JP2001297794A - Nonaqueous electrolyte secondary cell and electrolyte used by the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cell with safety and excellent charging and discharging efficiency and cycle characteristics at high temperature and a long shelf life. SOLUTION: The nonaqueous secondary cell uses the nonaqueous electrolyte, with fiashing point of more than 70 deg.C, containing more than 90 weight % of at least one kind of nonaqueous solvent selected from organic solvents whose relative dielectric constant is more than 25, further, at least one kind of vinylene carbonate compound shown by the formula (I) is added to the above nonaqueous electrolyte. In the formula, R1 and R2, independent with each other, represents hydrogen atom or alkyl group whose number of carbon is 1-4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte used therefor. More specifically, the present invention relates to a non-aqueous electrolyte secondary battery using an electrolyte obtained by adding a vinylene carbonate compound to a specific non-aqueous solvent, and an electrolyte used therefor. The secondary battery of the present invention is excellent in safety, charge and discharge efficiency and cycle characteristics under high temperature,
Excellent storage stability.

[0002]

2. Description of the Related Art With the recent reduction in the weight and size of electric products, demand for lithium secondary batteries having a high energy density has been increasing. Further, with the expansion of the application field of lithium secondary batteries, further improvement in battery characteristics is also demanded. Conventionally, secondary batteries using lithium metal as a negative electrode have been actively studied for a long time as batteries capable of achieving high capacity.However, metal lithium grows in a dendrite shape by repeated charge and discharge, and eventually becomes Has reached the positive electrode, and the occurrence of a short circuit inside the battery has been the biggest technical problem preventing practical use.

[0003] On the other hand, for example, coke,
A non-aqueous electrolyte secondary battery using a carbonaceous material capable of inserting and extracting lithium such as artificial graphite and natural graphite has been proposed. In such a non-aqueous electrolyte secondary battery,
Since lithium does not exist in a metallic state, formation of dendrites is suppressed, and battery life and safety can be improved. In particular, non-aqueous electrolyte secondary batteries using graphite-based carbonaceous materials such as artificial graphite and natural graphite have been receiving attention as meeting the demand for higher capacity.

In a lithium secondary battery using the above carbonaceous material, a high dielectric constant solvent for a non-aqueous electrolyte is usually used.
Cyclic carbonates such as propylene carbonate and ethylene carbonate are widely used. In non-aqueous electrolyte secondary batteries using non-graphite carbonaceous materials such as coke,
A solvent containing propylene carbonate can be suitably used. On the other hand, the graphite-based carbonaceous material alone or
In a non-aqueous electrolyte secondary battery in which lithium is mixed with another negative electrode material capable of inserting and extracting lithium and used as a negative electrode, when a solvent containing propylene carbonate is used, the decomposition reaction of propylene carbonate proceeds rapidly on the electrode surface during charging. This makes it impossible to smoothly insert and extract lithium into the graphite electrode.

On the other hand, since ethylene carbonate is less decomposed, ethylene carbonate is frequently used as a high dielectric constant solvent in a non-aqueous electrolyte secondary battery using a graphite-based negative electrode. However, it cannot be said that problems such as deterioration of cycle characteristics due to decomposition of the catalyst are sufficient. Further, ethylene carbonate has a higher freezing point of 36.4 ° C. than propylene carbonate, and therefore is not used alone, and is generally used in a mixture with a low-viscosity solvent. For such a reason, a mixed solvent of ethylene carbonate and diethyl carbonate or the like is usually used for an electrolyte for a lithium secondary battery using a graphite-based negative electrode, but a low-viscosity solvent generally has a low boiling point. When added in large amounts, the performance of the electrolytic solution is good when added in large amounts, but there is a problem in that the flash point of the solvent is lowered. Conversely, when added in small amounts, there are problems in terms of electrical conductivity and viscosity at low temperatures.

In such a situation, Japanese Patent Application Laid-Open No. 8-45
No. 545 proposes an electrolyte containing vinylene carbonate and its derivative in a non-aqueous electrolyte battery using a graphite-based carbon material for a negative electrode. Also, Japanese Patent Application Laid-Open
Japanese Patent Application Publication No. 1-283667 proposes an electrolyte containing propylene carbonate and vinylene carbonate in a lithium ion battery using a negative electrode made of lithium manganese oxide and a negative electrode made of a graphite-based carbon material. However, the above-mentioned problems cannot be solved because a large amount of chain carbonate, which is a low boiling point solvent, is mixed and used.

On the other hand, γ-butyrolactone, which is a cyclic ester, has a high relative dielectric constant, a low freezing point, and can be used without mixing a low-viscosity solvent. Also, the decomposition reaction of γ-butyrolactone proceeds on the graphite electrode surface during charging,
Deterioration of characteristics as a battery is a problem. JP-A-11-3
No. 1525 discloses that in order to suppress the decomposition of γ-butyrolactone in a non-aqueous electrolyte secondary battery using a graphite-based carbon material for the negative electrode, γ-butyrolactone is used as a main component, and about 15 to 35% by volume as an auxiliary component. Of ethylene carbonate, and more practically 16% of diethyl carbonate.
A solvent for an electrolytic solution having a composition containing at least volume% has been proposed.

[0008]

However, with respect to the electrolyte proposed in the above-mentioned publication, a certain effect can be seen, but further improvement is desired. The present invention provides a non-aqueous electrolyte secondary battery capable of exhibiting good battery characteristics even when a non-aqueous solvent having a relatively high flash point and a relative dielectric constant of 25 or more is used as a main solvent, and an electrolyte used therefor. The purpose is to provide.

[0009]

Means for Solving the Problems As a result of intensive studies in view of the above circumstances, the present inventors have found that a specific non-aqueous solvent is used as a solvent for an electrolyte of a non-aqueous electrolyte secondary battery, and that a specific non-aqueous solvent is used. It has been found that a secondary battery having high charge / discharge efficiency, excellent cycle characteristics, and improved safety can be obtained by using the vinylene carbonate compound as described above, and the present invention has been completed.

That is, the gist of the present invention is as follows. A negative electrode, a positive electrode, and a nonaqueous electrolyte secondary battery including at least a nonaqueous electrolyte solution including a solute and a nonaqueous solvent, wherein the nonaqueous solvent has a relative dielectric constant of at least one selected from solvents having a dielectric constant of 25 or more. A non-aqueous solvent containing at least one vinylene carbonate compound represented by the following general formula (I), containing at least 90% by weight of a solvent and having a flash point of at least 70 ° C. Aqueous electrolyte secondary battery

[0011]

Embedded image

(Wherein R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

2. A non-aqueous electrolyte for a secondary battery, comprising at least a negative electrode and a positive electrode capable of inserting and extracting lithium.A non-aqueous electrolyte comprising a solute and a non-aqueous solvent, wherein the non-aqueous solvent Contains 90% by weight or more of at least one solvent selected from solvents having a relative dielectric constant of 25 or more, has a flash point of 70 ° C. or more, and further contains vinylene represented by the following general formula (I) in the non-aqueous solvent. Non-aqueous electrolyte solution characterized by adding at least one carbonate compound

[0014]

Embedded image

(Wherein R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms);
It is in.

The non-aqueous solvent used in the secondary battery of the present invention is obtained by adding at least one vinylene carbonate compound of the formula (I) to at least one solvent selected from solvents having a relative dielectric constant of 25 or more. Is preferred. The amount of the vinylene carbonate compound of the formula (I) added is preferably 0.01 to 10% by weight based on the total amount of the nonaqueous solvent and the vinylene carbonate compound of the formula (I). Further, the negative electrode used in the secondary battery of the present invention preferably contains a carbonaceous substance capable of inserting and extracting lithium.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The non-aqueous electrolyte secondary battery of the present invention contains 90% by weight of a negative electrode, a positive electrode, at least one solvent selected from solutes and solvents having a relative dielectric constant of 25 or more, and contains the same. It has a flash point of 70 ° C. or higher and at least a non-aqueous electrolyte comprising a non-aqueous solvent to which at least one vinylene carbonate compound of the formula (I) is added.

The solvent having a relative dielectric constant of 25 or more used in the present invention is not particularly limited, but specific examples thereof include, for example, ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, γ-valerolactone. And the like, among which ethylene carbonate, propylene carbonate and γ-butyrolactone are preferred. These solvents may be used as a mixture of two or more kinds, and the combination is not particularly limited.

A vinylene carbonate compound represented by the following general formula (I) is added to the non-aqueous solvent used in the present invention.

[0020]

Embedded image

(Wherein R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

In the formula (I), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When R ¹ and R ² are an alkyl group having 1 to 4 carbon atoms, specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
Examples include a sec-butyl group and a tert-butyl group.
Of these, a methyl group and an ethyl group are preferred. And
Specific examples of such a vinylene carbonate compound of the formula (I) include, for example, vinylene carbonate, methyl vinylene carbonate, ethyl vinylene carbonate,
4,5-dimethylvinylene carbonate, 4,5-diethylvinylene carbonate and the like can be mentioned.

Of these, vinylene carbonate and 4,5-dimethylvinylene carbonate are preferred, and vinylene carbonate is particularly preferred. These may be used as a mixture of two or more. The amount of the vinylene carbonate compound of the formula (I) used in the present invention is preferably 0.01 to 10% by weight based on the total amount of the nonaqueous solvent and the vinylene carbonate compound represented by the general formula (I). %, More preferably 0.1 to 7% by weight, and particularly preferably 0.5 to 5% by weight.

The nonaqueous solvent used in the present invention contains 90% by weight or more of a solvent having a relative dielectric constant of 25 or more. In the present invention, a non-aqueous solvent in which vinylene carbonate of the formula (I) is added to a solvent having a relative dielectric constant of 25 or more is preferable. Further, the non-aqueous solvent preferably has a composition containing at least 20% by weight of ethylene carbonate or propylene carbonate. Further, if ethylene carbonate is contained in a large amount, the low-temperature characteristics are deteriorated. Therefore, the content is preferably 70% by weight or less, preferably 50% by weight or less in a non-aqueous solvent.

In the present invention, it is preferable to use at least one solvent selected from solvents having a relative dielectric constant of 25 or more and a flash point of 70 ° C. or more as the non-aqueous solvent. Non-aqueous solvents other than the above, such as dialkyl (e.g., those having 1 to 4 carbon atoms) such as dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, and ethyl methyl carbonate, provided that the flash point is 70C or higher. (Preferable) cyclic ethers such as carbonate, tetrahydrofuran and 2-methyltetrahydrofuran; chain ethers such as dimethoxyethane and dimethoxymethane; chain esters such as methyl acetate and ethyl propionate; sulfolane, diethyl sulfone, ethylene sulfite and dimethyl sal Fight, diethyl sulfite, professional Sulfur-containing organic solvents such as Nsuruton, trimethyl phosphate, it can be added the phosphorus-containing organic solvents such as triethyl phosphate and the like.

The electrolyte used in the present invention uses a lithium salt as a solute. The type of the lithium salt that can be used is not particularly limited as long as it can be used as a solute of the electrolytic solution. For example, LiClO ₄ , LiPF ₆ , LiB
An inorganic lithium salt selected from F ₄ , LiCF ₃ SO ₃ ,
LiN (CF ₃ SO ₂ ) ₂ , LiN (CF ₃ CF ₂ SO
₂ ) ₂ , LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ),
Fluorine-containing organic lithium salts such as LiC (CF ₃ SO ₂ ) ₃ can be used. Among them, LiPF ₆ , LiBF ₄
It is preferable to use These lithium salts may be used as a mixture of two or more kinds. The molar concentration of the lithium salt in the solute in the electrolyte is desirably 0.5 to 3.0 mol / liter. Less than 0.5 mol / l or 3.
If it exceeds 0 mol / liter, the electric conductivity of the electrolytic solution tends to decrease, and the performance of the battery tends to decrease.

As the material of the negative electrode constituting the battery of the present invention, a material containing a carbonaceous substance capable of inserting and extracting lithium is preferable. Specific examples of the carbonaceous material include, for example, thermal decomposition products of organic substances under various thermal decomposition conditions, artificial graphite,
And natural graphite. Preferably artificial graphite and graphitized mesophase spherules, graphitized mesophase pitch-based carbon fiber, other artificial graphite and purified natural graphite, or the like, produced by high-temperature heat treatment of graphitic pitch obtained from various raw materials. A material obtained by treating various surfaces including graphite on a pitch is used.

These graphite-based carbon materials preferably have a lattice plane (002 plane) d value (interlayer distance) of 0.335 to 0.34 nm, as determined by X-ray diffraction according to the Gakushin method. Those having a thickness of 335 to 0.337 nm are more preferred. The ash content is preferably 1% by weight or less,
It is more preferably at most 0.1% by weight, particularly preferably at most 0.1% by weight. Further, the crystallite size (Lc) determined by X-ray diffraction by the Gakushin method is preferably 30 nm or more, more preferably 50 nm or more, and 1 nm or more.
It is particularly preferable that the thickness be 00 nm or more.

The median diameter of the carbonaceous material measured by the laser diffraction / scattering method is preferably 1 to 100 μm, more preferably 3 to 50 μm, and more preferably 5 to 4 μm.
The thickness is more preferably 0 μm, and particularly preferably 7 to 30 μm. The BET specific surface area is 0.3 to 25.
Is preferably from 0m ² / g, 0.5~20.0m ²
/ G, more preferably 0.7 to 15.0 m ² / g.
g, more preferably 0.8 to 10.0 m ² / g.
Is particularly preferred. In Raman spectrum analysis using argon ion laser light, 1580
Range ～1620Cm ^-1 peak P _A (peak intensity I _A) and the peak P in the range of 1350 ^-1
_B is the intensity ratio R = I _B / I _A of (peak intensity I _B) 0 to
1.2 Preferably, the half-value width of the peak in the range of 1580~1620cm ^-1 26cm ^-1 or less, and particularly preferably between 25 cm ^-1 or less.

A negative electrode material capable of inserting and extracting lithium can be further mixed with these carbonaceous materials and used. Examples of the negative electrode material capable of occluding and releasing lithium other than the carbonaceous material include metal oxide materials such as tin oxide and silicon oxide, as well as lithium metal and various lithium alloys. These negative electrode materials may be used as a mixture of two or more.

The method for producing a negative electrode using these negative electrode materials is not particularly limited. For example, a negative electrode can be manufactured by adding a binder, a thickener, a conductive material, a solvent, and the like to a negative electrode material as needed to form a slurry, applying the slurry to a current collector substrate, and drying. Alternatively, the negative electrode material may be directly roll-formed into a sheet electrode,
A pellet electrode can be obtained by compression molding.

The binder used in the production of the electrode is not particularly limited as long as it is a material that is stable with respect to the solvent and the electrolyte used in the production of the electrode. Specific examples thereof include polyvinylidene fluoride, polytetrafluoroethylene, styrene / butadiene rubber, isoprene rubber, and butadiene rubber.

Examples of the thickener include carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, and casein.
Examples of the conductive material include metal materials such as copper and nickel, and carbon materials such as graphite and carbon black. As the material of the current collector for the negative electrode, metals such as copper, nickel, and stainless steel are used, and among these, copper foil is preferable from the viewpoint of easy processing into a thin film and cost.

As the material of the positive electrode constituting the battery of the present invention, a material capable of occluding and releasing lithium, such as a lithium transition metal composite oxide material such as lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide is used. Can be used. The method for manufacturing the positive electrode is not particularly limited, and the positive electrode can be manufactured according to the above-described method for manufacturing the negative electrode. As for the shape, a binder, a conductive material, a solvent, and the like are added to the positive electrode material as necessary and mixed, and then applied to a current collector substrate to form a sheet electrode, or a pellet electrode formed by press molding. It can be.

As the material of the current collector for the positive electrode, a metal such as aluminum, titanium and tantalum or an alloy thereof is used. Among these, aluminum or its alloy is desirable in terms of energy density because it is lightweight. The material and shape of the separator used in the battery of the present invention are not particularly limited. However, it is preferable to select from materials that are stable with respect to the electrolyte and have excellent liquid retention properties, and it is preferable to use a porous sheet or nonwoven fabric made of a polyolefin such as polyethylene or polypropylene as a raw material.

The method for producing the battery of the present invention having at least the negative electrode, the positive electrode, and the non-aqueous electrolyte is not particularly limited, and can be appropriately selected from commonly employed methods. The shape of the battery is not particularly limited, a cylinder type in which the sheet electrode and the separator are spiral, a cylinder type having an inside-out structure in which the pellet electrode and the separator are combined,
A coin type in which a pellet electrode and a separator are laminated can be used.

[0037]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to these Examples as long as the gist of the present invention is not exceeded.

Example 1 LiCoO as a positive electrode active material
_Two85 parts by weight of carbon black 6 parts by weight, polyfluoride
Vinylidene KF-1000 (trade name, manufactured by Kureha Chemical Co., Ltd.) 9
Parts by weight, mixed and separated with N-methyl-2-pyrrolidone.
Thickness of the positive electrode current collector is
Apply evenly on 0 μm aluminum foil, dry,
A positive electrode was punched out into a disk having a diameter of 12.5 mm. Negative electrode
As an active material, the lattice plane (002 plane) in X-ray diffraction
d value is 0.336 nm, crystallite size (Lc) is 100
nm or more (652 nm), ash content 0.07% by weight,
Median diameter of 12 μm by laser diffraction / scattering method, BET
7.5m specific surface area^Two/ G, argon ion laser
1580-1 in Raman spectrum analysis using light
620cm^-1Peak P in the range_A(Peak intensity I_A)
1350-1370cm^-1Peak P in the range_B(Pee
Strength I_B) Intensity ratio R = I _B/ I_AIs 0.12, 15
80 ~ 1620cm^-1The full width at half maximum of the peak in the range of 19 is 19.
9cm^-1NG-7 natural graphite powder (Kansai Thermochemical Co., Ltd.)
5% by weight of polyvinylidene fluoride in 95 parts by weight
Parts were mixed and dispersed with N-methyl-2-pyrrolidone.
A 18 μm thick rally-shaped current collector
Apply evenly on copper foil, and after drying, circle with a diameter of 12.5 mm
The negative electrode was punched out in a disk shape.

As for the electrolytic solution, lithium hexafluorophosphate (Li) was sufficiently dried in a dry argon atmosphere.
Using PF ₆ ) as a solute, vinylene carbonate was dissolved at a rate of 2% by weight in 98% by weight of a mixture of propylene carbonate and ethylene carbonate (1: 1 by volume), and LiPF ₆ was further dissolved at a rate of 1 mol / L. Prepared. Using these positive electrode, negative electrode, and electrolytic solution, the positive electrode was housed in a stainless steel can that also serves as a positive electrode conductor, and the negative electrode was placed thereon via a polyethylene separator impregnated with the electrolytic solution. . The can body and the sealing plate also serving as the negative electrode conductor were caulked and sealed via an insulating gasket to produce a coin-type battery.

Comparative Example 1 A mixture of propylene carbonate and ethylene carbonate (1: 1 by volume) was mixed with Li
A coin-type battery was produced in the same manner as in Example 1, except that an electrolyte prepared by dissolving PF ₆ at a rate of 1 mol / liter was used.

Example 2 Ethylene carbonate and γ-
Except that an electrolyte prepared by dissolving vinylene carbonate at a ratio of 2% by weight in 98% by weight of a butyrolactone mixture (1: 1 by volume) and further dissolving LiPF ₆ at a ratio of 1 mol / L was used. A coin-type battery was manufactured in the same manner as in Example 1.

Comparative Example 2 Ethylene carbonate and γ-
LiPF was added to a mixture of butyrolactone (1: 1 by volume).
_A coin-type battery was produced in the same manner as in Example 1, except that an electrolytic solution prepared by dissolving ₆ at a ratio of 1 mol / liter was used.

Example 3 Propylene carbonate and γ
98% by weight of a mixture of butyrolactone (1: 1 by volume)
A coin-type battery was produced in the same manner as in Example 1, except that an electrolyte prepared by dissolving vinylene carbonate at a ratio of 2% by weight and further dissolving LiPF ₆ at a ratio of 1 mol / liter was used. .

Comparative Example 3 Propylene carbonate and γ
-Butyrolactone mixture (1: 1 by volume) with LiP
Except for using the F ₆ 1 mol / liter electrolyte solution prepared by dissolving at a rate of in the same manner as in Example 1 to prepare a coin battery.

Example 4 2% by weight of 4,5-dimethylvinylene carbonate was added to 98% by weight of a mixture of propylene carbonate and ethylene carbonate (1: 1 by volume).
, And an electrolytic solution prepared by further dissolving LiPF ₆ at a rate of 1 mol / liter was used to produce a coin-type battery in the same manner as in Example 1. The batteries prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were subjected to a charge / discharge test at 25 ° C. at a constant current of 0.5 mA, a charge end voltage of 4.2 V, and a discharge end voltage of 2.5 V. Example 1
Table 1 shows the electrical conductivity at 20 ° C. and −30 ° C. of the electrolytic solution used in No. 3. In addition, the measurement of the electric conductivity was measured using the electric conductivity meter (Toa Denpasha Co., Ltd., CM-30S). Table 2 shows the discharge capacity per charge of the negative electrode and the charge / discharge efficiency in the first cycle in each battery. Here, the charging / discharging efficiency is obtained from the following equation.

[0046]

## EQU1 ## Charge / discharge efficiency (%) = [(discharge capacity) / (charge capacity)] × 100

According to Tables 1 and 2, in the case of the comparative example, the decomposition and decomposition of the electrolyte proceed excessively, so that both the capacity and the efficiency are not sufficient. , Has a relatively high conductivity, when the battery,
Excellent capacity and charge / discharge efficiency.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

According to the present invention, it is possible to manufacture a battery which is excellent in safety, has excellent charge / discharge efficiency, and excellent cycle characteristics and storage characteristics even at high temperatures, and makes a non-aqueous electrolyte secondary battery compact. , Can contribute to high performance.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Noriko Shima, Inventor, Tsukuba Research Laboratory, Tsukuba Research Laboratory, Mitsubishi Chemical Co., Ltd., Tsukuba Research Institute, Inc., Tsukuba Research Institute (72) Hitoshi Suzuki, 8-chome, Ami-machi, Inashiki-gun, Ibaraki Pref. No.3-1 F-term in Tsukuba Research Laboratory, Mitsubishi Chemical Corporation (reference) HA01 HA02 HA04 HA13 HA14 HA19

Claims (8)

[Claims] 1. A non-aqueous electrolyte secondary battery comprising at least a negative electrode, a positive electrode, and a non-aqueous electrolyte comprising a solute and a non-aqueous solvent, wherein the non-aqueous solvent is a solvent having a relative dielectric constant of 25 or more. It contains at least one selected solvent at 90% by weight or more, has a flash point of 70 ° C. or more, and has at least one vinylene carbonate compound represented by the following general formula (I) added to the nonaqueous solvent. Non-aqueous electrolyte secondary battery characterized by the following. Embedded image (Wherein, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) 2. The non-aqueous solvent comprises at least one solvent selected from solvents having a relative dielectric constant of 25 or more and a flash point of 70 ° C. or more and at least one vinylene carbonate compound of the formula (I). The non-aqueous electrolyte secondary battery according to 1. 3. The vinylene carbonate compound of the formula (I) is added in an amount of 0.01 to 10% by weight of the total amount of the nonaqueous solvent and the vinylene carbonate compound of the formula (I). Non-aqueous electrolyte secondary battery. 4. The non-aqueous electrolyte according to claim 1, wherein the solvent having a relative dielectric constant of 25 or more is selected from ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, and γ-valerolactone. Rechargeable battery. 5. The non-aqueous electrolyte secondary battery according to claim 1, wherein the non-aqueous solvent contains at least 20% by weight of ethylene carbonate or propylene carbonate. 6. The non-aqueous electrolyte secondary battery according to claim 1, wherein the negative electrode contains a carbon material capable of inserting and extracting lithium. 7. The negative electrode material has a lattice plane (0
The non-aqueous electrolyte secondary battery according to any one of claims 1 to 6, further comprising a graphite-based carbonaceous material having a d value of 0.335 to 0.34 nm (surface 02). 8. A non-aqueous electrolytic solution for a secondary battery, comprising at least a negative electrode and a positive electrode capable of inserting and extracting lithium, wherein the non-aqueous electrolytic solution is composed of a solute and a non-aqueous solvent. Wherein the non-aqueous solvent contains at least 90% by weight of at least one solvent selected from solvents having a relative dielectric constant of 25 or more and has a flash point of 70 ° C. or more. A non-aqueous electrolyte solution comprising at least one vinylene carbonate compound represented by the formula: Embedded image (Wherein, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)