JP2003007333A - Non-aqueous electrolyte and non-aqueous electrolyte secondary battery using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high energy density non-aqueous electrolyte secondary battery having high charge / discharge efficiency, excellent capacity retention characteristics, and excellent battery characteristics and safety in a wide temperature range, and its use. Provide a non-aqueous electrolyte. SOLUTION: A lactone compound selected from γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, δ-caprolactone or ε-caprolactone, and a general formula (1) (In the formula, A represents a nitrogen-containing heterocyclic ring having a carbonyl group, R represents an alkyl group, an alkenyl group, or a (hetero) aryl group, and n represents a natural number. However, when n is 2 or more, R represents A non-aqueous electrolytic solution obtained by dissolving a lithium salt as an electrolyte in a non-aqueous solvent containing a nitrogen-containing heterocyclic compound represented by the following formula:

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a non-aqueous electrolyte solution and a non-aqueous electrolyte secondary battery using the same. More particularly, the present invention relates to a high energy density non-aqueous electrolyte secondary battery having high charge / discharge efficiency, excellent capacity retention characteristics, and excellent battery characteristics and safety in a wide temperature range, and a non-aqueous electrolyte solution that provides the same.

[0002]

2. Description of the Related Art With the recent lightening and miniaturization of electric products, development of lithium secondary batteries having a high energy density has been desired more than ever, and the application fields of lithium secondary batteries are expanding. Accordingly, improvement of battery characteristics is also demanded. In the lithium secondary battery, the solvent of the electrolytic solution is decomposed on the surface of the electrode, which causes a decrease in charge / discharge efficiency and capacity maintenance. For example, in a non-aqueous electrolyte secondary battery in which various graphite-based electrode materials are used alone or as a negative electrode by mixing with a negative electrode material capable of inserting and extracting lithium, an electrolyte solution using propylene carbonate as a main solvent It is known that when is used, a decomposition reaction of the solvent occurs on the surface of the negative electrode, and smooth insertion and release of lithium into graphite becomes impossible.

On the other hand, when ethylene carbonate is used as an electrolyte solvent, it decomposes less than propylene carbonate, but since ethylene carbonate is a solid at room temperature and has a high viscosity, it has the drawback of being difficult to handle. In addition, γ-butyrolactone has low viscosity and high dielectric constant, which is an excellent property desired for a non-aqueous solvent for a non-aqueous electrolytic solution, but electrochemical decomposition occurs on both positive and negative electrode surfaces. It has drawbacks. JP-A-11-
No. 31525 describes that by using γ-butyrolactone as a main solvent and an electrolyte solution containing about 15 to 35% by volume of ethylene carbonate as a sub-solvent, decomposition of the solvent on the electrode surface can be suppressed. Has been done.

[0004]

The electrolytic solution using γ-butyrolactone and ethylene carbonate in combination has an electrochemical acid resistance as compared with the electrolytic solution using ethylene carbonate and a low-viscosity solvent other than γ-butyrolactone. Volatile,
Since the reduction resistance is poor, there is a problem in the capacity retention rate of the battery at high temperatures, and further improvement has been desired.

Further, since the composition of the electrolytic solution affects the charge / discharge characteristics and capacity maintenance characteristics of the lithium secondary battery, it has been studied to improve the above-mentioned characteristics by adding various compounds to the electrolytic solution. (JP-A-3-57169, 8)
-321313, 10-14529, 11-2
No. 73728, JP-A No. 2000-285962). However, no effective compound has been known yet for an electrolyte solvent containing a lactone compound in the solvent.

The present invention is intended to provide a non-aqueous electrolyte solution which has a battery characteristic such as excellent charge / discharge characteristics and capacity maintenance characteristics in a wide temperature range and which provides a highly safe non-aqueous electrolyte secondary battery. To do.

[0007]

Means for Solving the Problems The present inventors have conducted various studies to solve the above problems, and as a result, have found that the lactone compound and the general formula (1)

[0008]

[Chemical 3]

(In the formula, A represents a nitrogen-containing heterocycle having a carbonyl group, R represents an alkyl group, an alkenyl group or a (hetero) aryl group, and n represents a natural number, provided that n is 2 or more. , R may be different from each other.) A lithium secondary battery using a non-aqueous electrolyte solution in which a lithium salt is dissolved in a non-aqueous solvent containing a nitrogen-containing heterocyclic compound represented by From time to time, a lithium ion permeable and stable coating is efficiently generated on the electrode surface to suppress the decomposition of the electrolytic solution, so that in a wide temperature range, excellent battery characteristics such as charge / discharge efficiency and capacity maintenance characteristics are obtained.
Moreover, they have found that they have high safety, and have completed the present invention.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a solvent containing an lactone compound is used as a solvent of an electrolytic solution. As the lactone compound, a 5- to 7-membered ring lactone such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, δ-caprolactone and ε-caprolactone can be usually used. Of these, γ-butyrolactone is preferred. Some lactone compounds can be used in combination.

The lactone compound is a non-aqueous solvent of 10 to 9
Used to account for 9.9% by weight. It is preferably used so as to occupy 12 to 99% by weight, particularly 15 to 98% by weight. The lactone compound may be used in combination with other non-aqueous solvent that is commonly used in non-aqueous electrolytes. Examples of such a non-aqueous solvent include cyclic carbonate, chain carbonate, carboxylic acid ester, chain ether and the like.

Examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate and vinyl ethylene carbonate. As the chain carbonate, dimethyl carbonate, diethyl carbonate, di-n-
Propyl carbonate, diisopropyl carbonate,
n-propyl isopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, di-t-
Butyl carbonate, n-butyl isobutyl carbonate, n-butyl-t-butyl carbonate, isobutyl-t-butyl carbonate, ethyl methyl carbonate, methyl-n-propyl carbonate, n-butyl methyl carbonate, isobutyl methyl carbonate, t
-Butyl methyl carbonate, ethyl-n-propyl carbonate, n-butyl ethyl carbonate, isobutyl ethyl carbonate, t-butyl ethyl carbonate, n-butyl-n-propyl carbonate, isobutyl-n-propyl carbonate, t-butyl-n- Propyl carbonate, n-butyl isopropyl carbonate, isobutyl isopropyl carbonate, t-butyl isopropyl carbonate, etc. are used. Among them,
Dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate are preferred.

Examples of the carboxylic acid ester include methyl acetate, ethyl acetate, acetic acid-n-propyl acetate, acetic acid-isopropyl, acetic acid-n-butyl acetate, isobutyl acetate, acetic acid-t-
Butyl, methyl propionate, ethyl propionate, propionate-n-propyl, propionate-isopropyl, propionate-n-butyl, propionate isobutyl, propionate-t-butyl and the like are used, among which ethyl acetate, Methyl propionate and ethyl propionate are preferred.

As the chain ether, dimethoxymethane, 1,2-dimethoxyethane, diethoxymethane,
1,2-diethoxyethane, ethoxymethoxymethane,
Ethoxymethoxyethane, etc. are used.
1,2-dimethoxyethane and 1,2-diethoxyethane are preferred. These solvents are non-aqueous solvents 0 to 89.9.
Used to account for weight percent.

In the present invention, the non-aqueous solvent contains the nitrogen-containing heterocyclic compound represented by the general formula (1). In the compound of the general formula (1), the nitrogen-containing heterocycle having a carbonyl group represented by A may be a single ring or may be condensed with a benzene ring or the like. The number of carbonyl groups in the ring is 1 to 4. Specific examples of the nitrogen-containing heterocycle include pyrrolidine,
Examples thereof include imidazolidine, oxazolidine, thiazolidine, piperidine, pyrimidine, oxazine, (iso) indoline, benzimidazole, benzoxazole, benzothiazole, quinoline, quinazoline and benzoxazine.

In the compound of the general formula (1), when R represents an alkyl group, the alkyl group is an alkyl group having 1 to 4 carbon atoms which may have a substituent, preferably a methyl group or an ethyl group. It is a base. When R represents an alkenyl group, the alkenyl group is a C2-C4 alkenyl group which may have a substituent, and is preferably a vinyl group.

When R represents a (hetero) aryl group, the (hetero) aryl group is a phenyl group or a pyridyl group which may have a substituent. The following compounds may be mentioned as specific examples of the nitrogen-containing heterocyclic compound represented by the general formula (1). 1) Pyrrolidine compound 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-vinyl-2-pyrrolidone, 1,5-dimethyl-2-pyrrolidone, 1-isopropyl-2-pyrrolidone, 1-n- Butyl-2-pyrrolidone, 1-methyl-3
-Pyrrolidone, 1-ethyl-3-pyrrolidone, 1-vinyl-3-pyrrolidone and other 1-alkyl (or alkenyl) pyrrolidone compounds; 1-phenyl-2-pyrrolidone, 1-phenyl-3-pyrrolidone and other 1-aryl Pyrrolidone compounds; N-alkylsuccinimide compounds such as N-methylsuccinimide, N-ethylsuccinimide, N-cyclohexylsuccinimide and N-isobutylsuccinimide; N such as N-vinylsuccinimide
-Alkenylsuccinimide compound; N-phenylsuccinimide, N- (p-tolyl) succinimide, N-
N- (hetero) arylsuccinimide compounds such as (3-pyridyl) succinimide. 2) (iso) indoline compound 1-methyl-2-indolinone, 1-ethyl-2-indolinone, 1-vinyl-2-indolinone, 1-methyl-3-indolinone, 1-ethyl-3-indolinone,
1-Alkyl (or alkenyl) indolinone compounds such as 1-vinyl-3-indolinone; 1-phenyl-2-
1-Aryl indolinone compounds such as indolinone; N
N such as -methylphthalimide and N-ethylphthalimide
-Alkylphthalimide compounds; N-alkenylphthalimide compounds such as N-vinylphthalimide; N-arylphthalimide compounds such as N-phenylphthalimide. 3) Imidazolidine compounds 1,3-dimethylimidazolidine-2,5-dione, 1
1,3-dialkyl (such as -ethyl-3-methylimidazolidin-2,5-dione, 1,3-diethylimidazolidin-2,5-dione, 1,3-divinylimidazolidin-2,5-one ( Or alkenyl) imidazolidine-2,5-dione compounds; 1-alkyl-3 such as 1-methyl-3-phenylimidazolidine-2,5-dione
An aryl imidazolidine-2,5-dione compound;
1,3-Diarylimidazolidine-2,5-dione compounds such as 1,3-diphenylimidazolidine-2,5-dione; 1,3-dimethyl-2-imidazolidinone, 1
-Ethyl-3-methyl-2-imidazolidinone, 1,3
-Diethyl-2-imidazolidinone, 1,3-divinyl-2-imidazolidinone, 1,3-dimethyl-4-imidazolidinone, 1-ethyl-3-methyl-4-imidazolidinone, 3-ethyl -1-Methyl-4-imidazolidinone, 1,3-diethyl-4-imidazolidinone, 1,
1,3-Dialkyl (or alkenyl) imidazolidinone compounds such as 3-divinyl-4-imidazolidinone; 1
-Methyl-3-phenyl-2-imidazolidinone, 1-
1 such as methyl-3-phenyl-4-imidazolidinone and 3-methyl-1-phenyl-4-imidazolidinone
(3) -Alkyl-3 (1) -arylimidazolidinone compounds; 1,3-diarylimidazolidinone such as 1,3-diphenyl-2-imidazolidinone and 1,3-diphenyl-4-imidazolidinone Compound. 4) Benzimidazole compound 1,3-dimethyl-2,3-dihydrobenzimidazol-2-one, 1-ethyl-3-methyl-2,3-dihydrobenzimidazol-2-one, 1,3-diethyl-2 , 3-dihydrobenzimidazol-2-one,
1,3-Dialkyl (or alkenyl) -2,3-dihydrobenzimidazol-2-one compounds such as 1,3-divinyl-2,3-dihydrobenzimidazol-2-one; 1-methyl-3-phenyl- 1,3-Alkyl-3-, such as 2,3-dihydrobenzimidazol-2-one
Aryl-2,3-dihydrobenzimidazole-2-
On compound; 1,3-diaryl- such as 1,3-diphenyl-2,3-dihydrobenzimidazol-2-one
2,3-dihydrobenzimidazol-2-one compound. 5) Oxazolidine compounds 3-methyl-2-oxazolidone, 3-ethyl-2-oxazolidone, 3-methyl-4-oxazolidone, 3-
3-Alkyloxazolidone compounds such as ethyl-4-oxazolidone, 3-methyl-5-oxazolidone, 3-ethyl-5-oxazolidone; 3-vinyl-2-oxazolidone, 3-vinyl-4-oxazolidone, 3-vinyl-5. 3-alkenyl oxazolidone compounds such as oxazolidone; 3-phenyl-2-oxazolidone, 3-
3-aryloxazolidone compounds such as phenyl-4-oxazolidone and 3-phenyl-5-oxazolidone;
3-methyloxazolidine-2,4-dione, 3-ethyloxazolidine-2,4-dione, 3-vinyloxazolidine-2,4-dione, 3-methyloxazolidine-2,5-dione, 3-ethyloxazolidine-2 , 5
3-alkyl (or alkenyl) oxazolidinedione compounds such as dione and 3-vinyloxazolidine-2,5-dione; 3 such as 3-phenyloxazolidine-2,4-dione and 3-phenyloxazolidine-2,5-dione -Aryloxazolidinedione compounds. 6) Benzoxazole compound 3-methyl-2,3-dihydrobenzoxazole-2
3-alkyl (or alkenyl) -2,3-dihydrobenzo such as 3-one, 3-ethyl-2,3-dihydrobenzoxazol-2-one, 3-vinyl-2,3-dihydrobenzoxazol-2-one Oxazole compounds;
3-phenyl-2,3-dihydrobenzoxazole-
3-Aryl-2,3-dihydrobenzoxazol-2-one compounds such as 2-one. 7) Thiazolidine compound 3-methyl-2-thiazolidone, 3-ethyl-2-thiazolidone, 3-vinyl-2-thiazolidone, 3-methyl-4-thiazolidone, 3-ethyl-4-thiazolidone,
3-Alkyl (or alkenyl) thiazolidone compounds such as 3-vinyl-4-thiazolidone, 3-methyl-5-thiazolidone, 3-ethyl-5-thiazolidone and 3-vinyl-5-thiazolidone; 3-phenyl-2-thiazolidone , 3-phenyl-4-thiazolidone, 3-phenyl-5-thiazolidone and other 3-arylthiazolidone compounds; 3-methylthiazolidine-2,4-dione, 3-ethylthiazolidine-2,4-dione, 3- Vinylthiazolidine-2,4-dione, 3-methylthiazolidine-
3,5-dione, 3-ethylthiazolidine-2,5-dione, 3-vinylthiazolidine-2,5-dione and the like 3
-Alkyl (or alkenyl) thiazolidinedione compound; 3-phenylthiazolidine-2,4-dione, 3-
3-Aryl thiazolidinedione compounds such as phenylthiazolidine-2,5-dione. 8) Benzothiazole compound 3-methyl-2,3-dihydrobenzothiazole-2-
3-alkyl (or alkenyl) -2, such as on, 3-vinyl-2,3-dihydrobenzothiazol-2-one,
3-dihydrobenzothiazol-2-one compound; 3-
3-Aryl-2,3-dihydrobenzothiazol-2-one compounds such as phenyl-2,3-dihydrobenzothiazol-2-one. 9) Piperidine compounds 1-methyl-2-piperidone, 1-ethyl-2-piperidone, 1-vinyl-2-piperidone, 1-methyl-3-
Piperidone, 1-ethyl-3-piperidone, 1-vinyl-3-piperidone, 1-methyl-4-piperidone, 1-
1- (Substituted) alkyl (or alkenyl) piperidone compounds such as ethyl-4-piperidone, 1-vinyl-4-piperidone, 1-morpholinomethyl-2-piperidone, 1-piperidinomethyl-2-piperidone; 1-phenyl-2 -Piperidone, 1-phenyl-3-piperidone, 1
1-Arylpiperidone compounds such as phenyl-4-piperidone. 10) Quinoline compound 3,4-dihydro-1-methyl-2-quinolone, 3,4
3,4-dihydro-1-alkylquinolone compounds such as -dihydro-1-methyl-3-quinolone and 3,4-dihydro-1-methyl-quinolin-4-one; 3,4-dihydro-1-phenyl- 2-quinolone, 3,4-dihydro-1-phenyl-3-quinolone, 3,4-dihydro-1
-Phenyl-4-quinolone, etc. 3,4-dihydro-1-
Arylquinolone compounds. 11) Pyrimidine compound 1,3-dimethylhexahydropyrimidin-2-one,
1,3-diethylhexahydropyrimidin-2-one,
1,3-divinylhexahydropyrimidin-2-one,
1,3-dimethylhexahydropyrimidin-4-one,
1-ethyl-3-methylhexahydropyrimidine-4-
On, 3-ethyl-1-methylhexahydropyrimidin-4-one, 1,3-diethylhexahydropyrimidin-4-one, 1,3-divinylhexahydropyrimidin-4-one, 1,3-dimethylhexahydro 1, such as pyrimidin-5-one, 1-ethyl-3-methylhexahydropyrimidin-5-one, 1,3-diethylhexahydropyrimidin-5-one and 1,3-divinylhexahydropyrimidin-5-one 3-Dialkyl (or alkenyl) hexahydropyrimidinone compounds; 1-methyl-
3-phenylhexahydropyrimidin-2-one, 1-
1-Alkyl-3-, such as methyl-3-phenylhexahydropyrimidin-4-one, 3-methyl-1-phenylhexahydropyrimidin-4-one, and 1-methyl-3-phenylhexahydropyrimidin-5-one. Arylhexahydropyrimidinone compound; 1,3-diphenylhexahydropyrimidin-2-one, 1,3-diphenylhexahydropyrimidin-4-one, 1,3-diphenylhexahydropyrimidin-5-one 3-Diarylhexahydropyrimidinone compound; 1,3-dimethylhexahydropyrimidine-2,4-dione, 1,3
-Diethylhexahydropyrimidine-2,4-dione,
1-ethyl-3-methyl-hexahydropyrimidine-
2,4-dione, 3-ethyl-1-methyl-hexahydropyrimidine-2,4-dione, 1,3-divinylhexahydropyrimidine-2,4-dione, 1,3-dimethylhexahydropyrimidine-2, 5-dione, 1-ethyl-3-methyl-hexahydropyrimidine-2,5-dione, 1,3-diethylhexadropyrimidine-2,5
-Dione, 1,3-divinylhexahydropyrimidine-
1,3-Dialkyl (or alkenyl) hexahydropyrimidinedione compounds such as 2,5-dione; 1-methyl-3-phenylhexahydropyrimidine-2,4-dione, 3-methyl-1-phenylhexahydropyrimidine- 1- (3) -Alkyl-3 (1) -arylhexahydropyrimidinedione compounds such as 2,4-dione and 1-methyl-3-phenylhexahydropyrimidine-2,5-dione; 1,3-diphenylhexahydro Pyrimidine-
1,3-Diarylhexahydropyrimidinedione compounds such as 2,4-dione and 1,3-diphenylhexahydropyrimidine-2,5-dione; 1,3-dimethylhexahydropyrimidine-2,4,5-trione, 1,3-
Diethyl hexahydropyrimidine-2,4,5-trione, 1-ethyl-3-methylhexahydropyrimidine-
2,4,5-Trione, 3-ethyl-1-methylhexahydropyrimidine-2,4,5-trione, 1,3-divinylhexahydropyrimidine-2,4,5-trione, 1,3-dimethylhexa Hydropyrimidine-2,
4,6-trione, 1,3-diethylhexahydropyrimidine-2,4,6-trione, 1-ethyl-3-methylhexahydropyrimidine-2,4,6-trione, 3
-Ethyl-1-methylhexahydropyrimidine-2,
1,3-Dialkyl (or alkenyl) hexahydropyrimidinetrione compounds such as 4,6-trione and 1,3-divinylhexahydropyrimidine-2,4,6-trione; 1-methyl-3-phenylhexahydropyrimidine- 2,4,5-Trione, 3-methyl-1-phenylhexahydropyrimidine-2,4,5-trione, 1-
Methyl-3-phenylhexahydropyrimidine-2,
1 (3)-such as 4,6-trione and 3-methyl-1-phenylhexahydropyrimidine-2,4,6-trione
Alkyl-3 (1) -arylhexahydropyrimidinetrione compounds; 1 such as 1,3-diphenylhexahydropyrimidine-2,4,5-trione and 1,3-diphenylhexahydropyrimidine-2,4,6-trione ，
3-Diarylhexahydropyrimidinetrione compound; 1,3-dimethylhexahydropyrimidinetetraone, 1,3-diethylhexahydropyrimidinetetraone, 1-ethyl-3-methylhexahydropyrimidinetetraone, 1,3-divinylhexa 1,3-Dialkyl (or alkenyl) hexahydropyrimidinetetraone compounds such as hydropyrimidinetetraone; 1-methyl-
1 such as 3-phenylhexahydropyrimidinetetraone
(3) -Alkyl-3 (1) -arylhexahydropyrimidinetetraone compounds; 1,3-diarylhexahydropyrimidinetetraone compounds such as 1,3-diphenylhexahydropyrimidinetetraone. 12) Quinazoline compounds 1,3-dimethyl-1,2,3,4-tetrahydroquinazolin-2-one, 1,3-diethyl-1,2,3,4
-Tetrahydroquinazolin-2-one, 1-ethyl-3
-Methyl-1,2,3,4-tetrahydroquinazoline-
2-one, 3-ethyl-1-methyl-1,2,3,4-
Tetrahydroquinazolin-2-one, 1,3-divinyl-1,2,3,4-tetrahydroquinazolin-2-one, 1,3-dimethyl-1,2,3,4-tetrahydroquinazolin-4-one, 1 , 3-diethyl-1,2,
3,4-Tetrahydroquinazolin-4-one, 1-ethyl-3-methyl-1,2,3,4-tetrahydroquinazolin-4-one, 3-ethyl-1-methyl-1,2,
3,4-tetrahydroquinazolin-4-one, 1,3-
Divinyl-1,2,3,4-tetrahydroquinazoline-
1,3-dialkyl (or alkenyl)-, such as 4-one
1,2,3,4-tetrahydroquinazolinone compound; 1
-Methyl-3-phenyl-1,2,3,4-tetrahydroquinazolin-2-one, 3-methyl-1-phenyl-
1,2,3,4-tetrahydroquinazolin-2-one,
1 (3 such as 1-methyl-3-phenyl-1,2,3,4-tetrahydroquinazolin-4-one and 3-methyl-1-phenyl-1,2,3,4-tetrahydroquinazolin-4-one. ) -Alkyl-3 (1) -aryl-1,
2,3,4-Tetrahydroquinazolinone compound; 1,3
-Diphenyl-1,2,3,4-tetrahydroquinazolin-2-one, 1,3-diphenyl-1,2,3,4-
1,3-Diaryl-1,2,3,4-tetrahydroquinazolinone compounds such as tetrahydroquinazolin-4-one; 1,3-dimethyl-1,2,3,4-tetrahydroquinazolin-2,4-dione, 1 , 3-diethyl-1,
2,3,4-tetrahydroquinazoline-2,4-dione, 1-ethyl-3-methyl-1,2,3,4-tetrahydroquinazoline-2,4-dione, 3-ethyl-1-
Methyl-1,2,3,4-tetrahydroquinazoline-
2,4-dione, 1,3-divinyl-1,2,3,4-
1,3-such as tetrahydroquinazoline-2,4-dione
Dialkyl (or alkenyl) -1,2,3,4-tetrahydroquinazoline-2,4-dione compound; 1-methyl-3-phenyl-1,2,3,4-tetrahydroquinazoline-2,4-dione, 3 -Methyl-1-phenyl-
1,2,3,4-Tetrahydroquinazoline-2,4-dione and other 1 (3) -alkyl-3 (1) -aryl-
1,2,3,4-tetrahydroquinazoline-2,4-dione compound; 1,3-diaryl-1, such as 1,3-diphenyl-1,2,3,4-tetrahydroquinazoline-2,4-dione 2,3,4-tetrahydroquinazoline-
2,4-dione compound. 13) Oxazine compound 2-methyl-2H-3,4,5,6-tetrahydro-
1,2-oxazin-3-one, 2-ethyl-2H-
3,4,5,6-tetrahydro-1,2-oxazine-
3-one, 2-vinyl-2H-3,4,5,6-tetrahydro-1,2-oxazin-3-one, 2-methyl-
2H-3,4,5,6-tetrahydro-1,2-oxazin-4-one, 2-ethyl-2H-3,4,5,6-
Tetrahydro-1,2-oxazin-4-one, 2-vinyl-2H-3,4,5,6-tetrahydro-1,2-
Oxazin-4-one, 2-methyl-2H-3,4
5,6-Tetrahydro-1,2-oxazin-5-one, 2-ethyl-2H-3,4,5,6-tetrahydro-1,2-oxazin-5-one, 2-vinyl-2H-
3,4,5,6-tetrahydro-1,2-oxazine-
5-one, 2-methyl-2H-3,4,5,6-tetrahydro-1,2-oxazin-6-one, 2-ethyl-
2H-3,4,5,6-tetrahydro-1,2-oxazin-6-one, 2-vinyl-2H-3,4,5,6-
Tetrahydro-1,2-oxazin-6-one, 3-methyl-2H-3,4,5,6-tetrahydro-1,3-
Oxazin-2-one, 3-ethyl-2H-3,4
5,6-Tetrahydro-1,3-oxazin-2-one, 3-vinyl-2H-3,4,5,6-tetrahydro-1,3-oxazin-2-one, 3-methyl-2H-
3,4,5,6-tetrahydro-1,3-oxazine-
4-one, 3-ethyl-2H-3,4,5,6-tetrahydro-1,3-oxazin-4-one, 3-vinyl-
2H-3,4,5,6-tetrahydro-1,3-oxazin-4-one, 3-methyl-2H-3,4,5,6-
Tetrahydro-1,3-oxazin-5-one, 3-ethyl-2H-3,4,5,6-tetrahydro-1,3-
Oxazin-5-one, 3-vinyl-2H-3,4
5,6-Tetrahydro-1,3-oxazin-5-one, 3-methyl-2H-3,4,5,6-tetrahydro-1,3-oxazin-6-one, 3-ethyl-2H-
3,4,5,6-tetrahydro-1,3-oxazine-
6-one, 3-vinyl-2H-3,4,5,6-tetrahydro-1,3-oxazin-6-one, 4-methyl-
2H-3,4,5,6-tetrahydro-1,4-oxazin-2-one, 4-ethyl-2H-3,4,5,6-
Tetrahydro-1,4-oxazin-2-one, 4-vinyl-2H-3,4,5,6-tetrahydro-1,4-
Oxazin-2-one, 4-methyl-2H-3,4
5,6-Tetrahydro-1,4-oxazin-3-one, 4-ethyl-2H-3,4,5,6-tetrahydro-1,4-oxazin-3-one, 4-vinyl-2H-
3,4,5,6-tetrahydro-1,4-oxazine-
N-alkyl oxazinone compounds such as 3-one; 2-phenyl-2H-3,4,5,6-tetrahydro-1,2
-Oxazin-3-one, 2-phenyl-2H-3,
4,5,6-Tetrahydro-1,2-oxazine-4-
On, 2-phenyl-2H-3,4,5,6-tetrahydro-1,2-oxazin-5-one, 2-phenyl-
2H-3,4,5,6-tetrahydro-1,2-oxazin-6-one, 3-phenyl-2H-3,4,5,6
-Tetrahydro-1,3-oxazin-2-one, 3-
Phenyl-2H-3,4,5,6-tetrahydro-1,
3-oxazin-4-one, 3-phenyl-2H-3,
4,5,6-Tetrahydro-1,3-oxazine-5-
On, 3-phenyl-2H-3,4,5,6-tetrahydro-1,3-oxazin-6-one, 4-phenyl-
2H-3,4,5,6-tetrahydro-1,4-oxazin-2-one, 4-phenyl-2H-3,4,5,6
-N such as tetrahydro-1,4-oxazin-3-one
-Aryl oxazinone compounds. 14) Benzoxazine compound 4-methyl-2,3-dihydro-4H-1,4-benzoxazin-2-one, 4-ethyl-2,3-dihydro-4H-1,4-benzoxazin-2-one , 4-vinyl-2,3-dihydro-4H-1,4-benzoxazin-2-one, 4-methyl-2,3-dihydro-4H
-1,4-benzoxazin-3-one, 4-ethyl-
2,3-Dihydro-4H-1,4-benzoxazine-
3-one, 4-vinyl-2,3-dihydro-4H-1,
4-Alkyl (or alkenyl) -1,4-benzoxazine compounds such as 4-benzoxazin-3-one; 4
4-phenyl-2,3-dihydro-4H-1,4-benzoxazin-2-one, 4-phenyl-2,3-dihydro-4H-1,4-benzoxazin-3-one and the like 4
-Aryl-1,4-benzoxazine compounds.

Among these nitrogen-containing heterocycles, 1-
Methyl-2-pyrrolidone, 1-vinyl-2-pyrrolidone, 3-methyl-2-oxazolidone, 3-vinyl-2
-Oxazolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-divinyl-2-imidazolidinone,
1,3-dimethylhexahydropyrimidin-2-one,
1,3-divinylhexahydropyrimidin-2-one,
3-methyl-2H-3,4,5,6-tetrahydro-
1,3-oxazin-2-one and 3-vinyl-2H-
3,4,5,6-tetrahydro-1,3-oxazine-
2-one is preferred.

The nitrogen-containing heterocyclic compound represented by the general formula (1) may be used alone or in combination of two or more kinds, but the amount thereof present in the non-aqueous solvent is usually 0.1 to 10% by weight. , Preferably 0.5 to 5% by weight. It is presumed that the nitrogen-containing heterocyclic compound represented by the general formula (1) forms a lithium ion-permeable and highly stable film on the electrode surface and prevents decomposition of the electrolytic solution. If the amount present in the electrolytic solution is too small, the film formation will be incomplete, and the desired effect will not be sufficiently exhibited. On the contrary, if the amount is too large, the battery characteristics are adversely affected.

The electrolytic solution according to the present invention may further contain a known film forming agent, overcharge preventing agent, dehydrating agent, deoxidizing agent and the like. For example, unsaturated cyclic carbonates such as vinylene carbonate; saturated cyclic carbonates having an alkenyl group such as vinylethylene carbonate; saturated cyclic carbonates having an aryl group such as phenylethylene carbonate; cyclic sulfites such as ethylene sulfite; Cyclic sultone: A film-forming agent such as cyclic carboxylic acid anhydride such as succinic anhydride, malonic anhydride, maleic anhydride and phthalic anhydride can be contained in the electrolytic solution. When such a film-forming agent is contained, the charge / discharge efficiency and capacity retention characteristics are further improved. The film-forming agent is preferably added to the non-aqueous solvent in an amount of 0.1 to 5% by weight.

Further, for example, Japanese Patent Laid-Open No. 8-203560.
No. 7-302614, No. 9-50822.
JP-A-8-273700, JP-A-9-17447
Benzene derivatives described in each publication, etc .;
-106835, JP-A-9-171840, JP-A-10-32258, JP-A-7-302614, JP-A-7-302614, and JP-A-11-162512.
And the derivatives thereof described in JP-B Nos. 2939469 and 2963898, etc .; Pyrrole derivatives described in JP-A-9-45369, JP-A-10-32158 and the like; JP-A-7- 32
0778, aromatic compounds such as aniline derivatives described in JP-A-7-302614 and the like; Patent 29
The overcharge state can be prevented by incorporating an overcharge inhibitor such as an ether compound described in JP-A-83205 or the like; a compound described in JP-A No. 2001-15158 into the electrolytic solution. The overcharge inhibitor is preferably contained in the non-aqueous solvent in an amount of 0.1 to 5% by weight.

A lithium salt is used as the solute of the electrolytic solution according to the present invention. Any lithium salt can be used as long as it can be used as a solute. Specific examples include 1) inorganic lithium salt: LiPF _6, LiAsF _6, LiB
_{F 4, LiAlF 4, LiAlF 6} , LiSiF inorganic fluoride salts ₆ and the like, perhalogenate 2) organic lithium salts such as LiClO _4: organic sulfonates such as _{LiCF 3 SO 3, LiN (CF} 3 SO 2) ₂ , LiN (C ₂ F ₅ S
O ₂ ) ₂ , LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ) and other perfluoroalkyl sulfonic acid imide salts, LiC (CF
Perfluoroalkyl sulfonic acid methide salt such as ₃ SO ₂ ) ₃ , LiPF ₃ (C ₂ F ₅ ) ₃ , LiBF ₂ (CF ₃ ) ₂ , L
iBF ₃ (CF ₃₎ salts a part of the fluorine inorganic fluoride salts was replaced by perfluoroalkyl groups such as, LiB (CF ₃
COO) ₄ , LiB (OCOCF ₂ COO) ₂ , LiB
Examples thereof include lithium tetrakis (perfluorocarboxylate) borate salts such as (OCOC ₂ F ₄ COO) ₂ .

These lithium salts may be used alone or in two types.
The above may be mixed and used. Among the above lithium salts
Is in terms of solubility, ionic dissociation and electrical conductivity characteristics,
LiPF₆, LiBF_Four, LiN (CF₃SO₂)₂, Li
N (C₂F_FiveSO₂)₂, LiN (CF₃SO₂) (C_FourF₉S
O₂), LiPF₃(CF₃)₃, LiPF₃(C₂F _Five)₃,
LiBF₂(C₂F_Five)₂, LiB (OCOCF₂COO)₂
Is preferred, and LiPF₆Or LiBF_FourIs more preferable.
Particularly, the non-aqueous solvent contains 60% by weight or more of γ-butyrolactone.
If included, LiBF_FourIs 50% of the total lithium salt
% Or more is preferable.

The concentration of the lithium salt in the electrolytic solution is 0.5 to
The electrolytic solution is prepared so as to have a concentration of 3 mol / liter. If the concentration is too low, the electric conductivity of the electrolytic solution becomes insufficient, and if the concentration is too high, the electric conductivity decreases due to an increase in viscosity, or the lithium salt tends to precipitate at low temperatures, resulting in battery performance. Will fall. For the negative electrode of the battery according to the present invention, any material capable of inserting and extracting lithium can be used. Specific examples include thermal decomposition products of organic substances under various thermal decomposition conditions, carbonaceous materials such as artificial graphite and natural graphite; metal oxide materials; lithium metal; various lithium alloys.

As the carbonaceous material, artificial graphite and purified natural graphite produced by subjecting easily graphitizable pitch obtained from various raw materials to high temperature heat treatment, and those obtained by subjecting these graphites to various surface treatments including pitch. preferable. As the graphite material, the lattice plane (002 plane) obtained by X-ray diffraction by the Gakushin method
The d value (interlayer distance) of is preferably 0.335 to 0.34 nm, more preferably 0.335 to 0.337 nm. The ash content is preferably 1% by weight or less, more preferably 0.5% by weight or less, still more preferably 0.1% by weight or less. The crystallite size (Lc) determined by X-ray diffraction by Gakshin method is preferably 30 nm or more. The crystallite size (Lc) is preferably 50 nm or more, more preferably 100 nm or more. The median diameter by the laser diffraction / scattering method is preferably 1 μm to 100 μm, and 3 μm to 50 μm
Is more preferable, 5 μm to 40 μm is still more preferable, and 7
Those having a thickness of μm to 30 μm are particularly preferable. BET specific surface area is a 0.5m ² /g~25.0m ² / g, 0.7
Preferably ^{m 2 /g~20.0m 2 / g, 1.0m} 2 / g
~15.0m more preferably ² / g, 1.5m ² / ^g~1
It is more preferably 0.0 m ² / g. In Raman spectrum analysis using argon ion laser light, 1
Range 580～1620Cm ^-1 peak P _A (peak intensity I _A) and the peak P _B in the range of 1350 ^-1
Intensity ratio of the (peak intensity _{I B) R = I B /} I A is 0
0.5, the half-value width of the peak in the range of 1580～1620Cm ^-1 is 26cm ^-1 or less, 1580～1620Cm ^-1
It is preferable that the half value width of the peak in the range is 25 cm ^-1 or less.

Further, the carbonaceous material may be mixed with another negative electrode material capable of inserting and extracting lithium. As the negative electrode material capable of inserting and extracting lithium other than the carbonaceous material, Ag, Zn, Al, Ga, In, Si,
Ge, Sn, Pb, P, Sb, Bi, Cu, Ni, S
Alloys of metals such as r and Ba with Li; metal oxide materials such as oxides of these metals; lithium metals, among which Sn oxides, Si oxides, Al oxides, Sn, S
i, a lithium alloy of Al, and metallic lithium are preferable.

These negative electrode materials may be used alone or in combination of two or more. The negative electrode is manufactured by a usual method. For example, a negative electrode is manufactured by adding a binder, a thickener, a conductive material, a solvent, and the like to the negative electrode material to form a slurry, applying the slurry to the substrate of the current collector, and drying.
Further, the negative electrode material may be roll-formed as it is to form a sheet electrode, or compression-molded to form a pellet electrode.

Any binder, thickener and conductive material can be used as long as they are stable with respect to the solvent used in the production of the electrode, the electrolytic solution and other materials used in the battery. Usually, polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene rubber, isoprene rubber, butadiene rubber and the like are used as the binder.
As the thickener, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein and the like are used.

As the conductive material, metal materials such as copper and nickel; conductive carbonaceous materials such as graphite and carbon black are used. Examples of the material of the current collector include metals such as copper, nickel and stainless steel.
An inexpensive copper foil is preferable because it can be easily processed into a thin film. For the positive electrode of the battery, lithium transition metal composite oxide materials such as lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide, as well as various known materials capable of inserting and extracting lithium can be used. . Further, the positive electrode can be manufactured according to the above-mentioned negative electrode.

As a material for the positive electrode current collector, a metal such as aluminum, titanium or tantalum or an alloy thereof is used. Among these, aluminum or its alloy is preferable. As a separator for separating and melting the positive electrode and the negative electrode of the battery, as long as it is stable to the electrolytic solution and has sufficient liquid retention,
Any one can be used. For example, porous sheets and non-woven fabrics made of polyolefin such as polyethylene and polypropylene are used.

The battery according to the present invention can be produced by appropriately selecting one of the methods used in ordinary non-aqueous electrolyte secondary batteries.
You can choose. The battery can be of any shape commonly used. For example, a cylinder type in which a sheet electrode and a separator are formed in a spiral shape, a cylinder type in which an inside-out structure is combined with a pellet electrode and a separator, and a coin type in which pellet electrodes and a separator are stacked are listed.

[0032]

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. Example 1 A non-aqueous solvent containing 95% by weight of γ-butyrolactone and 5% by weight of 1-methylpyrrolidone was prepared, and 1 mol of sufficiently dried lithium borofluoride (LiBF ₄ ) was added thereto under a dry argon atmosphere. The electrolytic solution was prepared by dissolving the solution at a ratio of 1 / liter.

Example 2 Except that 3-methyl-2-oxazolidone was used instead of 1-methylpyrrolidone.
An electrolytic solution was prepared in the same manner as in Example 1. Example 3 Instead of 1-methylpyrrolidone, 1,3-
An electrolytic solution was prepared in the same manner as in Example 1 except that dimethyl-2-imidazolidinone was used.

Example 4 An electrolytic solution was prepared in the same manner as in Example 1 except that 1-vinylpyrrolidone was used instead of 1-methylpyrrolidone. (Example 5) A non-aqueous solvent containing 90% by weight of γ-butyrolactone, 5% by weight of 1-vinylpyrrolidone and 5% by weight of vinylene carbonate was prepared, and LiBF ₄ was dissolved therein to a concentration of 1 mol / liter for electrolysis. It was a liquid.

Example 6 A non-aqueous solvent containing 19% by weight of γ-butyrolactone, 19% by weight of ethylene carbonate, 60% by weight of ethylmethyl carbonate and 2% by weight of 1-methylpyrrolidone was prepared, and the mixture was sufficiently dried in a dry argon atmosphere. Then, dried LiBF ₄ was dissolved to 1 mol / liter to prepare an electrolytic solution.

(Example 7) 18% by weight of γ-butyrolactone, 18% by weight of ethylene carbonate, 60% by weight of ethylmethyl carbonate, 2% by weight of 1-methylpyrrolidone
And 2% by weight of vinylene carbonate were prepared as a non-aqueous solvent, and L was thoroughly dried under a dry argon atmosphere.
iBF ₄ was dissolved to 1 mol / liter to prepare an electrolytic solution.

Example 8 18% by weight of γ-butyrolactone, 18% by weight of ethylene carbonate, 60% by weight of ethylmethyl carbonate, 2% by weight of 1-methylpyrrolidone
A non-aqueous solvent containing 2% by weight of vinylene carbonate was prepared, and fully dried lithium hexafluorophosphate (LiPF ₆ ) was dissolved in the non-aqueous solvent in a dry argon atmosphere so as to be 1 mol / liter, and an electrolytic solution was prepared. And

(Example 9) 18% by weight of γ-butyrolactone, 18% by weight of ethylene carbonate, 60% by weight of ethylmethyl carbonate, 2% by weight of 1-methylpyrrolidone
And 2% by weight of vinylene carbonate were prepared as a non-aqueous solvent, and L was thoroughly dried under a dry argon atmosphere.
iBF ₄ was dissolved to a concentration of 0.5 mol / liter, and Li was sufficiently dried in a dry argon atmosphere.
PF ₆ was dissolved at 0.5 mol / liter to prepare an electrolytic solution.

Comparative Example 1 γ-butyrolactone was mixed with Li
An electrolytic solution was prepared by dissolving BF ₄ at 1 mol / liter. (Comparative Example 2) A non-aqueous solvent containing 95% by weight of γ-butyrolactone and 5% by weight of vinylene carbonate was prepared, and LiBF _{4 was used.}
Was dissolved so as to be 1 mol / liter to prepare an electrolytic solution.

(Comparative Example 3) With propylene carbonate,
LiPF ₆ was dissolved at 1 mol / liter to prepare an electrolytic solution. (Comparative Example 4) A non-aqueous solvent containing 95% by weight of propylene carbonate and 5% by weight of vinylene carbonate was prepared.
F ₆ was dissolved to be 1 mol / liter to prepare an electrolytic solution. (Production of positive electrode) 85% by weight of LiCoO ₂ as a positive electrode active material, 6% by weight of carbon black and 9% by weight of polyvinylidene fluoride KF-1000 (trade name, manufactured by Kureha Chemical Co., Ltd.) were added and mixed, and 1-methylpyrrolidone was mixed. Which was made into a slurry and uniformly applied onto a 20 μm thick aluminum foil, which is a positive electrode current collector, and dried to have a diameter of 12.5.
It was punched out into a disk shape of mm to obtain a positive electrode. (Production of Negative Electrode) The d value of the lattice plane (002 plane) in X-ray diffraction was 0.336 nm, and the crystallite size (Lc) was 100.
nm or more (264 nm), ash content 0.04% by weight, median diameter by laser diffraction / scattering method is 17 μm, BET
The specific surface area was 8.9 m ² / g, and the Raman spectrum analysis using argon ion laser light was 1580 to 1
Peak P _A (peak intensity I _A ) in the range of 620 cm ⁻¹ and 1
The intensity ratio R = I _B / I _A with the peak P _B (peak intensity I _B ) in the range of 350 to 1370 cm ⁻¹ is 0.15, 158.
The full width at half maximum of the peak in the range of ⁰ to 1620 cm ^-1 is 22.2.
cm ^-1 artificial graphite powder KS-44 (manufactured by Timcal,
Brand name) To 94% by weight, styrene-butadiene rubber (SBR) dispersed with distilled water was added so that the solid content was 6% by weight. This was mixed with a disperser to form a slurry, which was uniformly applied onto a copper foil having a thickness of 18 μm, which is a negative electrode current collector, dried, and then punched into a disk shape having a diameter of 12.5 mm to obtain a negative electrode. (Fabrication of coin type cell) A battery was fabricated using the above positive electrode, negative electrode and electrolytic solution. The positive electrode was housed in a stainless steel can that also serves as the positive electrode conductor, and the negative electrode was placed on the positive electrode via a polyethylene separator impregnated with the electrolytic solution. The can body and the sealing plate which also serves as the negative electrode conductor were caulked and sealed via an insulating gasket to produce a coin cell. (Evaluation of coin-shaped cell) At 25 ° C, a charge / discharge test was performed at a charge end voltage of 4.2 V, a discharge end voltage of 2.5 V, and a constant current of 0.5 mA, and the discharge capacity at the second cycle was changed to the charge capacity at the second cycle. The value divided by was used as the second cycle charge / discharge efficiency.

In the fifth cycle, after charging under the same conditions, the battery was stored in a charged state at 85 ° C. for 72 hours and then discharged. A value obtained by dividing the value charged at the sixth cycle under the same conditions at 25 ° C. by the charge capacity at the fourth cycle was defined as the capacity retention rate. Using the electrolytic solutions of Examples 1 to 9 and Comparative Examples 1 to 4, the secondary batteries manufactured by the method described above were evaluated. The results are shown in Table 1.

[0042]

[Table 1]

[0043]

According to the present invention, it is possible to provide a safe non-aqueous electrolyte secondary battery having high charge / discharge efficiency, excellent capacity retention characteristics, and excellent battery characteristics in a wide temperature range.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takashi Fujii             3-3-1 Chuo 8-chome, Ami Town, Inashiki District, Ibaraki Prefecture             Within Mitsubishi Chemical Corporation (72) Inventor Makoto Ue             3-3-1 Chuo 8-chome, Ami Town, Inashiki District, Ibaraki Prefecture             Within Mitsubishi Chemical Corporation F term (reference) 5H029 AJ02 AJ05 AK03 AL07 AL12                       AM02 AM03 AM07 DJ09 HJ01

Claims (10)

[Claims] 1. A lactone compound and a compound represented by the general formula (1): (In the formula, A represents a nitrogen-containing heterocycle having a carbonyl group, R represents an alkyl group, an alkenyl group or a (hetero) aryl group, and n represents a natural number, provided that when n is 2 or more, R represents May be different from each other.) A non-aqueous electrolyte solution comprising a lithium salt dissolved in a non-aqueous solvent containing a nitrogen-containing heterocyclic compound. 2. The non-aqueous solvent contains a lactone compound in an amount of 10 to 9
9.8% by weight and a nitrogen-containing heterocyclic compound in an amount of 0.1 to 10
The non-aqueous electrolyte solution according to claim 1, wherein the non-aqueous electrolyte solution is contained in a weight percentage. 3. The lactone compound is selected from the group consisting of γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, δ-caprolactone and ε-caprolactone. Item 3. The non-aqueous electrolyte solution according to Item 1 or 2. 4. The nitrogen-containing heterocyclic compound is 1-alkylpyrrolidone compound, 1-alkylpiperidone compound, 3
An alkyloxazolidone compound, a 1,3-dialkylimidazolidinone compound, a 1,3-dialkylhexahydropyrimidinone compound and an N-alkyloxazinone compound. 4. The non-aqueous electrolyte solution according to any one of 1 to 3. 5. The nitrogen-containing heterocyclic compound is 1-methyl-
2-pyrrolidone, 1-vinyl-2-pyrrolidone, 3-methyl-2-oxazolidone, 3-vinyl-2-oxazolidone, 1,3-dimethyl-2-imidazolidinone,
1,3-divinyl-2-imidazolidinone, 1,3-dimethylhexahydropyrimidin-2-one, 1,3-divinylhexahydropyrimidin-2-one, 3-methyl-2H-3,4,5, 6-Tetrahydro-1,3-oxazin-2-one and 3-vinyl-2H-3,4,5,
The non-aqueous electrolyte solution according to claim 1, which is selected from the group consisting of 6-tetrahydro-1,3-oxazin-2-one. 6. The lithium salt is LiPF ₆ , LiB
_{F 4, LiCF 3 SO 3,} LiN (CF 3 SO 2) 2, Li
N (C ₂ F ₅ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) (C ₄ F ₉ S
O ₂ ), LiPF ₃ (C ₂ F ₅ ) ₃ and LiB (CF ₃ CO
The non-aqueous electrolyte solution according to claim 1, which is selected from the group consisting of O) ₄ . 7. The non-aqueous solvent is selected from the group consisting of vinylene carbonate, vinyl ethylene carbonate, phenyl ethylene carbonate, ethylene sulfite, propane sultone, succinic anhydride, malonic anhydride, maleic anhydride and phthalic anhydride. The non-aqueous electrolyte solution according to claim 1, further comprising a film-forming agent. 8. The non-aqueous electrolyte solution according to claim 7, wherein the non-aqueous solvent contains a film-forming agent in an amount of 0.1 to 5% by weight. 9. 10 to 99.9% by weight of γ-butyrolactone; ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate,
Diisopropyl carbonate, n-propyl isopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, di-t-butyl carbonate, n
-Butyl isobutyl carbonate, n-butyl-t-butyl carbonate, isobutyl-t-butyl carbonate, ethyl methyl carbonate, methyl-n-propyl carbonate, n-butyl methyl carbonate, isobutyl methyl carbonate, t-butyl methyl carbonate, ethyl- n-propyl carbonate, n-butyl ethyl carbonate, isobutyl ethyl carbonate, t
-Butyl ethyl carbonate, n-butyl-n-propyl carbonate, isobutyl-n-propyl carbonate, t-butyl-n-propyl carbonate, n-butyl isopropyl carbonate, isobutyl isopropyl carbonate, t-butyl isopropyl carbonate,
Methyl acetate, ethyl acetate, acetic acid-n-propyl, acetic acid-
Isopropyl, n-butyl acetate, isobutyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, propionate 0 to 89.9% by weight of one selected from the group consisting of -t-butyl, dimethoxymethane, 1,2-dimethoxyethane, 1,2-diethoxymethane, diethoxyethane and ethoxymethoxymethane; 1) [Chemical formula 2] (In the formula, A represents a nitrogen-containing heterocycle having a carbonyl group, R represents an alkyl group, an alkenyl group or a (hetero) aryl group, and n represents a natural number, provided that when n is 2 or more, R represents 0.1 to 10% by weight of a nitrogen-containing heterocyclic compound represented by the formula: vinylene carbonate, vinylethylene carbonate, phenylethylene carbonate, ethylene sulfite, propane sultone, succinic anhydride, malonic anhydride. Acid, maleic anhydride and phthalic anhydride in a non-aqueous solvent containing 0 to 5% by weight of a compound selected from the group consisting of LiPF ₆ , Li
BF ₄ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , L
iN (C ₂ F ₅ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) (C ₄ F _{9
SO 2), LiPF 3 (C} 2 F 5) 3, LiB (CF 3 CO
O) ₄ is a lithium salt selected from the group consisting of dissolved therein, a non-aqueous electrolyte solution. 10. The negative electrode containing metallic lithium, a lithium alloy, or a material capable of inserting and extracting lithium, a positive electrode containing a material capable of inserting and extracting lithium, and any one of claims 1 to 9. A non-aqueous electrolyte secondary battery comprising the electrolyte described in 1.