KR20210126569A - Composition for electrolyte, non-aqueous electrolyte and non-aqueous electrolyte secondary battery - Google Patents

Abstract

(식 중, R¹ 은, 탄소 원자수 1 ∼ 8 의 탄화수소기이고, R² ∼ R⁵ 는, 각각 독립적으로, 수소 원자, 탄소 원자수 1 ∼ 8 의 탄화수소기 등이고, R⁶ 은, 탄소 원자수 1 ∼ 8 의 탄화수소기 등이고, n = 1 ∼ 4 의 정수이다)A composition for an electrolyte comprising at least one compound selected from the group consisting of compounds represented by the following general formula (1) and the like, and at least one compound selected from a solvent and a dispersion medium.

(Wherein, R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, R ² to R ⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, etc., and R ⁶ is a carbon atom It is a hydrocarbon group of the number 1-8, etc., and n = an integer of 1-4)

Description

Composition for electrolyte, non-aqueous electrolyte and non-aqueous electrolyte secondary battery

The present invention relates to a composition for an electrolyte, a nonaqueous electrolyte, and a nonaqueous electrolyte secondary battery.

BACKGROUND OF THE INVENTION Non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries are small, lightweight, have high energy density, and can be repeatedly charged and discharged, and are widely used as power sources for portable electronic devices such as portable personal computers, handy video cameras, and information terminals. have. Moreover, from a viewpoint of an environmental problem, the practical application of the electric vehicle using a nonaqueous electrolyte secondary battery and the hybrid vehicle which used electric power as a part of power is implemented. Therefore, in recent years, the further performance improvement of a secondary battery is calculated|required.

A nonaqueous electrolyte secondary battery is comprised by members, such as a positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte. A positive electrode and a negative electrode are normally equipped with the electrical power collector and the electrode mixture layer formed on the electrical power collector. The electrode mixture layer is formed by, for example, applying, on a current collector, a slurry composition obtained by dispersing an electrode active material capable of occluding and releasing lithium ions, a binder, and the like in a dispersion medium, and drying.

As a method of improving the performance of a secondary battery, a method of using an additive in a non-aqueous electrolyte has been proposed. For example, vinylene carbonate (for example, refer patent document 1), methylphenyl carbonate (for example, refer patent document 2), (tetrafluorobenzo-1,2-dioxyl)-pentafluoro Phenyl-borane (see, for example, Patent Document 3), methyl pyruvate (see, for example, Patent Document 4), dimethyl malonate (see, for example, Patent Document 5), N,N-dimethylsulfone Amide (see, for example, Patent Document 6), vinylsulfonamide (see, for example, Patent Document 7), pentafluorophenylmethyl oxalate (see, for example, Patent Document 8), phenylsilane (eg, refer to Patent Document 8) For example, refer to patent document 9), etc., are said to be able to improve battery performance, such as cycling characteristics, charging/discharging capacity, and storage characteristics under high temperature, to a nonaqueous electrolyte.

Japanese Laid-Open Patent Publication No. 2000-123867 Japanese Patent Laid-Open No. Hei 08-293323 Japanese Patent Publication No. 2008-532248 International Publication No. 2006/070546 Japanese Laid-Open Patent Publication No. 2002-367673 Japanese Laid-Open Patent Publication No. 2004-259697 Japanese Patent Laid-Open No. 2013-93242 Japanese Laid-Open Patent Publication No. 2007-112737 Japanese Laid-Open Patent Publication No. 2008-210769

However, although many electrolyte additives have been developed to improve battery performance, cycle characteristics (capacity retention of battery capacity after repeated charging and discharging) are not sufficient, and not only improvement of cycle characteristics but also capacity for charging and discharging in a short time The excellent rate characteristic with little fall was also calculated|required together, and it was necessary to improve cycling characteristics and a rate characteristic at the same time.

Accordingly, an object of the present invention is to provide a composition for an electrolyte capable of improving cycle characteristics and rate characteristics of a nonaqueous electrolyte secondary battery.

That is, the present invention is a composition for an electrolyte comprising at least one compound selected from the group consisting of compounds represented by the following general formulas (1) to (4), and at least one compound selected from a solvent and a dispersion medium.

[Formula 1]

(Wherein, R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, and R ² to R ⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms. An alkoxy group or the following formula (1-a), R ⁶ is a nitro group, a sulfonic acid group, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a formula (1-b) or In the following formula (1-c), when R ⁶ is a hydrocarbon group having 1 to 8 carbon atoms, n = an integer of 1 to 4, R ⁶ is a nitro group, a sulfonic acid group, or a hydrocarbon group having 1 to 6 carbon atoms In the case of an alkoxy group or the following formula (1-b), n = 1, and when R ⁶ is the following formula (1-c), n = 2)

[Formula 2]

(in the formula, ※ indicates the bonding position)

[Formula 3]

(In the formula, R ⁷ is the following formula (1-d) or the following formula (1-e))

[Formula 4]

(wherein, R ⁸ to R ¹⁶ are each independently a hydrogen atom, an unsubstituted hydrocarbon group having 1 to 8 carbon atoms, a hydrocarbon group having 1 to 8 carbon atoms in which some of the hydrogen atoms are substituted with fluorine atoms; An unsubstituted C1-C6 alkoxy group, a C1-C6 alkoxy group in which a part of hydrogen atoms are substituted with a fluorine atom, an unsubstituted C1-C6 thioalkoxy group, a part of hydrogen atom is an acyl group having a thioalkoxy group having 1 to 6 carbon atoms, a sulfonyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms substituted with a fluorine atom, * indicates a bonding position)

[Formula 5]

(Wherein, when m = 1 or 2 and m = 1, R ¹⁷ to R ¹⁹ are each independently a hydrocarbon group having 1 to 8 carbon atoms, and R ¹⁸ and R ¹⁹ are linked to form a ring may be formed, and when m = 2, R ¹⁷ and R ¹⁹ are each independently a hydrocarbon group having 1 to 8 carbon atoms, and R ¹⁸ is a single bond)

[Formula 6]

(Wherein, R ²⁰ and R ²¹ are each independently a hydrocarbon group having 1 to 8 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ²² to R ³¹ are each independently a hydrogen atom; a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a nitro group)

ADVANTAGE OF THE INVENTION According to this invention, the composition for electrolytes which can improve the cycling characteristics and rate characteristic of a nonaqueous electrolyte secondary battery can be provided.

1 is a longitudinal sectional view schematically showing an example of the structure of a coin-type battery of a nonaqueous electrolyte secondary battery of the present invention.
Fig. 2 is a schematic diagram showing the basic configuration of a cylindrical battery of a nonaqueous electrolyte secondary battery of the present invention.
Fig. 3 is a perspective view showing the internal structure of the cylindrical battery of the nonaqueous electrolyte secondary battery of the present invention as a cross section.

<Composition for Electrolyte>

The composition for electrolyte of the present invention contains at least one compound selected from the group consisting of compounds represented by the following general formulas (1) to (4), and at least one compound selected from solvents and dispersion media.

[Formula 7]

(Wherein, R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, and R ² to R ⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms. An alkoxy group or the following formula (1-a), R ⁶ is a nitro group, a sulfonic acid group, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a formula (1-b) or In the following formula (1-c), when R ⁶ is a hydrocarbon group having 1 to 8 carbon atoms, n = an integer of 1 to 4, R ⁶ is a nitro group, a sulfonic acid group, or a hydrocarbon group having 1 to 6 carbon atoms In the case of an alkoxy group or the following formula (1-b), n = 1, and when R ⁶ is the following formula (1-c), n = 2)

[Formula 8]

(in the formula, ※ indicates the bonding position)

[Formula 9]

(wherein, R ⁷ is the following formula (1-d) or the following formula (1-e))

[Formula 10]

(wherein, R ⁸ to R ¹⁶ are each independently a hydrogen atom, an unsubstituted hydrocarbon group having 1 to 8 carbon atoms, a hydrocarbon group having 1 to 8 carbon atoms in which some of the hydrogen atoms are substituted with fluorine atoms; An unsubstituted C1-C6 alkoxy group, a C1-C6 alkoxy group in which a part of hydrogen atoms are substituted with a fluorine atom, an unsubstituted C1-C6 thioalkoxy group, a part of hydrogen atom is an acyl group having a thioalkoxy group having 1 to 6 carbon atoms, a sulfonyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms substituted with a fluorine atom, * indicates a bonding position)

[Formula 11]

(Wherein, when m = 1 or 2 and m = 1, R ¹⁷ to R ¹⁹ are each independently a hydrocarbon group having 1 to 8 carbon atoms, and R ¹⁸ and R ¹⁹ are linked to form a ring may be formed, and when m = 2, R ¹⁷ and R ¹⁹ are each independently a hydrocarbon group having 1 to 8 carbon atoms, and R ¹⁸ is a single bond)

[Formula 12]

(Wherein, R ²⁰ and R ²¹ are each independently a hydrocarbon group having 1 to 8 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ²² to R ³¹ are each independently a hydrogen atom; a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a nitro group)

A compound represented by the general formula (1), the hydrocarbon group of R ¹ ~ R indicating the number of carbon atoms ^51-8 is, for example, there may be mentioned an aliphatic hydrocarbon group, aromatic hydrocarbon group or the like.

Specifically, methyl group, ethyl group, propyl group, i-propyl group, butyl group, 2-butyl group, i-butyl group, t-butyl group, pentyl group, 2-pentyl group, 3-pentyl group, i-pen Saturation such as tyl group, hexyl group, 2-hexyl group, 3-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, norbornane group Unsaturated aliphatic hydrocarbon groups such as aliphatic hydrocarbon group, vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, norbornene group, phenyl group, methylphenyl group, ethylphenyl group Aromatic hydrocarbon groups, such as a phenylmethyl group, a phenylethyl group, and a benzyl group, are mentioned. The saturated aliphatic hydrocarbon group and the unsaturated aliphatic hydrocarbon group may have a linear structure, a branched structure, or a cyclic structure.

Examples of the alkoxy group having 1 to 6 carbon atoms representing R ² to R ⁵ include a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and a cyclo A hexyloxy group etc. are mentioned.

R ⁶ carbon atoms, represents a hydrocarbon group of 1 to 8, for example, R ¹ ~ R ⁵ hydrocarbon groups of 1 to 8 carbon atoms in the are the same.

R ⁶ represents the carbon atoms alkoxy groups of 1 to 6, for example, an alkoxy group of R ² ~ carbon atoms in R ^5: 1-6 are the same.

As a specific example of the compound represented by the general formula (1), R ¹ is a hydrocarbon group ^{having 1 to 8 carbon atoms, R 2} to R ⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or carbon An alkoxy group having 1 to 6 atoms or the formula (1-a), R ⁶ is a nitro group, a sulfonic acid group, a hydrocarbon group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, n When =1, for example, although the compound represented by the following 1-1 to 1-61 is mentioned, it is not limited to these.

[Formula 13]

[Formula 14]

[Formula 15]

As a specific example of the compound represented by the general formula (1), R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, R ² to R ⁵ are a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ⁶ is In the case of the formula (1-b) or the formula (1-c), and when n = 1 or 2, for example, compounds represented by the following 1-62 to 1-70 are exemplified, no.

[Formula 16]

As a specific example of the compound represented by the general formula (1), R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, R ² to R ⁵ are a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ⁶ is When it is a C1-C8 hydrocarbon group and is an integer of n=2-4, for example, although the compound represented by following 1-71 to 1-78 is mentioned, It is not limited to these.

[Formula 17]

[Formula 18]

From the viewpoint of excellent cycle characteristics and rate characteristics, R ¹ of the compound represented by the general formula (1) is preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and a methyl group, an allyl group, or t-butyl group. It is more preferably a group or a benzyl group, R ² to R ⁵ are preferably a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, or the formula (1-a), and R ⁶ is a nitro group. , a sulfonic acid group, a saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, the formula (1-b) or the formula (1-c) is preferable. Among them, 1-1, 1-2, 1-16, 1-17, 1-37, 1-39, 1-40, 1-41, 1-50, 1-51, 1-52, 1- 54, 1-56, 1-62, 1-64, 1-67, 1-70, 1-72, 1-75, 1-77 and 1-78 are more preferable, and 1-1, More preferred are compounds represented by 1-37, 1-39, 1-40, 1-52, 1-62, 1-70, 1-72, 1-75, 1-77 and 1-78.

As a method for producing the compound represented by the general formula (1), for example, a carbonate compound such as methyl 4-methylphenyl carbonate is methyl chloroformate with respect to a phenol compound such as 4-methylphenol in the presence of an organic base. It can be efficiently obtained by reacting chloroformates such as

A compound represented by the general formula (2), R ⁷ of the formula (1-d) and the formula (1-e) the number of carbon atoms in the unsubstituted, representing R ⁸ ~ R ¹⁶ in the 1-8 represents Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a 2-butyl group, an i-butyl group, a t-butyl group, a pentyl group, a 2-pentyl group, and a 3-pentyl group. , i-pentyl group, hexyl group, 2-hexyl group, 3-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, norbor and unsaturated aliphatic hydrocarbon groups such as saturated aliphatic hydrocarbon groups such as warm group, vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, cyclopentenyl group and cyclohexenyl group, and aromatic hydrocarbon groups such as phenyl group. R ⁸ to R ¹⁶ may be one in which a part of hydrogen atoms in these hydrocarbon groups are substituted with fluorine atoms. The saturated aliphatic hydrocarbon group and the unsaturated aliphatic hydrocarbon group may have a linear structure, a branched structure, or a cyclic structure.

A compound represented by the general formula (2), the formula (1-d) and the number of carbon atoms in the unsubstituted, representing R ⁸ ~ R ¹⁶ in the formula (1-e) represents a R ⁷ a 1-6 alkoxy group, there may be mentioned that a compound represented by the general formula (1), R ² ~ R number of carbon atoms represents a ^5-alkoxy group of one to six same. R ⁸ to R ¹⁶ may be one in which a part of hydrogen atoms in the alkoxy group are substituted with fluorine atoms.

A compound represented by the general formula (2), of the formula (1-d), and the formula number of carbon atoms in the unsubstituted, representing R ⁸ ~ R ¹⁶ in (1-e) 1 ~ 6 represents the R ⁷ thioalkoxy group is a compound represented by the general formula ^(1), R 1 ~ R represents an alkoxy group of ⁵ carbon atoms, 1 to 6, it can be given in place of the oxygen atom by a sulfur atom bonded group. R ⁸ to R ¹⁶ may be one in which a part of hydrogen atoms in the thioalkoxy group are substituted with fluorine atoms.

Hydrocarbon group of sulfonyl group or acyl group having carbon atoms 1 to 8, there may be mentioned that a compound represented by the general formula ^(1), R 1 ~ R ⁵ represents the number of carbon atoms hydrocarbon group of 1 to 8 the same.

Specific examples of the compound represented by the general formula (2) include, but are not limited to, compounds represented by the following 2-1 to 2-24.

[Formula 19]

[Formula 20]

From the viewpoint of excellent cycle characteristics and rate characteristics ^{, R 8} , R ⁹ , R ¹¹ and R ^{12 in} the formula (1-d) representing ^{R 7} of the compound represented by the general formula (2) are hydrogen atoms. Preferably, as R ¹⁰ , a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a thioalkoxy group having 1 to 4 carbon atoms, a fluoromethoxy group, or fluorothi It is preferably an omethoxy group, a sulfonyl group having an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an acyl group having an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and a methoxy group, thiomethoxy group, trifluoromethoxy group or methyl group. It is more preferable that it is a sulfonyl group. From the viewpoint of excellent cycle characteristics and rate characteristics ^{, R 14} to R ¹⁶ in the formula (1-e) representing ^{R 7} of the compound represented by the general formula (2) are preferably a hydrogen atom. Among them, compounds represented by 2-1, 2-2, 2-6, 2-7, 2-10, 2-11, 2-12, 2-14, 2-18 and 2-22 are more preferable. , compounds represented by 2-1, 2-10, 2-11, 2-12, 2-14 and 2-22 are more preferable.

As a method for producing a compound represented by the general formula (2), for example, an oxalic acid ester compound such as diphenyl oxalate is efficiently produced by reacting an alcohol compound such as phenol with oxalyl chloride in the presence of an organic base. can be obtained

As the hydrocarbon group of 1 to 8 carbon atoms representing ^{R 17} to R ¹⁹ in the compound represented by the general formula (3), the compound ^{represented by the general formula (1) has 1} to carbon atoms representing R 1 to R ^{5 .} The same thing as the hydrocarbon group of 8 is mentioned.

Specific examples of the compound represented by the general formula (3) include compounds represented by the following 3-1 to 3-14, but are not limited thereto.

[Formula 21]

From the viewpoint of excellent cycle characteristics and rate characteristics, the compound represented by the general formula (3) is preferably an aliphatic hydrocarbon having 1 to 3 carbon atoms as ^{R 17 when m = 1, more preferably a methyl group or an ethyl group} Preferably, R ¹⁸ and R ¹⁹ are preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms or ^{a cyclohexyl group in which R 18} and R ¹⁹ form a ring, and when m = 2, R ¹⁷ and R ^{As 19,} it is preferable that it is a C1-C3 aliphatic hydrocarbon group. Among them, the compounds represented by 3-1, 3-6, 3-9, 3-10 and 3-12 are more preferable, and the compounds represented by 3-1, 3-9 and 3-12 are still more preferable. .

As a method for producing the compound represented by the general formula (3), for example, a sulfonic acid oxime compound such as propanone methanesulfonic acid oxime is acetone oxime in the presence of an organic base to a sulfonyl chloride such as methanesulfonyl chloride. It can obtain efficiently by making these oxime compounds react.

As the hydrocarbon group of 1 to 8 carbon atoms representing ^{R 20} to R ³¹ in the compound represented by the general formula (4), the compound ^{represented by the general formula (1) has 1} to carbon atoms representing R 1 to R ^{5 .} The same thing as the hydrocarbon group of 8 is mentioned. Examples of the alkoxy group having 1 to 6 carbon atoms for ^{R 20} to R ³¹ include the same groups as the alkoxy group having 1 to 6 carbon atoms for ^{R 2} to R ^{5 in the compound represented by the general formula (1).}

Specific examples of the compound represented by the general formula (4) include, but are not limited to, compounds represented by the following 4-1 to 4-24.

[Formula 22]

[Formula 23]

From the viewpoint of excellent cycle characteristics and rate characteristics, R ²⁰ and R ²¹ in the compound represented by the general formula (4) are preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, more preferably a methyl group, R ²² , R ²³ , R ²⁵ to R ²⁸ , R ³⁰ and R ³¹ are preferably a hydrogen atom or a fluorine atom, more preferably a hydrogen atom, and R ²⁴ and R ²⁹ are a hydrogen atom, a fluorine atom, and the number of carbon atoms. It is preferable that they are a 1-3 aliphatic hydrocarbon group, a C1-C3 alkoxy group, or a nitro group, and it is more preferable that they are a fluorine atom or a nitro group. Among them, the compounds represented by 4-1, 4-3, 4-9, 4-13, 4-16 and 4-19 are more preferable, and the compounds represented by 4-3, 4-13 and 4-16 above. This is more preferable.

As a method for producing the compound represented by the general formula (4), for example, a silane compound such as bis(4-fluorophenoxy)dimethylsilane is added to a chlorosilane compound such as dimethyldichlorosilane in the presence of an organic base. In contrast, it can be efficiently obtained by reacting a phenol compound such as 4-fluorophenol.

The form of the composition for an electrolyte of the present invention is not particularly limited, and a liquid form obtained using an organic solvent as a solvent, a polymer gel obtained by dissolving a polymer compound in an organic solvent and gelled as a solvent or dispersion medium, is used. , a polymer form obtained by using a polymer as a dispersion medium without using a solvent, and the like.

As a solvent used for the composition for electrolytes of this invention, the organic solvent normally used for the nonaqueous electrolyte of a nonaqueous electrolyte secondary battery can be used. Specific examples of the organic solvent include, for example, a saturated cyclic carbonate compound, a saturated cyclic ester compound, a sulfoxide compound, a sulfone compound, an amide compound, a saturated chain carbonate compound, a chain ether compound, a cyclic ether compound, and saturated chain ester compounds. Only 1 type may be used for these organic solvents, and may be used in combination of 2 or more type. Among these organic solvents, a saturated cyclic carbonate compound, a saturated cyclic ester compound, a sulfoxide compound, a sulfone compound, and an amide compound are preferable from the viewpoint of having a high dielectric constant and increasing the dielectric constant of the composition for electrolyte. A cyclic carbonate compound is more preferable.

Examples of the saturated cyclic carbonate compound include ethylene carbonate, 1,2-propylene carbonate, 1,3-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, and 1,1-dimethyl Ethylene carbonate etc. are mentioned.

Examples of the saturated cyclic ester compound include γ-butyrolactone, γ-valerolactone, γ-caprolactone, δ-hexanolactone, and δ-octanolactone.

As a sulfoxide compound, dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, diphenyl sulfoxide, thiophene etc. are mentioned, for example.

Examples of the sulfone compound include dimethylsulfone, diethylsulfone, dipropylsulfone, diphenylsulfone, sulfolane (also referred to as tetramethylenesulfone), 3-methylsulfolane, 3,4-dimethylsulfolane, 3, 4-diphenymethylsulfolane, sulfolene, 3-methylsulfolene, 3-ethylsulfolene, 3-bromomethylsulfolene, etc. are mentioned. Among these, sulfolane and tetramethylsulfolane are preferable.

Examples of the amide compound include N-methylpyrrolidone, dimethylformamide, and dimethylacetamide.

Among organic solvents, in that the viscosity of the composition for electrolyte can be lowered and the mobility of electrolyte ions can be increased to provide excellent battery characteristics such as power density, saturated chain carbonate compounds, chain ether compounds, cyclic Ether compounds and saturated chain ester compounds are preferred. In addition, a saturated chain carbonate compound is particularly preferable because it is low in viscosity and the performance of the composition for an electrolyte at a low temperature can be improved.

Examples of the saturated chain carbonate compound include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl butyl carbonate, methyl-t-butyl carbonate, diisopropyl carbonate, and t-butylpropyl carbonate.

Examples of the chain ether compound and the cyclic ether compound include dimethoxyethane, ethoxymethoxyethane, diethoxyethane, tetrahydrofuran, dioxolane, dioxane, 1,2-bis(methoxycarbonyl). Oxy)ethane, 1,2-bis(ethoxycarbonyloxy)ethane, 1,2-bis(ethoxycarbonyloxy)propane, ethylene glycol bis(trifluoroethyl)ether, propylene glycolbis(trifluoro ethyl) ether, ethylene glycol bis (trifluoromethyl) ether, diethylene glycol bis (trifluoroethyl) ether, etc. are mentioned, Among these, dioxolane is preferable.

As a saturated chain ester compound, the monoester compound and diester compound whose total number of carbon atoms in a molecule|numerator is 2-8 are preferable, As a specific compound, For example, methyl formate, ethyl formate, methyl acetate, acetic acid. Ethyl, propyl acetate, isobutyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethyl acetate, trimethyl ethyl acetate, methyl malonate, ethyl malonate, methyl succinate, ethyl succinate, 3-methyl Methyl oxypropionate, 3-methoxyethyl propionate, ethylene glycol diacetyl, propylene glycol diacetyl, etc. are mentioned, Methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, methyl propionate. , and ethyl propionate are preferable.

As another organic solvent, acetonitrile, propionitrile, nitromethane, these derivatives, and various ionic liquids can also be used, for example.

Examples of the polymer used in the preparation of the polymer gel composition include polyethylene oxide, polypropylene oxide, polyvinyl chloride, polyacrylonitrile, polymethyl methacrylate, polyethylene, polyvinylidene fluoride, polyhexafluoropropylene, and the like. can be heard

Polyethylene oxide, polypropylene oxide, polystyrenesulfonic acid, etc. are mentioned as a polymer|macromolecule used for preparation of a polymeric composition.

There is no particular limitation on the blending ratio in the polymer gel form or polymeric composition, and the method of complexing, and known blending ratios and known complexing methods in the art may be employed.

The content of at least one compound selected from the group consisting of compounds represented by the general formulas (1) to (4) is preferably 0.01 mass % to 10 mass %, and 0.05 mass % with respect to the composition for electrolyte of the present invention. % - 10 mass % are more preferable, and it is still more preferable that they are 0.1 mass % - 5 mass %. When the content of the compound represented by the general formulas (1) to (4) is less than 0.01 mass%, the effect of improving the cycle characteristics and rate characteristics of the nonaqueous electrolyte secondary battery using the composition for electrolyte of the present invention may not be sufficient. On the other hand, when content of the compound represented by General formula (1)-(4) is more than 10 mass %, the effect suitable for a compounding quantity is not acquired but a bad influence may be exerted on a battery characteristic on the contrary.

The form of the composition for electrolyte of the present invention is not particularly limited, but from the viewpoint of a simple manufacturing process, it is preferable to include a solvent, and more preferably a liquid form.

<Non-aqueous electrolyte>

The nonaqueous electrolyte of the present invention contains the above-described composition for an electrolyte and a supporting electrolyte. Examples of the supporting electrolyte include alkali metal salts such as lithium salt, sodium salt and potassium salt, magnesium salt, and calcium salt.

It does not specifically limit as a lithium salt used for the nonaqueous electrolyte of this invention, A well-known lithium salt can be used. Specific examples of the lithium salt include, for example, LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiN(CF ₃ SO ₂ ) ₂ , LiN(C ₂ F ₅ SO ₂ ) ₂ , LiN(SO ₂ F) ₂ , LiC(CF ₃ SO ₂ ) ₃ , LiB(CF ₃ SO ₃ ) ₄ , LiB(C ₂ O ₄ ) ₂ , LiBF ₂ (C ₂ O ₄ ), LiSbF ₆ , LiSiF ₅ , LiSCN, LiClO ₄ , LiCl, LiF, LiBr, LiI, LiAlF ₄ , LiAlCl ₄ , LiPO ₂ F ₂ and derivatives thereof, and the like.

LiPF ₆ , LiBF ₄ , LiClO ₄ , LiCF ₃ SO ₃ , LiN(CF ₃ SO ₂ ) ₂ , LiN(C ₂ F ₅ SO ₂ ) ₂ , LiN(SO _{2 )} F) ₂ , LiPO ₂ F ₂ , LiC(CF ₃ SO ₂ ) ₃ , LiCF ₃ SO ₃ Derivatives and LiC(CF ₃ SO ₂ ) _{3 At} least one lithium salt selected from the group consisting of derivatives may be used. desirable.

In the polymer electrolyte composition, LiN(CF ₃ SO ₂ ) ₂ , LiN(C ₂ F ₅ SO ₂ ) ₂ , LiN(SO ₂ F) ₂ , LiC(CF ₃ SO ₂ ) ₃ , LiB(CF ₃ SO) ₃ ) It is preferable to use at least one selected from the group consisting of ₄ and LiB(C ₂ O ₄ ) _{2 .}

It does not specifically limit as a sodium salt and potassium salt used for the nonaqueous electrolyte of this invention, A well-known sodium salt and potassium salt can be used.

It does not specifically limit as a magnesium salt and a calcium salt used for the nonaqueous electrolyte of this invention, A well-known magnesium salt and a calcium salt can be used.

When the concentration of the supporting electrolyte in the non-aqueous electrolyte is too low, sufficient current density may not be obtained in some cases, and on the other hand, if it is too high, the stability of the non-aqueous electrolyte may be impaired, so 0.5 mol/L to 7 mol/L It is preferable, and it is more preferable that they are 0.8 mol/L - 1.8 mol/L.

Although the use of the nonaqueous electrolyte of this invention is not specifically limited, It can utilize suitably as a nonaqueous electrolyte used for a nonaqueous electrolyte secondary battery.

The nonaqueous electrolyte of the present invention may further contain known electrolyte additives, such as an electrode film former, an antioxidant, a flame retardant, and an overcharge inhibitor, for improvement of battery life and safety. The concentration in the case of using the electrolyte additive is 0.01 mass % to 10 mass relative to the non-aqueous electrolyte, since the concentration of the electrolyte additive cannot exhibit the effect of addition when it is too small, and the characteristic of the non-aqueous electrolyte secondary battery is rather adversely affected when the concentration is too large. % is preferable, and it is more preferable that they are 0.1 mass % - 5 mass %.

<Non-aqueous electrolyte secondary battery>

The nonaqueous electrolyte secondary battery of the present invention includes a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, and the above-described nonaqueous electrolyte. In the present invention, it is preferable to interpose a separator between the positive electrode and the negative electrode. Hereinafter, the nonaqueous electrolyte secondary battery of the present invention will be described.

The positive electrode used by this invention can be manufactured according to a well-known method. For example, a positive electrode in which an electrode mixture layer is formed on a current collector can be manufactured by applying an electrode mixture paste obtained by slurrying a mixture containing a positive electrode active material, a binder, and a conductive aid with an organic solvent or water to a current collector and drying it. have.

A well-known thing can be used for a positive electrode active material. As a well-known positive electrode active material, a lithium transition metal composite oxide, a lithium containing transition metal phosphate compound, a lithium containing silicate compound, a lithium containing transition metal sulfate compound, etc. are mentioned, for example. As a transition metal of a lithium transition metal composite oxide, vanadium, titanium, chromium, manganese, iron, cobalt, nickel, copper, etc. are preferable. Only 1 type may be used for these positive electrode active materials, and may be used in combination of 2 or more type.

Specific examples of the lithium transition metal composite oxide include lithium cobalt composite oxides such as _{LiCoO 2} , lithium nickel composite oxides such as _{LiNiO 2 , lithium manganese composite oxides such as LiMnO 2} , LiMn ₂ O ₄ , Li ₂ MnO ₃ , and these A substance in which some of the transition metal atoms, which are the main constituents of a lithium transition metal composite oxide, are substituted with other metals such as aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, lithium, nickel, copper, zinc, magnesium, gallium, zirconium, etc. and the like. Lithium transition metal composite oxides in which a part of the transition metal atoms as the main element are substituted with other metals are, for example, Li _1.1 Mn _1.8 Mg _0.1 O ₄ , Li _1.1 Mn _1.85 Al _0.05 O ₄ , LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , LiNi _0.8 Co _0.1 Mn _0.1 O ₂ , LiNi _0.5 Mn _0.5 O ₂ , LiNi _0.80 Co _0.17 Al _0.03 O ₂ , LiNi _0.80 Co _0.15 Al _0.05 O ₂ , LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiNi _0.6 Co _0.2 Mn _0.2 O ₂ , LiMn _1.8 Al _0.2 O ₄ , LiNi _0.5 Mn _1.5 O ₄ , Li ₂ MnO ₃ -LiMO ₂ (M=Co, Ni, Mn) and the like.

As the transition metal of the lithium-containing transition metal phosphate compound, vanadium, titanium, manganese, iron, cobalt, nickel and the like are preferable, and specific examples include, for example, LiFePO ₄ , LiM _x Fe _1-x PO ₄ (M = iron phosphate compounds such as Co, Ni, Mn), _{cobalt phosphate compounds such as LiCoPO 4 ,} and some transition metal atoms that are the main constituents of these lithium transition metal phosphate compounds are aluminum, titanium, vanadium, chromium, manganese, and vanadium phosphate compounds such as those substituted with other metals such as iron, cobalt, lithium, nickel, copper, zinc, magnesium, gallium, zirconium, and niobium, and Li ₃ V ₂ (PO ₄ ) _{3 .}

_{Li 2} FeSiO ₄ etc. are mentioned as a lithium containing silicate compound.

A lithium-containing transition metal sulfate compound, LiFeSO _4, LiFeSO there may be mentioned ₄ F or the like.

As the positive electrode active material, sulfur, a sulfur-modified organic compound, a sulfur-carbon composite, or Li ₂ S _x (x = 1 to 8) can also be used.

As the sulfur, all of various types of sulfur, such as powdered sulfur, insoluble sulfur, precipitated sulfur, and colloidal sulfur, can be used. From the viewpoint of uniformly dispersing in the electrode mixture paste, powdered sulfur is preferable.

The sulfur-modified organic compound includes sulfur, a polyacrylonitrile compound, an elastomer compound, a pitch compound, a polynuclear aromatic ring compound, an aliphatic hydrocarbon oxide, a polyether compound, a polythienoacene compound, a polyamide compound, a hexachlorobutadiene compound, and the like. It can be manufactured by mixing and heat-denaturing|denaturing at 250 degreeC - 600 degreeC in a non-oxidizing gas atmosphere. The non-oxidizing gas atmosphere has an oxygen concentration of less than 5% by volume, preferably less than 2% by volume, and more preferably an atmosphere substantially free of oxygen, that is, an atmosphere of an inert gas such as nitrogen, helium, or argon. I mean that it is a sulfur gas atmosphere. It is preferable that the sulfur content in a sulfur-modified organic compound is 25 mass % - 80 mass % from a viewpoint of obtaining a larger charge/discharge capacity. Among these sulfur-modified organic compounds, a sulfur-modified polyacrylonitrile compound is preferable from the viewpoint of obtaining large charge/discharge capacity and stable cycle characteristics.

A sulfur-carbon composite is a product in which sulfur and carbon are mechanically complexed, sulfur and carbon are chemically complexed, or a single sulfur is contained in pores of porous carbon, and is a secondary, which can occlude and release lithium ions. It refers to one that can be used as an electrode active material for a battery. The sulfur content in the sulfur-carbon composite is preferably 25% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, from the viewpoint of not increasing the charge/discharging capacity when too small, and lowering the electron conductivity when too large. do. A known method can be employed for the method of supporting single sulfur in the pores of the porous carbon.

The sulfur content in the sulfur-modified organic compound and the sulfur-carbon complex can be calculated by elemental analysis using a CHN analyzer capable of analyzing sulfur and oxygen, for example, a vario MICRO cube manufactured by Elemental.

When the particle diameter of the positive electrode active material is too large, a uniform and smooth electrode mixture layer may not be obtained. On the other hand, when the particle diameter is too small, the handling property in the slurrying step is reduced, so the average particle diameter (D50) of the positive electrode active material is 0.5 It is preferable that they are micrometer - 100 micrometers, It is more preferable that they are 1 micrometer - 50 micrometers, It is more preferable that they are 1 micrometer - 30 micrometers.

In the present invention, the average particle diameter (D50) means a 50% particle diameter measured by a laser diffraction light scattering method. A particle diameter is a volume-based diameter, and the diameter of a secondary particle is measured by the laser diffraction light scattering method.

The positive electrode active material can have a desired particle size by a method such as pulverization or granulation. Dry grinding performed in gas may be sufficient as grinding|pulverization, and wet grinding performed in liquids, such as water, may be sufficient as it. Industrial grinding methods include, for example, a ball mill, a roller mill, a turbo mill, a jet mill, a cyclone mill, a hammer mill, a pin mill, a rotary mill, a vibrating mill, a planetary mill, an attritor, and a bead mill. have.

A well-known thing can be used for a binder. Specific examples of the binder include, for example, styrene-butadiene rubber, butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene-diene rubber, styrene-isoprene rubber, fluororubber, polyethylene, polypropylene, polyacrylamide, Polyamide, polyamideimide, polyimide, polyacrylonitrile, polyurethane, polyvinylidene fluoride, polytetrafluoroethylene, styrene-acrylic acid ester copolymer, ethylene-vinyl alcohol copolymer, polymethyl methacrylate, poly Acrylate, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, polyvinyl ether, polyvinyl chloride, acrylic acid, polyacrylic acid, methylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, cellulose nanofiber, starch, etc. have. A binder may use only 1 type, and may use it in combination of 2 or more type.

It is preferable that it is 0.5 mass part - 30 mass parts with respect to 100 mass parts of positive electrode active materials, and, as for content of a binder, it is more preferable that they are 1 mass part - 20 mass parts.

As a conductive support agent, a well-known thing can be used as a conductive support agent of an electrode. As a specific example of a conductive support agent, For example, natural graphite, artificial graphite, coal tar pitch, carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, roller black, disk black, carbon nano Carbon materials, such as a tube, vapor-grown carbon fiber (VGCF), exfoliated graphite, graphene, fullerene, and needle coke; Metal powders, such as an aluminum powder, a nickel powder, and a titanium powder; conductive metal oxides such as zinc oxide and titanium oxide; and sulfides such as La ₂ S ₃ , Sm ₂ S ₃ , Ce ₂ S ₃ , and TiS _{2 .}

It is preferable that they are 0.0001 micrometer - 100 micrometers, and, as for the average particle diameter (D50) of a conductive support agent, it is more preferable that they are 0.01 micrometer - 50 micrometers.

With respect to 100 mass parts of electrode active materials, it is preferable that content of a conductive support agent is 0.1 mass part - 50 mass parts normally, it is preferable that they are 0.5 mass part - 30 mass parts, It is more preferable that they are 1 mass part - 20 mass parts.

As a solvent for preparing the electrode mixture paste of a positive electrode, For example, propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, Acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, 1,3-dioxolane, nitromethane, N-methylpyrrolidone, N,N-dimethylformamide, dimethylacetamide, Methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyl triamine, N,N-dimethylaminopropylamine, polyethylene oxide, tetrahydrofuran, dimethyl sulfoxide, sulfolane, γ-butyrolactone, water, alcohol etc. are mentioned. The amount of the solvent used can be adjusted according to the application method selected when coating the electrode mixture paste, for example, in the case of application by the doctor blade method, with respect to 100 parts by mass of the total amount of the positive electrode active material, the binder and the conductive auxiliary agent, It is preferable that they are 15 mass parts - 300 mass parts, and it is more preferable that they are 30 mass parts - 200 mass parts.

The electrode mixture paste of the positive electrode may contain, in addition to the above components, other components such as, for example, a viscosity modifier, a reinforcing material, an antioxidant, a pH adjuster, and a dispersing agent, as long as the effects of the present invention are not impaired. As these other components, a well-known thing can be used by a well-known compounding ratio.

Production of the electrode mixture paste WHEREIN: When disperse|distributing or dissolving a positive electrode active material, a binder, and a conductive support agent in a solvent, all may be collectively added to a solvent, and a dispersion process may be carried out, and you may add separately and disperse|distribute it. In a solvent, since a binder, a conductive support agent, and a positive electrode active material can be uniformly disperse|distributed to a solvent, when it adds and disperse|distributes in order of a positive electrode active material, these is preferable. When the electrode mixture paste contains other components, the other components may be collectively added and subjected to dispersion treatment, but dispersion treatment is preferably carried out every time another component is added one by one.

The dispersion treatment method is not particularly limited, but as an industrial method, for example, a conventional ball mill, sand mill, bead mill, cyclone mill, pigment disperser, pounder, ultrasonic disperser, homogenizer, rotation/revolution mixer , planetary mixer, fillmix, jet paster, etc. can be used.

As the current collector, a conductive material such as titanium, titanium alloy, aluminum, aluminum alloy, nickel, stainless steel, nickel-plated steel, or carbon is used. Examples of the shape of the current collector include a foil shape, a plate shape, a network shape, a foam shape, and a nonwoven fabric shape, and the current collector may be either porous or non-porous. Moreover, in order to improve adhesiveness and an electrical characteristic, these electrically-conductive materials may be surface-treated. Among these electrically-conductive materials, from a viewpoint of electroconductivity and price, aluminum is preferable, and aluminum foil is especially preferable. The thickness of the current collector is not particularly limited, but is usually 5 µm to 30 µm.

The method of applying the electrode mixture paste of the positive electrode on the current collector is not particularly limited, and for example, a die coater method, a comma coater method, a curtain coater method, a spray coater method, a gravure coater method, a flexo coater method, a knife coater method method, a doctor blade method, a reverse roll method, a brush application method, a dip method, etc. can be used. The die coater method, the knife coater method, the doctor blade method, and the comma coater method are preferable at the point which makes it possible to obtain the surface state of a favorable application layer according to the viscosity and dryness of the electrode mixture paste.

Application|coating with respect to the electrical power collector top of the electrode mixture paste of a positive electrode may be performed to the single side|surface of an electrical power collector, and may be performed to both surfaces. When apply|coating to both surfaces of an electrical power collector, you may apply|coat in order one by one side, and you may apply|coat both surfaces simultaneously. Moreover, it may apply|coat continuously to the surface of an electrical power collector, you may apply|coat it intermittently, and you may apply|coat in stripe shape. The thickness, length, and width of the coating layer can be appropriately determined according to the size of the battery and the like.

It does not specifically limit as a method of drying the electrode mixture paste of the positive electrode apply|coated on the electrical power collector, A well-known method can be used. As a drying method, drying by drying by warm air, hot air, low humidity wind, vacuum drying, standing still in a heating furnace etc., or irradiating, for example, far infrared rays, infrared rays, an electron beam, etc. is mentioned, for example. You may implement these drying methods in combination. Although the temperature in the case of heating is generally about 50 degreeC - 180 degreeC, conditions, such as temperature, can be set suitably according to the application amount of the electrode mixture paste, the boiling point of the solvent used, etc. By this drying, volatile components, such as a solvent, are volatilized from the coating film of an electrode mixture paste, and an electrode mixture layer is formed on an electrical power collector.

When a material not containing lithium, such as a sulfur-modified organic compound and a sulfur-carbon composite, is used as the positive electrode active material, lithium may be doped in advance. The method of doping to the said material may just follow a well-known method. For example, a semi-cell is made by using metallic lithium for the counter electrode, and lithium is inserted by an electrolytic doping method of electrochemically doping lithium, or after attaching a metallic lithium foil to the electrode, in the electrolyte solution. A method of inserting lithium by a paste doping method in which it is left to stand and dope using the diffusion of lithium to an electrode, a mechanical doping method in which a positive electrode active material and lithium metal are mechanically collided to insert lithium, etc., but these is not limited to

The negative electrode used by this invention can be manufactured according to a well-known method. For example, a negative electrode having an electrode mixture layer formed on the current collector can be manufactured by applying an electrode mixture paste obtained by slurrying a mixture containing a negative electrode active material, a binder, and a conductive aid to an organic solvent or water on a current collector and drying it. have.

A well-known thing can be used for a negative electrode active material. Known negative electrode active materials include, for example, natural graphite, artificial graphite, non-graphitizable carbon, easily graphitized carbon, lithium, lithium alloy, silicon, silicon alloy, silicon oxide, tin, tin alloy, tin oxide, phosphorus, germanium. , indium, copper oxide, antimony sulfide, titanium oxide, iron oxide, manganese oxide, cobalt oxide, nickel oxide, lead oxide, ruthenium oxide, tungsten oxide, zinc oxide, LiVO ₂ , Li ₂ VO ₄ , Li ₄ Ti ₅ O ₁₂ and complex oxides such as titanium niobium oxide. Only 1 type may be used for these negative electrode active materials, and may be used in combination of 2 or more type.

As the negative electrode active material, sulfur, a sulfur-modified organic compound, a sulfur-carbon composite, and Li ₂ S _x (x = 1 to 8) can also be used. As the sulfur, sulfur-modified organic compound, and sulfur-carbon composite that can be used as the negative electrode active material, the same sulfur and sulfur-modified organic compounds and sulfur-carbon composite that can be used as the positive electrode active material can be used.

If the particle diameter of the negative electrode active material is too large, a uniform and smooth electrode mixture layer may not be obtained. On the other hand, if the particle diameter is too small, the handling property in the slurrying step is lowered. Therefore, the average particle diameter (D50) of the negative electrode active material is 0.01 It is preferable that they are micrometer - 100 micrometers, It is more preferable that they are 0.5 micrometer - 50 micrometers, It is more preferable that they are 1 micrometer - 30 micrometers.

A negative electrode active material can be made into a desired particle size by methods, such as grinding|pulverization and granulation. Dry grinding performed in gas may be sufficient as grinding|pulverization, and wet grinding performed in liquids, such as water, may be sufficient as it. Industrial grinding methods include, for example, a ball mill, a roller mill, a turbo mill, a jet mill, a cyclone mill, a hammer mill, a pin mill, a rotary mill, a vibrating mill, a planetary mill, an attritor, and a bead mill. have.

A well-known thing can be used for a binder. As a specific example of a binder, the thing similar to the binder used for a positive electrode is mentioned. A binder may use only 1 type, and may use it in combination of 2 or more type.

It is preferable that they are 1 mass part - 30 mass parts with respect to 100 mass parts of negative electrode active materials, and, as for content of a binder, it is more preferable that they are 1 mass part - 20 mass parts.

As a conductive support agent, a well-known thing can be used as a conductive support agent of an electrode. As a specific example of a conductive support agent, the thing similar to the conductive support agent used for a positive electrode is mentioned.

It is preferable that they are 0.0001 micrometer - 100 micrometers, and, as for the average particle diameter (D50) of a conductive support agent, it is more preferable that they are 0.01 micrometer - 50 micrometers.

It is preferable that they are 0 mass parts - 50 mass parts normally, it is preferable that they are 0 mass parts - 30 mass parts, and, as for content of a conductive support agent, it is more preferable that they are 0.5 mass parts - 20 mass parts.

As a solvent for preparing the electrode mixture paste of a negative electrode, the thing similar to the solvent used for preparing the electrode mixture paste of a positive electrode is mentioned. The amount of the solvent used can be adjusted according to the application method selected when coating the electrode mixture paste, for example, in the case of application by the doctor blade method, with respect to 100 parts by mass of the total amount of the negative electrode active material, the binder and the conductive auxiliary agent, It is preferable that they are 15 mass parts - 300 mass parts, and it is more preferable that they are 30 mass parts - 200 mass parts.

The negative electrode electrode mixture paste may contain, in addition to the above components, other components such as, for example, a viscosity modifier, a reinforcing material, an antioxidant, a pH adjuster, and a dispersing agent, as long as the effects of the present invention are not impaired. As these other components, a well-known thing can be used by a well-known compounding ratio.

Preparation of the electrode mixture paste of the negative electrode can be produced by blending and dispersing in the same process as the manufacturing process of the electrode mixture paste of the positive electrode, except that a negative electrode active material is used instead of the positive electrode active material.

As the current collector, an electrically-conductive material such as titanium, titanium alloy, aluminum, aluminum alloy, copper, nickel, stainless steel, nickel-plated steel, or carbon is used. Examples of the shape of the current collector include a foil shape, a plate shape, a network shape, a foam shape, and a nonwoven fabric shape, and the current collector may be either porous or non-porous. Moreover, in order to improve adhesiveness and an electrical characteristic, these electrically-conductive materials may be surface-treated. Among these electrically-conductive materials, from a viewpoint of stability in a negative electrode potential, electroconductivity, and price, copper is preferable, and copper foil is especially preferable. Although there is no restriction|limiting in particular as for the thickness of an electrical power collector, Usually, it is 3 micrometers - 30 micrometers.

In the case where the negative electrode active material is a metal or metal alloy such as lithium, lithium alloy, tin, or a tin alloy, the metal or alloy is prepared in the form of, for example, a plate or sheet, without using a binder, a conductive aid, or a solvent to prepare an electrode mixture paste. It can also be used in forms, such as a phase or a film form. In addition, when the alloy is used as the negative electrode active material, a current collector is not required because the negative electrode active material itself has high electronic conductivity, but depending on the configuration of the battery, a metal material that does not form an alloy with the negative electrode active material is used as a negative electrode It can also be used as a collector.

Although the method of apply|coating the electrode mixture paste of a negative electrode on an electrical power collector is not specifically limited, For example, the coating method used when manufacturing a positive electrode is mentioned.

The application of the electrode mixture paste of the negative electrode onto the current collector may be applied to one side of the current collector or to both sides. When apply|coating to both surfaces of an electrical power collector, you may apply|coat in order one by one side, and you may apply|coat both surfaces simultaneously. Moreover, it may apply|coat continuously to the surface of an electrical power collector, you may apply|coat it intermittently, and you may apply|coat in stripe shape. The thickness, length, and width of the coating layer can be appropriately determined according to the size of the battery and the like.

It does not specifically limit as a method of drying the electrode mixture paste of the negative electrode apply|coated on the electrical power collector, A well-known method can be used. As a drying method, drying by drying by warm air, hot air, low humidity wind, vacuum drying, leaving still in a heating furnace etc., or irradiating, for example, far infrared rays, infrared rays, an electron beam, etc. is mentioned, for example. You may implement these drying methods in combination. Although the temperature in the case of heating is generally about 50 degreeC - 180 degreeC, conditions, such as temperature, can be set suitably according to the application amount of the electrode mixture paste, the boiling point of the solvent used, etc. By this drying, volatile components, such as a solvent, are volatilized from the coating film of an electrode mixture paste, and an electrode mixture layer is formed on an electrical power collector.

When a material having a large initial irreversible reaction such as silicon-based, tin-based, or sulfur-based material is used as the negative electrode active material, lithium may be doped in advance. The method of doping to the said material may just follow a well-known method. For example, a semi-cell is made using metallic lithium for the counter electrode, and lithium is inserted by an electrolytic doping method of electrochemically doping lithium, or a metallic lithium foil is attached to an electrode and then left in an electrolyte solution, and the electrode is A method of inserting lithium by a paste doping method in which lithium is doped using diffusion of lithium into no.

As a separator, a polymer film, a glass film, etc. which are normally used can be used without limitation in particular. Specific examples of the polymer film include, for example, polyethylene, polypropylene, polyvinylidene fluoride, polyvinylidene chloride, polyacrylonitrile, polyacrylamide, polytetrafluoroethylene, polysulfone, polyethersulfone, poly Carbonate, polyamide, polyimide, polyethers such as polyethylene oxide and polypropylene oxide, various celluloses such as carboxymethyl cellulose and hydroxypropyl cellulose, poly(meth)acrylic acid and various esters and a film made of a polymer compound or derivative thereof, a copolymer or mixture thereof, etc., and these films are coated with a ceramic material such as alumina or silica, magnesium oxide, aramid resin, or polyvinylidene fluoride. there is These films can be used independently, and these polymer films can also be superposed|polymerized and used as a multilayer film. In addition, various additives can be used for these polymer films, and the kind and content in particular are not restrict|limited. Among these polymer films, films made of polyethylene, polypropylene, polyvinylidene fluoride, and polysulfone are preferably used.

As for these polymer films, those made microporous are used so that a nonaqueous electrolyte may permeate and ions may permeate|transmit easily. As the microporous method, a film is formed while microphase-separating a solution of a polymer compound and a solvent, and the solvent is extracted and removed to make it porous, and a film is formed by extruding a molten polymer compound with a high draft. Then, a "stretching method" in which heat treatment is performed, the crystals are arranged in one direction, and a gap is formed between the crystals by stretching to achieve porosity, and the like are appropriately selected depending on the polymer film used.

The nonaqueous electrolyte secondary battery of the present invention is not particularly limited in its shape, and can be a battery of various shapes, such as a coin-type battery, a cylindrical battery, a prismatic battery, and a laminate-type battery. 1 is a longitudinal sectional view schematically showing an example of the structure of a coin-type battery of a nonaqueous electrolyte secondary battery of the present invention. Fig. 2 is a schematic diagram showing the basic configuration of a cylindrical battery of a nonaqueous electrolyte secondary battery of the present invention. Fig. 3 is a perspective view showing the internal structure of the cylindrical battery of the nonaqueous electrolyte secondary battery of the present invention as a cross section.

The coin-type nonaqueous electrolyte secondary battery 10 shown in FIG. 1 includes a positive electrode current collector 1a, a positive electrode mixture layer 1 formed on the positive electrode current collector 1a and capable of releasing lithium ions, and a positive electrode. A positive electrode case 4 accommodating a positive electrode composed of the current collector 1a and the positive electrode mixture layer 1, the negative electrode current collector 2a, and the negative electrode current collector 2a are formed on the positive electrode mixture layer 1 ) a negative electrode case (5) accommodating a negative electrode comprising a negative electrode mixture layer (2) capable of occluding and releasing lithium ions, a negative electrode current collector (2a) and a negative electrode mixture layer (2), and a separator ( 7) is provided. The inside of the positive electrode case 4 and the negative electrode case 5 is filled with the nonaqueous electrolyte 3 . In addition, peripheral portions of the positive electrode case 4 and the negative electrode case 5 are sealed by being caulked through a polypropylene gasket 6 .

The cylindrical nonaqueous electrolyte secondary battery 10 ′ shown in FIGS. 2 and 3 includes an electrode body in which a negative electrode plate 19 and a positive electrode plate 21 are wound through a separator 7 , and a case accommodating the electrode body ( 23) and a pair of insulating plates 24 arranged to sandwich the electrode body. The positive electrode plate 21 is composed of a positive electrode current collector 1a and a positive electrode mixture layer 1 formed on the positive electrode current collector 1a and capable of releasing lithium ions. The negative electrode plate 19 is formed on the negative electrode current collector 2a and the negative electrode current collector 2a, and the negative electrode mixture layer 2 capable of occluding and releasing lithium ions released from the positive electrode mixture layer 1 . is composed of The inside of the case 23 is filled with the non-aqueous electrolyte 3 . At the open end of the case 23 , the positive electrode terminal 17 , the safety valve 26 formed inside the positive electrode terminal 17 , and the PTC (Positive Temperature Coefficient) element 27 are caulked through the gasket 6 . It is sealed. The negative electrode plate 19 is connected to the negative electrode terminal 18 via the negative electrode lead 20 . The positive electrode plate 21 is connected to the positive electrode terminal 17 via the positive electrode lead 22 .

As an exterior member used for the positive electrode case 4, the negative electrode case 5, and the case 23, a metal container, a laminated film, etc. are mentioned. The thickness of the exterior member is normally 0.5 mm or less, Preferably it is 0.3 mm or less. Examples of the shape of the exterior member include a flat shape (thin shape), a square shape, a cylindrical shape, a coin shape, and a button shape.

The metal container can be formed of, for example, stainless steel, aluminum, or an aluminum alloy. As an aluminum alloy, the alloy containing elements, such as magnesium, zinc, and a silicon, is preferable. Aluminum or aluminum alloy WHEREIN: By content of transition metals, such as iron, copper, nickel, and chromium, being 1 mass % or less, the long-term reliability and heat dissipation property in a high-temperature environment can be improved remarkably.

As the laminate film, a multilayer film having a metal layer between the resin films can be used. As for a metal layer, aluminum foil or aluminum alloy foil is preferable for weight reduction. The resin film can use polymeric materials, such as polypropylene, polyethylene, nylon, and a polyethylene terephthalate, for example. The laminate film can be sealed by thermal fusion to form an exterior member.

As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment. It is a range which does not deviate from the summary of this invention WHEREIN: It can implement in various forms which performed changes, improvement, etc. which those skilled in the art can implement.

Example

Below, an Example and a comparative example are shown and this invention is demonstrated more concretely. In addition, this invention is not limited by these Examples.

<Production of positive electrode A>

_{94.0 parts by mass of NCM622 (LiNi 0.6} Co _0.2 Mn _0.2 O ₂ , manufactured by Beijing Tangcheng Co., Ltd.) as a positive electrode active material, 3.0 parts by mass of acetylene black (Denka Black, manufactured by Denka Corporation) as a conductive aid, and polyvinylidene fluoride (Kureha) as a binder ) was used in 3.0 parts by mass and 90 parts by mass of N-methylpyrrolidone as a solvent, and dispersed using a planetary mixer to obtain a slurry-like electrode mixture paste. This electrode mixture paste was apply|coated to the single side|surface of the electrical power collector which consists of aluminum foil (15 micrometers in thickness) by the doctor blade method, and after drying at 90 degreeC, it press-molded. Thereafter, the electrode was cut to a predetermined size, and vacuum dried at 130°C for 3 hours immediately before use to prepare a positive electrode A.

<Production of negative electrode A>

96.6 parts by mass of artificial graphite (MAGD: manufactured by Hitachi Chemical Co., Ltd.) as a negative electrode active material, 0.4 parts by mass of acetylene black (Denka Black, manufactured by Denka Corporation) as a conductive aid, and styrene-butadiene rubber (40% by mass aqueous dispersion, Nippon) as a binder Electrode mixture in the form of a slurry using 2.0 parts by mass of Xeon), 1.0 parts by mass of sodium carboxymethylcellulose (CMCNa: manufactured by Daicel Finecam) and 120 parts by mass of water as a solvent, and dispersed using a planetary mixer. A paste was obtained. This electrode mixture paste was apply|coated to the single side|surface of the electrical power collector which consists of copper foil (10 micrometers in thickness) by the doctor blade method, and after drying at 90 degreeC, it press-molded. Thereafter, the electrode was cut to a predetermined size and vacuum dried at 130° C. for 3 hours immediately before use to prepare a negative electrode A.

<Production of Battery-1>

[Example 1]

_{A solution in which LiPF 6} was dissolved at a concentration of 1.0 mol/L as a supporting electrolyte in a mixed solvent composed of 50% by volume of ethylene carbonate and 50% by volume of diethyl carbonate was prepared. 1.0 mass % of compound 1-1 was added to this, and it was set as the non-aqueous electrolyte.

The positive electrode A cut into the disk shape and the negative electrode A cut into the disk shape were used, and a polypropylene film (manufactured by Celgard Co., Ltd.) was sandwiched as a separator and held in the case. Then, the nonaqueous electrolyte prepared earlier was poured into the case, and it sealed with a caulking machine, and the nonaqueous electrolyte secondary battery (phi 20mm, 3.2mm thickness coin type) of Example 1 was produced. The cycle characteristics and rate characteristics of the produced nonaqueous electrolyte secondary battery were evaluated by the method of charge/discharge evaluation-1, and the results are shown in Table 1.

[Example 2]

With respect to the nonaqueous electrolyte, a nonaqueous electrolyte secondary battery of Example 2 was produced in the same manner as in Example 1 except that 0.1 mass% of compound 1-1 was added. The cycle characteristics and rate characteristics of the produced nonaqueous electrolyte secondary battery were evaluated by the method of charge/discharge evaluation-1, and the results are shown in Table 1.

[Example 3]

With respect to the nonaqueous electrolyte, a nonaqueous electrolyte secondary battery of Example 3 was produced in the same manner as in Example 1 except that 5.0 mass% of compound 1-1 was added. The cycle characteristics and rate characteristics of the produced nonaqueous electrolyte secondary battery were evaluated by the method of charge/discharge evaluation-1, and the results are shown in Table 1.

[Examples 4 to 25]

Nonaqueous electrolyte secondary batteries of Examples 4 to 25 were produced in the same manner as in Example 1 except that the compound shown in Table 1 was added to the nonaqueous electrolyte instead of the compound 1-1. In the parentheses appended to the compound number in Table 1, the weight fraction (mass %) of each additive compound in the nonaqueous electrolyte is indicated. The cycle characteristics and rate characteristics of the produced nonaqueous electrolyte secondary battery were evaluated by the method of charge/discharge evaluation-1, and the results are shown in Table 1.

[Comparative Examples 1 to 7]

In the same manner as in Example 1 except that the following compounds 5-1 to 5-7 were added to the nonaqueous electrolyte instead of the compound 1-1, nonaqueous electrolyte secondary batteries of Comparative Examples 1 to 7 were produced. The cycle characteristics and rate characteristics of the produced nonaqueous electrolyte secondary battery were evaluated by the method of charge/discharge evaluation-1, and the results are shown in Table 1.

[Formula 24]

[Comparative Example 8]

A nonaqueous electrolyte secondary battery of Comparative Example 8 was produced in the same manner as in Example 1 except that Compound 1-1 was not added. The cycle characteristics and rate characteristics of the produced nonaqueous electrolyte secondary battery were evaluated by the method of charge/discharge evaluation-1, and the results are shown in Table 1.

<Charge/Discharge Evaluation-1>

The nonaqueous electrolyte secondary batteries of Examples 1-25 and Comparative Examples 1-8 are put in a 25 degreeC thermostat, the charge termination voltage shall be 4.20V, the discharge termination voltage shall be 2.75V, and the charge rate of 0.2C and the discharge rate of 0.2C The charge-discharge test was performed 5 times, and the charge-discharge test of 2C of charge rates and 2C of discharge rates was further implemented 5 times. Then, it put in a 45 degreeC thermostat, the charge rate 0.5C and the discharge rate 0.5C performed the charge/discharge test 100 times, a total of 110 times, and the discharge capacity (mAh/g) per positive electrode active material was measured. The ratio of the discharge capacity of the 5th time to the discharge capacity of the 10th time (L1), and the ratio of the discharge capacity of the 110th time to the discharge capacity of the 11th time (L2, L2 = the discharge capacity of the 110th time / the discharge capacity of the 11th time) are shown in the table. 1 is shown.

<Production of yellow-modified polyacrylonitrile>

A mixture of 200 parts by mass of sulfur (manufactured by Sigma Aldorich, particle diameter 200 µm, powder) and 100 parts by mass of polyacrylonitrile powder (manufactured by Sigma Aldorich, classified through a sieve having an opening diameter of 30 µm) was placed in an alumina tamman tube. Then, the opening of the alumina tamman tube was covered with a rubber stopper equipped with a thermocouple, a gas inlet tube and a gas outlet tube. While introducing argon gas into the alumina tamman tube at a flow rate of 100 cc/min, the mixture was heated at a temperature increase rate of 5°C/min, and when 100°C was reached, the argon gas was stopped. After that, heating was stopped at 360°C, but the temperature rose to 400°C. After cooling to near room temperature, the reaction product was taken out from the alumina tamman tube. The obtained reaction product was grind|pulverized and sulfur-modified polyacrylonitrile (it may be called SPAN) was obtained. The average particle diameter and sulfur content of SPAN were as follows.

·Average particle diameter 10 ㎛

· Sulfur content 38.4 mass%

<Production of positive electrode B>

90.0 parts by mass of SPAN as a positive electrode active material, 5.0 parts by mass of acetylene black (Denka Black, manufactured by Denka Corporation) as a conductive aid, 3.0 parts by mass of styrene-butadiene rubber (40% by mass aqueous dispersion, manufactured by Nippon Zeon) as a binder, carboxy Using 2.0 parts by mass of sodium methylcellulose (CMCNa, manufactured by Daicel Finecam) and 120 parts by mass of water as a solvent, it was dispersed using a rotation/revolution mixer to obtain a slurry-like electrode mixture paste. This electrode mixture paste was apply|coated to the single side|surface of the electrical power collector which consists of carbon-coated aluminum foil (thickness 22 micrometers) by the doctor blade method, after drying at 90 degreeC, it press-molded. Thereafter, the electrode was cut to a predetermined size, and vacuum dried at 130 DEG C for 3 hours immediately before use. Then, using metallic lithium as a counter electrode, a half cell using the nonaqueous electrolyte of Comparative Example 8 was prepared, and lithium was doped electrochemically to produce a positive electrode B.

<Production of Battery-2>

[Example 26]

In a mixed solvent consisting of 50% by volume of ethylene carbonate and diethyl carbonate of 50 volume% to prepare a solution in which LiPF ₆ was dissolved at a concentration of 1.0 ㏖ / ℓ. 1.0 mass % of compound 1-37 was added to this, and it was set as the non-aqueous electrolyte.

The positive electrode B cut into the disk shape and the negative electrode A cut into the disk shape were used, and a polypropylene film (manufactured by Celgard) was sandwiched as a separator and held in the case. Then, the nonaqueous electrolyte prepared previously was poured into the case, and it sealed with a caulking machine, and produced the nonaqueous electrolyte secondary battery (phi 20mm, 3.2mm thickness coin type) of Example 26. The cycle characteristics and rate characteristics of the produced nonaqueous electrolyte secondary battery were evaluated by the method of charge/discharge evaluation-2, and the results are shown in Table 2.

[Examples 27 to 29]

Nonaqueous electrolyte secondary batteries of Examples 27 to 29 were produced in the same manner as in Example 26 except that the compound shown in Table 2 was added instead of Compound 1-37. The cycle characteristics and rate characteristics of the produced nonaqueous electrolyte secondary battery were evaluated by the method of charge/discharge evaluation-2, and the results are shown in Table 2.

[Comparative Example 9]

A nonaqueous electrolyte secondary battery of Comparative Example 9 was produced in the same manner as in Example 26 except that Compound 1-37 was not added. The cycle characteristics and rate characteristics of the produced nonaqueous electrolyte secondary battery were evaluated by the method of charge/discharge evaluation-2, and the results are shown in Table 2.

<Charge/Discharge Evaluation-2>

Examples 26-29 and the nonaqueous electrolyte secondary battery of the comparative example 9 are put into a 25 degreeC thermostat, the charge-end voltage shall be 3.0V, the discharge end voltage shall be 0.7V, and the charge/discharge rate of 0.2C and the discharge rate of 0.2C shall be set as 0.7V. The test was performed 5 times, and the charge-discharge test of 2C of charge rates and 2C of discharge rates was further performed 5 times. Then, it put in a 45 degreeC thermostat, the charge rate 0.5C and the discharge rate 0.5C performed the charge/discharge test 100 times, a total of 110 times, and the discharge capacity (mAh/g) per positive electrode active material was measured. The ratio of the discharge capacity of the 5th time to the discharge capacity of the 10th time (L3), and the ratio of the discharge capacity of the 110th time to the discharge capacity of the 11th time (L4, L4 = the discharge capacity of the 110th time / the discharge capacity of the 11th time) are shown in the table. 2 is shown.

From the results of Tables 1 and 2, by using the composition for electrolyte of the present invention, a nonaqueous electrolyte secondary battery having improved cycle characteristics and rate characteristics can be produced.

1: positive mix layer
1a: positive electrode current collector
2: negative electrode mixture layer
2a: negative electrode current collector
3: non-aqueous electrolyte
4: positive electrode case
5: negative electrode case
6: gasket
7: separator
10: coin-type non-aqueous electrolyte secondary battery
10': Cylindrical non-aqueous electrolyte secondary battery
17: positive terminal
18: negative terminal
19: negative plate
20: negative electrode lead
21: positive plate
22: positive electrode lead
23 : case
24: insulation plate
26: safety valve
27: PTC element

Claims (8)

at least one compound selected from the group consisting of compounds represented by the following general formulas (1) to (4);
A composition for an electrolyte comprising at least one selected from a solvent and a dispersion medium.

(Wherein, R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, and R ² to R ⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms. An alkoxy group or the following formula (1-a), R ⁶ is a nitro group, a sulfonic acid group, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a formula (1-b) or In the following formula (1-c), when R ⁶ is a hydrocarbon group having 1 to 8 carbon atoms, n = an integer of 1 to 4, R ⁶ is a nitro group, a sulfonic acid group, or a hydrocarbon group having 1 to 6 carbon atoms In the case of an alkoxy group or the following formula (1-b), n = 1, and when R ⁶ is the following formula (1-c), n = 2)

(in the formula, ※ indicates the bonding position)

(In the formula, R ⁷ is the following formula (1-d) or the following formula (1-e))

(wherein, R ⁸ to R ¹⁶ are each independently a hydrogen atom, an unsubstituted hydrocarbon group having 1 to 8 carbon atoms, a hydrocarbon group having 1 to 8 carbon atoms in which some of the hydrogen atoms are substituted with fluorine atoms; An unsubstituted C1-C6 alkoxy group, a C1-C6 alkoxy group in which a part of hydrogen atoms are substituted with a fluorine atom, an unsubstituted C1-C6 thioalkoxy group, a part of hydrogen atom is an acyl group having a thioalkoxy group having 1 to 6 carbon atoms, a sulfonyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms substituted with a fluorine atom, * indicates a bonding position)

(Wherein, when m = 1 or 2 and m = 1, R ¹⁷ to R ¹⁹ are each independently a hydrocarbon group having 1 to 8 carbon atoms, and R ¹⁸ and R ¹⁹ are linked to form a ring may be formed, and when m = 2, R ¹⁷ and R ¹⁹ are each independently a hydrocarbon group having 1 to 8 carbon atoms, and R ¹⁸ is a single bond)

(Wherein, R ²⁰ and R ²¹ are each independently a hydrocarbon group having 1 to 8 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ²² to R ³¹ are each independently a hydrogen atom; a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a nitro group) The method of claim 1,
^{The composition for electrolytes containing the compound whose R<1>} in the said General formula (1) is a methyl group, an allyl group, t-butyl group, or a benzyl group. The method of claim 1,
In the formula (2), R ⁷ is the formula (1-d), in the formula (1-d) R ⁸ , R ⁹ , R ¹¹ and R ¹² are a hydrogen atom, and R ¹⁰ is A composition for an electrolyte comprising a compound that is a methoxy group, a thiomethoxy group, a trifluoromethoxy group, or a methylsulfonyl group. The method of claim 1,
A composition for an electrolyte comprising a compound in which ^{R 7} in the formula (2) is the formula (1-e), and R ¹⁴ to R ^{16 in the formula (1-e) are a hydrogen atom.} The method of claim 1,
A composition for an electrolyte comprising a compound in which ^{R 17} in the general formula (3) is a methyl group or an ethyl group. The method of claim 1,
In the formula (4), R ²⁰ and R ²¹ are methyl groups, R ²⁴ and R ²⁹ are fluorine atoms or nitro groups, and R ²² , R ²³ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R A composition for an electrolyte, comprising a compound in which ³⁰ and R ^{31 are hydrogen atoms.} The composition for an electrolyte according to any one of claims 1 to 6;
A non-aqueous electrolyte comprising a supporting electrolyte. positive pole,
negative pole,
A non-aqueous electrolyte secondary battery comprising the non-aqueous electrolyte according to claim 7.

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