JP2000348760A - Nonaqueous electrolytic solution and secondary battery using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrolytic solution capable of furthering rapid operation of a pressure release device at an overcharge time to restrain the rise of a battery voltage and capable of preventing rapid rise of battery temperature and battery internal pressure by forming the electrolytic solution with a nonaqueous solvent containing a carbamate compound and an electrolyte. SOLUTION: A carbamate compound is expressed by the formula. A nonaqueous solvent is preferably formed with the carbamate compound and cyclic carbonic ester and/or chain carbonic ester. The carbamate compound is contained in the nonaqueous solvent by 0.01-99.5 wt.%, and a lithium salt is preferable for an electrolyte. As a specific compound of the formula, 2- methoxyethyl-N, p-methoxyphenyl-N, or N-diethylcarbamate can be offered. In the formula, R1 is 2-12C hydrocarbon containing an oxygen atom; and R2 and R3 each are 1-12C hydrocarbon that may contain oxygen, nitrogen or sulfur atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte having excellent overcharge prevention properties and a secondary battery using the same. More specifically, the present invention relates to a non-aqueous electrolyte using a non-aqueous solvent containing a carbamate compound and a non-aqueous electrolyte secondary battery using the same.

[0002]

BACKGROUND OF THE INVENTION A battery using a non-aqueous electrolyte has a high voltage, a high energy density, and a high reliability such as storability, so that it is widely used as a power source for consumer electronic devices. Have been. Among them, a lithium ion secondary battery is a typical non-aqueous electrolyte secondary battery.

As a non-aqueous electrolyte, LiBF ₄ , LiPF ₆ , and LiCl are used in a mixed solvent of a high dielectric constant carbonate compound solvent such as propylene carbonate and ethylene carbonate and a low viscosity solvent such as diethyl carbonate.
Solutions containing an electrolyte such as O ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , and Li ₂ SiF ₆ are often used.

[0004] On the other hand, research on electrodes has been advanced with the aim of increasing the capacity of batteries, and carbon materials capable of doping and undoping lithium ions have been used as negative electrodes of lithium ion secondary batteries. I have.

[0005] However, in the conventional explosion-proof sealed batteries, if the overcharge state continues for a long time, an abnormal exothermic reaction continues even after the current interrupting device or the pressure release device is operated, and the battery temperature becomes 50 to 60. The temperature rapidly increased from 300 ° C. to 300 ° C. to 400 ° C., and the internal pressure sometimes increased rapidly.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a non-aqueous solution that can promptly operate a pressure relief device at the time of overcharging to suppress a rise in battery voltage and prevent a rapid rise in battery temperature and battery internal pressure. The purpose is to provide an electrolytic solution. Another object of the present invention is to provide a secondary battery including such a non-aqueous electrolyte.

[0007]

[Means for Solving the Problems]

That is, the present invention relates to a non-aqueous electrolyte comprising a non-aqueous solvent containing a carbamate compound represented by the general formula (1) and an electrolyte.

Embedded image (Wherein, R ¹ is a hydrocarbon group containing an oxygen atom having 2 to 12 carbon atoms, R ² and R ³ are a hydrocarbon group having 1 to 12 carbon atoms, and R ² and R ³ are oxygen, (It may or may not contain at least one nitrogen or sulfur atom, and R ² and R ³ may be the same or different.)

When the non-aqueous solvent is composed of the carbamate compound represented by the general formula (1) and a cyclic carbonate and / or a chain carbonate, the overcharge preventing property and the battery properties are improved. In particular, a non-aqueous electrolyte having excellent low-temperature characteristics and cycle characteristics can be provided.

The carbamate compound represented by the general formula (1) is preferably contained in the non-aqueous solvent in an amount of 0.01 to 99.5% by weight, and the electrolyte is preferably a lithium salt. Such an electrolyte can be effectively used as an electrolyte for a primary or secondary battery.

Further, the present invention provides a method for doping lithium metal, a lithium-containing alloy, and lithium ion as a negative electrode active material.
A negative electrode containing any of the undoped carbon materials, a positive oxide containing any of a composite oxide of lithium and a transition metal as a positive electrode active material, a carbon material or a mixture thereof, and the above-described nonaqueous electrolyte And a lithium ion secondary battery including the same.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Next, each constitution of the non-aqueous electrolyte according to the present invention and a non-aqueous electrolyte secondary battery using this non-aqueous electrolyte will be described in detail.

Carbamate Compound In the present invention, the carbamate compound contained in the non-aqueous solvent is a compound represented by the following general formula (1).

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Here, R ¹ is a hydrocarbon group containing an oxygen atom having 2 to 12 carbon atoms. Specific examples thereof include the following alkoxyalkyl groups. (1) methoxymethyl group, ethoxymethyl group, n-propyloxymethyl group, isopropyloxymethyl group (2) 1-methoxyethyl group, 2-methoxyethyl group,
1-ethoxyethyl group, 2-ethoxyethyl group, 1-
n-propyloxyethyl group, 2-n-propyloxyethyl group, 1-isopropyloxyethyl group, 2-
Isopropyloxyethyl group

(3) 1-methoxy-n-propyl group, 2
-Methoxy-n-propyl group, 1-ethoxy-n-propyl group, 2-ethoxy-n-propyl group, 1-n-propyloxy-n-propyl group, 2-n-propyloxy-n-propyl group, 1-isopropyloxy-n
-Propyl group, 2-isopropyloxy-n-propyl group

(4) 1-methoxy-isopropyl group, 2
-Methoxy-isopropyl group, 1-ethoxy-isopropyl group, 2-ethoxy-isopropyl group, 1-n-propyloxy-isopropyl group, 2-n-propyloxy-isopropyl group, 1-isopropyloxy-isopropyl group, 2- Isopropyloxy-isopropyl group

R ¹ is an o-methoxyphenyl group, an o-ethoxyphenyl group, an o- (n-propyloxy) phenyl group, an m-methoxyphenyl group, an m-ethoxyphenyl group, an m- (n- Examples thereof include an alkoxyphenyl group such as a propyloxy) phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a p- (n-propyloxy) phenyl group, and an acetyl group.

Among these, a 2-methoxyethyl group,
A 1-methoxy-n-propyl group and a p-methoxyphenyl group are preferred.

R ² and R ³ are a hydrocarbon group having 1 to 12 carbon atoms, which may be a saturated or unsaturated hydrocarbon group, or a linear or branched hydrocarbon group. It may be. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2 -Methyl-2-propenyl group, 1-
Methylenepropyl group, 1-methyl-2-propenyl group, 1,2-
Dimethylvinyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-methyl-2-methylpropyl group, 2,2 -Aliphatic hydrocarbon groups such as dimethylpropyl group, hexyl group, octyl group, nonyl group and decyl group. Further, it may be an aromatic hydrocarbon group such as a phenyl group, a toluyl group, a methoxyphenyl group, and a naphthyl group.

Further, R ² and R ³ may be a hydrocarbon group containing at least one of oxygen, nitrogen and sulfur atoms, for example, a hydrocarbon group having an alkoxy group, an amino group or a thioether group. For example, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2-methoxythioethyl group, a 2-ethoxythioethyl group, a pyridyl group and the like can be exemplified. R ² and R ³ may be bonded directly or via one or more nitrogen, sulfur and / or oxygen atoms, and examples thereof include piperidine, piperazine, pyrrolidine, and morpholine. it can

R ² and R ³ are preferably an alkyl group having 1 to 12 carbon atoms among the above examples, and among them, an ethyl group, an n-propyl group and an isopropyl group are particularly preferable. R ² and R ³ may be the same or different from each other.

Specific examples of the compound represented by the general formula (1) include 2-methoxyethyl-N, N-diethylcarbamate represented by the formula (2) and p-type represented by the formula (3) Methoxyphenyl-N, N-diethyl carbamate and the like can be mentioned.

[0023]

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[0024]

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Such a carbamate compound represented by the above general formula (1) can be used alone or in combination of two or more, and promotes prompt operation of the pressure relief device at the time of overcharge. In addition, it is possible to suppress a rise in battery voltage and prevent a rapid rise in battery temperature and battery internal pressure.

Non-Aqueous Solvent The non-aqueous electrolyte according to the present invention uses a non-aqueous solvent containing the above-mentioned carbamate compound as an additive or as a non-aqueous solvent. As the non-aqueous solvent, solvents that are usually used as non-aqueous solvents for batteries, such as carbonate compounds, can be used as they are.

The carbamate compound is at least 0.001% by weight, preferably 0.01 to 99.5% by weight based on the total amount of the nonaqueous solvent (the total amount of the carbamate compound and other nonaqueous solvents).
%, More preferably 0.01 to 70% by weight, particularly preferably 0.05 to 30% by weight. Within this range, when the battery is overcharged, prompt operation of the pressure release device is promoted, and a rise in battery voltage can be suppressed, and a rapid rise in battery temperature and battery internal pressure can be prevented.

In the present invention, when a non-aqueous solvent containing the above-mentioned carbamate compound and a cyclic carbonate and / or a chain carbonate among general non-aqueous solvents is used, rapid heat generation of the battery due to overcharging and the like are prevented. This is preferable because it can provide a nonaqueous electrolytic solution that can prevent the occurrence of a battery and further has excellent battery characteristics, particularly excellent low-temperature characteristics and cycle characteristics.

As the cyclic carbonate, a compound represented by the following general formula (4) or (5) can be used.

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[0030]

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[0031] Here, R ⁴ and R ⁵ are included in the equation (4) and (5) represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁴ and R ⁵ are independently identical or different May be. Among them, the alkyl group has 1 to 3 carbon atoms.
Is preferred, and specific examples include a methyl group, an ethyl group, and an n-propyl group.

Specific examples of the cyclic carbonate represented by the above formulas (4) and (5) include ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, and 1,2-butyl carbonate. Pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate and the like. These cyclic carbonates may be used in combination of two or more kinds.

Examples of the chain carbonate include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, and the like. May be used in combination.

When such a cyclic ester carbonate is used, the electric conductivity of the solvent can be increased due to its high dielectric constant. In addition, when the chain carbonate is contained in the non-aqueous solvent, the viscosity of the non-aqueous electrolyte can be lowered, the solubility of the electrolyte is further increased, and the electric conductivity at room temperature or low temperature is excellent. Electrolyte solution. Therefore, the charge / discharge efficiency of the battery and low-temperature characteristics such as charge / discharge efficiency and load characteristics at low temperatures can be improved.

When the cyclic carbonate and / or chain carbonate represented by formula (4) or (5) is used as the non-aqueous solvent, the carbamate compound represented by formula (1) is used. Is 0.00 with respect to the total amount of the nonaqueous solvent containing it (the total amount of the carbamate compound and the cyclic carbonate and / or chain carbonate).
1% by weight or more, preferably 0.01 to 99.5% by weight,
More preferably, it is contained in an amount of 0.01 to 70% by weight, particularly preferably 0.05 to 30% by weight.

When the cyclic carbonate and the chain carbonate are used in combination as the non-aqueous solvent component, the mixing ratio is expressed by weight ratio, and the cyclic carbonate: chain carbonate is 5: 95-95: 5, preferably 20:
80 to 85:15.

As the non-aqueous solvent, a solvent which is widely used as a non-aqueous solvent for batteries can be further added. (1) Chain esters such as methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, and ethyl propionate (2) Phosphate esters such as trimethyl phosphate (3) dimethoxyethane (4) Cyclic ether such as tetrahydrofuran (5) Amide such as dimethylformamide (6) Cyclic ester such as γ-butyrolactone (7) Cyclic sulfone such as sulfolane (8) Methyl-N, N-dimethylcarbamate (9) Cyclic carbamate such as N-methyloxazolidinone (10) Cyclic amide such as N-methylpyrrolidone (11) Cyclic urea such as N, N-dimethylimidazolidinone

[0038] according to a non-aqueous electrolytic solution present invention the non-aqueous electrolyte solution, a metal salt as an electrolyte has become a non-aqueous solvent containing a carbamate compound described above as the electrolyte, a nonaqueous solvent containing, for example, carbamate compounds Is the dissolved electrolyte. The electrolyte is usually 0.1 to 3 mol / l, preferably 0.5 to 2 mol / l.
It is desirable that the compound is contained in the non-aqueous electrolyte at a concentration of mol / liter. Further, an additive such as a stabilizer may be added as necessary.

As the electrolyte to be used, any metal salt which is usually used as an electrolyte for a non-aqueous electrolyte can be used. Specific examples of the _{electrolyte, LiPF 6, LiBF 4, LiClO} 4, LiAsF 6, Li
Lithium salts such as ₂ SiF ₆ , LiC ₄ F ₉ SO ₃ , and LiC ₈ F ₁₇ SO ₃ are exemplified.

Further, a lithium salt represented by the following general formula can also be used. LiOSO ₂ R ³ , LiN (SO ₂ R
⁴ ) (SO ₂ R ⁵ ), LiC (SO ₂ R ⁶ ) (SO ₂ R ⁷ ) (SO
₂ R ⁸ ), LiN (SO ₂ OR ⁹ ) (SO ₂ OR ¹⁰ ) (where R ³
~ R ¹⁰ may be the same or different from each other,
A perfluoroalkyl group having 1 to 6 carbon atoms).

Of these, LiPF ₆ , LiBF ₄ ,
LiOSO ₂ R ³ , LiN (SO ₂ R ⁴ ) (SO ₂ R ⁵ ), LiC (S
O ₂ R ⁶ ) (SO ₂ R ⁷ ) (SO ₂ R ⁸ ), LiN (SO ₂ OR ⁹ ) (S
O ₂ OR ¹⁰ ) are preferred, and they may be used alone or in combination of two or more.

Such a non-aqueous electrolyte according to the present invention is suitable not only as a non-aqueous electrolyte for a lithium ion secondary battery but also as a non-aqueous electrolyte for a primary battery.

The non-aqueous electrolyte secondary battery according to the secondary batteries present invention, a negative electrode, a positive electrode,
It is basically configured to include the above-described non-aqueous electrolyte, and a separator is usually provided between the negative electrode and the positive electrode.

As the negative electrode active material constituting the negative electrode, any of lithium metal, a lithium alloy, and a carbon material capable of doping / de-doping lithium ions can be used. Among these, a carbon material capable of doving / de-doping lithium ions is preferable. Such a carbon material may be graphite or amorphous carbon, and activated carbon, carbon fiber, carbon black, mesocarbon microbeads and the like are used.

As the positive electrode active material constituting the positive electrode, Mo is used.
Transition metal oxides or sulfides such as S ₂ , TiS ₂ , MnO ₂ , V ₂ O ₅ , LiCoO ₂ , LiMnO ₂ , LiMn ₂
A composite oxide composed of lithium and a transition metal such as O ₄ and LiNiO ₂ can be used. Among these, a composite oxide composed of lithium and a transition metal is particularly preferable. When the negative electrode is a lithium metal or lithium alloy, a carbon material can be used as the positive electrode. Also, as a positive electrode,
A mixture of a composite oxide of lithium and a transition metal and a carbon material can also be used.

The separator is a porous membrane, and usually a microporous polymer film is suitably used. In particular, a porous polyolefin film is preferable, and specific examples thereof include a porous polyethylene film, a porous polypropylene film, and a multilayer film of a porous polyethylene film and polypropylene.

Such a non-aqueous electrolyte secondary battery can be formed in a cylindrical shape, a coin shape, a square shape, or any other shape. However, the basic structure of the battery is the same regardless of the shape, and the design can be changed according to the purpose.
Next, the structures of the cylindrical and coin type batteries will be described. The negative electrode active material, the positive electrode active material, and the separator constituting each battery are commonly used.

For example, in the case of a cylindrical non-aqueous electrolyte secondary battery, a negative electrode formed by applying a negative electrode active material to a negative electrode current collector and a positive electrode active material formed by applying a positive electrode active material to a positive electrode current collector are formed. A positive electrode and a non-aqueous electrolyte are injected through a severator,
It is housed in a battery can with an insulating plate placed above and below the wound body.

The non-aqueous electrolyte secondary battery according to the present invention can be applied to a coin-type non-aqueous electrolyte secondary battery. In a coin-type battery, a disk-shaped negative electrode, a separator, a disk-shaped positive electrode, and a stainless steel plate are housed in a coin-type battery can in a state of being stacked in this order.

[0050]

Next, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

(Example 1) <Preparation of non-aqueous electrolyte> Ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed with EC: DEC =
After mixing at a ratio of 58:42 (weight ratio), 5 parts by weight of 2-methoxyethyl-N, N-diethylcarbamate (hereinafter sometimes abbreviated as 2MMECA) was added to 95 parts by weight of the mixed solvent, A non-aqueous solvent was prepared so that the amount of 2MMECA was 5% by weight based on the entire non-aqueous solvent (the total amount of EC, DEC, and 2MMECA). Next, LiPF ₆ as an electrolyte was dissolved in a non-aqueous solvent, and the electrolyte concentration was 1.
A non-aqueous electrolyte was prepared so as to be 0 mol / liter.

<Preparation of Negative Electrode> Mesocarbon microbeads (trade name: MCMB6-28, d manufactured by Osaka Gas Co., Ltd.)
002 = 0.337 nm, density 2.17 g / cm ³ ) 90 parts by weight of carbon powder and 10 parts by weight of polyvinylidene fluoride (PVDF) as a binder were mixed, and N-
The paste was dispersed in methylpyrrolidone to prepare a paste-like negative electrode mixture slurry. Next, this negative electrode mixture slurry was applied to a negative electrode current collector made of a 20-μm-thick strip-shaped copper foil, and dried to obtain a strip-shaped carbon negative electrode. The thickness of the negative electrode mixture after drying is 2
It was 5 μm. Furthermore, this strip electrode is 15 mm in diameter.
And then compression-molded to form a negative electrode.

<Preparation of Positive Electrode> L manufactured by Honjo Chemical Co., Ltd.
iCoO ₂ (product name: HLC-21, average particle size 8 μm)
91 parts by weight of fine particles, 6 parts by weight of graphite as a conductive material, and polyvinylidene fluoride (PV) as a binder
DF) was mixed with 3 parts by weight to prepare a positive electrode mixture, and dispersed in N-methylpyrrolidone to obtain a positive electrode mixture slurry.
This slurry was applied to a 20-μm-thick aluminum foil positive electrode current collector, dried, and compression-molded to obtain a belt-shaped positive electrode. The thickness of the positive electrode mixture after drying was 40 μm. Thereafter, the strip-shaped electrode was punched into a disk having a diameter of 15 mm to obtain a positive electrode.

<Preparation of Battery> A disk-shaped negative electrode and a disk-shaped positive electrode thus obtained, and a separator made of a microporous polypropylene film having a thickness of 25 μm and a diameter of 19 mm were prepared. After each of the negative electrode, the separator, and the positive electrode were laminated in the order of a 2032-sized stainless steel battery can, the nonaqueous electrolyte was injected into the separator.
Then, a stainless steel plate (2.4 m thick) was placed in the battery can.
m, diameter 15.4 mm), and the battery can lid was caulked via a polypropylene gasket. As a result, a button-type non-aqueous electrolyte secondary battery having a diameter of 20 mm and a height of 3.2 mm was able to be maintained while maintaining the airtightness in the battery.

Using the button-type secondary battery thus produced, the battery voltage and gas generation during overcharging of the battery were evaluated by the following methods. First, only 2.8 V-
1 mA charge / discharge was performed between 4.2V. Next, the operation of charging at a constant current of 1 mA for 12 minutes and suspending for 3 minutes was repeated 30 times, and then the battery thickness (referred to as a post-test battery thickness) and the battery voltage (referred to as an end voltage) were measured. The battery expansion coefficient was calculated from the measured battery thickness before and after the test by the following equation. Battery expansion coefficient (%) = {(battery thickness after test−battery thickness before test) / (battery thickness before test)} × 100

Table 1 shows the measurement results. The larger the gas generation amount, that is, the larger the battery expansion coefficient, the more preferable it is because the increase in the battery voltage is suppressed, that is, the end voltage is reduced and the prompt operation of the pressure relief device is promoted. The expansion of the battery is due to the generated gas,
It is not due to expansion of other members.

Example 2 In Example 1, p-methoxyphenyl-N, N-diethylcarbamate (hereinafter abbreviated as MOPhECA) was used in place of 2-methoxyethyl-N, N-diethylcarbamate. Except for the above, the same procedure as in Example 1 was carried out to prepare a non-aqueous electrolyte, and a battery was produced. The battery expansion coefficient and battery voltage were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 A non-aqueous electrolyte solution was prepared and a battery was fabricated in the same manner as in Example 1 except that 2-methoxyethyl-N, N-diethylcarbamate was not added. The battery expansion coefficient and the battery voltage were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0059]

[Table 1] * EC: DEC = 58: 42 (weight ratio)

[0060]

The non-aqueous electrolyte according to the present invention promotes the rapid operation of the pressure relief device during overcharging and suppresses a rise in battery voltage, thereby preventing a rapid rise in battery temperature and battery internal pressure. can do. Further, since the present invention uses the non-aqueous electrolyte as described above, it was possible to provide a secondary battery capable of preventing a rapid rise in battery temperature and battery internal pressure.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroaki Tan 580-32, Takuji, Nagaura-shi, Sodegaura-shi, Chiba Inside of Mitsui Chemicals, Inc. 32 Mitsui Chemicals Co., Ltd. (72) Tatsurei Ishida, Inventor Tatsuji Nagaura, Sodegaura-shi, Chiba 580-32 32 Inventor Hitoshi Onishi, Insugaura-shi, Chiba Takuji, Nagaura, 580 No. 32 F term in Mitsui Chemicals, Inc. (reference) 5H029 AJ05 AJ12 AK02 AK03 AK05 AK06 AK18 AL06 AL07 AL12 AM02 AM03 AM04 AM05 AM07 DJ08 EJ11 HJ01 HJ02

Claims (11)

[Claims] 1. A non-aqueous electrolyte comprising a non-aqueous solvent containing a carbamate compound represented by the general formula (1) and an electrolyte. Embedded image (In the formula, R ¹ is a hydrocarbon group containing an oxygen atom having 2 to 12 carbon atoms, and R ² and R ³ are a hydrocarbon group having 1 to 12 carbon atoms which may contain oxygen, nitrogen and sulfur atoms. And they may be the same or different) 2. The non-aqueous electrolyte according to claim 1, wherein R ¹ in the general formula (1) is an alkoxyalkyl group or an alkoxyphenyl group. 3. The compound of the formula (1) wherein R ² and R
^3. The non-aqueous electrolyte according to claim 1, wherein ³ is an alkyl group having 1 to 12 carbon atoms. 4. A compound represented by the general formula (1)
The non-aqueous electrolyte according to claim 1, wherein the non-aqueous electrolyte is -methoxyethyl-N, N-diethylcarbamate or p-methoxyphenyl-N, N-diethylcarbamate. 5. The method according to claim 1, wherein said non-aqueous solvent comprises a carbamate compound represented by the general formula (1) and a cyclic carbonate and / or a chain carbonate. The non-aqueous electrolyte according to any one of the above. 6. The non-aqueous electrolyte according to claim 5, wherein said cyclic ester carbonate is a compound selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate and vinylene carbonate. 7. The non-aqueous electrolyte according to claim 5, wherein said chain carbonate is a compound selected from the group consisting of dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate. 8. The method according to claim 1, wherein the carbamate compound represented by the general formula (1) is contained in an amount of 0.01 to 99.5% by weight based on the whole nonaqueous solvent. The non-aqueous electrolyte according to any one of the above. 9. The non-aqueous electrolyte according to claim 1, wherein said electrolyte is a lithium salt. 10. A secondary battery comprising the non-aqueous electrolyte according to claim 1. 11. A negative electrode containing any of lithium metal, a lithium-containing alloy, and a carbon material capable of doping / dedoping lithium ions as a negative electrode active material, a composite oxide of lithium and a transition metal as a positive electrode active material, A lithium ion secondary battery comprising: a positive electrode containing any one of a material and a mixture thereof; and the nonaqueous electrolyte according to claim 1.