JP2001256995A - Nonaqueous electrolytic solution and its secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous electrolytic solution and its secondary battery maintaining low variation rate of electric capacity and internal resistance at the time of repeating charge and discharge and improving battery cycle characteristics. SOLUTION: The nonaqueous electrolytic solution comprising an electrolytic salt dissolved into an organic solvent is added with an oxygen-contained aliphatic compound having an alkynyl and/or alkynylene with no active hydrogen.

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 to which a compound having a specific carbon-carbon triple bond is added, and a non-aqueous electrolyte secondary battery using the non-aqueous electrolyte. Specifically, by adding an oxygen-containing aliphatic compound having a carbon-carbon triple bond having no active hydrogen to the electrolyte, a non-aqueous electrolyte and a non-aqueous electrolyte having a small rate of change in electric capacity and internal resistance during repeated charge and discharge. The present invention relates to an electrolyte secondary battery.

[0002]

2. Description of the Related Art With the spread of portable electronic devices such as portable personal computers and handy video cameras in recent years, non-aqueous electrolyte secondary batteries having high voltage and high energy density have been used as power sources. It has become widely used. Also, due to environmental problems, battery vehicles and hybrid vehicles that use batteries as part of power are being put to practical use.

[0003] However, the non-aqueous electrolyte secondary battery shows a decrease in electric capacity and an increase in internal resistance by repeating charge and discharge, and thus lacks reliability as a stable power supply source.

[0004] In order to improve the stability of the nonaqueous electrolyte secondary battery, various additives have been proposed for the electrolyte. For example,
JP-A-6-84523 proposes to add an amine compound, and although the cycle characteristics are improved, there is a disadvantage that the capacity is reduced.
No. 1 proposes arylalkyl ether compounds and arylaryl ether compounds, but these have not been satisfactory. In addition, Japanese Patent Application Laid-Open No. 5-159
No. 787 proposes to suppress a decrease in circuit voltage during storage by adding an alcohol such as propargyl alcohol having a carbon-carbon triple bond. However, the addition of alcohols having active hydrogen is not practical because it impairs the safety of the electrolytic solution.

As described above, additives selected from compounds known as stabilizers for various organic substances, although exhibiting a stabilizing effect, are not satisfactory, and have remarkable cycle characteristics due to alkyl groups and alkynyl groups. No difference in effect was suggested.

Accordingly, an object of the present invention is to provide a non-aqueous electrolyte and a non-aqueous electrolyte secondary battery having a small rate of change in electric capacity and internal resistance during repeated charging and discharging, and having improved cycle characteristics of the battery. It is in.

[0007]

As a result of the study, the present inventors have found that when producing a non-aqueous electrolyte, an oxygen-containing aliphatic compound having a carbon-carbon triple bond having no active hydrogen is added to the electrolyte. By doing so, it has been found that the above object can be achieved.

[0008] The present invention has been made based on the above-mentioned findings, and it is an object of the present invention to provide a non-aqueous electrolytic solution in which an electrolyte salt is dissolved in an organic solvent, wherein an oxygen-containing aliphatic compound having an alkynyl group and / or an alkynylene group having no active hydrogen is used. It is intended to provide a non-aqueous electrolyte solution characterized by being added.

The present invention also relates to a non-aqueous electrolyte secondary battery having a non-aqueous electrolyte, a positive electrode and a negative electrode, wherein an oxygen-containing aliphatic compound having an alkynyl group and / or an alkynylene group having no active hydrogen is added. A non-aqueous electrolyte secondary battery characterized by using the above-mentioned non-aqueous electrolyte.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The oxygen-containing aliphatic compound having an alkynyl group and / or an alkynylene group having no active hydrogen used in the present invention includes, for example, a compound represented by the general formula (I).

[0012]

Embedded image (Wherein, R ₁ and R ₃ are an alkyl group having 1 to 8 carbon atoms,
R ₂ represents an alkenyl group or an alkynyl group;
4 represents an alkylene group, alkenylene group, or alkynylene group, provided that any one of R ₁ , R ₂ , and R ₃ is an alkynyl group or an alkynylene group, and X ₁ and X ₂ are an ether bond, an ester bond, Ester bond, n is 0
Or represents the number of 1)

In the general formula (I), the alkyl groups represented by R ₁ and R ₃ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl, and the alkenyl groups include vinyl and Propenyl, butenyl and the like, as the alkynyl group, propargyl,
1,1-dimethyl-2-propynyl, 1-methyl-2-
Ethyl-2-propynyl, 1-methyl-1-isobutyl-2-propynyl and the like can be mentioned.

The alkylene group represented by R ₂ is ethylene, propylene, etc., the alkenylene group is vinylene, butenylene, etc., and the alkynylene group is ethynylene, propynylene, 2-butynylene, 1,1,1,2.
4,4-tetramethyl-2-butynylene, 1,4-dimethyl-1,4-diethyl-2-butynylene, 1,4-dimethyl-1,4-diisobutyl-2-butynylene and the like can be mentioned.

More specifically, the compounds represented by the above general formula (I) include the following compound Nos. 1 to 7. However, the present invention is not limited at all by the following compounds.

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

The compound represented by the above general formula (I) can be synthesized by performing a usual esterification reaction, etherification reaction or carbonic esterification reaction using an alkynyl compound such as propargyl alcohol.

These are compounds which easily undergo self-polymerization,
It is considered that a polymerization reaction occurs at the electrode interface in the early stage of the cycle, thereby forming a stable film and suppressing an increase in interface resistance due to the cycle. In order to exhibit this effect, 0.01 to 10%
It is desirable to add the above compound in the amount of volume%, more desirably 0.1 to 5 volume%.

In the present invention, the alkynyl group having no active oxygen and / or the oxygen-containing aliphatic compound having an alkynylene group is used alone or in combination with another non-aqueous solvent as an electrolytic solution. It is particularly preferred to combine with a chain carbonate and a cyclic carbonate. By combining in this way, it is possible to provide not only excellent cycle characteristics but also an electrolyte solution in which the viscosity of the electrolyte solution, the electric capacity of the obtained battery, and the output are well balanced.

Examples of other solvents used in the non-aqueous electrolyte of the present invention are listed below. However, the present invention is not particularly limited, and an increase in interface resistance can be suppressed by adding it to the entire electrolytic solution.

Since the cyclic carbonate compound has a high relative dielectric constant, it plays a role in increasing the dielectric constant of the electrolytic solution. Specifically, cyclic carbonates such as ethylene carbonate, propylene carbonate, vinylene carbonate, butylene carbonate, and γ -Butyrolactone, γ-
Examples include cyclic esters such as valerolactone, tetramethylsulfolane, dimethylsulfoxide, N-methylpyrrolidone, dimethylformamide, and derivatives thereof.

The chain carbonate or the like can lower the viscosity of the electrolytic solution. Therefore, battery characteristics such as output density can be improved, for example, the mobility of electrolyte ions can be increased. Further, since the viscosity is low, the performance of the electrolyte at a low temperature can be improved. Specifically, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl-n-butyl carbonate, methyl-t-butyl carbonate, di-i
Chain carbonates such as -propyl carbonate, t-butyl-i-propyl carbonate, dimethoxyethane,
Chain ethers such as ethoxymethoxyethane and diethoxyethane, cyclic ethers such as tetrahydrofuran, dioxolan, and dioxane; chain esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, and ethyl propionate; acetonitrile; Examples include propionitrile, nitromethane, and derivatives thereof.

The phosphorus-containing organic compound can increase the flame retardancy of the electrolytic solution. Therefore, the safety of the nonaqueous electrolyte secondary battery can be enhanced. As the phosphorus-containing organic compound, it is desirable to use at least one or more phosphorus-containing compounds selected from the group consisting of phosphate esters, phosphonate esters and phosphinate esters. Specifically, phosphoric acid esters such as trimethyl phosphate and triethyl phosphate, phosphonic acid esters such as diethyl methane phosphonate and di- (2,2,2-trifluoroethyl) methane phosphonate, and phosphinic acid esters are used. be able to. Further, a mixture of a plurality of these may be used.

The alkylene biscarbonate compound represented by the following general formula (II) can lower the volatility of the electrolytic solution, and has excellent storage characteristics at high temperatures, so that the battery characteristics at high temperatures can be improved. can do. This structure is not particularly limited, but includes 1,2-bis (methoxycarbonyloxy) ethane, 1,2-bis (ethoxycarbonyloxy) ethane, 1,2-bis (ethoxycarbonyloxy) propane, and the like. Can be used.

[0031]

Embedded image (In the formula, R ₄ and R ₆ each independently represent an alkyl group having 1 to 4 carbon atoms, and R ₅ represents a linear or branched alkylene group having 1 to 3 carbon atoms.)

The alkyl groups represented by R ₄ and R ₆ include methyl, ethyl, propyl, butyl and the like.
Examples of the alkylene group represented by ₅ include ethylene and the like.

As the above-mentioned chain carbonate, a compound represented by the following general formula (III) is preferable because it has particularly excellent electric properties.

[0034]

Embedded image (In the formula, R ₇ and R ₈ each independently represent an alkyl group having 1 to 4 carbon atoms, and at least one represents an alkyl group having 3 or more carbon atoms.)

Here, examples of the alkyl group represented by R ₇ and R ₈ include methyl, ethyl, propyl, butyl and the like.

Since the terminal group of the glycol diether compound represented by the following general formula (IV) is substituted with a fluorine atom, the glycol diether compound exhibits an action like a surfactant at the electrode interface, and is non-aqueous. The affinity of the electrolyte for the electrode can be increased, and the initial internal resistance of the battery can be reduced and the mobility of lithium ions can be increased. This structure is not particularly limited, but ethylene glycol bis (trifluoroethyl) ether, i-propylene glycol (trifluoroethyl) ether, ethylene glycol bis (trifluoromethyl) ether, diethylene glycol bis (trifluoroethyl) ) Ether and the like can be used.

[0037]

Embedded image(Where R₉, R₁₁Is an alkyl group having 1 to 8 carbon atoms or
Is an alkyl group substituted with a halogen atom,_TenIs carbon
A branched or linear alkylene group having 1 to 4 atoms or halogen
N2 is an alkylene group substituted with a non-atom atom, 1 ≦ n2 ≦
4 represents the number R ₉, R_Ten, R₁₁Any one of is halo
Represents a group substituted with a gen atom)

The alkyl groups represented by R ₉ and R ₁₁ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and the like, and the alkylene groups represented by R ₁₀ include ethylene, propylene And the like.

As the electrolyte, a conventionally known electrolyte is used.
For example, LiPF₆, LiBF_Four, LiAs
F₆, LiCF_ThreeSO_Three, LiN (CF_ThreeSO_Two)_Two,
LiC (CF_ThreeSO_Two)_Three, LiSbF₆, LiSiF
_Five, LiAlF_Four, LiSCN, LiClO_Four, LiC
1, LiF, LiBr, LiI, LiAlCl_Four, Na
ClO_Four, NaBF_Four, NaI and the like.
LiPF₆, LiBF_Four, LiClO_Four, LiAsF₆
And an inorganic salt such as CF_ThreeSO_ThreeLi, N (CF _ThreeS
O_Two)_TwoLi, C (CF_ThreeSO_Two)_ThreeOrganic salt such as Li
One or a combination of two or more salts selected from the group consisting of
It is preferable because it has excellent electrical characteristics.

The above electrolyte has a concentration in the electrolyte of 0.1%.
It is preferable to dissolve in the above-mentioned organic solvent so as to be 3.0 to 3.0 mol / l, particularly 0.5 to 2.0 mol / l. If the concentration of the electrolytic solution is less than 0.1 mol / liter, a sufficient current density may not be obtained in some cases.
If it is higher than mol / liter, the stability of the electrolyte may be impaired.

The electrolyte of the present invention can be suitably used as a non-aqueous electrolyte constituting a primary or secondary battery, particularly a non-aqueous electrolyte secondary battery described later.

The electrode material includes a positive electrode and a negative electrode.
For the positive electrode, a slurry of a positive electrode active material, a binder, and a conductive material is used.
And apply it to a current collector and dry it to form a sheet.
Is used. As the positive electrode active material, TiS_Two,
TiS_Three, MoS_Three, FeS _Two, Li_(1-x)MnO_Two,
Li_(1-x)Mn_TwoO_Four, Li_(1-x)CoO_Two, Li_(1
-x)NiO_Two, LiV_TwoO_Three, V_TwoO_FiveEtc.
You. X in the examples of the positive electrode active material is a number of 0 to 1.
Is shown. Of these positive electrode active materials, lithium and transition metals
Are preferred, and LiCoO_Two, LiNi
O_Two, LiMn_TwoO_Four, LiMnO_Two, LiV_TwoO_Threeetc
Is preferred. Examples of binders for negative and positive electrode active materials
For example, polyvinylidene fluoride, polytetrafluoroethylene
Len, EPDM, SBR, NBR, fluoro rubber, etc.
But not limited to these.

As the negative electrode, one obtained by slurrying a negative electrode active material and a binder with a solvent is applied to a current collector and dried to form a sheet. Examples of the negative electrode active material include inorganic compounds such as lithium, lithium alloys and tin compounds, carbonaceous materials, and conductive polymers. In particular, a carbonaceous material that can store and release highly safe lithium ions is preferable. This carbonaceous material is not particularly limited, but graphite and petroleum-based coke, coal-based coke, petroleum-based pitch carbide, coal-based pitch carbide, phenolic resin, carbonized resin such as crystalline cellulose, and partially carbonized these Examples include carbon materials, furnace black, acetylene black, pitch-based carbon fibers, and PAN-based carbon fibers.

Examples of the conductive material for the positive electrode include graphite fine particles, carbon black such as acetylene black, and amorphous carbon fine particles such as needle coke, but are not limited thereto. As a solvent for forming a slurry, an organic solvent that dissolves a binder is usually used. For example, N-
Methylpyrrolidone, dimethylformamide, dimethylacetamide, methylethylketone, cyclohexanone,
Methyl acetate, methyl acrylate, diethyltriamine,
Examples include, but are not limited to, N-N-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran, and the like. In some cases, the active material is slurried with latex such as SBR by adding a dispersant, a thickener, and the like to water.

The current collector of the negative electrode usually contains copper, nickel,
Stainless steel, nickel-plated steel, or the like is used, and aluminum, stainless steel, nickel-plated steel, or the like is usually used for the positive electrode current collector.

In the non-aqueous electrolyte secondary battery of the present invention, a separator is used between the positive electrode and the negative electrode, but a commonly used polymer microporous film can be used without any particular limitation. For example,
Polyethers such as polyethylene, polypropylene, polyvinylidene fluoride, polyvinylidene chloride, polyacrylonitrile, polyacrylamide, polytetrafluoroethylene, polysulfone, polyethersulfone, polycarbonate, polyamide, polyimide, polyethylene oxide and polypropylene oxide, carboxymethylcellulose and hydroxy Examples thereof include films composed of various celluloses such as propylcellulose, polymer compounds mainly composed of poly (meth) acrylic acid and various esters thereof, derivatives thereof, and copolymers and mixtures thereof. Further, such a film may be used alone, or a multilayer film in which these films are laminated. Further, various additives may be used for these films, and the types and contents thereof are not particularly limited.
Among these microporous films, polyethylene, polypropylene, polyvinylidene fluoride, and polysulfone are preferably used for the nonaqueous electrolyte secondary battery of the present invention.

[0047] These separator films are microporous so that the electrolyte solution can permeate and ions easily permeate. The microporous method includes a phase separation method in which a film of a polymer compound and a solvent is formed while microphase-separating the solution, and the solvent is extracted and removed to form a porous layer. The film is extruded into a film, and then heat-treated, and the crystals are arranged in one direction. Further, a "stretching method" for forming a gap between the crystals by stretching to make the crystals porous, and the like are appropriately selected depending on the polymer film used. . In particular, a phase separation method is preferably used for polyethylene and polyvinylidene fluoride preferably used in the present invention.

The non-aqueous electrolyte secondary battery of the present invention having the above-mentioned structure is not particularly limited in its shape, and can be used as batteries of various shapes such as a coin type, a cylindrical type and a square type. FIG. 1 shows an example of a coin-type battery of the non-aqueous electrolyte secondary battery of the present invention, and FIGS. 2 and 3 show examples of a cylindrical battery.

In FIGS. 1 to 3, 1 is a negative electrode, 1 'is a negative electrode plate, 1 "is a negative electrode lead, 2 is a negative electrode current collector, 3 is a positive electrode and 3' is a positive electrode plate, 3" is a positive electrode lead, Is the positive electrode current collector,
5 is an electrolyte, 6 is a separator, 7 is a positive electrode terminal, 8 is a negative electrode terminal, 10 is a non-aqueous electrolyte secondary battery, 11 is a case, 1
2 is an insulating plate, 13 is a gasket, 14 is a safety valve, 15P
Each TC element is shown.

Although the function of the present invention is not clear,
This is presumably because in the initial cycle, the alkynyl group having no active hydrogen and / or the oxygen-containing aliphatic compound having an alkynylene group used in the present invention undergoes a polymerization reaction at the electrode interface to form a film. For this reason, the initial internal resistance increases as compared to the case where no additive is added, but since the film is stable, side reactions between the electrode and the electrolyte during the cycle can be suppressed, and the increase in the internal resistance due to the cycle can be suppressed. It is thought that it is possible.

[0051]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited by the following examples.

(Preparation of Positive Electrode) 90 parts by weight of LiMn ₂ O ₄ , 6 parts by weight of graphite and 4 parts by weight of polyvinylidene fluoride
The parts by weight were mixed to obtain a positive electrode material. This positive electrode material is
-Methyl-2-pyrrolidone to form a slurry. The slurry was applied to a positive electrode current collector made of aluminum, dried, and press-formed to obtain a positive electrode.

(Preparation of Negative Electrode) 90 parts by weight of a carbon material powder and 10 parts by weight of polyvinylidene fluoride were mixed to prepare a negative electrode material. This negative electrode material was dispersed in N-methyl-2-pyrrolidone to form a slurry. This slurry was applied to a negative electrode current collector made of copper, dried, and press-formed to obtain a negative electrode.

(Preparation of Electrolytic Solution) An organic solvent was used in Example 1-1.
To 1-8 and Comparative Examples 1-1 to 1-5 at each volume%, and further, LiPF ₆ was dissolved at a concentration of 1 mol / liter, and the test compounds (described in Tables 1 and 2) were dissolved. A non-aqueous electrolyte was obtained by adding the components (volume%) shown in Tables 1 and 2.

(Preparation of Battery) The above-mentioned electrode was welded to a case, and a coin-type non-aqueous electrolyte secondary battery shown in FIG. 1 containing an electrolyte was contained through a microporous polypropylene film having a thickness of 25 μm. It was created.

(Evaluation method) Using the above nonaqueous electrolyte secondary battery, at 20 ° C. and 60 ° C., 4.2 V, 1 mA / c
m ² , charge for 4 hours with constant current and constant voltage, and 0.5 m
Charging / discharging was performed at a constant current of A / cm ² with a final voltage of 3.0 V, and the discharge capacity (mAh), the initial value of the internal resistance (Ω), and the discharge capacity maintenance rate (%) after 50 cycles of charge / discharge. ) And internal resistance, that is, resistance maintenance (Ω), to evaluate the cycle characteristics (stability). Table 1 shows the results at 20 ° C.
Table 2 shows the results at 60 ° C.

[Examples 1-1 to 1-9 and Comparative Example 1-1]
~ 1-3] LiPF6 was added to a mixed solvent of ethylene carbonate and dimethyl carbonate at a volume ratio of 1: 1 at a ratio of 1 mol /
The test compound (Table 1) was added to the electrolyte dissolved at a concentration of 1 liter.
) To obtain an electrolyte solution.

[Examples 1-10 and Comparative Examples 1-4] A mixed solvent of 30% by volume of ethylene carbonate, 60% by volume of diethyl carbonate and 10% by volume of triethyl phosphate, and a concentration of LiPF ₆ of 1 mol / L were used. A test compound (see Tables 1 and 2) was added to the electrolytic solution dissolved in the above to prepare an electrolytic solution.

Example 1-11 and Comparative Example 1-5 30% by volume of ethylene carbonate, 10% by volume of 1,2-bis (ethoxycarbonyloxy) ethane and ethyl-n
-40% by volume of butyl carbonate, 10% by volume of ethylene glycol bis (trifluoroethyl) ether,
Triethyl phosphate was added to a 10% by volume mixed solvent, and L
A test compound (see Tables 1 and 2) was added to an electrolytic solution in which iPF ₆ was dissolved at a concentration of 1 mol / liter to obtain an electrolytic solution.

[0060]

[Table 1]

[0061]

[Table 2]

As is clear from the evaluation results in Tables 1 and 2, the alkynyl group and / or alkynylene group having no active hydrogen according to the present invention shown in Examples 1-1 to 1-11 is provided. A non-aqueous electrolyte secondary battery using an electrolyte to which an oxygen-containing aliphatic compound is added has a small decrease in discharge capacity and an increase in internal resistance due to charge and discharge even at 60 ° C. However, in Comparative Examples 1-1, 1-4, and 1-5 where no additive was added, the discharge capacity after charge and discharge was significantly reduced, and the internal resistance was also greatly increased. Further, in Comparative Example 1-2 in which a compound having an alkynyl group having active hydrogen was added, and in Comparative Example 1-3 in which an oxygen-containing aromatic compound having an alkynyl group having no active hydrogen was added, the initial discharge capacity was small. The internal resistance is large. Further, the capacity retention rate after 50 cycles is small, and the rise in internal resistance is large.

[0063]

As described above, the use of the non-aqueous electrolyte solution of the present invention to which an alkynyl group having no active hydrogen and / or an oxygen-containing aliphatic compound having an alkynylene group is added enables the charge and discharge to be repeated. It is possible to provide a nonaqueous electrolyte secondary battery having a small rate of change in electric capacity and internal resistance and excellent cycle characteristics.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view schematically showing an example of the structure of a coin-type non-aqueous electrolyte secondary battery of the present invention.

FIG. 2 is a schematic diagram showing a basic configuration of a lithium secondary battery (cylindrical type) as a non-aqueous electrolyte secondary battery of the present invention.

FIG. 3 is a perspective view showing a cross section of an internal structure of a lithium secondary battery (cylindrical type) as a nonaqueous electrolyte secondary battery of the present invention.

[Explanation of symbols]

 1: negative electrode 1 ': negative electrode plate 1 ": negative electrode lead 2: negative electrode current collector 3: positive electrode 3': positive electrode plate 3": positive electrode lead 4: positive electrode current collector 5: electrolytic solution 6: separator 7: positive electrode terminal 8 : Negative electrode terminal 10: non-aqueous electrolyte secondary battery 11: case 12: insulating plate 13: gasket 14: safety valve 15: PTC element

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Naohiro Kubota 7-35 Higashiogu, Arakawa-ku, Tokyo Asahi Denka Kako Kogyo Co., Ltd. Asahi Denka Kogyo Co., Ltd. F-term (reference) 5H029 AJ03 AJ05 AJ06 AK03 AL06 AM03 AM05 AM07 BJ02 BJ03 BJ12 BJ14 EJ11 HJ01 HJ02

Claims (8)

[Claims] 1. A non-aqueous electrolyte comprising a non-aqueous electrolyte in which an electrolyte salt is dissolved in an organic solvent, wherein an alkynyl group having no active hydrogen and / or an oxygen-containing aliphatic compound having an alkynylene group is added. . 2. The non-aqueous electrolyte according to claim 1, wherein the oxygen-containing aliphatic compound having an alkynyl group and / or an alkynylene group having no active hydrogen is a compound represented by the following general formula (I). Embedded image (Wherein, R ₁ and R ₃ are an alkyl group having 1 to 8 carbon atoms,
R ₂ represents an alkenyl group or an alkynyl group;
4 represents an alkylene group, alkenylene group, or alkynylene group, provided that any one of R ₁ , R ₂ , and R ₃ is an alkynyl group or an alkynylene group, and X ₁ and X ₂ are an ether bond, an ester bond, Ester bond, n is 0
Or represents the number of 1) 3. The compound represented by the above general formula (I)
3. The non-aqueous electrolyte according to claim 2, wherein the electrolyte is present in an amount of 0.01 to 10% by volume. 4. The non-aqueous electrolytic solution according to claim 1, wherein the electrolytic solution contains at least one kind of a cyclic carbonate compound and at least one kind of a chain carbonate compound. 5. The non-aqueous electrolyte according to claim 2, which contains at least one phosphorus-containing compound. 6. The following general formulas (II), (III) and (IV)
Contains at least one compound represented by any of
The non-aqueous electrolyte according to claim 2, wherein Embedded image(Where R_Four, R₆Are each independently an alkyl group having 1 to 4 carbon atoms.
Alkyl group to R_FiveIs linear or branched having 1 to 3 carbon atoms
Represents an alkylene group)(Where R₇, R₈Are each independently an alkyl group having 1 to 4 carbon atoms.
Represents an alkyl group, at least one of which has 3 or more carbon atoms.
Represents an alkyl group)(Where R₉, R₁₁Is an alkyl group having 1 to 8 carbon atoms or
Is an alkyl group substituted with a halogen atom,_TenIs carbon
A branched or linear alkylene group having 1 to 4 atoms or halogen
N2 is an alkylene group substituted with a non-atom atom, 1 ≦ n2 ≦
4 represents the number R ₉, R_Ten, R₁₁Any one of is halo
Represents a group substituted with a gen atom) 7. The method according to claim 7, wherein the electrolyte salt is lithium ion and PF
₆, BF_Four, ClO _FourAnd AsF₆A selected from
Inorganic salt and lithium ion
SO_ThreeCF_Three, N (CF_ThreeSO_Two)_Two, C (CF_ThreeSO
_Two)_ThreeAnd organic salts composed of these derivatives?
A combination of one or more salts selected from the group consisting of
The non-aqueous electrolytic solution according to any one of claims 1 to 6, comprising: 8. A non-aqueous electrolyte secondary battery having a non-aqueous electrolyte, a positive electrode and a negative electrode, wherein the non-aqueous electrolyte according to claim 1 is used. Next battery.