JP2022042755A - Nonaqueous electrolyte and nonaqueous electrolyte battery including the same - Google Patents

Abstract

To provide a nonaqueous electrolyte excellent in balance between the suppressing effect of gas generation during initial charge/discharge and battery capacity after high-temperature storage.SOLUTION: There are provided: a nonaqueous electrolyte containing (I) a compound represented by the following general formula (1), (II) a solute, and (III) a nonaqueous solvent; and a nonaqueous electrolyte battery. [In the general formula (1), Y represents a sulfur atom, a phosphorus atom or a carbon atom. When Y represents a sulfur atom, a=2 and b=1, when Y represents a phosphorus atom, a=1 and b=2, and when Y represents a carbon atom, a=1 and b=1. Z represents a 1-12C chain aliphatic hydrocarbon group, and any hydrogen atom of the chain aliphatic hydrocarbon group may be substituted with a fluorine atom. A plurality of R's each independently represent a fluorine atom, a 1-10C alkoxy group, a 2-10C alkenyloxy group, a 2-10C alkynyloxy group, a 6-15C aryloxy group or OLi. When b is 2, the plurality of R's may be the same or different.]SELECTED DRAWING: None

Description

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

In recent years, in batteries, which are electrochemical devices, information-related equipment and communication equipment, that is, power storage systems for small and high energy density applications such as personal computers, video cameras, digital cameras, mobile phones, and smartphones, electric vehicles, and hybrid vehicles. , Fuel cell vehicle auxiliary power supply, energy storage system for large-scale, power applications such as power storage are attracting attention. One of the candidates is non-aqueous electrolyte batteries such as lithium-ion batteries, which have high energy density and voltage and high capacity, and are currently being actively researched and developed.

Non-aqueous electrolytes used in non-aqueous electrolyte batteries include lithium hexafluorophosphate (hereinafter also referred to as LiPF ₆ ) and bis (fluorosulfonylimide) as solutes in solvents such as cyclic carbonates, chain carbonates, and esters. A non-aqueous electrolyte solution in which a fluorine-containing electrolyte such as lithium (hereinafter also referred to as FSI) and lithium tetrafluoroborate (hereinafter also referred to as LiBF ₄ ) is dissolved is suitable for obtaining a high voltage and high capacity battery. It is often used because of its existence. However, a non-aqueous electrolyte battery using such a non-aqueous electrolytic solution is not always satisfactory in terms of battery characteristics such as cycle characteristics and output characteristics.

For example, in the case of a lithium ion secondary battery, when a lithium cation is inserted into the negative electrode at the time of initial charging, the negative electrode and the lithium cation, or the negative electrode and the electrolytic solution solvent react with each other, and lithium oxide, lithium carbonate, or alkyl carbonate are formed on the surface of the negative electrode. It forms a film containing lithium as the main component. The film on the surface of the electrode is called Solid Electrolyte Interface (SEI), and its properties such as further suppressing the reductive decomposition of the solvent and suppressing the deterioration of the battery performance have a great influence on the battery performance. Similarly, a film of decomposition products is formed on the surface of the positive electrode, which is also known to play an important role in suppressing oxidative decomposition of the solvent and suppressing gas generation inside the battery.

In order to improve durability such as cycle characteristics and high temperature storage characteristics, and battery characteristics such as input / output characteristics, it is important to form a stable SEI with high ionic conductivity and low electron conductivity. Therefore, attempts have been made to positively form a good SEI by adding a small amount (usually 0.001% by mass or more and 10% by mass or less) of a compound called an additive to the electrolytic solution.

So far, optimization of various battery components such as active materials for positive and negative electrodes has been studied as a means for improving durability such as cycle characteristics and high temperature storage characteristics of non-aqueous electrolyte batteries. Non-aqueous electrolyte-related technology is no exception, and it has been proposed to suppress deterioration due to decomposition of the non-aqueous electrolyte on the surface of an active positive electrode or negative electrode with various additives. Patent Document 1 proposes to improve each battery property such as high temperature storage property by adding vinylene carbonate to a non-aqueous electrolytic solution. This method is to prevent decomposition on the surface of the non-aqueous electrolytic solution by coating the electrode with a polymer film obtained by polymerizing vinylene carbonate, but there is a problem that a large amount of gas is generated during high temperature storage. In order to solve this problem, the addition of lithium difluorophosphate disclosed in Patent Document 2 is effective, and by using vinylene carbonate and lithium difluorophosphate together, the gas is maintained at high high temperature storage characteristics. It is known that a battery that suppresses the generation of phosphoric acid can be obtained.

Further, by containing a compound having two or more fluorosulfonyl groups in the molecule as a single additive rather than a combination of a plurality of additives in the non-aqueous electrolytic solution, the amount of gas generated in the continuously charged state is small. Patent Document 3 discloses that the battery characteristics are excellent after continuous charging and after high temperature storage.

Japanese Patent No. 3438636 Japanese Patent No. 3439085 Japanese Patent No. 4655536

However, non-aqueous electrolyte batteries having excellent high-temperature storage characteristics while suppressing gas generation are still in demand.

The present invention has been made in view of the above circumstances, and provides a non-aqueous electrolyte solution and a non-aqueous electrolytic solution battery having an excellent balance between the effect of suppressing gas generation at the time of initial charge / discharge and the battery capacity after high temperature storage. The purpose is to do.

In view of this problem, the present inventors have conducted extensive studies on a compound having a difluorophosphonyl group in the molecule and another phosphonyl group in the molecule as an additive in the non-aqueous electrolyte solution, and difluoro in the molecule. By containing a compound having a phosphonyl group and a sulfonyl group or a compound having a difluorophosphonyl group and a carbonyl group in the molecule, the effect of suppressing gas generation at the time of initial charge / discharge and the battery after high temperature storage We have found that a non-aqueous electrolyte battery having an excellent balance with the capacity (hereinafter, also referred to as “high temperature storage characteristic”) can be obtained, and have completed the present invention.

By using the non-aqueous electrolytic solution and the non-aqueous electrolytic solution battery of the present invention, it is possible to improve the efficiency at the time of manufacturing the non-aqueous electrolytic solution battery, and to achieve miniaturization and high capacity of the non-aqueous electrolytic solution battery. ..

Although the mechanism by which the present invention exerts the above effects has not been completely clarified, a compound having a difluorophosphonyl group and another phosphonyl group in the molecule, and a difluorophosphonyl group and a sulfonyl group in the molecule It is considered that the compound having the above or the compound having the difluorophosphonyl group and the carbonyl group in the molecule forms a good film on the electrode.

［一般式（１）中、Ｙは硫黄原子、リン原子、又は炭素原子を表す。Ｙが硫黄原子の場合、a＝２かつb＝１であり、Ｙがリン原子の場合、a＝１かつb＝２であり、Ｙが炭素原子の場合、a＝１かつb＝１である。
Ｚは炭素数１～１２の鎖状脂肪族炭化水素基を表し、当該鎖状脂肪族炭化水素基の任意の水素原子はフッ素原子に置換されていても良い。
Ｒはそれぞれ互いに独立してフッ素原子、炭素数１～１０のアルコキシ基、炭素数２～１０のアルケニルオキシ基、炭素数２～１０のアルキニルオキシ基、炭素数６～１５のアリールオキシ基、又はＯＬｉを表し、当該アルコキシ基、アルケニルオキシ基、アルキニルオキシ基、及びアリールオキシ基中の炭素原子－炭素原子結合間には、酸素原子が含まれていてもよい。また、当該アルコキシ基、アルケニルオキシ基、アルキニルオキシ基、及びアリールオキシ基の任意の水素原子はフッ素原子に置換されていても良い。ｂが２である場合、複数のＲは同一でも異なっていても良い。］ That is, the present inventors have found that the above problems can be solved by the following configurations.
<1>
(I) A compound represented by the following general formula (1),
A non-aqueous electrolytic solution containing (II) a solute and (III) a non-aqueous organic solvent.

[In the general formula (1), Y represents a sulfur atom, a phosphorus atom, or a carbon atom. When Y is a sulfur atom, a = 2 and b = 1, when Y is a phosphorus atom, a = 1 and b = 2, and when Y is a carbon atom, a = 1 and b = 1. ..
Z represents a chain aliphatic hydrocarbon group having 1 to 12 carbon atoms, and any hydrogen atom of the chain aliphatic hydrocarbon group may be substituted with a fluorine atom.
R is a fluorine atom, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, an aryloxy group having 6 to 15 carbon atoms, or an aryloxy group having 6 to 15 carbon atoms, respectively. It represents OLi, and an oxygen atom may be contained between the carbon atom-carbon atom bond in the alkoxy group, the alkenyloxy group, the alkynyloxy group, and the aryloxy group. Further, any hydrogen atom of the alkoxy group, alkenyloxy group, alkynyloxy group, and aryloxy group may be substituted with a fluorine atom. When b is 2, a plurality of Rs may be the same or different. ]

<2>
The non-aqueous electrolytic solution according to <1>, wherein R in the general formula (1) is a fluorine atom.

<3>
The non-aqueous electrolytic solution according to <1>, wherein R in the general formula (1) is an alkynyloxy group having 2 to 10 carbon atoms.

<4>
The non-aqueous electrolytic solution according to any one of <1> to <3>, wherein Z in the general formula (1) is a fluorine-substituted or unsubstituted alkylene group having 1 to 4 carbon atoms.

<5>
The non-aqueous electrolytic solution according to <1>, wherein the compound represented by the general formula (1) is at least one selected from the group consisting of compounds represented by the following formulas (1a) to (1h).

<6>
Item 6. The non-aqueous electrolytic solution according to any one of <1> to <5>, wherein the non-aqueous organic solvent contains at least one selected from the group consisting of cyclic carbonate and chain carbonate.

<7>
The cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate, and the chain carbonate is a group consisting of ethylmethyl carbonate, dimethyl carbonate, diethyl carbonate, and methylpropyl carbonate. The non-aqueous electrolyte solution according to <6>, which is at least one selected from.

<8>
The non-item according to any one of <1> to <7>, wherein the content of (I) is 0.01% by mass to 5.0% by mass with respect to the total amount of (I) to (III). Water electrolyte.

<9>
Further, vinylene carbonate, lithium bis (oxalate) borate, lithium tetrafluorooxalatrate, lithium difluorobis (oxalate) phosphate, lithium fluorosulfonate, bis (fluorosulfonyl) imide lithium, lithium difluorophosphate, 1,3 -Containing at least one selected from the group consisting of propensultone and 1,3-propane sultone in an amount of 0.01% by mass to 5.0% by mass based on the total amount of the non-aqueous electrolytic solution, <1> to The non-aqueous electrolyte solution according to any one of <8>.

<10>
A non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, and the non-aqueous electrolytic solution according to any one of <1> to <9>.

According to the present invention, it is possible to provide a non-aqueous electrolyte solution and a non-aqueous electrolytic solution battery having an excellent balance between the effect of suppressing gas generation at the time of initial charge / discharge and the battery capacity after high temperature storage.

The configurations and combinations thereof in the following embodiments are examples, and the configurations can be added, omitted, replaced, or otherwise modified without departing from the spirit of the present invention. Further, the present invention is not limited to the embodiments, but only to the scope of claims.

In the present specification, "to" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.

In the present specification, the initial charge / discharge time means the first charge / discharge operation for stabilizing the battery. Specifically, it refers to a 10-cycle charge / discharge operation for stabilizing the battery.

[1. Electrolyte for non-water batteries]
The electrolytic solution for a non-aqueous battery of the present invention is a non-aqueous electrolytic solution containing (I) a compound represented by the following general formula (1), (II) a solute, and (III) a non-aqueous organic solvent.

[In the general formula (1), Y represents a sulfur atom, a phosphorus atom, or a carbon atom. When Y is a sulfur atom, a = 2 and b = 1, when Y is a phosphorus atom, a = 1 and b = 2, and when Y is a carbon atom, a = 1 and b = 1. ..
Z represents a chain aliphatic hydrocarbon group having 1 to 12 carbon atoms, and any hydrogen atom of the chain aliphatic hydrocarbon group may be substituted with a fluorine atom.
R is a fluorine atom, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, an aryloxy group having 6 to 15 carbon atoms, or an aryloxy group having 6 to 15 carbon atoms, respectively. It represents OLi, and an oxygen atom may be contained between the carbon atom-carbon atom bond in the alkoxy group, the alkenyloxy group, the alkynyloxy group, and the aryloxy group. Further, any hydrogen atom of the alkoxy group, alkenyloxy group, alkynyloxy group, and aryloxy group may be substituted with a fluorine atom. When b is 2, a plurality of Rs may be the same or different. ]

<(I) About the compound represented by the general formula (1)>
The compound represented by the general formula (1) will be described.
In the general formula (1), Y represents a sulfur atom, a phosphorus atom, or a carbon atom.

In the general formula (1), Z represents a chain aliphatic hydrocarbon group having 1 to 12 carbon atoms.

Examples of the chain aliphatic hydrocarbon group having 1 to 12 carbon atoms represented by Z include a linear or branched alkylene group having 1 to 12 carbon atoms and a linear or carbon having 2 to 12 carbon atoms. Examples thereof include a branched alkaneylene group having a number of 3 to 12, a linear chain having 2 to 12 carbon atoms, a branched alkaneylene group having 3 to 12 carbon atoms, and the like.

Specific examples of the alkylene group in which Z represents an alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a sec-butylene group, a tert-butylene group and an n-pentylene. Groups, -CH ₂ CH (C ₃ H ₇ ) -groups and the like can be mentioned.

Specific examples of the alkenylene group in the case where Z represents an alkenylene group include an ethenylene group and a propenylene group.

Specific examples of the alkynylene group in the case where Z represents an alkynylene group include an ethynylene group and a propynylene group.

In the chain aliphatic hydrocarbon group represented by Z, any hydrogen atom may be substituted with a fluorine atom. Hydrocarbon groups in which any hydrogen atom is replaced with a fluorine atom include a difluoromethylene group, a fluoromethylene group, a tetrafluoroethylene group, a 1,1-difluoroethylene group, a 1,1-difluoropropylene group, and 1,1. Examples thereof include a 2,2-tetrafluoropropylene group, a 1,1-difluorobutylene group and a 1,1,2,2-tetrafluorobutylene group.

Z is preferably a fluorine-substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group, a difluoromethylene group or an ethylene group.

In the general formula (1), R are independently each other, a fluorine atom, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, and 6 to 6 carbon atoms. Represents 15 aryloxy groups, or OLi.

Specific examples of the alkoxy group in the case where R represents an alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group and the like.

Examples of the alkenyloxy group in the case where R represents an alkenyloxy group having 2 to 10 carbon atoms include a vinyloxy group, an allyloxy group, a 2-propenyloxy group, a 2-butenyloxy group and the like.

When R represents an alkynyloxy group having 2 to 10 carbon atoms, the alkynyloxy group includes
Propargyl oxy group and the like can be mentioned.

Examples of the aryloxy group when R represents an aryloxy group having 6 to 15 carbon atoms include a phenyloxy group and a naphthyloxy group.

When R represents an alkoxy group, an alkenyloxy group, an alkynyloxy group, or an aryloxy group, an oxygen atom may be contained between carbon atoms in the group. Specific examples thereof include 2-methoxyethoxy group and 2-ethoxyethoxy group.

When R represents an alkoxy group, an alkenyloxy group, an alkynyloxy group, or an aryloxy group, any hydrogen atom in the group may be substituted with a fluorine atom. Specifically, fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 3-fluoropropoxy group, 3,3,3-trifluoropropoxy group, 2,2. Examples thereof include a 3,3,3-pentafluoropropoxy group, a 2,2,3,3-tetrafluoropropoxy group and a hexafluoroisopropoxy group.

R is preferably a fluorine atom or a hexafluoroisopropoxy group, and more preferably a fluorine atom from the viewpoint of high temperature storage characteristics (particularly in combination with other additives described later).

Further, R is preferably an alkynyloxy group having 2 to 10 carbon atoms, and particularly preferably a propargyloxy group, because the effect of suppressing gas generation at the time of initial charge / discharge is greater.

The compound represented by the general formula (1) is preferably at least one selected from the group consisting of the compounds represented by the above formulas (1a) to (1h). More preferably, it is (1a), (1b), or (1h).

In the non-aqueous electrolytic solution of the present invention, the compound represented by the above general formula (1) is preferably used as an additive.

In the non-aqueous electrolyte solution of the present invention, the content of (I) with respect to the total amount (100% by mass) of the above (I) to (III) is both the amount of gas generated during the initial charge and discharge and the capacity after high temperature storage. From the viewpoint of the above, 0.01% by mass to 5.0% by mass is preferable. It is more preferably 0.2% by mass to 3.0% by mass, and further preferably 0.5% by mass to 2.0% by mass.

As the compound represented by the general formula (1), only one kind may be used, or a plurality of kinds may be used.

The method for synthesizing the compound represented by the general formula [1] is not particularly limited, and an available raw material can be used in combination with ordinary reactions.
For example, the methods described in Chemische Berichte (1980), 113, 142-151. And Z. anorg. Allg. Chem. (1987), 555, 109-117.
Specifically, when R in the above general formula [1] is a fluorine atom, a known fluoride (a known fluoride is used as a raw material in which all the fluorine atoms on the fluorine atom and the phosphorus atom are replaced with chlorine atoms. For example, HF, NaF, KF, etc.) may be used to replace all the chlorine atoms with fluorine atoms.

<(II) Solute>
The non-aqueous electrolyte solution of the present invention contains a solute.
Examples of the solute include at least one cation selected from the group consisting of alkali metal ions and alkaline earth metal ions, hexafluorophosphate anion, tetrafluoroborate anion, trifluoromethanesulfonic acid anion, and fluorosulfonic acid. Anion, bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, (trifluoromethanesulfonyl) (fluorosulfonyl) imide anion, bis (difluorophosphonyl) imide anion, (difluorophosphonyl) (fluorosulfonyl) imide It is preferably an ionic salt consisting of a pair of at least one anion selected from the group consisting of anions and (difluorophosphonyl) (trifluoromethanesulfonyl) imide anions.

The cation of the ionic salt is lithium, sodium, potassium, or magnesium, and the anions are hexafluorophosphate anion, tetrafluoroborate anion, trifluoromethanesulfonic acid anion, bis (trifluoromethanesulfonyl) imide anion, and bis. At least one selected from the group consisting of (fluorosulfonyl) imide anion and bis (difluorophosphonyl) imide anion is preferable from the viewpoint of high solubility in the non-aqueous organic solvent and its electrochemical stability.

The concentration of these solutes is not particularly limited, but the lower limit is preferably 0.5 mol / L or more, more preferably 0.7 mol / L or more, and further preferably 0.9 mol with respect to the total amount of the non-aqueous electrolytic solution. It is / L or more, and the upper limit is preferably in the range of 2.5 mol / L or less, more preferably 2.2 mol / L or less, and further preferably 2.0 mol / L or less. These solutes may be used alone or in combination of two or more.

<(III) Non-aqueous organic solvent>
The type of the non-aqueous organic solvent used in the non-aqueous electrolytic solution of the present invention is not particularly limited, and any non-aqueous organic solvent can be used. Specifically, ethyl methyl carbonate (hereinafter, also referred to as "EMC"), dimethyl carbonate (hereinafter, also referred to as "DMC"), diethyl carbonate (hereinafter, also referred to as "DEC"), methylpropyl carbonate, ethyl. Propyl carbonate, methyl butyl carbonate, 2,2,2-trifluoroethyl methyl carbonate, 2,2,2-trifluoroethyl ethyl carbonate, 2,2,2-trifluoroethylpropyl carbonate, bis (2,2,2) -Trifluoroethyl) carbonate, 1,1,1,3,3,3-hexafluoro-1-propylmethyl carbonate, 1,1,1,3,3,3-hexafluoro-1-propylethyl carbonate, 1 , 1,1,3,3,3-hexafluoro-1-propylpropyl carbonate, bis (1,1,1,3,3,3-hexafluoro-1-propyl) carbonate, ethylene carbonate (hereinafter, "EC" ”), Propylene carbonate (hereinafter, also referred to as“ PC ”), butylene carbonate, fluoroethylene carbonate (hereinafter, also referred to as“ FEC ”), difluoroethylene carbonate, methyl acetate, ethyl acetate, methyl propionate, Ethyl propionate, methyl 2-fluoropropionate, ethyl 2-fluoropropionate, diethyl ether, dibutyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrachloride, furan, tetrahydropyran, 1,3- It is preferably at least one selected from the group consisting of dioxane, 1,4-dioxane, N, N-dimethylformamide, acetonitrile, propionitrile, dimethylsulfoxide, sulfolane, γ-butyrolactone, and γ-valerolactone.
Further, in the present invention, an ionic liquid having a salt structure may be used as the non-aqueous organic solvent.

Further, the non-aqueous organic solvent is preferably at least one selected from the group consisting of cyclic carbonates and chain carbonates, because it is excellent in cycle characteristics at high temperatures. Further, it is preferable that the non-aqueous organic solvent is at least one selected from the group consisting of esters because it is excellent in input / output characteristics at low temperatures.

Specific examples of the cyclic carbonate include EC, PC, butylene carbonate, FEC and the like, and at least one selected from the group consisting of EC, PC and FEC is preferable.

Specific examples of the above chain carbonate include EMC, DMC, DEC, methylpropyl carbonate, ethylpropyl carbonate, 2,2,2-trifluoroethylmethyl carbonate, 2,2,2-trifluoroethylethyl carbonate, 1,1, Examples thereof include 1,3,3,3-hexafluoro-1-propylmethyl carbonate and 1,1,1,3,3,3-hexafluoro-1-propylethyl carbonate, among which EMC, DMC and DEC. And at least one selected from the group consisting of methylpropyl carbonate.

Specific examples of the ester include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, ethyl 2-fluoropropionate and the like.

<About other additives>
As long as the gist of the present invention is not impaired, generally used additive components may be added to the non-aqueous electrolytic solution of the present invention at any ratio. Specific examples of other additives include cyclohexylbenzene, cyclohexylfluorobenzene, fluorobenzene, biphenyl, difluoroanisole, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, 2-fluorobiphenyl, vinylene carbonate, and dimethylvinylene. Carbonate, vinylethylene carbonate, fluoroethylene carbonate, trans-difluoroethylene carbonate, methylpropargyl carbonate, ethylpropargyl carbonate, dipropargyl carbonate, maleic anhydride, succinic anhydride, propanesarton, 1,3-propanesulton, 1,3 -Propensulton, Butansulton, Methylenemethanedisulfonate, Dimethylenemethanedisulfonate, Trimethylenemethanedisulfonate, Methylmethanesulfonate, 1,6-diisosyanatohexane, Tris (trimethylsilyl) borate, Succinonitrile, (ethoxy) Pentafluorocyclotriphosphazene, lithium difluorobis (oxalate) phosphate, sodium difluorobis (oxalate) phosphate, potassium difluorobis (oxalate) phosphate, lithium difluorooxalatoboate, sodium difluorooxalathoate, difluorooxalat Potassium borate, lithium bis (oxalate) borate, sodium bis (oxalate) borate, potassium bis (oxalate) borate, lithium tetrafluorooxalatrate, sodium tetrafluorooxalatrate, tetrafluorooxalatric acid Overcharging of potassium, lithium tris (oxalate) phosphate, lithium difluorophosphate, lithium ethylfluorophosphate, lithium fluorophosphate, ethensulfonylfluoride, trifluoromethanesulfonylfluoride, methanesulfonylfluoride, phenyldifluorophosphate, etc. Examples thereof include compounds having a preventive effect, a negative electrode film forming effect and a positive electrode protection effect.

The content of the other additive in the non-aqueous electrolytic solution is preferably 0.01% by mass or more and 8.0% by mass or less with respect to the total amount of the non-aqueous electrolytic solution.

Further, the ionic salt listed as the solute has a negative electrode film as an "other additive" when the content in the non-aqueous electrolytic solution is smaller than the lower limit of 0.5 mol / L, which is the lower limit of the suitable concentration of the solute. It can exert a forming effect and a positive electrode protection effect. In this case, the content in the non-aqueous electrolytic solution is preferably 0.01% by mass or more and 5.0% by mass or less. Examples of the ionic salt in this case include lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, lithium fluorosulfonate (hereinafter, also referred to as LiSO _3F ). Sodium fluorosulfonate, potassium fluorosulfonate, magnesium fluorosulfonate, bis (trifluoromethanesulfonyl) imide lithium, bis (trifluoromethanesulfonyl) imide sodium, bis (trifluoromethanesulfonyl) imide potassium, bis (trifluoromethanesulfonyl) imide magnesium , Bis (fluorosulfonyl) imide lithium, bis (fluorosulfonyl) imide sodium, bis (fluorosulfonyl) imide potassium, bis (fluorosulfonyl) imide magnesium, (trifluoromethanesulfonyl) (fluorosulfonyl) imide lithium, (trifluoromethanesulfonyl) (Fluorosulfonyl) imide sodium, (trifluoromethanesulfonyl) (fluorosulfonyl) imide potassium, (trifluoromethanesulfonyl) (fluorosulfonyl) imide magnesium, bis (difluorophosphonyl) imide lithium, bis (difluorophosphonyl) imide sodium, bis (Difluorophosphonyl) imide potassium, bis (difluorophosphonyl) imide magnesium, (difluorophosphonyl) (fluorosulfonyl) imide lithium, (difluorophosphonyl) (fluorosulfonyl) imide sodium, (difluorophosphonyl) (fluorosulfonyl) Imopotassium, (difluorophosphonyl) (fluorosulfonyl) imidemagnesium, (difluorophosphonyl) (trifluoromethanesulfonyl) imidelithium, (difluorophosphonyl) (trifluoromethanesulfonyl) imide sodium, (difluorophosphonyl) (trifluoromethanesulfonyl) ) Imidpotassium, (difluorophosphonyl) (trifluoromethanesulfonyl) imidemagnesium and the like.

Further, an alkali metal salt other than the above-mentioned solutes (lithium salt, sodium salt, potassium salt, magnesium salt) may be used as an additive. Specific examples thereof include carboxylates such as lithium acrylate, sodium acrylate, lithium methacrylate and sodium methacrylate, and sulfates such as lithium methyl sulfate, sodium methyl sulfate, lithium ethyl sulfate and sodium ethyl sulfate. ..

Among the above-mentioned other additives, the non-aqueous electrolytic solution of the present invention includes vinylene carbonate, lithium bis (oxalate) borate, lithium tetrafluorooxalatrate, lithium difluorobis (oxalat), lithium fluorosulfonate, and the like. At least one selected from the group consisting of bis (fluorosulfonyl) imide lithium, lithium difluorophosphate, 1,3-propensulton and 1,3-propanesulton, 0.01 mass by mass with respect to the total amount of non-aqueous electrolyte solution. It is preferable to contain% to 5.0% by mass from the viewpoint of improving high temperature storage characteristics. In addition, at least one selected from vinylene carbonate, 1,3-propanesulton, bis (fluorosulfonyl) imide lithium, and lithium difluorophosphate has a high effect of reducing the amount of gas generated during initial charge and discharge. , More preferred.

Further, the non-aqueous electrolytic solution of the present invention may contain a polymer, and the non-aqueous electrolytic solution is pseudo-solidified by a gelling agent or a crosslinked polymer as in the case of being used in a non-aqueous electrolytic solution battery called a polymer battery. It is also possible to use it. Polymer solid electrolytes also include those containing a non-aqueous organic solvent as a plasticizer.

The polymer is not particularly limited as long as it is an aprotic polymer capable of dissolving the compound represented by the general formula (1), the solute and other additives. Examples thereof include polymers having a polyethylene oxide in the main chain or side chains, homopolymers or copolymers of polyvinylidene fluoride, methacrylic acid ester polymers, polyacrylonitrile and the like. When adding a plasticizer to these polymers, the aprotic non-aqueous organic solvent among the above-mentioned non-aqueous organic solvents is preferable.

[2. Non-aqueous electrolyte battery]
The non-aqueous electrolyte battery of the present invention contains a positive electrode and a negative electrode as well as the above-mentioned non-aqueous electrolyte solution of the present invention, and at least (a) the above-mentioned non-aqueous electrolyte solution of the present invention and (b) a positive electrode. , (C) It is preferable to include a negative electrode having at least one selected from the group consisting of a negative electrode material containing a lithium metal and a negative electrode material capable of storing and releasing lithium, sodium, potassium, or magnesium. Further, it is preferable to include (d) a separator, an exterior body and the like.

<(A) Positive electrode>
(A) The positive electrode preferably contains at least one oxide and / or polyanionic compound as the positive electrode active material.

[Positive electrode active material]
In the case of a lithium ion secondary battery in which the cation in the non-aqueous electrolytic solution is mainly lithium, (a) the positive electrode active material constituting the positive electrode is not particularly limited as long as it is various materials capable of charging and discharging. For example, (A) a lithium transition metal composite oxide containing at least one metal of nickel, manganese, and cobalt and having a layered structure, (B) a lithium manganese composite oxide having a spinel structure, (C) lithium. Examples thereof include those containing at least one of the contained olivine-type phosphate and (D) lithium excess layered transition metal oxide having a layered rock salt-type structure.

((A) Lithium Transition Metal Composite Oxide)
Examples of the lithium transition metal composite oxide containing at least one metal of (A) nickel, manganese, and cobalt and having a layered structure, which is an example of the positive electrode active material, include, for example, lithium-cobalt composite oxide and lithium-. Nickel composite oxide, lithium-nickel-cobalt composite oxide, lithium-nickel-cobalt-aluminum composite oxide, lithium-cobalt-manganese composite oxide, lithium-nickel-manganese composite oxide, lithium-nickel-manganese-cobalt Examples include composite oxides. In addition, some of the transition metal atoms that are the main constituents of these lithium transition metal composite oxides are Al, Ti, V, Cr, Fe, Cu, Zn, Mg, Ga, Zr, Si, B, Ba, Y, Sn. Those substituted with other elements such as may be used.

Specific examples of the lithium-cobalt composite oxide and the lithium-nickel composite oxide include lithium cobalt oxide (LiCo _0.98 Mg _0. ) to which dissimilar elements such as LiCoO ₂ , LiNiO ₂ and Mg, Zr, Al and Ti are added. ₀₁ Zr _0.01 O ₂ , LiCo _0.98 Mg _0.01 Al _0.01 O ₂ , LiCo _0.975 Mg _0.01 Zr _0.005 Al _0.01 O ₂ etc.), WO2014 / 034043 Lithium cobalt oxide or the like in which a rare earth compound is adhered to the described surface may be used. Further, as described in JP-A-2002-151707, a LiCoO ₂ particle powder having a part of the particle surface coated with aluminum oxide may be used.

The lithium-nickel-cobalt composite oxide and the lithium-nickel-cobalt-aluminum composite oxide are represented by the general formula [1-1].
Li _a Ni _1-b-c Co _b M ¹ _c O ₂ [1-1]
In the formula [1-1], M ¹ is at least one element selected from the group consisting of Al, Fe, Mg, Zr, Ti, and B, a is 0.9 ≦ a ≦ 1.2, and b. , C satisfy the conditions of 0.1 ≦ b ≦ 0.3 and 0 ≦ c ≦ 0.1.
These can be prepared according to, for example, the production method described in JP-A-2009-137834 and the like. Specifically, LiNi _0.8 Co _0.2 O ₂ , LiNi _0.85 Co _0.10 Al _0.05 O ₂ , LiNi _0.87 Co _0.10 Al _0.03 O ₂ , LiNi _0.6 . Co _0.3 Al _0.1 O ₂ and the like can be mentioned.

Specific examples of the lithium-cobalt-manganese composite oxide and the lithium-nickel-manganese composite oxide include LiNi _0.5 Mn _0.5 O ₂ and LiCo _0.5 Mn _0.5 O ₂ .

Examples of the lithium-nickel-manganese-cobalt composite oxide include a lithium-containing composite oxide represented by the general formula [1-2].
Li _d Ni _e Mn _{f Cog} M ² _h O ₂ [1-2]
In the formula [1-2], M ² is at least one element selected from the group consisting of Al, Fe, Mg, Zr, Ti, B and Sn, and d is 0.9 ≦ d ≦ 1.2. , E, f, g and h satisfy the conditions of e + f + g + h = 1, 0 ≦ e ≦ 0.9, 0 ≦ f ≦ 0.5, 0 ≦ g ≦ 0.5, and h ≧ 0.
Lithium-nickel-manganese-cobalt composite oxides contain manganese in the range shown in the general formula [1-2] in order to improve structural stability and improve safety at high temperatures in lithium secondary batteries. It is preferable, and in particular, those further containing cobalt in the range represented by the general formula [1-2] in order to enhance the high rate characteristics of the lithium ion secondary battery are more preferable.
Specifically, for example, Li [Ni _1/3 Mn _1/3 Co _1/3 ] O ₂ and Li [Ni _0.45 Mn _0.35 Co _0.2 ] having a charge / discharge region of 4.3 V or higher. O ₂ , Li [Ni _0.5 Mn _0.3 Co _0.2 ] O ₂ , Li [Ni _0.6 Mn _0.2 Co _0.2 ] O ₂ , Li [Ni _0.49 Mn _0.3 Co _0.2 Zr _0.01 ] O ₂ , Li [Ni _0.49 Mn _0.3 Co _0.2 Mg _0.01 ] O _2, Li [Ni _0.8 Mn _0.1 Co _0.1 ] O ₂ And so on.

((B) Lithium-manganese composite oxide having a spinel structure)
Examples of the (B) lithium manganese composite oxide having a spinel structure, which is an example of the positive electrode active material, include a spinel-type lithium manganese composite oxide represented by the general formula [1-3].
Li _j (Mn _2-k M ³ _k ) O ₄ [1-3]
In the formula [1-3], M ³ is at least one metal element selected from the group consisting of Ni, Co, Fe, Mg, Cr, Cu, Al and Ti, and j is 1.05 ≦ j ≦ 1. 15 and k is 0 ≦ k ≦ 0.20.
Specifically, for example, LiMnO ₂ , LiMn ₂ O ₄ , LiMn _1.95 Al _0.05 O ₄ , LiMn _1.9 Al _0.1 O ₄ , LiMn _1.9 Ni _0.1 O ₄ , LiMn _{1 .5} Ni _0.5 O ₄ and the like can be mentioned.

((C) Lithium-containing olivine phosphate)
Examples of the (C) lithium-containing olivine-type phosphate which is an example of the positive electrode active material include those represented by the general formula [1-4].
LiFe _1-n M ⁴ _n PO ₄ [1-4]
In the formula [1-4], M ⁴ is at least one selected from Co, Ni, Mn, Cu, Zn, Nb, Mg, Al, Ti, W, Zr and Cd, and n is 0 ≦ n ≦. It is 1.
Specifically, for example, LiFePO ₄ , LiCoPO ₄ , LiNiPO ₄ , LiMnPO ₄ , and the like can be mentioned, and among them, LiFePO ₄ and / or LiMnPO ₄ are preferable.

((D) Lithium excess layered transition metal oxide)
Examples of the lithium excess layered transition metal oxide having the layered rock salt type structure (D), which is an example of the positive electrode active material, include those represented by the general formula [1-5].
xLiM ⁵ O ₂ · (1-x) Li ₂ M ⁶ O ₃ [1-5]
In the formula [1-5], x is a number satisfying 0 <x <1, M ⁵ is at least one metal element having an average oxidation number of ³⁺ , and M ⁶ is an average oxidation number. Is at least one metal element in which is ⁴⁺ . In the formula [1-5], M ⁵ is one kind of metal element preferably selected from trivalent Mn, Ni, Co, Fe, V and Cr, but is equivalent in divalent and tetravalent. The average oxidation number may be trivalent with the metal of.
Further, in the formula [1-5], M ⁶ is one or more metal elements preferably selected from Mn, Zr, and Ti. Specifically, 0.5 [LiNi _0.5 Mn _0.5 O ₂ ], 0.5 [Li ₂ MnO ₃ ], 0.5 [LiNi _1/3 Co _1/3 Mn _1/3 O ₂ ] -0.5 [Li ₂ MnO ₃ ], 0.5 [LiNi _0.375 Co _0.25 Mn _0.375 O ₂ ]-0.5 [Li ₂ MnO ₃ ], 0.5 [LiNi _0.375 Co _0.125 Fe _0.125 Mn _0.375 O ₂ ] ・ 0.5 [Li ₂ MnO ₃ ], 0.45 [LiNi _0.375 Co _0.25 Mn _0.375 O ₂ ] ・ 0.10 [Li ₂ TiO ₃ ], 0.45 [Li ₂ MnO ₃ ] and the like can be mentioned.
The positive electrode active material (D) represented by this general formula [1-5] is known to exhibit a high capacity at a high voltage charge of 4.4 V (Li standard) or higher (for example, US Pat. No. 7, 7). , 135,252).
These positive electrode active materials can be prepared according to, for example, the production methods described in JP-A-2008-270201, WO2013 / 118661, JP-A-2013-030284, and the like.
As the positive polymer active material, at least one selected from the above (A) to (D) may be contained as a main component, but other substances may be contained, for example, FeS ₂ , TiS ₂ , TiO ₂ , V. Examples thereof include transition element chalcogenides such as _{2O 5} , MoO ₃ , and MoS ₂ , conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole, activated carbon, polymers that generate radicals, and carbon materials.

[Positive current collector]
(B) The positive electrode has a positive electrode current collector. As the positive electrode current collector, for example, aluminum, stainless steel, nickel, titanium, alloys thereof, or the like can be used.

[Positive electrode active material layer]
(A) In the positive electrode, for example, a positive electrode active material layer is formed on at least one surface of a positive electrode current collector. The positive electrode active material layer is composed of, for example, the above-mentioned positive electrode active material, a binder, and, if necessary, a conductive agent.

Examples of the binder include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether coweight-containing material, styrene butadiene rubber (SBR), carboxymethyl cellulose or a salt thereof, methyl cellulose or a salt thereof, and cellulose acetate phthalate. Alternatively, the salt thereof, hydroxypropylmethyl cellulose or a salt thereof, polyvinyl alcohol or a salt thereof and the like can be mentioned.

As the conductive agent, for example, a carbon material such as acetylene black, ketjen black, furnace black, carbon fiber, graphite (granular graphite or flake graphite), fluorinated graphite can be used. For the positive electrode, it is preferable to use acetylene black or ketjen black having low crystallinity.

<(C) Negative electrode>
The negative electrode material is not particularly limited, but in the case of a lithium battery and a lithium ion battery, a lithium metal, an alloy of a lithium metal and another metal, an intermetal compound, various carbon materials (artificial graphite, natural graphite, etc.), and a metal Oxides, metal nitrides, tin (single), tin compounds, silicon (single), silicon compounds, activated carbons, conductive polymers and the like are used.

The carbon material includes, for example, graphitized carbon, non-graphitized carbon (hard carbon) having a (002) plane spacing of 0.37 nm or more, and graphite having a (002) plane spacing of 0.34 nm or less. And so on. More specifically, there are pyrolytic carbon, coke, glassy carbon fiber, calcined organic polymer compound, activated carbon, carbon black and the like. Of these, coke includes pitch coke, needle coke, petroleum coke and the like. The organic polymer compound calcined body refers to a carbonized product obtained by calcining a phenol resin, a furan resin, or the like at an appropriate temperature. The carbon material is preferable because the change in the crystal structure due to the occlusion and release of lithium is very small, so that a high energy density can be obtained and excellent cycle characteristics can be obtained. The shape of the carbon material may be fibrous, spherical, granular or scaly. Further, an amorphous carbon or a graphite material whose surface is coated with amorphous carbon is more preferable because the reactivity between the material surface and the electrolytic solution is low.
(C) The negative electrode preferably contains at least one type of negative electrode active material.

[Negative electrode active material]
In the case of a lithium ion secondary battery in which the cation in the non-aqueous electrolyte solution is mainly lithium, (c) the negative electrode active material constituting the negative electrode can be dope / dedope of lithium ions. For example, (E) a carbon material having a d-value of the lattice plane (002 surface) of 0.340 nm or less in X-ray diffraction, and (F) a carbon having a d-value of the lattice surface (002 surface) of more than 0.340 nm in X-ray diffraction. With materials, oxides of one or more metals selected from (G) Si, Sn, Al, one or more metals selected from (H) Si, Sn, Al, alloys containing these metals, or these metals or alloys. Examples thereof include alloys with lithium and those containing at least one selected from (I) lithium titanium oxide. One of these negative electrode active materials can be used alone, and two or more of them can be used in combination.

((E) A carbon material having a d value of 0.340 nm or less on the lattice plane (002 plane) in X-ray diffraction)
Examples of the carbon material having a d value of the lattice plane (002 plane) of 0.340 nm or less in (E) X-ray diffraction, which is an example of the negative electrode active material, include thermally decomposed carbons, coke (for example, pitch coke, needle coke, etc.). Examples include petroleum coke), graphites, calcined organic polymer compound (for example, phenol resin, furan resin, etc. calcined at an appropriate temperature and carbonized), carbon fiber, activated charcoal, etc., and these are graphitized. But it may be. The carbon material has a (002) plane spacing (d002) measured by X-ray diffraction method of 0.340 nm or less, and among them, graphite having a true density of 1.70 g / cm ³ or more, or graphite thereof. Highly crystalline carbon materials having similar properties are preferred.

((F) Carbon material in which the d value of the lattice plane (002 plane) in X-ray diffraction exceeds 0.340 nm)
Amorphous carbon is mentioned as a carbon material in which the d value of the lattice plane (002 plane) in (F) X-ray diffraction, which is an example of the negative electrode active material, exceeds 0.340 nm, and this is a high temperature of 2000 ° C. or higher. It is a carbon material whose lamination order hardly changes even if it is heat-treated. Examples thereof include graphitized carbon (hard carbon), mesocarbon microbeads (MCMB) calcined at 1500 ° C. or lower, mesophase bitch carbon fiber (MCF), and the like. Carbotron (registered trademark) P manufactured by Kureha Corporation is a typical example.

(Oxide of one or more metals selected from (G) Si, Sn, Al)
Examples of the oxide of one or more metals selected from (G) Si, Sn, and Al, which are examples of the negative electrode active material, include silicon oxide, tin oxide, and the like, which can be doped and dedoped with lithium ions. ..
There are SiO _x and the like having a structure in which ultrafine particles of Si are dispersed in SiO ₂ . When this material is used as the negative electrode active material, charging and discharging are smoothly performed because Si that reacts with Li is ultrafine particles, while the SiO _x particles themselves having the above structure have a small surface surface, so that the negative electrode active material layer. The paintability of the composition (paste) for forming the negative electrode and the adhesiveness of the negative electrode mixture layer to the current collector are also good.
Since SiO _x has a large volume change with charge and discharge, the capacity can be increased and good charge / discharge cycle characteristics can be achieved by using SiO _x and the graphite of the negative electrode active material (E) in a specific ratio in combination with the negative electrode active material. Can be compatible with.

((H) One or more metals selected from Si, Sn, Al, alloys containing these metals, or alloys of these metals or alloys with lithium)
Examples of the negative electrode active material (H) one or more metals selected from Si, Sn, and Al, alloys containing these metals, or alloys of these metals or alloys with lithium include, for example, silicon, tin, and aluminum. Examples thereof include metals, silicon alloys, tin alloys, aluminum alloys, and materials in which these metals and alloys are alloyed with lithium during charge and discharge can also be used.
Preferred specific examples thereof include metal simple substances (for example, powdery ones) such as silicon (Si) and tin (Sn) described in WO2004 / 100293 and Japanese Patent Laid-Open No. 2008-016424, and the metal alloys thereof. , Compounds containing the metal, alloys containing tin (Sn) and cobalt (Co) in the metal, and the like. When the metal is used for the electrode, it is preferable because it can develop a high charge capacity and the volume expansion / contraction due to charging / discharging is relatively small. Further, it is known that these metals, when used for the negative electrode of a lithium ion secondary battery, alloy with Li at the time of charging, and thus develop a high charging capacity, which is also preferable.
Further, for example, a negative electrode active material formed of silicon pillars having a submicron diameter, a negative electrode active material made of fibers made of silicon, and the like described in WO2004 / 042851 and WO2007 / 083155 may be used. ..

((I) Lithium Titanium Oxide)
Examples of the (I) lithium titanate oxide which is an example of the negative electrode active material include lithium titanate having a spinel structure and lithium titanate having a rams delight structure.
Examples of lithium titanate having a spinel structure include Li _{4 + α} Ti ₅ O ₁₂ (α changes within the range of 0 ≦ α ≦ 3 depending on the charge / discharge reaction). Examples of lithium titanate having a rams delight structure include Li _{2 + β} Ti ₃ O ₇ (β changes within the range of 0 ≦ β ≦ 3 due to a charge / discharge reaction). These negative electrode active materials can be prepared according to, for example, the production methods described in JP-A-2007-018883, JP-A-2009-176752 and the like.

On the other hand, in the case of a sodium ion secondary battery in which the cation in the non-aqueous electrolytic solution is mainly sodium, hard carbon, oxides such as TiO _{2 ,} V2 O ₅ and MoO ₃ are used as the negative electrode active material. For example, in the case of a sodium ion secondary battery in which the cation in the non-aqueous electrolytic solution is mainly sodium, sodium-containing transition metal composite oxides such as NaFeO ₂ , NaCrO ₂ , NaNiO ₂ , NamnO ₂ , and NaCoO ₂ are used as positive electrode active materials. A mixture of multiple transition metals such as Fe, Cr, Ni, Mn, and Co of those sodium-containing transition metal composite oxides, and some of the transition metals of those sodium-containing transition metal composite oxides are other than other transition metals. Substituted with the metal of Na ₂ FeP ₂ O ₇ , NaCo ₃ (PO ₄ ) ₂ P ₂ O ₇ and other transition metal phosphate compounds, TiS ₂ , FeS ₂ and other sulfides, or polyacetylene and polypara. Conductive polymers such as phenylene, polyaniline, and polypyrrole, activated carbon, radical-generating polymers, carbon materials, and the like are used.

[Negative electrode current collector]
(C) The negative electrode has a negative electrode current collector. As the negative electrode current collector, for example, copper, stainless steel, nickel, titanium, alloys thereof, or the like can be used.

[Negative electrode active material layer]
(C) In the negative electrode, for example, a negative electrode active material layer is formed on at least one surface of a negative electrode current collector. The negative electrode active material layer is composed of, for example, the above-mentioned negative electrode active material, a binder, and, if necessary, a conductive agent.

Examples of the binder include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether coweight-containing material, styrene butadiene rubber (SBR), carboxymethyl cellulose or a salt thereof, methyl cellulose or a salt thereof, and cellulose acetate phthalate. Alternatively, the salt thereof, hydroxypropylmethyl cellulose or a salt thereof, polyvinyl alcohol or a salt thereof and the like can be mentioned.

As the conductive agent, for example, a carbon material such as acetylene black, ketjen black, furnace black, carbon fiber, graphite (granular graphite or flake graphite), fluorinated graphite can be used.

<Manufacturing method of electrodes ((a) positive electrode and (c) negative electrode)>
The electrode is obtained, for example, by dispersing and kneading an active substance, a binder, and a conductive agent, if necessary, in a solvent such as N-methyl-2-pyrrolidone (NMP) or water in a predetermined blending amount. It can be obtained by applying the paste to a current collector and drying it to form an active material layer. It is preferable that the obtained electrode is compressed by a method such as a roll press to adjust the electrode to an appropriate density.

<(D) Separator>
The above-mentioned non-aqueous electrolyte battery may be provided with (d) a separator. As the separator for preventing contact between (a) the positive electrode and (c) the negative electrode, polyolefins such as polypropylene and polyethylene, and non-woven fabrics and porous sheets made of cellulose, paper, glass fiber and the like are used. These films are preferably microporous so that the non-aqueous electrolytic solution can easily permeate and allow ions to permeate.

Examples of the polyolefin separator include a film that electrically insulates the positive electrode and the negative electrode, such as a microporous polymer film such as a porous polyolefin film, and is permeable to lithium ions. As a specific example of the porous polyolefin film, for example, the porous polyethylene film may be used alone, or the porous polyethylene film and the porous polypropylene film may be laminated and used as a multilayer film. Further, a film obtained by combining a porous polyethylene film and a polypropylene film can be mentioned.

<Exterior body>
In constructing the non-aqueous electrolyte battery, as the exterior body of the non-aqueous electrolyte battery, for example, a metal can such as a coin type, a cylindrical type, or a square type, or a laminated exterior body can be used. Examples of the metal can material include a nickel-plated iron steel plate, a stainless steel plate, a nickel-plated stainless steel plate, aluminum or an alloy thereof, nickel, titanium and the like.

As the laminated exterior body, for example, an aluminum laminated film, a SUS laminated film, a silica-coated polypropylene, a laminated film such as polyethylene, or the like can be used.

The configuration of the non-aqueous electrolytic solution battery according to the present embodiment is not particularly limited, but for example, an electrode element in which a positive electrode and a negative electrode are arranged to face each other and a non-aqueous electrolytic solution are encapsulated in an exterior body. Can be configured as The shape of the non-aqueous electrolyte battery is not particularly limited, but an electrochemical device having a shape such as a coin shape, a cylinder shape, a square shape, or an aluminum laminated sheet type can be assembled from each of the above elements.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these descriptions.

[Preparation of non-aqueous electrolyte solution according to Examples and Comparative Examples]
<Comparative Example 1>
(Preparation of Comparative Non-Water Electrolyte Solution 1)
EC, FEC, EMC, and DMC were mixed in a volume ratio of 2: 1: 3: 4 in a glove box having a dew point of −60 ° C. or lower. Then, while keeping the internal temperature at 40 ° C. or lower, LiPF ₆ was added in an amount having a concentration of 1.0 mol / L with respect to the total amount of the non-aqueous electrolytic solution, and methylenebis (sulfonylfluoride) (hereinafter, also referred to as “MBSF”) was added. Was added to a concentration of 1.0% by mass based on the total amount of MBSF, solute, and non-aqueous organic solvent, and the mixture was stirred for 1 hour to dissolve to prepare a comparative non-aqueous electrolytic solution 1.

<Reference example 1>
(Preparation of reference non-aqueous electrolyte solution 1)
As other additives, lithium difluorobis (oxalat) phosphate (hereinafter, also referred to as “DFBOP”) was added to the concentration shown in Table 1 without adding MBSF, except that the solution was dissolved. A reference non-aqueous electrolytic solution 1 was obtained in the same manner as in the preparation of the comparative non-aqueous electrolytic solution 1.

<Examples 1, 6, 11, and 14>
(Preparation of non-aqueous electrolytes 1, 6, 11, and 14)
MBSF is changed to a compound represented by the general formula (1), which is represented by the above formula (1a), the above formula (1b), the above formula (1g), or the above formula (1h), respectively. Obtained non-aqueous electrolytes 1, 6, 11, and 14 in the same manner as in the preparation of the comparative non-aqueous electrolyte 1.

<Examples 2 to 5>
(Preparation of non-aqueous electrolyte solutions 2 to 5)
After the compound represented by the formula (1a) was dissolved, the additives shown in Table 1 were added as other additives to the concentrations shown in Table 1, and the compounds were not water except that they were dissolved. Non-aqueous electrolytic solutions 2 to 5 were obtained in the same manner as in the preparation of the electrolytic solution 1. In Table 1 below, VC means vinylene carbonate, TFOP means lithium tetrafluorooxalatrate, FS means lithium fluorosulfonate, and PRS means 1,3-propensultone.

<Examples 7 to 10>
(Preparation of non-aqueous electrolytes 7 to 10)
After the compound represented by the formula (1b) was dissolved, the additives shown in Table 1 were further added as other additives so as to have the concentrations shown in Table 1, and the components were not water except that they were dissolved. Non-aqueous electrolytic solutions 7 to 10 were obtained in the same manner as in the preparation of the electrolytic solution 6. In Table 1 below, BOB means lithium bis (oxalate) borate, FSI means bis (fluorosulfonyl) imide lithium, and DFP means lithium difluorophosphate.

<Examples 12 and 13>
(Preparation of non-aqueous electrolytes 12 and 13)
After the compound represented by the formula (1 g) was dissolved, the additives shown in Table 1 were further added as other additives so as to have the concentrations shown in Table 1, and the components were not water except that they were dissolved. Non-aqueous electrolytic solutions 12 and 13 were obtained in the same manner as in the preparation of the electrolytic solution 11.

<Examples 15 and 16>
(Preparation of non-aqueous electrolytes 15 and 16)
After the compound represented by the formula (1h) was dissolved, the additives shown in Table 1 were further added as other additives so as to have the concentrations shown in Table 1, and the components were not water except that they were dissolved. Non-aqueous electrolytic solutions 15 and 16 were obtained in the same manner as in the preparation of the electrolytic solution 14.

In Table 1 below, the amount of the compound represented by (I) general formula (1) added is the content with respect to the total amount of (I), (II) solute, and (III) non-aqueous organic solvent. The addition amount of the other additives is the content with respect to the total amount of the above (I) to (III).

Although the MBSF used in Comparative Example 1 is not a compound represented by the general formula (1), it is described in the column of "Compound represented by the general formula (1)" in Table 1 below for convenience. ing.

[Manufacturing of non-aqueous electrolyte battery]
(Manufacturing of NCM622 positive electrode)
LiNi _0.6 Mn _0.2 Co _0.2 O ₂ powder 92.0% by mass is mixed with 3.5% by mass of polyvinylidene fluoride as a binder and 4.5% by mass of acetylene black as a conductive material, and further N -Methyl-2-pyrrolidone was added to prepare a positive electrode mixture paste. This paste was applied to both sides of an aluminum foil (A1085), dried and pressurized, and then punched to a size of 4 × 5 cm to obtain a test NCM622 positive electrode.

(Preparation of silicon-containing graphite negative electrode)
To 85% by mass of artificial graphite powder, 7% by mass of nanosilicon, 3% by mass of conductive material (HS-100), 2% by mass of carbon nanotube (VGCF), 2% by mass of styrene butadiene rubber, 1% by mass of sodium carboxymethyl cellulose and water. Was mixed to prepare a negative mixture paste. This paste was applied to one side of a copper foil, dried and pressurized, and then punched to a size of 4 × 5 cm to obtain a silicon-containing graphite negative electrode for testing.

(Manufacturing of non-aqueous electrolyte battery)
Silicon-containing graphite negative electrode with terminals welded to the above-mentioned NCM622 positive electrode in an argon atmosphere with a dew point of -50 ° C or less, sandwiched between two polyethylene separators (5 x 6 cm) on both sides, and the terminals are welded to the outside in advance. The two sheets were sandwiched so that the negative electrode active material surface faced the positive electrode active material surface. Then, they are placed in an aluminum laminate bag having an opening on one side, a non-aqueous electrolytic solution is vacuum-injected, and then the opening is heat-sealed to form an aluminum laminate according to Examples and Comparative Examples. A mold battery was made. The non-aqueous electrolytic solution shown in Table 1 was used.

〔evaluation〕
-Initial battery volume measurement-
The capacity of the assembled battery specified by the weight of the positive electrode active material was 72 mAh. The battery was completely immersed in silicone oil, and the volume of the battery was measured by the Archimedes method. This was used as the initial battery volume.
-First charge / discharge-
The battery was placed in a constant temperature bath at 25 ° C. and connected to the charging / discharging device in that state. The battery was charged to 4.2 V at a charging rate of 0.2 C (current value that fully charges in 5 hours). After maintaining 4.2 V for 1 hour, the battery was discharged to 3.0 V at a discharge rate of 0.2 C. This was set as one charge / discharge cycle, and a total of 10 cycles of charge / discharge were performed to stabilize the battery.

<Measurement of gas generated during initial charge / discharge>
The volume of the stabilized battery was measured by the Archimedes method in the same manner as the initial battery volume measurement. Then, the value obtained by subtracting the initial battery volume from the volume obtained here was taken as the amount of gas generated during the initial charge / discharge.

<Measurement of battery capacity after storage at 60 ° C for 4 weeks>
Next, after charging to 4.2 V at a charging rate of 0.2 C, the battery was removed from the charging / discharging device and placed in a constant temperature bath at 60 ° C. After 4 weeks, the battery was taken out from the constant temperature bath, allowed to stand at room temperature for 24 hours, and then discharged to 3.0 V at a discharge rate of 0.2 C. Subsequently, the battery was charged to 4.2 V at a charge rate of 0.2 C and discharged to 3.0 V at a discharge rate of 0.2 C, and the capacity obtained by the discharge at this time was used as the battery capacity after storage at 60 ° C. ..

Table 1 shows the measurement results of the amount of gas generated during the initial charge and discharge and the battery capacity after storage at 60 ° C. The amount of gas generated during the initial charge and discharge and the battery capacity after storage at 60 ° C. are both shown as relative values with the value of Comparative Example 1 as 100.

As is clear from Table 1, the non-aqueous electrolyte battery containing the non-aqueous electrolytic solution of the present invention has an excellent balance between the effect of suppressing gas generation at the time of initial charge / discharge and the battery capacity after high temperature storage.
As shown in Reference Example 1, the oxalate salt such as DFBOP has the same amount of gas generated at the time of initial charge / discharge as in Comparative Example 1, and improves the battery capacity after storage at 60 ° C. By using it in combination with the compound represented by the general formula (1) as in the present invention, surprisingly, the battery capacity after storage at 60 ° C. is further improved without significantly deteriorating the amount of gas generated at the time of initial charge / discharge. It turned out that it was possible (Examples 8 and 12). It was also found that when the compound represented by the general formula (1) is used in combination with other additives other than DFBOP, both of the above characteristics can be exhibited in a well-balanced manner (Examples 2 to 5, 7, 9). 10, 13, 15, 16).

Claims (10)

(I) The compound represented by the following general formula (1),
A non-aqueous electrolytic solution containing (II) a solute and (III) a non-aqueous organic solvent.

[In the general formula (1), Y represents a sulfur atom, a phosphorus atom, or a carbon atom. When Y is a sulfur atom, a = 2 and b = 1, when Y is a phosphorus atom, a = 1 and b = 2, and when Y is a carbon atom, a = 1 and b = 1. ..
Z represents a chain aliphatic hydrocarbon group having 1 to 12 carbon atoms, and any hydrogen atom of the chain aliphatic hydrocarbon group may be substituted with a fluorine atom.
R is a fluorine atom, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, an aryloxy group having 6 to 15 carbon atoms, or an aryloxy group having 6 to 15 carbon atoms, respectively. It represents OLi, and an oxygen atom may be contained between the carbon atom-carbon atom bond in the alkoxy group, the alkenyloxy group, the alkynyloxy group, and the aryloxy group. Further, any hydrogen atom of the alkoxy group, alkenyloxy group, alkynyloxy group, and aryloxy group may be substituted with a fluorine atom. When b is 2, a plurality of Rs may be the same or different. ] The non-aqueous electrolytic solution according to claim 1, wherein R in the general formula (1) is a fluorine atom. The non-aqueous electrolytic solution according to claim 1, wherein R in the general formula (1) is an alkynyloxy group having 2 to 10 carbon atoms. The non-aqueous electrolytic solution according to any one of claims 1 to 3, wherein Z in the general formula (1) is a fluorine-substituted or unsubstituted alkylene group having 1 to 4 carbon atoms. The non-aqueous electrolytic solution according to claim 1, wherein the compound represented by the general formula (1) is at least one selected from the group consisting of compounds represented by the following formulas (1a) to (1h).

The non-aqueous electrolytic solution according to any one of claims 1 to 5, wherein the non-aqueous organic solvent contains at least one selected from the group consisting of cyclic carbonate and chain carbonate. The cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate, and the chain carbonate is a group consisting of ethylmethyl carbonate, dimethyl carbonate, diethyl carbonate, and methylpropyl carbonate. The non-aqueous electrolyte solution according to claim 6, which is at least one selected from the above. The non-aqueous electrolysis according to any one of claims 1 to 7, wherein the content of (I) is 0.01% by mass to 5.0% by mass with respect to the total amount of (I) to (III). liquid. Furthermore, vinylene carbonate, lithium bis (oxalat) borate, lithium tetrafluorooxalatrate, lithium difluorobis (oxalat), lithium fluorosulfonate, bis (fluorosulfonyl) imide lithium, lithium difluorophosphate, 1,3 -Claim 1 to 5.0%, which contains at least one selected from the group consisting of propensulton and 1,3-propanesulton in an amount of 0.01% by mass to 5.0% by mass based on the total amount of the non-aqueous electrolytic solution. Item 8. The non-aqueous electrolytic solution according to any one of 8. A non-aqueous electrolyte battery comprising the positive electrode, the negative electrode, and the non-aqueous electrolytic solution according to any one of claims 1 to 9.