JP2015149234A - Nonaqueous electrolyte for battery and lithium secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte for a battery capable of suppressing reduction in capacity maintenance factor after preservation, reducing battery resistance in an initial period (before preservation) and after preservation, and suppressing increase of battery resistance caused by preservation.SOLUTION: The nonaqueous electrolyte for a battery includes: an additive A that is a cyclic sulfate ester compound; and an additive B that is a compound having a 1,3-dithietane 1,1,3,3- tetraoxide skeleton.

Description

  The present invention relates to a non-aqueous electrolyte for a battery, and a chargeable / dischargeable lithium secondary battery used for a power source of a portable electronic device, a vehicle-mounted device, and power storage.

2. Description of the Related Art In recent years, lithium secondary batteries have been widely used as electronic devices such as mobile phones and laptop computers, electric vehicles, and power storage sources. In particular, recently, there has been a rapid increase in demand for batteries with high capacity, high output, and high energy density that can be mounted on hybrid vehicles and electric vehicles.
The lithium secondary battery is mainly composed of a positive electrode and a negative electrode containing a material capable of occluding and releasing lithium, and a non-aqueous electrolyte for a battery containing a lithium salt and a non-aqueous solvent.
As the positive electrode active material used for the positive electrode, for example, lithium metal oxides such as LiCoO ₂ , LiMnO ₂ , LiNiO ₂ , and LiFePO ₄ are used.
In addition, as the non-aqueous electrolyte, a mixed solvent (non-aqueous solvent) of carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, LiPF ₆ , LiBF ₄ , LiN (SO ₂ CF ₃ ) ₂ , LiN A solution in which a Li electrolyte such as (SO ₂ CF ₂ CF ₃ ) ₂ is mixed is used.
On the other hand, negative electrode active materials used for negative electrodes include metal lithium, metal compounds capable of occluding and releasing lithium (metal simple substance, oxide, alloy with lithium, etc.) and carbon materials, particularly lithium. Lithium secondary batteries using coke, artificial graphite, and natural graphite that can be occluded and released have been put into practical use.

As an attempt to improve battery performance, it has been proposed to include various additives in a non-aqueous electrolyte for batteries.
For example, a battery non-aqueous electrolyte containing a cyclic sulfate as an additive as a battery non-aqueous electrolyte capable of improving the capacity maintenance performance of the battery and suppressing the decrease in the release voltage during battery charge storage Is known (see, for example, Patent Document 1).
In addition, as a non-aqueous electrolyte for a battery that realizes an improvement in the output characteristics of the battery by keeping the resistance value (particularly the initial resistance value) of the battery low, 1,3-dithietane-1,1,3,3- A battery non-aqueous electrolyte containing a compound having a tetraoxide skeleton is known (for example, see Patent Document 2).

International Publication No. 2012/053644 Pamphlet International Publication No. 2011-136189 Pamphlet

  However, with respect to a battery non-aqueous electrolyte containing an additive and a battery using such a battery non-aqueous electrolyte, a decrease in capacity retention after storage is suppressed, and further, initial (before storage) and after storage In some cases, it is required to reduce the battery resistance of the battery and to suppress the increase in battery resistance due to storage.

  The present invention has been made to meet the above-mentioned problems, and an object of the present invention is to suppress a decrease in capacity maintenance rate after storage, and further to reduce battery resistance after initial (before storage) and after storage. It is possible to provide a non-aqueous electrolyte for a battery and a lithium secondary battery that can suppress an increase in battery resistance due to storage.

As a result of intensive studies, the present inventors have found that a non-aqueous electrolyte for a battery includes, as additives, a cyclic sulfate ester compound and a compound having a 1,3-dithietane-1,1,3,3-tetraoxide skeleton. By adding the combination, it is possible to suppress a decrease in capacity maintenance ratio after storage, and further, to reduce the battery resistance after storage (before storage) and after storage, and to suppress an increase in battery resistance due to storage, The present invention has been completed.
That is, the means for solving the above problems are as follows.

<1> A non-aqueous electrolyte for a battery comprising an additive A which is a cyclic sulfate compound and an additive B which is a compound having a 1,3-dithietane-1,1,3,3-tetraoxide skeleton. .
<2> The non-aqueous electrolyte for a battery according to <1>, wherein the additive A is a compound represented by the following general formula (I).

[In General Formula (I), R ¹ represents a group represented by General Formula (II) or a group represented by Formula (III), and R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Represents a group represented by the general formula (II) or a group represented by the formula (III).
In the general formula (II), R ³ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a formula (IV). Represents a group. The wavy line in general formula (II), formula (III), and formula (IV) represents the bonding position.
When the cyclic sulfate ester compound represented by the general formula (I) includes two groups represented by the general formula (II), the two groups represented by the general formula (II) are the same. Or they may be different from each other. ]

<3> In the general formula (I), the R ¹ is a group represented by the general formula (II) (provided that, in the general formula (II), the R ³ is a fluorine atom having 1 to 1 carbon atoms). 3 alkyl group, a halogenated alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a group represented by the above formula (IV)), or represented by the above formula (III). R ² is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group represented by the general formula (II) (in the general formula (II), R ³ is fluorine An atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a group represented by the formula (IV)), or the above formula The nonaqueous electrolytic solution for batteries according to <2>, which is a group represented by (III).

<4> In the general formula (I), the R ¹ is a group represented by the general formula (II) (in the general formula (II), R ³ is a fluorine atom, a methyl group, ethyl A group, a trifluoromethyl group, a methoxy group, an ethoxy group, or a group represented by the formula (IV)) or a group represented by the formula (III), and the R ² is a hydrogen atom or The nonaqueous electrolytic solution for batteries according to <2> or <3>, which is a methyl group.

<5> The nonaqueous electrolytic solution for a battery according to any one of <2> to <4>, wherein the additive B is a cyclic sulfone compound represented by the following general formula (V).

[In General Formula (V), R ¹ , R ² , R ³ and R ⁴ are each independently
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
A substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms,
A substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms,
-SiR ⁷ R ⁸ R ⁹ group (R ⁷ , R ⁸ and R ⁹ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a phenyl group),
-CO ₂ R ¹⁰ group ^{(R 10} is. Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group or a -SiR ⁷ R ⁸ R ⁹ group,),
-COR ¹¹ group (R ¹¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a phenyl group),
—P (O) (OR ¹² ) ₂ groups (R ¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or the aforementioned —SiR ⁷ R ⁸ R ⁹ group.) ,
-SO ₂ R ¹³ group ^{(R 13} represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a phenyl group.),
-SO ₂ ^{(OR 14)} group ^{(R 14} is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group or a -SiR ⁷ R ⁸ R ⁹ group,.), Or, —B (OR ¹⁵ ) ₂ group (R ¹⁵ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or the —SiR ⁷ R ⁸ R ⁹ group).
R ¹ and R ² may be bonded to each other to form a C 3-7 cycloalkane group together with the carbon atom to which R ¹ and R ² are bonded. Methylene group represented by (VI) (in general formula (VI), R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a group having 2 to 12 carbon atoms. Represents a dialkylamino group, R ⁵ and R ⁶ may be bonded together to form a C 3-7 cycloalkane group together with the carbon atom to which R ⁵ and R ⁶ are bonded. May be.
R ³ and R ⁴ may be bonded to each other to form a cycloalkane group having 3 to 7 carbon atoms together with the carbon atom to which R ³ and R ⁴ are bonded. Methylene group represented by (VI) (in general formula (VI), R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a group having 2 to 12 carbon atoms. Represents a dialkylamino group, R ⁵ and R ⁶ may be bonded together to form a C 3-7 cycloalkane group together with the carbon atom to which R ⁵ and R ⁶ are bonded. May be. ]

<6> In the general formula (V), each of R ¹ and R ² independently represents a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted carbon. A C 2-6 alkenyl group, or a —SiR ⁷ R ⁸ R ⁹ group (the R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 6 carbon atoms, An alkenyl group or a phenyl group), or
The R ¹ and the R ² are bonded to each other to form a C3-C6 cycloalkane group together with the carbon atom to which the R ¹ and the R ² are bonded, or the R ¹ and the R ² Are methylene groups represented by the general formula (VI) (in the general formula (VI), R ⁵ and R ⁶ are each independently a hydrogen atom or a dialkylamino group having 2 to 12 carbon atoms). Represents a group),
R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, or —SiR. ⁷ R ⁸ R ⁹ group (wherein R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group). Or
The R ³ and the R ⁴ are bonded to each other to form a C 3-6 cycloalkane group together with the carbon atom to which the R ³ and the R ⁴ are bonded, or the R ³ and the R ⁴ Are methylene groups represented by the general formula (VI) (in the general formula (VI), R ⁵ and R ⁶ are each independently a hydrogen atom or a dialkylamino group having 2 to 12 carbon atoms). The non-aqueous electrolyte for a battery according to <5>, which represents a group.

<7> In the general formula (V), R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, or an allyl group. , A trimethylsilyl group, a dimethyl t-butylsilyl group, a triethylsilyl group, or a triisopropylsilyl group, or
The R ¹ and the R ² are bonded to each other to form a cyclopentyl group together with the carbon atom to which the R ¹ and the R ² are bonded, or the R ¹ and the R ² are combined to form the general Forming a methylene group represented by the formula (VI) (in the general formula (VI), one of R ⁵ and R ⁶ is a hydrogen atom, and the other of R ⁵ and R ⁶ is a dimethylamino group). And
R ³ and R ⁴ are each independently a hydrogen atom, fluorine atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, allyl group, trimethylsilyl group, dimethyl t-butylsilyl group, triethyl A silyl group or a triisopropylsilyl group, or
The R ³ and the R ⁴ are bonded to each other to form a cyclopentyl group together with the carbon atom to which the R ³ and the R ⁴ are bonded, or the R ³ and the R ⁴ are combined to form the general Forming a methylene group represented by the formula (VI) (in the general formula (VI), one of R ⁵ and R ⁶ is a hydrogen atom, and the other of R ⁵ and R ⁶ is a dimethylamino group). <5> or <6> The nonaqueous electrolyte for batteries according to <6>.

<8> In the general formula (V), R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an isopropyl group. The nonaqueous electrolytic solution for a battery according to any one of <5> to <7>.

<9> Further, at least one selected from the group consisting of a carbonate compound having a carbon-carbon unsaturated bond, a carbonate compound having a fluorine atom, a fluorophosphate compound, and a cyclic sultone compound (preferably vinylene carbonate, vinylethylene Carbonate, 4-fluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, lithium monofluorophosphate, lithium difluorophosphate, lithium difluorobis (oxalato) phosphate, tetrafluoro (oxalato) phosphorus <1>-<8> containing additive C which is at least one selected from the group consisting of lithium acid, 1,3-propane sultone, and 1,3-propene sultone) Non-aqueous electrolyte for batteries
<10> The nonaqueous electrolytic solution for batteries according to <9>, wherein the content of the additive C is 0.001% by mass to 10% by mass.
<11> The non-aqueous electrolyte for a battery according to any one of <1> to <10>, wherein the content of the additive A is 0.001% by mass to 10% by mass.
<12> The non-aqueous electrolyte for a battery according to any one of <1> to <11>, wherein the content of the additive B is 0.001% by mass to 10% by mass.
<13> Positive electrode, metal lithium, lithium-containing alloy, metal or alloy capable of alloying with lithium, oxide capable of doping / de-doping lithium ion, transition metal capable of doping / dedoping lithium ion The negative electrode containing at least one selected from the group consisting of a nitride and a carbon material capable of being doped / undoped with lithium ions as a negative electrode active material, and any one of <1> to <12> A non-aqueous electrolyte for a battery, and a lithium secondary battery.
<14> Positive electrode, metal lithium, lithium-containing alloy, metal or alloy capable of alloying with lithium, oxide capable of doping / de-doping lithium ion, transition metal capable of doping / dedoping lithium ion The negative electrode containing at least one selected from the group consisting of a nitride and a carbon material capable of being doped / undoped with lithium ions as a negative electrode active material, and any one of <1> to <12> A lithium secondary battery obtained by charging and discharging a lithium secondary battery comprising a nonaqueous electrolyte for a battery.

  According to the present invention, it is possible to suppress a decrease in capacity retention rate after storage, and further to reduce battery resistance after storage (before storage) and after storage, and to suppress an increase in battery resistance due to storage. An electrolytic solution and a lithium secondary battery can be provided.

It is typical sectional drawing of the coin-type battery which shows an example of the lithium secondary battery of this invention.

  Hereinafter, the non-aqueous electrolyte for batteries and the lithium secondary battery of the present invention will be described in detail.

[Non-aqueous electrolyte for batteries]
The non-aqueous electrolyte for batteries of the present invention (hereinafter also simply referred to as “non-aqueous electrolyte”) includes additive A, which is a cyclic sulfate compound, and 1,3-dithietane-1,1,3,3-tetra And additive B which is a compound having an oxide skeleton.

For non-aqueous electrolytes containing additives and batteries using such non-aqueous electrolytes, the decrease in capacity retention rate after storage is suppressed, and further, battery resistance after initial (before storage) and after storage is reduced. In some cases, it is required to suppress an increase in battery resistance due to storage.
Here, the addition of the additive A to the non-aqueous electrolyte is effective for reducing the capacity retention rate after storage. In addition, the addition of the additive B to the nonaqueous electrolytic solution is effective for reducing the initial (before storage) battery resistance.
As a result of intensive studies, the inventors have added both additive A and additive B to the non-aqueous electrolyte solution, so that the effects of additive A and additive B are not counteracted with each other, It was found that the decrease in the capacity retention rate after storage can be suppressed, the battery resistance after storage (before storage) and after storage can be reduced, and the increase in battery resistance due to storage can also be suppressed. In general, when two or more kinds of additives are added to the non-aqueous electrolyte, the effects of the individual additives are often canceled out, and thus the above findings are unexpected findings. Furthermore, the effect of reducing battery resistance after storage and the effect of suppressing increase in battery resistance due to storage were unexpected effects.
The reason why the effect of the combination of the additive A and the additive B is obtained is not clear, but is presumed as follows.
That is,
(1) A film derived from the additive A is first formed on the electrode surface by initial charge and discharge;
(2) After the above (1), the coating component derived from the additive B supplements the coating derived from the additive A, and the additive B is applied to the electrode surface site where the additive A has not been able to act. At least one of acting,
It is considered that decomposition of the solvent on the electrode surface was effectively suppressed by this combination, and the above-described effect was produced.
If additive A and additive B act randomly on the formation of the coating, it is originally expected that, for example, additive B will act on the electrode surface site where the action of the additive A-derived component is preferred. Even the effects will not be demonstrated.
However, in the present invention, it is considered that the additives A and B sufficiently exert their respective characteristics by the mechanisms (1) and (2) described above, and further produce an unexpected effect. .

As described above, according to the nonaqueous electrolytic solution of the present invention, it is possible to suppress a decrease in capacity retention rate after storage, and further, it is possible to reduce initial (before storage) and post-storage battery resistance, and battery resistance due to storage. Can also be suppressed.
According to the nonaqueous electrolytic solution of the present invention, the battery resistance after storage can be reduced, and the increase in battery resistance due to storage can be suppressed, so that the effect of extending the life of the battery (that is, the effect of improving the storage performance of the battery) is achieved. Expected to have.

The effect of suppressing the increase in battery resistance due to storage can be evaluated by examining the ratio of the battery resistance after storage to the battery resistance before storage (hereinafter also referred to as “ratio [after storage / before storage]”). As this ratio [after storage / before storage] is smaller, the increase in battery resistance due to storage is suppressed.
Further, in the present invention, the concept of “suppression of battery resistance increase due to storage” includes no increase in battery resistance due to storage, small increase in battery resistance due to storage, and battery resistance due to storage. This includes everything that is reduced rather than increased.

  Hereinafter, the components of the nonaqueous electrolytic solution of the present invention will be specifically described.

<Additive A (cyclic sulfate ester compound)>
The nonaqueous electrolytic solution of the present invention contains an additive A that is a cyclic sulfate compound.
Although there is no restriction | limiting in particular as additive A (cyclic sulfate ester compound), For example, the compound represented by the following general formula (I), 2,2-dioxo-1,3,2-dioxathiolane, 4-methyl-2 , 2-dioxo-1,3,2-dioxathiolane, 4-ethyl-2,2-dioxo-1,3,2-dioxathiolane, 4-propyl-2,2-dioxo-1,3,2-dioxathiolane, 4, -Butyl-2,2-dioxo-1,3,2-dioxathiolane, catechol sulfate, 1,2-cyclohexyl sulfate.
The additive A (cyclic sulfate ester compound) is preferably a compound represented by the following general formula (I) in that the effect of the present invention is more effectively exhibited.

In General Formula (I), R ¹ represents a group represented by General Formula (II) or a group represented by Formula (III), R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, The group represented by general formula (II) or the group represented by formula (III) is represented.
In the general formula (II), R ³ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a formula (IV). Represents a group. The wavy line in general formula (II), formula (III), and formula (IV) represents the bonding position.
When the cyclic sulfate ester compound represented by the general formula (I) includes two groups represented by the general formula (II), the two groups represented by the general formula (II) are the same. Or they may be different from each other.

In the general formula (I), examples of the “halogen atom” include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
As the halogen atom, a fluorine atom is preferable.

In the general formula (I), the “alkyl group having 1 to 6 carbon atoms” is a linear or branched alkyl group having 1 to 6 carbon atoms, and includes a methyl group, an ethyl group, a propyl group, and an isopropyl group. Group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, 2-methylbutyl group, 1-methylpentyl group, neopentyl group, 1-ethylpropyl group, hexyl group, 3,3-dimethylbutyl Specific examples include groups.
As a C1-C6 alkyl group, a C1-C3 alkyl group is more preferable.

In the general formula (I), the “halogenated alkyl group having 1 to 6 carbon atoms” is a linear or branched halogenated alkyl group having 1 to 6 carbon atoms, such as a fluoromethyl group or a difluoromethyl group. Group, trifluoromethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroisopropyl group, perfluoro Specific examples include isobutyl, chloromethyl, chloroethyl, chloropropyl, bromomethyl, bromoethyl, bromopropyl, methyl iodide, ethyl iodide, propyl iodide and the like.
As the halogenated alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms is more preferable.

In the general formula (I), the “C 1-6 alkoxy group” is a linear or branched alkoxy group having 1 to 6 carbon atoms, and includes a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. Group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, 2-methylbutoxy group, 1-methylpentyloxy group, neopentyloxy group, 1-ethylpropoxy group, hexyloxy group, Specific examples include 3,3-dimethylbutoxy group.
As a C1-C6 alkoxy group, a C1-C3 alkoxy group is more preferable.

R ¹ in the general formula (I) is preferably a group represented by the general formula (II) (in the general formula (II), R ³ is a fluorine atom, an alkyl group having 1 to 3 carbon atoms, or a carbon number. A halogenated alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a group represented by formula (IV)), or a group represented by formula (III).
R ² in the general formula (I) is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group represented by the general formula (II) (in the general formula (II), R ³ is a fluorine atom Or an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a group represented by the formula (IV)), or It is a group represented by the formula (III), more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

When R ¹ in General Formula (I) is a group represented by General Formula (II), R ³ in General Formula (II) is a halogen atom, an alkyl group having 1 to 6 carbon atoms, as described above, A halogenated alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a group represented by the formula (IV), more preferably R ³ is a fluorine atom or a group having 1 to 3 carbon atoms. An alkyl group, a halogenated alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a group represented by the formula (IV), more preferably a fluorine atom, a methyl group, an ethyl group, A trifluoromethyl group, a methoxy group, an ethoxy group, or a group represented by the formula (IV).
When R ² in the general formula (I) is a group represented by the general formula (II), the preferred range of R ^{3 in} the general formula (II) is that R ¹ in the general formula (I) is generally This is the same as the preferred range of R ³ in the case of the group represented by the formula (II).

A preferred form of the general formula (I) from the viewpoint that the effects of the present invention are more effectively exhibited,
R ¹ is a group represented by general formula (II) (in general formula (II), R ³ is a fluorine atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, or a carbon number. 1 to 3 alkoxy groups or a group represented by formula (IV)), or a group represented by formula (III), wherein R ² is a hydrogen atom, having 1 to 3 carbon atoms. An alkyl group, a group represented by general formula (II) (in general formula (II), R ³ is a fluorine atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, or 1 carbon atom. Or a group represented by formula (IV)), or a group represented by formula (III).
A more preferred form of the general formula (I) is a group in which R ¹ is represented by the general formula (II) (in the general formula (II), R ³ represents a fluorine atom, a methyl group, an ethyl group, a trifluoromethyl group, a methoxy group, Group, an ethoxy group, or a group represented by formula (IV)) or a group represented by formula (III), in which R ² is a hydrogen atom or a methyl group.
A more preferred form of the general formula (I) is a combination wherein R ¹ is a group represented by the formula (III) and R ² is a hydrogen atom (most preferably 1,2: 3,4-di-O— Sulfanyl-meso-erythritol).

In the general formula (I), the cyclic sulfate compound in which R ¹ is a group represented by the general formula (II) is a cyclic sulfate compound represented by the following general formula (XII).

In the general formula (XII), ^{R 2} and ^{R 3} are the same meanings as ^{R 2} and ^{R 3} in formulas (I) and (II).

As the cyclic sulfate compound represented by the general formula (XII), R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ³ is a halogen atom or an alkyl group having 1 to 6 carbon atoms. , A compound having a halogenated alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a group represented by the formula (IV) is preferable.
Furthermore, as the cyclic sulfate compound represented by the general formula (XII), R ² is a hydrogen atom or a methyl group, and R ³ is a fluorine atom, a methyl group, an ethyl group, a trifluoromethyl group, a methoxy group. A compound which is a group, an ethoxy group, or a group represented by the formula (IV) is particularly preferable.

  As the cyclic sulfate compound represented by the general formula (I), 4-methylsulfonyloxymethyl-2,2-dioxo-1,3,2-dioxathiolane, 4-ethylsulfonyloxymethyl-2,2- Dioxo-1,3,2-dioxathiolane, bis ((2,2-dioxo-1,3,2-dioxathiolan-4-yl) methyl) sulfate, or 4,4′-bis (2,2-dioxo-1) 3,2-dioxathiolane, more preferably 4-methylsulfonyloxymethyl-2,2-dioxo-1,3,2-dioxathiolane, 4-ethylsulfonyloxymethyl-2,2-dioxo-1,3. , 2-dioxathiolane, bis ((2,2-dioxo-1,3,2-dioxathiolan-4-yl) methyl) sulfate, or 4, '-Bis (2,2-dioxo-1,3,2-dioxathiolane, particularly preferably 4-methylsulfonyloxymethyl-2,2-dioxo-1,3,2-dioxathiolane, 4-ethylsulfonyloxy Methyl-2,2-dioxo-1,3,2-dioxathiolane, or bis ((2,2-dioxo-1,3,2-dioxathiolan-4-yl) methyl) sulfate.

Specific examples [Exemplary Compound A-1 to Exemplified Compound A-30] of the cyclic sulfate compound represented by General Formula (I) in the present invention are shown below by clearly indicating each substituent in General Formula (I). Although described in the table, the present invention is not limited to these compounds.
In the structures of the following exemplary compounds, “Me” represents a methyl group, “Et” represents an ethyl group, “Pr” represents a propyl group, “iPr” represents an isopropyl group, “Bu” represents a butyl group, and “tBu” Is a tertiary butyl group, “Pent” is a pentyl group, “Hex” is a hexyl group, “OMe” is a methoxy group, “OEt” is an ethoxy group, “OPr” is a propoxy group, “OBu” Represents a butoxy group, “OPent” represents a pentyloxy group, and “OHex” represents a hexyloxy group. Further, the “wavy line” in R ^{1 to} R ³ represents a coupling position.
In some cases, stereoisomers derived from the substituents at the 4-position and 5-position of the 2,2-dioxo-1,3,2-dioxathiolane ring may be formed, and both are compounds included in the present invention.

  Among the cyclic sulfate compounds represented by the general formula (I), when two or more asymmetric carbons exist in the molecule, stereoisomers (diastereomers) exist, respectively, unless otherwise specified. , A mixture of the corresponding diastereomers.

  Although there is no restriction | limiting in particular in the method to synthesize | combine the cyclic sulfate ester compound represented by general formula (I), For example, it synthesize | combines by the synthesis method of Paragraphs 0062-0068 of international publication 2012/053644 pamphlet. it can.

The nonaqueous electrolytic solution of the present invention may contain only one type of additive A (for example, a compound represented by the general formula (I)), or may contain two or more types.
Although there is no restriction | limiting in particular in content (when it is 2 or more types) of additive A in the non-aqueous electrolyte of this invention, From a viewpoint with which the effect of this invention is show | played more effectively. The total amount of the nonaqueous electrolytic solution is preferably 0.001% by mass to 10% by mass, and more preferably 0.05% by mass to 5% by mass.

<Additive B>
The nonaqueous electrolytic solution of the present invention contains an additive B which is a compound having a 1,3-dithietane-1,1,3,3-tetraoxide skeleton.
The additive B is preferably a compound represented by the following general formula (V).

In general formula (V), R ¹ , R ² , R ³ and R ⁴ are each independently
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
A substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms,
A substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms,
-SiR ⁷ R ⁸ R ⁹ group (R ⁷ , R ⁸ and R ⁹ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a phenyl group),
-CO ₂ R ¹⁰ group ^{(R 10} is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or -SiR ⁷ R ⁸ R ⁹ group.)
-COR ¹¹ group (R ¹¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a phenyl group),
_{^{-P (O) (OR 12)}} 2 group ^{(R 12} represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or -SiR ⁷ R ⁸ R ⁹ group.)
-SO ₂ R ¹³ group ^{(R 13} represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a phenyl group.),
—SO ₂ (OR ¹⁴ ) group (R ¹⁴ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or a —SiR ⁷ R ⁸ R ⁹ group), or — B (OR ¹⁵ ) ₂ group (R ¹⁵ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or a —SiR ⁷ R ⁸ R ⁹ group).
R ¹ and R ² may be bonded to each other to form a C 3-7 cycloalkane group together with the carbon atom to which R ¹ and R ² are bonded. (In the general formula (VI), R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a dialkylamino group having 2 to 12 carbon atoms) R ⁵ and R ⁶ may be bonded to each other to form a cycloalkane group having 3 to 7 carbon atoms together with the carbon atom to which R ⁵ and R ⁶ are bonded.
R ³ and R ⁴ may be bonded to each other to form a cycloalkane group having 3 to 7 carbon atoms together with the carbon atom to which R ³ and R ⁴ are bonded. (In the general formula (VI), R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a dialkylamino group having 2 to 12 carbon atoms) R ⁵ and R ⁶ may be bonded to each other to form a C 3-7 cycloalkane group together with the carbon atom.

In the general formula (V), “alkyl group having 1 to 10 carbon atoms” means methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, 2-methylbutyl, 1-methylpentyl. Specific examples thereof include neopentyl, 1-ethylpropyl, hexyl, 3,3-dimethylbutyl, heptyl, octyl, nonyl and decyl.
As for carbon number of the said alkyl group, 1-6 are preferable.

In the general formula (V), “C2-C10 alkenyl group” means vinyl, allyl, butenyl, buten-3-yl, pentenyl, penten-4-yl, hexenyl, hexen-5-yl, heptenyl. Specific examples include octenyl, nonenyl, and decenyl.
As for carbon number of the said alkenyl group, 2-6 are preferable.

In the general formula (V), “C2-C10 alkynyl group” means ethynyl, propargyl, butyn-4-yl, butyn-3-yl, pentynyl, pentyn-4-yl, hexyn-5-yl. Specific examples include heptin-7-yl, octin-8-yl, nonin-9-yl, and decyn-10-yl.
As for carbon number of the said alkynyl group, 2-6 are preferable.

  In the general formula (V) (specifically, in the general formula (VI)), the “dialkylamino group having 2 to 12 carbon atoms” refers to an amino acid having a linear or branched alkyl group having 2 to 12 carbon atoms. Specific examples are dimethylamino, diethylamino, dipropylamino, dibutylamino, dipentylamino, dihexylamino, diisopropylamino, diisobutylamino, methylethylamino, methylpropylamino, methylbutylamino, methylpentylamino, methylhexylamino As mentioned.

In general formula (V), examples of the substituent in the “substituted or unsubstituted alkyl group having 1 to 10 carbon atoms” include 1 to 10 fluorine atoms, and 1 to 2 —SiR ¹⁷ R ¹⁸ R ^{19 respectively.} Groups (R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a phenyl group. Specific examples of —SiR ¹⁷ R ¹⁸ R ¹⁹ group And trimethylsilyl, triethylsilyl, triisopropylsilyl, dimethyl-t-butylsilyl, dimethylvinylsilyl, dimethylallylsilyl, dimethylphenylsilyl, diphenylmethylsilyl, triphenylsilyl, etc.), hydroxyl, cyano, acetyl , Propionyl, benzoyl, carboxyl, methoxycarbonyl, ethoxy Rubonyl, trimethylsilyloxycarbonyl, trimethylsilylmethoxycarbonyl, 2-trimethylsilylethoxycarbonyl, phenyl, pyridyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, trifluoromethylsulfonyl, difluorophenylsulfonyl, phenylsulfonyl, methoxysulfonyl, ethoxysulfonyl, propoxysulfonyloxy , Butoxysulfonyloxy, fluorosulfonyloxy, trimethylsilyloxysulfonyl, phosphono, dimethylphosphono, diethylphosphono, bis (trimethylsilylmethyl) phosphono, bis (trimethylsilylethyl) phosphono, bis (cyanoethyl) phosphono, bis (methylsulfonylethyl) phosphono Bis (phenylsulfonylethyl) phospho , Dihydroxyboryl, dimethoxy boryl, Jietokishiboriru, bis (trimethylsilyloxy) boryl, and the like as a specific example.

In the general formula (V), examples of the substituent in the “substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms” include 1 to 10 fluorine atoms and 1 to 2 —SiR ¹⁷ R ¹⁸ R ^{19, respectively.} Groups (R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a phenyl group. Specific examples of —SiR ¹⁷ R ¹⁸ R ¹⁹ group And trimethylsilyl, triethylsilyl, triisopropylsilyl, dimethyl-t-butylsilyl, dimethylvinylsilyl, dimethylallylsilyl, dimethylphenylsilyl, diphenylmethylsilyl, triphenylsilyl, etc.), hydroxyl, cyano, acetyl , Propionyl, benzoyl, carboxyl, methoxycarbonyl, ethoxy Carbonyl, trimethylsilyloxycarbonyl, trimethylsilylmethoxycarbonyl, 2-trimethylsilylethoxycarbonyl, phenyl, pyridyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, trifluoromethylsulfonyl, difluorophenylsulfonyl, phenylsulfonyl, methoxysulfonyl, ethoxysulfonyl, propoxysulfonyloxy , Butoxysulfonyloxy, fluorosulfonyloxy, trimethylsilyloxysulfonyl, phosphono, dimethylphosphono, diethylphosphono, bis (trimethylsilylmethyl) phosphono, bis (trimethylsilylethyl) phosphono, bis (cyanoethyl) phosphono, bis (methylsulfonylethyl) phosphono Bis (phenylsulfonylethyl) phos Bruno, dihydroxyboryl, dimethoxy boryl, Jietokishiboriru, bis (trimethylsilyloxy) boryl, and the like as a specific example.

In the general formula (V), examples of the substituent in the “substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms” include 1 to 10 fluorine atoms, and 1 to 2 —SiR ¹⁷ R ¹⁸ R ^{19 respectively.} Groups (R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a phenyl group. Specific examples of —SiR ¹⁷ R ¹⁸ R ¹⁹ group As trimethylsilyl, triethylsilyl, triisopropylsilyl, dimethyl-t-butylsilyl, dimethylvinylsilyl, dimethylallylsilyl, dimethylphenylsilyl, diphenylmethylsilyl, triphenylsilyl, etc.), hydroxyl, cyano, acetyl , Propionyl, benzoyl, carboxyl, methoxycarbonyl, ethoxy Carbonyl, trimethylsilyloxycarbonyl, trimethylsilylmethoxycarbonyl, 2-trimethylsilylethoxycarbonyl, phenyl, pyridyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, trifluoromethylsulfonyl, difluorophenylsulfonyl, phenylsulfonyl, methoxysulfonyl, ethoxysulfonyl, propoxysulfonyloxy , Butoxysulfonyloxy, fluorosulfonyloxy, trimethylsilyloxysulfonyl, phosphono, dimethylphosphono, diethylphosphono, bis (trimethylsilylmethyl) phosphono, bis (trimethylsilylethyl) phosphono, bis (cyanoethyl) phosphono, bis (methylsulfonylethyl) phosphono Bis (phenylsulfonylethyl) phos Bruno, dihydroxyboryl, dimethoxy boryl, Jietokishiboriru, bis (trimethylsilyloxy) boryl, and the like as a specific example.

In the general formula (V), R ¹ and R ² are bonded to each other, and may be formed together with the carbon atom to which R ¹ and R ² are bonded. Examples include propane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and the like.

In general formula (V), R ³ and R ⁴ are bonded to each other, and may be formed together with the carbon atom to which R ³ and R ⁴ are bonded. Examples include propane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and the like.

In general formula (V) (specifically, in general formula (VI)), R ⁵ and R ⁶ may be bonded to each other, and may be formed together with the carbon atom to which R ⁵ and R ⁶ are bonded. Examples of the “˜7 cycloalkane group” include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and the like.

In the general formula (V), “—SiR ⁷ R ⁸ R ⁹ group (R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or phenyl” Examples of “representing a group” include trimethylsilyl, triethylsilyl, triisopropylsilyl, dimethyl-t-butylsilyl, dimethylvinylsilyl, dimethylallylsilyl, dimethylphenylsilyl, diphenylmethylsilyl, triphenylsilyl and the like.

In general formula (V), “—CO ₂ R ¹⁰ group (R ¹⁰ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or a —SiR ⁷ R ⁸ R ⁹ group”. ) "Includes carboxy, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, isobutoxycarbonyl, t- Butoxycarbonyl, trimethylsilyloxycarbonyl, trimethylsilylmethyloxycarbonyl, 2-trimethylsilylethyloxycarbonyl, 2,2,2-trifluoroethyloxycarbonyl, 2-cyanoethyloxycarbonyl, phenyl Oxycarbonyl, and the like.

In the general formula (V), as “—COR ¹¹ group (R ¹¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or phenyl group)”, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, Examples include heptanoyl, octanoyl, nonanoyl, decanoyl, isobutyryl, pivaloyl, benzoyl, trifluoroacetyl, and the like.

In formula (V), ^{"- P (O) (OR 12} ) 2 group ^{(R 12} is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group or a -SiR ⁷ R ^8, R ⁹ represents phosphono, dimethoxyphosphono, diethoxyphosphono, dipropoxyphosphono, dibutoxyphosphono, dipentoxyphosphono, dihexyloxyphosphono, diheptyloxyphosphono, dioctyl Oxyphosphono, dinonyloxyphosphono, didecyloxyphosphono, diisobutoxyphosphono, bis (trimethylsilyloxy) phosphono, bis (trimethylsilylmethyloxy) phosphono, bis (2-trimethylsilylethyloxy) phosphono, 2,2, 2-trifluoroethyloxyphosphono, 2-cyanoethyloxyphosphono, phenyl Kishihosuhono, and the like.

In the general formula (V), “—SO ₂ R ¹³ group (R ¹³ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a phenyl group)” includes methylsulfonyl, ethylsulfonyl, Examples include propylsulfonyl, butylsulfonyl, pentylsulfonyl, hexylsulfonyl, heptylsulfonyl, octylsulfonyl, nonylsulfonyl, decylsulfonyl, isobutylsulfonyl, t-butylsulfonyl, phenylsulfonyl, trifluoromethylsulfonyl, and the like.

In formula (V), _"- SO 2 ^{(OR 14)} group ^{(R 14} is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or -SiR ⁷ R ⁸ R ⁹ group Represents methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, butoxysulfonyl, pentoxysulfonyl, hexyloxysulfonyl, heptyloxysulfonyl, octyloxysulfonyl, nonyloxysulfonyl, decyloxysulfonyl, isobutoxysulfonyl, t- Butoxysulfonyl, trimethylsilyloxysulfonyl, trimethylsilylmethyloxysulfonyl, 2-trimethylsilylethyloxysulfonyl, 2,2,2-trifluoroethyloxysulfonyl, 2-cyanoethyloxysulfonyl, phenyloxy Cisulfonyl, and the like.

In formula (V), "- ^{B (OR} _{15) 2} group ^{(R 15} is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or -SiR ⁷ R ⁸ R ⁹ group Are represented by boryl, dimethoxyboryl, diethoxyboryl, dipropoxyboryl, dibutoxyboryl, dipentoxyboryl, dihexyloxyboryl, diheptyloxyboryl, dioctyloxyboryl, dinonyloxyboryl, didecyloxyboryl, diisobutoxy Boryl, di-t-butoxyboryl, ditrimethylsilyloxyboryl, bis (trimethylsilylmethyloxy) boryl, bis (2-trimethylsilylethyloxy) boryl, bis (2,2,2-trifluoroethyloxy) boryl, bis ((2- Cyanoethyloxy) boryl, phenyloxybo Le, and the like.

A preferred form of the general formula (V) is
R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, or —SiR ⁷ R ⁸ R ⁹ group (R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group), or
R ¹ and R ² are bonded to each other to form a cycloalkane group having 3 to 6 carbon atoms together with the carbon atom to which R ¹ and R ² are bonded, or R ¹ and R ² are united in general. A methylene group represented by the formula (VI) (in the general formula (VI), R ⁵ and R ⁶ each independently represents a hydrogen atom or a C 2-12 dialkylamino group) is formed. ,
R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, or —SiR ⁷ R ⁸ R ⁹ group (R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group), or
R ³ and R ⁴ are bonded to each other to form a cycloalkane group having 3 to 6 carbon atoms together with the carbon atom to which R ³ and R ⁴ are bonded, or R ³ and R ⁴ are combined together in general. A methylene group represented by the formula (VI) (in the general formula (VI), R ⁵ and R ⁶ each independently represents a hydrogen atom or a C 2-12 dialkylamino group) is formed. It is a form.

More preferably among the above forms,
R ¹ and R ² are each independently a hydrogen atom, fluorine atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, allyl group, trimethylsilyl group, dimethyl t-butylsilyl group, triethylsilyl group Or a triisopropylsilyl group, or
R ¹ and R ² are bonded to each other to form a cyclopentyl group together with the carbon atom to which R ¹ and R ² are bonded, or R ¹ and R ² are integrally represented by the general formula (VI). Methylene group (in the general formula (VI), one of R ⁵ and R ⁶ is a hydrogen atom, and the other of R ⁵ and R ⁶ is a dimethylamino group),
R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an allyl group, a trimethylsilyl group, a dimethyl t-butylsilyl group, or a triethylsilyl group. Or a triisopropylsilyl group, or
R ³ and R ⁴ are bonded to each other to form a cyclopentyl group together with the carbon atom to which R ³ and R ⁴ are bonded, or R ³ and R ⁴ are integrally represented by the general formula (VI). In the general formula (VI), one of R ⁵ and R ⁶ is a hydrogen atom, and the other of R ⁵ and R ⁶ is a dimethylamino group.

Another preferred form of general formula (V) is
R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms), a substituted or unsubstituted carbon number 2 to 2; An alkenyl group having 10 (more preferably 2 to 6 carbon atoms), or a —SiR ⁷ R ⁸ R ⁹ group (R ⁷ , R ⁸ and R ⁹ are each independently 1 to 10 carbon atoms (more preferably carbon atoms) 1 to 6) an alkyl group, an alkenyl group having 2 to 10 carbon atoms (more preferably an alkenyl group having 2 to 6 carbon atoms), or a phenyl group), or R ¹ and R ² are bonded to each other. A cycloalkane group having 3 to 7 carbon atoms (more preferably 3 to 6 carbon atoms) is formed together with
R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms), a substituted or unsubstituted carbon number 2 to 2; An alkenyl group having 10 (more preferably 2 to 6 carbon atoms), or a —SiR ⁷ R ⁸ R ⁹ group (R ⁷ , R ⁸ and R ⁹ are each independently 1 to 10 carbon atoms (more preferably carbon atoms) 1 to 6) an alkyl group, an alkenyl group having 2 to 10 carbon atoms (more preferably an alkenyl group having 2 to 6 carbon atoms), or a phenyl group), or R ³ and R ⁴ are bonded to each other. In this mode, a cycloalkane group having 3 to 7 carbon atoms (more preferably 3 to 6 carbon atoms) is formed together with the carbon atoms.

Among the above “another preferred forms”, more preferably,
R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a trimethylsilyl group, a dimethyl t-butylsilyl group, a triethylsilyl group, or a triethyl group. An isopropylsilyl group or a cyclopentyl group together with the carbon atoms to which R ¹ and R ² are bonded together,
R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a trimethylsilyl group, a dimethyl t-butylsilyl group, a triethylsilyl group, or a triethyl group. It is an isopropylsilyl group or a form that forms a cyclopentyl group together with the carbon atoms to which R ³ and R ⁴ are bonded together.

Among the preferred forms described above (including “another preferred form”), a more preferred form is that R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a methyl group, an ethyl group, or propyl. Group, or an isopropyl group (more preferably, a hydrogen atom, a methyl group, or an ethyl group),
A particularly preferred form is that R ¹ is a methyl group, an ethyl group, a propyl group, or an isopropyl group (more preferably, a methyl group or an ethyl group), R ² is a hydrogen atom, and R ³ is a methyl group. , An ethyl group, a propyl group, or an isopropyl group (more preferably, a methyl group or an ethyl group), and R ⁴ is a hydrogen atom.

The compound represented by the general formula (V) is preferably a compound other than the compound in which R ¹ , R ² , R ³ and R ^{4 in} the general formula (V) are all hydrogen atoms.

Moreover, in the compound represented by general formula (V), depending on the combination of R ¹ , R ² , R ³ and R ⁴ , isomers having different steric relative configurations may exist. In this case, as an additive for lithium secondary batteries of the present invention, only one of them may be used, or a mixture of both may be used.

Specific examples [Exemplary Compound B-1 to Exemplified Compound B-118] of the compound represented by the general formula (V) in the present invention are represented by R ¹ , R ² , R ³ and R ⁴ in the general formula (V). Although clearly shown in the following table, the present invention is not limited to these compounds.

In the structures of the following exemplary compounds, “Me” represents a methyl group, “Et” represents an ethyl group, “Pr” represents a propyl group, “iPr” represents an isopropyl group, “Bu” represents a butyl group, and “sBu” Is a secondary butyl group, “iBu” is an isobutyl group, “tBu” is a tertiary butyl group, “Pent” is a pentyl group, “Hex” is a hexyl group, “Hept” is a heptyl group, “Oct”. "Represents an octyl group," Non "represents a nonyl group," Dec "represents a decyl group, and" Ph "represents a phenyl group.
Among the following exemplary compounds, in the exemplary compounds in which at least one of R ¹ and R ² and at least one of R ³ and R ⁴ are other than a hydrogen atom, cis-type and trans-type stereoisomers may exist. In this case, the exemplified compound may be either one of both isomers or a mixture of both isomers.

Although there is no restriction | limiting in particular in the method of synthesize | combining the compound represented by general formula (V), For example, it can synthesize | combine by the method described in the following known literatures.
Chemishche Berichte, 1981, 114, 3378-3384.
Chemishche Berichte, 1991, 124, 1805-1807.
Chemishche Berichte, 1993, 126, 537-542.
Chemishche Berichte, 1993, 126, 537-542.
Chemishche Berichte, 1996, 129, 161-168.
Angewandte Chemie, 1980, 92, 223-224
Russian Journal of Organic Chemistry, 1993, 29, 479-481.
Russian Journal of Organic Chemistry, 1995, 31, 543-544.
Russian Journal of Organic Chemistry, 1995, 31, 543-544.
Phosphorous, Slufur and Silicon and Related Elements, 1994, 94, 477-478.
Journal of American Chemical Society, 1996, 108, 2358-2366.
SU 311908 (1971)

The nonaqueous electrolytic solution of the present invention may contain only one type of additive B, or may contain two or more types.
Although there is no restriction | limiting in particular in content (when it is 2 or more types) of additive B in the non-aqueous electrolyte of this invention, From a viewpoint with which the effect of this invention is show | played more effectively. The total amount of the non-aqueous electrolyte is preferably 0.001% by mass to 10% by mass, more preferably 0.1% by mass to 8% by mass, and 0.5% by mass to 8% by mass. It is particularly preferable that the mass range.

In addition, from the viewpoint of more effectively achieving the effect of the present invention (effect by the combination of additive A and additive B), the content mass ratio [additive B / additive A] in the non-aqueous electrolyte is: It is preferably 0.01 to 3.00, more preferably 0.10 to 3.00, and still more preferably 0.20 to 2.60.
Further, from the viewpoint of further reducing the battery resistance after storage, the content ratio [Additive B / Additive A] is more preferably 0.20 to 0.90, and preferably 0.30 to 0.70. It is particularly preferred that

  Although there is no restriction | limiting in particular in the total content of the additive A in the nonaqueous electrolyte of this invention, and the additive B, From a viewpoint with which the effect of this invention is show | played more effectively, it is made into the whole quantity of a nonaqueous electrolyte. On the other hand, it is preferably 0.001% by mass to 10% by mass, more preferably 0.1% by mass to 8% by mass, and 0.5% by mass to 8% by mass. Particularly preferred.

In the non-aqueous electrolyte solution of the present invention, a preferable combination of the additive A and the additive B is a combination formed by arbitrarily combining the above-described preferable form of the additive A and the above-described preferable form of the additive B. is there.
Among these, from the viewpoint that the effect of the present invention is particularly noticeable,
As additive A, in general formula (I), R ¹ is a group represented by general formula (II) (in general formula (II), R ³ is a fluorine atom, a methyl group, an ethyl group, a trifluoromethyl group, A methoxy group, an ethoxy group, or a group represented by formula (IV)) or a group represented by formula (III), and a cyclic sulfate ester compound in which R ² is a hydrogen atom or a methyl group, and In the general formula (V), as additive B, R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, methyl group, ethyl group, propyl group, or isopropyl group (more preferably More preferably, a cyclic sulfone compound which is a hydrogen atom, a methyl group, or an ethyl group);
As additive A, in general formula (I), R ¹ is a group represented by general formula (II) (in general formula (II), R ³ is a fluorine atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. Or a group represented by formula (IV)) or a group represented by formula (III), and a cyclic sulfate ester compound in which R ² is a hydrogen atom or a methyl group, and
As the additive B, in the general formula (V), R ¹ is a methyl group, an ethyl group, a propyl group, or an isopropyl group (more preferably a methyl group or an ethyl group), and R ² is a hydrogen atom, It is particularly preferable to use a cyclic sulfone compound in which R ³ is a methyl group, an ethyl group, a propyl group, or an isopropyl group (more preferably a methyl group or an ethyl group), and R ⁴ is a hydrogen atom.

<Additive C>
The nonaqueous electrolytic solution of the present invention is further at least one selected from the group consisting of a carbonate compound having a carbon-carbon unsaturated bond, a carbonate compound substituted with a fluorine atom, a fluorophosphate compound, and a cyclic sultone compound. It is preferable to contain an additive C.
When the nonaqueous electrolytic solution of the present invention contains the additive C, the above-described effects of the present invention are more effectively exhibited. The reason for this is considered that the additive C strengthens the film formed on the electrode surface by the additive A and the additive B, whereby the decomposition of the solvent on the electrode surface is more effectively suppressed.

(Carbonate compound having a carbon-carbon unsaturated bond)
Examples of the carbonate compound having a carbon-carbon unsaturated bond include methyl vinyl carbonate, ethyl vinyl carbonate, divinyl carbonate, methyl propynyl carbonate, ethyl propynyl carbonate, dipropynyl carbonate, methyl phenyl carbonate, ethyl phenyl carbonate, diphenyl carbonate, and the like. Carbonates; vinylene carbonate, methyl vinylene carbonate, 4,4-dimethyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, vinyl ethylene carbonate, 4,4-divinyl ethylene carbonate, 4,5-divinyl ethylene carbonate, ethynyl ethylene carbonate, 4,4-diethynyl ethylene carbonate, 4,5-diethynyl ethylene carbonate, propylene Le ethylene carbonate, 4,4-propynyl carbonate, cyclic carbonates such as 4,5-di-propynyl carbonate; and the like. Among these, preferably, methyl phenyl carbonate, ethyl phenyl carbonate, diphenyl carbonate, vinylene carbonate, vinyl ethylene carbonate, 4,4-divinyl ethylene carbonate, 4,5-divinyl ethylene carbonate, more preferably vinylene carbonate, Vinyl ethylene carbonate.
The form containing a carbonate compound having a carbon-carbon unsaturated bond as additive C is particularly advantageous in that the capacity retention rate after storage can be maintained higher and the increase in battery resistance due to storage can be further suppressed. It is.

(Carbonate compound having fluorine atom)
Examples of the carbonate compound having a fluorine atom include methyl trifluoromethyl carbonate, ethyl trifluoromethyl carbonate, bis (trifluoromethyl) carbonate, methyl (2,2,2-trifluoroethyl) carbonate, ethyl (2,2,2). -Chain carbonates such as trifluoroethyl) carbonate and bis (2,2,2-trifluoroethyl) carbonate; 4-fluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, 4 -Cyclic carbonates such as trifluoromethylethylene carbonate; Of these, 4-fluoroethylene carbonate, 4,4-difluoroethylene carbonate, and 4,5-difluoroethylene carbonate are preferable.

(Fluorophosphate compound)
Examples of the fluorophosphate compound include lithium difluorophosphate, lithium monofluorophosphate, lithium difluorobis (oxalato) phosphate, lithium tetrafluoro (oxalato) phosphate, difluorophosphoric acid, monofluorophosphoric acid, methyl difluorophosphate, Examples include ethyl difluorophosphate, dimethyl fluorophosphate, and diethyl fluorophosphate. Among these, lithium difluorophosphate, lithium monofluorophosphate, lithium difluorobis (oxalato) phosphate, and lithium tetrafluoro (oxalato) phosphate are preferable.
The form containing a fluorophosphate compound as additive C is particularly advantageous in that the battery resistance before storage can be further reduced, the battery resistance after storage can be further reduced, and the increase in battery resistance due to storage can be further suppressed. is there.

(Cyclic sultone compound)
Examples of cyclic sultone compounds include 1,3-propane sultone, 1,4-butane sultone, 1,3-propene sultone, 1-methyl-1,3-propene sultone, 2-methyl-1,3-propene sultone, 3- Examples include sultone such as methyl-1,3-propene sultone. Of these, 1,3-propane sultone and 1,3-propene sultone are preferable.

  The above-mentioned additive C includes vinylene carbonate, vinyl ethylene carbonate, 4-fluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, lithium monofluorophosphate, lithium difluorophosphate, difluorobis ( Oxalato) lithium phosphate, tetrafluoro (oxalato) lithium phosphate, 1,3-propane sultone, and 1,3-propene sultone are particularly preferred.

When the nonaqueous electrolytic solution of the present invention contains the additive C, the additive C contained may be only one kind or two or more kinds.
When the non-aqueous electrolyte of the present invention contains the additive C, the content thereof (the total content when there are two or more) is not particularly limited, but the effects of the present invention are more effective. From the viewpoint of being made, it is preferably 0.001% by mass to 10% by mass, more preferably in the range of 0.05% by mass to 5% by mass, with respect to the total amount of the non-aqueous electrolyte. More preferably, it is in the range of 4% by mass to 4% by mass, more preferably in the range of 0.1% by mass to 2% by mass, and particularly preferably in the range of 0.1% by mass to 1% by mass. .

  Moreover, when the non-aqueous electrolyte of this invention contains the additive C, the total content of the additive A, the additive B, and the additive C is from the viewpoint that the effect of the present invention is more effectively exhibited. The total amount of the non-aqueous electrolyte is preferably 0.001% by mass to 10% by mass, more preferably 0.1% by mass to 8% by mass, and 0.5% by mass to 8% by mass. It is particularly preferable that the mass range.

Moreover, the nonaqueous electrolytic solution of the present invention may contain other additives other than those described above.
Other additives can be appropriately selected from the additives described in, for example, International Publication No. 2012/053644 pamphlet, International Publication No. 2011-136189 pamphlet, and the like.

Next, other components of the nonaqueous electrolytic solution will be described.
The nonaqueous electrolytic solution generally contains an electrolyte and a nonaqueous solvent.

<Nonaqueous solvent>
As the non-aqueous solvent in the present invention, various known ones can be appropriately selected, but it is preferable to use a cyclic aprotic solvent and / or a chain aprotic solvent.
In order to improve the safety of the battery, when aiming to improve the flash point of the solvent, it is preferable to use a cyclic aprotic solvent as the non-aqueous solvent.

(Cyclic aprotic solvent)
As the cyclic aprotic solvent, cyclic carbonate, cyclic carboxylic acid ester, cyclic sulfone, and cyclic ether can be used.
The cyclic aprotic solvent may be used alone or in combination of two or more.
The mixing ratio of the cyclic aprotic solvent in the non-aqueous solvent is 10% by mass to 100% by mass, more preferably 20% by mass to 90% by mass, and particularly preferably 30% by mass to 80% by mass. By setting it as such a ratio, the electroconductivity of the electrolyte solution relating to the charge / discharge characteristics of the battery can be increased.
Specific examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, and the like. Of these, ethylene carbonate and propylene carbonate having a high dielectric constant are preferably used. In the case of a battery using graphite as the negative electrode active material, ethylene carbonate is more preferable. Moreover, you may use these cyclic carbonates in mixture of 2 or more types.

Specific examples of the cyclic carboxylic acid ester include γ-butyrolactone, δ-valerolactone, alkyl substitution products such as methyl γ-butyrolactone, ethyl γ-butyrolactone, and ethyl δ-valerolactone.
The cyclic carboxylic acid ester has a low vapor pressure, a low viscosity, a high dielectric constant, and can lower the viscosity of the electrolytic solution without lowering the degree of dissociation between the flash point of the electrolytic solution and the electrolyte. For this reason, since it has the feature that the conductivity of the electrolytic solution, which is an index related to the discharge characteristics of the battery, can be increased without increasing the flammability of the electrolytic solution, when aiming to improve the flash point of the solvent, It is preferable to use a cyclic carboxylic acid ester as the cyclic aprotic solvent. Of the cyclic carboxylic acid esters, γ-butyrolactone is most preferred.
The cyclic carboxylic acid ester is preferably used by mixing with another cyclic aprotic solvent. For example, a mixture of a cyclic carboxylic acid ester and a cyclic carbonate and / or a chain carbonate can be mentioned.

Examples of the cyclic sulfone include sulfolane, 2-methylsulfolane, 3-methylsulfolane, dimethyl sulfone, diethyl sulfone, dipropyl sulfone, methylethyl sulfone, methylpropyl sulfone and the like.
An example of a cyclic ether is dioxolane.

(Chain aprotic solvent)
As the chain aprotic solvent of the present invention, a chain carbonate, a chain carboxylic acid ester, a chain ether, a chain phosphate, or the like can be used.
The mixing ratio of the chain aprotic solvent in the non-aqueous solvent is 10% by mass to 100% by mass, more preferably 20% by mass to 90% by mass, and particularly preferably 30% by mass to 80% by mass.
Specific examples of the chain carbonate include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, methyl butyl carbonate, ethyl butyl carbonate, dibutyl carbonate, methyl pentyl carbonate, Examples include ethyl pentyl carbonate, dipentyl carbonate, methyl heptyl carbonate, ethyl heptyl carbonate, diheptyl carbonate, methyl hexyl carbonate, ethyl hexyl carbonate, dihexyl carbonate, methyl octyl carbonate, ethyl octyl carbonate, dioctyl carbonate, and methyltrifluoroethyl carbonate. These chain carbonates may be used as a mixture of two or more.

Specific examples of the chain carboxylic acid ester include methyl pivalate.
Specific examples of the chain ether include dimethoxyethane.
Specific examples of the chain phosphate ester include trimethyl phosphate.

(Solvent combination)
The nonaqueous solvent used in the nonaqueous electrolytic solution of the present invention may be used alone or in combination. Further, only one or more types of cyclic aprotic solvents may be used, or only one or more types of chain aprotic solvents may be used, or cyclic aprotic solvents and chain proticity may be used. You may mix and use a solvent. When the load characteristics and low temperature characteristics of the battery are particularly intended to be improved, it is preferable to use a combination of a cyclic aprotic solvent and a chain aprotic solvent as the nonaqueous solvent.
Furthermore, in view of the electrochemical stability of the electrolytic solution, it is most preferable to apply a cyclic carbonate to the cyclic aprotic solvent and a chain carbonate to the chain aprotic solvent. Further, the conductivity of the electrolytic solution related to the charge / discharge characteristics of the battery can be increased by a combination of the cyclic carboxylic acid ester and the cyclic carbonate and / or the chain carbonate.

As a combination of cyclic carbonate and chain carbonate, specifically, ethylene carbonate and dimethyl carbonate, ethylene carbonate and methyl ethyl carbonate, ethylene carbonate and diethyl carbonate, propylene carbonate and dimethyl carbonate, propylene carbonate and methyl ethyl carbonate, propylene carbonate and Diethyl carbonate, ethylene carbonate and propylene carbonate and methyl ethyl carbonate, ethylene carbonate and propylene carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate, ethylene carbonate and methyl ethyl carbonate Diethyl carbonate, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate, ethylene carbonate, propylene carbonate and methyl ethyl carbonate And diethyl carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate.
The mixing ratio of the cyclic carbonate and the chain carbonate is expressed as a mass ratio, and the cyclic carbonate: chain carbonate is 5:95 to 80 to 20, more preferably 10:90 to 70:30, particularly preferably 15:85. ~ 55: 45. By setting it as such a ratio, since the raise of the viscosity of electrolyte solution can be suppressed and the dissociation degree of electrolyte can be raised, the conductivity of the electrolyte solution in connection with the charge / discharge characteristic of a battery can be raised. In addition, the solubility of the electrolyte can be further increased. Therefore, since it can be set as the electrolyte solution excellent in the electrical conductivity in normal temperature or low temperature, the load characteristic of the battery from normal temperature to low temperature can be improved.

  Specific examples of combinations of cyclic carboxylic acid esters and cyclic carbonates and / or chain carbonates include γ-butyrolactone and ethylene carbonate, γ-butyrolactone and ethylene carbonate and dimethyl carbonate, and γ-butyrolactone and ethylene carbonate and methylethyl. Carbonate, γ-butyrolactone and ethylene carbonate and diethyl carbonate, γ-butyrolactone and propylene carbonate, γ-butyrolactone and propylene carbonate and dimethyl carbonate, γ-butyrolactone and propylene carbonate and methyl ethyl carbonate, γ-butyrolactone and propylene carbonate and diethyl carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate, γ-butyrolactone, Tylene carbonate and propylene carbonate and dimethyl carbonate, γ-butyrolactone and ethylene carbonate, propylene carbonate and methyl ethyl carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate and diethyl carbonate, γ-butyrolactone, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, γ-butyrolactone, ethylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, ethylene carbonate, methyl ethyl carbonate, diethyl carbonate, γ-butyrolactone, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, γ-butyrolactone, ethylene carbonate And professional Ren carbonate, dimethyl carbonate and methyl ethyl carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate, methyl ethyl carbonate and diethyl carbonate, γ-butyrolactone and ethylene carbonate Propylene carbonate, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate, γ-butyrolactone and sulfolane, γ-butyrolactone and ethylene carbonate and sulfolane, γ-butyrolactone and propylene carbonate and sulfolane, γ-butyrolactone, ethylene carbonate, propylene carbonate and sulfolane, γ -Butyrolactone and sul Such as orchids and dimethyl carbonate.

(Other solvents)
The nonaqueous electrolytic solution according to the present invention may contain a solvent other than the above as a nonaqueous solvent. Specific examples of the other solvent include amides such as dimethylformamide, chain carbamates such as methyl-N, N-dimethylcarbamate, cyclic amides such as N-methylpyrrolidone, N, N-dimethylimidazolidinone and the like. Examples thereof include boron compounds such as cyclic urea, trimethyl borate, triethyl borate, tributyl borate, trioctyl borate, trimethylsilyl borate, and polyethylene glycol derivatives represented by the following general formula.
HO (CH ₂ CH ₂ O) _a H
HO [CH ₂ CH (CH ₃ ) O] _b H
CH ₃ O (CH ₂ CH ₂ O) _c H
CH ₃ O [CH ₂ CH (CH ₃ ) O] _d H
CH ₃ O (CH ₂ CH ₂ O) _e CH ₃
CH ₃ O [CH ₂ CH (CH ₃ ) O] _f CH _{3
C 9 H 19 PhO (CH 2} CH 2 O) g [CH (CH 3) O] h CH 3
(Ph is a phenyl group)
CH ₃ O [CH ₂ CH (CH ₃ ) O] _i CO [OCH (CH ₃ ) CH ₂ ] _j OCH ₃
In the above formula, a to f are integers of 5 to 250, g to j are integers of 2 to 249, 5 ≦ g + h ≦ 250, and 5 ≦ i + j ≦ 250.

<Electrolyte>
The nonaqueous electrolytic solution of the present invention can contain various known electrolytes. Any electrolyte can be used as long as it is normally used as an electrolyte for a non-aqueous electrolyte.
Specific examples of the electrolyte in the present invention include (C ₂ H ₅ ) ₄ NPF ₆ , (C ₂ H ₅ ) ₄ NBF ₄ , (C ₂ H ₅ ) ₄ NClO ₄ , (C ₂ H ₅ ) ₄ NAsF ₆ , (C ₂ H ₅ ) ₄ N ₂ SiF ₆ , (C ₂ H ₅ ) ₄ NOSO ₂ C _k F _{(2k + 1)} (k = 1 to 8), (C ₂ H ₅ ) ₄ NPF _n [C _k F _{(2k + 1)} ] _(6-n) tetraalkylammonium salts such as (n = 1 to 5, integers of k = 1 to 8), LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , Li ₂ SiF ₆ , LiOSO ₂ Lithium salts such as C _k F _{(2k + 1)} (k = 1 to 8), LiPF _n [C _k F _{(2k + 1)} ] _(6-n) (n = 1 to 5, k = 1 to 8) Is mentioned. Moreover, the lithium salt represented by the following general formula can also be used.

_{^{LiC (SO 2 R 27) (}} SO 2 R 28) (SO 2 R 29), LiN (SO 2 OR 30) (SO 2 OR 31), LiN (SO 2 R 32) (SO 2 R 33) ( where R ^{27 to} R ³³ may be the same as or different from each other, and are a C 1-8 perfluoroalkyl group). These electrolytes may be used alone or in combination of two or more.
Of these, lithium salts are particularly desirable, and LiPF ₆ , LiBF ₄ , LiOSO ₂ C _k F _{(2k + 1)} (k = 1 to 8), LiClO ₄ , LiAsF ₆ , LiNSO ₂ [C _k F _{( 2k + 1)] 2 (k} = 1~8 _{integer), LiPF n [C k F} (2k + 1)] (6-n) (n = 1~5, k = 1~8 integer) are preferred.
The electrolyte according to the present invention is usually preferably contained in the nonaqueous electrolytic solution at a concentration of 0.1 mol / L to 3 mol / L, preferably 0.5 mol / L to 2 mol / L.

In the nonaqueous electrolytic solution of the present invention, when a cyclic carboxylic acid ester such as γ-butyrolactone is used in combination as a nonaqueous solvent, it is particularly desirable to contain LiPF ₆ . Since LiPF ₆ has a high degree of dissociation, the conductivity of the electrolytic solution can be increased, and the reductive decomposition reaction of the electrolytic solution on the negative electrode can be suppressed. LiPF ₆ may be used alone, or LiPF ₆ and other electrolytes may be used. Any other electrolyte can be used as long as it is normally used as an electrolyte for a non-aqueous electrolyte, but lithium salts other than LiPF ₆ are preferred among the specific examples of the lithium salts described above. .
Specific examples include LiPF ₆ and LiBF ₄ , LiPF ₆ and LiN [SO ₂ C _k F _{(2k + 1)} ] ₂ (k = 1 to 8), LiPF ₆ , LiBF ₄ and LiN [SO ₂ C _k F _{( 2k + 1)} ] (k = 1 to 8).

The ratio of LiPF _{6 in} the lithium salt is 1% by mass to 100% by mass, preferably 10% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass. Such an electrolyte is preferably contained in the nonaqueous electrolytic solution at a concentration of 0.1 mol / L to 3 mol / L, preferably 0.5 mol / L to 2 mol / L.

The nonaqueous electrolytic solution of the present invention may contain at least one compound other than the above-mentioned compounds as an additive as long as the object of the present invention is not hindered.
Specific examples of other compounds include sulfate esters such as dimethyl sulfate, diethyl sulfate, ethylene sulfate, propylene sulfate, butene sulfate, pentene sulfate and vinylene sulfate; and sulfur compounds such as sulfolane, 3-sulfolene and divinyl sulfone, Can be mentioned.
These compounds may be used alone or in combination of two or more.
Of these, ethylene sulfate, propylene sulfate, butene sulfate, and pentene sulfate are preferred.

  The non-aqueous electrolyte of the present invention is not only suitable as a non-aqueous electrolyte for a lithium secondary battery, but also a non-aqueous electrolyte for a primary battery, a non-aqueous electrolyte for an electrochemical capacitor, and an electric double layer capacitor. It can also be used as an electrolytic solution for aluminum electrolytic capacitors.

[Lithium secondary battery]
The lithium secondary battery of the present invention includes a negative electrode, a positive electrode, and the nonaqueous electrolytic solution of the present invention.
Usually, a separator is provided between the negative electrode and the positive electrode.

(Negative electrode)
The negative electrode active material constituting the negative electrode includes metallic lithium, a lithium-containing alloy, a metal or alloy that can be alloyed with lithium, an oxide that can be doped / undoped with lithium ions, and a doped / undoped lithium ion. At least one selected from the group consisting of possible transition metal nitrides and carbon materials capable of doping and dedoping lithium ions (may be used alone or a mixture containing two or more thereof) May be used).
Examples of metals or alloys that can be alloyed with lithium (or lithium ions) include silicon, silicon alloys, tin, and tin alloys. Further, lithium titanate may be used.
Among these, carbon materials that can be doped / undoped with lithium ions are preferable. Examples of such carbon materials include carbon black, activated carbon, graphite materials (artificial graphite, natural graphite), amorphous carbon materials, and the like. The form of the carbon material may be any of a fibrous form, a spherical form, a potato form, and a flake form.

Specific examples of the amorphous carbon material include hard carbon, coke, mesocarbon microbeads (MCMB) fired at 1500 ° C. or less, and mesopause bitch carbon fiber (MCF).
Examples of the graphite material include natural graphite and artificial graphite. As artificial graphite, graphitized MCMB, graphitized MCF, and the like are used. Further, as the graphite material, a material containing boron can be used. As the graphite material, those coated with a metal such as gold, platinum, silver, copper and tin, those coated with amorphous carbon, and those obtained by mixing amorphous carbon and graphite can be used.

These carbon materials may be used alone or in combination of two or more.
As the carbon material, a carbon material having a (002) plane distance d (002) of 0.340 nm or less as measured by X-ray analysis is particularly preferable. Further, as the carbon material, graphite having a true density of 1.70 g / cm ³ or more or a highly crystalline carbon material having properties close thereto is also preferable. When the carbon material as described above is used, the energy density of the battery can be further increased.

(Positive electrode)
Examples of the positive electrode active material constituting the positive electrode include transition metal oxides or transition metal sulfides such as MoS ₂ , TiS ₂ , MnO ₂ , and V ₂ O ₅ , LiCoO ₂ , LiMnO ₂ , LiMn ₂ O ₄ , LiNiO ₂ , LiNi _X Co _(1-X) O ₂ [0 <X <1], composite oxides composed of lithium and transition metals such as LiFePO ₄ , polyaniline, polythiophene, polypyrrole, polyacetylene, polyacene, dimercaptothiadiazole, polyaniline complex Examples thereof include conductive polymer materials. Among these, a composite oxide composed of lithium and a transition metal is particularly preferable. When the negative electrode is lithium metal or a lithium alloy, a carbon material can be used as the positive electrode. In addition, a mixture of a composite oxide of lithium and a transition metal and a carbon material can be used as the positive electrode.
Said positive electrode active material may be used by 1 type, and may mix and use 2 or more types. When the positive electrode active material has insufficient conductivity, it can be used together with a conductive auxiliary agent to constitute a positive electrode. Examples of the conductive assistant include carbon materials such as carbon black, amorphous whiskers, and graphite.

(Separator)
The separator is a film that electrically insulates the positive electrode and the negative electrode and transmits lithium ions, and examples thereof include a porous film and a polymer electrolyte.
A microporous polymer film is preferably used as the porous film, and examples of the material include polyolefin, polyimide, polyvinylidene fluoride, and polyester.
In particular, porous polyolefin is preferable. Specifically, a porous polyethylene film, a porous polypropylene film, or a multilayer film of a porous polyethylene film and a polypropylene film can be exemplified. On the porous polyolefin film, other resin excellent in thermal stability may be coated.
Examples of the polymer electrolyte include a polymer in which a lithium salt is dissolved, a polymer swollen with an electrolytic solution, and the like.
The nonaqueous electrolytic solution of the present invention may be used for the purpose of obtaining a polymer electrolyte by swelling a polymer.

(Battery configuration)
The lithium secondary battery which concerns on embodiment of this invention contains said negative electrode active material, a positive electrode active material, and a separator.
The lithium secondary battery of the present invention can take various known shapes, and can be formed into a cylindrical shape, a coin shape, a square shape, a film shape, or any other shape. However, the basic structure of the battery is the same regardless of the shape, and the design can be changed according to the purpose.
As an example of the lithium secondary battery (nonaqueous electrolyte secondary battery) of the present invention, a coin-type battery shown in FIG.
In the coin-type battery shown in FIG. 1, a disc-shaped negative electrode 2, a separator 5 into which a non-aqueous electrolyte is injected, a disc-shaped positive electrode 1, and spacer plates 7 and 8 such as stainless steel or aluminum as necessary are arranged in this order. In a laminated state, the positive electrode can 3 (hereinafter also referred to as “battery can”) and the sealing plate 4 (hereinafter also referred to as “battery can lid”) are accommodated. The positive electrode can 3 and the sealing plate 4 are caulked and sealed via a gasket 6.
In this example, the nonaqueous electrolytic solution of the present invention can be used as the nonaqueous electrolytic solution injected into the separator 5.

The lithium secondary battery of the present invention is obtained by charging / discharging a lithium secondary battery (lithium secondary battery before charge / discharge) including a negative electrode, a positive electrode, and the non-aqueous electrolyte of the present invention. Lithium secondary batteries may be used.
That is, the lithium secondary battery of the present invention is prepared by first preparing a lithium secondary battery before charging / discharging including the negative electrode, the positive electrode, and the non-aqueous electrolyte of the present invention, and then before charging / discharging. It may be a lithium secondary battery (charged / discharged lithium secondary battery) produced by charging / discharging the lithium secondary battery one or more times.

  The use of the lithium secondary battery of the present invention is not particularly limited, and can be used for various known uses. For example, notebook computers, mobile computers, mobile phones, headphone stereos, video movies, LCD TVs, handy cleaners, electronic notebooks, calculators, radios, backup power applications, motors, automobiles, electric cars, motorcycles, electric bikes, bicycles, electric bicycles It can be widely used regardless of whether it is a small portable device or a large device, such as a lighting fixture, a game machine, a watch, a power tool, a camera.

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.
In the following examples, “wt%” represents mass%.
In the following examples, “addition amount” represents the content in the finally obtained non-aqueous electrolyte (that is, the amount relative to the total amount of the finally obtained non-aqueous electrolyte).

[Example 1]
A lithium secondary battery was produced by the following procedure.
<Production of negative electrode>
20 parts by mass of artificial graphite, 80 parts by mass of natural graphite, 1 part by mass of carboxymethyl cellulose and 2 parts by mass of SBR latex were kneaded with an aqueous solvent to prepare a paste-like negative electrode mixture slurry.
Next, this negative electrode mixture slurry was applied to a negative electrode current collector made of a strip-shaped copper foil having a thickness of 18 μm, dried, and then compressed by a roll press to form a sheet-shaped negative electrode comprising a negative electrode current collector and a negative electrode active material layer Got. The coating density of the negative electrode active material layer at this time was 10 mg / cm ² , and the packing density was 1.5 g / ml.

<Preparation of positive electrode>
90 parts by mass of LiCoO ₂ , 5 parts by mass of acetylene black and 5 parts by mass of polyvinylidene fluoride were kneaded using N-methylpyrrolidinone as a solvent to prepare a paste-like positive electrode mixture slurry.
Next, this positive electrode mixture slurry is applied to a positive electrode current collector made of a strip-shaped aluminum foil having a thickness of 20 μm, dried, and then compressed by a roll press to form a sheet-like positive electrode comprising a positive electrode current collector and a positive electrode active material. Obtained. The coating density of the positive electrode active material layer at this time was 30 mg / cm ² , and the packing density was 2.5 g / ml.

<Preparation of non-aqueous electrolyte>
As a non-aqueous solvent, ethylene carbonate (EC), dimethyl carbonate (DMC), and methyl ethyl carbonate (EMC) were mixed at a ratio of 30:35:35 (mass ratio), respectively, to obtain a mixed solvent.
In the obtained mixed solvent, LiPF ₆ as an electrolyte was dissolved so that the electrolyte concentration in the finally obtained nonaqueous electrolytic solution was 1 mol / liter.
With respect to the solution obtained above, the exemplary compound A-1 (addition amount 0.5 wt%) as additive A (cyclic sulfate ester compound) and additive B (1,3-dithietane-1, The exemplified compound B-6 (addition amount 0.5 wt%) as a compound having a 1,3,3-tetraoxide skeleton was added to obtain a non-aqueous electrolyte.

<Production of coin-type battery>
The above-mentioned negative electrode was 14 mm in diameter and the above-mentioned positive electrode was 13 mm in diameter, and each was punched into a disk shape to obtain coin-shaped electrodes (negative electrode and positive electrode). Further, a microporous polyethylene film having a thickness of 20 μm was punched into a disk shape having a diameter of 17 mm to obtain a separator.
The obtained coin-shaped negative electrode, separator, and coin-shaped positive electrode are laminated in this order in a battery can (2032 size) made of stainless steel, and 20 μl of the non-aqueous electrolyte is injected to be contained in the separator, the positive electrode, and the negative electrode. Soaked.
Further, an aluminum plate (thickness 1.2 mm, diameter 16 mm) and a spring are placed on the positive electrode, and the battery can be sealed by caulking the battery can lid through a polypropylene gasket, and the diameter is 20 mm and height. A coin-type lithium secondary battery (hereinafter referred to as a test battery) having the configuration shown in FIG.
Each measurement was implemented about the obtained coin-type battery (battery for a test).

[Evaluation method]
<Charge / discharge characteristics of battery: capacity retention after storage at high temperature>
The coin-type battery was charged at a constant current of 4.2 mA at a constant current of 1 mA in a constant temperature bath at 25 ° C., and the discharge capacity was measured when discharged to 2.85 V at a constant current of 1 mA in the constant temperature bath at 25 ° C. The initial discharge capacity [mAh].
Thereafter, the battery was charged at a constant voltage of 4.2 V, and then the coin-type battery after charging was stored in a thermostat at 80 ° C. for 2 days, and then discharged to 2.85 V at a constant current of 1 mA in a thermostat at 25 ° C. The discharge capacity at the time was measured and set as the discharge capacity [mAh] after storage at high temperature, and the capacity retention rate [%] after storage at high temperature was determined by the following formula.

Capacity retention ratio after storage at high temperature in Example 1 [%]
= (Discharge capacity after high temperature storage [mAh] / Initial discharge capacity [mAh])

  Similarly, the initial discharge capacity [mAh] and the discharge capacity [mAh] after high-temperature storage were measured for the coin-type battery of Comparative Example 1 described later, and the capacity retention rate [%] after high-temperature storage in Comparative Example 1 was measured. Asked.

From the above results, the capacity retention rate after high-temperature storage in Example 1 [%] (relative value;%) when the capacity retention rate [%] after high-temperature storage in Comparative Example 1 is 100% according to the following formula. As a result, “capacity maintenance rate after high-temperature storage [%]” was obtained.
The obtained results are shown in Table 1.

Capacity maintenance rate after high temperature storage [%]
= (Capacity maintenance rate after high temperature storage test in Example 1 [%] / Capacity maintenance rate after high temperature storage in Comparative Example 1 [%]) × 100 [%]

<Battery resistance characteristics: battery resistance before storage (initial)>
The coin-type battery is charged at a constant voltage of 4.2 V, and then the charged coin-type battery is cooled to −20 ° C. in a constant temperature bath and discharged at −20 ° C. with a 0.2 mA constant current. The DC resistance [Ω] (−20 ° C.) of the coin-type battery was measured by measuring the potential drop for 10 seconds from the start, and the obtained value was defined as the resistance value before storage [Ω] (−20 ° C.). .
Similarly, a resistance value [Ω] (−20 ° C.) before storage was measured for a coin-type battery of Comparative Example 1 described later.
From these results, the resistance value before storage in Example 1 (relative value;%) when the resistance value [Ω] (−20 ° C.) before storage in Comparative Example 1 is defined as 100% by the following formula. As “battery resistance before storage [%]”.
The obtained results are shown in Table 1.

Battery resistance before storage [%]
= (Initial resistance value [Ω] in Example 1 / Initial resistance value [Ω] in Comparative Example 1) × 100 [%]

<Battery resistance characteristics: Battery resistance after storage>
The coin-type battery is charged at a constant voltage of 4.2 V, and then the coin-type battery after charging is stored in a thermostat at 80 ° C. for 2 days, and then the direct current of the coin-type battery is measured in the same manner as the initial battery resistance. Resistance [Ω] (−20 ° C.) was measured, and the obtained value was defined as resistance value [Ω] (−20 ° C.) after storage.
Similarly, the resistance value [Ω] (−20 ° C.) after storage was measured for a coin-type battery of Comparative Example 1 described later.
From these results, according to the following formula, the resistance value after storage in Comparative Example 1 [Ω] (−20 ° C.) as 100% as the resistance value after storage in Example 1 (relative value;%), “Battery resistance after storage [%]” was determined.
The obtained results are shown in Table 1.

Battery resistance after storage [%]
= (Resistance value after storage in Example 1 [Ω] / Resistance value after storage in Comparative Example 1 [Ω]) × 100 [%]

<Battery resistance characteristics: ratio [after storage / before storage]>
In order to examine the change in battery resistance due to storage, the ratio (ratio [after storage / before storage]) of the above “battery resistance [%] after storage” to the “battery resistance [%] before storage” was calculated.
As this ratio [after storage / before storage] is smaller, the increase in battery resistance due to storage is suppressed.

[Comparative Example 1]
In Example 1, a nonaqueous electrolytic solution was prepared in the same manner as in Example 1 except that Exemplified Compound A-1 and Exemplified Compound B-6 were not added (that is, there was no additive). The production and evaluation of the battery were performed in the same manner as in Example 1. The obtained results are shown in Table 1.

[Comparative Example 2]
In Example 1, a nonaqueous electrolytic solution was prepared in the same manner as in Example 1 except that Example Compound B-6 was not added. The production and evaluation of the battery were performed in the same manner as in Example 1. The obtained results are shown in Table 1.

[Comparative Example 3]
In Comparative Example 2, a nonaqueous electrolytic solution was prepared in the same manner as Comparative Example 2 except that Example Compound A-1 was changed to Example Compound A-22 having the same addition amount. The battery was manufactured and evaluated in the same manner as in Comparative Example 2. The obtained results are shown in Table 1.

[Comparative Example 4]
In Example 1, a nonaqueous electrolytic solution was prepared in the same manner as in Example 1 except that Example Compound A-1 was not added. The production and evaluation of the battery were performed in the same manner as in Example 1. The obtained results are shown in Table 1.

[Example 2]
A nonaqueous electrolytic solution was prepared in the same manner as in Example 1 except that Example Compound A-1 was changed to Example Compound A-22 having the same addition amount in Example 1. The production and evaluation of the battery were performed in the same manner as in Example 1. The obtained results are shown in Table 1.

Example 3
In Example 1, Exemplified Compound A-1 was changed to Exemplified Compound A-22 having the same addition amount, and Vinylene Carbonate (Addition amount 0.5 wt%) as Additive C was further added. Similarly, a non-aqueous electrolyte was prepared. The production and evaluation of the battery were performed in the same manner as in Example 1. The obtained results are shown in Table 1.

Example 4
In Example 1, Exemplified Compound A-1 was changed to Exemplified Compound A-22 with the same addition amount, and Lithium Difluorophosphate (Addition amount 0.5 wt%) as Additive C was further added. A non-aqueous electrolyte was prepared in the same manner as in 1. The production and evaluation of the battery were performed in the same manner as in Example 1. The obtained results are shown in Table 1.

-Description of Table 1-
-Exemplified compounds A-1 and A-22 are specific examples of the additive A which is a cyclic sulfate compound.
-Illustrative compound B-6 is a specific example of additive B which is a compound having a 1,3-dithietane-1,1,3,3-tetraoxide skeleton.
Vinylene carbonate is a specific example of additive C (specifically, a carbonate compound having a carbon-carbon unsaturated bond).
-Lithium difluorophosphate is a specific example of the additive C (specifically, fluorophosphate compound).

  As shown in Table 1, a combination of additive A, which is a cyclic sulfate compound, and additive B, which is a compound having a 1,3-dithietane-1,1,3,3-tetraoxide skeleton, was used. In Examples 1 to 4, compared with Comparative Example 1 in which neither additive A nor additive B was used, the capacity retention rate after storage at high temperature was equal to or higher, and the battery resistance before and after storage was reduced. , The increase in the ratio [after storage / before storage] was suppressed. That is, in Examples 1 to 4, the decrease in the capacity maintenance rate after storage was suppressed, and further, the battery resistance after storage (before storage) and after storage was reduced, and the increase in battery resistance due to storage was also suppressed. .

Compared with Examples 1 to 4, the battery resistance before storage increased in Comparative Example 2 in which Example Compound A-1 was used as Additive A and Additive B was not used.
Further, in Comparative Example 3 in which the exemplified compound A-22 was used as the additive A and the additive B was not used, the battery resistance after storage and the ratio [after storage / before storage] increased.
Moreover, in the comparative example 4 which did not use the additive A, the capacity | capacitance maintenance factor after high temperature storage fell.

Moreover, in Example 3 using vinylene carbonate which is a carbonate compound having a carbon-carbon unsaturated bond as additive C, the capacity retention rate after high-temperature storage is higher than that in Example 2, and the ratio [ After storage / before storage] was further reduced.
Moreover, in Example 4 using lithium difluorophosphate which is a fluorophosphate compound as additive C, compared with Example 2, the battery resistance before storage, the battery resistance after storage, and the ratio [storage After / before storage] was further reduced.

[Examples 5 and 6]
In Example 2, a nonaqueous electrolytic solution was prepared in the same manner as in Example 2 except that the content of the additive A and the content of the additive B were changed as shown in Table 2 below. The production and evaluation of the battery were performed in the same manner as in Example 1. The obtained results are shown in Table 2.

  As shown in Table 2, in Examples 5 and 6, as in Example 2, the decrease in capacity retention rate after storage is suppressed, and further, battery resistance after initial (before storage) and after storage is reduced. The increase in battery resistance due to storage was also suppressed.

1 Positive electrode 2 Negative electrode 3 Positive electrode can 4 Sealing plate 5 Separator 6 Gasket 7 and 8 Spacer plate

Claims (14)

  A non-aqueous electrolyte for a battery comprising an additive A which is a cyclic sulfate compound and an additive B which is a compound having a 1,3-dithietane-1,1,3,3-tetraoxide skeleton. The battery nonaqueous electrolyte solution according to claim 1, wherein the additive A is a compound represented by the following general formula (I).

[In General Formula (I), R ¹ represents a group represented by General Formula (II) or a group represented by Formula (III), and R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Represents a group represented by the general formula (II) or a group represented by the formula (III).
In the general formula (II), R ³ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a formula (IV). Represents a group. The wavy line in general formula (II), formula (III), and formula (IV) represents the bonding position.
When the cyclic sulfate ester compound represented by the general formula (I) includes two groups represented by the general formula (II), the two groups represented by the general formula (II) are the same. Or they may be different from each other. ] In the general formula (I), the R ¹ is a group represented by the general formula (II) (in the general formula (II), the R ³ is a fluorine atom, an alkyl having 1 to 3 carbon atoms). A group, a halogenated alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a group represented by the formula (IV)), or a group represented by the formula (III) And R ² is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group represented by the general formula (II) (in the general formula (II), the R ³ is a fluorine atom, carbon An alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a group represented by the formula (IV)), or the formula (III) The nonaqueous electrolytic solution for a battery according to claim 2, which is a group represented by: In the general formula (I), the R ¹ is a group represented by the general formula (II) (in the general formula (II), the R ³ is a fluorine atom, a methyl group, an ethyl group, A fluoromethyl group, a methoxy group, an ethoxy group, or a group represented by the formula (IV)) or a group represented by the formula (III), and the R ² is a hydrogen atom or a methyl group. The non-aqueous electrolyte for batteries according to claim 2 or claim 3. The non-aqueous electrolyte for a battery according to any one of claims 1 to 4, wherein the additive B is a cyclic sulfone compound represented by the following general formula (V).

[In General Formula (V), R ¹ , R ² , R ³ and R ⁴ are each independently
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
A substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms,
A substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms,
-SiR ⁷ R ⁸ R ⁹ group (R ⁷ , R ⁸ and R ⁹ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a phenyl group),
-CO ₂ R ¹⁰ group ^{(R 10} is. Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group or a -SiR ⁷ R ⁸ R ⁹ group,),
-COR ¹¹ group (R ¹¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a phenyl group),
—P (O) (OR ¹² ) ₂ groups (R ¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or the aforementioned —SiR ⁷ R ⁸ R ⁹ group.) ,
-SO ₂ R ¹³ group ^{(R 13} represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a phenyl group.),
-SO ₂ ^{(OR 14)} group ^{(R 14} is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group or a -SiR ⁷ R ⁸ R ⁹ group,.), Or, —B (OR ¹⁵ ) ₂ group (R ¹⁵ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or the —SiR ⁷ R ⁸ R ⁹ group).
R ¹ and R ² may be bonded to each other to form a C 3-7 cycloalkane group together with the carbon atom to which R ¹ and R ² are bonded. Methylene group represented by (VI) (in general formula (VI), R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a group having 2 to 12 carbon atoms. Represents a dialkylamino group, R ⁵ and R ⁶ may be bonded together to form a C 3-7 cycloalkane group together with the carbon atom to which R ⁵ and R ⁶ are bonded. May be.
R ³ and R ⁴ may be bonded to each other to form a cycloalkane group having 3 to 7 carbon atoms together with the carbon atom to which R ³ and R ⁴ are bonded. Methylene group represented by (VI) (in general formula (VI), R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a group having 2 to 12 carbon atoms. Represents a dialkylamino group, R ⁵ and R ⁶ may be bonded together to form a C 3-7 cycloalkane group together with the carbon atom to which R ⁵ and R ⁶ are bonded. May be. ] In the general formula (V), R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted carbon number of 2 to 2. 6 alkenyl group, or -SiR ⁷ R ⁸ R ⁹ group (wherein R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, Or a phenyl group), or
The R ¹ and the R ² are bonded to each other to form a C3-C6 cycloalkane group together with the carbon atom to which the R ¹ and the R ² are bonded, or the R ¹ and the R ² Are methylene groups represented by the general formula (VI) (in the general formula (VI), R ⁵ and R ⁶ are each independently a hydrogen atom or a dialkylamino group having 2 to 12 carbon atoms). Represents a group),
R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, or —SiR. ⁷ R ⁸ R ⁹ group (wherein R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group). Or
The R ³ and the R ⁴ are bonded to each other to form a C 3-6 cycloalkane group together with the carbon atom to which the R ³ and the R ⁴ are bonded, or the R ³ and the R ⁴ Are methylene groups represented by the general formula (VI) (in the general formula (VI), R ⁵ and R ⁶ are each independently a hydrogen atom or a dialkylamino group having 2 to 12 carbon atoms). The nonaqueous electrolytic solution for a battery according to claim 5, which represents a group. In the general formula (V), R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an allyl group, or a trimethylsilyl group. , A dimethyl t-butylsilyl group, a triethylsilyl group, or a triisopropylsilyl group, or
The R ¹ and the R ² are bonded to each other to form a cyclopentyl group together with the carbon atom to which the R ¹ and the R ² are bonded, or the R ¹ and the R ² are combined to form the general Forming a methylene group represented by the formula (VI) (in the general formula (VI), one of R ⁵ and R ⁶ is a hydrogen atom, and the other of R ⁵ and R ⁶ is a dimethylamino group). And
R ³ and R ⁴ are each independently a hydrogen atom, fluorine atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, allyl group, trimethylsilyl group, dimethyl t-butylsilyl group, triethyl A silyl group or a triisopropylsilyl group, or
The R ³ and the R ⁴ are bonded to each other to form a cyclopentyl group together with the carbon atom to which the R ³ and the R ⁴ are bonded, or the R ³ and the R ⁴ are combined to form the general Forming a methylene group represented by the formula (VI) (in the general formula (VI), one of R ⁵ and R ⁶ is a hydrogen atom, and the other of R ⁵ and R ⁶ is a dimethylamino group). The non-aqueous electrolyte for batteries according to claim 5 or 6. 6. The general formula (V), wherein R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an isopropyl group. The nonaqueous electrolytic solution for a battery according to any one of to 7.   The additive C further comprises at least one additive C selected from the group consisting of a carbonate compound having a carbon-carbon unsaturated bond, a carbonate compound having a fluorine atom, a fluorophosphate compound, and a cyclic sultone compound. The nonaqueous electrolytic solution for a battery according to claim 8.   The non-aqueous electrolyte for a battery according to claim 9, wherein the content of the additive C is 0.001% by mass to 10% by mass.   The non-aqueous electrolyte for a battery according to any one of claims 1 to 10, wherein a content of the additive A is 0.001% by mass to 10% by mass.   The non-aqueous electrolyte for a battery according to any one of claims 1 to 11, wherein a content of the additive B is 0.001% by mass to 10% by mass.   A positive electrode and metallic lithium, a lithium-containing alloy, a metal or alloy that can be alloyed with lithium, an oxide that can be doped / undoped with lithium ions, a transition metal nitride that can be doped / undoped with lithium ions, And a negative electrode containing at least one selected from the group consisting of carbon materials capable of being doped / undoped with lithium ions as a negative electrode active material, and the non-battery according to any one of claims 1 to 12. A lithium secondary battery comprising a water electrolyte.   A positive electrode and metallic lithium, a lithium-containing alloy, a metal or alloy that can be alloyed with lithium, an oxide that can be doped / undoped with lithium ions, a transition metal nitride that can be doped / undoped with lithium ions, And a negative electrode containing at least one selected from the group consisting of carbon materials capable of being doped / undoped with lithium ions as a negative electrode active material, and the non-battery according to any one of claims 1 to 12. A lithium secondary battery obtained by charging and discharging a lithium secondary battery containing a water electrolyte.