-aqueous electrolyte solution. A non-aqueous electrolytic solution characterized by being not more than 06% by mass.

(Y ¹ represents a chain hydrocarbon group having 1 to 20 carbon atoms.)   2. The non-aqueous electrolyte solution according to claim 1, wherein the content of the halogenated isocyanate compound is 0.000005 mass% or more and 0.055 mass% or less with respect to the total amount of the non-aqueous electrolyte solution. The non-aqueous electrolyte solution according to claim 1 or 2, wherein the halogenated isocyanate compound is represented by the following general formula (2).

(Y ² represents a chain hydrocarbon group having 1 to 20 carbon atoms, and X ² represents a halogen atom.)   The diisocyanate compound represented by the general formula (1) is at least one selected from the group consisting of trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate and octamethylene diisocyanate. The non-aqueous electrolyte solution according to any one of claims 1 to 3.   It further contains at least one selected from the group consisting of a cyclic carbonate compound having a carbon-carbon unsaturated bond, a cyclic carbonate compound having a halogen atom, a nitrile compound, cyclohexylbenzene, t-amylbenzene, t-butylbenzene, and a sulfonate ester. The non-aqueous electrolyte solution according to claim 1, wherein the non-aqueous electrolyte solution is a non-aqueous electrolyte solution.   The non-aqueous electrolyte solution according to claim 1, comprising at least one nitrile compound. A non-aqueous electrolyte secondary battery comprising a positive electrode having a positive electrode active material capable of occluding and releasing metal ions and a negative electrode having a negative electrode active material capable of occluding and releasing metal ions,
A non-aqueous electrolyte secondary battery comprising the non-aqueous electrolyte solution according to claim 1.