JP6980502B2 - Non-aqueous electrolyte for batteries and lithium secondary batteries - Google Patents

Description

The present disclosure relates to a non-aqueous electrolyte solution for a battery and a lithium secondary battery.

In recent years, lithium secondary batteries have been widely used as a power source for electronic devices such as mobile phones and notebook personal computers, electric vehicles, and power storage. 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 installed in hybrid vehicles and electric vehicles.
Conventionally, various studies have been made on a lithium secondary battery containing a non-aqueous electrolytic solution (also referred to as a non-aqueous electrolytic solution secondary battery or the like).

For example, Patent Document 1 discloses the following non-aqueous electrolyte secondary battery as a non-aqueous electrolyte secondary battery capable of suppressing capacity deterioration and maintaining a stable battery capacity for a long period of time. ..
That is, (A) a negative electrode containing a carbon material having a true specific gravity of 1.60 to 2.20 g / cm ³ as a negative electrode active material, (B) a positive electrode containing a positive electrode active material, and (C) a lithium salt are dissolved in an organic solvent. In the non-aqueous electrolytic solution secondary battery provided with the non-aqueous electrolytic solution and (D) separation film, a specific polyvalent carboxylic substance is contained in the non-aqueous electrolytic solution in which (C) a lithium salt is dissolved in an organic solvent. A non-aqueous electrolytic solution secondary battery containing an acid ester compound is described.

Further, in Patent Document 2, in a non-aqueous electrolytic solution secondary battery using a cathode containing a transition metal and lithium, deterioration of the non-aqueous electrolytic solution secondary battery due to the transition metal eluted from the cathode is suppressed and stored at a high temperature. The following non-aqueous electrolytic solution secondary battery is disclosed as a non-aqueous electrolytic solution secondary battery capable of maintaining a small internal resistance and a high electric capacity even after being charged and discharged at a high temperature.
That is, in the non-aqueous electrolytic solution secondary battery having a non-aqueous electrolytic solution in which a lithium-deinsertable anode, a cathode containing a transition metal and lithium, and a lithium salt are dissolved in an organic solvent, the non-aqueous electrolytic solution contains the above-mentioned non-aqueous electrolytic solution. Discloses a non-aqueous electrolytic solution secondary battery containing a specific polyvalent carboxylic acid ester compound.

Further, Patent Document 3 discloses the following lithium secondary battery as a lithium secondary battery using an organic solvent as an electrolytic solution and having improved overcharge resistance without impairing the storage characteristics of the battery. Has been done.
That is, it is a lithium secondary battery having a negative electrode that stores and releases lithium ions, a positive electrode that stores and releases lithium ions, a separator containing porosity, and a non-aqueous electrolytic solution in which an electrolyte is dissolved in a solvent. The non-aqueous electrolytic solution is disclosed by a lithium secondary battery containing a compound that is oxidized at a voltage higher than the charge termination voltage of the lithium secondary battery and a compound that suppresses the reaction in a voltage region equal to or lower than the charge termination voltage. Has been done.

Further, Patent Document 4 includes a cathode, a lithium ion permeable separator, an anode containing unmodified natural or synthetic graphite, and an electrolyte solution containing propylene carbonate or butylene carbonate in contact with the anode. The electrolyte solution further comprises an electrolyte salt containing a lithium cation, the electrolyte solution further comprises a particular fluorobenzene composition, the electrolyte solution and the electrodes are in ionic conductive contact with each other, rechargeable lithium or lithium. Ion electrochemical batteries are disclosed.

International Publication No. 2016/76145 Japanese Unexamined Patent Publication No. 2013-118168 Japanese Unexamined Patent Publication No. 2001-343423 Japanese Patent Publication No. 2004-51829

For a battery using a non-aqueous electrolyte solution, it may be required to suppress at least one of the battery resistance before storing the battery and the increase in battery resistance due to storage.
An object of the present disclosure is a non-aqueous electrolyte solution for a battery capable of suppressing at least one of a battery resistance before storage of a battery and an increase in battery resistance due to storage, and a lithium ion using this non-aqueous electrolyte solution for a battery. The next battery is to be provided.

The means for solving the above problems include the following aspects.
<1> A non-aqueous electrolytic solution for a battery containing a compound represented by the following formula (1).

In formula (1), R ^{1 to} R ³ independently have a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, a fluorinated hydrocarbon group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. Represents a hydrocarbon oxy group or a fluorinated hydrocarbon oxy group having 1 to 10 carbon atoms, and R ^{4 to} R ⁸ independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 3 carbon atoms, or a hydrocarbon group having 1 to 3 carbon atoms. Represents a fluorinated hydrocarbon group having 1 to 3 carbon atoms, a hydrocarbon oxy group having 1 to 3 carbon atoms, or a fluorinated hydrocarbon oxy group having 1 to 3 carbon atoms, and L ¹ is a single bond, an oxygen atom, or an oxygen atom. Represents an alkylene group having 1 to 3 carbon atoms.

<2> The non-aqueous electrolytic solution for a battery according to <1>, further containing at least one selected from the group consisting of compounds represented by the following formulas (2) to (9).

In the formula (2), R ^{21 to} R ²⁴ independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 6 carbon atoms, or a fluorinated hydrocarbon group having 1 to 6 carbon atoms.
In the formula (3), R ^{31 to} R ³⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a group represented by the formula (a), or a group represented by the formula (b). Represents. In the formula (a) and the formula (b), * represents a bonding position.
In the formula (4), R ^{41 to} R ⁴⁴ independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 6 carbon atoms, or a fluorinated hydrocarbon group having 1 to 6 carbon atoms. However, R ^{41 to} R ⁴⁴ do not become hydrogen atoms at the same time.
In formula (5), R ⁵¹ and R ⁵² independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 6 carbon atoms, or a fluorinated hydrocarbon group having 1 to 6 carbon atoms.
In formula (6), R ^{61 to} R ⁶³ each independently represent a fluorine atom or an —OLi group, and ^{at least one of R 61 to} R ⁶³ is a −OLi group.
In the formula (7), R ^{71 to} R ⁷⁶ independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 3 carbon atoms, or a fluorinated hydrocarbon group having 1 to 3 carbon atoms.
In the formula (8), R ^{81 to} R ⁸⁴ independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 3 carbon atoms, or a fluorinated hydrocarbon group having 1 to 3 carbon atoms.

<3> At least one selected from the group consisting of the compounds represented by the formulas (2) to (7) is a compound represented by the following formula (2-1) and the following formula (2-2). ), The compound represented by the following formula (3-1), the compound represented by the following formula (3-2), the compound represented by the following formula (3-3), the following formula (4). A compound represented by -1), a compound represented by the following formula (4-2), a compound represented by the following formula (5-1), a compound represented by the following formula (6-1), and a compound represented by the following formula. It is composed of a compound represented by (6-2), a compound represented by the following formula (7-1), a compound represented by the following formula (8-1), and a compound represented by the above formula (9). The non-aqueous electrolyte solution for a battery according to <2>, which is at least one selected from the group.

<4> The total content of the compounds represented by the above formulas (2) to (7) with respect to the total amount of the non-aqueous electrolytic solution for batteries is 0.001% by mass to 10% by mass <2> or. The non-aqueous electrolyte solution for a battery according to <3>.

<5> The compound represented by the formula (1) is at least one of the compound represented by the following formula (1-1) and the compound represented by the following formula (1-2) <1> to <. The non-aqueous electrolyte solution for a battery according to any one of 4>.

<6> Any one of <1> to <5> in which the content of the compound represented by the above formula (1) with respect to the total amount of the non-aqueous electrolytic solution for a battery is 0.001% by mass to 10% by mass. The non-aqueous electrolyte solution for batteries described in.

<7> Positive electrode and
Metallic lithium, lithium-containing alloys, metals or alloys that can be alloyed with lithium, oxides that can be doped / dedoped with lithium ions, transition metal nitrified products that can be doped / dedoped with lithium ions, and lithium. A negative electrode containing at least one selected from the group consisting of carbon materials capable of ion doping and dedoping as a negative electrode active material, and a negative electrode.
The non-aqueous electrolytic solution for a battery according to any one of <1> to <6>.
Lithium secondary battery including.
<8> A lithium secondary battery obtained by charging / discharging the lithium secondary battery according to <7>.

According to the present disclosure, a non-aqueous electrolyte solution for a battery capable of suppressing at least one of a battery resistance before storage of a battery and an increase in battery resistance due to storage, and a lithium ion using this non-aqueous electrolyte solution for a battery The next battery is provided.

It is a schematic perspective view which shows the example of the laminated type battery which is an example of the lithium secondary battery of this disclosure. FIG. 3 is a schematic cross-sectional view in the thickness direction of a laminated electrode body housed in the laminated battery shown in FIG. 1. It is the schematic which shows the example of the coin-type battery which is another example of the lithium secondary battery of this disclosure.

In the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
In the present specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means.

[Non-water electrolyte for batteries]
The non-aqueous electrolytic solution for batteries (hereinafter, also simply referred to as “non-aqueous electrolytic solution”) of the present disclosure contains a compound represented by the following formula (1).
According to the non-aqueous electrolytic solution of the present disclosure, at least one of the battery resistance before storage of the battery and the increase in battery resistance due to storage can be suppressed. Although the reason why such an effect is exhibited is not clear, the formula (1) in the non-aqueous electrolyte solution is used on the electrode of the battery before and / or during storage of the battery containing the non-aqueous electrolyte solution. It is considered that a low resistance film derived from the represented compound is formed.

In the present specification, the concept of "suppressing the increase in battery resistance due to storage" includes a state in which the battery resistance increases due to storage but the degree of increase is suppressed, a state in which the battery resistance does not change due to storage, and storage. All of the conditions in which the battery resistance is rather reduced later are included.

<Compound represented by the formula (1)>

In formula (1), R ^{1 to} R ³ independently have a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, a fluorinated hydrocarbon group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. Represents a hydrocarbon oxy group or a fluorinated hydrocarbon oxy group having 1 to 10 carbon atoms, and R ^{4 to} R ⁸ independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 3 carbon atoms, or a hydrocarbon group having 1 to 3 carbon atoms. Represents a fluorinated hydrocarbon group having 1 to 3 carbon atoms, a hydrocarbon oxy group having 1 to 3 carbon atoms, or a fluorinated hydrocarbon oxy group having 1 to 3 carbon atoms, and L ¹ is a single bond, an oxygen atom, or an oxygen atom. Represents an alkylene group having 1 to 3 carbon atoms.

In the formula (1), ^{the hydrocarbon group having 1 to 10 carbon atoms represented by R 1 to} R ³ may be a linear hydrocarbon group, or a hydrocarbon group having a branched and / or ring structure. May be.
As ^{the hydrocarbon group having 1 to 10 carbon atoms represented by R 1 to} R ³ , an alkyl group or an aryl group is preferable, and an alkyl group is more preferable.

In the formula (1), ^{the hydrocarbon group having 1 to 10 carbon atoms represented by R 1 to} R ³ preferably has 1 to 6 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 or 2 carbon atoms. 1 is particularly preferable.

In the formula (1), ^{the fluorinated hydrocarbon group having 1 to 10 carbon atoms represented by R 1 to} R ³ may be a linear fluorinated hydrocarbon group, and may have a branched and / or ring structure. It may be a fluorinated hydrocarbon group having.
As ^{the fluorinated hydrocarbon group having 1 to 10 carbon atoms represented by R 1 to} R ³ , an alkyl fluorinated group or an aryl fluorinated group is preferable, and an alkyl fluorinated group is more preferable.

In the formula (1), the ^{number of carbon atoms of the fluorohydrocarbon group having 1 to 10 carbon atoms represented by R 1 to} R ³ is preferably 1 to 6, more preferably 1 to 3, and further preferably 1 or 2. Preferably, 1 is particularly preferred.

In the formula (1), ^{the hydrocarbon oxy group having 1 to 10 carbon atoms represented by R 1 to} R ³ may be a linear hydrocarbon oxy group, or may be a hydrocarbon having a branched and / or ring structure. It may be a hydrocarbon oxy group.
As the hydrocarbon oxy group having 1 to 10 carbon atoms represented by ^{R 1 to} R ^{3, an alkoxy group or an aryl oxy group is preferable.}

In the formula (1), ^{the hydrocarbon oxy group having 1 to 10 carbon atoms represented by R 1 to} R ³ preferably has 1 to 6 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 or 2 carbon atoms. 1 is particularly preferable.

In the formula (1), ^{the fluorinated hydrocarbon oxy group having 1 to 10 carbon atoms represented by R 1 to} R ³ may be a linear fluorinated hydrocarbon oxy group, or may be branched and / or a ring. It may be a fluorinated hydrocarbon oxy group having a structure.
As ^{the fluorinated hydrocarbon oxy group having 1 to 10 carbon atoms represented by R 1 to} R ³ , a fluorinated alkoxy group or a fluorinated aryl oxy group is preferable.

In the formula (1), the number of carbon atoms of the fluorinated hydrocarbon oxy group having 1 to 10 carbon atoms represented by ^{R 1 to} R ^{3 is preferably 1 to 6, more preferably 1 to 3, and 1 or 2.} More preferably, 1 is particularly preferable.

In the formula (1), a hydrocarbon group having 1 to 3 carbon atoms represented by R ⁴ to R ⁸ may be a hydrocarbon group having a straight chain may be a hydrocarbon group having a branched ..
As the hydrocarbon group having 1 to 3 carbon atoms represented by ^{R 1 to} R ^{3, an alkyl group is preferable.}

In the formula ^(1), the carbon number of the hydrocarbon group having 1 to 3 carbon atoms represented by R 4 to R ^8, preferably 1 or 2, and more preferably 1.

In the formula (1), ^{the fluorinated hydrocarbon group having 1 to 3 carbon atoms represented by R 4 to} R ⁸ may be a linear fluorinated hydrocarbon group or a branched fluorinated hydrocarbon. It may be a group.
As the fluorinated hydrocarbon group having 1 to 3 carbon atoms represented by ^{R 1 to} R ^{3, an alkyl fluorinated group is preferable.}

In the formula ^(1), as the number of carbon atoms of the fluorinated hydrocarbon group having 1 to 3 carbon atoms represented by R 4 to R ^8, preferably 1 or 2, and more preferably 1.

In the formula (1), ^{the hydrocarbon oxy group having 1 to 3 carbon atoms represented by R 4 to} R ⁸ may be a linear hydrocarbon oxy group or a branched hydrocarbon oxy group. May be.
As the hydrocarbon oxy group having 1 to 3 carbon atoms represented by ^{R 1 to} R ^{3, an alkoxy group is preferable.}

In the formula (1), the number of carbon atoms of the hydrocarbon oxy group having 1 to 3 carbon atoms represented by ^{R 4 to} R ^{8 is preferably 1 or 2, and more preferably 1.}

In the formula (1), the fluorinated hydrocarbon oxy group having 1 to 3 carbon atoms represented by ^{R 4 to} R ^{8 may be a linear fluorinated hydrocarbon oxy group or a branched fluoride.} It may be a hydrocarbon oxy group.
As the fluorinated hydrocarbon oxy group having 1 to 3 carbon atoms represented by ^{R 1 to} R ^{3, a fluorinated alkoxy group is preferable.}

In the formula ^(1), as the number of carbon atoms of the fluorinated hydrocarbon group having 1 to 3 carbon atoms represented by R 4 to R ^8, preferably 1 or 2, and more preferably 1.

In formula (1), L ¹ represents a single bond, an oxygen atom (that is, an −O— group), or an alkylene group having 1 to 3 carbon atoms.
The number of carbon atoms of the alkylene group having 1 to 3 carbon atoms represented by L ^1, 1 or 2 are preferred, 1 being more preferred.
In the formula (1), as the ^{L 1,} a single bond is particularly preferred.

Specific examples of the compound represented by the formula (1) include compounds represented by the following formulas (1-1) to (1-14) (hereinafter, compounds (1-1) to compound (1), respectively. -14)), but the compound represented by the formula (1) is not limited to these specific examples.
Of these, compound (1-1) or compound (1-2) is particularly preferable.

The non-aqueous electrolytic solution of the present disclosure may contain only one type of the compound represented by the formula (1), or may contain two or more types.
The content of the compound represented by the formula (1) (total content in the case of two or more kinds) with respect to the total amount of the non-aqueous electrolytic solution of the present disclosure is preferably 0.001% by mass to 10% by mass. It is more preferably 0.005% by mass to 5% by mass, further preferably 0.01% by mass to 1% by mass, and particularly preferably 0.1% by mass to 1% by mass.

The non-aqueous electrolytic solution of the present disclosure may contain at least one selected from the group consisting of compounds represented by the following formulas (2) to (9).
Hereinafter, the compounds represented by the formulas (2) to (9) will be described.

<Compound represented by the formula (2)>
The non-aqueous electrolytic solution of the present disclosure may contain at least one compound represented by the following formula (2).
When the non-aqueous electrolytic solution of the present disclosure contains a compound represented by the following formula (2), the compound represented by the following formula (2) and the compound represented by the above-mentioned formula (1) is contained. In particular, it is possible to suppress an increase in battery resistance due to storage as compared with a comparative non-aqueous electrolyte solution that does not contain.

In the formula (2), R ^{21 to} R ²⁴ independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 6 carbon atoms, or a fluorinated hydrocarbon group having 1 to 6 carbon atoms.

In the formula (2), ^{the preferred embodiment of the hydrocarbon group having 1 to 6 carbon atoms represented by R 21 to} R ^{24 is R 4} in the formula (1) except that the hydrocarbon group has 1 to 6 carbon atoms. it is the same as the preferred embodiment of the hydrocarbon having 1 to 3 carbon atoms represented by to R ^8.
As the ^{carbon number of the hydrocarbon group having 1 to 6 carbon atoms represented by R 21 to} R ²⁴ , 1 to 3 is preferable, 1 or 2 is more preferable, and 1 is particularly preferable.

Specific examples of the compound represented by the formula (2) include the compounds represented by the following formulas (2-1) to the following formula (2-9) (hereinafter, each of the compounds (2-1) to the compound (2). -9)), but the compound represented by the formula (2) is not limited to these specific examples.
Of these, compound (2-1) or compound (2-2) is particularly preferable.

When the non-aqueous electrolyte solution of the present disclosure contains a compound represented by the formula (2), the content of the compound represented by the formula (2) with respect to the total mass of the non-aqueous electrolyte solution (when two or more kinds are used). The total content) is preferably 0.001% by mass to 10% by mass, more preferably 0.005% by mass to 5% by mass, further preferably 0.01% by mass to 1% by mass, and 0.1% by mass. ~ 1% by mass is particularly preferable.

<Compound represented by the formula (3)>
The non-aqueous electrolytic solution of the present disclosure may contain at least one compound represented by the following formula (3).
When the non-aqueous electrolytic solution of the present disclosure contains a compound represented by the following formula (3), the compound represented by the following formula (3) and the compound represented by the above formula (1) is contained. It is possible to suppress at least one of the battery resistance before storage of the battery and the increase in battery resistance due to storage as compared with the non-aqueous electrolytic solution for comparison which does not contain.

In the formula (3), R ^{31 to} R ³⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a group represented by the formula (a), or a group represented by the formula (b). Represents. In the formula (a) and the formula (b), * represents a bonding position.

In the formula (3), ^{the preferred embodiment of the hydrocarbon group having 1 to 6 carbon atoms represented by R 31 to} R ^{34 is R 4} in the formula (1) except that the hydrocarbon group has 1 to 6 carbon atoms. it is the same as the preferred embodiment of the hydrocarbon having 1 to 3 carbon atoms represented by to R ^8.
As the ^{carbon number of the hydrocarbon group having 1 to 6 carbon atoms represented by R 31 to} R ³⁴ , 1 to 3 is preferable, 1 or 2 is more preferable, and 1 is particularly preferable.

Specific examples of the compound represented by the formula (3) include the compounds represented by the following formulas (3-1) to the following formula (3-6) (hereinafter, each of the compounds (3-1) to the compound (3). -6)), but the compound represented by the formula (3) is not limited to these specific examples.
Of these, compound (3-1) to compound (3-3) are particularly preferable.

When the non-aqueous electrolyte solution of the present disclosure contains a compound represented by the formula (3), the content of the compound represented by the formula (3) with respect to the total mass of the non-aqueous electrolyte solution (when two or more kinds are used). The total content) is preferably 0.001% by mass to 10% by mass, more preferably 0.005% by mass to 5% by mass, further preferably 0.01% by mass to 1% by mass, and 0.1% by mass. ~ 1% by mass is particularly preferable.

<Compound represented by the formula (4)>
The non-aqueous electrolytic solution of the present disclosure may contain at least one compound represented by the following formula (4).
When the non-aqueous electrolytic solution of the present disclosure contains a compound represented by the following formula (4), the compound represented by the following formula (4) and the compound represented by the above-mentioned formula (1) is contained. It is possible to suppress at least one of the battery resistance before storage of the battery and the increase in battery resistance due to storage as compared with the non-aqueous electrolytic solution for comparison which does not contain.

In the formula (4), R ^{41 to} R ⁴⁴ independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 6 carbon atoms, or a fluorinated hydrocarbon group having 1 to 6 carbon atoms. However, R ^{41 to} R ⁴⁴ do not become hydrogen atoms at the same time.

In the formula (4), ^{the preferred embodiment of the hydrocarbon group having 1 to 6 carbon atoms represented by R 41 to} R ^{44 is R 4} in the formula (1) except that the hydrocarbon group has 1 to 6 carbon atoms. it is the same as the preferred embodiment of the hydrocarbon having 1 to 3 carbon atoms represented by to R ^8.
However, it is also preferable that the hydrocarbon group having 1 to 6 carbon atoms represented by ^{R 41 to} R ^{44 is an alkenyl group.}
As the ^{carbon number of the hydrocarbon group having 1 to 6 carbon atoms represented by R 41 to} R ⁴⁴ , 1 to 3 is preferable, 1 or 2 is more preferable, and 1 is particularly preferable.

In the formula (4), ^{the preferred embodiment of the fluorinated hydrocarbon group having 1 to 6 carbon atoms represented by R 41 to} R ⁴⁴ is in the formula (1) except that the carbon number is 1 to 6. it is the same as the preferred embodiment of fluorocarbon having 1 to 3 carbon atoms represented by R ⁴ to R ^8.
However, it is also preferable that the fluorinated hydrocarbon group having 1 to 6 carbon atoms represented by ^{R 41 to} R ^{44 is a fluorinated alkenyl group.}
As ^{the carbon number of the fluorohydrocarbon group having 1 to 6 carbon atoms represented by R 41 to} R ⁴⁴ , 1 to 3 is preferable, 1 or 2 is more preferable, and 1 is particularly preferable.

Specific examples of the compound represented by the formula (4) include the compounds represented by the following formulas (4-1) to the following formula (4-5) (hereinafter, each of the compounds (4-1) to the compound (4). -5)), but the compound represented by the formula (4) is not limited to these specific examples.
Of these, compound (4-1) or compound (4-2) is particularly preferable.

When the non-aqueous electrolyte solution of the present disclosure contains a compound represented by the formula (4), the content of the compound represented by the formula (4) with respect to the total mass of the non-aqueous electrolyte solution (when two or more kinds are used). The total content) is preferably 0.001% by mass to 10% by mass, more preferably 0.005% by mass to 5% by mass, further preferably 0.01% by mass to 1% by mass, and 0.1% by mass. ~ 1% by mass is particularly preferable.

<Compound represented by the formula (5)>
The non-aqueous electrolytic solution of the present disclosure may contain at least one compound represented by the following formula (5).
When the non-aqueous electrolytic solution of the present disclosure contains a compound represented by the following formula (5), the compound represented by the following formula (5) and the compound represented by the above-mentioned formula (1) is contained. In particular, it is possible to suppress an increase in battery resistance due to storage as compared with a comparative non-aqueous electrolyte solution that does not contain.

In formula (5), R ⁵¹ and R ⁵² independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 6 carbon atoms, or a fluorinated hydrocarbon group having 1 to 6 carbon atoms.

In the formula (5), ^{a preferred embodiment of the hydrocarbon group having 1 to 6 carbon atoms represented by R 51} or R ^{52 is R 4} in the formula (1) except that the hydrocarbon group has 1 to 6 carbon atoms. it is the same as the preferred embodiment of the hydrocarbon having 1 to 3 carbon atoms represented by to R ^8.
As the ^{carbon number of the hydrocarbon group having 1 to 6 carbon atoms represented by R 51} or R ⁵² , 1 to 3 is preferable, 1 or 2 is more preferable, and 1 is particularly preferable.

In the formula (5), ^{the preferred embodiment of the fluorinated hydrocarbon group having 1 to 6 carbon atoms represented by R 51} or R ⁵² is in the formula (1) except that the carbon number is 1 to 6. it is the same as the preferred embodiment of fluorocarbon having 1 to 3 carbon atoms represented by R ⁴ to R ^8.
The ^{number of carbon atoms of the fluorohydrocarbon group having 1 to 6 carbon atoms represented by R 51} or R ⁵² is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

Specific examples of the compound represented by the formula (5) include the compounds represented by the following formulas (5-1) to the following formula (5-11) (hereinafter, each of the compounds (5-1) to the compound (5). -11)), but the compound represented by the formula (5) is not limited to these specific examples.
Of these, compound (5-1) is particularly preferable.

When the non-aqueous electrolyte solution of the present disclosure contains a compound represented by the formula (5), the content of the compound represented by the formula (5) with respect to the total mass of the non-aqueous electrolyte solution (when two or more kinds are used). The total content) is preferably 0.001% by mass to 10% by mass, more preferably 0.005% by mass to 5% by mass, further preferably 0.01% by mass to 1% by mass, and 0.1% by mass. ~ 1% by mass is particularly preferable.

<Compound represented by the formula (6)>
The non-aqueous electrolytic solution of the present disclosure may contain at least one compound represented by the following formula (6).
When the non-aqueous electrolytic solution of the present disclosure contains a compound represented by the following formula (6), the compound represented by the following formula (6) and the compound represented by the above-mentioned formula (1) is contained. In particular, the battery resistance before storing the battery can be suppressed as compared with the non-aqueous electrolytic solution for comparison which does not contain.

In formula (6), R ^{61 to} R ⁶³ each independently represent a fluorine atom or an —OLi group, and ^{at least one of R 61 to} R ⁶³ is a −OLi group.

Specific examples of the compound represented by the formula (6) include the compounds represented by the following formula (6-1) and the following formula (6-2) (hereinafter, the compound (6-1) and the compound (6, respectively). -2)), but the compound represented by the formula (6) is not limited to these specific examples.

When the non-aqueous electrolyte solution of the present disclosure contains a compound represented by the formula (6), the content of the compound represented by the formula (6) with respect to the total mass of the non-aqueous electrolyte solution (when two or more kinds are used). The total content) is preferably 0.001% by mass to 10% by mass, more preferably 0.005% by mass to 5% by mass, further preferably 0.01% by mass to 1% by mass, and 0.1% by mass. ~ 1% by mass is particularly preferable.

<Compound represented by the formula (7)>
The non-aqueous electrolytic solution of the present disclosure may contain at least one compound represented by the following formula (7).
When the non-aqueous electrolytic solution of the present disclosure contains a compound represented by the following formula (7), the compound represented by the following formula (7) and the compound represented by the above-mentioned formula (1) is contained. It is possible to suppress at least one of the battery resistance before storage of the battery and the increase in battery resistance due to storage as compared with the non-aqueous electrolytic solution for comparison which does not contain.

In the formula (7), R ^{71 to} R ⁷⁶ independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 3 carbon atoms, or a fluorinated hydrocarbon group having 1 to 3 carbon atoms.

In the formula (7), the preferred embodiment of the hydrocarbon group having 1 to 3 carbon atoms represented by ^{R 71 to} R ⁷⁶ is the hydrocarbon group having 1 to 3 carbon atoms represented by ^{R 4 to} R ^{8 in the formula (1).} Similar to the preferred embodiment of hydrocarbons.
As the carbon number of the hydrocarbon group having 1 to 3 carbon atoms represented by ^{R 71 to} R ^{76, 1 or 2 is preferable, and 1 is more preferable.}

In the formula (7), the preferred embodiment of the fluorinated hydrocarbon group having 1 to 3 carbon atoms represented by ^{R 71 to} R ⁷⁶ is the carbon number 1 to 1 represented by ^{R 4 to} R ^{8 in the formula (1).} This is the same as the preferred embodiment of the fluorinated hydrocarbon of 3.
The number of carbon atoms of the fluorohydrocarbon group having 1 to 3 carbon atoms represented by ^{R 71 to} R ^{76 is preferably 1 or 2, and more preferably 1.}

Specific examples of the compound represented by the formula (7) include compounds represented by the following formulas (7-1) to (7-21) (hereinafter, compounds (7-1) to compounds (7, respectively). -21)), but the compound represented by the formula (7) is not limited to these specific examples.
Of these, compound (7-1) is particularly preferable.

When the non-aqueous electrolyte solution of the present disclosure contains a compound represented by the formula (7), the content of the compound represented by the formula (7) with respect to the total mass of the non-aqueous electrolyte solution (when two or more kinds are used). The total content) is preferably 0.001% by mass to 10% by mass, more preferably 0.005% by mass to 5% by mass, further preferably 0.01% by mass to 1% by mass, and 0.1% by mass. ~ 1% by mass is particularly preferable.

<Compound represented by the formula (8)>
The non-aqueous electrolytic solution of the present disclosure may contain at least one compound represented by the following formula (8).
When the non-aqueous electrolytic solution of the present disclosure contains a compound represented by the following formula (8), the compound represented by the following formula (8) and the compound represented by the above formula (1) is contained. In particular, it is possible to suppress an increase in battery resistance due to storage as compared with a comparative non-aqueous electrolyte solution that does not contain.

In the formula (8), R ^{81 to} R ⁸⁴ independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 3 carbon atoms, or a fluorinated hydrocarbon group having 1 to 3 carbon atoms.

Specific examples of the compound represented by the formula (8) include compounds represented by the following formulas (8-1) to (8-21) (hereinafter, compounds (8-1) to compound (8, respectively). -21)), but the compound represented by the formula (8) is not limited to these specific examples.
Of these, compound (8-1) is particularly preferable.

When the non-aqueous electrolyte solution of the present disclosure contains a compound represented by the formula (8), the content of the compound represented by the formula (8) with respect to the total mass of the non-aqueous electrolyte solution (when two or more kinds are used). The total content) is preferably 0.001% by mass to 10% by mass, more preferably 0.005% by mass to 5% by mass, further preferably 0.01% by mass to 1% by mass, and 0.1% by mass. ~ 1% by mass is particularly preferable.

<Compound represented by the formula (9)>
The non-aqueous electrolytic solution of the present disclosure may contain a compound represented by the following formula (9) (hereinafter, also referred to as “compound (9)”).
When the non-aqueous electrolytic solution of the present disclosure contains compound (9), it is compared with a comparative non-aqueous electrolytic solution containing compound (9) and not containing the compound represented by the above formula (1). In particular, it is possible to suppress an increase in battery resistance due to storage.

When the non-aqueous electrolyte solution of the present disclosure contains a compound represented by the formula (9), the content of the compound represented by the formula (9) with respect to the total amount of the non-aqueous electrolyte solution is 0.001% by mass or more. 10% by mass is preferable, 0.005% by mass to 5% by mass is more preferable, 0.01% by mass to 1% by mass is further preferable, and 0.1% by mass to 1% by mass is particularly preferable.

As at least one selected from the group consisting of the compounds represented by the formulas (2) to (7), the compound (2-1), the compound (2-2), the compound (3-1), and the compound ( Compound represented by 3-2), compound (3-3), compound (4-1), compound (4-2), compound (5-1), compound (6-1), compound (6-2). ), Compound (7-1), compound (8-1), and compound (9), preferably at least one selected from the group.

When the non-aqueous electrolyte solution of the present disclosure contains at least one selected from the group consisting of the compounds represented by the following formulas (2) to (9), the non-aqueous electrolyte solution of the present disclosure is based on the total amount of the non-aqueous electrolyte solution of the present disclosure. The total content of the compounds represented by the following formulas (2) to (9) is preferably 0.001% by mass to 10% by mass, more preferably 0.05% by mass to 5% by mass. , 0.1% by mass to 4% by mass, more preferably 0.1% by mass to 2% by mass, and particularly preferably 0.1% by mass to 1% by mass.

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

(Non-aqueous solvent)
The non-aqueous electrolyte solution generally contains a non-aqueous solvent.
As the non-aqueous solvent, various known ones can be appropriately selected, but it is preferable to use at least one selected from a cyclic aprotic solvent and a chain aprotic solvent.

When aiming to improve the flash point of the solvent in order to improve the safety of the battery, it is preferable to use a cyclic aprotic solvent as the non-aqueous solvent.

(Cyclic aprotic solvent)
As the cyclic aprotic solvent, a cyclic carbonate, a cyclic carboxylic acid ester, a cyclic sulfone, and a 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 such a ratio, the conductivity of the electrolytic solution related 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, and 2,3-pentylene carbonate. 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 alkyl substituents such as γ-butyrolactone, δ-valerolactone, methyl γ-butyrolactone, ethyl γ-butyrolactone, and ethyl δ-valerolactone.
The cyclic carboxylic acid ester has a low vapor pressure, a low viscosity, and a high dielectric constant, and can reduce the viscosity of the electrolytic solution without lowering the flash point of the electrolytic solution and the degree of dissociation of the electrolyte. Therefore, it has a 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. It is preferable to use a cyclic carboxylic acid ester as the cyclic aprotic solvent. γ-Butyrolactone is most preferred.

Further, 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.

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 methylethyl carbonate, γ-butyrolactone and propylene carbonate and diethyl carbonate, γ-Buchirolactone, ethylene carbonate and propylene carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate and dimethyl carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate and methylethyl carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate and diethyl carbonate, γ-Buchirolactone, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, γ-butyrolactone, ethylene carbonate, dimethyl carbonate and diethyl carbonate, γ-butyrolactone, ethylene carbonate, methyl ethyl carbonate and diethyl carbonate, γ-butyrolactone, ethylene carbonate and dimethyl carbonate. And methyl ethyl carbonate and diethyl carbonate, γ-butyrolactone and ethylene carbonate and propylene carbonate and dimethyl carbonate and methyl ethyl carbonate, γ-butyrolactone and ethylene carbonate and propylene carbonate and dimethyl carbonate and diethyl carbonate, γ-butyrolactone and ethylene carbonate and propylene carbonate. And methyl ethyl carbonate and diethyl carbonate, γ-butyrolactone and ethylene carbonate and propylene carbonate and dimethyl carbonate and methyl ethyl carbonate and diethyl carbonate, γ-butyrolactone and sulfolane, γ-butyrolactone and ethylene carbonate and sulforane, γ-butyrolactone and propylene carbonate. Sulfolane, γ-butyrolactone, ethylene carbonate, propylene carbonate, sulfolane, γ-bu Examples thereof include tyrolactone, sulfolane and dimethyl carbonate.

Examples of the cyclic sulfone include sulfolane, 2-methylsulfolane, 3-methylsulfolane, dimethylsulfone, diethylsulfone, dipropylsulfone, methylethylsulfone, methylpropylsulfone and the like.
Dioxolane can be mentioned as an example of the cyclic ether.

(Chain aprotic solvent)
As the chain aprotic solvent, a chain carbonate, a chain carboxylic acid ester, a chain ether, a chain phosphate ester and 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.

Specifically, as the chain carbonate, 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 thereof include ethylpentyl carbonate, dipentyl carbonate, methylheptyl carbonate, ethylheptyl carbonate, diheptyl carbonate, methylhexyl carbonate, ethylhexyl carbonate, dihexyl carbonate, methyloctyl carbonate, ethyloctyl carbonate, dioctyl carbonate, methyltrifluoroethyl carbonate and the like. Two or more kinds of these chain carbonates may be mixed and used.

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

(Combination of solvents)
The non-aqueous solvent contained in the non-aqueous electrolytic solution of the present disclosure may be only one kind or two or more kinds.
Further, even if only one or more kinds of cyclic aprotic solvents are used, one or more kinds of chain aprotic solvents are used, or cyclic aprotic solvents and chain-like protonic properties are used. Solvents may be mixed and used. When it is particularly intended to improve the load characteristics and low temperature characteristics of the battery, it is preferable to use a combination of a cyclic aprotic solvent and a chain aprotic solvent as the non-aqueous solvent.

Further, from the viewpoint 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 also be enhanced by the combination of the cyclic carboxylic acid ester and the cyclic carbonate and / or the chain carbonate.

Specific combinations of cyclic carbonate and chain carbonate include 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, and propylene carbonate. Ethylene 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 and 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, methyl ethyl carbonate and diethyl. Examples thereof include 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 by mass ratio, and the cyclic carbonate: chain carbonate is 5:95 to 80:20, more preferably 10:90 to 70:30, and particularly preferably 15:85. ~ 55:45. By setting such a ratio, it is possible to suppress an increase in the viscosity of the electrolytic solution and increase the degree of dissociation of the electrolyte, so that the conductivity of the electrolytic solution related to the charge / discharge characteristics of the battery can be increased. In addition, the solubility of the electrolyte can be further increased. Therefore, since the electrolytic solution having excellent electrical conductivity at normal temperature or low temperature can be obtained, the load characteristics of the battery at normal temperature to low temperature can be improved.

(Other solvents)
Examples of the non-aqueous solvent include other solvents other than the above.
Specific examples of the other solvent include amides such as dimethylformamide, chain carbamates such as methyl-N and N-dimethylcarbamate, cyclic amides such as N-methylpyrrolidone, and N, N-dimethylimidazolidinone. Examples thereof include boron compounds such as cyclic urea, trimethyl borate, triethyl borate, tributyl borate, trioctyl borate, and trimethylsilyl borate, and polyethylene glycol derivatives represented by the following general formulas.
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.

(Electrolytes)
As the non-aqueous electrolyte solution of the present disclosure, various known electrolytes can be used, and any of them can be used as long as it is usually used as an electrolyte for a non-aqueous electrolyte solution.

Specific examples of the electrolyte 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 _{(2 k + 1)} (integer of k = 1 to 8), (C ₂ H ₅ ) ₄ NPF _n [C _k F _{(2 k + 1)} ] _(6-n) Tetraalkylammonium salts such as (n = 1-5, k = 1-8 integers), LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , Li ₂ SiF ₆ , LiOSO ₂ C _k F. _{(2k + 1) (k =} 1~8 _integer) include lithium salts such as _{LiPF n [C k F (2k} + 1)] (6-n) (n = 1~5, k = 1~8 integer) .. Further, a lithium salt represented by the following general formula can also be used.

LiC (SO ₂ R ⁷ ) (SO ₂ R ⁸ ) (SO ₂ R ⁹ ), LiN (SO ₂ OR ¹⁰ ) (SO ₂ OR ¹¹ ), LiN (SO ₂ R ¹² ) (SO ₂ R ¹³ ) (here R ^{7 to} R ¹³ may be the same or different from each other, and are perfluoroalkyl groups having 1 to 8 carbon atoms). These electrolytes may be used alone or in combination of two or more.
Of these, a lithium salt is preferable, and _{further, LiPF 6, LiBF 4, LiOSO} 2 C k F (2k + 1) (k = 1~8 _{integer), 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 is usually preferably contained in a non-aqueous 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 non-aqueous electrolytic solution of the present disclosure, when a cyclic carboxylic acid ester such as γ-butyrolactone is used in combination as the non-aqueous solvent, it is particularly desirable to contain _{LiPF 6.} Since LiPF ₆ has a high degree of dissociation, it is possible to increase the conductivity of the electrolytic solution, and further has an effect of suppressing the reduction decomposition reaction of the electrolytic solution on the negative electrode. LiPF ₆ may be used alone, or LiPF ₆ and other electrolytes may be used. As the other electrolyte, any one that is usually used as an electrolyte for a non-aqueous electrolyte solution can be used, but among the specific examples of the above-mentioned lithium salts, lithium salts _{other than LiPF 6} are preferable. ..
Specific examples include LiPF ₆ and LiBF ₄ , LiPF ₆ and LiN [SO ₂ C _k F _{(2 k + 1)} ] ₂ (integer of k = 1 to 8), LiPF ₆ and LiBF ₄ and LiN [SO ₂ C _k F _{(SO 2 C k F). 2k + 1)} ] (an integer of k = 1 to 8) and the like are exemplified.

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

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

[Lithium secondary battery]
The lithium secondary battery of the present disclosure includes a positive electrode, a negative electrode, and a non-aqueous electrolytic solution of the present disclosure.

<Negative electrode>
The negative electrode may include a negative electrode active material and a negative electrode current collector.
Negative electrode active materials in the negative electrode include metallic lithium, lithium-containing alloys, metals or alloys that can be alloyed with lithium, oxides that can be doped / dedoped with lithium ions, and lithium ions that can be doped / dedoped. At least one selected from the group consisting of transition metal nitridates and carbon materials capable of doping and dedoping lithium ions (may be used alone, or a mixture containing two or more of these may be used. Good) can be used.
Examples of the metal or alloy that can be alloyed with lithium (or lithium ion) include silicon, a silicon alloy, tin, and a tin alloy. Further, lithium titanate may be used.
Among these, a carbon material capable of doping and dedoping lithium ions is 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 fibrous, spherical, potato-like, and flake-like forms.

Specific examples of the amorphous carbon material include hard carbon, coke, mesocarbon microbeads (MCMB) fired at 1500 ° C. or lower, mesophase pitch carbon fiber (MCF), and the like.
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 or the like can also be used. Further, as the graphite material, a material coated with a metal such as gold, platinum, silver, copper or tin, a material coated with amorphous carbon, or a mixture of amorphous carbon and graphite can also be used.

These carbon materials may be used alone or in admixture of two or more.
As the carbon material, a carbon material having a surface spacing d (002) of the (002) plane measured by X-ray analysis of 0.340 nm or less 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 a property close to that of graphite is also preferable. When the carbon material as described above is used, the energy density of the battery can be further increased.

The material of the negative electrode current collector in the negative electrode is not particularly limited, and any known material can be used.
Specific examples of the negative electrode current collector include metal materials such as copper, nickel, stainless steel, and nickel-plated steel. Of these, copper is particularly preferable from the viewpoint of ease of processing.

<Positive electrode>
The positive electrode may include a positive electrode active material and a positive electrode current collector.
The positive electrode active material in the positive _{electrode, MoS 2, TiS 2, MnO} 2, transition metal oxides such as V 2 _{O 5} or a transition metal _{sulfide, LiCoO 2, LiMnO 2, LiMn} 2 O 4, LiNiO 2, LiNi X Co _(1-X) O ₂ [0 <X <1], _{Li 1 + α} Me _1-α O _{2 having an α-NaFeO type 2} crystal structure (Me is a transition metal element containing Mn, Ni and Co, 1.0. ≦ (1 + α) / ( 1-α) ≦ 1.6), LiNi x Co y Mn z O 2 [x + y + z = 1,0 < x <1,0 <y <1,0 <z <1 ] (e.g., LiNi _0.33 Co _0.33 Mn _0.33 O ₂ , LiNi _0.5 Co _0.2 Mn _0.3 O ₂ etc.), LiFePO ₄ , LiMnPO ₄ and other composite oxides consisting of lithium and transition metals, Examples thereof include conductive polymer materials such as polyaniline, polythiophene, polypyrrole, polyacetylene, polyacene, dimercaptothiazol, and polyaniline complex. Among these, a composite oxide composed of lithium and a transition metal is particularly preferable. When the negative electrode is a lithium metal or a lithium alloy, a carbon material can also be used as the positive electrode. Further, as the positive electrode, a mixture of a composite oxide of lithium and a transition metal and a carbon material can also be used.
The positive electrode active material may be used alone or in combination of two or more. If the positive electrode active material has insufficient conductivity, it can be used together with a conductive auxiliary agent to form a positive electrode. Examples of the conductive auxiliary agent include carbon materials such as carbon black, amorphous whiskers, and graphite.

The material of the positive electrode current collector in the positive electrode is not particularly limited, and any known material can be used.
Specific examples of the positive electrode current collector include metal materials such as aluminum, aluminum alloys, stainless steel, nickel, titanium, and tantalum; carbon materials such as carbon cloth and carbon paper; and the like.

<Separator>
The lithium secondary battery of the present disclosure preferably contains a separator between the negative electrode and the positive electrode.
The separator is a membrane that electrically insulates the positive electrode and the negative electrode and allows lithium ions to pass through, and examples thereof include a porous membrane and a polyelectrolyte.
As the porous film, a microporous polymer film is preferably used, and examples thereof include polyolefin, polyimide, polyvinylidene fluoride, polyester and the like.
In particular, porous polyolefin is preferable, and 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. The porous polyolefin film may be coated with another resin having excellent thermal stability.
Examples of the polymer electrolyte include a polymer in which a lithium salt is dissolved, a polymer inflated with an electrolytic solution, and the like.
The non-aqueous electrolyte solution of the present disclosure may be used for the purpose of swelling a polymer to obtain a polymer electrolyte.

<Battery configuration>
The lithium secondary battery of the present disclosure can take various known shapes, and can be formed into a cylindrical type, a coin type, a square type, a laminated type, a film type, 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.

An example of the lithium secondary battery of the present disclosure is a laminated battery.
FIG. 1 is a schematic perspective view showing an example of a laminated battery which is an example of the lithium secondary battery of the present disclosure, and FIG. 2 is a thickness of a laminated electrode body housed in the laminated battery shown in FIG. It is a schematic sectional view of a direction.
The laminated battery shown in FIG. 1 contains a non-aqueous electrolytic solution (not shown in FIG. 1) and a laminated electrode body (not shown in FIG. 1), and the peripheral edge thereof is sealed. Provided is a laminated exterior body 1 whose inside is hermetically sealed. As the laminated exterior body 1, for example, a laminated exterior body made of aluminum is used.
As shown in FIG. 2, the laminated electrode body housed in the laminated exterior body 1 is a laminated body in which a positive electrode plate 5 and a negative electrode plate 6 are alternately laminated via a separator 7, and a laminated body of the laminated body. A separator 8 that surrounds the periphery is provided. The positive electrode plate 5, the negative electrode plate 6, the separator 7, and the separator 8 are impregnated with the non-aqueous electrolytic solution of the present disclosure.
The plurality of positive electrode plates 5 in the laminated electrode body are all electrically connected to the positive electrode terminal 2 via the positive electrode tab (not shown), and a part of the positive electrode terminal 2 is the laminated exterior body 1. It protrudes outward from the peripheral end (Fig. 1). A portion of the peripheral end of the laminated exterior body 1 on which the positive electrode terminal 2 protrudes is sealed with an insulating seal 4.
Similarly, the plurality of negative electrode plates 6 in the laminated electrode body are all electrically connected to the negative electrode terminal 3 via the negative electrode tab (not shown), and a part of the negative electrode terminal 3 is the laminated exterior. It protrudes outward from the peripheral end of the body 1 (FIG. 1). A portion of the peripheral end of the laminated exterior body 1 on which the negative electrode terminal 3 protrudes is sealed with an insulating seal 4.
In the laminated battery according to the above example, the number of positive electrode plates 5 is 5 and the number of negative electrode plates 6 is 6, and the positive electrode plate 5 and the negative electrode plate 6 are located on both sides of the separator 7 via the separator 7. The outer layers are all laminated so as to be the negative electrode plate 6. However, it goes without saying that the number of positive electrode plates, the number of negative electrode plates, and the arrangement of the laminated battery are not limited to this example, and various changes may be made.

Another example of the lithium secondary battery of the present disclosure is a coin-type battery.
FIG. 3 is a schematic perspective view showing an example of a coin-type battery, which is another example of the lithium secondary battery of the present disclosure.
In the coin-type battery shown in FIG. 3, a disk-shaped negative electrode 12, a separator 15 injected with a non-aqueous electrolyte solution, a disk-shaped positive electrode 11, and, if necessary, spacer plates 17 and 18 made of stainless steel or aluminum are arranged in this order. In a laminated state, it is stored between the positive electrode can 13 (hereinafter, also referred to as “battery can”) and the sealing plate 14 (hereinafter, also referred to as “battery can lid”). The positive electrode can 13 and the sealing plate 14 are caulked and sealed via the gasket 16.
In this example, the non-aqueous electrolytic solution of the present disclosure is used as the non-aqueous electrolytic solution to be injected into the separator 15.

The lithium secondary battery of the present disclosure is obtained by charging / discharging a lithium secondary battery (lithium secondary battery before charging / discharging) containing a negative electrode, a positive electrode, and the non-aqueous electrolytic solution of the present disclosure. It may be a lithium secondary battery.
That is, in the lithium secondary battery of the present disclosure, first, a lithium secondary battery before charging / discharging including a negative electrode, a positive electrode, and the non-aqueous electrolytic solution of the present disclosure is prepared, and then the lithium secondary battery before charging / discharging is manufactured. It may be a lithium secondary battery (charged / discharged lithium secondary battery) manufactured by charging / discharging the lithium secondary battery one or more times.

The use of the lithium secondary battery of the present disclosure is not particularly limited, and it can be used for various known uses. For example, notebook computer, mobile computer, mobile phone, headphone stereo, video movie, LCD TV, handy cleaner, electronic organizer, calculator, radio, backup power supply application, motor, car, electric car, bike, electric bike, bicycle, electric It can be widely used regardless of whether it is a small portable device or a large device such as a bicycle, a lighting device, a game machine, a clock, an electric tool, a camera, etc.

Hereinafter, examples of the present disclosure will be shown, but the present disclosure is not limited to the following examples.
In the following examples, the "addition amount" represents the content of the finally obtained non-aqueous electrolytic solution with respect to the total amount.
Further, "wt%" means mass%.

[Example 1]
A coin-type lithium secondary battery (hereinafter, also referred to as “coin-type battery”) having the configuration shown in FIG. 3 was produced by the following procedure.

<Manufacturing of negative electrode>
Natural graphite-based graphite (97 parts by mass), carboxymethyl cellulose (1 part by mass) and SBR latex (2 parts by mass) were kneaded with an aqueous solvent to prepare a paste-like negative electrode mixture slurry.
Next, this negative electrode mixture slurry is 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 consisting of the negative electrode current collector and the negative electrode active material layer. A negative electrode was obtained. At this time, the coating density of the negative electrode active material layer was 10 mg / cm ² , and the packing density was 1.5 g / ml.

<Manufacturing of positive electrode>
LiNi _0.5 Mn _0.3 Co _0.2 O ₂ (90 parts by mass), acetylene black (5 parts by mass) and polyvinylidene fluoride (5 parts by mass) are kneaded and pasted using N-methylpyrrolidinone as a solvent. A positive positive mixture slurry was prepared.
Next, this positive electrode mixture slurry is applied to a positive electrode current collector of a strip-shaped aluminum foil having a thickness of 20 μm, dried, and then compressed by a roll press to form a sheet-shaped positive electrode composed of a positive electrode current collector and a positive electrode active material. Got At this time, the coating density of the positive electrode active material layer was 30 mg / cm ² , and the packing density was 2.5 g / ml.

<Preparation of non-aqueous electrolyte solution>
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) to obtain a mixed solvent.
_{LiPF 6} , which is an electrolyte, was dissolved in the obtained mixed solvent so that the electrolyte concentration in the finally prepared non-aqueous electrolyte solution was 1 mol / liter.
With respect to the obtained solution, the content of the compound (1-1), which is a specific example of the compound represented by the formula (1), as an additive is the content with respect to the total mass of the non-aqueous electrolytic solution finally prepared. Addition was made so as to be 0.5% by mass (that is, the addition amount was 0.5% by mass) to obtain a non-aqueous electrolytic solution.

<Making coin-type batteries>
The above-mentioned negative electrode was punched in a disk shape with a diameter of 14 mm and the above-mentioned positive electrode was punched in a disk shape, respectively, to obtain a coin-shaped negative electrode and a coin-shaped positive electrode, respectively. 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 were laminated in this order in a stainless steel battery can (2032 size), and then 20 μl of a non-aqueous electrolytic solution was injected into the battery can. It was impregnated in the separator, the positive electrode and the negative electrode.
Next, an aluminum plate (thickness 1.2 mm, diameter 16 mm) and a spring were placed on the positive electrode, and the battery was sealed by crimping the battery can lid via a polypropylene gasket.
As a result, a coin-type battery having a diameter of 20 mm and a height of 3.2 mm and having the configuration shown in FIG. 3 (that is, a coin-type lithium secondary battery) was obtained.

<Evaluation>
The following evaluations were carried out on the obtained coin-type batteries.

(Battery resistance before storage (-10 ° C))
The coin-type battery was repeatedly charged and discharged at a constant voltage of 4.4 V three times, and then charged to a constant voltage of 4.4 V. By keeping the charged coin-type battery at -10 ° C in a constant temperature bath, discharging it at a constant current of 0.2 mA at -10 ° C, and measuring the potential drop in 10 seconds from the start of discharge, the coin-type battery- The DC resistance [Ω] at 10 ° C. was measured. The obtained value was taken as the battery resistance (-10 ° C.) before storage.
Similarly, the battery resistance (-10 ° C.) before storage was measured for the coin-type battery of Comparative Example 1 described later.
Table 1 shows the battery resistance (-10 ° C.) before storage of Example 1 as a relative value when the battery resistance (-10 ° C.) before storage of Comparative Example 1 is 100.

(Battery resistance after storage (-10 ° C))
The coin-type battery was repeatedly charged and discharged at a constant voltage of 4.4 V three times, and then charged to a constant voltage of 4.4 V. The charged coin-type battery was stored at 85 ° C. for 6 hours in a constant temperature bath. By keeping the stored coin-type battery at -10 ° C in a constant temperature bath, discharging it at a constant current of 0.2 mA at -10 ° C, and measuring the potential drop in 10 seconds from the start of discharge, the coin-type battery- The DC resistance [Ω] at 10 ° C. was measured. The obtained value was taken as the battery resistance (-10 ° C.) after storage.
Similarly, the battery resistance (-10 ° C.) after storage was measured for the coin-type battery of Comparative Example 1 described later.
Table 1 shows the battery resistance (-10 ° C.) after storage of Example 1 as a relative value when the battery resistance (-10 ° C.) after storage of Comparative Example 1 is 100.

(Ratio [after / before storage])
The ratio [after storage / before storage] was determined by dividing the battery resistance (-10 ° C.) after storage by the battery resistance (-10 ° C.) before storage.
Similarly, the ratio [after storage / before storage] was calculated for the coin-type battery of Comparative Example 1 described later.
Table 1 shows the ratio of Example 1 [after storage / before storage] as a relative value when the ratio of Comparative Example 1 [after storage / before storage] is 100.
The ratio [after storage / before storage] indicates the change in battery resistance due to storage. The smaller the ratio [after storage / before storage], the better the effect of suppressing the increase in battery resistance due to storage.

[Examples 2 and 3]
The same operation as in Example 1 was carried out except that the type or the amount of the compound represented by the formula (1) was changed as shown in Table 1.
The results are shown in Table 1.

[Comparative Example 1]
The same operation as in Example 1 was carried out except that the non-aqueous electrolytic solution did not contain the compound represented by the formula (1).
The results are shown in Table 1.

As shown in Table 1, in Examples 1 to 3 in which the compound represented by the formula (1) was contained in the non-aqueous electrolytic solution, the non-aqueous electrolytic solution did not contain the compound represented by the formula (1). Compared with Comparative Example 1, the ratio [after storage / before storage] (that is, the increase in battery resistance due to storage) was suppressed.

[Example 101]
(Battery resistance before storage (-20 ° C))
The coin-type battery obtained in "Making a coin-type battery" of Example 2 was repeatedly charged and discharged at a constant voltage of 4.25 V three times, and then charged to a constant voltage of 4.25 V. The charged coin-type battery is kept warm at -20 ° C in a constant temperature bath, discharged at a constant current of 0.2 mA at -20 ° C, and the potential drop in 10 seconds from the start of discharge is measured to direct current of the coin-type battery. The resistance [Ω] was measured. The obtained value was taken as the battery resistance (-20 ° C.) before storage.
Similarly, the battery resistance (-20 ° C.) before storage was measured for the coin-type battery of Comparative Example 101 described later.
Table 2 shows the battery resistance (-20 ° C.) before storage of Example 101 as a relative value when the battery resistance (-20 ° C.) before storage of Comparative Example 101 is 100.

(Battery resistance after storage (-20 ° C))
The coin-type battery obtained in "Making a coin-type battery" of Example 2 was repeatedly charged and discharged at a constant voltage of 4.25 V three times, and then charged to a constant voltage of 4.25 V. The charged coin-type battery was stored at 60 ° C. for 5 days in a constant temperature bath. The coin-type battery after storage is kept at -20 ° C in a constant temperature bath, discharged at a constant current of 0.2 mA at -20 ° C, and the potential drop in 10 seconds from the start of discharge is measured to direct current of the coin-type battery. The resistance [Ω] was measured. The obtained value was taken as the battery resistance (-20 ° C.) after storage.
Similarly, the battery resistance (-20 ° C.) after storage was measured for the coin-type battery of Comparative Example 101 described later.
Table 2 shows the battery resistance (-20 ° C.) after storage of Example 101 as a relative value when the battery resistance (-20 ° C.) after storage of Comparative Example 101 is 100.

(Ratio [after / before storage])
By dividing the battery resistance (-20 ° C.) after storage by the battery resistance (-20 ° C.) before storage, the ratio [after storage / before storage] (that is, the ratio of battery resistance due to storage) was determined.
Similarly, the ratio [after storage / before storage] was calculated for the coin-type battery of Comparative Example 101 described later.
Table 2 shows the ratio of Example 101 [after storage / before storage] as a relative value when the ratio of Comparative Example 101 [after storage / before storage] is 100.

[Comparative Example 101]
The same operation as in Example 101 was performed except that the non-aqueous electrolytic solution did not contain the compound represented by the formula (1).
The results are shown in Table 2.

[Examples 102 to 108]
Except for the fact that the non-aqueous electrolytic solution further contains specific examples of the compounds represented by the formulas (2) to (9) shown in Table 2 as an additive in an addition amount of 0.5% by mass. The same operation as in Example 101 was performed.
The results are shown in Table 2.

[Comparative Examples 102 to 108]
The same operation as in Examples 102 to 108 was carried out except that the non-aqueous electrolytic solution did not contain the compound represented by the formula (1).
The results are shown in Table 2.

In Table 2, Examples 101 to 108 in which the non-aqueous electrolytic solution contains the compound represented by the formula (1) and Comparative Examples in which the non-aqueous electrolytic solution did not contain the compound represented by the formula (1). Comparing 101 to 108, respectively, it can be seen that in Examples 101 to 108, at least one of the battery resistance and the ratio [after storage / before storage] before storage is suppressed.
Specifically, in Example 101, the battery resistance and ratio [after storage / before storage] before storage are suppressed as compared with Comparative Example 101.
In Example 102, the ratio [after storage / before storage] is suppressed as compared with Comparative Example 102.
In Example 103, the battery resistance before storage is suppressed as compared with Comparative Example 103.
In Example 104, the ratio [after storage / before storage] is suppressed as compared with Comparative Example 104.
In Example 105, the ratio [after storage / before storage] is suppressed as compared with Comparative Example 105.
In Example 106, the ratio [after storage / before storage] is suppressed as compared with Comparative Example 106.
In Example 107, the battery resistance before storage is suppressed as compared with Comparative Example 107.
In Example 108, the ratio [after storage / before storage] is suppressed as compared with Comparative Example 108.

1 Laminated exterior body 2 Positive electrode terminal 3 Negative electrode terminal 4 Insulation seal 5 Positive electrode plate 6 Negative electrode plate 7, 8 Separator 11 Positive electrode 12 Negative electrode 13 Positive electrode can 14 Seal plate 15 Separator 16 Gasket 17, 18 Spacer plate

Claims (7)

The compound represented by the following formula (1) and
The compound represented by the following formula (2), the compound represented by the following formula (3), the compound represented by the following formula (6), the compound represented by the following formula (7), and the following formula (8). At least one selected from the group consisting of the compound represented by the compound and the compound represented by the following formula (9), and
A non-aqueous electrolyte solution for batteries containing.

[In the formula (1), R ^{1 to} R ³ independently have a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, a fluorinated hydrocarbon group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms. Represents a hydrocarbon oxy group of 10 or a fluorinated hydrocarbon oxy group having 1 to 10 carbon atoms, and R ^{4 to} R ⁸ independently represent a hydrogen atom, a fluorine atom, and a hydrocarbon group having 1 to 3 carbon atoms. Alternatively, it represents a fluorinated hydrocarbon group having 1 to 3 carbon atoms, a hydrocarbon oxy group having 1 to 3 carbon atoms, or a fluorinated hydrocarbon oxy group having 1 to 3 carbon atoms, and L ¹ is a single bond, an oxygen atom, and the like. Alternatively, it represents an alkylene group having 1 to 3 carbon atoms. ]

[In the formula (2), R ^{21 to} R ²⁴ independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 6 carbon atoms, or a fluorinated hydrocarbon group having 1 to 6 carbon atoms.
In the formula (3), R ^{31 to} R ³⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a group represented by the formula (a), or a group represented by the formula (b). Represents. In the formula (a) and the formula (b), * represents a bonding position.
In formula (6), R ^{61 to} R ⁶³ each independently represent a fluorine atom or an —OLi group, and ^{at least one of R 61 to} R ⁶³ is a −OLi group.
In the formula (7), R ^{71 to} R ⁷⁶ independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 3 carbon atoms, or a fluorinated hydrocarbon group having 1 to 3 carbon atoms.
In the formula (8), R ^{81 to} R ⁸⁴ independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 3 carbon atoms, or a fluorinated hydrocarbon group having 1 to 3 carbon atoms. ] The compound represented by the formula (2) , the compound represented by the formula (3), the compound represented by the formula (6), the compound represented by the formula (7), and the compound represented by the formula (8). At least one selected from the group consisting of the compound represented by the above formula (9) and the compound represented by the above formula (9) is a compound represented by the following formula (2-1) and represented by the following formula (2-2). compounds, compounds represented by the following formula (3-1), compounds represented by the following formula (3-2), compounds represented by the following formula (3-3), under following formula (6-1 ), The compound represented by the following formula (6-2), the compound represented by the following formula (7-1), the compound represented by the following formula (8-1), and the above formula ( The non-aqueous electrolyte solution for a battery according to claim 1 , which is at least one selected from the group consisting of the compounds represented by 9).

When the compound represented by the formula (2) is contained, the content of the compound represented by the formula (2) is 0.001% by mass to 10% by mass with respect to the total amount of the non-aqueous electrolytic solution for batteries. And
When the compound represented by the formula (3) is contained, the content of the compound represented by the formula (3) is 0.001% by mass to 10% by mass with respect to the total amount of the non-aqueous electrolytic solution for batteries. And
When the compound represented by the formula (6) is contained, the content of the compound represented by the formula (6) is 0.001% by mass to 10% by mass with respect to the total amount of the non-aqueous electrolytic solution for batteries. And
When the compound represented by the formula (7) is contained, the content of the compound represented by the formula (7) is 0.001% by mass to 10% by mass with respect to the total amount of the non-aqueous electrolytic solution for batteries. And
When the compound represented by the formula (8) is contained, the content of the compound represented by the formula (8) is 0.001% by mass to 10% by mass with respect to the total amount of the non-aqueous electrolytic solution for batteries. And
When the compound represented by the formula (9) is contained, the content of the compound represented by the formula (9) is 0.001% by mass to 10% by mass with respect to the total amount of the non-aqueous electrolytic solution for batteries. The non-aqueous electrolyte solution for a battery according to claim 1 or 2. The compound represented by the formula (1) is, of claims 1 to 3 is at least one of compounds represented by the compounds and the following formula represented by the following formula (1-1) (1-2) The non-aqueous electrolyte solution for a battery according to any one of the following items.

The invention according to any one of claims 1 to 4 , wherein the content of the compound represented by the above formula (1) with respect to the total amount of the non-aqueous electrolytic solution for a battery is 0.001% by mass to 10% by mass. Non-aqueous electrolyte for batteries. With the positive electrode
Metallic lithium, lithium-containing alloys, metals or alloys that can be alloyed with lithium, oxides that can be doped / dedoped with lithium ions, transition metal nitrified products that can be doped / dedoped with lithium ions, and lithium. A negative electrode containing at least one selected from the group consisting of carbon materials capable of ion doping and dedoping as a negative electrode active material, and a negative electrode.
The non-aqueous electrolytic solution for a battery according to any one of claims 1 to 5.
Lithium secondary battery including. A lithium secondary battery obtained by charging / discharging the lithium secondary battery according to claim 6.

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