JP2008027673A - Nonaqueous electrolytic solution and nonaqueous electrolyte battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain nonaqueous electrolyte providing a battery of high capacity and excellent storing property, and to obtain a nonaqueous electrolyte battery manufactured by using it. <P>SOLUTION: The nonaqueous electrolyte contains 0.001 vol.% or more and less than 2 capacity% of a compound expressed by a general formula (1) in nonaqueous solvent. Alternatively, the nonaqueous electrolyte contains 0.001 vol.% or more and less than 10 vol.% of the compound expressed by the general formula (1) in the nonaqueous solvent, and further contains annular carbonates with unsaturated bonding in the electrolyte. R<SP>1</SP>and R<SP>2</SP>in the general formula (1) each independently indicate alkyl group with carbon numbers from 1 to 12 containing ether bonding in their structures, as well as being replaced by fluorine atom. R<SP>3</SP>indicates alkyl group with carbon numbers from 1 to 12 which can be replaced by the fluorine atom. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a non-aqueous electrolyte and a non-aqueous electrolyte battery using the same.

Non-aqueous electrolyte batteries such as lithium secondary batteries are being put to practical use in a wide range of applications from so-called consumer power sources such as mobile phones and laptop computers to in-vehicle power sources for automobiles and the like. However, the demand for higher performance for non-aqueous electrolyte batteries in recent years is increasing, and there is a demand for improvement in battery characteristics.
The electrolyte used for the non-aqueous electrolyte battery is usually composed mainly of an electrolyte and a non-aqueous solvent. The main components of the non-aqueous solvent include cyclic carbonates such as ethylene carbonate and propylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate; cyclic carboxylic acid esters such as γ-butyrolactone and γ-valerolactone. It is used.

In order to improve battery characteristics such as load characteristics, cycle characteristics, and storage characteristics of such non-aqueous electrolyte batteries, various studies have been made on non-aqueous solvents and electrolytes.
Patent Document 1 describes that load characteristics and low-temperature characteristics are improved by using a fluorinated ether having a specific structure as a solvent.
In Patent Document 2, when a mixture of an asymmetric chain carbonate and a cyclic carbonate having a double bond is used as a non-aqueous solvent, the cyclic carbonate having a double bond reacts preferentially with the negative electrode and a good quality is formed on the negative electrode surface. It has been proposed that a film is formed, which suppresses the formation of a non-conductive film on the negative electrode surface due to the asymmetric chain carbonate, thereby improving storage characteristics and cycle characteristics.
JP 2006-49037 A Japanese Patent Laid-Open No. 11-185806

  However, the demand for higher performance of batteries in recent years is increasing, and it is required to achieve battery characteristics such as high capacity, high temperature storage characteristics, and cycle characteristics at a higher level. The non-aqueous electrolyte secondary battery using the electrolyte described in 2 has not yet been satisfactory.

As a result of various studies to achieve the above object, the present inventors have found that the above problems can be solved by including a compound having a specific structure in the electrolytic solution, thereby completing the present invention. It came to.
That is, the gist of the present invention is (i) a non-aqueous electrolyte solution containing an electrolyte and a non-aqueous solvent that dissolves the electrolyte, and the non-aqueous electrolyte solution contains a compound represented by the following general formula (1) as a non-aqueous solvent. A non-aqueous electrolyte containing 0.001% by volume or more and less than 2% by volume, and

(In General Formula (1), R ¹ and R ² each independently have an ether bond in the structure, and may be substituted with a fluorine atom. R ³ represents an alkyl group having 1 to 12 carbon atoms which may be substituted with a fluorine atom.)
(Ii) In a non-aqueous electrolyte containing an electrolyte and a non-aqueous solvent that dissolves the electrolyte, the non-aqueous electrolyte contains a compound represented by the following general formula (1) in an amount of 0.001% by volume to 10% in the non-aqueous solvent. The present invention resides in a non-aqueous electrolytic solution characterized in that it contains less than volume% and further contains a cyclic carbonate having an unsaturated bond in the electrolytic solution.

(In the general formula (1), R ¹ , R ² and R ³ are as defined above.)
Another gist of the present invention is (iii) a non-aqueous electrolyte battery including a negative electrode and a positive electrode capable of occluding and releasing lithium ions, and a non-aqueous electrolyte, wherein the non-aqueous electrolyte is the above non-aqueous electrolyte. It exists in the non-aqueous electrolyte battery characterized by being.

  According to the present invention, a non-aqueous electrolyte battery having a high capacity and excellent storage characteristics can be provided, and the non-aqueous electrolyte battery can be reduced in size and performance.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. However, the description of constituent elements described below is an example (representative example) of an embodiment of the present invention, and is not specified by these contents.
<Non-aqueous electrolyte>
The non-aqueous electrolyte solution of the present invention contains an electrolyte and a non-aqueous solvent that dissolves the electrolyte, as is the case with conventional non-aqueous electrolyte solutions.
(Electrolytes)
As the electrolyte, a lithium salt is usually used. The lithium salt is not particularly limited as long as it is known to be used for this purpose. Any lithium salt can be used, and specific examples include the following.

For example, inorganic lithium salts such as LiPF ₆ and LiBF ₄ ; LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , lithium cyclic 1,2-perfluoroethanedisulfonylimide Lithium cyclic 1,3-perfluoropropane disulfonylimide, LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ), LiC (CF ₃ SO ₂ ) ₃ , LiPF ₄ (CF ₃ ) ₂ , Li
PF ₄ (C ₂ F ₅ ) ₂ , LiPF ₄ (CF ₃ SO ₂ ) ₂ , LiPF ₄ (C ₂ F ₅ SO ₂ ) ₂ , LiBF ₂ (CF ₃ ) ₂ , LiBF ₂ (C ₂ F ₅ ) ₂ , LiBF ₂ (CF ₃ SO ₂ ) ₂ , LiBF ₂ (C ₂ F ₅ S
And fluorine-containing organic lithium salts such as O ₂ ) ₂ and lithium bis (oxalate) borate.

Of these, LiPF ₆ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ or LiN (C ₂ F ₅ SO ₂ ) ₂ are preferable from the viewpoint of improving battery performance, and in particular, LiPF ₆ or LiB.
F ₄ is preferred.
These lithium salts may be used alone or in combination of two or more.
A preferred example in the case of using two or more types in combination is the combined use of LiPF ₆ and LiBF ₄ , which has an effect of improving cycle characteristics. In this case, the proportion of LiBF _{4 in} the total of both is preferably 0.01% by weight or more, particularly preferably 0.1% by weight or more, preferably 20% by weight or less, particularly preferably 5% by weight or less. is there. If the lower limit is not reached, it may be difficult to obtain the desired effect.

Another example is the combined use of an inorganic lithium salt and a fluorine-containing organic lithium salt. In this case, the proportion of the inorganic lithium salt in the total of both is 70% by weight or more and 99% by weight or less. It is desirable. Examples of the fluorine-containing organic lithium salt include LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , lithium cyclic 1,2-perfluoroethanedisulfonylimide, lithium cyclic 1,3-perfluoropropane. It is preferably any of disulfonylimide. The combined use of both has the effect of suppressing deterioration due to high temperature storage.

When the non-aqueous solvent contains 55% by volume or more of γ-butyrolactone, the lithium salt is preferably LiBF ₄ or a combination of LiBF ₄ and another. In this case, LiBF ₄ preferably accounts for 40 mol% or more of the lithium salt. Particularly preferably, the proportion of LiBF _{4 in} the lithium salt is 40 mol% or more and 95 mol% or less, and the rest is Li
The combination is selected from the group consisting of PF ₆ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ and LiN (C ₂ F ₅ SO ₂ ) ₂ .

The concentration of these electrolytes in the non-aqueous electrolytic solution is not particularly limited in order to exhibit the effects of the present invention, but is usually 0.5 mol / liter or more, preferably 0.6 mol / liter or more, more Preferably it is 0.7 mol / liter or more. The upper limit is usually 3 mol / liter or less, preferably 2 mol / liter or less, more preferably 1.8 mol / liter or less, and still more preferably 1.5 mol / liter or less. If the concentration is too low, the electrical conductivity of the electrolyte solution may be insufficient. On the other hand, if the concentration is too high, the electrical conductivity may decrease due to an increase in viscosity, and the battery performance may decrease. .
(Non-aqueous solvent)
The non-aqueous solvent can also be appropriately selected from conventionally known solvents for non-aqueous electrolyte solutions. Examples thereof include cyclic carbonates having no unsaturated bond, chain carbonates, cyclic ethers, chain ethers, cyclic carboxylic acid esters, chain carboxylic acid esters, and phosphorus-containing organic solvents.

Examples of the cyclic carbonates having no unsaturated bond include alkylene carbonates having an alkylene group having 2 to 4 carbon atoms such as ethylene carbonate, propylene carbonate, and butylene carbonate. Among these, ethylene carbonate, propylene carbonate, and the like. Is preferable from the viewpoint of improving battery characteristics, and ethylene carbonate is particularly preferable.
As the chain carbonates, dialkyl carbonates are preferable, and the number of carbon atoms of the alkyl group constituting each is preferably 1 to 5, particularly preferably 1 to 4. Specifically, for example, symmetric chain alkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-n-propyl carbonate; asymmetric chain alkyls such as ethyl methyl carbonate, methyl-n-propyl carbonate, and ethyl-n-propyl carbonate Examples thereof include dialkyl carbonates such as carbonates. Among these, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate are preferable from the viewpoint of improving battery characteristics (particularly, high load discharge characteristics).

Examples of cyclic ethers include tetrahydrofuran and 2-methyltetrahydrofuran.
Examples of chain ethers include dimethoxyethane and dimethoxymethane.
Examples of cyclic carboxylic acid esters include γ-butyrolactone and γ-valerolactone.

Examples of chain carboxylic acid esters include methyl acetate, methyl propionate, ethyl propionate, and methyl butyrate.
Examples of the phosphorus-containing organic solvent include trimethyl phosphate, triethyl phosphate, dimethyl ethyl phosphate, methyl diethyl phosphate, ethylene methyl phosphate, ethylene ethyl phosphate, and the like.

These may be used alone or in combination of two or more, but it is preferable to use in combination of two or more. For example, it is preferable to use a high dielectric constant solvent such as alkylene carbonates or cyclic carboxylic acid esters in combination with a low viscosity solvent such as dialkyl carbonates or chain carboxylic acid esters.
One preferred combination of non-aqueous solvents is a combination mainly composed of alkylene carbonates and dialkyl carbonates. Among them, the total of alkylene carbonates and dialkyl carbonates in the nonaqueous solvent is 70% by volume or more, preferably 80% by volume or more, more preferably 90% by volume or more, and the alkylene carbonates and dialkyl carbonates. The proportion of alkylene carbonate with respect to the total is 5% or more, preferably 10% or more, more preferably 15% or more, usually 50% or less, preferably 35% or less, more preferably 30% or less, still more preferably 25 % Or less. Use of a combination of these non-aqueous solvents is preferable because the balance between cycle characteristics and high-temperature storage characteristics (particularly, remaining capacity and high-load discharge capacity after high-temperature storage) of a battery produced using the non-aqueous solvent is improved.

  Specific examples of preferred combinations of alkylene carbonates and dialkyl carbonates include ethylene carbonate and dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and ethyl methyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate, Examples include ethyl methyl carbonate, ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.

A combination in which propylene carbonate is further added to a combination of these ethylene carbonate and dialkyl carbonates is also mentioned as a preferable combination.
In the case of containing propylene carbonate, the volume ratio of ethylene carbonate to propylene carbonate is preferably 99: 1 to 40:60, particularly preferably 95: 5 to 50:50. Furthermore, the proportion of propylene carbonate in the whole non-aqueous solvent is 0.1% by volume or more, preferably 1% by volume or more, more preferably 2% by volume or more, and the upper limit is usually 20% by volume or less, preferably 8% by volume. % Or less, more preferably 5% by volume or less. It is preferable to contain propylene carbonate in this concentration range, since the low temperature characteristics are further excellent while maintaining the combination characteristics of ethylene carbonate and dialkyl carbonates.

  Among the combinations of ethylene carbonate and dialkyl carbonates, those containing asymmetric chain alkyl carbonates as dialkyl carbonates are more preferred, especially ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, ethylene carbonate, diethyl carbonate and ethyl. Methyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate, which contain ethylene carbonate, symmetric chain alkyl carbonates, and asymmetric chain alkyl carbonates, have a good balance between cycle characteristics and large current discharge characteristics. preferable. Among them, the asymmetric chain alkyl carbonate is preferably ethyl methyl carbonate, and the alkyl group of the alkyl carbonate preferably has 1 to 2 carbon atoms.

Other examples of preferred non-aqueous solvents include one organic solvent selected from the group consisting of ethylene carbonate, propylene carbonate, γ-butyrolactone and γ-valerolactone, or two or more organic solvents selected from the group The mixed solvent becomes 60% by volume or more of the whole. The non-aqueous electrolyte using this mixed solvent is less likely to evaporate or leak when used at high temperatures. Among these, the total of ethylene carbonate and γ-butyrolactone in the nonaqueous solvent is 80% by volume or more, preferably 90% by volume or more, and the volume ratio of ethylene carbonate and γ-butyrolactone is 5:95 to 45%. : 55, or the total of ethylene carbonate and propylene carbonate in the non-aqueous solvent is 80% by volume or more, preferably 90% by volume or more, and the volume ratio of ethylene carbonate to propylene carbonate is 30:70 to Use of a material having a ratio of 60:40 generally improves the balance between cycle characteristics and large current discharge characteristics.

  It is also preferable to use a phosphorus-containing organic solvent as the non-aqueous solvent. When the phosphorus-containing organic solvent is contained in the non-aqueous solvent in an amount of usually 5% by volume or more, preferably 10% by volume or more, and the upper limit is 80% by volume or less, the flammability of the electrolytic solution can be lowered. . In particular, when a phosphorus-containing organic solvent is used in combination with a nonaqueous solvent selected from the group consisting of ethylene carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone, and dialkyl carbonate, cycle characteristics and large current discharge characteristics This is preferable because the balance is improved.

In this specification, the capacity of the non-aqueous solvent is a measured value at 25 ° C., but the measured value at the melting point is used for a solid at 25 ° C. such as ethylene carbonate.
(Compound represented by the general formula (1))
The non-aqueous electrolyte solution according to the present invention contains the above-described electrolyte and a non-aqueous solvent, which contains a compound represented by the following general formula (1).

(In General Formula (1), R ¹ and R ² each independently have an ether bond in the structure, and may be substituted with a fluorine atom. R ³ represents an alkyl group having 1 to 12 carbon atoms which may be substituted with a fluorine atom.)
In the general formula (1), in the definition of R ¹ , R ² , R ³ , examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n Examples include a linear, branched or cyclic alkyl group such as -butyl group, i-butyl group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group, and cyclohexyl group. The carbon number of R ¹ and R ² is usually 1 or more as the lower limit, and preferably 8 or less, more preferably 6 or less as the upper limit. The carbon number of R ³ is usually 1 or more as a lower limit, preferably 2 or more, more preferably 3 or more, and the upper limit is usually 12 or less, preferably 8 or less.

The alkyl group of R ¹ and R ² may contain an ether bond in the structure. Examples of the group having an ether bond in the structure of the alkyl group include a methoxymethyl group and 1-methoxy group. Examples include an alkoxyalkyl group such as an ethyl group, a 2-methoxyethyl group, an ethoxymethyl group, a 1-ethoxyethyl group, and a 2-ethoxyethyl group.
Furthermore, the alkyl group may be substituted with a fluorine atom, and examples of the group substituted with a fluorine atom include partial alkyl groups such as trifluoromethyl group, trifluoroethyl group, and pentafluoroethyl group. Alkyl group and perfluoroalkyl group.

The total carbon number of the compound represented by the general formula (1) is preferably 5 or more, more preferably 6 or more, further preferably 7 or more, and the upper limit is preferably 14 or less, more preferably 12 or less.
On the other hand, when the upper limit is exceeded, the viscosity may increase and the battery performance may decrease.
Specific examples of the compound represented by the general formula (1) include the following compounds.
1,1,1,2,3,3,3-heptafluoro-2-methoxy-propane,
1,1,1,2,3,3,3-heptafluoro-2-ethoxy-propane,
1,1,1,2,3,3,3-heptafluoro-2-propoxy-propane,
1,1,1,2,3,3,3-heptafluoro-2-butoxy-propane,
1,1,1,2,3,3,4,4,4-nonafluoro-2-methoxy-butane,
1,1,1,2,3,3,4,4,4-nonafluoro-2-ethoxy-butane,
1,1,1,2,3,3,4,4,4-nonafluoro-2-propoxybutane,
1,1,1,2,3,3,4,4,4-nonafluoro-2-butoxy-butane,
1,1,1,2,3,4,4,4-octafluoro-2-methoxy-3-trifluoromethyl-butane,
1,1,1,2,3,4,4,4-octafluoro-2-ethoxy-3-trifluoromethyl-butane,
1,1,1,2,3,4,4,4-octafluoro-2-propoxy-3-trifluoromethyl-butane,
1,1,1,2,3,4,4,4-octafluoro-2-butoxy-3-trifluoromethyl-butane,
1,1,1,2,3,4,4,4-octafluoro-2,3-bis (methoxy) butane, 1,1,1,2,3,4,4,4-octafluoro-2 3-bis (ethoxy) butane, 1,1,1,2,3,4,4,4-octafluoro-2,3-bis (propoxy) butane,
1,1,1,2,3,4,4,4-octafluoro-2,3-bis (butoxy) butane,

1,1,1,2,3,3,4,4,5,5,5-undecafluoro-2-methoxy-pentane,
1,1,1,2,3,3,4,4,5,5,5-undecafluoro-2-ethoxy-pentane,
1,1,1,2,3,3,4,4,5,5,5-undecafluoro-2-propoxy-pentane,
1,1,1,2,3,3,4,4,5,5,5-undecafluoro-2-butoxy-pentane,
1,1,1,2,2,3,4,4,5,5,5-undecafluoro-3-methoxy-pentane,
1,1,1,2,2,3,4,4,5,5,5-undecafluoro-3-ethoxy-pentane,
1,1,1,2,2,3,4,4,5,5,5-undecafluoro-3-propoxy-pentane,
1,1,1,2,2,3,4,4,5,5,5-undecafluoro-3-butoxy-pentane,
1,1,1,2,3,4,4,5,5,5-decafluoro-2-methoxy-3-trifluoromethyl-pentane,
1,1,1,2,3,4,4,5,5,5-decafluoro-2-ethoxy-3-trifluoromethyl-pentane,
1,1,1,2,3,4,4,5,5,5-decafluoro-2-propoxy-3-trifluoromethyl-pentane,
1,1,1,2,3,4,4,5,5,5-decafluoro-2-butoxy-3-trifluoromethyl-pentane,
1,1,1,2,3,3,4,5,5,5-decafluoro-2-methoxy-4-trifluoromethyl-pentane,
1,1,1,2,3,3,4,5,5,5-decafluoro-2-ethoxy-4-trifluoromethyl-pentane,
1,1,1,2,3,3,4,5,5,5-decafluoro-2-propoxy-4-trifluoromethyl-pentane,
1,1,1,2,3,3,4,5,5,5-decafluoro-2-butoxy-4-trifluoromethyl-pentane,
1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane,
1,1,1,2,2,3,4,5,5,5-decafluoro-3-ethoxy-4-trifluoromethyl-pentane,
1,1,1,2,2,3,4,5,5,5-decafluoro-3-propoxy-4-trifluoromethyl-pentane,
1,1,1,2,2,3,4,5,5,5-decafluoro-3-butoxy-4-trifluoromethyl-pentane,

1,1,1,2,3,3,4,4,5,5,5-undecafluoro-2- (2,2,2-trifluoroethoxy) -pentane,
1,1,1,2,2,3,4,4,5,5,5-undecafluoro-3- (2,2,2-trifluoroethoxy) -pentane,
1,1,1,2,3,4,4,5,5,5-decafluoro-2- (2,2,2-trifluoroethoxy) -3-trifluoromethyl-pentane,
1,1,1,2,3,3,4,5,5,5-decafluoro-2- (2,2,2-trifluoroethoxy) -4-trifluoromethyl-pentane,
1,1,1,2,2,3,4,5,5,5-decafluoro-3- (2,2,2-trifluoroethoxy) -4-trifluoromethyl-pentane,
1,1,2,3,3,4,4,5,5,5-decafluoro-2-methoxy-pentane,
1,1,2,3,3,4,4,5,5,5-decafluoro-2-ethoxy-pentane,
1,1,2,3,3,4,4,5,5,5-decafluoro-2-propoxy-pentane, 1,1,2,3,3,4,4,5,5,5-deca Fluoro-2-butoxy-pentane,
1,1,2,2,3,4,4,5,5,5-decafluoro-3-methoxy-pentane,
1,1,2,2,3,4,4,5,5,5-decafluoro-3-ethoxy-pentane,
1,1,2,2,3,4,4,5,5,5-decafluoro-3-propoxy-pentane, 1,1,2,2,3,4,4,5,5,5-deca Fluoro-3-butoxy-pentane,

1,1,2,3,4,4,5,5,5-nonafluoro-2-methoxy-3-trifluoromethyl-pentane,
1,1,2,3,4,4,5,5,5-nonafluoro-2-ethoxy-3-trifluoromethyl-pentane,
1,1,2,3,4,4,5,5,5-nonafluoro-2-propoxy-3-trifluoromethyl-pentane,
1,1,2,3,4,4,5,5,5-nonafluoro-2-butoxy-3-trifluoromethyl-pentane,
1,1,2,3,3,4,5,5,5-nonafluoro-2-methoxy-4-trifluoromethyl-pentane,
1,1,2,3,3,4,5,5,5-nonafluoro-2-ethoxy-4-trifluoromethyl-pentane,
1,1,2,3,3,4,5,5,5-nonafluoro-2-propoxy-4-trifluoromethyl-pentane,
1,1,2,3,3,4,5,5,5-nonafluoro-2-butoxy-4-trifluoromethyl-pentane,
1,1,2,2,3,4,5,5,5-nonafluoro-3-methoxy-4-trifluoromethyl-pentane,
1,1,2,2,3,4,5,5,5-nonafluoro-3-ethoxy-4-trifluoromethyl-pentane,
1,1,2,2,3,4,5,5,5-nonafluoro-3-propoxy-4-trifluoromethyl-pentane,
1,1,2,2,3,4,5,5,5-nonafluoro-3-butoxy-4-trifluoromethyl-pentane,

1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluoro-2-methoxy-hexane,
1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluoro-2-ethoxy-hexane,
1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluoro-2-propoxy-hexane,
1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluoro-2-butoxy-hexane,
1,1,1,2,2,3,4,4,5,5,6,6,6-tridecafluoro-3-methoxy-hexane,
1,1,1,2,2,3,4,4,5,5,6,6,6-tridecafluoro-3-ethoxy-hexane,
1,1,1,2,2,3,4,4,5,5,6,6,6-tridecafluoro-3-propoxy-hexane,
1,1,1,2,2,3,4,4,5,5,6,6,6-tridecafluoro-3-butoxy-hexane,

1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-methoxy-3-trifluoromethyl-hexane,
1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-ethoxy-3-trifluoromethyl-hexane,
1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-propoxy-3-trifluoromethyl-hexane,
1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-butoxy-3-trifluoromethyl-hexane,
1,1,1,2,3,3,4,5,5,6,6,6-dodecafluoro-2-methoxy-4-trifluoromethyl-hexane,
1,1,1,2,3,3,4,5,5,6,6,6-dodecafluoro-2-ethoxy-4-trifluoromethyl-hexane,
1,1,1,2,3,3,4,5,5,6,6,6-dodecafluoro-2-propoxy-4-trifluoromethyl-hexane,
1,1,1,2,3,3,4,5,5,6,6,6-dodecafluoro-2-butoxy-4-trifluoromethyl-hexane,
1,1,1,2,3,3,4,4,5,6,6,6-dodecafluoro-2-methoxy-5-trifluoromethyl-hexane,
1,1,1,2,3,3,4,4,5,6,6,6-dodecafluoro-2-ethoxy-5-trifluoromethyl-hexane,
1,1,1,2,3,3,4,4,5,6,6,6-dodecafluoro-2-propoxy-5-trifluoromethyl-hexane,
1,1,1,2,3,3,4,4,5,6,6,6-dodecafluoro-2-butoxy-5-trifluoromethyl-hexane,
1,1,1,2,3,3,4,4,5,5,6,6,7,7,7-pentadecafluoro-2-methoxy-heptane,
1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-methoxy-3-trifluoromethyl-heptane.

Among these, preferred compounds include those having a total carbon number of 6 or more. These compounds are shown below.
1,1,1,2,3,3,3-heptafluoro-2-propoxy-propane,
1,1,1,2,3,3,3-heptafluoro-2-butoxy-propane,
1,1,1,2,3,3,4,4,4-nonafluoro-2-ethoxy-butane,
1,1,1,2,3,3,4,4,4-nonafluoro-2-propoxybutane,
1,1,1,2,3,3,4,4,4-nonafluoro-2-butoxy-butane,
1,1,1,2,3,4,4,4-octafluoro-2-methoxy-3-trifluoromethyl-butane,
1,1,1,2,3,4,4,4-octafluoro-2-ethoxy-3-trifluoromethyl-butane,
1,1,1,2,3,4,4,4-octafluoro-2-propoxy-3-trifluoromethyl-butane,
1,1,1,2,3,4,4,4-octafluoro-2-butoxy-3-trifluoromethyl-butane,
1,1,1,2,3,4,4,4-octafluoro-2,3-bis (methoxy) butane, 1,1,1,2,3,4,4,4-octafluoro-2 3-bis (ethoxy) butane, 1,1,1,2,3,4,4,4-octafluoro-2,3-bis (propoxy) butane,
1,1,1,2,3,4,4,4-octafluoro-2,3-bis (butoxy) butane,

1,1,1,2,3,3,4,4,5,5,5-undecafluoro-2-methoxy-pentane,
1,1,1,2,3,3,4,4,5,5,5-undecafluoro-2-ethoxy-pentane,
1,1,1,2,3,3,4,4,5,5,5-undecafluoro-2-propoxy-pentane,
1,1,1,2,3,3,4,4,5,5,5-undecafluoro-2-butoxy-pentane,
1,1,1,2,2,3,4,4,5,5,5-undecafluoro-3-methoxy-pentane,
1,1,1,2,2,3,4,4,5,5,5-undecafluoro-3-ethoxy-pentane,
1,1,1,2,2,3,4,4,5,5,5-undecafluoro-3-propoxy-pentane,
1,1,1,2,2,3,4,4,5,5,5-undecafluoro-3-butoxy-pentane,

1,1,1,2,3,4,4,5,5,5-decafluoro-2-methoxy-3-trifluoromethyl-pentane,
1,1,1,2,3,4,4,5,5,5-decafluoro-2-ethoxy-3-trifluoromethyl-pentane,
1,1,1,2,3,4,4,5,5,5-decafluoro-2-propoxy-3-trifluoromethyl-pentane,
1,1,1,2,3,4,4,5,5,5-decafluoro-2-butoxy-3-trifluoromethyl-pentane,
1,1,1,2,3,3,4,5,5,5-decafluoro-2-methoxy-4-trifluoromethyl-pentane,
1,1,1,2,3,3,4,5,5,5-decafluoro-2-ethoxy-4-trifluoromethyl-pentane,
1,1,1,2,3,3,4,5,5,5-decafluoro-2-propoxy-4-trifluoromethyl-pentane,
1,1,1,2,3,3,4,5,5,5-decafluoro-2-butoxy-4-trifluoromethyl-pentane,
1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane,
1,1,1,2,2,3,4,5,5,5-decafluoro-3-ethoxy-4-trifluoromethyl-pentane,
1,1,1,2,2,3,4,5,5,5-decafluoro-3-propoxy-4-trifluoromethyl-pentane,
1,1,1,2,2,3,4,5,5,5-decafluoro-3-butoxy-4-trifluoromethyl-pentane,

1,1,1,2,3,3,4,4,5,5,5-undecafluoro-2- (2,2,2-trifluoroethoxy) -pentane,
1,1,1,2,2,3,4,4,5,5,5-undecafluoro-3- (2,2,2-trifluoroethoxy) -pentane,
1,1,1,2,3,4,4,5,5,5-decafluoro-2- (2,2,2-trifluoroethoxy) -3-trifluoromethyl-pentane,
1,1,1,2,3,3,4,5,5,5-decafluoro-2- (2,2,2-trifluoroethoxy) -4-trifluoromethyl-pentane,
1,1,1,2,2,3,4,5,5,5-decafluoro-3- (2,2,2-trifluoroethoxy) -4-trifluoromethyl-pentane,
1,1,2,3,3,4,4,5,5,5-decafluoro-2-methoxy-pentane,
1,1,2,3,3,4,4,5,5,5-decafluoro-2-ethoxy-pentane,
1,1,2,3,3,4,4,5,5,5-decafluoro-2-propoxy-pentane, 1,1,2,3,3,4,4,5,5,5-deca Fluoro-2-butoxy-pentane,
1,1,2,2,3,4,4,5,5,5-decafluoro-3-methoxy-pentane,
1,1,2,2,3,4,4,5,5,5-decafluoro-3-ethoxy-pentane,
1,1,2,2,3,4,4,5,5,5-decafluoro-3-propoxy-pentane, 1,1,2,2,3,4,4,5,5,5-deca Fluoro-3-butoxy-pentane,

1,1,2,3,4,4,5,5,5-nonafluoro-2-methoxy-3-trifluoromethyl-pentane,
1,1,2,3,4,4,5,5,5-nonafluoro-2-ethoxy-3-trifluoromethyl-pentane,
1,1,2,3,4,4,5,5,5-nonafluoro-2-propoxy-3-trifluoromethyl-pentane,
1,1,2,3,4,4,5,5,5-nonafluoro-2-butoxy-3-trifluoromethyl-pentane,
1,1,2,3,3,4,5,5,5-nonafluoro-2-methoxy-4-trifluoromethyl-pentane,
1,1,2,3,3,4,5,5,5-nonafluoro-2-ethoxy-4-trifluoromethyl-pentane,
1,1,2,3,3,4,5,5,5-nofluoro-2-propoxy-4-trifluoromethyl-pentane,
1,1,2,3,3,4,5,5,5-nonafluoro-2-butoxy-4-trifluoromethyl-pentane,
1,1,2,2,3,4,5,5,5-nonafluoro-3-methoxy-4-trifluoromethyl-pentane,
1,1,2,2,3,4,5,5,5-nonafluoro-3-ethoxy-4-trifluoromethyl-pentane,
1,1,2,2,3,4,5,5,5-nonafluoro-3-propoxy-4-trifluoromethyl-pentane,
1,1,2,2,3,4,5,5,5-nonafluoro-3-butoxy-4-trifluoromethyl-pentane,

1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluoro-2-methoxy-hexane,
1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluoro-2-ethoxy-hexane,
1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluoro-2-propoxy-hexane,
1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluoro-2-butoxy-hexane,
1,1,1,2,2,3,4,4,5,5,6,6,6-tridecafluoro-3-methoxy-hexane,
1,1,1,2,2,3,4,4,5,5,6,6,6-tridecafluoro-3-ethoxy-hexane,
1,1,1,2,2,3,4,4,5,5,6,6,6-tridecafluoro-3-propoxy-hexane,
1,1,1,2,2,3,4,4,5,5,6,6,6-tridecafluoro-3-butoxy-hexane,

1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-methoxy-3-trifluoromethyl-hexane,
1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-ethoxy-3-trifluoromethyl-hexane,
1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-propoxy-3-trifluoromethyl-hexane,
1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-butoxy-3-trifluoromethyl-hexane,
1,1,1,2,3,3,4,5,5,6,6,6-dodecafluoro-2-methoxy-4-trifluoromethyl-hexane,
1,1,1,2,3,3,4,5,5,6,6,6-dodecafluoro-2-ethoxy-4-trifluoromethyl-hexane,
1,1,1,2,3,3,4,5,5,6,6,6-dodecafluoro-2-propoxy-4-trifluoromethyl-hexane,
1,1,1,2,3,3,4,5,5,6,6,6-dodecafluoro-2-butoxy-4-trifluoromethyl-hexane,
1,1,1,2,3,3,4,4,5,6,6,6-dodecafluoro-2-methoxy-5-trifluoromethyl-hexane,
1,1,1,2,3,3,4,4,5,6,6,6-dodecafluoro-2-ethoxy-5
-Trifluoromethyl-hexane,
1,1,1,2,3,3,4,4,5,6,6,6-dodecafluoro-2-propoxy-5-trifluoromethyl-hexane,
1,1,1,2,3,3,4,4,5,6,6,6-dodecafluoro-2-butoxy-5-trifluoromethyl-hexane,
1,1,1,2,3,3,4,4,5,5,6,6,7,7,7-pentadecafluoro-2-methoxy-heptane,
1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-methoxy-3-trifluoromethyl-heptane.

More preferable compounds include those having a total carbon number of 7 or more. These compounds are shown below.
1,1,1,2,3,3,4,4,4-nonafluoro-2-propoxybutane,
1,1,1,2,3,3,4,4,4-nonafluoro-2-butoxy-butane,
1,1,1,2,3,4,4,4-octafluoro-2-ethoxy-3-trifluoromethyl-butane,
1,1,1,2,3,4,4,4-octafluoro-2-propoxy-3-trifluoromethyl-butane,
1,1,1,2,3,4,4,4-octafluoro-2-butoxy-3-trifluoromethyl-butane,
1,1,1,2,3,4,4,4-octafluoro-2,3-bis (ethoxy) butane, 1,1,1,2,3,4,4,4-octafluoro-2 3-bis (propoxy) butane,
1,1,1,2,3,4,4,4-octafluoro-2,3-bis (butoxy) butane,

1,1,1,2,3,3,4,4,5,5,5-undecafluoro-2-ethoxy-pentane,
1,1,1,2,3,3,4,4,5,5,5-undecafluoro-2-propoxy-pentane,
1,1,1,2,3,3,4,4,5,5,5-undecafluoro-2-butoxy-pentane,
1,1,1,2,2,3,4,4,5,5,5-undecafluoro-3-ethoxy-pentane,
1,1,1,2,2,3,4,4,5,5,5-undecafluoro-3-propoxy-pentane,
1,1,1,2,2,3,4,4,5,5,5-undecafluoro-3-butoxy-pentane,
1,1,1,2,3,4,4,5,5,5-decafluoro-2-methoxy-3-trifluoromethyl-pentane,
1,1,1,2,3,4,4,5,5,5-decafluoro-2-ethoxy-3-trifluoromethyl-pentane,
1,1,1,2,3,4,4,5,5,5-decafluoro-2-propoxy-3-trifluoromethyl-pentane,
1,1,1,2,3,4,4,5,5,5-decafluoro-2-butoxy-3-trifluoromethyl-pentane,
1,1,1,2,3,3,4,5,5,5-decafluoro-2-methoxy-4-trifluoromethyl-pentane,
1,1,1,2,3,3,4,5,5,5-decafluoro-2-ethoxy-4-trifluoromethyl-pentane,
1,1,1,2,3,3,4,5,5,5-decafluoro-2-propoxy-4-trifluoromethyl-pentane,
1,1,1,2,3,3,4,5,5,5-decafluoro-2-butoxy-4-trifluoromethyl-pentane,
1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane,
1,1,1,2,2,3,4,5,5,5-decafluoro-3-ethoxy-4-trifluoromethyl-pentane,
1,1,1,2,2,3,4,5,5,5-decafluoro-3-propoxy-4-trifluoromethyl-pentane,
1,1,1,2,2,3,4,5,5,5-decafluoro-3-butoxy-4-trifluoromethyl-pentane,

1,1,1,2,3,3,4,4,5,5,5-undecafluoro-2- (2,2,2-trifluoroethoxy) -pentane,
1,1,1,2,2,3,4,4,5,5,5-undecafluoro-3- (2,2,2-trifluoroethoxy) -pentane,
1,1,1,2,3,4,4,5,5,5-decafluoro-2- (2,2,2-trifluoroethoxy) -3-trifluoromethyl-pentane,
1,1,1,2,3,3,4,5,5,5-decafluoro-2- (2,2,2-trifluoroethoxy) -4-trifluoromethyl-pentane,
1,1,1,2,2,3,4,5,5,5-decafluoro-3- (2,2,2-trifluoroethoxy) -4-trifluoromethyl-pentane,
1,1,2,3,3,4,4,5,5,5-decafluoro-2-ethoxy-pentane,
1,1,2,3,3,4,4,5,5,5-decafluoro-2-propoxy-pentane, 1,1,2,3,3,4,4,5,5,5-deca Fluoro-2-butoxy-pentane,
1,1,2,2,3,4,4,5,5,5-decafluoro-3-ethoxy-pentane,
1,1,2,2,3,4,4,5,5,5-decafluoro-3-propoxy-pentane, 1,1,2,2,3,4,4,5,5,5-deca Fluoro-3-butoxy-pentane,

1,1,2,3,4,4,5,5,5-nonafluoro-2-methoxy-3-trifluoromethyl-pentane,
1,1,2,3,4,4,5,5,5-nonafluoro-2-ethoxy-3-trifluoromethyl-pentane,
1,1,2,3,4,4,5,5,5-nonafluoro-2-propoxy-3-trifluoromethyl-pentane,
1,1,2,3,4,4,5,5,5-nonafluoro-2-butoxy-3-trifluoromethyl-pentane,
1,1,2,3,3,4,5,5,5-nonafluoro-2-methoxy-4-trifluoromethyl-pentane,
1,1,2,3,3,4,5,5,5-nonafluoro-2-ethoxy-4-trifluoromethyl-pentane,
1,1,2,3,3,4,5,5,5-nofluoro-2-propoxy-4-trifluoromethyl-pentane,
1,1,2,3,3,4,5,5,5-nonafluoro-2-butoxy-4-trifluoromethyl-pentane,
1,1,2,2,3,4,5,5,5-nonafluoro-3-methoxy-4-trifluoromethyl-pentane,
1,1,2,2,3,4,5,5,5-nonafluoro-3-ethoxy-4-trifluoromethyl-pentane,
1,1,2,2,3,4,5,5,5-nonafluoro-3-propoxy-4-trifluoromethyl-pentane,
1,1,2,2,3,4,5,5,5-nonafluoro-3-butoxy-4-trifluoromethyl-pentane,

1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluoro-2-methoxy-hexane,
1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluoro-2-ethoxy-hexane,
1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluoro-2-propoxy-hexane,
1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluoro-2-butoxy-hexane,
1,1,1,2,2,3,4,4,5,5,6,6,6-tridecafluoro-3-methoxy-hexane,
1,1,1,2,2,3,4,4,5,5,6,6,6-tridecafluoro-3-ethoxy-hexane,
1,1,1,2,2,3,4,4,5,5,6,6,6-tridecafluoro-3-propoxy-hexane,
1,1,1,2,2,3,4,4,5,5,6,6,6-tridecafluoro-3-butoxy-hexane,
1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-methoxy-3-trifluoromethyl-hexane,
1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-ethoxy-3-trifluoromethyl-hexane,
1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-propoxy-3-trifluoromethyl-hexane,
1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-butoxy-3-trifluoromethyl-hexane,
1,1,1,2,3,3,4,5,5,6,6,6-dodecafluoro-2-methoxy-4-trifluoromethyl-hexane,
1,1,1,2,3,3,4,5,5,6,6,6-dodecafluoro-2-ethoxy-4-trifluoromethyl-hexane,
1,1,1,2,3,3,4,5,5,6,6,6-dodecafluoro-2-propoxy-4-trifluoromethyl-hexane,
1,1,1,2,3,3,4,5,5,6,6,6-dodecafluoro-2-butoxy-4-trifluoromethyl-hexane,
1,1,1,2,3,3,4,4,5,6,6,6-dodecafluoro-2-methoxy-5-trifluoromethyl-hexane,
1,1,1,2,3,3,4,4,5,6,6,6-dodecafluoro-2-ethoxy-5-trifluoromethyl-hexane,
1,1,1,2,3,3,4,4,5,6,6,6-dodecafluoro-2-propoxy-5-trifluoromethyl-hexane,
1,1,1,2,3,3,4,4,5,6,6,6-dodecafluoro-2-butoxy-5-trifluoromethyl-hexane,
1,1,1,2,3,3,4,4,5,5,6,6,7,7,7-pentadecafluoro-2-methoxy-heptane,
1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-methoxy-3-trifluoromethyl-heptane.

The compound represented by the general formula (1) can be synthesized by a method known per se.
The compound represented by the general formula (1) may be used alone or in combination of two or more. The proportion of the compound represented by the general formula (1) in the non-aqueous solvent is usually 0.001% by volume or more, preferably 0.1% by volume or more, more preferably 0.2% by volume or more, particularly preferably 0. .25% by volume or more. If the concentration is lower than this, the effects of the present invention may be difficult to express. On the other hand, if the concentration is too high, the storage characteristics of the battery may deteriorate, so the upper limit is usually less than 2% by volume, preferably 1.8% by volume or less, more preferably 1.5% by volume or less.

  Further, when the non-aqueous electrolyte contains cyclic carbonates having an unsaturated bond, the ratio of the compound represented by the general formula (1) in the non-aqueous solvent is usually 0.001% by volume or more, Preferably it is 0.1 volume% or more, More preferably, it is 0.2 volume% or more, Most preferably, it is 0.25 volume% or more. If the concentration is lower than this, the effects of the present invention may be difficult to express. On the other hand, if the concentration is too high, it may not be uniformly compatible in the electrolytic solution or the storage characteristics of the battery may deteriorate. Therefore, the upper limit is usually less than 10% by volume, preferably 5% by volume or less, more preferably. Is 3% by volume or less, more preferably 2% by volume or less, and particularly preferably 1.5% by volume or less.

  When the non-aqueous electrolyte solution according to the present invention is used, the reason why the storage characteristics of the non-aqueous electrolyte secondary battery are excellent is not clear, and the present invention is not limited to the following operation principle, The compound represented by the formula (1) partially reacts on the negative electrode and the positive electrode in a charged state to form a fluorine-containing film, and this film is in contact with other electrolyte components and electrode activity even in a high temperature atmosphere. It is considered that side reactions with substances can be suppressed, and as a result, side reactions occurring inside the battery during high temperature storage can be suppressed and storage characteristics can be improved.

Furthermore, the electrolytic solution containing the compound represented by the general formula (1) has a good affinity with the electrode layer, improves the impregnation property of the electrolytic solution into the electrode layer, and has the performance originally possessed by the electrode active material. It will be possible to withdraw.
However, the compound represented by the general formula (1) is easy to be reduced as compared with a compound not containing a fluorine atom, and when the addition amount increases, side reactions on the negative electrode side increase, and battery characteristics may deteriorate. is there. When used in combination with a cyclic carbonate having an unsaturated bond, the negative electrode film derived from the cyclic carbonate having an unsaturated bond suppresses an excessive reaction on the negative electrode side of the compound represented by the general formula (1). It is considered that the positive electrode film derived from the compound represented by the formula (1) can suppress an excessive reaction on the positive electrode side of the cyclic carbonate having an unsaturated bond.

(Cyclic carbonates having an unsaturated bond)
Since cyclic carbonates having an unsaturated bond form a protective film on the surface of the negative electrode, the cycle characteristics of the battery can be improved.
Examples of cyclic carbonates having an unsaturated bond include vinylene carbonate, methyl vinylene carbonate, ethyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, 4,5-diethyl vinylene carbonate, fluorovinylene carbonate, trifluoromethyl vinylene carbonate, and the like. Vinylene carbonate compounds; vinyl ethylene carbonate, 4-methyl-4-vinylethylene carbonate, 4-ethyl-4-vinylethylene carbonate, 4-n-propyl-4-vinylethylene carbonate, 5-methyl-4-vinylethylene carbonate , 4,4-divinylethylene carbonate, vinylethylene carbonate such as 4,5-divinylethylene carbonate; 4,4-dimethyl-5-methyleneethylene car Sulfonates, such as methylene ethylene carbonate compounds such as 4,4-diethyl-5-methylene ethylene carbonate. Among these, vinylene carbonate, vinyl ethylene carbonate, 4-methyl-4-vinyl ethylene carbonate or 4,5-divinyl ethylene carbonate is preferable from the viewpoint of improving cycle characteristics, and among them, vinylene carbonate or vinyl ethylene carbonate is more preferable. Vinylene carbonate is preferred. These may be used alone or in combination of two or more.

When using 2 or more types together, it is preferable to use together vinylene carbonate and vinyl ethylene carbonate.
When the non-aqueous electrolyte contains a cyclic carbonate having an unsaturated bond, the proportion of the cyclic carbonate having an unsaturated bond in the non-aqueous electrolyte is not particularly limited in order to exhibit the effects of the present invention, but the lower limit. Is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, particularly preferably 0.3% by weight or more, and most preferably 0.5% by weight or more. The upper limit is preferably 8% by weight or less, more preferably 4% by weight or less, and particularly preferably 3% by weight or less.

  In addition, the cyclic carbonate having an unsaturated bond in the molecule is likely to react with the charged positive electrode material, and if the electrolyte contains the cyclic carbonate having an unsaturated bond, the amount of gas generated may increase during high-temperature storage. In some cases, sufficient battery characteristics may not be obtained, but when used in combination with the compound represented by the general formula (1), side reactions with the positive electrode material can be suppressed, and both improvement of cycle characteristics and suppression of gas generation can be achieved. Is particularly preferable.

(Other compounds)
The non-aqueous electrolyte solution according to the present invention may contain various other compounds such as a conventionally known overcharge inhibitor as an auxiliary agent as long as the effects of the present invention are not impaired.
As an overcharge inhibitor, aromatic compounds such as biphenyl, alkylbiphenyl such as 2-methylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran, etc. A partially fluorinated product of the aromatic compound such as 2-fluorobiphenyl, 3-fluorobiphenyl, 4-fluorobiphenyl, o-cyclohexylfluorobenzene, p-cyclohexylfluorobenzene; 2,4-difluoroanisole, 2,5-difluoro; Examples thereof include fluorine-containing anisole compounds such as anisole, 2,6-difluoroanisole and 3,5-difluoroanisole.

  Of these, aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, and dibenzofuran are preferable. Two or more of these may be used in combination. When two or more types are used in combination, in particular, a combination of cyclohexylbenzene and t-butylbenzene or t-amylbenzene, biphenyl, alkylbiphenyl, terphenyl, terphenyl partially hydrogenated product, cyclohexylbenzene, t-butylbenzene The balance between overcharge prevention characteristics and high-temperature storage characteristics is obtained by using a combination selected from oxygen-free aromatic compounds such as t-amylbenzene and oxygen-containing aromatic compounds such as diphenyl ether and dibenzofuran. From the point of view, it is preferable.

The proportion of the overcharge inhibitor in the non-aqueous electrolyte is usually 0.1% by weight or more, preferably 0.2% by weight or more, particularly preferably 0.3% by weight or more, and most preferably 0.5% by weight or more. The upper limit is usually 5% by weight or less, preferably 3% by weight or less, and particularly preferably 2% by weight or less. When the concentration is lower than this lower limit, the effect of the overcharge inhibitor hardly appears.
Other auxiliaries include carbonates such as fluoroethylene carbonate, difluoroethylene carbonate, trifluoroethylene carbonate, tetrafluoroethylene carbonate, trifluoropropylene carbonate, erythritan carbonate, spiro-bis-dimethylene carbonate, and methoxyethyl-methyl carbonate. Compound: succinic anhydride, glutaric anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, glutaconic anhydride, diglycolic anhydride, cyclohexanedicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride and phenylsuccinic anhydride Carboxylic acid anhydrides such as 2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-divinyl-2,4,8,10-tetraoxaspiro [5.5 Spiro compounds such as undecane; ethylene sulfite, propylene sulfite, 1,3-propane sultone, 1,4-butane sultone, 1,3-propene sultone, 1,4-butene sultone, methyl methane sulfonate, ethyl methane sulfonate, methyl- Methoxymethanesulfonate, methyl-2-methoxyethanesulfonate, busulfan, diethylene glycol dimethanesulfonate, 1,2-ethanediol bis (2,2,2-trifluoroethanesulfonate), 1,4-butanediol bis (2,2 , 2-trifluoroethanesulfonate), sulfolane, sulfolene, dimethylsulfone, diphenylsulfone, N, N-dimethylmethanesulfonamide, N, N-diethylmethanesulfonamide, and other sulfur-containing compounds; Nitrogen-containing compounds such as til-2-pyrrolidinone, 1-methyl-2-piperidone, 3-methyl-2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone and N-methylsuccinimide; heptane, octane, Nonane, decane, cycloheptane, methylcyclohexane, ethylcyclohexane, propylcyclohexane, n-butylcyclohexane, t-butylcyclohexane, dicyclohexyl and other hydrocarbon compounds, fluorobenzene, difluorobenzene, hexafluorobenzene fluorinated benzene, etc. . Two or more of these may be used in combination.

  The ratio of these auxiliaries in the non-aqueous electrolyte solution is not particularly limited in order to exhibit the effects of the present invention, but is usually 0.01% by weight or more, preferably 0.1% by weight or more, particularly preferably. Is 0.2% by weight or more, and the upper limit is usually 5% by weight or less, preferably 3% by weight or less, particularly preferably 1% by weight or less. By adding these auxiliaries, capacity maintenance characteristics and cycle characteristics after high temperature storage can be improved. If the concentration is lower than this lower limit, the effect of the auxiliary agent may be hardly exhibited. On the other hand, if the concentration is too high, battery characteristics such as high load discharge characteristics may deteriorate.

(Preparation of electrolyte)
The nonaqueous electrolytic solution according to the present invention can be prepared by dissolving an electrolyte, a compound represented by the general formula (1), and other compounds as required in a nonaqueous solvent. In preparing the non-aqueous electrolyte solution, each raw material is preferably dehydrated in advance in order to reduce the water content when the electrolyte solution is used. Usually, it is good to dehydrate to 50 ppm or less, preferably 30 ppm or less, particularly preferably 10 ppm or less. Moreover, you may implement dehydration, a deoxidation process, etc. after electrolyte solution preparation.
The non-aqueous electrolyte of the present invention is suitable for use as a secondary battery among non-aqueous electrolyte batteries, that is, as an electrolyte for a non-aqueous electrolyte secondary battery, for example, a lithium secondary battery. Hereinafter, a non-aqueous electrolyte secondary battery using the electrolyte of the present invention will be described.

<Non-aqueous electrolyte secondary battery>
The non-aqueous electrolyte secondary battery of the present invention is a non-aqueous electrolyte battery including a negative electrode and a positive electrode capable of inserting and extracting lithium ions, and a non-aqueous electrolyte, and the non-aqueous electrolyte is the above-described electrolyte. It is characterized by being.
(Battery configuration)
A non-aqueous electrolyte secondary battery according to the present invention is similar to a conventionally known non-aqueous electrolyte secondary battery except that it is prepared using the above-described electrolyte of the present invention. A non-aqueous electrolyte battery including a positive electrode and a non-aqueous electrolyte, usually obtained by housing the positive electrode and the negative electrode in a case through a porous membrane impregnated with the non-aqueous electrolyte according to the present invention. . Therefore, the shape of the secondary battery according to the present invention is not particularly limited, and may be any of a cylindrical shape, a square shape, a laminate shape, a coin shape, a large size, and the like.

(Negative electrode)
As the negative electrode active material, a carbonaceous material or metal compound capable of inserting and extracting lithium, a lithium metal, a lithium alloy, or the like can be used. These negative electrode active materials may be used alone or in combination of two or more. Among these, preferred are carbonaceous materials and metal compounds capable of occluding and releasing lithium.
Among the carbonaceous materials, graphite and graphite whose surface is coated with amorphous carbon as compared with graphite are particularly preferable.
The graphite preferably has a lattice plane (002 plane) d value (interlayer distance) of 0.335 to 0.338 nm, particularly 0.335 to 0.337 nm, as determined by X-ray diffraction using the Gakushin method. The crystallite size (Lc) determined by X-ray diffraction by the Gakushin method is usually 30 nm or more, preferably 50 nm or more, and particularly preferably 100 nm or more. The ash content is usually 1% by weight or less, preferably 0.5% by weight or less, particularly preferably 0.1% by weight or less.

  The graphite surface coated with amorphous carbon is preferably graphite having a d-value of 0.335 to 0.338 nm on the lattice plane (002 plane) in X-ray diffraction as a core material. A carbonaceous material having a larger d-value on the lattice plane (002 plane) in X-ray diffraction than the core material is attached, and the d-value on the lattice plane (002 plane) in X-ray diffraction is greater than that of the core material and the core material. The ratio with respect to the carbonaceous material having a large is 99/1 to 80/20 by weight. When this is used, a negative electrode having a high capacity and hardly reacting with the electrolytic solution can be produced.

The particle size of the carbonaceous material is a median diameter by a laser diffraction / scattering method, and is usually 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, most preferably 7 μm or more, and usually 100 μm or less, preferably 50 μm or less, More preferably, it is 40 micrometers or less, Most preferably, it is 30 micrometers or less.
The specific surface area of the carbonaceous material by the BET method is usually 0.3 m ² / g or more, preferably 0.5
m ² / g or more, more preferably 0.7 m ² / g or more, and most preferably 0.8 m ² / g or more and usually 25.0 m ² / g or less, preferably 20.0 m ² / g, more Preferably it is 15.0 m < ² > / g or less, Most preferably, it is 10.0 m < ² > / g or less.

Further, the carbonaceous material is analyzed by Raman spectrum using argon ion laser light, the peak is the peak intensity of the peak P _A in the range of 1570~1620cm ^-1 I _A, in the range of 1300~1400cm ^-1 P If the peak intensity of the _B was I _B, R value represented by the ratio of I _B and _{I a (= I B / I} a) is what is preferably in the range of 0.01 to 0.7. Further, the half width of the peak in the range of 1570～1620Cm ^-1 is, 26cm ^-1 or less, are preferred in particular 25 cm ^-1 or less.

  Examples of metal compounds capable of inserting and extracting lithium include compounds containing metals such as Ag, Zn, Al, Ga, In, Si, Ge, Sn, Pb, P, Sb, Bi, Cu, Ni, Sr, and Ba. These metals are used as simple substances, oxides, alloys with lithium, and the like. In the present invention, those containing an element selected from Si, Sn, Ge and Al are preferred, and oxides or lithium alloys of metals selected from Si, Sn and Al are more preferred. These may be in the form of powder or thin film, and may be crystalline or amorphous.

Lithium is a metal compound that can occlude and release lithium, or its oxides and alloys with lithium generally have higher capacity per unit weight than carbonaceous materials typified by graphite. It is suitable for a secondary battery.
The average grain system of the metal compound capable of occluding and releasing lithium or an oxide thereof or an alloy with lithium is not particularly limited in order to exhibit the effects of the present invention, but is usually 50 μm or less, preferably 20 μm or less, It is particularly preferably 10 μm or less, usually 0.1 μm or more, preferably 1 μm or more, particularly preferably 2 μm or more. When this upper limit is exceeded, the expansion of the electrode increases, and the cycle characteristics may deteriorate. Moreover, when less than this minimum, it becomes difficult to collect current and there is a possibility that the capacity is not sufficiently developed.

(Positive electrode)
Examples of the positive electrode active material include materials capable of inserting and extracting lithium, such as lithium transition metal composite oxide materials such as lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide. These compounds include Li _X CoO ₂ , Li _X NiO ₂ , Li _X MnO ₂ , Li _X Co _{1- y My} O ₂ , Li _X Ni _{1- y My} O ₂ , Li _X Mn _{1- y My} O ₂ or the like, where M is usually at least one selected from Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, V, Sr, and Ti. , and those that are 0.4 ≦ x ≦ 1.2,0 ≦ y ≦ 0.6, Li X Mn a Ni b Co c O 2 ( where, 0.4 ≦ x ≦ 1.2, a + b + c = 1) Is mentioned.

Especially represented by _{Li X Co 1-y M y} O 2, Li X Ni 1-y M y O 2, Li X Mn 1-y M y O 2 , etc., cobalt, nickel, and other part of manganese Li _x Mn _a Ni _b Co _c O ₂ (where 0.4 ≦ x ≦ 1.2, a + b + c = 1, | ab | <0.
The compound represented by 1) is preferable because the structure can be stabilized.
The positive electrode active materials may be used alone or in combination.

  In addition, a material in which a substance having a composition different from that of the substance constituting the main cathode active material is attached to the surface of the cathode active material can be used. Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate And sulfates such as aluminum sulfate and carbonates such as lithium carbonate, calcium carbonate and magnesium carbonate.

  The amount of the surface adhering substance is not particularly limited in order to exhibit the effect of the present invention, but is preferably 0.1 ppm or more, more preferably 1 ppm or more as a lower limit by mass with respect to the positive electrode active material, The upper limit is preferably 10 ppm or more, preferably 20% or less, more preferably 10% or less, still more preferably 5% or less. The surface adhering substance can suppress the oxidation reaction of the non-aqueous electrolyte solution on the surface of the positive electrode active material, and can improve the battery life. However, when the amount of the adhering quantity is too small, the effect is not sufficiently exhibited. If the amount is too large, the resistance may increase in order to inhibit the entry and exit of lithium ions.

(electrode)
As the binder for binding the active material, any material can be used as long as it is a material that is stable with respect to the solvent and the electrolyte used in manufacturing the electrode. For example, fluororesins such as polyvinylidene fluoride and polytetrafluoroethylene, polyolefins such as polyethylene and polypropylene, polymers having unsaturated bonds such as styrene / butadiene rubber, isoprene rubber and butadiene rubber, and copolymers thereof, ethylene / acrylic Examples thereof include acrylic acid polymers such as acid copolymers and ethylene / methacrylic acid copolymers, and copolymers thereof.

The electrode may contain a thickener, a conductive material, a filler, etc. in order to increase mechanical strength and electrical conductivity.
Examples of the thickener include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, and casein.

Examples of the conductive material include a metal material such as copper or nickel, and a carbon material such as graphite or carbon black.
The electrode may be manufactured by a conventional method. For example, it can be formed by adding a binder, a thickener, a conductive material, a solvent or the like to a negative electrode or a positive electrode active material to form a slurry, applying the slurry to a current collector, drying it, and then pressing it.

In addition, a material obtained by adding a binder or a conductive material to an active material is roll-formed as it is to form a sheet electrode, a pellet electrode is formed by compression molding, and an electrode is formed on the current collector by a technique such as vapor deposition, sputtering, or plating. A thin film of material can also be formed.
When graphite is used as the negative electrode active material, the density of the negative electrode active material layer after drying and pressing is usually 1.45 g / cm ³ or more, preferably 1.55 g / cm ³ or more, particularly preferably 1.60 g. / Cm ³ or more.

Further, the density after drying and pressing of the positive electrode active material layer is usually 2.0 g / cm ³ or more, preferably 3.0 g / cm ³ or more.
Various types of current collectors can be used, but metals and alloys are usually used. Examples of the current collector for the negative electrode include copper, nickel, and stainless steel, with copper being preferred. Examples of the positive electrode current collector include metals such as aluminum, titanium, and tantalum, and alloys thereof, and aluminum or an alloy thereof is preferable.

(Separator, exterior body)
A porous film (separator) is interposed between the positive electrode and the negative electrode to prevent a short circuit. In this case, the electrolytic solution is used by impregnating the porous membrane. The material and shape of the porous film are not particularly limited as long as it is stable to the electrolytic solution and excellent in liquid retention, and a porous sheet or nonwoven fabric made of polyolefin such as polyethylene and polypropylene is preferable.
The material of the battery casing used in the battery according to the present invention is also arbitrary, and nickel-plated iron, stainless steel, aluminum or an alloy thereof, nickel, titanium, a laminate film, or the like is used.
The operating voltage of the non-aqueous electrolyte secondary battery of the present invention described above is usually in the range of 2V to 6V.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.
In addition, each evaluation method of the battery obtained by the following Example and the comparative example is shown below.
[Capacity evaluation]
The non-aqueous electrolyte secondary battery is charged to 4.2 V at a constant current corresponding to 0.2 C at 25 ° C. in a state of being sandwiched between glass plates in order to enhance the adhesion between the electrodes, and then 0.2 C The battery was discharged to 3 V at a constant current of. This is done for 3 cycles to stabilize the battery. In the 4th cycle, after charging to 4.2V with a constant current of 0.5C, charging is carried out until the current value reaches 0.05C with a constant voltage of 4.2V. The initial discharge capacity was determined by discharging to 3 V at a constant current of 0.2C.
Here, 1C represents a current value for discharging the reference capacity of the battery in one hour, and 0.2C represents a current value of 1/5 thereof.

[Evaluation of high-temperature storage characteristics]
The battery for which the capacity evaluation test has been completed is charged to 4.2 V at a constant current of 0.5 C at 25 ° C., and then charged to a current value of 0.05 C at a constant voltage of 4.2 V, and then at 85 ° C. Stored for 1 day. Next, after discharging to 25V at a constant current of 0.2C to 3V, charging to 4.2V at a constant current of 0.5C, charging until a current value of 0.05V at a constant voltage of 4.2V It was carried out, discharged to 3 V at a constant current of 1 C, and the 1 C discharge capacity after the storage test was measured. The ratio of the 1C discharge capacity after storage to the initial discharge capacity was determined, and this was defined as the 1C discharge capacity (%) after high temperature storage.

(Example 1)
[Manufacture of negative electrode]
The d-value of the lattice plane (002 plane) in X-ray diffraction is 0.336 nm, the crystallite size (Lc) is 652 nm, the ash content is 0.07 wt%, the median diameter by laser diffraction / scattering method is 12 μm, and the ratio by BET method The half-value width of a peak whose surface area is 7.5 m ² / g and R value (= I _B / I _A ) determined from Raman spectrum analysis using argon ion laser light is 0.12, 1570 to 1620 cm ^−1. Was mixed with 94 parts by weight of natural graphite powder having a weight of 19.9 cm ⁻¹ and 6 parts by weight of polyvinylidene fluoride, and N-methyl-2-pyrrolidone was added to form a slurry. This slurry was uniformly applied to one side of a 12 μm thick copper foil, dried, and then pressed so that the density of the negative electrode active material layer was 1.65 g / cm ³ to obtain a negative electrode.

[Production of positive electrode]
90 parts by weight of LiCoO ₂ , 4 parts by weight of carbon black and 6 parts by weight of polyvinylidene fluoride (manufactured by Kureha Chemical Co., Ltd., trade name “KF-1000”) are mixed, and N-methyl-2-pyrrolidone is added to form a slurry. After uniformly applying and drying on both surfaces of a 15 μm thick aluminum foil, the positive electrode active material layer was pressed to a density of 3.0 g / cm ³ to obtain a positive electrode.

[Manufacture of electrolyte]
Ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane in a dry argon atmosphere LiPF ₆ which was sufficiently dried in the mixture (volume ratio 20: 40: 39: 1) was dissolved at a ratio of 1.0 mol / liter to obtain an electrolytic solution.

[Manufacture of lithium secondary batteries]
The positive electrode, the negative electrode, and the polyethylene separator were laminated in the order of the negative electrode, the separator, the positive electrode, the separator, and the negative electrode to produce a battery element. The battery element was inserted into a bag made of a laminate film in which both surfaces of aluminum (thickness: 40 μm) were coated with a resin layer while projecting positive and negative terminals, and then the electrolyte was poured into the bag and vacuum sealed. Then, a sheet-like lithium secondary battery was produced, and the high-temperature storage characteristics were evaluated. The evaluation results are shown in Table 1.

(Example 2)
Mixture of ethylene carbonate, diethyl carbonate, ethyl methyl carbonate and 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane (volume ratio 20 : 40: 38.5: 1.5), except that an electrolyte prepared by dissolving LiPF ₆ sufficiently dried at a ratio of 1.0 mol / liter was used. A sheet-like lithium secondary battery was prepared and the high-temperature storage characteristics were evaluated. The evaluation results are shown in Table 1.

(Example 3)
Mixture of ethylene carbonate, diethyl carbonate, ethyl methyl carbonate and 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane (volume ratio 20 : 40: 38.5: 1.5) 2 parts by weight of vinylene carbonate was mixed with 98 parts by weight, and sufficiently dried LiPF ₆ was dissolved to a ratio of 1.0 mol / liter. A sheet-like lithium secondary battery was produced in the same manner as in Example 1 except that the electrolytic solution was used, and the high-temperature storage characteristics were evaluated. The evaluation results are shown in Table 1.

Example 4
Mixture of ethylene carbonate, diethyl carbonate, ethyl methyl carbonate and 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane (volume ratio 20 : 40: 35: 5) An electrolyte prepared by mixing 2 parts by weight of vinylene carbonate with 98 parts by weight and dissolving LiPF ₆ sufficiently dried to a ratio of 1.0 mol / liter is used. Except that, a sheet-like lithium secondary battery was produced in the same manner as in Example 1, and the high-temperature storage characteristics were evaluated. The evaluation results are shown in Table 1.

(Example 5)
In the electrolytic solution of Example 3, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane was replaced with 1,1,1, A sheet-like lithium secondary battery was produced in the same manner as in Example 3 except that 1,2,2,3,4,5,5,5-decafluoro-3-ethoxy-4-trifluoromethyl-pentane was used. The high-temperature storage characteristics were evaluated. The evaluation results are shown in Table 1.

(Example 6)
In the electrolytic solution of Example 3, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane was replaced with 1,1,1, A sheet-like lithium secondary battery was produced in the same manner as in Example 3, except that 1,2,2,3,4,5,5,5-decafluoro-3-propoxy-4-trifluoromethyl-pentane was used. The high-temperature storage characteristics were evaluated. The evaluation results are shown in Table 1.

(Comparative Example 1)
An electrolyte prepared by dissolving LiPF ₆ sufficiently dried in a mixture of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate (volume ratio 20:40:40) to a ratio of 1.0 mol / liter was used. Except for the above, a sheet-like lithium secondary battery was produced in the same manner as in Example 1, and the high-temperature storage characteristics were evaluated. The evaluation results are shown in Table 1.

(Comparative Example 2)
Mixture of ethylene carbonate, diethyl carbonate, ethyl methyl carbonate and 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane (volume ratio 20 : 40: 35: 5) LiPF ₆ sufficiently dried to 1
. A sheet-like lithium secondary battery was produced in the same manner as in Example 1 except that an electrolytic solution prepared by dissolving at a rate of 0 mol / liter was used, and the high-temperature storage characteristics were evaluated. The evaluation results are shown in Table 1.

(Comparative Example 3)
98 parts by weight of a mixture of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate (volume ratio 20:40:40) was mixed with 2 parts by weight of vinylene carbonate, and then sufficiently dried LiPF ₆ was added at 1.0 mol / liter. A sheet-like lithium secondary battery was produced in the same manner as in Example 1 except that an electrolytic solution prepared by dissolving at a ratio was used, and the high-temperature storage characteristics were evaluated. The evaluation results are shown in Table 1.

(Comparative Example 4)
Mixture of ethylene carbonate, diethyl carbonate, ethyl methyl carbonate and 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane (volume ratio 20 : 40:30:10) 2 parts by weight of vinylene carbonate was mixed with 98 parts by weight, and LiPF ₆ sufficiently dried was dissolved at a ratio of 1.0 mol / liter to prepare an electrolytic solution. The phase was separated and could not be evaluated.

  As is clear from Table 1, it can be seen that the battery according to the present invention is excellent in battery characteristics after high-temperature storage.

Claims (3)

In a non-aqueous electrolyte solution containing an electrolyte and a non-aqueous solvent that dissolves the electrolyte, the non-aqueous electrolyte solution contains 0.001% by volume or more and less than 2% by volume of the compound represented by the following general formula (1) A non-aqueous electrolyte characterized by containing.

(In General Formula (1), R ¹ and R ² each independently have an ether bond in the structure, and may be substituted with a fluorine atom. R ³ represents an alkyl group having 1 to 12 carbon atoms which may be substituted with a fluorine atom.) In a non-aqueous electrolyte solution containing an electrolyte and a non-aqueous solvent that dissolves the electrolyte, the non-aqueous electrolyte solution contains 0.001% by volume or more and less than 10% by volume of the compound represented by the following general formula (1) in the non-aqueous solvent. A non-aqueous electrolytic solution containing a cyclic carbonate having an unsaturated bond in the electrolytic solution.

(In the general formula (1), R ¹ , R ² and R ³ are as defined above.)   A non-aqueous electrolyte battery comprising a negative electrode and a positive electrode capable of inserting and extracting lithium ions, and a non-aqueous electrolyte solution, wherein the non-aqueous electrolyte solution is the non-aqueous electrolyte solution according to claim 1 or 2. A non-aqueous electrolyte battery.