JP7033455B2 - Non-aqueous electrolyte solution and power storage device using it - Google Patents

Description

The present invention relates to a non-aqueous electrolyte solution and a power storage device using the same.

With the rapid progress of portable electronic devices such as mobile phones and notebook personal computers, there is an increasing demand for higher capacity batteries used for their main power supply and backup power supply, such as nickel-cadmium batteries and nickel-cadmium batteries. Power storage devices such as lithium-ion secondary batteries, which have a higher energy density than hydrogen batteries, are attracting attention.

As the electrolytic solution of the lithium ion secondary battery, LiPF ₆ , LiBF ₄ , LiN (CF ₃ )
SO ₂ ) ₂ , LiCF ₃ (CF ₂ ) ₃ A mixed solvent of an electrolyte such as SO ₃ with a high dielectric constant solvent such as ethylene carbonate and propylene carbonate and a low viscosity solvent such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate. A typical example is a non-aqueous electrolyte solution dissolved in.

Further, as the negative electrode active material of the lithium ion secondary battery, a carbonaceous material capable of occluding and releasing lithium ions is mainly used, and natural graphite, artificial graphite, amorphous carbon and the like are typical examples. Can be mentioned. Metal or alloy-based negative electrodes using silicon, tin, or the like are also known with the aim of further increasing the capacity. As the positive electrode active material, a transition metal composite oxide capable of occluding and releasing lithium ions is mainly used, and typical examples of the transition metal include cobalt, nickel, manganese, iron and the like.

Since such a lithium ion secondary battery uses a positive electrode and a negative electrode having high activity, it is known that the charge / discharge capacity decreases due to a side reaction between the electrode and the electrolytic solution, and the battery characteristics are improved. Therefore, various studies have been made on non-aqueous organic solvents and electrolytes.

Patent Document 1 proposes a technique for improving the high temperature storage characteristics of a battery by using an electrolytic solution to which an alkylnitrile is added.
Patent Document 2 proposes a technique for improving ionic conductivity by using an electrolytic solution using alkoxymononitrile as a solvent.
Patent Document 3 proposes a technique for improving low-temperature charge / discharge performance by using an electrolytic solution containing a cyanoethoxy compound.
Patent Document 4 describes a technique for improving the charge / discharge efficiency of a battery by suppressing the decomposition reaction of the electrolytic solution on the negative electrode by using an electrolytic solution to which a nitrile compound having a carbon-carbon unsaturated bond is added. Has been proposed.
In Patent Document 5, by using an electrolytic solution containing an organic compound having two or more cyano groups, a large dipole moment due to the polarization of the cyano group is oxidatively decomposed on the positive electrode during charging at a high voltage. It has been proposed that this suppresses the battery characteristics and improves the battery characteristics.

Japanese Unexamined Patent Publication No. 10-189008 Japanese Unexamined Patent Publication No. 2005-267857 Japanese Unexamined Patent Publication No. 2000-77096 Japanese Patent Application Laid-Open No. 2003-86248 Japanese Unexamined Patent Publication No. 7-176322

The nitrile compounds described in Patent Documents 1 to 5 have a problem that a reduction side reaction also proceeds on the negative electrode and the effect of improving the battery characteristics is insufficient. Further, the effect of the action on the positive electrode is weak, and there is a problem that the effect of improving the durability characteristics in the continuous charge durability test and the high temperature storage durability test of the battery is insufficient.

The present invention is intended to solve the above problems, and is excellent in initial charge / discharge efficiency and rate characteristics after durability test in a power storage device, and further reduces gas generation and continuous charge capacity after durability test. An object of the present invention is to provide a non-aqueous electrolyte solution and a power storage device using the non-aqueous electrolyte solution.

As a result of various studies to achieve the above object, the present inventors have found that the above problems can be solved by containing a specific nitrile in the electrolytic solution, and have completed the present invention. .. The gist of the aspect of the present invention is as shown below.

(A) A non-aqueous electrolyte solution for a power storage device including a positive electrode and a negative electrode, wherein the non-aqueous electrolyte solution is composed of a cyclic carbonate having a carbon-carbon unsaturated bond and a fluorine-containing cyclic carbonate together with an electrolyte and a non-aqueous solvent. A non-aqueous electrolyte solution containing at least one selected compound and a compound represented by the formula (1).

(In the formula, R is an aliphatic hydrocarbon group having 2 or more and 10 or less carbon atoms, and n is an integer of 4 or more and 8 or less. However, when there are a plurality of Rs, they are different even if they are the same. May be good.)

(B) The non-aqueous electrolyte solution according to (a), wherein R is an alkylene group having 2 or more carbon atoms and 10 or less carbon atoms in the formula (1).
(C) The non-aqueous electrolyte solution according to (a) or (b), wherein n is an integer of 4 or more and 6 or less in the formula (1).
(D) Described in any one of (a) to (c), wherein the content of the compound represented by the above formula (1) with respect to the total amount of the non-aqueous electrolyte solution is 0.001% by mass or more and 10% by mass or less. Non-aqueous electrolyte solution.

(E) The cyclic carbonate having a carbon-carbon unsaturated bond is vinylene carbonate,
The non-aqueous electrolyte solution according to any one of (a) to (d), which is at least one selected from the group consisting of vinyl ethylene carbonate and ethynyl ethylene carbonate.
(F) The non-aqueous electrolyte solution according to (e), wherein the content of the cyclic carbonate having a carbon-carbon unsaturated bond with respect to the total amount of the non-aqueous electrolyte solution is 0.001% by mass or more and 50% by mass or less.

(G) The fluorine-containing cyclic carbonate is monofluoroethylene carbonate, 4,4.
The non-aqueous electrolyte solution according to any one of (a) to (f), which is at least one selected from the group consisting of difluoroethylene carbonate and 4,5-difluoroethylene carbonate.
(H) The content of the fluorine-containing cyclic carbonate with respect to the total amount of the non-aqueous electrolyte solution is 0.001.
The non-aqueous electrolytic solution according to (g), which is 50% by mass or more and 50% by mass or less.

(I) Sulfur-containing organic compounds, phosphorus-containing organic compounds, organic compounds having a cyano group other than the above formula (1), organic compounds having an isocyanate group, silicon-containing compounds, aromatic compounds,
From the group consisting of a fluorine-free carboxylic acid ester, a cyclic compound having multiple ether bonds, a compound having an isocyanuric acid skeleton, a monofluorophosphate, a difluorophosphate, a borate, a oxalate and a fluorosulfonate. The non-aqueous electrolyte solution according to any one of (a) to (h), which contains at least one selected compound.
(J) Sulfur-containing organic compound, phosphorus-containing organic compound, organic compound having a cyano group other than the above formula (1), organic compound having an isocyanate group, silicon-containing compound, aromatic compound,
From the group consisting of a fluorine-free carboxylic acid ester, a cyclic compound having multiple ether bonds, a compound having an isocyanuric acid skeleton, a monofluorophosphate, a difluorophosphate, a borate, a oxalate and a fluorosulfonate. The total content of at least one selected compound with respect to the total amount of the non-aqueous electrolyte solution is 0.001% by mass or more and 50% by mass or less (i).
). The non-aqueous electrolyte solution.

(K) A power storage device comprising a negative electrode and a positive electrode, and the non-aqueous electrolyte solution according to any one of (a) to (j).
(L) The negative electrode has a negative electrode active material layer on a current collector, and the negative electrode active material layer is a simple substance metal of silicon, an alloy and a compound, a simple substance metal of tin, an alloy and a compound, a carbonaceous material, and a carbonaceous material. The power storage device according to (k), which contains at least one selected from the group consisting of lithium titanium composite oxides.
(M) The positive electrode has a positive electrode active material layer on a current collector, and the positive electrode active material layer includes a lithium-cobalt composite oxide, a lithium-cobalt-nickel composite oxide, and a lithium-manganese composite oxide. It contains at least one selected from the group consisting of a lithium-cobalt-manganese composite oxide, a lithium-nickel composite oxide, a lithium-nickel-manganese composite oxide, and a lithium-cobalt-nickel-manganese composite oxide. The power storage device according to k) or (l).

According to the present invention, there is provided a non-aqueous electrolyte solution for realizing a power storage device having excellent initial charge / discharge efficiency and rate characteristics after a durability test, and further reducing gas generation and continuous charge capacity after the durability test. can. As a result, it is possible to achieve miniaturization, high performance, and high safety of the power storage device.

In a power storage device manufactured using the non-aqueous electrolyte solution of the present invention, the action of improving the initial charge / discharge efficiency and the rate characteristics after the durability test, and reducing the gas generation and continuous charging capacity after the durability test. The principle is not clear, but it can be considered as follows. However, the present invention is not limited to the actions / principles described below.

Usually, in the nitrile compounds represented by Patent Documents 1 to 5, the cyano group is coordinated with the metal oxide in the positive electrode active material to suppress the oxidative decomposition of the non-aqueous electrolyte solution, and the storage test and continuous charging are performed. It has the effect of suppressing gas generation after endurance tests such as tests and reducing the continuous charging capacity in continuous charging tests. However, these nitrile compounds have a small binding energy to the metal oxide, and the bond is easily broken during the durability test, so that the effect of suppressing the oxidation reaction of the non-aqueous electrolyte solution is small. Furthermore, since compounds having a cyano group have low reduction resistance,
Reduction side reactions proceed significantly on the negative electrode. Further, these reduction side reactions cannot be suppressed by using an additive known as a negative electrode film forming agent in combination. As a result, the initial charge / discharge efficiency is lowered, leading to capacity loss of the power storage device.

On the other hand, in the non-aqueous electrolyte solution of the present invention, the compound represented by the formula (1) contains ether oxygen and a cyano group via an aliphatic hydrocarbon group. Therefore, the ether oxygen and the cyano group can be used to perform chelate coordination with the metal oxide of the positive electrode, and the binding energy with the metal oxide becomes large. Furthermore, by having a specific number or more of ether oxygen and cyano groups, the coordination points with the metal oxide of the positive electrode are increased, and a larger binding energy can be obtained. as a result,
It is possible to stably protect the metal oxide of the positive electrode and suppress the oxidative decomposition of the non-aqueous electrolyte solution, and suppress the side reaction at the interface between the positive electrode and the electrolyte solution, which is represented by gas generation and continuous charge capacity. , Battery characteristics are improved. Further, by stably coordinating to the metal oxide of the positive electrode, the reaction at the negative electrode is reduced, so that it also has a function of suppressing an unnecessary decrease in capacity at the negative electrode. As a result, the charge / discharge efficiency at the negative electrode represented by the initial charge / discharge efficiency is improved. Further, since ether oxygen has a high polarity, the compound represented by the formula (1) can effectively interact with the cation in the non-aqueous electrolyte solution. As a result, the movement of cations during charging and discharging is improved, so that the compound represented by the formula (1) also has an effect of improving the rate characteristics of the power storage device. Therefore, by using the compound represented by the formula (1), the initial charge / discharge efficiency and the rate characteristics after the durability test are improved without deteriorating the characteristics of the power storage device, and the gas generation and the continuous after the durability test are further improved. The charge capacity can be reduced.

Further, by coexisting a cyclic carbonate having a carbon-carbon unsaturated bond and / or a fluorine-containing cyclic carbonate, a cyclic carbonate having a carbon-carbon unsaturated bond,
And / or the reducing decomposition component of the fluorine-containing cyclic carbonate and the compound represented by the formula (1),
Alternatively, the reduced decomposition products thereof can interact with each other to form a high-quality composite protective film. As a result, side reactions on the negative electrode can be suppressed, and the battery characteristics after the durability test can be further improved, including the initial charge / discharge efficiency.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.
It can be arbitrarily modified and carried out without departing from the gist of the present invention.

1. 1. Non-aqueous electrolyte solution The non-aqueous electrolyte solution of the present invention is a non-aqueous electrolyte solution for a power storage device including a positive electrode and a negative electrode.
The non-aqueous electrolyte solution contains at least one compound selected from the group consisting of a cyclic carbonate having a carbon-carbon unsaturated bond and a fluorine-containing cyclic carbonate together with an electrolyte and a non-aqueous solvent, and a compound represented by the formula (1). It is characterized by containing. The "cyclic carbonate having a carbon-carbon unsaturated bond" does not include those corresponding to the "fluorine-containing cyclic carbonate". "

1-1-1. The compound represented by the formula (1) The non-aqueous electrolytic solution of the present invention contains the compound represented by the formula (1). In the compound represented by the formula (1), the optical isomers cannot be distinguished, and the isomers alone or a mixture thereof can be applied.

(During the ceremony,
R is an aliphatic hydrocarbon group having 2 or more and 10 or less carbon atoms, and n is an integer of 4 or more and 8 or less. However, when there are a plurality of Rs, they may be the same or different. )

R in the formula (1) is not particularly limited as long as it is an aliphatic hydrocarbon group having 2 or more and 10 or less carbon atoms, but it is an alkylene group having no substituent and a part of H of the alkylene is substituted with F. An alkylene group is preferable, and an alkylene group having no substituent is more preferable. When R is a group such as these, the chelate coordination to the positive electrode metal oxide using ether oxygen and the cyano group is not inhibited, so that the chelate coordination to the positive electrode can be performed more effectively, and after the durability test, it can be coordinated to the positive electrode. It is easy to obtain the effects of the present invention such as suppression of gas generation and reduction of the continuous charge capacity in the continuous charge test, and it is easy to obtain the effect of improving the rate characteristics because the interaction with the cation is not hindered, and the reaction at the negative electrode. It is preferable because the initial charge / discharge efficiency can be improved because it is suppressed.

The carbon number of R in the formula (1) is 2 or more, while it is 10 or less, preferably 4 or less, more preferably 3 or less, and most preferably 2. When R is within the above range, an effective chelating effect with the positive electrode metal can be obtained, and a more stable positive electrode surface is formed, which is preferable.

N in the formula (1) is 4 or more, while it is 8 or less, preferably 7 or less, and most preferably 6 or less. When n is within the above range, the solubility in the electrolytic solution becomes high, and a non-aqueous electrolytic solution containing more compounds represented by the formula (1) can be obtained, which is preferable.

Examples of the compound represented by the formula (1) include the following compounds.

Of these, due to the ease of coordination of the positive electrode to the metal oxide and the high coordination bond energy,
The following compounds are preferred.

In particular, the following compounds are preferable because of their high solubility in a non-aqueous electrolytic solution.

The compound represented by the formula (1) may be used alone or in combination of two or more. The amount of the compound represented by the formula (1) (total amount in the case of two or more kinds) in the total amount of the non-aqueous electrolyte solution (100% by mass) is not particularly limited in order to exhibit the effect of the present invention. , Usually 0.001% by mass or more,
It is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.
3% by mass or more, particularly preferably 0.6% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, particularly preferably. Is 1.5% by mass or less, most preferably 1.0% by mass or less. Within this range, it is easy to control the initial charge / discharge efficiency, gas generation and rate characteristics after the durability test, continuous charge capacity, low temperature characteristics, cycle characteristics, and the like.

The method of blending the above compound with the non-aqueous electrolytic solution of the present invention is not particularly limited. In addition to the method of directly adding the compound to the electrolytic solution, a method of generating the compound by a chemical reaction in a battery or an electrolytic solution can be mentioned. Examples of the method of generating the above compound by a chemical reaction include a method of adding a compound other than these compounds and oxidizing or hydrolyzing a battery component such as an electrolytic solution to generate the compound. Further, there is also a method of producing a battery and generating it by applying an electric load such as charging / discharging.

Further, when the above compound is contained in a non-aqueous electrolytic solution and actually used for manufacturing a power storage device,
Even if the battery is disassembled and the non-aqueous electrolyte solution is taken out again, the content in the battery is often significantly reduced. Therefore, it is considered that the non-aqueous electrolyte solution extracted from the battery can be detected even in a very small amount of the above compound in the present invention. Further, when the above compound is actually used as a non-aqueous electrolyte solution for manufacturing a power storage device, the non-aqueous electrolyte solution obtained by disassembling the battery and extracting the battery again contains only a very small amount of the above compound. However, it is often detected on the positive electrode, the negative electrode, or the separator, which are other components of the power storage device. Therefore, when the above compounds are detected from the positive electrode, the negative electrode, and the separator, it can be assumed that the total amount thereof is contained in the non-aqueous electrolyte solution. Under this assumption, the specific compound is preferably contained so as to be within the range described later.

The non-aqueous electrolyte solution of the present invention further contains, in addition to the compound of the general formula (1), one or both of a cyclic carbonate having a carbon-carbon unsaturated bond and a fluorine-containing cyclic carbonate.

1-1-2. Cyclic carbonate with carbon-carbon unsaturated bond Cyclic carbonate with carbon-carbon unsaturated bond (hereinafter, "unsaturated cyclic carbonate")
As long as it is a cyclic carbonate having a carbon-carbon double bond or a carbon-carbon triple bond, any unsaturated carbonate can be used without particular limitation, but carbon is preferable. -A cyclic carbonate with a carbon double bond. In the present invention, the cyclic carbonate having an aromatic ring is also included in the unsaturated cyclic carbonate.

Examples of the unsaturated cyclic carbonate include vinylene carbonates, aromatic rings, ethylene carbonates substituted with a substituent having a carbon-carbon double bond or a carbon-carbon triple bond, phenyl carbonates, vinyl carbonates, and allyl carbonates. Examples thereof include catechol carbonates.

Examples of vinylene carbonates include vinylene carbonate, methylvinylene carbonate, 4,5-dimethylvinylene carbonate, phenylvinylene carbonate, 4,5.
-Diphenylvinylene carbonate, vinylvinylene carbonate, 4,5-divinylvinylene carbonate, allylvinylene carbonate, 4,5-diallylvinylene carbonate, 4-fluorovinylene carbonate, 4-fluoro-5-methylvinylene carbonate, 4-fluoro-5 -Phenylvinylene carbonate, 4-fluoro-5-vinylvinylene carbonate, 4-allyl-5-fluorovinylene carbonate and the like can be mentioned.

Specific examples of ethylene carbonates substituted with a substituent having an aromatic ring, a carbon-carbon double bond or a carbon-carbon triple bond include vinyl ethylene carbonate, 4,5-divinylethylene carbonate, and 4-methyl-5. Vinyl ethylene carbonate, 4-allyl-5
-Vinyl ethylene carbonate, ethynyl ethylene carbonate, 4,5-diethynyl ethylene carbonate, 4-methyl-5-ethynyl ethylene carbonate, 4-vinyl-5
-Ethynyl ethylene carbonate, 4-allyl-5-ethynyl ethylene carbonate, phenylethylene carbonate, 4,5-diphenylethylene carbonate, 4-phenyl-5-vinylethylene carbonate, 4-allyl-5-phenylethylene carbonate,
Allyl ethylene carbonate, 4,5-diallyl ethylene carbonate, 4-methyl-5
-Examples include allyl ethylene carbonate.

Among these, as unsaturated cyclic carbonates particularly preferable to be used in combination, vinylene carbonate, methylvinylene carbonate, 4,5-dimethylvinylene carbonate, vinylvinylene carbonate, 4,5-vinylvinylene carbonate, allylvinylene carbonate, 4, 5-Diallyl vinylene carbonate, vinylethylene carbonate,
4,5-Divinylethylene carbonate, 4-Methyl-5-vinylethylene carbonate, Allylethylene carbonate, 4,5-Diallylethylene carbonate, 4-Methyl-
5-allyl ethylene carbonate, 4-allyl-5-vinylethylene carbonate, ethynylethylene carbonate, 4,5-diethynylethylene carbonate, 4-methyl-5
Examples thereof include ethynyl ethylene carbonate and 4-vinyl-5-ethynyl ethylene carbonate. Further, vinylene carbonate, vinylethylene carbonate and ethynylethylene carbonate are preferable because they form a more stable interface protective film, vinylene carbonate and vinylethylene carbonate are more preferable, and vinylene carbonate is further preferable.

The molecular weight of the unsaturated cyclic carbonate is not particularly limited and is arbitrary as long as the effect of the present invention is not significantly impaired. The molecular weight is preferably 80 or more, more preferably 85 or more, and
Further, it is preferably 250 or less, and more preferably 150 or less. Within this range, it is easy to secure the solubility of the unsaturated cyclic carbonate in the non-aqueous electrolyte solution, and the effect of the present invention is likely to be sufficiently exhibited. The method for producing unsaturated cyclic carbonate is not particularly limited.
It is possible to arbitrarily select and manufacture a known method.

As the unsaturated cyclic carbonate, one type may be used alone, or two or more types may be used in combination in any combination and ratio. Further, the blending amount of the unsaturated cyclic carbonate is not particularly limited and is arbitrary as long as the effect of the present invention is not significantly impaired. The blending amount of the unsaturated cyclic carbonate can be 0.001% by mass or more in 100% by mass of the non-aqueous electrolyte solution, preferably 0.0.
It is 1% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and can be 10% by mass or less, preferably 5% by mass or less, more preferably 4 by mass. It is mass% or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less. Within this range, the power storage device is likely to exhibit a sufficient effect of improving cycle characteristics, and
It is easy to avoid a situation in which the high temperature storage characteristics deteriorate, the amount of gas generated increases, and the discharge capacity retention rate decreases.

Cyclic carbonate (2) having a carbon-carbon unsaturated bond with the compound represented by the above formula (1)
The mass ratio of the compound represented by the formula (1): the cyclic carbonate having a carbon-carbon unsaturated bond can be 1: 100 or more, preferably 10:10.
It is 0 or more, more preferably 20: 100 or more, still more preferably 25: 100 or more, and 1
It can be 0000: 100 or less, preferably 500: 100 or less, more preferably 300: 100 or less, still more preferably 100: 100 or less, and particularly preferably 75: 1.
It is 00 or less, most preferably 50: 100 or less. Within this range, battery characteristics, especially durability characteristics, can be significantly improved. This principle is not clear, but it is thought that by mixing at this ratio, the side reaction of the additive on the electrode can be minimized.

1-1-3. Fluorine-containing cyclic carbonate Examples of the fluorine-containing cyclic carbonate include a fluorinated cyclic carbonate having an alkylene group having 2 or more and 6 or less carbon atoms and a derivative thereof, and examples thereof include a fluorinated product of ethylene carbonate (hereinafter, “fluorinated ethylene carbonate”). ), And its derivatives. Examples of the derivative of the fluorinated product of ethylene carbonate include a fluorinated product of ethylene carbonate substituted with an alkyl group (for example, an alkyl group having 1 or more and 4 or less carbon atoms). Of these, fluorinated ethylene carbonate having a fluorine number of 1 or more and 8 or less, and derivatives thereof are preferable.

By using the compound represented by the formula (1) in combination with the fluorine-containing cyclic carbonate in the non-aqueous electrolytic solution of the present invention, the durability characteristics of the battery using this electrolytic solution can be improved.

Examples of the fluorinated ethylene carbonate having a fluorine number of 1 or more and 8 or less and its derivatives include monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, 4-fluoro-4-methylethylene carbonate, 4,
5-Difluoro-4-methylethylene carbonate, 4-fluoro-5-methylethylene carbonate, 4,4-difluoro-5-methylethylene carbonate, 4- (fluoromethyl) -ethylene carbonate, 4- (difluoromethyl) -ethylene Ethylene,
4- (Trifluoromethyl) -ethylene carbonate, 4- (fluoromethyl) -4-fluoroethylene carbonate, 4- (fluoromethyl) -5-fluoroethylene carbonate, 4-fluoro-4,5-dimethylethylene carbonate, 4 , 5-Difluoro-4
, 5-Dimethylethylene carbonate, 4,4-difluoro-5,5-dimethylethylene carbonate and the like. Of these, monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, and 4,5-difluoroethylene carbonate are preferable because they give high ionic conductivity to the electrolytic solution and easily form a stable interface protection film.

As the fluorinated cyclic carbonate, one type may be used alone, or two or more types may be used in combination in any combination and ratio. The amount of the fluorinated cyclic carbonate (total amount in the case of two or more kinds) is preferably 0.001% by mass or more, more preferably 0.0 in 100% by mass of the electrolytic solution.
It is 1% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, most preferably 1.2% by mass or more, and preferably. It is 10% by mass or less, more preferably 7% by mass or less, further preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably 2% by mass or less. When the fluorinated cyclic carbonate is used as the non-aqueous solvent, the blending amount is preferably 1% by volume or more, more preferably 5% by volume or more, still more preferably 10% by volume or more in 100% by volume of the non-aqueous solvent. Further, it is preferably 50% by volume or less, more preferably 35% by volume or less, still more preferably 25% by volume or less.

Further, as the fluorine-containing cyclic carbonate, a cyclic carbonate having an unsaturated bond and a fluorine atom (hereinafter, may be referred to as “fluorinated unsaturated cyclic carbonate”) can also be used. If the number of fluorines in the fluorinated unsaturated cyclic carbonate is 1 or more,
There are no particular restrictions. The number of fluorines can be 6 or less, preferably 4 or less, more preferably 1 or 2.

Examples of the fluorinated unsaturated cyclic carbonate include a fluorinated vinylene carbonate derivative, a fluorinated ethylene carbonate derivative substituted with a substituent having an aromatic ring or a carbon-carbon double bond, and the like.

As the fluorinated vinylene carbonate derivative, 4-fluorovinylene carbonate,
Examples thereof include 4-fluoro-5-methylvinylene carbonate, 4-fluoro-5-phenylvinylene carbonate, 4-allyl-5-fluorovinylene carbonate, 4-fluoro-5-vinylvinylene carbonate and the like.

Examples of the fluorinated ethylene carbonate derivative substituted with an aromatic ring or a substituent having a carbon-carbon double bond include 4-fluoro-4-vinylethylene carbonate and 4-fluoro-.
4-allyl ethylene carbonate, 4-fluoro-5-vinylethylene carbonate, 4
-Fluoro-5-allylethylene carbonate, 4,4-difluoro-4-vinylethylene carbonate, 4,4-difluoro-4-allylethylene carbonate, 4,5-difluoro-4-vinylethylene carbonate, 4,5-difluoro -4-allylethylene carbonate, 4-fluoro-4,5-divinylethylene carbonate, 4-fluoro-4
, 5-Diallyl ethylene carbonate, 4,5-Difluoro-4,5-Divinylethylene carbonate, 4,5-Difluoro-4,5-Diallylethylene carbonate, 4-Fluoro-4-phenylethylene carbonate, 4-Fluoro-5 -Phenylethylene carbonate, 4,4-difluoro-5-phenylethylene carbonate, 4,5-difluoro-4-phenylethylene carbonate and the like can be mentioned.

Among these, as the fluorinated unsaturated cyclic carbonate, 4-fluorovinylene carbonate, 4-fluoro-5-methylvinylene carbonate, 4-fluoro-5-vinylvinylene carbonate, 4-allyl-5-fluorovinylene carbonate, 4 -Fluoro-4-vinylethylene carbonate, 4-fluoro-4-allylethylene carbonate, 4-fluoro-5-vinylethylene carbonate, 4-fluoro-5-allylethylene carbonate, 4,4-difluoro-4-vinylethylene carbonate , 4,4-Difluoro-4-allylethylene carbonate, 4,5-difluoro-4-vinylethylene carbonate, 4,5-difluoro-4-allylethylene carbonate, 4-fluoro-4,
5-Divinylethylene carbonate, 4-fluoro-4,5-diallylethylene carbonate, 4,5-difluoro-4,5-divinylethylene carbonate, 4,5-difluoro-4,5-diallylethylene carbonate have stable interfaces. It is preferable because it forms a protective film.

The molecular weight of the fluorinated unsaturated cyclic carbonate is not particularly limited. The molecular weight is preferably 50 or more and 250 or less. Within this range, it is easy to secure the solubility of the fluorinated cyclic carbonate in the non-aqueous electrolyte solution, and the effect of the present invention is likely to be exhibited. The method for producing the fluorinated unsaturated cyclic carbonate is not particularly limited, and a known method can be arbitrarily selected for production. The molecular weight is more preferably 100 or more, and more preferably 200 or less.

As the fluorinated unsaturated cyclic carbonate, one type may be used alone, or two or more types may be used in combination in any combination and ratio.

The amount of the fluorinated unsaturated cyclic carbonate (total amount in the case of two or more kinds) is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and further preferably 0 in 100% by mass of the electrolytic solution. .1% by mass or more, particularly preferably 0.2% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 4% by mass or less, and particularly preferably 3% by mass. It is as follows. Within this range, the power storage device tends to exhibit a sufficient effect of improving the cycle characteristics, and it is easy to avoid a situation in which the high temperature storage characteristics deteriorate, the amount of gas generated increases, and the discharge capacity retention rate decreases. ..

The mass ratio of the compound represented by the formula (1) to the fluorine-containing cyclic carbonate can be such that the compound represented by the formula (1): the fluorine-containing cyclic carbonate can be 1: 100 or more, preferably 10 :. 100 or more, more preferably 20: 100 or more, still more preferably 25: 1
It is 00 or more and can be 10000: 100 or less, preferably 500: 100.
Below, it is more preferably 300: 100 or less, still more preferably 100: 100 or less, particularly preferably 75: 100 or less, and most preferably 50: 100 or less. Within this range, battery characteristics, especially durability characteristics, can be significantly improved. This principle is not clear, but it is thought that by mixing at this ratio, the side reaction of the additive on the electrode can be minimized.

The cyclic carbonate having a carbon-carbon unsaturated bond and the fluorine-containing cyclic carbonate may be used in any combination and ratio.

The total amount of the cyclic carbonate having a carbon-carbon unsaturated bond and the fluorine-containing cyclic carbonate is preferably 0.002% by mass or more, more preferably 0.0 in 100% by mass of the electrolytic solution.
2% by mass or more, more preferably 0.2% by mass or more, particularly preferably 0.4% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass. % Or less, particularly preferably 6% by mass or less. If it is within this range, the above equation (1)
An effective composite film with the compound represented by) is formed, the power storage device tends to exhibit a sufficient effect of improving cycle characteristics, the high temperature storage characteristics are lowered, the amount of gas generated is increased, and the discharge capacity is maintained. It is easy to avoid a situation where the rate drops.

The total mass ratio of the compound represented by the formula (1) to the cyclic carbonate having a carbon-carbon unsaturated bond and the fluorine-containing cyclic carbonate is the compound represented by the formula (1): carbon-carbon unsaturated bond. The total of the cyclic carbonate having and the fluorine-containing cyclic carbonate is 1:20.
It can be 0 or more, preferably 10:200 or more, more preferably 10:100 or more, still more preferably 20:100 or more, and 10000: 100 or less, preferably 500: 100 or less. More preferably 300: 100 or less, still more preferably 100: 100 or less, particularly preferably 75: 100 or less, and most preferably 50: 100.
It is as follows. Within this range, battery characteristics, especially durability characteristics, can be significantly improved. This principle is not clear, but it is thought that by mixing at this ratio, the side reaction of the additive on the electrode can be minimized.

1-2. Sulfur-containing organic compounds, phosphorus-containing organic compounds, organic compounds having cyano groups other than the above formula (1), organic compounds having isocyanate groups, silicon-containing compounds, aromatic compounds, fluorine-free carboxylic acid esters, formula (1). Cyclic compounds having multiple ether bonds other than and compounds having an isocyanuric acid skeleton, monofluorophosphates, difluorophosphates, borates, oxalates and fluorosulfonates.

Aspects of the present invention include a sulfur-containing organic compound, a phosphorus-containing organic compound, an organic compound having a cyano group other than the formula (1), an organic compound having an isocyanate group, and silicon, in addition to the compound represented by the formula (1). Compounds, aromatic compounds, fluorine-free carboxylic acid esters, cyclic compounds having a plurality of ether bonds other than the formula (1) and compounds having an isocyanuric acid skeleton, monofluorophosphates, difluorophosphates, borates, It can contain at least one compound (compound of group (II)) selected from the group consisting of oxalate and fluorosulfonate. This is because, by using these in combination, side reactions on the positive and negative sides that can be caused by the compound represented by the formula (1) can be efficiently suppressed.

Among them, a sulfur-containing organic compound, a phosphorus-containing organic compound, an organic compound having a cyano group other than the formula (1), an aromatic compound, a fluorine-free carboxylic acid ester, and a cyclic compound having a plurality of ether bonds other than the formula (1). At least one compound selected from the group consisting of compounds is
It is preferable because a high-quality composite film is formed on the negative electrode and the initial battery characteristics and the battery characteristics after the durability test are improved in a well-balanced manner. At least one compound selected from the group consisting of carboxylic acid esters is more preferable. The reason is that these compounds, which form a relatively low molecular weight coating on the negative electrode,
Since the negative electrode coating formed is dense, it is possible to efficiently suppress deterioration due to side reactions of the compound represented by the formula (1). In this way, side reactions can be effectively suppressed, resistance increases can be suppressed, volume changes can be suppressed by suppressing side reactions at the initial stage and at high temperature endurance, safety after high temperature endurance can be ensured, and rate characteristics can be improved. ..

The method for blending the above compound with the non-aqueous electrolytic solution of the present invention is not particularly limited. In addition to the method of directly adding the compound to the electrolytic solution, a method of generating the compound in a battery or an electrolytic solution can be mentioned. Examples of the method for generating the above compound include a method in which a compound other than these compounds is added and a battery component such as an electrolytic solution is oxidized or hydrolyzed to generate the compound. Further, there is also a method of producing a battery and generating it by applying an electric load such as charging / discharging.

Further, when the above compound is contained in a non-aqueous electrolytic solution and actually used for manufacturing a power storage device,
Even if the battery is disassembled and the non-aqueous electrolyte solution is taken out again, the content in the battery is often significantly reduced. Therefore, it is considered that the non-aqueous electrolyte solution extracted from the battery can be detected even in a very small amount of the above compound in the present invention. Further, when the above compound is actually used as a non-aqueous electrolyte solution for producing a power storage device, the non-aqueous electrolyte solution obtained by disassembling the battery and extracting the battery again contains only a very small amount of the above compound. However, it is often detected on the positive electrode, the negative electrode, or the separator, which are other components of the power storage device. Therefore, when the above compounds are detected from the positive electrode, the negative electrode, and the separator, it can be assumed that the total amount thereof is contained in the non-aqueous electrolyte solution. Under this assumption, the specific compound is preferably contained so as to be within the range described later.

The compounds of group (II) will be described below. However, regarding monofluorophosphate, difluorophosphate, borate, oxalate and fluorosulfonate, "1-
3. 3. The description in "Electrolyte" applies. Further, with respect to the compound represented by the formula (1) to be combined with the above compound, the above description regarding the compound represented by the formula (1) is applied including examples and preferable examples. Further, in an embodiment containing a certain compound, other compounds in the compound may be contained.

1-2-1. Sulfur-containing organic compound The non-aqueous electrolyte solution of the present invention may further contain a sulfur-containing organic compound. The sulfur-containing organic compound is not particularly limited as long as it is an organic compound having at least one sulfur atom in the molecule, but is preferably an organic compound having an S = O group in the molecule, and has a chain. Examples thereof include a cyclic sulfonic acid ester, a cyclic sulfonic acid ester, a chain sulfate ester, a cyclic sulfate ester, a chain sulfite ester, and a cyclic sulfite ester. However, those corresponding to fluorosulfonates are not "1-2-1. Sulfur-containing organic compounds" but are included in fluorosulfonates, which are electrolytes described later.

By using the compound represented by the formula (1) in combination with the sulfur-containing organic compound in the non-aqueous electrolytic solution of the present invention, the durability characteristics of the battery using this electrolytic solution can be improved.

Among them, a chain sulfonic acid ester, a cyclic sulfonic acid ester, a chain sulfate ester, a cyclic sulfate ester, a chain sulfite ester and a cyclic sulfite ester are preferable, and a compound having _two S (= O) groups is more preferable.

These esters may have substituents. Here, the substituent is a group composed of one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom and a halogen atom, and is preferably a carbon atom. , A group composed of one or more atoms selected from the group consisting of hydrogen atoms, oxygen atoms and halogen atoms, and more preferably one or more atoms selected from the group consisting of carbon atoms, hydrogen atoms and oxygen atoms. It is a constructed base. The substituents include a halogen atom; an unsubstituted or halogen-substituted alkyl group, an alkenyl group, an alkynyl group, an aryl group or an alkoxy group; a cyano group; an isocyanato group;
Examples thereof include an alkoxycarbonyloxy group; an acyl group; a carboxy group; an alkoxycarbonyl group; an acyloxy group; an alkylsulfonyl group; an alkoxysulfonyl group; a dialkoxyphosphantriyl group; a dialkoxyphosphoryl group and a dialkoxyphosphoryloxy group. Of these, a halogen atom; an alkoxy group; an unsubstituted or halogen-substituted alkyl group, an alkenyl group or an alkynyl group; an isocyanato group; a cyano group; an alkoxycarbonyloxy group; an acyl group; an alkoxycarbonyl group; an acyloxy group. ,
More preferably, it is a halogen atom, an unsubstituted alkyl group, an alkoxycarbonyloxy group; an acyl group; an alkoxycarbonyl group or an acyloxy group, and more preferably, a halogen atom, an unsubstituted alkyl group and an alkoxycarbonyl group. Examples and preferred examples of these substituents apply to the substituents in the definition of A ¹² and A ¹³ in formula (2-2-1) described below and A ¹⁴ in formula (2--2-2). ..

More preferably, it is a chain sulfonic acid ester and a cyclic sulfonic acid ester, among others.
The chain sulfonic acid ester represented by the formula (2-2-1) and the cyclic sulfonic acid ester represented by the formula (2--2-2) are preferable, and the cyclic sulfonic acid ester represented by the formula (2-2-2) is preferable. Preferably better than sulfonic acid esters.

1-2-1-1. Chain sulfonic acid ester represented by the formula (2-2-1)

(In the formula, A12 is an n21-valent hydrocarbon group having ¹ or more and ¹² or less carbon atoms which may have a substituent.
A ¹³ is a hydrocarbon group having 1 or more and 12 or less carbon atoms which may have a substituent.
n ²¹ is an integer of 1 or more and 4 or less.
When n ²¹ is 2, A ¹² and A ¹³ may be the same or different. )
In formula (2-2-1), A ¹² and A ¹³ do not form a ring together, thus formula (2-2-1) is a chain sulfonic acid ester.

For n ²¹ , an integer of 1 or more and 3 or less is preferable, an integer of 1 or more and 2 or less is more preferable, and 2 is further preferable.

As an n21-valent hydrocarbon group having ¹ or more and ¹² or less carbon atoms in A12,
Monovalent hydrocarbon groups such as alkyl groups, alkenyl groups, alkynyl groups and aryl groups;
Divalent hydrocarbon groups such as alkylene group, alkenylene group, alkynylene group and arylene group;
A trivalent hydrocarbon group such as an alkanetriyl group, an alkentelyyl group, an alkynetriyl group and an arenetriyl group;
A tetravalent hydrocarbon group such as an alkanetetrayl group, an alkenetetrayl group, an alkynetetrayl group and an arenetetrayl group;
And so on.

Of these, a divalent hydrocarbon group such as an alkylene group, an alkenylene group, an alkynylene group and an arylene group is preferable, and an alkylene group is more preferable. These correspond to the case where n ²¹ is 2.

Among the n21-valent hydrocarbon groups having ¹ to 12 carbon atoms, the monovalent hydrocarbon groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and sec-butyl. Group, i-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, neopentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylpropyl group, 1,2- Alkyl group having 1 to 5 carbon atoms such as dimethylpropyl group; vinyl group, 1
-Carbons such as propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group Alkenyl group of number 2 or more and 5 or less; ethynyl group, 1-propynyl group, 2
-Alkynyl groups having 2 or more and 5 or less carbon atoms such as propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group and 4-pentynyl group Can be mentioned.

Examples of the divalent hydrocarbon group include an alkylene group having 1 or more and 5 or less carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group and a pentamethylene group; a vinylene group, a 1-propenylene group and a 2-propenylene group. Alkenylene groups having 2 or more and 5 or less carbon atoms such as 1-butenylene group, 2-butenylene group, 1-pentenylene group, 2-pentenylene group; ethynylene group,
Examples thereof include an alkynylene group having 2 or more and 5 or less carbon atoms such as a propynylene group, a 1-butynylene group, a 2-butynylene group, a 1-pentynylene group and a 2-pentynylene group, preferably a methylene group, an ethylene group, a trimethylene group and a tetra. 1 carbon number of methylene group, pentamethylene group, etc.
It is an alkylene group of ~ 5, more preferably an alkylene group having 2 or more and 5 or less carbon atoms such as an ethylene group, a trimethylene group, a tetramethylene group and a pentamethylene group, and further preferably a trimethylene group, a tetramethylene group and a pentamethylene group. It is an alkylene group having 3 or more and 5 or less carbon atoms such as a group.

Examples of the trivalent and tetravalent hydrocarbon groups include trivalent and tetravalent hydrocarbon groups corresponding to the above monovalent hydrocarbon groups.

The n21-valent hydrocarbon group having ¹ or more and ¹² or less carbon atoms having a substituent in A12 is a combination of the above-mentioned substituent and the above-mentioned n21-valent hydrocarbon group having ¹ or more and 12 or less carbon atoms. Means a group. As A ¹² , an n21-valent hydrocarbon group having ¹ or more carbon atoms and 5 or less carbon atoms having no substituent is preferable.

As the hydrocarbon group having 1 or more and ¹² or less carbon atoms in A13, a monovalent hydrocarbon group such as an alkyl group, an alkenyl group, an alkynyl group and an aryl group is preferable, and an alkyl group is more preferable. Hydrocarbon groups having 1 or more and 12 or less carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, i-butyl group, tert-butyl group and n. -Pentyl group, isopentyl group, sec-pentyl group, neopentyl group, 1-
Examples thereof include an alkyl group having 1 to 5 carbon atoms such as a methylbutyl group, a 2-methylbutyl group, a 1,1-dimethylpropyl group and a 1,2-dimethylpropyl group, preferably a methyl group, an ethyl group and an n-propyl group. , N-butyl group and n-pentyl group, more preferably a methyl group, an ethyl group and an n-propyl group, and further preferably an ethyl group and an n-propyl group.

The hydrocarbon group having 1 or more and ¹² or less carbon atoms having a substituent in A13 means a group in which the above-mentioned substituent and the above-mentioned hydrocarbon group having 1 or more and 12 or less carbon atoms are combined. As ^A13 , a hydrocarbon group having 1 or more and 5 or less carbon atoms which may have a substituent is preferable, and more preferably, a hydrocarbon group having 1 or more and 5 or less carbon atoms having a substituent is preferable. An alkyl group having an alkoxycarbonyl group as a substituent is more preferable. Among them, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 1-methoxycarbonylpropyl group, 1-ethoxy A carbonylpropyl group, a 2-methoxycarbonylpropyl group, a 2-ethoxycarbonylpropyl group, a 3-methoxycarbonylpropyl group and a 3-ethoxycarbonylpropyl group are preferable, and a 1-methoxycarbonylethyl group and a 1-ethoxycarbonylethyl group are more preferable. Is.

1-2-1-2. Cyclic sulfonic acid ester represented by the formula (2-2-2)

( ^In the formula, A14 is a divalent hydrocarbon group having 1 or more and 12 or less carbon atoms which may have a substituent.)
Examples of the divalent hydrocarbon group having 1 or more and 12 or less carbon atoms in A ¹⁴ include an alkylene group, an alkenylene group, an alkynylene group, an arylene group and the like, and an alkylene group and an alkenylene group are preferable.

Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms include an alkylene group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group and a pentamethylene group; a vinylene group and a 1-propenylene group. , 2-propenylene group, 1-butenylene group, 2-butenylene group, 1-pentenylene group, 2-pentenylene group and other alkenylene groups having 2 to 5 carbon atoms;
Examples thereof include an alkynylene group having 2 to 5 carbon atoms such as an ethynylene group, a propynylene group, a 1-butynylene group, a 2-butynylene group, a 1-pentynylene group and a 2-pentynylene group.

Of these, preferably an alkylene group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group and a pentamethylene group, a vinylene group, a 1-propenylene group, a 2-propenylene group and a 1-butenylene group. , 2-Butenylene group, 1-Pentenylene group, 2-Pentenylene group and other alkenylene groups having 2 to 5 carbon atoms, more preferably alkylene groups having 3 to 5 carbon atoms such as trimethylene group, tetramethylene group and pentamethylene group. Group and 1
-Alkenylene group having 3 to 5 carbon atoms such as a propenylene group, a 2-propenylene group, a 1-butenylene group, a 2-butenylene group, a 1-pentenylene group, a 2-pentenylene group, and more preferably a trimethylene group and a 1-propenylene group. Group, 2-propenylene group.

The divalent hydrocarbon group having 1 or more and 12 or less carbon atoms having a substituent in A ¹⁴ is a group in which the above-mentioned substituent and the above-mentioned divalent hydrocarbon group having 1 or more and 12 or less carbon atoms are combined. Means that. A ¹⁴ is preferably a divalent hydrocarbon group having 1 or more and 5 or less carbon atoms having no substituent.
Examples of the sulfur-containing organic compound include the following.

≪Chainous sulfonic acid ester≫
Fluorosulfuric acid esters such as methyl fluorosulfonate and ethyl fluorosulfonate;
Methyl methanesulphonate, ethyl methanesulphonate, 2-propinyl methanesulphonate, 3-butynyl methanesulphonate, busulfan, methyl 2- (methanesulfonyloxy) propionate, ethyl 2- (methanesulfonyloxy) propionate, 2- (Methanesulfonyloxy) 2-propynyl propionic acid, 2- (methanesulfonyloxy) propionate 3-butynyl, methyl methanesulfonyloxyacetate, ethyl methanesulfonyloxyacetate, 2-propynyl methanesulfonyloxyacetic acid and methanesulfonyloxyacetic acid 3
-Methane sulfonic acid esters such as butynyl;
Methyl vinyl sulfonate, ethyl vinyl sulfonate, allyl vinyl sulfonate, propargyl vinyl sulfonate, methyl allyl sulfonate, ethyl allyl sulfonate, allyl allyl sulfonate, propargyl allyl sulfonate and 1,2-bis (vinyl sulfonate) ) Alkenyl sulfonic acid ester such as ethane;
Methanedisulfonic acid methoxycarbonylmethyl, methanedisulfonic acid ethoxycarbonylmethyl, methanedisulfonic acid 1-methoxycarbonylethyl, methanedisulfonic acid 1-
Ethoxycarbonylethyl, 1,2-ethanedisulfonic acid methoxycarbonylmethyl, 1
, 2-Ethandisulfonic acid ethoxycarbonylmethyl, 1,2-Ethandisulfonic acid 1-
Methoxycarbonylethyl, 1,2-ethanedisulfonic acid 1-ethoxycarbonylethyl, 1,3-propanedisulfonic acid methoxycarbonylmethyl, 1,3-propanedisulfonic acid ethoxycarbonylmethyl, 1,3-propanedisulfonic acid 1-methoxycarbonyl Ethyl, 1-ethoxycarbonylethyl 1,3-propanedisulfonic acid, methoxycarbonylmethyl 1,3-butanedisulfonic acid, ethoxycarbonylmethyl 1,3-butanedisulfonic acid, 1-methoxycarbonylethyl 1,3-butanedisulfonic acid, Alkyl disulfonic acid esters such as 1,3-butane disulfonic acid 1-ethoxycarbonylethyl;

≪Cyclic sulfonic acid ester≫
1,3-Propane sulton, 1-fluoro-1,3-propane sulton, 2-fluoro-1,3-propane sulton, 3-fluoro-1,3-propane sulton, 1-methyl-
1,3-Propane sulton, 2-methyl-1,3-propanesulton, 3-methyl-1,
3-Propane Sultone, 1-Propene-1,3-Sultone, 2-Propene-1,3-Sultone, 1-Fluoro-1-Propene-1,3-Sultone, 2-Fluoro-1-Propene-
1,3-Sultone, 3-Fluoro-1-propene-1,3-sultone, 1-Fluoro-2
-Propene-1,3-sultone, 2-fluoro-2-propene-1,3-sultone, 3-
Fluoro-2-propene-1,3-sultone, 1-methyl-1-propene-1,3-sultone, 2-methyl-1-propene-1,3-sultone, 3-methyl-1-propene-1,
3-Sultone, 1-Methyl-2-Propen-1,3-Sultone, 2-Methyl-2-Propen-1,3-Sultone, 3-Methyl-2-Propen-1,3-Sultone, 1,4- Sultone compounds such as butane sultone and 1,5-pentane sultone;
Disulfonate compounds such as methylene methane disulfonate and ethylene methane disulfonate;
1,2,3-oxathiazolidine-2,2-dioxide, 3-methyl-1,2,3-oxathiazolidine-2,2-dioxide, 3H-1,2,3-oxathiazole-2,2
-Dioxide, 5H-1,2,3-oxathiazole-2,2-dioxide, 1,2,4
-Oxatiazolidine-2,2-dioxide, 1,2,5-oxathiazolidine-2,2
-Dioxide, 1,2,3-oxathiadinane-2,2-dioxide, 3-methyl-1,
Nitrogen-containing compounds such as 2,3-oxathiadinane-2,2-dioxide, 5,6-dihydro-1,2,3-oxathiadin-2,2-dioxide and 1,2,4-oxathiadinane-2,2-dioxide ..

1,2,3-oxathiaphoslan-2,2-dioxide, 3-methyl-1,2,3-oxathiaphoslan-2,2-dioxide, 3-methyl-1,2,3-oxati Aphoslan-2,2,3-trioxide, 3-methoxy-1,2,3-oxathiaphoslan-2,2
, 3-Trioxide, 1,2,4-oxathiaphoslan-2,2-dioxide, 1,2,
5-oxathiaphoslan-2,2-dioxide, 1,2,3-oxathiaphosphinan-
2,2-Dioxide, 3-Methyl-1,2,3-oxathiaphosphinan-2,2-dioxide, 3-methyl-1,2,3-oxathiaphosphinan-2,2,3-trioxide, 3-Methoxy-1,2,3-oxathiaphosphinan-2,2,3-trioxide, 1
, 2,4-oxathiaphosphinan-2,2-dioxide, 1,2,5-oxathiaphosphinan-2,2-dioxide and 1,2,6-oxathiaphosphinan-2,2-dioxide, etc. Phosphorus-containing compound.

≪Chain Sulfuric Acid Ester≫
Dialkyl sulphate compounds such as dimethyl sulphate, ethyl methyl sulphate and diethyl sulphate.

≪Cyclic sulfate ester≫
1,2-Ethylene sulphate, 1,2-propylene sulphate, 1,3-propylene sulphate, 1,2-butylene sulphate, 1,3-butylen sulphate, 1,
An alkylene sulfate compound such as 4-butylene sulphate, 1,2-pentylen sulphate, 1,3-pentylen sulphate, 1,4-pentylen sulphate and 1,5-pentylen sulphate.

≪Chain sulfite ester≫
Dialkylsulfite compounds such as dimethylsulfite, ethylmethylsulfite and diethylsulfite.

≪Cyclic sulfite ester≫
1,2-Ethylene sulphite, 1,2-propylene sulphite, 1,3-propylene sulphite, 1,2-butylene sulphite, 1,3-butylen sulphite, 1,
An alkylene sulfite compound such as 4-butylen sulphite, 1,2-pentylen sulphite, 1,3-pentylen sulphite, 1,4-pentylensulfite and 1,5-pentylensulfite.

Of these, methyl 2- (methanesulfonyloxy) propionate, ethyl 2- (methanesulfonyloxy) propionate, 2- (methanesulfonyloxy) propionic acid 2
-Propinyl, 1-methoxycarbonylethyl propanedisulfonic acid, 1-ethoxycarbonylethyl propanedisulfonic acid, 1-methoxycarbonylethyl butanedisulfonic acid, 1-ethoxycarbonylethyl butanedisulfonic acid, 1,3-propanesulton, 1-
Propen-1,3-sultone, 1,4-butane sultone, 1,2-ethylenesulfate, 1,2-ethylenesulfite, methyl methanesulphonate and ethyl methanesultone are preferable from the viewpoint of improving initial efficiency, and propanedisulfone. Acid 1-methoxycarbonylethyl, propanedisulfonic acid 1-ethoxycarbonylethyl, butanedisulfonic acid 1-methoxycarbonylethyl, butanedisulfonic acid 1-ethoxycarbonylethyl, 1,3-propanesultone, 1-propen-1,3-sultone , 1,2-ethylene sultone, 1,
2-Ethylene sulphite is more preferred, 1,3-propanesulton, 1-propene-
1,3-Sultone is more preferred.

As the sulfur-containing organic compound, one type may be used alone, or two or more types may be used in combination in any combination and ratio.

The content of the sulfur-containing organic compound (total amount in the case of two or more types) is 100% by mass of the electrolytic solution.
It can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.3% by mass or more, and particularly preferably 0.6% by mass. % Or more, and can be 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1.5% by mass.
Hereinafter, it is most preferably 1.0% by mass or less. Within this range, it is easy to control output characteristics, load characteristics, low temperature characteristics, cycle characteristics, high temperature storage characteristics, and the like.

The mass ratio of the compound represented by the above formula (1) to the sulfur-containing organic compound can be such that the compound represented by the formula (1): the sulfur-containing organic compound is 1: 100 or more, preferably 10: 1
00 or more, more preferably 20: 100 or more, still more preferably 25: 100 or more,
It can be 10000: 100 or less, preferably 500: 100 or less, more preferably 300: 100 or less, still more preferably 100: 100 or less, and particularly preferably 75:
It is 100 or less, most preferably 50: 100 or less. Within this range, battery characteristics, especially durability characteristics, can be significantly improved. This principle is not clear, but it is thought that by mixing at this ratio, the side reaction of the additive on the electrode can be minimized.

1-2-2. Phosphorus-Containing Organic Compound The non-aqueous electrolyte solution of the present invention may further contain a phosphorus-containing organic compound. The phosphorus-containing organic compound is not particularly limited as long as it is an organic compound having at least one phosphorus atom in the molecule. A battery using the non-aqueous electrolytic solution of the present invention containing a phosphorus-containing organic compound can improve durability characteristics.

As the phosphorus-containing organic compound, a phosphoric acid ester, a phosphonic acid ester, a phosphinic acid ester, and a phosphite ester are preferable, a phosphoric acid ester and a phosphonic acid ester are more preferable, and a phosphonic acid ester is further preferable. These esters may have substituents. Here, the substituent is a group composed of one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom and a halogen atom, and is preferably a carbon atom. , A group composed of one or more atoms selected from the group consisting of hydrogen atom, oxygen atom and halogen atom. The substituents include a halogen atom; an unsubstituted or halogen-substituted alkyl group, an alkenyl group, an alkynyl group, an aryl group or an alkoxy group; a cyano group; an isocyanato group; an alkoxycarbonyloxy group; an acyl group; a carboxy group; an alkoxycarbonyl group. Examples thereof include an acyloxy group; an alkylsulfonyl group; an alkoxysulfonyl group; a dialkoxyphosphantriyl group; a dialkoxyphosphoryl group and a dialkoxyphosphoryloxy group. Among these, a halogen atom; an alkoxy group; an alkoxycarbonyloxy group; an acyl group; a carboxyl group, an acyloxy group and the like are preferable, a halogen atom and an acyloxy group are more preferable, and an acyloxy group is further preferable. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an acryloyloxy group, a methacryloyloxy group, a crotonyloxy group and the like, and an acryloyloxy group is preferable. Examples and preferred examples of these substituents apply to the substituents ⁱⁿ the definition of A6 to A8 in the ^formula (2-3-1) described later.

More preferably, it is a phosphoric acid ester and a phosphonic acid ester, and among them, the formula (2-3-
The phosphoric acid ester represented by 1) and the phosphonic acid ester represented by the formula (2-3-2) are preferable.

1-2-2-1. Phosphoric acid ester represented by the formula (2-3-1)

(In the formula, A ⁶ , A ⁷ and A ⁸ are alkyl groups, alkenyl groups or alkynyl groups having 1 or more and 5 or less carbon atoms which may independently have a substituent, but A ⁶ -At least one of A8 has a carbon ^- carbon unsaturated bond.)

As the alkyl group, alkenyl group or alkynyl group having 1 to 5 carbon atoms, the methyl group, the ethyl group, the n-propyl group, the i-propyl group, the n-butyl group, the sec-butyl group, the i-butyl group and the tert- Butyl group, n-pentyl group, isopentyl group, sec-pentyl group, neopentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylpropyl group,
Alkyl groups such as 1,2-dimethylpropyl group; vinyl group, 1-propenyl group, 2-propenyl group (allyl group), isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1- Alkenyl groups such as pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group; ethynyl group, 1-propynyl group, 2-propynyl group (propargyl group),
Examples thereof include alkynyl groups such as 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group and 4-pentynyl group, and include methyl group, ethyl group and n-. Propyl group, n-butyl group, n-pentyl group, vinyl group, 2-propenyl group (
Allyl group), 3-butenyl group, 4-pentenyl group, 2-propynyl group (propargyl group)
, 3-Butynyl group and 4-pentynyl group are preferable, and methyl group, ethyl group, 2-propenyl group (allyl group) and 2-propynyl group (propargyl group) are more preferable.
Ethyl groups and 2-propenyl groups (allyl groups) are more preferred.

The alkyl group having 1 or more and 5 or less carbon atoms, an alkenyl group or an alkynyl group having a substituent is a group in which the above-mentioned substituent and the above-mentioned alkyl group having 1 or more and 5 or less carbon atoms, an alkenyl group or an alkynyl group are combined. , And preferably a 2-acryloyloxymethyl group and a 2-acryloyloxyethyl group.

Examples of the compound represented by the formula (2-3-1) include the following.
<Compound with one carbon-carbon unsaturated bond>
Compounds having a vinyl group such as dimethylvinyl phosphate, diethyl vinyl phosphate, dipropyl vinyl phosphate, dibutyl vinyl phosphate and dipentyl vinyl phosphate;
Compounds having an allyl group such as allyldimethylphosphate, allyldiethylphosphate, allyldipropylphosphate, allyldibutylphosphate and allyldipentylphosphate;
Compounds having a propargyl group such as propargyldimethyl phosphate, propargyl diethyl phosphate, propargyl dipropyl phosphate, propargyl dibutyl phthalate and propargyl dipentyl phosphate;
It has a 2-acryloyloxymethyl group such as 2-acryloyloxymethyldimethylphosphate, 2-acryloyloxymethyldiethylphosphate, 2-acryloyloxymethyldipropylphosphate, 2-acryloyloxymethyldibutylphosphate and 2-acryloyloxymethyldipentylphosphate. Compound;
It has a 2-acryloyloxyethyl group such as 2-acryloyloxyethyldimethylphosphate, 2-acryloyloxyethyldiethylphosphate, 2-acryloyloxyethyldipropylphosphate, 2-acryloyloxyethyldibutylphosphate and 2-acryloyloxyethyldipentylphosphate. Compound;

<Compound with two carbon-carbon unsaturated bonds>
Compounds having a vinyl group such as methyldivinyl phosphate, ethyldivinyl phosphate, propyldivinyl phosphate, butyldivinyl phosphate and pentyldivinyl phosphate;
Compounds having an allyl group such as diallylmethyl phosphate, diallyl ethyl phosphate, diallyl propyl phosphate, diallyl butyl phosphate and diallyl pentyl phosphate;
Compounds having a propargyl group such as dipropargylmethyl phosphate, dipropargyl ethyl phosphate, dipropargyl propyl phosphate, dipropargyl butyl phosphate and dipropargyl pentyl phosphate;
Bis (2-acryloyloxymethyl) methyl phosphate, bis (2-acryloyloxymethyl) ethyl phosphate, bis (2-acryloyloxymethyl) propyl phosphate, bis (2-acryloyloxymethyl) butyl phosphate and bis (2-
Acryloyloxymethyl) Compounds having a 2-acryloyloxymethyl group such as pentyl phosphate;
Bis (2-acryloyloxyethyl) methyl phosphate, bis (2-acryloyloxyethyl) ethyl phosphate, bis (2-acryloyloxyethyl) propyl phosphate, bis (2-acryloyloxyethyl) butyl phosphate and bis (2-
Acryloyloxyethyl) Compounds having a 2-acryloyloxyethyl group such as pentyl phosphate;

<Compound with three carbon-carbon unsaturated bonds>
Trivinyl phosphate, Triallyl phosphate, Tripropargyl phosphate,
Tris (2-acryloyloxymethyl) phosphate, tris (2-acryloyloxyethyl) phosphate, etc. Of these, compounds having three carbon-carbon unsaturated bonds are preferable from the viewpoint of improving battery characteristics, and triallyl phosphate and tris (2-acryloyloxymethyl) phosphate and tris (2-acryloyloxymethyl) phosphate. 2-Acryloyloxyethyl) phosphate is more preferred.

1-2-2-2. Phosphonate ester represented by the formula (2-3-2)

(In the formula, A ⁹ , A ¹⁰ and A ¹¹ are independently unsubstituted or halogen substituted and have 1 to 1 carbon atoms.
It is an alkyl group, an alkenyl group or an alkynyl group of 5.
n ³² is an integer of 0 to 6. )

As the alkyl group, alkenyl group or alkynyl group having 1 to 5 carbon atoms, the methyl group, the ethyl group, the n-propyl group, the i-propyl group, the n-butyl group, the sec-butyl group, the i-butyl group and the tert- Butyl group, n-pentyl group, isopentyl group, sec-pentyl group, neopentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylpropyl group,
Alkyl groups such as 1,2-dimethylpropyl group; vinyl group, 1-propenyl group, 2-propenyl group (allyl group), isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1- Alkenyl groups such as pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group; ethynyl group, 1-propynyl group, 2-propynyl group (propargyl group),
Examples thereof include alkynyl groups such as 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group and 4-pentynyl group, and include methyl group, ethyl group and n-. Propyl group, n-butyl group, n-pentyl group, vinyl group, 2-propenyl group (
Allyl group), 3-butenyl group, 4-pentenyl group, 2-propynyl group (propargyl group)
, 3-Butynyl group and 4-pentynyl group are preferable, and methyl group, ethyl group, 2-propenyl group (allyl group) and 2-propynyl group (propargyl group) are more preferable.
Ethyl groups and 2-propynyl groups (propargyl groups) are more preferred.
Examples of the phosphonic acid ester represented by the formula (2-3-2) include the following compounds.

<Compound of n ³² = 0 in formula (2-3-2)>
Trimethylphosphonoformate, methyldiethylphosphonoformate, methyldipropylphosphonoformate, methyldibutylphosphonoformate, triethylphosphonoformate, ethyl dimethylphosphonoformate, ethyldipropylphosphonoformate, ethyl Dibutylphosphonoformate, Tripropylphosphonoformate, Propyldimethylphosphonoformate, Propyldiethylphosphonoformate, Propyldibutylphosphonoformate, Tributylphosphonoformate, Butyldimethylphosphonoformate, Butyldiethylphosphomate Noformate, butyldipropylphosphonoformate, methylbis (2,2,2-trifluoroethyl) phosphonoformate, ethyl bis (2,2,2-trifluoroethyl) phosphonoformate, propylbis (2,2,2-trifluoroethyl) phosphonoformate, butyl bis (2,2,2-trifluoroethyl) phosphonoformate and the like.

<Compound of n ³² = 1 in the formula (2-3-2)>
Trimethylphosphonoacetate, methyldiethylphosphonoacetate, methyldipropylphosphonoacetate, methyldibutylphosphonoacetate, triethylphosphonoacetate, ethyldimethylphosphonoacetate, ethyldipropylphosphonoacetate, ethyldibutylphosphonoacetate, tripropyl Phosphonoacetate,
Propyl dimethylphosphonoacetate, propyl diethylphosphonoacetate, propyldibutylphosphonoacetate, tributylphosphonoacetate, butyldimethylphosphonoacetate, butyldiethylphosphonoacetate, butyldipropylphosphonoacetate, methylbis (2,2,2) -Trifluoroethyl) phosphonoacetate, ethyl bis (2,2,2-trifluoroethyl) phosphonoacetate, propyl bis (2,2,2-trifluoroethyl) phosphonoacetate, butyl bis (2,2) 2
-Trifluoroethyl) phosphonoacetate, allyl dimethylphosphonoacetate, allyl diethylphosphonoacetate, 2-propynyl dimethylphosphonoacetate, 2
-Propinyl diethylphosphonoacetate, etc.

<Compound of n ³² = 2 in the formula (2-3-2)>
Trimethyl 3-phosphonopropionate, methyl 3- (diethylphosphono) propionate, methyl 3- (dipropylphosphono) propionate, methyl 3- (dibutylphosphono) propionate, triethyl 3-phosphonopropionate, ethyl 3-
(Dimethylphosphono) propionate, ethyl 3- (dipropylphosphono) propionate, ethyl 3- (dibutylphosphono) propionate, tripropyl 3-phosphonopropionate, propyl 3- (dimethylphosphono) propionate, propyl 3 -
(Diethylphosphono) propionate, propyl 3- (dibutylphosphono) propionate, tributyl 3-phosphonopropionate, butyl 3- (dimethylphosphono) propionate, butyl 3- (dibutylphosphono) propionate, butyl 3-( Dipropylphosphono) propionate, methyl 3- (bis (2,2,2-trifluoroethyl) phosphono) propionate, ethyl 3- (bis (2,2,2-trifluoroethyl) phosphono) propionate, propyl 3- (Bis (2,2,2-trifluoroethyl) phosphono) Propylonate, Butyl 3- (Bis (2,2,2-trifluoroethyl))
Phosphono) propionate, etc.

<Compound of n ³² = 3 in formula (2-3-2)>
Trimethyl 4-phosphonobutylate, methyl 4- (diethylphosphono) butyrate, methyl 4- (dipropylphosphono) butyrate, methyl 4- (dibutylphosphono)
Butyrate, Triethyl 4-phosphonobutylate, Ethyl 4- (dimethylphosphono)
Butylate, ethyl 4- (dipropylphosphono) butylate, ethyl 4- (dibutylphosphono) butylate, tripropyl 4-phosphonobutylate, propyl 4- (dimethylphosphono) butylate, propyl 4- (diethylphosphono) Butylate, propyl 4- (dibutylphosphono) butylate, tributyl 4-phosphonobutylate, butyl 4- (dimethylphosphono) butylate, butyl 4- (diethylphosphono) butylate, butyl 4- (dipropylphosphono) butylate etc.

From the viewpoint of improving battery characteristics, compounds of n ³² = 0, 1 and 2 are preferable, compounds of n ³² = 0 and 1 are more preferable, compounds of n ³² = 1 are more preferable, and among compounds of n ³² = 1, among the compounds of n 32 = 1. Compounds in which A ⁹ to A ¹¹ are saturated hydrocarbon groups are preferable. In particular, trimethylphosphonoacetate, triethylphosphonoacetate, 2-propynyldimethylphosphonoacetate, and 2-propynyldiethylphosphonoacetate are preferable.

As the phosphorus-containing organic compound, one type may be used alone, or two or more types may be used in combination in any combination and ratio.

The content of the phosphorus-containing organic compound (total amount in the case of two or more kinds) is 100% by mass of the electrolytic solution.
It can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.4% by mass or more, and particularly preferably 0.6% by mass or more. It can be 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1.2% by mass or less.
Most preferably, it is 0.9% by mass or less. Within this range, it is easy to control output characteristics, load characteristics, low temperature characteristics, cycle characteristics, high temperature storage characteristics, and the like.

The mass ratio of the compound represented by the above formula (1) to the phosphorus-containing organic compound can be such that the compound represented by the formula (1): the phosphorus-containing organic compound is 1: 100 or more, preferably 10: 1
00 or more, more preferably 20: 100 or more, still more preferably 25: 100 or more,
It can be 10000: 100 or less, preferably 500: 100 or less, more preferably 300: 100 or less, still more preferably 100: 100 or less, and particularly preferably 75:
It is 100 or less, most preferably 50: 100 or less. Within this range, battery characteristics, especially durability characteristics, can be significantly improved. This principle is not clear, but it is thought that by mixing at this ratio, the side reaction of the additive on the electrode can be minimized.

1-2-3. Organic compound having a cyano group other than the formula (1) The non-aqueous electrolyte solution of the present invention may contain an organic compound having a cyano group other than the formula (1). The organic compound having a cyano group other than the formula (1) is not particularly limited as long as it is an organic compound other than the formula (1) having at least one cyano group in the molecule, but is preferably the formula (2). 4-1), a compound represented by the formula (2-4-2) and the formula (2-4-3).
A compound represented by the formulas (2-4-2) and (2-4-3) is more preferable, and a compound represented by the formula (2-4-2) is more preferable. When the organic compound having a cyano group other than the formula (1) is also a cyclic compound having a plurality of ether bonds other than the formula (1), it belongs to the cyclic compound having a plurality of ether bonds other than the formula (1). May be acceptable.
In the non-aqueous electrolyte solution of the present invention, by using a compound represented by the formula (1) and an organic compound having a cyano group other than the formula (1) in combination, durability characteristics can be obtained in a battery using this electrolyte solution. Can be improved.

1-2-3-1. Compound represented by the formula (2-4-1) A ¹ -CN (2-4-1)
(In the formula, A ¹ represents a hydrocarbon group having 2 or more carbon atoms and 20 or less carbon atoms.)

The molecular weight of the compound represented by the formula (2-4-1) is not particularly limited. The molecular weight is preferably 55 or more, more preferably 65 or more, still more preferably 80 or more, and also.
It is preferably 310 or less, more preferably 185 or less, still more preferably 155 or less.
It is as follows. Within this range, it is easy to secure the solubility of the compound represented by the formula (2-4-1) in the non-aqueous electrolyte solution, and the effect of the present invention is likely to be exhibited. The method for producing the compound represented by the formula (2-4-1) is not particularly limited, and a known method can be arbitrarily selected for production.

In the formula (2-4-1), examples of the hydrocarbon group having 2 or more and 20 or less carbon atoms include an alkyl group, an alkenyl group, an alkynyl group and an aryl group, and include an ethyl group, an n-propyl group and is.
o-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, tert-amyl group, hexyl group, heptyl group, octyl group, nonyl Alkyl group such as group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group; vinyl group, 1-propenyl group, isopropenyl group , 1-butenyl, 1-pentenyl group and other alkenyl groups; ethynyl group, 1-propynyl group,
Alkinyl groups such as 1-butynyl group and 1-pentynyl group; phenyl group, tolyl group, ethylphenyl group, n-propylphenyl group, i-propylphenyl group, n-butylphenyl group,
Aryl groups such as sec-butylphenyl group, i-butylphenyl group, tert-butylphenyl group, trifluoromethylphenyl group, xsilyl group, benzyl group, phenethyl group, methoxyphenyl group, ethoxyphenyl group and trifluoromethoxyphenyl group. Etc. are preferable.

Among them, linear or branched alkyl groups having 2 or more and 15 or less carbon atoms and alkenyl groups having 2 or more and 4 or less carbon atoms are more preferable from the viewpoint that the ratio of cyano groups to the whole molecule is large and the effect of improving battery characteristics is high. , A linear or branched alkyl group having 2 or more and 12 or less carbon atoms is more preferable, and a linear or branched alkyl group having 4 or more and 11 or less carbon atoms is particularly preferable.

Examples of the compound represented by the formula (2-4-1) include propionitrile, butyronitrile, pentanenitrile, hexanenitrile, heptanenitrile, octanenitrile, pelargononitrile, decanenitrile, undecanenitrile, dodecanenitrile, and cyclopentanecarbohydrate. Nitrile, cyclohexanecarbonitrile, acrylonitrile, methacrylonitrile, crotononitrile, 3-methylcrotononitrile, 2-methyl-2-butennitril,
Examples thereof include 2-pentenenitrile, 2-methyl-2-pentenenitrile, 3-methyl-2-pentenenitrile and 2-hexenenitrile.

Of these, pentanenitrile, octanenitrile, decanenitrile, dodecanenitrile and crotononitrile are preferable, and pentanenitrile, decanenitrile, dodecanenitrile and crotononitrile are more preferable, from the viewpoints of compound stability, battery characteristics and manufacturing aspects.
Pentanenitrile, decanenitrile and crotononitrile are preferred.

As the compound represented by the formula (2-4-1), one kind may be used alone, or two or more kinds may be used together in any combination and ratio. The amount of the compound represented by the formula (2-4-1) (total amount in the case of two or more kinds) can be 0.001% by mass or more in 100% by mass of the non-aqueous electrolyte solution, and is preferable. 0.01% by mass or more, more preferably 0.1% by mass or more, and 10
It can be mass% or less, preferably 5 mass% or less, more preferably 3 mass% or less,
It is more preferably 2% by mass or less, particularly preferably 1% by mass or less, and most preferably 0.5% by mass or less. Within the above range, it is easy to control output characteristics, load characteristics, low temperature characteristics, cycle characteristics, high temperature storage characteristics, and the like.

1-2-3-2. Compound represented by formula (2-4-2) NC-A ² -CN (2-4-2)
(In the formula, A ² has 1 or more carbon atoms and 10 or less carbon atoms composed of one or more atoms selected from the group consisting of hydrogen atom, carbon atom, nitrogen atom, oxygen atom, sulfur atom, phosphorus atom and halogen atom. It is an organic group.)

Organic groups having 1 or more and 10 or less carbon atoms composed of one or more atoms selected from the group consisting of hydrogen atom, carbon atom, nitrogen atom, oxygen atom, sulfur atom, phosphorus atom and halogen atom are carbon atom and In addition to the organic group composed of hydrogen atom, the organic group which may contain a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, or a halogen atom is included. In an organic group which may contain a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom or a halogen atom, a part of carbon atoms in the skeleton of a group composed of a carbon atom and a hydrogen atom is replaced with these atoms. Includes organic groups that are or organic groups that have substituents composed of these atoms.

The molecular weight of the compound represented by the formula (2-4-2) is not particularly limited. The molecular weight is preferably 65 or more, more preferably 80 or more, still more preferably 90 or more, preferably 270 or less, more preferably 160 or less, still more preferably 13.
It is 5 or less. Within this range, it is easy to secure the solubility of the compound represented by the formula (2-4-2) in the non-aqueous electrolyte solution, and the effect of the present invention is likely to be exhibited. The method for producing the compound represented by the formula (2-4-2) is not particularly limited, and a known method can be arbitrarily selected for production.

A ² in the compound represented by the formula (2-4-2) includes an alkylene group or a derivative thereof, an alkenylene group or a derivative thereof, a cycloalkylene group or a derivative thereof, an alkynylene group or a derivative thereof, a cycloalkenylene group or a derivative thereof. , Aliren group or its derivative, carbonyl group or its derivative, sulfonyl group or its derivative, sulfinyl group or its derivative, phosphonyl group or its derivative, phosphinyl group or its derivative, amide group or its derivative, imide group or its derivative, ether Examples thereof include a group or a derivative thereof, a thioether group or a derivative thereof, a boric acid group or a derivative thereof, a bolan group or a derivative thereof, and the like.

Among them, from the viewpoint of improving battery characteristics, an alkylene group or a derivative thereof, an alkenylene group or a derivative thereof, a cycloalkylene group or a derivative thereof, an alkynylene group or a derivative thereof, an arylene group or a derivative thereof are preferable. Further, it is more preferable that A ² is an alkylene group having 2 or more and 5 or less carbon atoms which may have a substituent.

Examples of the compound represented by the formula (2-4-2) include malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimeronitrile, suberonitrile, azelanitrile, and the like.
Sevaconitrile, undecanedinitrile, dodecanedinitrile, methylmalononitrile,
Ethylmalononitrile, isopropylmalononitrile, tert-butylmalononitrile, methylsuccinonitrile, 2,2-dimethylsuccinonitrile, 2,3-dimethylsuccinonitrile, 2,3,3-trimethylsuccinonitrile, 2, 2,3,3-Tetramethylsuccinonitrile, 2,3-diethyl-2,3-dimethylsuccinonitrile, 2,2-
Diethyl-3,3-dimethylsuccinonitrile, bicyclohexyl-1,1-dicarbonitrile, bicyclohexyl-2,2-dicarbonitrile, bicyclohexyl-3,3-dicarbonitrile, 2,5-dimethyl- 2,5-hexanedicarbonitrile, 2,3-diisobutyl-2,3-dimethylsuccinonitrile, 2,2-diisobutyl-3,3-dimethylsuccinonitrile, 2-methylglutaronitrile, 2,3- Dimethylglutaronitrile, 2,4-dimethylglutaronitrile, 2,2,3,3-tetramethylglutaronitrile, 2,2,4,4-tetramethylglutaronitrile, 2,2,3,4- Tetramethylglutaronitrile, 2,3,3,4-tetramethylglutaronitrile, maleonitrile, fumaronitrile, 1,4-dicyanopentane, 2,6-dicyanoheptane, 2,7-dicyanooctane, 2,8-dicyanononane , 1,6-dicyanodecane, 1,2-didianobenzene, 1,3-dicyanobenzene, 1,4-dicyanobenzene, 3,3'-(ethylenedioxy) dipropionitrile, 3,3'-( Ethylenedithio) dipropionitrile and 3,
Examples thereof include 9-bis (2-cyanoethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane.

Of these, malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimeronitrile, suberonitrile, azelanitrile, sebaconitrile, undecanenitrile, dodecanenitrile and 3,9-bis (2-cyanoethyl) -2,4,8,1
0-Tetraoxaspiro [5,5] undecane and fumaronitrile are preferable from the viewpoint of improving high temperature storage durability characteristics. In addition, succinonitrile, glutaronitrile, adiponitrile, pimeronitrile, suberonitrile, glutaronitrile and 3,9-bis (2-cyanoethyl)
-2,4,8,10-Tetraoxaspiro [5,5] undecane is more preferable because it has a particularly excellent effect of improving high temperature storage durability characteristics and is less deteriorated by a side reaction at the electrode. Normal,
The smaller the molecular weight of the dinitrile compound, the larger the proportion of the cyano group in one molecule, and the higher the viscosity of the molecule, while the larger the molecular weight, the higher the boiling point of the compound. Therefore, succinosuccinonitrile, glutaronitrile, adiponitrile, and pimeronitrile are more preferable from the viewpoint of improving work efficiency.

As the compound represented by the formula (2-4-2), one type may be used alone, or two or more types may be used in combination in any combination and ratio. The amount of the compound represented by the formula (2-4-2) (total amount in the case of two or more kinds) can be 0.001% by mass or more in 100% by mass of the electrolytic solution, and is preferably 0. 01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0
.. It can be contained in an amount of 3% by mass or more, 10% by mass or less, preferably 5% by mass or less, and more preferably 3% by mass or less. When the above range is satisfied, the effects of output characteristics, load characteristics, low temperature characteristics, cycle characteristics, high temperature storage characteristics and the like are further improved.

1-2-3-3. The compound represented by the formula (2-4-3)

( ^In the formula, A3 has 1 or more and 12 or less carbon atoms composed of one or more atoms selected from the group consisting of hydrogen atom, carbon atom, nitrogen atom, oxygen atom, sulfur atom, phosphorus atom and halogen atom. It is an organic group, and n ⁴³ is an integer of 0 or more and 5 or less.)

An organic group having 1 or more and 12 or less carbon atoms composed of one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, and a halogen atom is defined as an organic group.
In addition to an organic group composed of a carbon atom and a hydrogen atom, it includes an organic group which may contain a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom or a halogen atom. In an organic group which may contain a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom or a halogen atom, a part of carbon atoms in the skeleton of a group composed of a carbon atom and a hydrogen atom is replaced with these atoms. Includes organic groups that are or organic groups that have substituents composed of these atoms.

The n ⁴³ is an integer of 0 or more and 5 or less, preferably 0 or more and 3 or less, more preferably 0 or more and 1 or less, and particularly preferably 0.

Further, the above A3 is preferably an organic group having ¹ or more and 12 or less carbon atoms composed of one or more kinds of atoms selected from the group consisting of a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom. It is more preferable that it is an organic group having 1 or more and 12 or less carbon atoms composed of one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom and an oxygen atom, and may have a substituent. It is more preferably an aliphatic hydrocarbon group having a number of 1 or more and 12 or less.

Here, the substituent represents a group composed of one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom and a halogen atom.

The substituents include a halogen atom; an unsubstituted or halogen-substituted alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group; an isocyanato group; an alkoxycarbonyloxy group; an acyl group; a carboxyl group; an alkoxycarbonyl group; an acyloxy group. Alkylsulfonyl group; Alkoxysulfonyl group; Dialkoxyphosphantriyl group; Dialkoxyphosphoryl group, Dialkoxyphosphoryloxy group and the like, preferably a halogen atom; an alkoxy group or an unsubstituted or halogen-substituted alkyl group. , More preferably a halogen atom or an unsubstituted or halogen-substituted alkyl group, and even more preferably an unsubstituted alkyl group.

The aliphatic hydrocarbon group is not particularly limited, but may have 1 or more carbon atoms, preferably 2 or more, more preferably 3 or more, and 12 or less, preferably 8 or less. Below, it is more preferably 6 or less.

As the aliphatic hydrocarbon group, an ^alkanthryl group, an alkanthtetrayl group, an alkanepentyl group, an alkanthtetrayl group, an alkanthryyl group, an alkentetetrayl group, an alkentepentyl group, and an alkene, depending on n43. Examples thereof include a tetrayl group, an alkyne triyl group, an alkyne tetrayl group, an alkyne pentayl group and an alkyne tetrayl group.

Of these, saturated hydrocarbon groups such as an alkanetriyl group, an alkanetetrayl group, an alkanepentyl group and an alkanetetrayl group are more preferable, and an alkanetriyl group is even more preferable.

Further, the compound represented by the above formula (2-4-3) is more preferably a compound represented by the formula (2-4-3').

^{( In} the formula, A4 and A5 ^are synonymous with A3 above.)
Further, it is more preferable that A ⁴ and A ⁵ are hydrocarbon groups having 1 or more and 5 or less carbon atoms which may have a substituent.

Hydrocarbon groups include methylene group, ethylene group, trimethylene group, tetraethylene group,
Pentamethylene group, vinylene group, 1-propenylene group, 2-propenylene group, 1-butenylene group, 2-butenylene group, 1-pentenylene group, 2-pentenylene group, ethynylene group,
Examples thereof include a propynylene group, a 1-butynylene group, a 2-butynylene group, a 1-pentynylene group and a 2-pentynylene group.

Of these, a methylene group, an ethylene group, a trimethylene group, a tetraethylene group and a pentamethylene group are preferable, and a methylene group, an ethylene group and a trimethylene group are more preferable.

It is preferable that A ⁴ and A ⁵ are not the same as each other but are different from each other.

The molecular weight of the compound represented by the formula (2-4-3) is not particularly limited. The molecular weight is preferably 90 or more, more preferably 120 or more, still more preferably 150 or more.
Further, it is preferably 450 or less, more preferably 300 or less, and further preferably 250 or less. Within this range, it is easy to secure the solubility of the compound represented by the formula (2-4-3) in the non-aqueous electrolyte solution, and the effect of the present invention is likely to be exhibited. The method for producing the compound represented by the formula (2-4-3) is not particularly limited, and a known method can be arbitrarily selected for production.

Examples of the compound represented by the formula (2-4-3) include the following compounds.

が保存特性向上の点から好ましい。 Of these

Is preferable from the viewpoint of improving storage characteristics.

The amount of the compound represented by the formula (2-4-3) (total amount in the case of two or more kinds) is the electrolytic solution 100.
It can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.3% by mass or more, and 10% by mass. It can be contained in a concentration of 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less. Within this range, it is easy to control output characteristics, load characteristics, low temperature characteristics, cycle characteristics, high temperature storage characteristics, and the like.

As the organic compound having a cyano group other than the formula (1), one kind may be used alone, or two or more kinds may be used together in any combination and ratio.

The mass ratio of the compound represented by the above formula (1) to the organic compound having a cyano group other than the formula (1) is the compound represented by the formula (1): the organic compound having a cyano group other than the formula (1). But 1: 1
It can be 00 or more, preferably 10: 100 or more, more preferably 20:100.
The above can be more preferably 25: 100 or more, 10000: 100 or less, preferably 500: 100 or less, more preferably 300: 100 or less, still more preferably 100: 100 or less, and particularly preferably 75: 100 or less, most preferably 50:10
It is 0 or less. Within this range, battery characteristics, especially durability characteristics, can be significantly improved. This principle is not clear, but it is thought that by mixing at this ratio, the side reaction of the additive on the electrode can be minimized.

1-2-4. Organic compound having an isocyanate group The non-aqueous electrolytic solution of the present invention can contain an organic compound having an isocyanate group.
The organic compound having an isocyanate group is not particularly limited as long as it is an organic compound having at least one isocyanate group in the molecule, but the number of isocyanate groups is limited to one molecule.
It is preferably 1 or more and 4 or less, more preferably 2 or more and 3 or less, and further preferably 2.

By using the compound represented by the formula (1) in combination with the compound having an isocyanate group in the non-aqueous electrolyte solution of the present invention, the durability characteristics of the battery using this electrolytic solution can be improved. The organic compound having an isocyanate group is preferably a linear or branched alkylene group, a cycloalkylene group, a structure in which a cycloalkylene group and an alkylene group are linked, an aromatic hydrocarbon group, an aromatic hydrocarbon group and an alkylene group. , Ether structure (-O-), ether structure (-O-) and alkylene group linked structure, carbonyl group (-C (= O)-), carbonyl group and alkylene group linked structure , A sulfonyl group (-S (= O)-), a compound in which an isocyanate group is bonded to a compound having a structure in which a sulfonyl group and an alkylene group are linked, or a structure in which these are halogenated, and the like, more preferably directly. A compound in which an isocyanate group is bonded to a chain or branched alkylene group, a cycloalkylene group, a structure in which a cycloalkylene group and an alkylene group are linked, an aromatic hydrocarbon group or a structure in which an aromatic hydrocarbon group and an alkylene group are linked. A compound in which an isocyanate group is bonded to a structure in which a cycloalkylene group and an alkylene group are linked is more preferable.
The molecular weight of the organic compound having an isocyanate group is not particularly limited. The molecular weight is preferably 80 or more, more preferably 115 or more, still more preferably 170 or more, and more preferably 300 or less, more preferably 230 or less. Within this range, it is easy to secure the solubility of the organic compound having an isocyanate group in the non-aqueous electrolyte solution, and the effect of the present invention is likely to be exhibited. The method for producing the organic compound having an isocyanate group is not particularly limited, and a known method can be arbitrarily selected for production. Further, a commercially available product may be used.

Examples of the organic compound having an isocyanate group include methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, tertiary butyl isocyanate, pentyl isocyanate hexyl isocyanate, cyclohexyl isocyanate, vinyl isocyanate, allyl isocyanate, ethynyl isocyanate, propargyl isocyanate and phenyl. Organic compounds having one isocyanate group such as isocyanate and fluorophenyl isocyanate;
Monomethylene diisocyanate, dimethylene diisocyanis, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisosia Natopropane, 1,4-diisosianato-2
-Butene, 1,4-diisosyanato-2-fluorobutane, 1,4-diisosyanato-2
, 3-Difluorobutane, 1,5-diisocyanato-2-pentene, 1,5-diisocyanato-2-methylpentane, 1,6-diisocyanato-2-hexene, 1,6-diisocyanato-3-hexene, 1,6 -Diisocyanato-3-fluorohexane, 1,6-diisocyanato-3,4-difluorohexane, toluene diisocyanate, xylene diisocyanate, tolylene diisocyanate, 1,2-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) Natomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, dicyclohexylmethane-1,1 '-Diisocyanate, dicyclohexylmethane-2,2'-diisocyanate, dicyclohexylmethane-3,3'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, bicyclo [2.2.1] heptane-2,5-diylbis ( Methyl isocyanate), bicyclo [2.2.1] heptane-2,6-diylbis (methylisocyanate), isophorone diisocyanate, carbonyldiisocyanate, 1,
4-Diisocyanatobutane-1,4-dione, 1,5-Diisocyanatopentane-1,5
-Organic compounds having two isocyanate groups such as dione, 2,2,4-trimethylhexamethylenediisocyanate, 2,4,4-trimethylhexamethylenediisocyanate;
And so on.

Of these, monomethylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 1, 3-Bis (isosyanatomethyl) cyclohexane, dicyclohexamethylene-4,4'-diisocyanis, bicyclo [2.2.1]
Heptane-2,5-diylbis (methylisocyanate), bicyclo [2.2.1] heptane-2,6-diylbis (methylisocyanate), isophorone diisosocyanate, 2,
Organic compounds having two isocyanate groups, such as 2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, are preferable from the viewpoint of improving storage characteristics, and hexamethylene diisocyanate, 1,3-. Bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, bicyclo [
2.2.1] Heptane-2,5-diylbis (methylisocyanate), bicyclo [2.
2.1] Heptane-2,6-diylbis (methylisocyanate), isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate are more preferable, 1 , 3-Bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, bicyclo [2.2.1] heptane-2,5-diylbis (methylisocyanate), bicyclo [2
.. 2.1] Heptane-2,6-diylbis (methylisocyanate) is more preferable.

The organic compound having an isocyanate group may be a trimer compound derived from a compound having at least two isocyanate groups in the molecule, or an aliphatic polyisocyanate to which a polyhydric alcohol is added. Examples thereof include biuret, isocyanurate, adduct and bifunctional type modified polyisocyanates represented by the basic structures of the formulas (2-5-1) to (2-5-4).

(In the formula, R ⁵¹ to R ⁵⁴ and R ^54'are independently divalent hydrocarbon groups (eg, tetramethylene group, hexamethylene group), and R ^53'is independently trivalent. It is a hydrocarbon group of.)

Organic compounds having at least two isocyanate groups in the molecule also include so-called blocked isocyanates that are blocked with a blocking agent to improve storage stability. Examples of the blocking agent include alcohols, phenols, organic amines, oximes, and lactams, and specific examples thereof include n-butanol, phenol, tributylamine, diethylethanolamine, methylethylketoxime, and ε-caprolactam. And so on.

For the purpose of accelerating the reaction based on the organic compound having an isocyanate group and obtaining a higher effect, a metal catalyst such as dibutyltin dilaurate or 1,8-diazabicyclo [5.4]
.. 0] It is also preferable to use an amine-based catalyst such as Undecene-7 in combination.

As the organic compound having an isocyanate group, one kind may be used alone, or two or more kinds may be used together in any combination and ratio.

The amount of the organic compound having an isocyanate group (in the case of two or more kinds, the total amount) is the electrolytic solution 10.
It can be 0.001% by mass or more, preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and 10% by mass or less in 0% by mass. It is preferably 5% by mass or less, more preferably 3% by mass or less. If it is in this range, the output characteristics,
It is easy to control load characteristics, low temperature characteristics, cycle characteristics, high temperature storage characteristics, etc.

The mass ratio of the compound represented by the above formula (1) to the organic compound having an isocyanate group can be 1: 100 or more for the compound represented by the formula (1): the organic compound having an isocyanate group. It is preferably 10: 100 or more, more preferably 20: 100 or more, still more preferably 25: 100 or more, and it can be 10000: 100 or less, preferably 500: 100 or less, more preferably 300: 100 or less, More preferably 100:
It is 100 or less, particularly preferably 75: 100 or less, and most preferably 50: 100 or less. Within this range, battery characteristics, especially durability characteristics, can be significantly improved. This principle is not clear, but it is thought that by mixing at this ratio, the side reaction of the additive on the electrode can be minimized.

1-2-5. Silicon-Containing Compound The non-aqueous electrolytic solution of the present invention may contain a silicon-containing compound. The silicon-containing compound is not particularly limited as long as it is a compound having at least one silicon atom in the molecule. In the non-aqueous electrolytic solution of the present invention, the durability characteristics can be improved by using the compound represented by the formula (1) and the silicon-containing compound in combination.

As the silicon-containing compound, a compound represented by the formula (2-6) is preferable.

(In the formula, R ⁶¹ , R ⁶² and R ⁶³ independently have a hydrogen atom, a halogen atom or one carbon atom.
It is a hydrocarbon group of 0 or less,
X ⁶¹ is an organic group containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom. )

As for the hydrocarbon group, examples and preferred examples of the hydrocarbon group in the formula (1) are applied. R ⁶¹ , R ⁶² and R ⁶³ are preferably hydrogen atom, fluorine atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, i-butyl group, tert. -A butyl group, a phenyl group, and more preferably a methyl group.

X ⁶¹ is an organic group containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom, and is preferably an organic group containing at least an oxygen atom or a silicon atom. Here, the organic group is a group composed of one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, a phosphorus atom and a halogen atom. show. Examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, a CN group, an isocyanato group, a fluoro group, an alkylsulfonic acid group and a trialkylsilyl group. A part of the monovalent organic group may be substituted with a fluorine atom. Further, the number of carbon atoms of the organic group can be 1 or more, preferably 3 or more, more preferably 5 or more, and can be 15 or less, preferably 12 or less, more preferably 8 or less. Is.

Of these, an alkylsulfonic acid group, a trialkylsilyl group, a boric acid group, a phosphoric acid group and a phosphorous acid group are preferable.

Examples of the silicon-containing compound include the following compounds.
Tris borate (trimethylsilyl), Tris borate (trimethoxysilyl), Tris borate (triethylsilyl), Tris borate (triethoxysilyl), Tris borate (dimethylvinylsilyl) and Tris borate (diethylvinylsilyl) Boric acid compounds such as: tris phosphate (trimethylsilyl), tris phosphate (triethylsilyl), tris phosphate (triethylsilyl)
Tripropylsilyl), Tris (triphenylsilyl) phosphate, Tris (trimethoxysilyl) phosphate, Tris (triethoxysilyl) phosphate, Tris (triphenoxysilyl) phosphate, Tris (dimethylvinylsilyl) phosphate And phosphoric acid compounds such as tris phosphate (diethylvinylsilyl);
Tris phosphite (trimethylsilyl), Tris lysate (triethylsilyl), Tris phosphite (tripropylsilyl), Tris phosphite (triphenylsilyl), Tris phosphite (trimethoxysilyl), phosphite Subphosphate compounds such as tris (triethoxysilyl), tris phosphite (triphenoxysilyl), tris phosphite (dimethylvinylsilyl) and tris phosphite (diethylvinylsilyl);
Sulfonic acid compounds such as trimethylsilyl methanesulfonic acid and trimethylsilyl tetrafluoromethanesulfonic acid;
Hexamethyldisilane, hexaethyldisilane, 1,1,2,2-tetramethyldisilane, 1,1,2,2-tetraethyldisilane, 1,2-diphenyltetramethyldisilane and 1,1,2,2-tetraphenyl Disilane compounds such as disilane;
And so on.

Of these, tris borate (trimethylsilyl), tris phosphate (trimethylsilyl), tris phosphite (trimethylsilyl), trimethylsilyl methanesulfonate, trimethylsilyl tetrafluoromethanesulfonate, hexamethyldisilane, hexaethyldisilane, 1,2- Diphenyltetramethyldisilane and 1,1,2,2-tetraphenyldisilane are preferred, with tris borate (trimethylsilyl), tris phosphate (trimethylsilyl), tris phosphite (trimethylsilyl) and hexamethyldisilane being more preferred.

In addition, these silicon-containing compounds may be used individually by 1 type, and 2 or more types may be used together by arbitrary combinations and ratios.

The silicon-containing compound (total amount in the case of two or more types) is 0.001 in 100% by mass of the electrolytic solution.
It can be mass% or more, preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and can be 10% by mass or less, preferably 5% by mass or less, more. It is preferably 3% by mass or less. Within this range, it is easy to control output characteristics, load characteristics, low temperature characteristics, cycle characteristics, high temperature storage characteristics, and the like.

The mass ratio of the compound represented by the above formula (1) to the silicon-containing compound (total amount in the case of two or more kinds) is 1: 100 or more for the compound represented by the formula (1): the silicon-containing compound. It can be preferably 10: 100 or more, more preferably 20: 100 or more, still more preferably 2
It can be 5: 100 or more and 10000: 100 or less, preferably 500:
It is 100 or less, more preferably 300: 100 or less, still more preferably 100: 100 or less, particularly preferably 75: 100 or less, and most preferably 50: 100 or less. Within this range, battery characteristics, especially durability characteristics, can be significantly improved. This principle is not clear, but it is thought that by mixing at this ratio, the side reaction of the additive on the electrode can be minimized.

1-2-6. Aromatic compound The non-aqueous electrolytic solution of the present invention may contain an aromatic compound. As an aromatic compound,
The organic compound has at least one aromatic ring in the molecule, but is not particularly limited.
It is preferably an aromatic compound represented by the formula (2-7-1) and the formula (2-7-2).

1-2-6-1. Aromatic compound represented by the formula (2-7-1)

(In the formula, the substituent X ⁷¹ represents an organic group which may have a halogen atom, a halogen atom or a hetero atom. The organic group which may have a hetero atom has 1 or more carbon atoms and 12 or less carbon atoms. Linear or branched or cyclic saturated hydrocarbon groups, groups having a carboxylic acid ester structure, groups having a carbonate structure (excluding cyclic carbonates having a carbon-carbon unsaturated bond and fluorine-containing cyclic carbonates), phosphorus. A group having an atom, a group having a sulfur atom, and a group having a silicon atom are shown. Further, each substituent further includes a halogen atom, a hydrocarbon group, an aromatic group, a halogen-containing hydrocarbon group, a halogen-containing aromatic group and the like. The number n ⁷¹ of the substituent X ⁷¹ may be 1 or more and 6 or less, and when a plurality of substituents are present, the respective substituents may be the same or different, and form a ring. May be.)

Among them, a linear or branched chain or a cyclic saturated hydrocarbon group having 1 to 12 carbon atoms, a group having a carboxylic acid ester structure, and a group having a carbonate structure are preferable from the viewpoint of battery characteristics. More preferably, it is a linear or branched or cyclic saturated hydrocarbon group having 3 or more and 12 or less carbon atoms, and a group having a carboxylic acid ester structure.

The number n ⁷¹ of the substituent X ⁷¹ is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, still more preferably 1 or more and 2 or less, and particularly preferably 1.
X ⁷¹ represents an organic group which may have a halogen atom, a halogen atom or a hetero atom.
Examples of the halogen atom include chlorine and fluorine, and fluorine is preferable.

Examples of the organic group having no heteroatom include linear, branched and cyclic saturated hydrocarbon groups having 3 to 12 carbon atoms, and the linear and branched organic groups include those having a ring structure. Will be. Specific examples of the linear, branched, and cyclic saturated hydrocarbon groups having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, and pentyl. Examples include a group, a tert-pentyl group, a cyclopentyl group, a cyclohexyl group, a butylcyclohexyl group, and the like. The number of carbon atoms is preferably 3 or more and 12 or less, more preferably 3 or more and 10 or less, still more preferably 3 or more and 8 or less, still more preferably 3 or more and 6 or less, and most preferably 3 or more and 5 or less.

Examples of the hetero atom constituting the organic group having a hetero atom include an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom and the like. Examples of those having an oxygen atom include a group having a carboxylic acid ester structure and a group having a carbonate structure. Examples of those having a sulfur atom include a group having a sulfonic acid ester structure. Examples of those having a phosphorus atom include a group having a phosphoric acid ester structure, a group having a phosphonic acid ester structure, and the like. Examples of those having a silicon atom include groups having a silicon-carbon structure.

Examples of the aromatic compound represented by the formula (2-7-1) include the following.
Assuming that X ⁷¹ is a halogen atom or an organic group which may have a halogen atom,
Examples thereof include chlorobenzene, fluorobenzene, difluorobenzene, trifluorobenzene, tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene and benzotrifluoride, and fluorobenzene and hexafluorobenzene are preferable. More preferably, it is fluorobenzene.

Assuming that X ⁷¹ is a hydrocarbon group having 1 or more and 12 or less carbon atoms
2,2-Diphenylpropane, 1,4-diphenylcyclohexane, cyclohexylbenzene, cyclohexylbenzene, cis-1-propyl-4-phenylcyclohexane, trans-1-propyl-4-phenylcyclohexane, cis-1-butyl-4- Examples thereof include phenylcyclohexane, trans-1-butyl-4-phenylcyclohexane, propylbenzene, butylbenzene, tert-butylbenzene and tert-amylbenzene, preferably 2,2-diphenylpropane, 1,4-diphenylcyclohexane and the like. Cyclopentylbenzene, cyclohexylbenzene, cis-1-propyl-4-phenylcyclohexane, trans-1-propyl-4-phenylcyclohexane, cis-1-butyl-4-phenylcyclohexane, trans-1-butyl-4-phenylcyclohexane,
Toluene, ethylbenzene, propylbenzene, butylbenzene, tert-butylbenzene, tert-amylbenzene, more preferably 2,2-diphenylpropane,
Cyclopentylbenzene, cyclohexylbenzene, 1,1-diphenylcyclohexane, tert-butylbenzene, tert-amylbenzene, and more preferably cyclohexylbenzene, tert-butylbenzene, tert-amylbenzene and the like.

Assuming that X ⁷¹ is a group having a carboxylic acid ester structure,
Phenyl acetate, benzyl acetate, 2-phenylethyl acetate, 3-phenylpropyl acetate, 4-phenylbutyl acetate, phenyl propionate, benzyl propionate, 2 propionic acid
-Phenylethyl, 3-phenylpropyl propionate, 4-phenylbutyl propionate, phenyl butyrate, benzyl butyrate, 2-phenylethyl butyrate, 3-phenylpropyl butyrate, 4-phenylbutyl butyrate, methyl phenylacetate, ethyl phenylacetate, Phenylacetic acid propyl, phenylacetic acid butyl, phenylacetic acid phenyl, phenylacetic acid benzyl, phenylacetic acid 2-phenylethyl, phenylacetic acid 3-phenylpropyl, phenylacetic acid 4-phenylbutyl, 2,2-dimethyl-phenylacetic acid methyl, 2,2 -Ethyl dimethyl-phenylacetic acid, propyl 2,2-dimethyl-phenylacetic acid, butyl 2,2-dimethyl-phenylacetic acid, phenyl 2,2-dimethyl-phenylacetic acid, benzyl 2,2-dimethyl-phenylacetic acid, 2,2 -Dimethyl-Phenylacetic Acid 2-Phenylethyl, 2,2-Dimethyl-Phenylacetic Acid 3-Phenylpropyl, 2,2-Dimethyl-Phenylacetic Acid 4-Phenylbutyl, 3-
Methyl phenylpropionate, ethyl 3-phenylpropionate, propyl 3-phenylpropionate, butyl 3-phenylpropionate, phenyl 3-phenylpropionate,
Benzyl 3-phenylpropionate, 2-phenylethyl 3-phenylpropionate, 3
-3-Phenylpropyl phenylpropionate, 4-phenylbutyl 3-phenylpropionate, methyl 4-phenylbutyrate, ethyl 4-phenylbutyrate, propyl 4-phenylbutyrate, butyl 4-phenylbutyrate, phenyl 4-phenylbutyrate, 4 -Phenylbutyrate benzyl, 4
-2-Phenylethyl phenylbutyrate, 3-Phenylpropyl 4-phenylbutyrate, 4-Phenylbutyl 4-phenylbutyrate, Methyl 5-phenylpentanoate, Ethyl 5-phenylvalerate,
Propyl 5-phenyl valerate, butyl 5-phenyl valerate, phenyl 5-phenyl valerate, benzyl 5-phenyl valerate, 2-phenylethyl 5-phenyl valerate, 3-phenylpropyl 5-phenyl valerate, 5- 4-Phenylbutyl phenylvalerate, methyl 1-phenylcyclopentanecarboxylate, ethyl 1-phenylcyclopentanecarboxylate, propyl 1-phenylcyclopentanecarboxylate, butyl 1-phenylcyclopentanecarboxylate, 1-phenylcyclopentanecarboxylic acid Phenyl Acid, 1-Phenyl Cyclopentane Carboxylic Acid benzyl, 1-Phenyl Cyclopentane Carboxylic Acid 2-Phenyl Ethyl, 1-Phenyl Cyclopentane Carboxylic Acid 3-Phenylpropyl, 1-Phenyl Cyclopentane Carboxylic Acid 4-Phenylbutyl, 2, Examples thereof include 2-bis (4-acetoxyphenyl) propane, preferably 2-phenylethyl acetate, 3-phenylpropyl acetate, 4-phenylbutyl acetate, 2-phenylethyl propionate, 3-phenylpropyl propionate, and the like. 4-Phenylbutyl propionate, 2-phenylethyl butyrate, 3-phenylpropyl butyrate,
4-Phenylbutyl butyrate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, 2-phenylethyl phenylacetate, 3-phenylpropyl phenylacetic acid, 4-phenylbutyl phenylacetate, 2,2-dimethyl-phenyl Methyl acetate, 2,2-dimethyl-phenylacetate, propyl 2,2-dimethyl-phenylacetate,
2,2-dimethyl-Phenylacetic acid butyl, 2,2-dimethyl-phenylacetic acid 2-phenylethyl, 2,2-dimethyl-phenylacetic acid 3-phenylpropyl, 2,2-dimethyl-phenylacetic acid 4-phenylbutyl, 3 -Methyl phenylpropionate, ethyl 3-phenylpropionate, propyl 3-phenylpropionate, butyl 3-phenylpropionate,
2-Phenylethyl 3-phenylpropionic acid, 3-phenylpropyl 3-phenylpropionic acid, 4-phenylbutyl 3-phenylpropionic acid, methyl 4-phenylbutyrate, 4
-Ethyl phenylbutyrate, propyl 4-phenylbutyrate, butyl 4-phenylbutyrate, 2-phenylethyl 4-phenylbutyrate, 3-phenylpropyl 4-phenylbutyrate, 4-phenylbutyl 4-phenylbutyrate, methyl 5-phenylvalerate , 5-Phenyl valerate ethyl, 5-phenyl valerate propyl, 5-phenyl valerate butyl, 5-phenyl valerate 2-phenylethyl, 5-phenyl valerate 3-phenylpropyl, 5-phenyl valerate 4-phenyl Butyl, 1-phenylcyclopentanecarboxylate methyl, 1-phenylcyclopentanecarboxylate ethyl, 1-phenylcyclopentanecarboxylate propyl, 1-phenylcyclopentanecarboxylate butyl, 1-phenylcyclopentanecarboxylate 2-phenylethyl, 1
-Phenylcyclopentanecarboxylic acid 3-phenylpropyl, more preferably 2-phenylethyl acetate, 3-phenylpropyl acetate, methyl phenylacetate, ethyl phenylacetate, 2-phenylethyl phenylacetate, 3-phenylpropyl phenylacetate. , 2, 2
-Methyl dimethyl-phenylacetate, ethyl 2,2-dimethyl-phenylacetate, 2-phenylethyl 2,2-dimethyl-phenylacetic acid, 3-phenylpropyl2,2-dimethyl-phenylacetic acid, methyl 3-phenylpropionate, Ethyl 3-phenylpropionate, 3-
2-Phenylethyl Phenylpropionate, 3-Phenylpropyl 3-Phenylpropionate, Methyl 5-Phenylvalerate, Ethyl 5-Phenylvalerate, 2-Phenylvalerate
Phenylethyl, 5-Phenylvaleric acid 3-Phenylpropyl, 1-Phenylcyclopentanecarboxylate methyl, 1-Phenylcyclopentanecarboxylic acid ethyl, 1-Phenylcyclopentanecarboxylic acid 2-Phenylethyl, 1-Phenylcyclopentanecarboxylic acid 3-
It is phenylpropyl, more preferably 2-phenylethyl acetate, 3-phenylpropyl acetate, methyl phenylacetate, ethyl phenylacetate, 2-phenylethyl phenylacetic acid, 3-phenylpropyl phenylacetic acid, 2,2-dimethyl-phenyl. Methyl acetate, 2,2
-Ethyl dimethyl-phenylacetate, 2-phenylethyl 2,2-dimethyl-phenylacetate, 3-phenylpropyl 2,2-dimethyl-phenylacetate, methyl 3-phenylpropionate, ethyl 3-phenylpropionate, 3-phenylpropi 2-Phenylethyl onate, 3-Phenylpropyl 3-phenylpropionate, Methyl 5-phenylvalerate, Ethyl 5-phenylvalerate, 2-Phenylethyl 5-phenylvalerate, 3-Phenylvaleric acid
Phenylpropyl, methyl 1-phenylcyclopentanecarboxylate, ethyl 1-phenylcyclopentanecarboxylate, 2-phenylethyl 1-phenylcyclopentanecarboxylate, 3-phenylpropyl-1-phenylcyclopentanecarboxylate.

Assuming that X ⁷¹ is a group having a carbonate structure,
2,2-bis (4-methoxycarbonyloxyphenyl) propane, 1,1-bis (4-)
Methoxycarbonyloxyphenyl) cyclohexane, diphenyl carbonate, methylphenyl carbonate, ethylphenyl carbonate, 2-tert-butylphenylmethyl carbonate, 2-tert-butylphenylethyl carbonate, bis (2-te)
rt-butylphenyl) carbonate, 4-tert-butylphenylmethyl carbonate, 4-tert-butylphenylethyl carbonate, bis (4-tert-butylphenyl) carbonate, benzylmethylcarbonate, benzylethylcarbonate, dibenzylcarbonate and the like. , Preferably 2,2-bis (4-methoxycarbonyloxyphenyl) propane, 1,1-bis (4-methoxycarbonyloxyphenyl) cyclohexane form, diphenyl carbonate, methylphenyl carbonate, more preferably diphenyl carbonate, Methylphenyl carbonate, more preferably methylphenyl carbonate or the like.

Assuming that X ⁷¹ is a group having a sulfonic acid ester structure,
Methylphenylsulfonate, ethylphenylsulfonate, diphenylsulfonate,
Phenylmethylsulfonate, 2-tert-butylphenylmethylsulfonate, 4-
Examples thereof include tert-butylphenylmethylsulfonate, cyclohexylphenylmethylsulfonate, etc., preferably methylphenylsulfonate, diphenylsulfonate, etc.
2-tert-butylphenylmethylsulfonate, 4-tert-butylphenylmethylsulfonate, cyclohexylphenylmethylsulfonate, more preferably methylphenylsulfonate, 2-tert-butylphenylmethylsulfonate, 4-t.
ert-Butylphenylmethylsulfonate, cyclohexylphenylmethylsulfonate.

Assuming that X ⁷¹ is a group having a silicon-carbon structure,
Examples thereof include trimethylphenylsilane, diphenylsilane, and diphenyltetramethyldisilane, and trimethylphenylsilane is preferable.

Assuming that X ⁷¹ is a group having a phosphate ester structure,
Triphenyl phosphate, tris (2-tert-butylphenyl) phosphate, tris (3-tert-butylphenyl) phosphate, tris (4-tert-butylphenyl) phosphate, tris (2-tert-amylphenyl) phosphate, tris ( 3-tert-amylphenyl) phosphate, tris (4-tert-amylphenyl) phosphate, tris (2-cyclohexylphenyl) phosphate, tris (3-tert-amylphenyl) phosphate
Examples thereof include cyclohexylphenyl) phosphate, tris (4-cyclohexylphenyl) phosphate, diethyl (4-methylbenzyl) phosphonate, and the like, preferably triphenyl phosphate, tris (2-tert-butylphenyl) phosphate, tris (
3-tert-butylphenyl) phosphate, tris (4-tert-butylphenyl) phosphate, tris (2-tert-amylphenyl) phosphate, tris (3-tert-butylphenyl) phosphate.
tert-amylphenyl) phosphate, tris (4-tert-amylphenyl) phosphate, tris (2-cyclohexylphenyl) phosphate, tris (3-cyclohexylphenyl) phosphate, tris (4-cyclohexylphenyl) phosphate, more preferred. Are tris (2-tert-butylphenyl) phosphate, tris (4-tert-butylphenyl) phosphate, tris (2-cyclohexylphenyl) phosphate, tris (4-cyclohexylphenyl) phosphate.

Assuming that X ⁷¹ is a group having a phosphonate ester structure,
Dimethylphenylphosphonate, diethylphenylphosphonate, methylphenylphenylphosphonate, ethylphenylphenylphosphonate, diphenylphenylphosphonate, dimethyl- (4-fluorophenyl) -phosphonate, dimethylbenzylphosphonate, diethylbenzylphosphonate, methylphenylbenzylphosphonate, ethylphenylbenzylphosphonate , Diphenylbenzylphosphonate, dimethyl- (4-fluorobenzyl) phosphonate, diethyl- (4-fluorobenzyl) phosphonate and the like, preferably dimethylphenylphosphonate, diethylphenylphosphonate, dimethyl- (4-fluorophenyl) -phosphonate, etc. Dimethylbenzylphosphonate, diethylbenzylphosphonate, dimethyl- (4-fluorobenzyl) phosphonate, diethyl- (4-fluorobenzyl) phosphonate, more preferably dimethylphenylphosphonate, diethylphenylphosphonate, dimethylbenzylphosphonate, diethylbenzylphosphonate, dimethyl -(4-Fluorobenzyl) phosphonate, diethyl- (
4-Fluorobenzyl) phosphonate.

Further, the aromatic compound represented by the formula (2-7-1) also includes a fluorinated product of the above aromatic compound. In particular,
Trifluoromethylbenzene, 2-fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, trifluoromethylbenzene, o-cyclohexylfluorobenzene, p
-Partially fluorinated material having a hydrocarbon group such as cyclohexylfluorobenzene; 2-
Partially fluorinated products having a carboxylic acid ester structure such as fluorophenyl acetate and 4-fluorophenyl acetate; trifluoromethoxybenzene, 2-fluoroanisole, 3-fluoroanisole, 4-fluoroanisole, 2,4-difluoroanisole, 2 , 5-Difluoroanisole, 2,6-difluoroanisole, 3,5-difluoroanisole, 4-trifluoromethoxyanisole and other partially fluorinated substances having an ether structure, preferably trifluoromethylbenzene, 2- Partially fluorinated material having a hydrocarbon group such as fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, o-cyclohexylfluorobenzene, p-cyclohexylfluorobenzene; carboxylic acid such as 2-fluorophenylacetate and 4-fluorophenylacetate. Partially fluorinated material having an acid ester structure; partially fluorinated material having an ether structure such as trifluoromethoxybenzene 2-fluoroanisole, 4-fluoroanisole, 2,4-difluoroanisole, 4-trifluoromethoxyanisole, etc. , More preferably a partially fluorinated product having a hydrocarbon group such as 2-fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, etc .; having a carboxylic acid ester structure such as 2-fluorophenylacetate, 4-fluorophenylacetate, etc. Partial fluoridation of things;
Trifluoromethoxybenzene, 2-fluoroanisole, 4-fluoroanisole, 2
, 4-Difluoroanisole, 4-trifluoromethoxyanisole and the like, which have an ether structure and are partially fluorinated.

1-2-6-2. Aromatic compound represented by the formula (2-7-2)

(In the formula, R ¹¹ to R ¹⁵ are independently hydrogen, halogen or unsubstituted or halogen-substituted hydrocarbon groups having 1 or more and 20 or less carbon atoms, and R ¹⁶ and R ¹⁷ are independently carbon. Number 1
It is a hydrocarbon group of 12 or more, and at least two of R ¹¹ to R ¹⁷ may be combined to form a ring, provided that the formula (2-7-2) has (A) and (2-7-2). B):
(A) At least one of R ¹¹ to R ¹⁵ is a halogen or an unsubstituted or halogen-substituted hydrocarbon group having 1 or more and 20 or less carbon atoms.
(B) The total number of carbon atoms of R ¹¹ to R ¹⁷ satisfies at least one of 3 or more and 20 or less).
It is an aromatic compound represented by. When at least two of R ¹¹ to R ¹⁷ form a ring together, it is preferable that two of R ¹¹ to R ¹⁷ form a ring together.

R ¹⁶ and R ¹⁷ are independently hydrocarbon groups having 1 or more and 12 or less carbon atoms (for example, an alkyl group and an aryl group), and R ¹⁶ and R ¹⁷ are together to form a ring (for example, a hydrocarbon group). It may form a cyclic group). From the viewpoint of initial efficiency and improvement of solubility and storage characteristics, R ^1
6 and R ¹⁷ are preferably hydrocarbon groups having 1 or more and 12 or less carbon atoms, or R ¹⁶ and R ¹
It is a cyclic group which is a hydrocarbon group formed by ⁷ together, more preferably a methyl group, an ethyl group, a propyl group, a butyl group, a tert-butyl group, or R ¹⁶ and R ¹⁷ together. It is a 5- to 8-membered cyclic group which is a hydrocarbon group formed therein, and more preferably a methyl group, an ethyl group, a cyclohexyl group formed by combining R ¹⁶ and R ¹⁷ , a cyclopentyl group, and the like.
Most preferably, it is a methyl group, an ethyl group, and a cyclohexyl group formed by combining R ¹⁶ and R ¹⁷ .

R ¹¹ to R ¹⁵ are independently hydrogen, halogen or unsubstituted or halogen-substituted hydrocarbon groups having 1 or more and 20 or less carbon atoms (for example, an alkyl group, an aryl group, an aralkyl group), and 2 of them. They may together form a ring (eg, a cyclic group that is a hydrocarbon group). From the viewpoint of initial efficiency and improvement of solubility and storage characteristics, hydrogen, fluorine, are preferable.
It is an unsubstituted or halogen-substituted hydrocarbon group having 1 or more and 12 or less carbon atoms, more preferably hydrogen, fluorine, or an unsubstituted or fluorine-substituted hydrocarbon group having 1 or more and 10 or less carbon atoms, and further preferably hydrogen. Fluorine, tert-butyl group, tert-pentyl group, tert
-Hexyl group, tert-heptyl group, methyl group, ethyl group, propyl group, butyl group, trifluoromethyl group, nonafluorotert-butyl group, 1-methyl-1-phenyl-ethyl group, 1-ethyl-1-phenyl -A propyl group, particularly preferably hydrogen, fluorine,
It is a tert-butyl group and a 1-methyl-1-phenyl-ethyl group, and most preferably hydrogen, a tert-butyl group and a 1-methyl-1-phenyl-ethyl group.

Any one of R ¹¹ to R ¹⁵ and R ¹⁶ may be combined to form a ring (for example, a cyclic group which is a hydrocarbon group). Preferably, R ¹¹ and R ¹⁶ are combined to form a ring (eg, a cyclic group that is a hydrocarbon group). In this case, R ¹⁷ is preferably an alkyl group. As compounds in which R ¹⁷ is a methyl group and R ¹¹ and R ¹⁶ form a ring together, 1-phenyl-1,3,3-trimethylindane and 2,3-dihydro1,3-dimethyl-1- (2-Methyl-2-phenylpropyl) -3-phenyl-1H-indane and the like can be mentioned.

Equations (2-7-2) are expressed in (A) and (B):
(A) At least one of R ¹¹ to R ¹⁵ is a halogen or an unsubstituted or halogen-substituted hydrocarbon group having 1 or more and 20 or less carbon atoms.
(B) The total number of carbon atoms of R ¹¹ to R ¹⁷ is 3 or more and 20 or less.
At least one of the conditions is satisfied.

The formula (2-7-2) preferably satisfies (A) from the viewpoint of suppressing oxidation on the positive electrode within the normal battery operating voltage range, and from the viewpoint of solubility in the electrolytic solution (2-7-2). It is preferable that B) is satisfied. Equation (2-7-2) may satisfy both (A) and (B).

Regarding (A), if at least one of R ¹¹ to R ¹⁵ is a halogen or an unsubstituted or halogen-substituted hydrocarbon group having 1 or more and 20 or less carbon atoms, the other is a hydrogen atom to form a ring. You may be doing it. From the viewpoint of solubility in the electrolytic solution, the carbon number of the unsubstituted or halogen-substituted hydrocarbon group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, still more preferably 1 or more and 3 or less, still more preferably. 1 or 2, most preferably 1.

Regarding (B), if the total number of carbon atoms of R ¹¹ to R ¹⁷ is 3 or more and 20 or less, then R ¹¹ to 20
At least two of R ¹⁷ may be combined to form a ring. When at least two of R ¹¹ to R ¹⁷ form a ring together, the carbons forming the ring that do not correspond to R ¹¹ to R ¹⁷ (R) are used to calculate the total number of carbon atoms. For ¹¹ to ^R15 , the carbon constituting the benzene ring to which they are bonded, and for ^R16 and ^R17 , the carbon at the benzyl position) is not counted. The total number of carbon atoms is preferably 3 or more and 14 or less, and more preferably 3 or more and 10 or less in terms of solubility in the electrolytic solution. For example, 1-phenyl-1,3,3-trimethylindane and 2,3-dihydro1,3-dimethyl are compounds in which R ¹⁷ is a methyl group and R ¹¹ and R ¹⁶ form a ring together. Examples thereof include -1- (2-methyl-2-phenylpropyl) -3-phenyl-1H-indane, which satisfy the condition of (B).

Examples of the aromatic compound represented by the formula (2-7-2) include the following.
R ¹⁶ and R ¹⁷ are independently hydrocarbon groups having 1 or more and 20 or less carbon atoms (however,
The total of R ¹⁶ and R ¹⁷ has 3 or more carbon atoms and 20 or less carbon atoms), and compounds in which R ¹¹ to R ¹⁵ are hydrogen (satisfying (B)).

2,2-Diphenylbutane, 3,3-diphenylpentane, 3,3-diphenylhexane, 4,4-diphenylheptane, 5,5-diphenyloctane, 6,6-diphenylnonane, 1,1-diphenyl-1, 1-ditert-butyl-methane.

A compound in which R ¹⁶ and R ¹⁷ form a ring together and R ¹¹ to R ¹⁵ are hydrogen (satisfying (B)).

1,1-diphenylcyclohexane, 1,1-diphenylcyclopentane, 1,1-diphenyl-4-methylcyclohexane.
It may be the following compound (although it may overlap with the above-exemplified compound, it is shown by the structural formula).

A compound (satisfying (A)) in which at least one of R ¹¹ to R ¹⁵ is a halogen or an unsubstituted or halogen-substituted hydrocarbon group having 1 or more and 20 or less carbon atoms.

1,3-bis (1-methyl-1-phenylethyl) -benzene, 1,4-bis (1-methyl-1-phenylethyl) -benzene.
It may be the following compound (although it may overlap with the above-exemplified compound, it is shown by the structural formula).

R ¹⁷ is a hydrocarbon group having 1 or more and 20 or less carbon atoms (for example, an alkyl group having 1 or more and 20 or less carbon atoms, preferably a methyl group), and R ¹¹ and R ¹⁶ together form a ring. Compound (satisfies (B)).
1-Phenyl-1,3,3-trimethylindane.
It may be the following compound (although it may overlap with the above-exemplified compound, it is shown by the structural formula).

Above all, it is preferable from the viewpoint of reducing property on the initial negative electrode.
2,2-Diphenylbutane, 3,3-diphenylpentane, 1,1-diphenyl-1,
1-ditert-butyl-methane, 1,1-diphenylcyclohexane, 1,1-diphenylcyclopentane, 1,1-diphenyl-4-methylcyclohexane, 1,3-bis (
1-Methyl-1-phenylethyl) -benzene, 1,4-bis (1-methyl-1-phenylethyl) -benzene, 1-phenyl-1,3,3-trimethylindane.

The following compounds may also be mentioned as preferred (although they may overlap with the above preferred compounds, they will be represented by structural formulas).

More preferable
2,2-Diphenylbutane, 1,1-diphenylcyclohexane, 1,1-diphenyl-4-methylcyclohexane, 1,3-bis (1-methyl-1-phenylethyl) -benzene, 1,4-bis (1) -Methyl-1-phenylethyl) -benzene, 1-phenyl-1
, 3,3-trimethyl indane.
The following compounds are also mentioned as more preferable (although they may overlap with the above-mentioned more preferable compounds, they are shown by the structural formula).

More preferred are 1,1-diphenylcyclohexane, 1,1-diphenyl-4-methylcyclohexane, 1,3-bis (1-methyl-1-phenylethyl) -benzene, 1,
4-Bis (1-methyl-1-phenylethyl) -benzene, 1-phenyl-1,3,3-
It is a trimethyl indane.
The following compounds are also mentioned as further preferable (although they may overlap with the above-mentioned more preferable compounds, they are shown by the structural formula).

Particularly preferred are 1,1-diphenylcyclohexane and 1,3-bis (1-methyl-1).
-Phenylethyl) -benzene, 1,4-bis (1-methyl-1-phenylethyl) -benzene, 1-phenyl-1,3,3-trimethylindane, which are represented by the following structural formulas.

The most preferable is a 1-phenyl-1,3,3-trimethylindane compound, which is represented by the following structural formula.

The aromatic compound may be used alone or in combination of two or more. Total amount of non-aqueous electrolyte solution (1)
(00% by mass), the amount of the aromatic compound (total amount in the case of two or more kinds) can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05. It is by mass or more, more preferably 0.1% by mass or more, still more preferably 0.4% by mass or more, and also.
It can be 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and particularly preferably 2.5% by mass or less. Within the above range, the effect of the present invention is likely to be exhibited, and an increase in battery resistance can be prevented.

The mass ratio of the compound represented by the above formula (1) to the aromatic compound (total amount in the case of two or more kinds) is 1: 100 or more for the compound represented by the formula (1): aromatic compound. It can be preferably 10: 100 or more, more preferably 20: 100 or more, still more preferably 25:10.
It can be 0 or more and 10000: 100 or less, preferably 500: 100 or less, more preferably 300: 100 or less, still more preferably 100: 100 or less, particularly preferably 75: 100 or less, and most preferably 50. : 100 or less. Within this range, battery characteristics, especially durability characteristics, can be significantly improved. This principle is not clear, but it is thought that by mixing at this ratio, the side reaction of the additive on the electrode can be minimized.

1-2-7. Fluorine-free carboxylic acid ester The non-aqueous electrolyte solution of the present invention may contain a fluorine-free carboxylic acid ester. In the non-aqueous electrolytic solution of the present invention, the durability characteristics can be improved by using the compound represented by the formula (1) in combination with the fluorine-free carboxylic acid ester. The fluorine-free carboxylic acid ester is not particularly limited as long as it is a carboxylic acid ester having no fluorine atom in the molecule, but is preferably a fluorine-free chain carboxylic acid ester, and more preferably a fluorine-free carboxylic acid ester. It is a saturated chain carboxylic acid ester. The total carbon number of the fluorine-free chain carboxylic acid ester is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more.
It is preferably 7 or less, more preferably 6 or less, still more preferably 5 or less.

Examples of the fluorine-free chain carboxylic acid ester include the following.
Methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, -tert-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-propionate Butyl, isobutyl propionate, -tert-butyl propionate, methyl butyrate, ethyl butyrate, n butyrate
-Propyl, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate, -tert-butyl butyrate, methyl isobutyrate, ethyl isobutyrate, n-propyl isobutyrate, isopropyl isobutyrate, n-butyl isobutyrate, isobutyl isobutyrate, isobutyric acid -Tert-Butyl, methyl valerate, ethyl valerate, n-propyl valerate, isopropyl valerate, n-butyl valerate, isobutyl valerate, -tert-butyl valerate, methyl hydroangelica, ethyl hydroangelica, Hydroangelic acid n-propyl, hydroangelic acid isopropyl, hydroangelic acid n-butyl, hydroangelic acid isobutyl, hydroangelic acid-te
rt-butyl, methyl isovalerate, ethyl isovalerate, n-propyl isovalerate, isopropyl isovalerate, n-butyl isovalerate, isobutyl isovalerate, -ter isovalerate
Saturated chain carboxylic acid esters such as t-butyl, methyl pivalate, ethyl pivalate, n-propyl pivalate, isopropyl pivalate, n-butyl pivalate, isobutyl pivalate, -tert-butyl pivalate, methyl acrylate. , Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, -tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-methacrylate
Propyl, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, -tert-butyl methacrylate, methyl crotonate, ethyl crotonate, n-propyl crotonate, isopropyl chromate, n-butyl crotonate, isobutyl crotonate , Crotonic acid-tert-butyl, 3-methyl butenoate, ethyl 3-butate, n-propyl 3-butate, isopropyl 3-butate, n-butyl 3-butenoate, 3-butenoate, 3- -Tert-Butyl butenoate, methyl 4-pentate, ethyl 4-pentate, n-propyl 4-pentenate, isopropyl 4-pentate, n-butyl 4-pentenate, isobutyl 4-pentene, 4-pentene Acid-tert-butyl, methyl 3-pentenate, ethyl 3-pentenate, n-propyl 3-pentenate, isopropyl 3-pentenate, n-butyl 3-pentenate, isobutyl 3-pentenate, 3-pentenoic acid -
tert-butyl, methyl 2-penteneate, ethyl 2-penteneate, n-pentenoate
Propyl, isopropyl 2-pentenate, n-butyl 2-pentenate, isobutyl 2-pentenate, -tert-butyl 2-pentenate, methyl 2-propate, ethyl 2-propate, n-propyl 2-propate , 2-Propylate isopropyl, 2-Propylate n
-Butyl, Isobutyl 2-Propine, -tert-butyl 2-Propinate, Methyl 3-Butyne, Ethyl 3-Butyne, n-propyl 3-Butyne, isopropyl 3-Butyne, n-3-Butyne Butyl, Isobutyl 3-Butyne, -tert-butyl 3-Butyne, Methyl 2-Butyne, Ethyl 2-Butyne, n-propyl 2-Butyne, Isopropyl 2-Butyne, n-Butyl 2-Butyne , 2-Isobutyl 2-butyneate, 2-butynate-te
rt-butyl, methyl 4-pentate, ethyl 4-pentate, n-propyl 4-pentate, isopropyl 4-pentate, n-butyl 4-pentate, isobutyl 4-pentate, -tert -Butyl, Methyl 3-Pentyne, Ethyl 3-Pentyne, n-propyl 3-Pentyne, isopropyl 3-Pentyne, n-butyl 3-Pentyne, Isobutyl 3-Pentyne, 3-tert-Pentinate- Butyl, Methyl 2-pentate, Ethyl 2-Pentyne, n-propyl 2-Pentyne, isopropyl 2-Pentyne, n-butyl 2-Pentyne, Isobutyl 2-Pentyne, -ter 2-Pentyne
Unsaturated chain carboxylic acid ester such as t-butyl.

Of these, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl propionate, ethyl propionate, n-propionate from the point that there are few side reactions at the negative electrode.
Propyl, n-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, n-butyl butyrate, methyl valerate, ethyl valerate, n-propyl valerate, n-butyl valerate, methyl pivalate, pivalic acid Ethyl, n-propyl pivalate, and n-butyl pivalate are preferable, and methyl acetate, ethyl acetate, and n acetate are used from the viewpoint of improving ionic conductivity by lowering the viscosity of the electrolytic solution.
-Propyl, n-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, n-butyl propionate are more preferred, methyl propionate, ethyl propionate, n-propyl propionate, n-butyl propionate. Is more preferable, and ethyl propionate and n-propyl propionate are particularly preferable.

As the fluorine-free carboxylic acid ester, one type may be used alone, or two or more types may be used in combination in any combination and ratio.

The amount of the fluorine-free carboxylic acid ester (total amount in the case of two or more kinds) can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.01% by mass or more in 100% by mass of the electrolytic solution. Is 0.1% by mass or more, more preferably 0.3% by mass or more, and particularly preferably 0.6.
It can be 0% by mass or more and 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1% by mass.
It is as follows. Within such a range, the increase in negative electrode resistance is suppressed, and the output characteristics, load characteristics, etc.
Easy to control low temperature characteristics, cycle characteristics, and high temperature storage characteristics.

The mass ratio of the compound represented by the above formula (1) to the fluorine-free carboxylic acid ester is the formula (1).
): The fluorine-free carboxylic acid ester can be 1: 100 or more, preferably 10: 100 or more, more preferably 20: 100 or more, still more preferably 25: 100 or more. It can be 10000: 100 or less, preferably 500.
: 100 or less, more preferably 300: 100 or less, still more preferably 100: 100 or less, particularly preferably 75: 100 or less, and most preferably 50: 100 or less. Within this range, battery characteristics, especially durability characteristics, can be significantly improved. This principle is not clear, but it is thought that by mixing at this ratio, the side reaction of the additive on the electrode can be minimized.

1-2-8. Cyclic compound having a plurality of ether bonds other than the formula (1) The cyclic compound having a plurality of ether bonds other than the formula (1) may be a cyclic compound having a plurality of ether bonds other than the formula (1) in the molecule. For example, the compound is not particularly limited, but is preferably a compound represented by the formula (2-10). The cyclic compound having a plurality of ether bonds other than the formula (1) contributes to the improvement of the high temperature storage property of the battery, and in the non-aqueous electrolyte solution of the present invention, the cyclic compound represented by the formula (1) is used. When used in combination, the durability characteristics of a battery using this electrolytic solution can be improved.

(In the formula, A ¹⁵ to A ²⁰ independently represent a hydrocarbon group having 1 or more and 5 or less carbon atoms which may have a hydrogen atom, a fluorine atom or a substituent. N ¹⁰¹ is 1 or more and 4 or less. Is an integer of n
When ¹⁰¹ is an integer of 2 or more, the plurality of A ¹⁷ and A ¹⁸ may be the same or different. )

Two selected from A ¹⁵ to A ²⁰ may be bonded to each other to form a ring. In this case, it is preferable to form a ring structure with A ¹⁷ and A ¹⁸ . The total number of carbon atoms of A ¹⁵ to A ²⁰ is preferably 0 or more and 8 or less, more preferably 0 or more and 4 or less, still more preferably 0 or more and 2 or less, and particularly preferably 0 or more and 1 or less.

As the substituent, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, and a cyano group, an isocyanato group, an ether group, a carbonate group, a carbonyl group, which may be substituted with a halogen atom or a fluorine atom, Examples thereof include a carboxy group, an alkoxycarbonyl group, an acyloxy group, a sulfonyl group, a phosphantriyl group and a phosphoryl group. Of these, an alkyl group, an alkenyl group, an alkynyl group, and an isocyanato group, a cyano group, an ether group, a carbonyl group, an alkoxycarbonyl group, and an acyloxy, which may be preferably substituted with a halogen atom, an alkoxy group, and a fluorine atom. Is the basis and
More preferably, it is an alkyl group, a cyano group and an ether group which are not substituted with a fluorine atom.

In the formula (2-10), n ¹⁰¹ is preferably an integer of 1 or more and 3 or less, more preferably an integer of 1 or more and 2 or less, and further preferably n ¹⁰¹ is 2.

Examples of the hydrocarbon group having 1 or more and 5 or less carbon atoms in A ¹⁵ to A ²⁰ include a monovalent hydrocarbon group such as an alkyl group, an alkenyl group, an alkynyl group and an aryl group;
Divalent hydrocarbon groups such as an alkylene group, an alkenylene group, an alkynylene group and an arylene group; and the like. Of these, an alkyl group and an alkylene group are preferable, and an alkyl group is more preferable. As a specific example,
Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, i-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-
Alkyl groups having 1 or more and 5 or less carbon atoms such as pentyl group, neopentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylpropyl group and 1,2-dimethylpropyl group;
Vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group,
An alkenyl group having 2 or more and 5 or less carbon atoms such as 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group and 4-pentenyl group;
Carbons such as ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group Alkinyl group with number 2 or more and 5 or less;
An alkylene group having 1 or more and 5 or less carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group;
An alkenylene group having 2 or more and 5 or less carbon atoms such as a vinylene group, a 1-propenylene group, a 2-propenylene group, a 1-butenylene group, a 2-butenylene group, a 1-pentenylene group, and a 2-pentenylene group;
Examples thereof include an alkynylene group having 2 or more and 5 or less carbon atoms such as an ethynylene group, a propynylene group, a 1-butynylene group, a 2-butynylene group, a 1-pentynylene group and a 2-pentynylene group. Of these, an alkylene group having 1 or more and 5 or less carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group and a pentamethylene group is preferable, and an ethylene group, a trimethylene group, a tetramethylene group and a pentamethylene group are more preferable. It is an alkylene group having 2 or more and 5 or less carbon atoms such as a methylene group, and more preferably an alkylene group having 3 or more and 5 or less carbon atoms such as a trimethylene group, a tetramethylene group and a pentamethylene group.

The hydrogen atom, fluorine atom, or hydrocarbon group having 1 or more and 5 or less carbon atoms in A ¹⁵ to A ²⁰ is a group obtained by combining a hydrogen atom, a fluorine atom, or the above-mentioned substituent and the above-mentioned hydrocarbon group having 1 or more and 5 or less carbon atoms. It is preferably a hydrogen atom, a hydrocarbon group having 1 or more and 5 or less carbon atoms having no substituent, and an alkylene group having an ether structure in which a part of the carbon chain of the alkylene group is substituted with an ether group. , More preferably a hydrogen atom.

Examples of the cyclic compound having a plurality of ether bonds other than the formula (1) include the following compounds.

等の化合物が好ましい。 Among these,

Etc. are preferred.

がより好ましい。

Is more preferable.

As the cyclic compound having a plurality of ether bonds other than the formula (1), one type may be used alone, or two or more types may be used in combination in any combination and ratio. The amount of the cyclic compound having a plurality of ether bonds other than the formula (1) (total amount in the case of two or more kinds) is 100% by mass of the electrolytic solution.
It can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.3% by mass or more, and 10% by mass or less. It can be, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less. When the above range is satisfied, it is easy to control output characteristics, load characteristics, low temperature characteristics, cycle characteristics, high temperature storage characteristics, and the like.

The mass ratio of the compound represented by the above formula (1) to the cyclic compound having a plurality of ether bonds other than the formula (1) (total amount in the case of two or more kinds) is the compound represented by the formula (1): The cyclic compound having a plurality of ether bonds other than the formula (1) can be 1: 100 or more, preferably 10: 100 or more, more preferably 20: 100 or more, still more preferably 25: 100 or more. It can be 10,000: 100 or less, preferably 500: 100 or less,
It is more preferably 300: 100 or less, further preferably 100: 100 or less, particularly preferably 75: 100 or less, and most preferably 50: 100 or less. Within this range, battery characteristics, especially durability characteristics, can be significantly improved. This principle is not clear, but it is thought that by mixing at this ratio, the side reaction of the additive on the electrode can be minimized.

1-3. Electrolyte The electrolyte is not particularly limited, and any known electrolyte can be used. In the case of a lithium secondary battery, a lithium salt is usually used. Specifically, LiPF ₆ and LiBF
_4. Inorganic lithium salts such as LiClO ₄ , LiAlF ₄ , LiSbF ₆ , LiTaF ₆ , LiWF ₇ ; Lithium tungstates such as LiWOF ₅ ; HCO ₂ Li, CH ₃ CO ₂ L
i, CH ₂ FCO ₂ Li, CHF ₂ CO ₂ Li, CF ₃ CO ₂ Li, CF ₃ CH ₂ CO ₂
Li, CF ₃ CF ₂ CO ₂ Li, CF ₃ CF ₂ CF ₂ CO ₂ Li, CF ₃ CF ₂ CF ₂ C
Lithium carboxylic acid salts such as F ₂ CO ₂ Li; FSO ₃ Li, CH ₃ SO ₃ Li, CH ₂
FSO ₃ Li, CHF ₂ SO ₃ Li, CF ₃ SO ₃ Li, CF ₃ CF ₂ SO ₃ Li, CF
₃ CF ₂ CF ₂ SO ₃ Li, CF ₃ CF ₂ CF ₂ CF ₂ SO ₃ Li and other sulfonic acid lithium salts; LiN (FCO) ₂ , LiN (FCO) (FSO ₂ ), LiN (FSO ₂ ) ₂ ,
LiN (FSO ₂ ) (CF ₃ SO ₂ ), LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ S)
O ₂ ) ₂ , Lithium Cyclic 1,2-Perfluoroethanedisulfonylimide, Lithium Cyclic 1,3-Perfluoropropanedisulfonylimide, LiN (CF ₃ SO ₂ ) (C ₄ F ₉ )
Lithium imide salts such as SO ₂ ); LiC (FSO ₂ ) ₃ , LiC (CF ₃ SO ₂ ) ₃ ,
Lithium methide salts such as LiC (C ₂ F ₅ SO ₂ ) ₃ ; Lithium (malonato) borate salts such as lithium bis (malonato) borate and lithium difluoro (malonato) borate;
Lithium (malonato) phosphate salts such as lithium tris (malonato) phosphate, lithium difluorobis (malonato) phosphate, lithium tetrafluoro (malonato) phosphate; etc.; LiPF ₄ (CF ₃ ) ₂ , LiPF ₄ (C ₂ F ₅ ) ₂ , LiP
F ₄ (CF ₃ SO ₂ ) ₂ , LiPF ₄ (C ₂ F ₅ SO ₂ ) ₂ , LiBF ₃ CF ₃ , LiB
F ₃ C ₂ F ₅ , LiBF ₃ C ₃ F ₇ , LiBF ₂ (CF ₃ ) ₂ , LiBF ₂ (C ₂ F ₅ )
₂ , LiBF ₂ (CF ₃ SO ₂ ) ₂ , LiBF ₂ (C ₂ F ₅ SO ₂ ) ₂ , etc. Fluorine-containing organic lithium salts; Lithium oxalate oxalate salts such as lithium difluorooxalate borate, lithium bis (oxalate) borate, etc. ;
Examples thereof include lithium oxarat phosphate salts such as lithium tetrafluorooxalat phosphate, lithium difluorobis (oxalate) oxalate, and lithium tris (oxalate) oxalate.

Among these, LiPF ₆ , LiSbF ₆ , LiTaF ₆ , FSO ₃ Li, CF ₃ S
O ₃ Li, LiN (FSO ₂ ) ₂ , LiN (FSO ₂ ) (CF ₃ SO ₂ ), LiN (CF)
₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , Lithium cyclic 1,2-perfluoroethanedisulfonylimide, Lithium cyclic 1,3-perfluoropropanedisulfonylimide,
LiC (FSO ₂ ) ₃ , LiC (CF ₃ SO ₂ ) ₃ , LiC (C ₂ F ₅ SO ₂ ) ₃ , Li
BF ₃ CF ₃ , LiBF ₃ C ₂ F ₅ , LiPF ₃ (CF ₃ ) ₃ , LiPF ₃ (C ₂ F ₅ )
_3. Lithium difluorooxalate borate, lithium bis (oxalate) borate, lithium difluorobis (oxalate) phosphate, etc. are preferable because they have the effect of improving output characteristics, high-rate charge / discharge characteristics, high-temperature storage characteristics, cycle characteristics, and the like. Also, Li
PF ₆ , FSO ₃ Li, LiN (FSO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , lithium difluorooxalate borate, lithium bis (oxalate) borate, lithium difluorobis (oxalate) phosphate are more preferred, LiPF ₆ , FSO ₃ Li, LiN
(FSO ₂ ) _2. Lithium bis (oxalate) borate is more preferable because it has the effect of further improving output characteristics, high-rate charge / discharge characteristics, high-temperature storage characteristics, cycle characteristics, etc., and from the viewpoint of electrolyte oxidation-reduction stability. LiPF ₆ is most preferred. In particular, LiPF ₆ decomposes in the system to produce Lewis acid PF ₅ , which causes deterioration of electrolytic solution stability, electrolytic solution physical properties, and battery characteristics. Therefore, when used at the same time as the compound represented by the formula (1), it is possible to exhibit excellent properties as an electrolyte while suppressing the adverse effects caused by Lewis acid.

The ratio of the molar content of the compound represented by the formula (1) to the molar content of the electrolyte contained in the non-aqueous electrolyte solution is not particularly limited in order to exhibit the effect of the present invention, but is usually 0. 043 or more, preferably 0.050 or more, more preferably 0.075 or more, still more preferably 0.0.
80 or more, particularly preferably 0.100 or more, usually 0.935 or less, preferably 0.850 or less, more preferably 0.760 or less, still more preferably 0.300 or less, particularly preferably 0.200. It is as follows. Within this range, battery characteristics, particularly continuous charge durability characteristics, can be significantly improved. This principle is not clear, but it is thought that mixing at this ratio facilitates efficient complex formation with the decomposition products of the electrolyte. The ratio of the molar content of the compound represented by the formula (1) to the molar content of the electrolyte is the formula (1).
) Is divided by the molar content of the electrolyte, and is an index representing the number of molecules of the compound represented by the formula (1) with respect to one molecule of the electrolyte.

The concentration of these electrolytes in the non-aqueous electrolyte solution is not particularly limited as long as the effect of the present invention is not impaired, but the electric conductivity of the electrolyte solution is kept in a good range to ensure good battery performance. From the point of view, the total molar concentration of lithium in the non-aqueous electrolyte solution is preferably 0.25 mol / L.
The above is more preferably 0.5 mol / L or more, still more preferably 1.1 mol / L or more, still more preferably 3.0 mol / L or less, still more preferably 2.5 mol / L or less, still more preferably 2. It is 0 mol / L or less. Within this range, the amount of lithium as charged particles is not too small, and the viscosity can be set in an appropriate range, so that it becomes easy to secure good electrical conductivity.

When two or more electrolytes are used in combination, it is also preferable that at least one is a salt selected from the group consisting of monofluorophosphate, difluorophosphate, borate, oxalate and fluorosulfonate. It is also more preferable that the salt is selected from the group consisting of sowing, monofluorophosphate, difluorophosphate, oxalate and fluorosulfonate. Of these, lithium salts are preferred. The salt selected from the group consisting of monofluorophosphate, difluorophosphate, borate, oxalate and fluorosulfonate can be 0.01% by mass or more, preferably 0.1% by mass. % Or more, and can be 20% by mass or less, preferably 10% by mass or less.

It is preferable that the electrolyte contains one or more selected from the group consisting of monofluorophosphate, difluorophosphate, borate, oxalate and fluorosulfonate, and one or more of other salts. .. Examples of other salts include the lithium salts exemplified above, and in particular, LiPF ₆ , LiN (FSO ₂ ) (CF ₃ SO ₂ ), LiN (CF ₃ SO ₂ ) ₂ , L.
iN (C ₂ F ₅ SO ₂ ) ₂ , Lithium Cyclic 1,2-Perfluoroethanedisulfonylimide, Lithium Cyclic 1,3-Perfluoropropanedisulfonylimide, LiC (FSO ₂ )
) ₃ , LiC (CF ₃ SO ₂ ) ₃ , LiC (C ₂ F ₅ SO ₂ ) ₃ , LiBF ₃ CF ₃ , L
iBF ₃ C ₂ F ₅ , LiPF ₃ (CF ₃ ) ₃ , LiPF ₃ (C ₂ F ₅ ) ₃ are preferred, L.
iPF ₆ is even more preferred. The other salts can be 0.01% by mass or more, preferably 0.1% by mass or more, and 20% by mass, from the viewpoint of ensuring an appropriate balance between the conductivity and the viscosity of the electrolytic solution. It can be less than or equal to, preferably 15% by mass or less, and more preferably 10% by mass or less.

1-3-1. Monofluorophosphate, difluorophosphate The monofluorophosphate and difluorophosphate are not particularly limited as long as they are salts having at least one monofluorophosphate or difluorophosphate structure in the molecule, respectively. In the non-aqueous electrolyte solution of the present invention, a battery using this electrolyte solution is used by using the compound represented by the above formula (1) in combination with one or more selected from monofluorophosphate and difluorophosphate. In, the durability characteristics can be improved.

The counter cations in monofluorophosphate and difluorophosphate are not particularly limited, and are lithium, sodium, potassium, magnesium, calcium, NR ¹²¹ R.
¹²² R ¹²³ R ¹²⁴ (in the formula, R ¹²¹ to R ¹²⁴ are independently hydrogen atoms or organic groups having 1 or more and 12 or less carbon atoms) and the like. The organic group represented by R ¹²¹ to R ¹²⁴ of the above ammonium having 1 or more and 12 or less carbon atoms is not particularly limited, and is, for example, substituted with an alkyl group which may be substituted with a fluorine atom, a halogen atom or an alkyl group. Examples thereof include a cycloalkyl group, an aryl group which may be substituted with a halogen atom or an alkyl group, a nitrogen atom-containing heterocyclic group which may have a substituent, and the like.
Among them, R ¹²¹ to R ¹²⁴ are independently preferably hydrogen atoms, alkyl groups, cycloalkyl groups, nitrogen atom-containing heterocyclic groups and the like. As the counter cation, lithium, sodium and potassium are preferable, and lithium is particularly preferable.

Examples of the monofluorophosphate and difluorophosphate include lithium monofluorophosphate, sodium monofluorophosphate, potassium monofluorophosphate, lithium difluorophosphate, sodium difluorophosphate, potassium difluorophosphate and the like. Lithium monofluorophosphate and lithium difluorophosphate are preferable, and lithium difluorophosphate is more preferable. As the monofluorophosphate and difluorophosphate, one type may be used alone, or two or more types may be used in combination in any combination and ratio.

The amount of one or more selected from monofluorophosphate and difluorophosphate (total amount in the case of two or more) can be 0.001% by mass or more, preferably 0.01% by mass.
As described above, it is more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, particularly preferably 0.3% by mass or more, and can be 5% by mass or less, preferably 3% by mass. % Or less, more preferably 2% by mass or less, still more preferably 1.5% by mass or less, and particularly preferably 1% by mass or less. Within this range, the effect of improving the initial irreversible capacity is remarkably exhibited.

The mass ratio of one or more (total amount in the case of two or more) selected from the compound represented by the above formula (1) and monofluorophosphate and difluorophosphate is represented by the formula (1). Compounds: Monofluorophosphate and difluorophosphate are preferably 1:99 to 99: 1, 10:
90 to 90:10 is more preferable, and 20:80 to 80:20 is particularly preferable. Within this range, the desired characteristics can be improved without deteriorating the characteristics of other batteries.

1-3-2. Borate Borate is not particularly limited as long as it is a salt having at least one boron atom in the molecule. However, those corresponding to oxalate shall be included in "1-3-3. Oxalate" described later, not "1-3-2. Borate". In the non-aqueous electrolyte solution of the present invention, by using the compound represented by the formula (1) in combination with borate, the durability characteristics of the battery using this electrolyte solution can be improved.

Examples of the counter cation in the borate include lithium, sodium, potassium, magnesium, calcium, rubidium, cesium, barium and the like, and lithium is preferable.

As the borate, a lithium salt is preferable, and a lithium borate-containing lithium salt can also be preferably used. For example, LiBF ₄ , LiBF ₃ CF ₃ , LiBF ₃ C ₂ F ₅ , LiBF ₃ C ₃
F ₇ , LiBF ₂ (CF ₃ ) ₂ , LiBF ₂ (C ₂ F ₅ ) ₂ , LiBF ₂ (CF ₃ SO ₂ )
) ₂ , LiBF ₂ (C ₂ F ₅ SO ₂ ) ₂ and the like. Above all, LiBF ₄ is more preferable because it has an effect of improving initial charge / discharge efficiency and high temperature cycle characteristics. Borate is
One type may be used alone, or two or more types may be used in any combination and ratio.

The amount of borate (total amount in the case of two or more kinds) can be 0.05% by mass or more.
It is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.3.
By mass or more, particularly preferably 0.4% by mass or more, and can be 10.0% by mass or less, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and further. It is preferably 2.0% by mass or less, and particularly preferably 1.0% by mass or less. Within this range, the side reaction of the battery negative electrode is suppressed and it is difficult to increase the resistance.

The mass ratio of the compound represented by the above formula (1) to the borate is preferably 1: 99 to 99: 1 for the compound represented by the formula (1): borate, 10: 90 to 90 :. 10 is more preferred, 2
0:80 to 80:20 is particularly preferable. Within this range, side reactions on the positive and negative sides in the battery are suppressed, and it is difficult to increase the resistance of the battery.

When borate and LiPF ₆ are used as the electrolyte, LiPF ₆ in the non-aqueous electrolyte solution is used.
The ratio of the molar content of borate to the molar content of is preferably 0.001 or more and 12 or less, more preferably 0.01 to 1.1, still more preferably 0.01 to 1.0, and 0.01. ~ 0.
7 is more preferable. Within this range, side reactions on the positive and negative sides in the battery are suppressed, and the charging / discharging efficiency of the battery is improved.

1-3-3. Oxalate The oxalate is not particularly limited as long as it is a compound having at least one oxalic acid structure in the molecule. In the non-aqueous electrolyte solution of the present invention, by using the compound represented by the formula (1) in combination with oxalate, the durability characteristics of the battery using this electrolytic solution can be improved.

As the oxalate, a metal salt represented by the formula (9) is preferable. This salt is a salt having an oxalate complex as an anion.

(In the formula, M ¹ is an element selected from the group consisting of Group 1 and Group 2 and aluminum (Al) in the periodic table.
M ² is an element selected from the group consisting of transition metals, groups 13, 14 and 15 of the periodic table.
R ⁹¹ is a group selected from the group consisting of halogens, alkyl groups having 1 or more and 11 or less carbon atoms and halogen-substituted alkyl groups having 1 or more and 11 or less carbon atoms.
a and b are positive integers
c is 0 or a positive integer,
d is an integer of 1 to 3. )
M ¹ is derived from the viewpoint of battery characteristics when the non-aqueous electrolyte solution of the present invention is used for a lithium secondary battery.
Lithium, sodium, potassium, magnesium and calcium are preferred, with lithium being particularly preferred.

Boron and phosphorus are particularly preferable for M ² in terms of electrochemical stability when used in a lithium secondary battery.

Examples of R ⁹¹ include fluorine, chlorine, methyl group, trifluoromethyl group, ethyl group, pentafluoroethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and ter.
Examples thereof include t-butyl group, and fluorine and trifluoromethyl group are preferable.

Examples of the metal salt represented by the formula (9) include the following.
Lithium oxalate borate salts such as lithium difluorooxalate borate and lithium bis (oxalate) borate;
Lithium oxalate phosphate salts such as lithium tetrafluorooxalat phosphate, lithium difluorobis (oxalate) oxalate, lithium tris (oxalate) oxalate;
Of these, lithium bis (oxalate) borate and lithium difluorobis (oxalate) phosphate are preferable, and lithium bis (oxalate) borate is more preferable.

As the oxalate, one type may be used alone, or two or more types may be used in combination in any combination and ratio.

The amount of oxalate (total amount in the case of two or more kinds) can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably. Is 0.3% by mass or more and can be 10% by mass or less, preferably 5% by mass.
Hereinafter, it is more preferably 3% by mass or less, further preferably 2% by mass or less, and particularly preferably 1% by mass or less. Within this range, it is easy to control output characteristics, load characteristics, low temperature characteristics, cycle characteristics, high temperature storage characteristics, and the like.

The mass ratio of the compound represented by the above formula (1) to the oxalate is the compound represented by the formula (1):
The oxalate is preferably 1:99 to 99: 1, more preferably 10:90 to 90:10, and particularly preferably 20:80 to 80:20. Within this range, side reactions on the positive and negative sides of the battery can be suppressed in a well-balanced manner, and the battery characteristics can be easily improved.

1-3-4. Fluorosulfuric acid salt The fluorosulfonic acid salt is not particularly limited as long as it is a salt having at least one fluorosulfonic acid structure in the molecule. In the non-aqueous electrolyte solution of the present invention, the above formula (1)
) In combination with the fluorosulfonate, the durability characteristics of the battery using this electrolytic solution can be improved.

The counter cations in the fluorosulfonate are not particularly limited, and lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, and NR ¹³¹ R ¹³² R ¹³³ R ¹³⁴ (in the formula, R ¹³¹ to R ¹³⁴ are Each of them independently includes a hydrogen atom or an organic group having 1 or more and 12 or less carbon atoms). The organic group represented by R ¹³¹ to R ¹³⁴ of the above ammonium having 1 or more and 12 or less carbon atoms is not particularly limited, and is, for example, substituted with an alkyl group which may be substituted with a fluorine atom, a halogen atom or an alkyl group. Examples thereof include a cycloalkyl group, an aryl group which may be substituted with a halogen atom or an alkyl group, a nitrogen atom-containing heterocyclic group which may have a substituent, and the like. Among them, R ¹³¹ to R ¹³⁴ are independently preferably hydrogen atoms, alkyl groups, cycloalkyl groups, nitrogen atom-containing heterocyclic groups and the like. As the counter cation, lithium, sodium and potassium are preferable, and lithium is particularly preferable.

Examples of the fluorosulfonate include lithium fluorosulfonate, sodium fluorosulfonate, potassium fluorosulfonate, rubidium fluorosulfonate, cesium fluorosulfonate, and the like, and lithium fluorosulfonate is preferable. Lithium screw (
An imide salt having a fluorosulfonic acid structure such as fluorosulfonyl) imide can also be used as the fluorosulfonic acid salt.

As the fluorosulfonate, one type may be used alone, or two or more types may be used in combination in any combination and ratio.

The content of the fluorosulfonate (total amount in the case of two or more kinds) can be 0.05% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more. It is more preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, and can be 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, and further. It is preferably 2% by mass or less, and particularly preferably 1% by mass or less. Within this range, there are few side reactions in the battery and it is difficult to increase the resistance.

The mass ratio of the compound represented by the above formula (1) to the fluorosulfonate is preferably 1:99 to 99: 1, preferably 1:99 to 99: 1, for the compound represented by the formula (1): fluorosulfonate. 90
: 10 is more preferable, and 20:80 to 80:20 is particularly preferable. Within this range, side reactions in the battery are appropriately suppressed, and the high temperature durability characteristics are unlikely to be deteriorated.

1-4. Non-aqueous solvent The non-aqueous solvent in the present invention is not particularly limited, and known organic solvents can be used. Specifically, cyclic carbonates (excluding cyclic carbonates having a carbon-carbon unsaturated bond and fluorine-containing cyclic carbonates), chain carbonates, cyclic and chain carboxylic acid esters, ether compounds, sulfone compounds, etc. Can be mentioned.

Further, in the present specification, the volume of the non-aqueous solvent is a measured value at 25 ° C., but for a solid substance at 25 ° C. such as ethylene carbonate, the measured value at the melting point is used.

1-4-1. Cyclic carbonate (excluding cyclic carbonates having a carbon-carbon unsaturated bond and fluorine-containing cyclic carbonates)
Examples of the cyclic carbonate include cyclic carbonate having an alkylene group having 2 to 4 carbon atoms.

Specific examples of the cyclic carbonate having an alkylene group having 2 to 4 carbon atoms include ethylene carbonate, propylene carbonate, and butylene carbonate. Of these, ethylene carbonate and propylene carbonate are particularly preferable from the viewpoint of improving battery characteristics resulting from the improvement of the degree of lithium ion dissociation.
As the cyclic carbonate, one type may be used alone, or two or more types may be used in combination in any combination and ratio.

The blending amount of the cyclic carbonate is not particularly limited and is arbitrary as long as the effect of the present invention is not significantly impaired, but the blending amount when one type is used alone is 5% by volume in 100% by volume of the non-aqueous solvent.
As mentioned above, it is more preferably 10% by volume or more. By setting this range, it is easy to avoid the decrease in electrical conductivity due to the decrease in the dielectric constant of the non-aqueous electrolyte solution, and to make the large current discharge characteristics of the power storage device, the stability with respect to the negative electrode, and the cycle characteristics within a good range. .. Further, it is 95% by volume or less, more preferably 90% by volume or less, still more preferably 85% by volume or less. By setting this range, the viscosity of the non-aqueous electrolyte solution can be set to an appropriate range, the decrease in ionic conductivity can be suppressed, and the load characteristics of the power storage device can be easily set to a good range.

1-4-2. Chain carbonate As the chain carbonate, a chain carbonate having 3 to 7 carbon atoms is preferable, and a chain carbonate having 3 to 7 carbon atoms is preferable.
The dialkyl carbonate of 7 is more preferable.

As the chain carbonate, dimethyl carbonate, diethyl carbonate, di-n-
Propyl carbonate, diisopropyl carbonate, n-propylisopropylcarbonate, ethylmethylcarbonate, methyl-n-propylcarbonate, n-butylmethylcarbonate, isobutylmethylcarbonate, tert-butylmethylcarbonate, ethyl-n-propylcarbonate, n-butylethyl Examples thereof include carbonate, isobutylethyl carbonate, tert-butylethyl carbonate and the like.

Of these, dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, n-propylisopropyl carbonate, ethylmethyl carbonate and methyl-n-propyl carbonate are preferable, and dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate are particularly preferable. be.

In addition, chain carbonates having a fluorine atom (hereinafter, "fluorinated chain carbonate").
May be described as) can also be preferably used.

The number of fluorine atoms contained in the fluorinated chain carbonate is not particularly limited as long as it is 1 or more, but is usually 6 or less, preferably 4 or less. When the fluorinated chain carbonate has a plurality of fluorine atoms, they may be bonded to the same carbon or to different carbons.

Examples of the fluorinated chain carbonate include fluorinated dimethyl carbonate and its derivatives.
Examples thereof include fluorinated ethylmethyl carbonate and its derivatives, fluorinated diethyl carbonate and its derivatives, and the like.

Examples of the fluorinated dimethyl carbonate and its derivatives include fluoromethylmethyl carbonate, difluoromethylmethylcarbonate, trifluoromethylmethylcarbonate, bis (fluoromethyl) carbonate, bis (difluoro) methylcarbonate, and bis (trifluoromethyl) carbonate. Be done.

Examples of the fluorinated ethylmethyl carbonate and its derivatives include 2-fluoroethylmethyl carbonate, ethylfluoromethylcarbonate, 2,2-difluoroethylmethylcarbonate, 2-fluoroethylfluoromethylcarbonate, ethyldifluoromethylcarbonate, 2,2,2. -Trifluoroethyl methyl carbonate, 2,2-difluoroethylfluoromethyl carbonate, 2-fluoroethyl difluoromethyl carbonate, ethyltrifluoromethyl carbonate and the like can be mentioned.

Examples of the fluorinated diethyl carbonate and its derivatives include ethyl- (2-fluoroethyl) carbonate, ethyl- (2,2-difluoroethyl) carbonate, bis (2-fluoroethyl) carbonate, and ethyl- (2,2,2-). Trifluoroethyl) carbonate, 2,2-difluoroethyl-2'-fluoroethyl carbonate, bis (2,2-difluoroethyl) carbonate, 2,2,2-trifluoroethyl-2'-fluoroethyl carbonate, 2, Examples thereof include 2,2-trifluoroethyl-2', 2'-difluoroethyl carbonate and bis (2,2,2-trifluoroethyl) carbonate.

As the chain carbonate, one type may be used alone, or two or more types may be used in combination in any combination and ratio. The blending amount of the chain carbonate is preferably 5% by volume or more, more preferably 10% by volume or more, still more preferably 15% by volume or more in 100% by volume of the non-aqueous solvent. By setting the lower limit in this way, the viscosity of the non-aqueous electrolyte solution can be set in an appropriate range, the decrease in ionic conductivity can be suppressed, and the large current discharge characteristics of the power storage device can be easily set in a good range. The chain carbonate is preferably 90% by volume or less, more preferably 85% by volume or less in 100% by volume of the non-aqueous solvent. By setting the upper limit in this way, it is easy to avoid a decrease in electrical conductivity due to a decrease in the dielectric constant of the non-aqueous electrolyte solution, and to easily set the large current discharge characteristic of the power storage device within a good range.

1-4-3. Cyclic and chain carboxylic acid esters The cyclic carboxylic acid esters preferably have 3 to 12 carbon atoms.
Specifically, gamma-butyrolactone, gamma-valerolactone, gamma-caprolactone,
Examples thereof include epsilon caprolactone. Of these, gamma-butyrolactone is particularly preferable from the viewpoint of improving battery characteristics resulting from the improvement in the degree of lithium ion dissociation.

As the cyclic carboxylic acid ester, one type may be used alone, or two or more types may be used in combination in any combination and ratio.

The blending amount of the cyclic carboxylic acid ester is usually preferably 5% by volume or more, more preferably 10% by volume or more in 100% by volume of the non-aqueous solvent. Within this range, the electric conductivity of the non-aqueous electrolyte solution can be improved, and the large current discharge characteristics of the power storage device can be easily improved. The blending amount of the cyclic carboxylic acid ester is preferably 50% by volume or less, more preferably 40% by volume or less. By setting the upper limit in this way, the viscosity of the non-aqueous electrolyte solution is set in an appropriate range, the decrease in electrical conductivity is avoided, the increase in negative electrode resistance is suppressed, and the large current discharge characteristics of the power storage device are in a good range. It becomes easy to do.

As the chain carboxylic acid ester, "1-2-7. Fluorine-free carboxylic acid ester"
The one shown in is mentioned.

When the chain carboxylic acid ester is used as the non-aqueous solvent, the blending amount is preferably 1% by volume or more, more preferably 5% by volume or more, still more preferably 10% by volume or more, still more, in 100% by volume of the non-aqueous solvent. It is preferably 20% by volume or more, and can be contained in an amount of 50% by volume or less, more preferably 45% by volume or less, still more preferably 40% by volume or less.

When the content of the chain carboxylic acid ester is within the above range, the electric conductivity of the non-aqueous electrolyte solution is improved, and the input / output characteristics and the charge / discharge rate characteristics of the non-aqueous electrolyte secondary battery can be easily improved. In addition, the increase in negative electrode resistance is suppressed, and the input / output characteristics and charge / discharge rate characteristics of the non-aqueous electrolyte secondary battery can be easily set in a good range.

When the chain carboxylic acid ester is used as a non-aqueous solvent, it is preferably used in combination with a cyclic carbonate, and more preferably in combination with a cyclic carbonate and a chain carbonate.

For example, when the cyclic carbonate and the chain carboxylic acid ester are used in combination, the content of the cyclic carbonate is not particularly limited and is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 15% by volume or more, preferably 20. The volume is usually 45% by volume or less, preferably 40% by volume or less, and the content of the chain carboxylic acid ester is usually 20% by volume or more, preferably 30% by volume or more, and usually 55% by volume or less, preferably 55% by volume or less. Is 50% by volume or less.

Further, when the cyclic carbonate, the chain carbonate and the chain carboxylic acid ester are used in combination, the content of the cyclic carbonate is not particularly limited and is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 15% by volume or more. , Preferably 20% by volume, and usually 45% by volume or less,
It is preferably 40% by volume or less, and the content of the chain carbonate is usually 25% by volume or more.
It is preferably 30% by volume or more, and usually 84% by volume or less, preferably 80% by volume or less. By setting the content within the above range, the viscosity of the non-aqueous electrolyte solution is also lowered to improve the ionic conductivity while lowering the low temperature precipitation temperature of the electrolyte, and even higher input / output can be obtained even at a low temperature. It is also preferable from the viewpoint of further reducing battery swelling.

1-4-4. Ether-based compound As the ether-based compound, a part of hydrogen may be substituted with fluorine and has 3 carbon atoms.
A chain ether of about 10 and a cyclic ether having 3 to 6 carbon atoms are preferable.

As a chain ether having 3 to 10 carbon atoms,
Diethyl ether, di (2-fluoroethyl) ether, di (2,2-difluoroethyl) ether, di (2,2,2-trifluoroethyl) ether, ethyl (2-fluoroethyl) ether, ethyl (2, 2,2-Trifluoroethyl) ether, ethyl (1
, 1,2,2-tetrafluoroethyl) ether, (2-fluoroethyl) (2,2,2)
-Trifluoroethyl) ether, (2-fluoroethyl) (1,1,2,2-tetrafluoroethyl) ether, (2,2,2-trifluoroethyl) (1,1,2,2-tetrafluoro) Ethyl) ether, ethyl-n-propyl ether, ethyl (3-fluoro-
n-propyl) ether, ethyl (3,3,3-trifluoro-n-propyl) ether, ethyl (2,2,3,3-tetrafluoro-n-propyl) ether, ethyl (2,2)
, 3,3,3-Pentafluoro-n-propyl) ether, 2-fluoroethyl-n-propyl ether, (2-fluoroethyl) (3-fluoro-n-propyl) ether, (
2-Fluoroethyl) (3,3,3-trifluoro-n-propyl) ether, (2-fluoroethyl) (2,2,3,3-tetrafluoro-n-propyl) ether, (2-fluoroethyl) ) (2,2,3,3,3-pentafluoro-n-propyl) ether, 2,
2,2-Trifluoroethyl-n-propyl ether, (2,2,2-trifluoroethyl) (3-fluoro-n-propyl) ether, (2,2,2-trifluoroethyl) (
3,3,3-trifluoro-n-propyl) ether, (2,2,2-trifluoroethyl) (2,2,3,3-tetrafluoro-n-propyl) ether, (2,2,2) -Trifluoroethyl) (2,2,3,3,3-pentafluoro-n-propyl) ether, 1
, 1,2,2-Tetrafluoroethyl-n-propyl ether, (1,1,2,2-tetrafluoroethyl) (3-fluoro-n-propyl) ether, (1,1,2,2-tetra Fluoroethyl) (3,3,3-trifluoro-n-propyl) ether, (1,1,1
2,2-Tetrafluoroethyl) (2,2,3,3-tetrafluoro-n-propyl) ether, (1,1,2,2-tetrafluoroethyl) (2,2,3,3,3- Pentafluoro-8n-propyl) ether, di-n-propyl ether, (n-propyl) (3-
Fluoro-n-propyl) ether, (n-propyl) (3,3,3-trifluoro-n)
-Propyl) ether, (n-propyl) (2,2,3,3-tetrafluoro-n-propyl) ether, (n-propyl) (2,2,3,3,3-pentafluoro-n-propyl) ) Ether, di (3-fluoro-n-propyl) ether, (3-fluoro-n-propyl) (3,3,3-trifluoro-n-propyl) ether, (3-fluoro-n-propyl) ( 2,2,3,3-tetrafluoro-n-propyl) ether, (3-fluoro-n-propyl) (2,2,3,3,3-pentafluoro-n-propyl) ether, di (3, 3,3-Trifluoro-n-propyl) ether, (3,3,3-trifluoro-
n-propyl) (2,2,3,3-tetrafluoro-n-propyl) ether, (3,3
, 3-Trifluoro-n-propyl) (2,2,3,3,3-pentafluoro-n-propyl) ether, di (2,2,3,3-tetrafluoro-n-propyl) ether, ( 2
, 2,3,3-Tetrafluoro-n-propyl) (2,2,3,3,3-pentafluoro-n-propyl) ether, di (2,2,3,3,3-pentafluoro-n) -Propyl)
Ether, di-n-butyl ether, dimethoxymethane, methoxyethoxymethane, methoxy (2-fluoroethoxy) methane, methoxy (2,2,2-trifluoroethoxy)
Methanemethoxy (1,1,2,2-tetrafluoroethoxy) methane, diethoxymethane, ethoxy (2-fluoroethoxy) methane, ethoxy (2,2,2-trifluoroethoxy) methane, ethoxy (1,1,1) 2,2-Tetrafluoroethoxy) Methane, Di (2-
Fluoroethoxy) methane, (2-fluoroethoxy) (2,2,2-trifluoroethoxy) methane, (2-fluoroethoxy) (1,1,2,2-tetrafluoroethoxy)
Methane Di (2,2,2-trifluoroethoxy) methane, (2,2,2-trifluoroethoxy) (1,1,2,2-tetrafluoroethoxy) methane, di (1,1,2,2- Tetrafluoroethoxy) methane, dimethoxyethane, methoxyethoxyethane, methoxy (2-fluoroethoxy) ethane, methoxy (2,2,2-trifluoroethoxy) ethane, methoxy (1,1,2,2-tetrafluoroethoxy) Ethane, diethoxyethane,
Ethoxy (2-fluoroethoxy) ethane, ethoxy (2,2,2-trifluoroethoxy) ethane, ethoxy (1,1,2,2-tetrafluoroethoxy) ethane, di (2-fluoroethoxy) ethane, (2) -Fluoroethoxy) (2,2,2-trifluoroethoxy) ethane, (2-fluoroethoxy) (1,1,2,2-tetrafluoroethoxy) ethane, di (2,2,2-trifluoroethoxy) Ethane, (2,2,2-trifluoroethoxy) (1,1,2,2-tetrafluoroethoxy) ethane, di (1,1,2,2-tetrafluoroethoxy) ethane, ethylene glycol di-n- Examples thereof include propyl ether, ethylene glycol di-n-butyl ether and diethylene glycol dimethyl ether.

Examples of the cyclic ether having 3 to 6 carbon atoms include tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 1,4-dioxane and the like, and fluorinated compounds thereof.

Among them, dimethoxymethane, diethoxymethane, ethoxymethoxymethane, ethylene glycol di-n-propyl ether, ethylene glycol di-n-butyl ether, and diethylene glycol dimethyl ether have high solvation ability to lithium ions and improve ionic dissociation. Dimethoxymethane, diethoxymethane, and ethoxymethoxymethane are preferable in terms of points, and particularly preferable because they have low viscosity and give high ionic conductivity.

As the ether compound, one kind may be used alone, or two or more kinds may be used in any combination and ratio.

The blending amount of the ether compound is usually 5% by volume or more, more preferably 10% by volume or more, still more preferably 15% by volume or more, and preferably 70% by volume or less in 100% by volume of the non-aqueous solvent. It is more preferably 60% by volume or less, still more preferably 50% by volume or less. Within this range, it is easy to secure the effect of improving the lithium ion dissociation degree of the chain ether and the ionic conductivity due to the decrease in viscosity. When the negative electrode active material is a carbonaceous material, the chain ether is combined with lithium ions. It is easy to avoid the situation where the capacity is reduced due to co-insertion.

1-4-5. Sulfone-based compound As the sulfone-based compound, a cyclic sulfone having 3 to 6 carbon atoms and a chain sulfone having 2 to 6 carbon atoms are preferable. The number of sulfonyl groups in one molecule is preferably 1 or 2.

Examples of the cyclic sulfone having 3 to 6 carbon atoms include monosulfone compounds such as trimethylene sulfone, tetramethylene sulfone, and hexamethylene sulfone; disulfone compounds such as trimethylene disulfone, tetramethylene disulfone, and hexamethylene disulfone. Can be mentioned.

Among them, tetramethylene sulfones, tetramethylene disulfones, hexamethylene sulfones, and hexamethylene disulfones are more preferable, and tetramethylene sulfones (sulfolanes) are particularly preferable, from the viewpoint of dielectric constant and viscosity.
As the sulfolanes, sulfolanes and / or sulfolane derivatives (hereinafter, sulfolanes may also be referred to as "sulfolanes") are preferable. As the sulfolane derivative, one in which one or more of the hydrogen atoms bonded on the carbon atom constituting the sulfolane ring is substituted with a fluorine atom or an alkyl group is preferable.

Among them, 2-methylsulfolane, 3-methylsulfolane, 2-fluorosulfolane,
3-Fluorosulfolane, 2,2-difluorosulfolane, 2,3-difluorosulfolane, 2,4-difluorosulfolane, 2,5-difluorosulfolane, 3,4-difluorosulfolane, 2-fluoro-3-methylsulfolane, 2 -Fluoro-2-methyl sulfolane, 3-fluoro-3-methyl sulfolane, 3-fluoro-2-methyl sulfolane, 4
-Fluoro-3-methyl sulfolane, 4-fluoro-2-methyl sulfolane, 5-fluoro-3-methyl sulfolane, 5-fluoro-2-methyl sulfolane, 2-fluoromethyl sulfolane, 3-fluoromethyl sulfolane, 2-difluoro Methyl sulfolane, 3-difluoromethyl sulfolane, 2-trifluoromethyl sulfolane, 3-trifluoromethyl sulfolane, 2-fluoro-3- (trifluoromethyl) sulfolane, 3-fluoro-
3- (Trifluoromethyl) sulfolane, 4-fluoro-3- (trifluoromethyl) sulfolane, 5-fluoro-3- (trifluoromethyl) sulfolane, etc. have high ionic conductivity and high input / output characteristics. preferable.

Further, as a chain sulfone having 2 to 6 carbon atoms,
Dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, n-propyl methyl sulfone, n-propyl ethyl sulfone, di-n-propyl sulfone, isopropyl methyl sulfone, isopropyl ethyl sulfone, diisopropyl sulfone, n-butyl methyl sulfone, n-butyl ethyl Sulfone, tert-butylmethyl sulfone, tert-butylethyl sulfone, monofluoromethylmethyl sulfone, difluoromethylmethyl sulfone, trifluoromethylmethyl sulfone, monofluoroethylmethyl sulfone, difluoroethylmethyl sulfone, trifluoroethylmethyl sulfone, pentafluoro Ethylmethyl sulfone, ethyl monofluoromethyl sulfone, ethyl difluoromethyl sulfone, ethyl trifluoromethyl sulfone, perfluoroethyl methyl sulfone, ethyl trifluoroethyl sulfone, ethyl pentafluoroethyl sulfone, di (trifluoroethyl) sulfone, perfluorodiethyl Sulfone, Fluoromethyl-n-propyl sulfone, Difluoromethyl-n-propyl sulfone, Trifluoromethyl-n-propyl sulfone, Fluoromethyl isopropyl sulfone, Difluoromethyl isopropyl sulfone, Trifluoromethyl isopropyl sulfone, Trifluoroethyl-n-propyl Sulfone,
Trifluoroethyl isopropyl sulfone, pentafluoroethyl-n-propyl sulfone, pentafluoroethyl isopropyl sulfone, trifluoroethyl-n-butyl sulfone, trifluoroethyl-tert-butyl sulfone, pentafluoroethyl-n-butyl sulfone, pentafluoro Ethyl-tert-butyl sulfone and the like can be mentioned.

Among them, dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, n-propyl methyl sulfone, isopropyl methyl sulfone, n-butyl methyl sulfone, tert
-Butylmethylsulfone, monofluoromethylmethylsulfone, difluoromethylmethylsulfone, trifluoromethylmethylsulfone, monofluoroethylmethylsulfone, difluoroethylmethylsulfone, trifluoroethylmethylsulfone, pentafluoroethylmethylsulfone, ethylmonofluoromethylsulfone , Ethyldifluoromethylsulfone, Ethyltrifluoromethylsulfone, Ethyltrifluoroethylsulfone, Ethylpentafluoroethylsulfone, Trifluoromethyl-n-propylsulfone, Trifluoromethylisopropylsulfone, Trifluoroethyl-n-butylsulfone, Trifluoro Ethyl-tert-butyl sulfone, trifluoromethyl-n-butyl sulfone, trifluoromethyl-tert-butyl sulfone and the like are preferable because they have high ionic conductivity and high input / output characteristics.

As the sulfone compound, one type may be used alone, or two or more types may be used in combination in any combination and ratio.

The blending amount of the sulfonic compound is usually preferably 0.3% by volume or more, more preferably 1% by volume or more, still more preferably 5% by volume or more, and preferably 40% by volume in 100% by volume of the non-aqueous solvent. By volume or less, more preferably 35% by volume or less, still more preferably 30% by volume or less. Within this range, it is easy to obtain the effect of improving durability such as cycle characteristics and storage characteristics, and the viscosity of the non-aqueous electrolyte solution can be set within an appropriate range to avoid a decrease in electrical conductivity. When the device is charged and discharged at a high current density, it is easy to avoid a situation in which the charge / discharge capacity retention rate is lowered.

1-4-6. Composition of Non-Aqueous Solvent As the non-aqueous solvent of the present invention, one of the above-exemplified non-aqueous solvents may be used alone, or two or more of them may be used in any combination and ratio.
For example, one of the preferred combinations of non-aqueous solvents is cyclic carbonate (provided, carbon-.
Cyclic carbonates with carbon unsaturated bonds and fluorine-containing cyclic carbonates are excluded. ) And a combination mainly composed of chain carbonate.

Among them, the total of the cyclic carbonate and the chain carbonate in the non-aqueous solvent is preferably 70% by volume or more, more preferably 80% by volume or more, still more preferably 90% by volume or more, and the cyclic carbonate and the chain carbonate. The ratio of the cyclic carbonate to the total of the above is preferably 5% by volume or more, more preferably 10% by volume or more, still more preferably 15% by volume.
Further, it is preferably 50% by volume or less, more preferably 35% by volume or less, still more preferably 30% by volume or less, and particularly preferably 25% by volume or less.

When a combination of these non-aqueous solvents is used, the balance between the cycle characteristics and the high temperature storage characteristics (particularly, the residual capacity after high temperature storage and the high load discharge capacity) of the battery produced by using the combination may be improved.
For example, a preferred combination of cyclic carbonate and chain carbonate is
Ethylene carbonate and dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and ethylmethyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and ethylmethyl carbonate, ethylene carbonate and diethyl carbonate and ethylmethyl carbonate, ethylene carbonate And dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate and the like.

Among the combinations of the cyclic carbonate and the chain carbonate, those containing asymmetric chain alkyl carbonates as the chain carbonate are more preferable, and in particular, ethylene carbonate, dimethyl carbonate and ethylmethyl carbonate, ethylene carbonate, diethyl carbonate and ethyl. Those containing ethylene carbonate, symmetric chain carbonates and asymmetric chain carbonates such as methyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate are preferable because they have a good balance between cycle characteristics and large current discharge characteristics.

Among these, the asymmetric chain carbonates are preferably ethylmethyl carbonates, and the alkyl groups of the chain carbonates are preferably 1 to 2 carbon atoms.

A combination of these ethylene carbonates and chain carbonates to which propylene carbonate is further added is also mentioned as a preferable combination.

When propylene carbonate is contained, the volume ratio of ethylene carbonate to propylene carbonate is preferably 99: 1 to 40:60, and particularly preferably 95: 5 to 50.
: 50. Further, the ratio of propylene carbonate to the total non-aqueous solvent is preferably 0.1% by volume or more, more preferably 1% by volume or more, further preferably 2% by volume or more, and preferably 20% by volume or less, more preferably. Is 8% by volume or less, more preferably 5% by volume or less.

It is preferable to contain propylene carbonate in this concentration range because the low temperature characteristics may be further excellent while maintaining the characteristics of the combination of ethylene carbonate and chain carbonate.

When the dimethyl carbonate is contained in the non-aqueous solvent, the ratio of the dimethyl carbonate in the total non-aqueous solvent is preferably 10% by volume or more, more preferably 20% by volume or more, still more preferably 25% by volume or more, particularly. It is preferably contained in an amount of 30% by volume or more, preferably 90% by volume or less, more preferably 80% by volume or less, still more preferably 75% by volume or less, and particularly preferably 70% by volume or less. The load characteristics of the battery may be improved.

Among these, by containing dimethyl carbonate and ethyl methyl carbonate and increasing the content of dimethyl carbonate to be higher than the content of ethyl methyl carbonate, the electric conductivity of the electrolytic solution can be maintained, and the battery characteristics after high temperature storage can be maintained. May be improved, which is preferable.

The volume ratio of dimethyl carbonate to ethyl methyl carbonate (dimethyl carbonate / ethyl methyl carbonate) in the total non-aqueous solvent is 1.1 or more in terms of improving the electrical conductivity of the electrolytic solution and improving the battery characteristics after storage. Is preferable, 1.5 or more is more preferable, and 2.5 or more is further preferable. The volume ratio (dimethyl carbonate / ethylmethyl carbonate) is preferably 40 or less, more preferably 20 or less, further preferably 10 or less, and particularly preferably 8 or less in terms of improving battery characteristics at low temperatures.

In the combination mainly composed of the above cyclic carbonate (excluding the cyclic carbonate having a carbon-carbon unsaturated bond and the fluorine-containing cyclic carbonate) and the chain carbonate, the cyclic carboxylic acid esters and the chain carboxylic acid esters, Other solvents such as cyclic ethers, chain ethers, sulfur-containing organic solvents, phosphorus-containing organic solvents, and aromatic fluorine-containing solvents may be mixed.

1-5. Auxiliary agent In the non-aqueous electrolyte battery of the present invention, an auxiliary agent may be appropriately used depending on the purpose in addition to the above compounds. Examples of the auxiliary agent include other auxiliary agents shown below.

1-5-1. Other Auxiliary Agents Other known auxiliary agents can be used for the non-aqueous electrolyte solution of the present invention. Other auxiliaries include carbonate compounds such as erythritan carbonate, spiro-bis-dimethylene carbonate, methoxyethyl-methyl carbonate; succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, anhydrous. Caroxyanhydrides such as itaconic acid, diglycolic anhydride, cyclohexanedicarboxylic acid anhydride, cyclopentanetetracarboxylic acid dianhydride and phenylsuccinic anhydride; 3,9-divinyl-2,4,8
, 10-Tetraoxaspiro [5.5] Spiro compounds such as undecane; Sulfur-containing compounds such as N, N-dimethylmethanesulfonate, N, N-diethylmethanesulfonamide; Triethyl phosphite, Triethyl phosphite, Phosphorus-containing compounds such as triphenyl phosphite, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, methyl dimethylphosphinate, ethyl diethylphosphinate, trimethylphosphin oxide, triethylphosphinoxide; 1-methyl-2-pyrrolidinone, Nitrogen-containing compounds such as 1-methyl-2-piperidone, 3-methyl-2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone and N-methylsuccinimide; Hydrocarbon compounds; 2-propynyl 2- (diethoxyphosphoryl) acetate, 1-methyl-2
-Propinyl 2- (diethoxyphosphoryl) acetate, 1,1-dimethyl-2-propynyl 2- (diethoxyphosphoryl) acetate, pentafluorophenylmethanesulfonate, pentafluorophenyltrifluoromethanesulfonate, pentafluorophenylacetate, trifluoroacetic acid Pentafluorophenyl, methylpentafluorophenyl carbonate, 2-propynyl 2- (methanesulfonyloxy) propionate, 2-methyl 2- (methanesulfonyloxy) propionate, 2-ethyl 2- (methanesulfonyloxy) propionate, methane 2-Propinyl sulfonyloxyacetic acid, 2-methyl methanesulfonyloxyacetic acid, 2-ethyl methanesulfonyloxyacetic acid, 2-ethyl methanesulfonyloxyacetic acid, 2-ethylmethyloxycarbonylphosphonate, lithium ethyl ethyloxycarbonylphosphonate, 2-propynyloxycarbonylphosphonate, lithium ethyl 2-propynyloxycarbonylphosphonate, 1-lithium ethyl Methyl-2-propynyloxycarbonylphosphonate, lithium ethyl
1,1-dimethyl-2-propynyloxycarbonylphosphonate, lithium methyl
Sulfate, Lithium Ethyl Sulfate, Lithium 2-Propinyl Sulfate, Lithium 1-Methyl-2-Propinyl Sulfate, Lithium 1,1-dimethyl-2-Propinyl Sulfate, Lithium 2,2,2-Trifluoroethyl Sulfate, Methyltrimethylsilyl Sulfate, Ethyl Trimethylsilyl Sulfate, 2-Propinyl Trimethylsilyl Sulfate, Dilithium Ethylene Disulfate, 2-Butin-1,4-Diyl Dimethanesulfonate, 2-Butin-
1,4-diyldiethanesulfonate, 2-butyne-1,4-diyldiformate,
2-Butin-1,4-diyl diacetate, 2-butyne-1,4-diyl dipropionate, 4-hexadiyne-1,6-diyl dimethanesulfonate, 2-propynyl
Methane sulfonate, 1-methyl-2-propynyl methane sulfonate, 1,1-dimethyl-2-propynyl methane sulfonate, 2-propynyl ethane sulfonate, 2
-Propinyl vinyl sulfonate, methyl 2-propynyl carbonate, ethyl
2-Propinyl Carbonate, Bis (2-Propinyl) Carbonate, Methyl 2-
Propinyl Ogizalate, Ethyl 2-Propinyl Ogizarate, Bis (2-Propinyl) Ogizarate, 2-Propinyl Acetate, 2-Propinyl Formate, 2-
Propinyl methacrylate, di (2-propynyl) glutarate, 2,2-dioxide-1,2-oxathiolan-4-yl acetate, 2,2-dioxide-1,2-oxathiolan-4-yl propionate, 5-methyl-1 , 2-Oxatiolan-4-
On 2,2-dioxide, 5,5-dimethyl-1,2-oxathiolan-4-one 2
, 2-Dioxide, 2-Isocyanatoethyl Acrylate, 2-Isocyanatoethyl
Methacrylate, 2-isocyanatoethyl crotonate, 2- (2-isocyanatoethoxy) ethyl acrylate, 2- (2-isocyanatoethoxy) ethyl methacrylate, 2- (2-isocyanatoethoxy) ethyl crotonate, 2-allyl anhydrous amber Acid, 2- (1-pentene-3-yl) anhydrous succinic acid, 2- (1-hexene-3-yl) sulphate anhydrous, 2- (1-heptene-3-yl) sulphate anhydrous, 2- ( 1-octene-3-yl) anhydrous succinic acid, 2- (1-nonene-3-yl) anhydrous succinic acid, 2- (3-butene-2)
-Il) anhydrous succinic acid, 2- (2-methylallyl) anhydrous succinic acid, 2- (3-methyl-3)
-Butene-2-yl) Anhydrous succinic acid and the like can be mentioned. Even if one of these is used alone, 2
Seeds or more may be used together. By adding these auxiliaries, the capacity retention characteristics and cycle characteristics after high temperature storage can be improved.

The blending amount of the other auxiliaries is not particularly limited and is arbitrary as long as the effects of the present invention are not significantly impaired. The other auxiliary agent is preferably 0.01% by mass in 100% by mass of the non-aqueous electrolyte solution.
It is the above, and it is 5% by mass or less. Within this range, the effects of other auxiliaries are likely to be sufficiently exhibited, and it is easy to avoid situations such as deterioration of battery characteristics such as high load discharge characteristics. The blending amount of the other auxiliary agent is more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, still more preferably 3% by mass or less, still more preferably 1% by mass or less. ..

2. 2. Energy storage device using a non-aqueous electrolyte solution The electricity storage device using the non-aqueous electrolyte solution of the present invention has a positive electrode, a negative electrode, a compound represented by the formula (1) as an electrolyte in a non-aqueous solvent, and carbon-carbon non-carbon. It is characterized by comprising a non-aqueous electrolyte solution in which at least one compound selected from the group consisting of a cyclic carbonate having a saturated bond and a fluorine-containing cyclic carbonate is dissolved.

The power storage device using the non-aqueous electrolyte solution of the present invention includes a lithium battery, a polyvalent cation battery, a metal air secondary battery, a secondary battery using an s-block metal other than the above, a lithium ion capacitor, and an electric double layer capacitor. Is preferable, a lithium battery and a lithium ion capacitor are more preferable, and a lithium battery is further preferable.

It is also preferable that the non-aqueous electrolyte solution used in these power storage devices is a so-called gel electrolyte that is pseudo-solidified with a polymer, a filler, or the like. The lithium salt of the present invention can also be used as an electrolyte salt of a solid electrolyte.

2-1. Lithium battery The lithium battery using the non-aqueous electrolyte solution of the present invention is provided on the current collector and the positive electrode having a positive electrode active material layer provided on the current collector, and on the current collector and the current collector. It comprises a negative electrode having a negative electrode active material layer and capable of storing and releasing ions, and the above-mentioned non-aqueous electrolyte solution of the present invention. The lithium battery in the present invention is a general term for a lithium primary battery and a lithium secondary battery.

<2-1-1. Battery configuration>
The lithium battery of the present invention has the same configuration as the conventionally known lithium battery except for the above-mentioned non-aqueous electrolyte solution of the present invention. Usually, the positive electrode and the negative electrode are laminated via a porous membrane (separator) impregnated with the non-aqueous electrolyte solution of the present invention, and these have a form of being housed in a case (exterior body). Therefore, the shape of the lithium battery of the present invention is not particularly limited, and may be any of a cylindrical type, a square type, a laminated type, a coin type, a large size, and the like.

2-1-2. Non-aqueous electrolytic solution As the non-aqueous electrolytic solution, the above-mentioned non-aqueous electrolytic solution of the present invention is used. It is also possible to mix and use other non-aqueous electrolytic solutions with the non-aqueous electrolytic solution of the present invention as long as the gist of the present invention is not deviated.

2-1-3. Negative electrode The negative electrode has a negative electrode active material layer on the current collector, and the negative electrode active material layer contains a negative electrode active material. Hereinafter, the negative electrode active material will be described.

The negative electrode active material is not particularly limited as long as it can electrochemically release metal ions. The negative electrode active material used in the lithium primary cell is not particularly limited as long as it can electrochemically release lithium ions. A specific example thereof is metallic lithium. The negative electrode active material used in the lithium secondary battery is not particularly limited as long as it can electrochemically occlude and release metal ions (for example, lithium ions). Specific examples of the negative electrode active material capable of releasing lithium ions include carbonaceous materials, alloy-based materials, lithium-containing metal composite oxide materials, and the like. These may be used alone or in combination of two or more.

<Negative electrode active material>
Examples of the negative electrode active material include carbonaceous materials, alloy-based materials, lithium-containing metal composite oxide materials and the like.

As a carbonaceous material used as a negative electrode active material,
(1) Natural graphite,
(2) A carbonaceous material obtained by heat-treating an artificial carbonaceous substance and an artificial graphite substance at least once in the range of 400 to 3200 ° C.
(3) A carbonaceous material in which the negative electrode active material layer is composed of at least two or more kinds of carbonaceous substances having different crystallinity and / or has an interface in which the carbonaceous substances having different crystalline properties are in contact with each other.
(4) A carbonaceous material in which the negative electrode active material layer is composed of at least two or more kinds of carbonaceous substances having different orientations and / or has an interface in which the carbonaceous substances having different orientations are in contact with each other.
The one selected from the above is preferable because it has a good balance between the initial irreversible capacity and the high current density charge / discharge characteristics. Further, as the carbonaceous materials (1) to (4), one kind may be used alone, or two or more kinds may be used in any combination and ratio.

The artificial carbonaceous material and the artificial graphite material in (2) above include natural graphite, coal-based coke, petroleum-based coke, coal-based pitch, petroleum-based pitch, and those obtained by oxidizing these pitches.
Pyrolysis of organic substances such as needle coke, pitch coke and partially graphitized carbon material, furnace black, acetylene black, and pitch carbon fiber, carbonizable organic substances and their carbonized substances, or carbonizable organic substances are benzene. , A solution dissolved in a low molecular weight organic solvent such as toluene, xylene, quinoline, n-hexane, and carbonized products thereof.

As alloy-based materials used as negative electrode active materials, if lithium can be occluded and released, lithium alone, single metals and alloys forming lithium alloys, or their oxides, carbides, nitrides, silicides, and sulfides. It may be either a substance or a compound such as a phospho compound, and is not particularly limited. The single metal and alloy forming the lithium alloy are preferably materials containing group 13 and group 14 metal / semi-metal elements (that is, excluding carbon), and more preferably aluminum, silicon and tin (hereinafter, "". It is a single metal (which may be abbreviated as "specific metal element") and an alloy or compound containing these atoms. These may be used alone or in combination of two or more in any combination and ratio.

As the negative electrode active material having at least one kind of atom selected from the specific metal element, one kind or two or more kinds of specific metal elements of any one kind of specific metal element, an alloy consisting of two or more kinds of specific metal elements are specified. Alloys consisting of metal elements and one or more other metal elements, as well as
Compounds containing one or more specific metal elements, and oxides and carbides of the compounds,
Examples include composite compounds such as nitrides, silicides, sulfides or phosphides. By using these metal simple substances, alloys or metal compounds as the negative electrode active material, it is possible to increase the capacity of the battery.

In addition, a compound in which these composite compounds are complicatedly bonded to several kinds of elements such as elemental metals, alloys or non-metal elements can also be mentioned. Specifically, for example, in silicon and tin, an alloy of these elements and a metal that does not operate as a negative electrode can be used. For example, in the case of tin, it is possible to use a complex compound containing 5 to 6 kinds of elements in combination with a metal that acts as a negative electrode other than tin and silicon, a metal that does not act as a negative electrode, and a non-metal element. can.

Among these negative electrode active materials, since the capacity per unit mass is large when made into a battery, a single metal of any one specific metal element, an alloy of two or more specific metal elements, and oxidation of a specific metal element. Materials, carbides, nitrides and the like are preferable, and silicon and / or tin metal alone, alloys, oxides and carbides, nitrides and the like are particularly preferable from the viewpoint of capacity per unit mass and environmental load.

The lithium-containing metal composite oxide material used as the negative electrode active material is not particularly limited as long as it can store and release lithium, but a material containing titanium and lithium is preferable from the viewpoint of high current density charge / discharge characteristics. A lithium-containing composite metal oxide material containing titanium is more preferable, and a composite oxide of lithium and titanium (hereinafter, may be abbreviated as "lithium titanium composite oxide"). That is, it is particularly preferable to use a lithium-titanium composite oxide having a spinel structure in a negative electrode active material for a power storage device because the output resistance is greatly reduced.

In addition, lithium and titanium of the lithium-titanium composite oxide are other metal elements such as Na.
, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb are preferably substituted with at least one element selected from the group.
The metal oxide is a lithium-titanium composite oxide represented by the formula (A), and in the formula (A), 0.7 ≦ x ≦ 1.5, 1.5 ≦ y ≦ 2.3, 0 ≦ It is preferable that z ≦ 1.6 because the structure at the time of doping / dedoping of lithium ions is stable.

Li _{x Ty M z O 4} (A)
[In the formula (A), M is Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Z.
Represents at least one element selected from the group consisting of n and Nb. ]

Among the compositions represented by the above formula (A),
(A) 1.2 ≦ x ≦ 1.4, 1.5 ≦ y ≦ 1.7, z = 0
(B) 0.9 ≦ x ≦ 1.1, 1.9 ≦ y ≦ 2.1, z = 0
(C) 0.7 ≦ x ≦ 0.9, 2.1 ≦ y ≦ 2.3, z = 0
This structure is particularly preferable because it has a good balance of battery performance.

A particularly preferable representative composition of the above compound is Li _4/3 Ti _5/3 O ₄ in (a), (
In b), it is Li ₁ Ti ₂ O ₄ , and in (c), it is Li _4/5 Ti _11/5 O ₄ . Also, Z ≠
As for the structure of 0, for example, Li _4/3 Ti _4/3 Al _1/3 O ₄ is preferable.

<Physical characteristics of carbonaceous materials>
When a carbonaceous material is used as the negative electrode active material, it is desirable that the material has the following physical properties.

(X-ray parameter)
The d value (interlayer distance) of the lattice planes (002 planes) obtained by X-ray diffraction of carbonaceous materials is preferably 0.335 nm or more, and usually 0.360 nm or less, which is 0.
.. It is preferably 350 nm or less, and more preferably 0.345 nm or less. The crystallite size (Lc) of the carbonaceous material determined by X-ray diffraction by the Gakushin method is preferably 1.0 nm or more, and more preferably 1.5 nm or more.

(Volume-based average particle size)
The mass-based average particle size of the carbonaceous material is a volume-based average particle size (median diameter) obtained by a laser diffraction / scattering method, and is usually 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, and further preferably 7 μm. The above is particularly preferable, and is usually 100 μm or less, 50 μm or less.
It is preferably m or less, more preferably 40 μm or less, further preferably 30 μm or less, and 25 μm or less.
M or less is particularly preferable.

If the volume-based average particle size is below the above range, the irreversible capacity may increase, resulting in a loss of initial battery capacity. On the other hand, if it exceeds the above range, a non-uniform coating surface tends to be formed when the electrode is produced by coating, which may not be desirable in the battery manufacturing process.
To measure the volume-based average particle size, laser diffraction / scattering particle size distribution is performed by dispersing carbon powder in a 0.2 mass% aqueous solution (about 10 mL) of polyoxyethylene (20) sorbitan monolaurate, which is a surfactant. This is performed using a total (LA-700 manufactured by HORIBA, Ltd.).

(Raman R value, Raman half width)
The Raman R value of the carbonaceous material is a value measured by the argon ion laser Raman spectral method, and is usually 0.01 or more, preferably 0.03 or more, more preferably 0.1 or more, and usually. It is 1.5 or less, preferably 1.2 or less, and more preferably 1 or less.
0.5 or less is particularly preferable.

The full width at half maximum of Raman around 1580 cm ^-1 of carbonaceous material is not particularly limited, but is usually 10 cm ^-1 or more, preferably 15 cm ^-1 or more, and usually 100 cm ^-1 or less, 80 cm ^-1 or less. It is preferably 60 cm ^-1 or less, more preferably 40 cm ^-1 or less.
The following are particularly preferred.

The Raman R value and the Raman half price range are indicators of the crystallinity of the surface of the carbonaceous material, but the carbonaceous material has appropriate crystallinity from the viewpoint of chemical stability, and Li enters by charging and discharging. It is preferable that the crystallinity is such that the site between the layers is not lost, that is, the charge acceptability is not deteriorated. When the negative electrode is densified by pressing after being applied to the current collector, it is preferable to take this into consideration because the crystals tend to be oriented in the direction parallel to the electrode plate. Raman R
When the value or the full width at half maximum of Raman is in the above range, a suitable film can be formed on the surface of the negative electrode to improve the storage characteristics, cycle characteristics, and load characteristics, and the efficiency is lowered due to the reaction with the non-aqueous electrolyte solution. And gas generation can be suppressed.

The Raman spectrum is measured using a Raman spectroscope (Raman spectroscope manufactured by Nippon Spectroscopy Co., Ltd.), in which the sample is naturally dropped into the measurement cell and filled, and the surface of the sample in the cell is irradiated with an argon ion laser beam. This is done by rotating the cell in a plane perpendicular to the laser beam. Regarding the obtained Raman spectrum, the intensity IA of the peak PA near 1580 cm ^-1 and 1
The intensity IB of the peak PB near 360 cm ^-1 was measured, and the intensity ratio R (R = IB / IA) was measured.
) Is calculated.

The Raman measurement conditions described above are as follows.
-Argon ion laser wavelength: 514.5 nm
-Laser power on the sample: 15-25mW
・ Resolution: 10 to 20 cm ^-1
-Measurement range: 1100 cm ^-1 to 1730 cm ^-1
・ Raman R value, Raman half width analysis: Background processing ・ Smoothing processing: Simple average, convolution 5 points

(BET specific surface area)
The BET specific surface area of the carbonaceous material is a value of the specific surface area measured by the BET method, and is usually 0.1 m ² · g ^-1 or more, preferably 0.7 m ² · g ^-1 or more. 0m ²・ g ^－
1 or more is more preferable, 1.5 m ² · g ^-1 or more is particularly preferable, and usually 100 m ² or more.
It is g ^-1 or less, preferably 25 m ² · g ^-1 or less, more preferably 15 m ² · g ^-1 or less, and particularly preferably 10 m ² · g ^-1 or less. When the value of the BET specific surface area is in the above range, the precipitation of lithium on the electrode surface can be suppressed, while the gas generation due to the reaction with the non-aqueous electrolyte solution can be suppressed.

To measure the specific surface area by the BET method, a surface area meter (fully automatic surface area measuring device manufactured by Okura Riken) is used to pre-dry the sample at 350 ° C for 15 minutes under nitrogen flow, and then nitrogen to atmospheric pressure is measured. Using a nitrogen-helium mixed gas accurately prepared so that the relative pressure value is 0.3, the nitrogen adsorption BET 1-point method by the gas flow method is performed.

(Circularity)
When the circularity is measured as the degree of sphere of the carbonaceous material, it is preferably within the following range. The circularity is "circularity = (perimeter of a corresponding circle having the same area as the projected particle shape) /
(Actual perimeter of the projected particle shape) ”, and when the circularity is 1, it becomes a theoretical true sphere.
The circularity of the particles in the carbonaceous material having a particle size in the range of 3 to 40 μm is preferably as close as 1, preferably 0.1 or more, particularly preferably 0.5 or more, and more preferably 0.8 or more.
0.85 or more is more preferable, and 0.9 or more is particularly preferable. As for the high current density charge / discharge characteristics, the larger the circularity, the better the filling property and the resistance between the particles can be suppressed, so that the high current density charge / discharge characteristics are improved. Therefore, it is preferable that the circularity is as high as the above range.

The circularity is measured using a flow type particle image analyzer (FPIA manufactured by Sysmex Corporation). About 0.2 g of the sample is dispersed in a 0.2 mass% aqueous solution (about 50 mL) of polyoxyethylene (20) sorbitan monolaurate as a surfactant, and an ultrasonic wave of 28 kHz is output 60.
After irradiation with W for 1 minute, the detection range is specified to 0.6 to 400 μm, and particles having a particle size in the range of 3 to 40 μm are measured.

The method for improving the circularity is not particularly limited, but a spherical shape is preferable because the shape of the interparticle voids when the electrode body is formed is adjusted. Examples of the spheroidizing treatment include a method of mechanically approaching a spherical shape by applying a shearing force and a compressive force, and a mechanical / physical treatment method of granulating a plurality of fine particles by a binder or the adhesive force of the particles themselves. Can be mentioned.

(Tap density)
The tap density of carbonaceous materials is usually 0.1 g · cm ^-3 or higher, and 0.5 g · cm ^-3 .
The above is preferable, 0.7 g · cm ^-3 or more is more preferable, 1 g · cm ^-3 or more is particularly preferable, 2 g · cm ^-3 or less is preferable, and 1.8 g · cm ^-3 or less is further preferable. 6.6 g · cm ^-3 or less is particularly preferable. When the tap density is in the above range, the battery capacity can be secured and the increase in resistance between particles can be suppressed.

To measure the tap density, pass through a sieve with a mesh opening of 300 μm, drop the sample into a tapping cell of 20 cm ³ to fill the sample up to the upper end surface of the cell, and then use a powder density measuring instrument (for example, manufactured by Seishin Enterprise Co., Ltd.). Using a tap densor), tapping with a stroke length of 10 mm is 100.
Perform 0 times, and calculate the tap density from the mass at that time and the mass of the sample.

(Orientation ratio)
The orientation ratio of the carbonaceous material is usually 0.005 or more, preferably 0.01 or more, preferably 0.0.
It is more preferably 15 or more, and usually 0.67 or less. When the orientation ratio is in the above range, excellent high-density charge / discharge characteristics can be ensured. The upper limit of the above range is the theoretical upper limit of the orientation ratio of the carbonaceous material.

The orientation ratio is measured by X-ray diffraction after pressure molding the sample. 0.47 g of sample with a diameter of 1
The molded body obtained by filling in a 7 mm molding machine and compressing with 58.8 MN · m ^-2 is set using clay so as to be flush with the surface of the sample holder for measurement, and X-ray diffraction is measured. .. From the peak intensities of (110) diffraction and (004) diffraction of the obtained carbon, (110) diffraction peak intensity / (
004) Calculate the ratio expressed by the diffraction peak intensity.

The X-ray diffraction measurement conditions are as follows. In addition, "2θ" indicates a diffraction angle.
・ Target: Cu (Kα ray) Graphite monochromator ・ Slit:
Divergence slit = 0.5 degrees Light receiving slit = 0.15 mm
Scattering slit = 0.5 degrees ・ Measurement range and step angle / measurement time:
(110) Surface: 75 degrees ≤ 2θ ≤ 80 degrees 1 degree / 60 seconds (004) Surface: 52 degrees ≤ 2θ ≤ 57 degrees 1 degree / 60 seconds

(Aspect ratio (powder))
The aspect ratio of the carbonaceous material is usually 1 or more, usually 10 or less, preferably 8 or less, and even more preferably 5 or less. Within the above range, streaks are suppressed during electrode plate formation, and more uniform coating is possible, so that excellent high current density charge / discharge characteristics can be ensured. The lower limit of the above range is the theoretical lower limit of the aspect ratio of the carbonaceous material.

The aspect ratio is measured by magnifying and observing particles of a carbonaceous material with a scanning electron microscope. Arbitrary 50 graphite particles fixed to the end face of a metal having a thickness of 50 μm or less are selected, and the stage on which the sample is fixed is rotated and tilted for each of them, and the carbonaceous material particles are observed three-dimensionally. The longest diameter A and the shortest diameter B orthogonal to the diameter A are measured, and the average value of A / B is obtained.

<Construction and manufacturing method of negative electrode>
Any known method can be used for producing the electrode as long as the effect of the present invention is not significantly impaired. For example, a binder, a solvent, and if necessary, a thickener, a conductive material, a filler, etc. are added to a negative electrode active material to form a slurry, which is applied to a current collector, dried, and then pressed to form a slurry. Can be done.

When an alloy-based material is used, a method such as a thin-film deposition method, a sputtering method, or a plating method may be used.
A method of forming a thin film layer (negative electrode active material layer) containing the above-mentioned negative electrode active material is also used.

(Current collector)
As the current collector for holding the negative electrode active material, a known one can be arbitrarily used. Examples of the current collector of the negative electrode include metal materials such as aluminum, copper, nickel, stainless steel, and nickel-plated steel, but copper is particularly preferable from the viewpoint of ease of processing and cost.

When the collector is made of a metal, the shape of the current collector may be, for example, a metal foil, a metal column, a metal coil, a metal plate, a metal thin film, an expanded metal, a punch metal, a foamed metal, or the like. Among them, a metal thin film is preferable, a copper foil is more preferable, and a rolled copper foil by a rolling method and an electrolytic copper foil by an electrolytic method are more preferable, both of which can be used as a current collector.

The thickness of the current collector is usually 1 μm or more, preferably 5 μm or more, and usually 100 μm or less, preferably 50 μm or less, from the viewpoint of securing battery capacity and handleability.

(Ratio of thickness between current collector and negative electrode active material layer)
The ratio of the thickness of the current collector to the negative electrode active material layer is not particularly limited, but the value of "(thickness of the negative electrode active material layer on one side immediately before the injection of the non-aqueous electrolyte solution) / (thickness of the current collector)". However, 150 or less is preferable, 20 or less is further preferable, 10 or less is particularly preferable, 0.1 or more is further preferable, 0.4 or more is further preferable, and 1 or more is particularly preferable. When the ratio of the thickness of the current collector to the negative electrode active material layer is within the above range, the battery capacity can be secured and the heat generation of the current collector during high current density charging / discharging can be suppressed.

(Binder)
The binder for binding the negative electrode active material is not particularly limited as long as it is a non-aqueous electrolyte solution or a material that is stable to the solvent used in the production of the electrode.
Specific examples include resin-based polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethylmethacrylate, aromatic polyamide, polyimide, cellulose, and nitrocellulose; SBR (styrene butadiene rubber), isoprene rubber, butadiene rubber, fluororubber, and NBR. (Acrylonitrile-butadiene rubber), rubber-like polymers such as ethylene / propylene rubber; styrene / butadiene / styrene block copolymer or hydrogen additive thereof; EPDM (ethylene / propylene / diene ternary copolymer), styrene / ethylene -Polyplastic elastomeric polymers such as butadiene-styrene copolymer, styrene-isoprene-styrene block copolymer or hydrogenated products thereof; syndiotactic-1,2-polybutadiene, polyvinyl acetate, ethylene and vinyl acetate Soft resinous polymers such as polymers and propylene / α-olefin copolymers; Fluorine-based polymers such as polyvinylidene fluoride, polytetrafluoroethylene, fluorinated polyvinylidene fluoride, and polytetrafluoroethylene / ethylene copolymers; Examples thereof include a polymer composition having ionic conductivity of alkali metal ions (particularly lithium ions). These may be used alone or in combination of two or more in any combination and ratio.

The ratio of the binder to the negative electrode active material is preferably 0.1% by mass or more, preferably 0.5% by mass.
The above is further preferable, 0.6% by mass or more is particularly preferable, 20% by mass or less is preferable, 15% by mass or less is more preferable, 10% by mass or less is further preferable, and 8% by mass or less is particularly preferable. When the ratio of the binder to the negative electrode active material is within the above range, the battery capacity and the strength of the negative electrode can be sufficiently secured.

In particular, when a rubbery polymer typified by SBR is contained in the main component, the ratio of the binder to the negative electrode active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, and is 0. It is more preferably 6.6% by mass or more, and usually 5% by mass or less, preferably 3% by mass or less, and further preferably 2% by mass or less. When a fluoropolymer represented by polyvinylidene fluoride is contained in the main component, the ratio to the negative electrode active material is usually 1% by mass or more, preferably 2% by mass or more, and further 3% by mass or more. It is preferable, and usually it is 15% by mass or less, preferably 10% by mass or less, and further preferably 8% by mass or less.

(Slurry forming solvent)
The solvent for forming the slurry is particularly limited as long as it is a solvent capable of dissolving or dispersing the negative electrode active material, the binder, and the thickener and the conductive material used as needed. Instead, either an aqueous solvent or an organic solvent may be used.
Examples of the aqueous solvent include water and alcohol, and examples of the organic solvent include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methylethylketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N, N-. Examples thereof include dimethylaminopropylamine, tetrahydrofuran (THF), toluene, acetone, diethyl ether, hexamethylphosphalamide, dimethyl sulfoxide, benzene, xylene, quinoline, pyridine, methylnaphthalene, hexane and the like.
In particular, when an aqueous solvent is used, it is preferable to contain a dispersant or the like together with the thickener and to make a slurry using a latex such as SBR. As these solvents, one type may be used alone, or two or more types may be used in any combination and ratio.

(Thickener)
Thickeners are typically used to adjust the viscosity of the slurry. The thickener is not particularly limited, and specific examples thereof include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof. These may be used alone or in combination of two or more in any combination and ratio.

When a thickener is further used, the ratio of the thickener to the negative electrode active material is usually 0.1% by mass.
As described above, 0.5% by mass or more is preferable, 0.6% by mass or more is further preferable, and usually 5% by mass or less, 3% by mass or less is preferable, and 2% by mass or less is further preferable. When the ratio of the thickener to the negative electrode active material is within the above range, it is possible to suppress a decrease in battery capacity and an increase in resistance, and it is possible to secure good coatability.

(Electrode density)
The electrode structure when the negative electrode active material is converted into an electrode is not particularly limited, but the density of the negative electrode active material existing on the current collector is preferably 1 g · cm ^-3 or more, and 1.2 g · cm ^-3 or more. Is more preferable, 1.3 g · cm ^-3 or more is particularly preferable, 2.2 g · cm ^-3 or less is preferable, 2.1 g · cm ^-3 or less is more preferable, and 2.0 g · cm ^-3 or less is more preferable. More preferably, 1.9 g · cm ^-3 or less is particularly preferable. When the density of the negative electrode active material existing on the current collector is within the above range, the destruction of the negative electrode active material particles is prevented, the initial irreversible capacity is increased, and the vicinity of the current collector / negative electrode active material interface is reached. While it is possible to suppress the deterioration of high current density charge / discharge characteristics due to the decrease in permeability of the non-aqueous electrolyte solution, it is possible to suppress the decrease in battery capacity and the increase in resistance.

(Thickness of negative electrode plate)
The thickness of the negative electrode plate is designed according to the positive electrode plate to be used, and is not particularly limited, but the thickness of the mixture layer after subtracting the metal leaf thickness of the core material is usually 15 μm or more, preferably 20 μm or more.
m or more, more preferably 30 μm or more, and usually 300 μm or less, preferably 280 μm
It is preferably m or less, more preferably 250 μm or less.

(Surface coating of negative electrode plate)
Further, a substance having a composition different from that attached to the surface of the negative electrode plate may be used. Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide and other oxides, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate and calcium sulfate. , Sulfates such as aluminum sulfate, carbonates such as lithium carbonate, calcium carbonate, magnesium carbonate and the like.

2-1-4. Positive electrode The positive electrode has a positive electrode active material layer on the current collector, and the positive electrode active material layer contains a positive electrode active material. Hereinafter, the positive electrode active material will be described.

<Positive electrode active material>
(composition)
The positive electrode active material is not particularly limited as long as it can electrochemically occlude metal ions. The positive electrode active material used in the lithium primary battery is not particularly limited as long as it can electrochemically occlude lithium ions. Specific examples thereof include graphite fluoride, manganese dioxide, thionyl chloride, iron disulfide, and copper oxide.

The positive electrode active material used in the lithium secondary battery is not particularly limited as long as it can electrochemically occlude and release metal ions (for example, lithium ions), but for example, lithium and at least one kind of transition metal. A substance containing the above is preferable. Specific examples include a lithium transition metal composite oxide and a lithium-containing transition metal phosphoric acid compound. These may be used alone or in combination of two or more.

The transition metals of the lithium transition metal composite oxide include V, Ti, Cr, Mn, Fe, Co,
Ni, Cu and the like are preferable, and specific examples thereof include a lithium-cobalt composite oxide such as LiCoO ₂ , a lithium-nickel composite oxide such as LiNiO ₂ , LiMnO ₂ , and LiMn ₂ O ₄ .
, Li ₂ MnO ₄ and other lithium-manganese composite oxides, LiNi _1/3 Mn _1/3 Co ₁
Lithium-nickel-manganese-cobalt composite oxides such as _{/ 3} O ₂ , LiNi _0.5 Mn _0.3 Co _0.2 O ₂ , and some of the transition metal atoms that are the main constituents of these lithium transition metal composite oxides. Na, K, B, F, Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, C
Examples thereof include those substituted with other elements such as u, Zn, Mg, Ga, Zr, Si, Nb, Mo, Sn and W. Substituted ones are LiNi _0.5 Mn _0.5 O ₂ and LiNi ₀ .
_{.. 85} Co _0.10 Al _0.05 O ₂ , LiNi _0.33 Co _0.33 Mn _0.33 O ₂
, LiNi _0.45 Co _0.10 Al _0.45 O ₂ , LiMn _1.8 Al _0.2 O ₄ , L
IMn _1.5 Ni _0.5 O ₄ and the like can be mentioned.

Transition Metals of Lithium-Containing Transition Metals The transition metals of phosphoric acid compounds include V, Ti, Cr, Mn, and Fe.
, Co, Ni, Cu and the like are preferable, and specific examples thereof include LiFePO ₄ , Li ₃ Fe ₂ (P).
O ₄ ) ₃ , iron phosphates such as LiFeP ₂ O ₇ , cobalt phosphates such as LiCoPO ₄ , and some of the transition metal atoms that are the main constituents of these lithium transition metal phosphate compounds are Al, Ti, V.
, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb, Si and the like substituted with other elements.

Further, it is preferable to include lithium phosphate in the positive electrode active material because the continuous charging characteristics are improved. Although the use of lithium phosphate is not limited, it is preferable to use a mixture of the above-mentioned positive electrode active material and lithium phosphate. The lower limit of the amount of lithium phosphate used is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass, based on the total of the positive electrode active material and lithium phosphate. % Or more, and the upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less.

(Surface coating)
Further, a substance having a composition different from that attached to the surface of the positive electrode active material may be used. Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide and other oxides, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate and calcium sulfate. , Sulfates such as aluminum sulfate, carbonates such as lithium carbonate, calcium carbonate, magnesium carbonate, carbon and the like.

These surface-adhering substances are, for example, dissolved or suspended in a solvent and impregnated and added to the positive electrode active material.
The method includes a method of drying, a method of dissolving or suspending a surface-adhering substance precursor in a solvent, impregnating and adding to the positive electrode active material, and then reacting by heating or the like, a method of adding to the positive electrode active material precursor and simultaneously firing. It can be attached to the surface of the positive electrode active material. In addition, when carbon is attached, a method of mechanically attaching carbonaceous material later in the form of activated carbon or the like can also be used.

The amount of the surface-adhering substance is the mass with respect to the positive electrode active material, and the lower limit is preferably 0.
It is used at 1 ppm or more, more preferably 1 ppm or more, further preferably 10 ppm or more, and the upper limit is preferably 20% or less, more preferably 10% or less, still more preferably 5% or less. The surface-adhering substance can suppress the oxidation reaction of the electrolytic solution on the surface of the positive electrode active material and improve the battery life, but if the adhering amount is too small, the effect is not sufficiently exhibited and many If it is too much, the resistance may increase because it blocks the ingress and egress of lithium ions.
In the present invention, a substance having a different composition attached to the surface of the positive electrode active material is also referred to as a “positive electrode active material”.

(shape)
Examples of the shape of the particles of the positive electrode active material include lumps, polyhedra, spheres, elliptical spheres, plates, needles, and columns as conventionally used. Further, the primary particles may be aggregated to form secondary particles.

(Tap density)
The tap density of the positive electrode active material is preferably 0.5 g / cm ³ or more, more preferably 0.8.
It is g / cm ³ or more, more preferably 1.0 g / cm ³ or more. When the tap density of the positive electrode active material is within the above range, the amount of the dispersion medium required for forming the positive electrode active material layer and the required amount of the conductive material and the binder can be suppressed, and as a result, the filling rate of the positive electrode active material and the battery can be suppressed. Capacity can be secured.
By using the composite oxide powder having a high tap density, a high-density positive electrode active material layer can be formed. Generally, the larger the tap density is, the more preferable it is, and there is no particular upper limit, but preferably 4.0 g / cm ³ or less, more preferably 3.7 g / cm ³ or less, still more preferably 3.5 g.
/ Cm ³ or less. Within the above range, deterioration of load characteristics can be suppressed.

In the present invention, the tap density is defined as the powder filling density (tap density) g / cc when 5 to 10 g of the positive electrode active material powder is placed in a 10 ml glass graduated cylinder and tapped 200 times with a stroke of about 20 mm. Ask.

(Mesian diameter d50)
The median diameter d50 (secondary particle diameter when the primary particles are aggregated to form secondary particles) of the particles of the positive electrode active material is preferably 0.3 μm or more, more preferably 0.5 μm or more, still more preferable. Is 0.8 μm or more, most preferably 1.0 μm or more, and the upper limit is preferably 30 μm or less, more preferably 27 μm or less, still more preferably 25 μm or less, and most preferably 22 μm or less. Within the above range, a high tap density product can be obtained, and deterioration of battery performance can be suppressed. On the other hand, when the positive electrode of the battery is manufactured, that is, when the active material and the conductive material, the binder, etc. are made into a slurry with a solvent and applied in a thin film form. , Problems such as streaks can be prevented. Here, by mixing two or more kinds of the positive electrode active materials having different median diameters d50, the filling property at the time of producing the positive electrode can be further improved. In the present invention, the median diameter d50 is measured by a known laser diffraction / scattering type particle size distribution measuring device. HORIBA as a particle size distribution meter
When LA-920 manufactured by the company is used, a 0.1 mass% sodium hexametaphosphate aqueous solution is used as a dispersion medium used for the measurement, and the measured refractive index is set to 1.24 after ultrasonic dispersion for 5 minutes. ..

(Average primary particle size)
When the primary particles are aggregated to form secondary particles, the average primary particle diameter of the positive electrode active material is preferably 0.05 μm or more, more preferably 0.1 μm or more, still more preferably 0. It is 2 μm or more, and the upper limit is preferably 5 μm or less, more preferably 4 μm or less.
It is more preferably 3 μm or less, and most preferably 2 μm or less. Within the above range, the powder filling property and the specific surface area can be secured and the deterioration of the battery performance can be suppressed, while the reversibility of charge / discharge can be ensured by obtaining an appropriate crystallinity. .. In the present invention, the primary particle size is measured by observation using a scanning electron microscope (SEM). Specifically, in a photograph with a magnification of 10000 times, the longest value of the intercept by the left and right boundary lines of the primary particles with respect to the horizontal straight line is obtained for any 50 primary particles, and the average value is taken. Be done.

(BET specific surface area)
The BET specific surface area of the positive electrode active material is preferably 0.1 m ² / g or more, more preferably 0.
2 m ² / g or more, more preferably 0.3 m ² / g or more, and the upper limit is 50 m ² / g or less.
It is preferably 40 m ² / g or less, more preferably 30 m ² / g or less. When the BET specific surface area is in the above range, the battery performance can be ensured and the coatability of the positive electrode active substance can be kept good. In the present invention, the BET specific surface area is determined by pre-drying the sample at 150 ° C. for 30 minutes under nitrogen flow using a surface area meter (for example, a fully automatic surface area measuring device manufactured by Okura Riken), and then atmospheric pressure. It is defined by the value measured by the nitrogen adsorption BET 1-point method by the gas flow method using a nitrogen helium mixed gas accurately prepared so that the value of the relative pressure of nitrogen with respect to the gas is 0.3.

(Manufacturing method of positive electrode active material)
As a method for producing a positive electrode active material, a general method is used as a method for producing an inorganic compound.
In particular, various methods can be considered for producing a spherical or elliptical spherical active material. For example, a raw material for a transition metal is dissolved or pulverized and dispersed in a solvent such as water, and the pH is adjusted while stirring. After preparing and recovering a spherical precursor and drying it as needed, LiOH and Li ₂ CO
_3. Examples thereof include a method of adding a Li source such as LiNO ₃ and firing at a high temperature to obtain an active substance.

For the production of the positive electrode, the above-mentioned positive electrode active material may be used alone, or one or more of different compositions may be used in combination or in any combination or ratio. A preferred combination in this case is LiMn ₂ O ₄ such as LiCoO ₂ and LiNi _0.33 Co _0.33 Mn _0.33 O ₂ .
Alternatively, it may be combined with a part of this Mn substituted with another transition metal or the like, or L.
Examples thereof include a combination of iCoO ₂ or a part of this Co substituted with another transition metal or the like.

<Construction and manufacturing method of positive electrode>
The configuration of the positive electrode will be described below. In the present invention, the positive electrode can be produced by forming a positive electrode active material layer containing a positive electrode active material and a binder on a current collector. The positive electrode using the positive electrode active material can be manufactured by a conventional method. That is, a positive electrode active material, a binder, and if necessary, a conductive material and a thickener are mixed in a dry manner to form a sheet, which is then pressure-bonded to the positive electrode current collector, or these materials are used as a liquid medium. A positive electrode can be obtained by forming a positive electrode active material layer on the current collector by applying the slurry as a slurry to the positive electrode current collector and drying it.

The content of the positive electrode active material in the positive electrode active material layer is preferably 80% by mass or more, more preferably 82% by mass or more, and particularly preferably 84% by mass or more. The upper limit is preferably 99.
It is mass% or less, more preferably 98% by mass or less. Within the above range, the electric capacity of the positive electrode active material in the positive electrode active material layer can be secured, and the strength of the positive electrode can be maintained. Application,
The positive electrode active material layer obtained by drying is preferably consolidated by a hand press, a roller press, or the like in order to increase the packing density of the positive electrode active material. The density of the positive electrode active material layer is preferably 1.5 g / cm ³ or more as a lower limit, more preferably 2 g / cm ³ or more, still more preferably 2.2 g / cm ³ or more as a lower limit, and preferably 5 g / cm as an upper limit. The range is ³ or less, more preferably 4.5 g / cm ³ or less, still more preferably 4 g / cm ³ or less. Within the above range, good charge / discharge characteristics can be obtained and an increase in electrical resistance can be suppressed.

(Conductive material)
As the conductive material, a known conductive material can be arbitrarily used. Specific examples include metal materials such as copper and nickel; graphite such as natural graphite and artificial graphite (graphite); carbon black such as acetylene black; carbon materials such as amorphous carbon such as needle coke. It should be noted that one of these may be used alone, or two or more of them may be used in any combination and ratio. The conductive material is usually 0.01% by mass or more, preferably 0 in the positive electrode active material layer.
.. It is used so as to contain 1% by mass or more, more preferably 1% by mass or more, and the upper limit is usually 50% by mass or less, preferably 30% by mass or less, more preferably 15% by mass or less. Within the above range, sufficient conductivity and battery capacity can be secured.

(Binder)
The binder used in the production of the positive electrode active material layer is not particularly limited, and in the case of the coating method, any material may be used as long as it is dissolved or dispersed in the liquid medium used in the production of the electrode, but as a specific example, it may be used. , Polyethylene, Polypropylene, Polyethylene terephthalate, Polymethylmethacrylate, Polyimide, Aromatic polyamide, Cellulose, Nitrocellulose and other resin polymers; SBR (Styrene-butadiene rubber), NBR (Acrylonitrile-butadiene rubber), Fluoro rubber, Isoprene rubber , Butadiene rubber, rubber-like polymer such as ethylene-propylene rubber; styrene / butadiene / styrene block copolymer or hydrogen additive thereof, EP
Thermoplastic elastomeric polymers such as DM (ethylene / propylene / diene ternary copolymer), styrene / ethylene / butadiene / ethylene copolymer, styrene / isoprene / styrene block copolymer or hydrogenated products thereof; Soft resinous polymers such as tick-1,2-polybutadiene, polyvinyl acetate, ethylene / vinyl acetate copolymer, propylene / α-olefin copolymer; polyvinylidene fluoride (PVdF), polytetrafluoroethylene, fluorination Fluorine-based polymers such as polyvinylidene fluoride and polytetrafluoroethylene / ethylene copolymers; polymer compositions having ionic conductivity of alkali metal ions (particularly lithium ions) can be mentioned. In addition, you may use one kind of these substances alone or 2
The seeds or more may be used in any combination and ratio.

The proportion of the binder in the positive electrode active material layer is usually 0.1% by mass or more, preferably 1% by mass or more.
More preferably, it is 1.5% by mass or more, and the upper limit is usually 80% by mass or less, preferably 60.
It is mass% or less, more preferably 40% by mass or less, and most preferably 10% by mass or less. If the proportion of the binder is too low, the positive electrode active material cannot be sufficiently retained, the mechanical strength of the positive electrode is insufficient, and the battery performance such as cycle characteristics may be deteriorated. On the other hand, if it is too high, it may lead to a decrease in battery capacity and conductivity.

(Slurry forming solvent)
The solvent for forming the slurry is particularly limited as long as it is a solvent capable of dissolving or dispersing a positive electrode active material, a conductive material, a binder and a thickener used as needed. However, either an aqueous solvent or an organic solvent may be used. Examples of the aqueous medium include water, a mixed medium of alcohol and water, and the like. Examples of the organic medium include aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as benzene, toluene, xylene and methylnaphthalene; heterocyclic compounds such as quinoline and pyridine; and ketones such as acetone, methylethylketone and cyclohexanone; Esters such as methyl acetate and methyl acrylate; diethylenetriamine, N, N
-Amines such as dimethylaminopropylamine; ethers such as diethyl ether, propylene oxide, tetrahydrofuran (THF); amides such as N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide; hexamethylphosphalamide, dimethyl Examples thereof include an aprotonic polar solvent such as sulfoxide.

In particular, when an aqueous medium is used, it is preferable to use a thickener and a latex such as styrene-butadiene rubber (SBR) to form a slurry. Thickeners are typically used to adjust the viscosity of the slurry. The thickener is not particularly limited, and specific examples thereof include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof. These may be used alone or in combination of two or more in any combination and ratio. When a thickener is further added, the ratio of the thickener to the active material is 0.1.
By mass or more, preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and the upper limit is 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less. It is a range. Within the above range, good coatability can be obtained, and a decrease in battery capacity and an increase in resistance can be suppressed.

(Current collector)
The material of the positive electrode current collector is not particularly limited, and any known material can be used.
Specific examples include metal materials such as aluminum, stainless steel, nickel plating, titanium, and tantalum; carbon materials such as carbon cloth and carbon paper. Of these, metal materials, especially aluminum, are preferable.

Examples of the shape of the current collector include metal foil, metal cylinder, metal coil, metal plate, metal thin film, expanded metal, punch metal, foamed metal, etc. in the case of metal material, and carbon plate, carbon in the case of carbon material. Examples include a thin film and a carbon column. Of these, a metal thin film is preferable. The thin film may be formed in a mesh shape as appropriate. The thickness of the thin film is arbitrary, but from the viewpoint of strength and handleability as a current collector, it is usually 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, and the upper limit is usually 1 mm or less, preferably 100 μm or less. , More preferably 50 μm or less.

Further, it is also preferable that the conductive auxiliary agent is applied to the surface of the current collector from the viewpoint of reducing the electronic contact resistance between the current collector and the positive electrode active material layer. Examples of the conductive auxiliary agent include carbon and precious metals such as gold, platinum and silver.

The ratio of the thickness of the current collector to the positive electrode active material layer is not particularly limited, but the value of (thickness of the positive electrode active material layer on one side immediately before the electrolytic solution injection) / (thickness of the current collector) is 20. It is preferably less than or equal to, more preferably 15 or less, most preferably 10 or less, and the lower limit is preferably 0.5 or more, more preferably 0.8 or more, and most preferably 1 or more. If it exceeds this range, the current collector may generate heat due to Joule heat during high current density charging / discharging. Within the above range, heat generation of the current collector during high current density charging / discharging can be suppressed, and battery capacity can be secured.

(Electrode area)
When the non-aqueous electrolyte solution of the present invention is used, it is preferable that the area of the positive electrode active material layer is larger than the outer surface area of the battery outer case from the viewpoint of enhancing the stability at high output and high temperature. Specifically, the total area of the electrodes of the positive electrode with respect to the surface area of the exterior of the secondary battery is preferably 15 times or more in terms of area ratio, and more preferably 40 times or more. The outer surface area of the outer case means the total area calculated from the dimensions of the length, width, and thickness of the case part filled with the power generation element excluding the protrusion part of the terminal in the case of the bottomed square shape. .. In the case of a bottomed cylindrical shape, the geometric surface area approximates the case portion filled with the power generation element excluding the protruding portion of the terminal as a cylinder. The total electrode area of the positive electrode is the geometrical surface area of the positive electrode mixture layer facing the mixture layer containing the negative electrode active material, and in the structure in which the positive electrode mixture layer is formed on both sides via the collector foil. , Refers to the sum of the areas calculated separately for each surface.

(Thickness of positive electrode plate)
The thickness of the positive electrode plate is not particularly limited, but from the viewpoint of high capacity and high output, the thickness of the mixture layer obtained by subtracting the metal leaf thickness of the core material is preferable as the lower limit with respect to one side of the current collector. Is 10 μm or more, more preferably 20 μm or more, and the upper limit is preferably 500 μm or less, more preferably 450 μm or less.

(Surface coating of positive electrode plate)
Further, a substance having a composition different from that attached to the surface of the positive electrode plate may be used. Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide and other oxides, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate and calcium sulfate. , Sulfates such as aluminum sulfate, carbonates such as lithium carbonate, calcium carbonate, magnesium carbonate, carbon and the like.

2-1-5. Separator A separator is usually interposed between the positive electrode and the negative electrode to prevent a short circuit. In this case, the non-aqueous electrolytic solution of the present invention is usually used by impregnating this separator.

The material and shape of the separator are not particularly limited, and known ones can be arbitrarily adopted as long as the effects of the present invention are not significantly impaired. Among them, resins, glass fibers, inorganic substances and the like formed of a material stable to the non-aqueous electrolyte solution of the present invention are used, and a porous sheet or a non-woven fabric-like material having excellent liquid retention property is used. Is preferable.

Materials for the resin and glass fiber separator include polyolefins such as polyethylene and polypropylene, aromatic polyamides, polytetrafluoroethylene, and polyether sulfone.
A glass filter or the like can be used. Of these, glass filters and polyolefins are preferable, and polyolefins are more preferable, and polypropylenes are particularly preferable. One of these materials may be used alone, two or more of them may be used in any combination and ratio, or laminated materials may be used. Specific examples of a product in which two or more types are laminated in an arbitrary combination include a three-layer separator in which polypropylene, polyethylene, and polypropylene are laminated in this order.

The thickness of the separator is arbitrary, but is usually 1 μm or more, preferably 5 μm or more, and 8
It is more preferably μm or more, and usually 50 μm or less, preferably 40 μm or less, 3
It is more preferably 0 μm or less. Within the above range, insulation and mechanical strength can be ensured, while battery performance such as rate characteristics and energy density can be ensured.

Further, when a porous material such as a porous sheet or a non-woven fabric is used as the separator, the porosity of the separator is arbitrary, but is usually 20% or more, preferably 35% or more, still more preferably 45% or more. Further, it is usually 90% or less, preferably 85% or less, and further preferably 75% or less. When the porosity is within the above range, insulation and mechanical strength can be ensured, while on the other hand.
It is possible to suppress film resistance and obtain good rate characteristics.

The average pore diameter of the separator is also arbitrary, but is usually 0.5 μm or less, 0.2 μm.
The following is preferable, and it is usually 0.05 μm or more. If the average hole diameter exceeds the above range, a short circuit is likely to occur. When the average pore diameter is in the above range, short circuit can be prevented, film resistance can be suppressed, and good rate characteristics can be obtained. On the other hand, as the inorganic material, oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate are used, and those in the form of particles or fibers are used. ..

As the form, a thin film such as a non-woven fabric, a woven fabric, or a microporous film is used. As the thin film shape, a thin film having a pore diameter of 0.01 to 1 μm and a thickness of 5 to 50 μm is preferably used.
In addition to the independent thin film shape described above, a separator formed by forming a composite porous layer containing the particles of the inorganic substance on the surface layer of the positive electrode and / or the negative electrode using a resin binder can be used. For example, alumina particles having a 90% particle size of less than 1 μm may be formed on both sides of the positive electrode by using a fluororesin as a binder to form a porous layer.

2-1-6. Battery design <Electrode group>
The electrode group has a laminated structure in which the positive electrode plate and the negative electrode plate are laminated via the separator.
And the structure in which the positive electrode plate and the negative electrode plate are spirally wound via the separator may be used. The ratio of the mass of the electrode group to the internal volume of the battery (hereinafter referred to as the electrode group occupancy rate) is usually 40% or more, preferably 50% or more, and usually 90% or less.
80% or less is preferable. When the electrode group occupancy rate is within the above range, the battery capacity can be secured, the deterioration of characteristics such as charge / discharge repetition performance and high temperature storage due to the increase in internal pressure can be suppressed, and the operation of the outgassing valve can be prevented. Can be done.

<Current collector structure>
The current collecting structure is not particularly limited, but it is preferable to have a structure that reduces the resistance of the wiring portion and the joint portion. When the electrode group has the above-mentioned laminated structure, a structure formed by bundling the metal core portions of each electrode layer and welding them to the terminals is preferably used. If the area of one electrode becomes large,
Since the internal resistance becomes large, it is also preferably used to reduce the resistance by providing a plurality of terminals in the electrode. In the case where the electrode group has the above-mentioned winding structure, the internal resistance can be reduced by providing a plurality of lead structures on the positive electrode and the negative electrode and bundling them in the terminals.

<Exterior case>
The material of the outer case is not particularly limited as long as it is a substance stable to the non-aqueous electrolytic solution used. Specifically, a nickel-plated steel plate, a metal such as stainless steel, aluminum or an aluminum alloy, a magnesium alloy, or a laminated film (laminated film) of a resin and an aluminum foil is used. From the viewpoint of weight reduction, aluminum or aluminum alloy metal or laminated film is preferably used.

For exterior cases using metals, the metals are welded together by laser welding, resistance welding, or ultrasonic welding to form a sealed structure, or the above metals are used to form a caulking structure via a resin gasket. Things can be mentioned. Examples of the outer case using the above-mentioned laminated film include those having a hermetically sealed structure by heat-sealing resin layers to each other. In order to improve the sealing property, a resin different from the resin used for the laminated film may be interposed between the resin layers. In particular, when the resin layer is heat-sealed via the current collecting terminal to form a closed structure, the metal and the resin are bonded to each other. Resin is preferably used. Further, the shape of the exterior body is also arbitrary, and may be any of, for example, a cylindrical type, a square shape, a laminated type, a coin type, and a large size.

<Protective element>
As a protective element, PTC (Posit) whose resistance increases when abnormal heat generation or excessive current flows.
IveTemperature Coefficient), a thermal fuse, a thermistor, a valve (current cutoff valve) that shuts off the current flowing through the circuit due to a sudden rise in battery internal pressure or internal temperature during abnormal heat generation can be used. It is preferable to select the protective element under conditions that do not operate under normal use with a high current, and it is more preferable to design the protective element so as not to cause abnormal heat generation or thermal runaway even without the protective element.

<2-2. Multivalent cation battery>
An oxide material or the like is used for the positive electrode, and a metal such as magnesium, calcium or aluminum or a compound containing these metals is used for the negative electrode. The electrolyte is a non-aqueous electrolyte solution in which magnesium salt, calcium salt, aluminum salt, etc. are dissolved in a non-aqueous solvent so as to give the same elements as the reaction active material species of the negative electrode, that is, magnesium ion, calcium ion, aluminum ion. By dissolving at least one compound selected from the group consisting of a cyclic carbonate having a carbon-carbon unsaturated bond and a fluorine-containing cyclic carbonate, and a compound represented by the formula (1), the compound is polyvalent. A non-aqueous electrolyte solution for a cationic battery can be prepared.

<2-3. Metal-air battery ＞
Metals such as zinc, lithium, sodium, magnesium, aluminum and calcium, and compounds containing these metals are used for the negative electrode. Since the positive electrode active material is oxygen, a porous gas diffusion electrode is used for the positive electrode. Carbon is preferable as the porous material. A lithium salt, a sodium salt, a magnesium salt, an aluminum salt, a calcium salt, etc. are dissolved in a non-aqueous solvent so that the same element as the negative electrode active material species, that is, lithium, sodium, magnesium, aluminum, calcium, etc. is given to the electrolyte. Using a non-aqueous electrolyte solution, at least one compound selected from the group consisting of a cyclic carbonate having a carbon-carbon unsaturated bond and a fluorine-containing cyclic carbonate, and a compound represented by the formula (1) are dissolved therein. By doing so, a non-aqueous electrolyte solution for a metal air cell can be prepared.

<2-4. Secondary battery using s-block metal other than the above>
The s-block element is a group 1 element (hydrogen, alkali metal), a group 2 element (berylium, magnesium and alkaline earth metal) and helium, and the s-block metal secondary battery is the above-mentioned s. -Represents a secondary battery that uses block metal as the negative electrode and / or electrolyte.
Specific examples of the s-block metal secondary battery other than the above include a lithium-sulfur battery, a sodium-sulfur battery, and a sodium-ion battery that use sulfur for the positive electrode.

<2-5. Lithium-ion capacitor>
A material that can form an electric double layer is used for the positive electrode, and a material that can occlude and release lithium ions is used for the negative electrode. Activated carbon is preferable as the positive electrode material. Further, as the negative electrode material, a carbonaceous material is preferable. The non-aqueous electrolyte solution contains at least one compound selected from the group consisting of a cyclic carbonate having a carbon-carbon unsaturated bond and a fluorine-containing cyclic carbonate, and a compound represented by the formula (1). Use an electrolytic solution.

<2-6. Electric Double Layer Capacitor>
Use a material capable of forming an electric double layer on the positive electrode and the negative electrode. Activated carbon is preferable as the positive electrode material and the negative electrode material. The non-aqueous electrolyte solution contains at least one compound selected from the group consisting of a cyclic carbonate having a carbon-carbon unsaturated bond and a fluorine-containing cyclic carbonate.
A non-aqueous electrolytic solution containing the compound represented by the formula (1) is used.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

The structure of the compound represented by the formula (1) used in this example is shown below.

In addition, the structure of other compounds used is shown below.

<Example 1-1 and Comparative Examples 1-1 to 1-4>
[Example 1-1]
[Preparation of non-aqueous electrolyte solution]
Ethylene carbonate (EC), ethyl methyl carbonate (in a dry argon atmosphere)
Mixed solvent consisting of EMC) and diethyl carbonate (DEC) (mixed volume ratio EC: EM)
LiPF ₆ , which is an electrolyte, was dissolved in C: DEC = 3: 4: 3) at a ratio of 1.2 mol / L. Then, 2.0% by mass of vinylene carbonate (VC) and 2.0% by mass of monofluoroethylene carbonate (MFEC) were blended to prepare a basic electrolytic solution. Further, 1.50% by mass of compound (1-1) was added to the basic electrolytic solution to prepare a non-aqueous electrolytic solution of Example 1-1.

[Preparation of positive electrode]
Lithium cobalt oxide (LiCoO ₂ ) 97% by mass as the positive electrode active material, acetylene black 1.5% by mass as the conductive material, and polyvinylidene fluoride (PVdF) as the binder 1.
5% by mass was mixed with a disperser in an N-methylpyrrolidone solvent to form a slurry. This was uniformly applied to both sides of an aluminum foil having a thickness of 15 μm, dried, and then pressed to obtain a positive electrode.

[Manufacturing of negative electrode]
Aqueous dispersion of natural graphite powder as a negative electrode active material, sodium carboxymethyl cellulose as a thickener (concentration of sodium carboxymethyl cellulose 1% by mass), and aqueous dispersion of styrene butadiene rubber as a binder (concentration of styrene butadiene rubber 50% by mass). ) Was added and mixed with a disperser to form a slurry. This slurry was uniformly applied to one side of a copper foil having a thickness of 10 μm, dried, and then pressed to obtain a negative electrode. In the negative electrode after drying, the mass ratio was such that natural graphite: sodium carboxymethyl cellulose: styrene butadiene rubber = 98: 1: 1.

[Manufacturing of lithium secondary battery]
The above positive electrode, negative electrode, and polypropylene separator can be used as the negative electrode, separator, positive electrode, and the like.
A battery element was manufactured by stacking a separator and a negative electrode in this order. This battery element is inserted into a bag made of a laminated film in which both sides of aluminum (thickness 40 μm) are coated with a resin layer while projecting positive and negative terminals, and then a non-aqueous electrolyte solution is injected into the bag. Vacuum sealing was performed to produce a sheet-shaped lithium secondary battery.

[Initial battery characteristic evaluation (initial charge / discharge efficiency)]
With the lithium secondary battery sandwiched between glass plates and pressurized, the lithium secondary battery is charged at a constant current of 0.05 C for 6 hours at 25 ° C., and then discharged at a constant current of 0.2 C to 3.0 V. The charge / discharge efficiency at this time was defined as the initial charge / discharge efficiency. Further, after constant current-constant voltage charging (also referred to as "CC-CV charging") (0.05C cut) up to 4.1V with a current corresponding to 0.2C, 4
It was left at 5 ° C. for 72 hours. Then, it was discharged to 3.0V with a constant current of 0.2C. Then, after CC-CV charging (0.05C cut) to 4.4V at 0.2C, 0.2.
It was discharged again to 3.0V at C to stabilize the initial battery characteristics. Here, 1C represents a current value for discharging the reference capacity of the battery in 1 hour, and 0.2C represents, for example, a current value of 1/5 of that.

[High temperature storage durability test (storage gas amount)]
The lithium secondary battery after the initial evaluation of battery characteristics is CC-CV charged (0.05C cut) at 0.2C to 4.4V at 25 ° C, then immersed in an ethanol bath and stored from the buoyancy at that time. The front battery volume was calculated. Then, it was stored at a high temperature at 85 ° C. for 1 day. A sufficiently cooled battery was immersed in an ethanol bath to measure the volume, and the change from the battery volume before storage was taken as the amount of storage gas.

Using the lithium secondary battery produced above, initial battery characteristic evaluation and high temperature storage durability test were carried out. The evaluation results are shown in Table 1 as relative values when Comparative Example 1-1 is 100.0%.
The same shall apply hereinafter.

[Comparative Example 1-1]
A lithium secondary battery was produced in the same manner as in Example 1-1 except that the electrolytic solution containing no compound (1-1) was used in the electrolytic solution of Example 1-1, and the above evaluation was carried out.

[Comparative Example 1-2]
In the electrolytic solution of Example 1-1, compound (2-1) 0.7 instead of compound (1-1).
A lithium secondary battery was produced in the same manner as in Example 1-1 except that 6% by mass was used, and the above evaluation was carried out. The compound (1-1) added in Example 1-1 and the compound (2-1) added in Comparative Example 1-2 have the same amount of substance.

[Comparative Example 1-3]
In the electrolytic solution of Example 1-1, compound (2-2) 1.1 instead of compound (1-1).
A lithium secondary battery was produced in the same manner as in Example 1-1 except that 3% by mass was used, and the above evaluation was carried out. In addition, the compound (1-1) added in Example 1-1 and the compound (2-2) added in Comparative Example 1-3 have the same amount of substance.

[Comparative Example 1-4]
In the electrolytic solution of Example 1-1, compound (2-3) 0.4 instead of compound (1-1)
A lithium secondary battery was produced in the same manner as in Example 1-1 except that 9% by mass was used, and the above evaluation was carried out. The amount of the compound (1-1) added in Example 1-1 and the compound (2-3) added in Comparative Example 1-4 are the same amount of substance.

From Table 1, when the non-aqueous electrolyte solution of Example 1-1 according to the present invention is used, the initial charge / discharge is performed as compared with the case where the compound represented by the formula (1) is not added (Comparative Example 1-1). Efficiency is improved and the amount of stored gas is reduced. That is, by adding the compound represented by the formula (1),
It was suggested that the decomposition of the non-aqueous electrolyte solution was suppressed, and the electrochemical side reaction of the decomposition product on the electrode was suppressed.
When a compound not included in the range of the formula (1) is used (Comparative Examples 1-2 to 1-4),
Although the amount of stored gas is reduced, the improvement effect is small, and the initial charge / discharge efficiency is also Example 1-1.
Inferior to. Therefore, it is clear that the battery using the electrolytic solution according to the present invention has superior characteristics.

<Examples 2-1 to 2-2 and Comparative Example 2-1>
[Example 2-1]
[Preparation of non-aqueous electrolyte solution]
The adjustment was made in the same manner as in Example 1-1.

[Preparation of positive electrode]
It was produced in the same manner as in Example 1-1.

[Manufacturing of negative electrode]
It was produced in the same manner as in Example 1-1.

[Manufacturing of lithium secondary battery]
It was produced in the same manner as in Example 1-1.

[Initial battery characteristic evaluation]
It was carried out in the same manner as in Example 1-1.

[Continuous charge endurance test (continuous charge capacity, continuous charge gas amount, rate characteristics after continuous charge)]
The lithium secondary battery after the initial evaluation of battery characteristics is CC-CV charged (0.05C cut) at 0.2C to 4.4V at 25 ° C., then immersed in an ethanol bath, and the initial buoyancy at that time is used. The battery volume was calculated. Then, at 60 ° C., constant voltage charging of 4.4 V was performed for 14 days, and the charging current capacity at this time was defined as the continuous charging capacity. Further, a sufficiently cooled battery was immersed in an ethanol bath to measure the volume, and the change from the initial battery volume was taken as the amount of continuous charging gas. Further, at 25 ° C., a constant current was discharged to 3.0 V at 0.2 C. After that, 25 ° C
After CC-CV charging (0.05C cut) to 4.4V with a constant current of 0.2C in
It was discharged again to 3.0V at 0.2C, and this was used as the recovery 0.2C capacity. Further, after CC-CV charging (0.05C cut) to 4.4V at 0.2C, the discharge was made to 3.0V at 0.5C, and this was used as the recovery 0.5C capacity. Then, the ratio of the recovery 0.5C capacity to the recovery 0.2C capacity was obtained, and this was used as the rate characteristic (%) after continuous charging.

The continuous charge capacity reflects the amount of electrochemical side reaction on the electrode during the continuous charge endurance test. That is, the smaller the continuous charge capacity, the more the electrochemical side reaction on the electrode during the continuous charge durability test is suppressed.

Using the lithium secondary battery produced above, initial battery characteristic evaluation and continuous charge durability test were carried out. The evaluation results are shown in Table 2 as relative values when Comparative Example 2-1 is 100.0%.
The same shall apply hereinafter.

[Comparative Example 2-1]
A lithium secondary battery was produced in the same manner as in Example 2-1 except that the electrolytic solution containing no compound (1-1) was used in the electrolytic solution of Example 2-1 and the above evaluation was carried out.

[Comparative Example 2-2]
In the electrolytic solution of Example 2-1, compound (2-1) 0.7 instead of compound (1-1).
A lithium secondary battery was produced in the same manner as in Example 2-1 except that 6% by mass was used, and the above evaluation was carried out. The compound (1-1) added in Example 2-1 and the compound (2-1) added in Comparative Example 2-2 have the same amount of substance.

[Comparative Example 2-3]
In the electrolytic solution of Example 2-1 instead of compound (1-1), compound (2-2) 1.1
A lithium secondary battery was produced in the same manner as in Example 2-1 except that 3% by mass was used, and the above evaluation was carried out. The amount of the compound (1-1) added in Example 2-1 and the compound (2-2) added in Comparative Example 2-3 are the same amount of substance.

[Comparative Example 2-4]
In the electrolytic solution of Example 2-1 instead of compound (1-1), compound (2-3) 0.4
A lithium secondary battery was produced in the same manner as in Example 2-1 except that 9% by mass was used, and the above evaluation was carried out. The compound (1-1) added in Example 2-1 and the compound (2-3) added in Comparative Example 2-4 have the same amount of substance.

From Table 2, when the non-aqueous electrolyte solution of Example 2-1 according to the present invention is used, the initial charge / discharge is compared with the case where the compound represented by the formula (1) is not added (Comparative Example 2-1). The efficiency is improved, and the value of the continuous charge gas amount and the continuous charge capacity is reduced. Furthermore, the rate characteristics after continuous charging are also improved. That is, it was suggested that the addition of the compound represented by the formula (1) suppressed the decomposition of the non-aqueous electrolyte solution and suppressed the electrochemical side reaction of the decomposed product on the electrode.

When the compound (2-1) not included in the range of the formula (1) is used (Comparative Example 2-2),
Although the values of the continuous charge gas amount and the continuous charge capacity are reduced, the improvement effect is small, and the initial charge / discharge efficiency is also inferior to that of Example 2-1. Therefore, it is clear that the battery using the electrolytic solution according to the present invention has superior characteristics.

<Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-5>
[Example 3-1]
[Preparation of non-aqueous electrolyte solution]
A mixed solvent consisting of EC and DEC under a dry air atmosphere (mixed volume ratio EC: DEC = 3:
LiPF ₆ , which is an electrolyte, was dissolved in 7) at a ratio of 1.0 mol / L. And VC
2.0% by mass was blended to prepare a basic electrolytic solution. Furthermore, the compound (1-
1) The non-aqueous electrolytic solution of Example 3-1 was prepared by blending 1.0% by mass.

[Preparation of positive electrode]
It was produced in the same manner as in Example 1-1.

[Manufacturing of negative electrode]
It was produced in the same manner as in Example 1-1.

[Manufacturing of lithium secondary battery]
It was produced in the same manner as in Example 1-1.

[Initial battery characteristic evaluation (initial charge / discharge efficiency)]
With the lithium secondary battery sandwiched between glass plates and pressurized, the lithium secondary battery is charged at a constant current of 0.05 C for 6 hours at 25 ° C., and then discharged at a constant current of 0.2 C to 3.0 V. The charge / discharge efficiency at this time was defined as the initial charge / discharge efficiency. Further, after constant current-constant voltage charging (also referred to as "CC-CV charging") (0.05C cut) up to 4.1V with a current corresponding to 0.2C, it is 0.
.. It was discharged to 3.0V with a constant current of 2C. Then, after CC-CV charging (0.05C cut) to 4.4V at 0.2C, the battery was discharged again to 3.0V at 0.2C to stabilize the initial battery characteristics. Here, 1C represents a current value for discharging the reference capacity of the battery in 1 hour, and 0.2C represents, for example, a current value of 1/5 of that.

[High temperature storage durability test (storage gas amount)]
It was produced in the same manner as in Example 1-1.

Using the lithium secondary battery produced above, initial battery characteristic evaluation and high temperature storage durability test were carried out. The evaluation results are shown in Table 3 as relative values when Comparative Example 3-1 is 100.0%.

[Example 3-2]
In the electrolytic solution of Example 3-1, compound (1-2) 1.0 was used instead of compound (1-1).
A lithium secondary battery was produced in the same manner as in Example 3-1 except that the mass% was used, and the above evaluation was carried out. The evaluation results are shown in Table 3 as relative values when Comparative Example 3-1 is 100.0%.

[Example 3-3]
A lithium secondary battery was produced in the same manner as in Example 3-1 except that 2.0% by mass of MFEC was used in place of VC in the electrolytic solution of Example 3-1 and the above evaluation was carried out. The evaluation results are shown in Table 3 as relative values when Comparative Example 3-2 is 100.0%.

[Example 3-4]
In the electrolytic solution of Example 3-2, a lithium secondary battery was prepared in the same manner as in Example 3-2 except that 2.0% by mass of MFEC was used instead of VC, and the above evaluation was carried out. The evaluation results are shown in Table 3 as relative values when Comparative Example 3-2 is 100.0%.

[Comparative Example 3-1]
A lithium secondary battery was produced in the same manner as in Example 3-1 except that the electrolytic solution containing no compound (1-1) was used in the electrolytic solution of Example 3-1 and the above evaluation was carried out. The evaluation results are shown in Table 3 as relative values when Comparative Example 3-1 is 100.0%.

[Comparative Example 3-2]
In the electrolytic solution of Example 3-3, a lithium secondary battery was prepared in the same manner as in Example 3-3 except that the electrolytic solution containing no compound (1-1) was used, and the above evaluation was carried out. The evaluation results are shown in Table 3 as relative values when Comparative Example 3-2 is 100.0%.

[Comparative Example 3-3]
A lithium secondary battery was produced in the same manner as in Example 3-1 except that the electrolytic solution containing no VC was used in the electrolytic solution of Example 3-1 and the above evaluation was carried out. The evaluation result is shown in Comparative Example 3-
Table 3 shows the relative values when 5 is 100.0%.

[Comparative Example 3-4]
In the electrolytic solution of Example 3-2, a lithium secondary battery was produced in the same manner as in Example 3-2 except that the electrolytic solution containing no VC was used, and the above evaluation was carried out. The evaluation result is shown in Comparative Example 3-
Table 3 shows the relative values when 5 is 100.0%.

[Comparative Example 3-5]
A lithium secondary battery was produced in the same manner as in Comparative Example 3-1 except that the electrolytic solution containing no VC was used in the electrolytic solution of Comparative Example 3-1 and the above evaluation was carried out. The evaluation result is shown in Comparative Example 3-
Table 3 shows the relative values when 5 is 100.0%.

From Table 3, when the non-aqueous electrolytic solution of Examples 3-1 to 3-4 according to the present invention is used, the formula (1) is used.
Compared with the case where the compound represented by (Comparative Examples 3-1 and 3-2) is not added, the initial charge / discharge efficiency is improved and the amount of stored gas is reduced. That is, the compound represented by the formula (1) and
By adding at least one compound selected from the group consisting of a cyclic carbonate having a carbon-carbon unsaturated bond and a fluorine-containing cyclic carbonate in combination, decomposition of the non-aqueous electrolyte solution is suppressed, and the decomposition product is placed on the electrode. It was suggested that electrochemical side reactions were suppressed.
When the compound represented by the formula (1) is added to the electrolytic solution containing no at least one compound selected from the group consisting of a cyclic carbonate having a carbon-carbon unsaturated bond and a fluorine-containing cyclic carbonate (comparison). Compared with Examples 3-3, 3-4) and the case where the compound represented by the formula (1) is not added (Comparative Example 3-5), the initial charge / discharge efficiency is lowered and the amount of stored gas is also increased. .. Therefore, it is clear that the battery using the electrolytic solution according to the present invention has superior characteristics.

According to the non-aqueous electrolyte solution of the present invention, the initial charge / discharge efficiency of the power storage device containing the non-aqueous electrolyte solution and the rate characteristics after the durability test can be improved, and the gas generation and the continuous charging capacity after the durability test can be reduced. , Useful. Therefore, the non-aqueous electrolytic solution and power storage device of the present invention can be used for various known applications. Specific examples include, for example, laptop computers, pen input computers, mobile computers, electronic book players, mobile phones, mobile fax machines, mobile copies, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, and mini discs. , Transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, automobiles, bikes, motorized bicycles, bicycles, lighting equipment, toys, game equipment, watches, power tools, strobes, cameras, homes Backup power supply for offices, backup power supply for offices, power supply for load leveling,
Examples include natural energy storage power sources.

Claims (13)

A non-aqueous electrolyte solution for a power storage device including a positive electrode and a negative electrode, wherein the non-aqueous electrolyte solution is selected from the group consisting of a cyclic carbonate having a carbon-carbon unsaturated bond and a fluorine-containing cyclic carbonate together with an electrolyte and a non-aqueous solvent. A non-aqueous electrolyte solution containing at least one compound and a compound represented by the formula (1).

(In the formula, R is an aliphatic hydrocarbon group having 2 or more and 4 or less carbon atoms, and n is an integer of 4 or more and 8 or less. However, when there are a plurality of Rs, they are different even if they are the same. May be good.)

The non-aqueous electrolytic solution according to claim 1, wherein R is an alkylene group having 2 or more carbon atoms and 4 or less carbon atoms in the formula (1). The non-aqueous electrolyte solution according to claim 1 or 2, wherein n is an integer of 4 or more and 6 or less in the formula (1). The content of the compound represented by the above formula (1) is 0.001% by mass with respect to the total amount of the non-aqueous electrolyte solution.
The non-aqueous electrolytic solution according to any one of claims 1 to 3, which is 10% by mass or less. The non-aqueous system according to any one of claims 1 to 4, wherein the cyclic carbonate having a carbon-carbon unsaturated bond is at least one selected from the group consisting of vinylene carbonate, vinylethylene carbonate and ethynylethylene carbonate. Electrolyte. The non-aqueous electrolyte solution according to claim 5, wherein the content of the cyclic carbonate having a carbon-carbon unsaturated bond with respect to the total amount of the non-aqueous electrolyte solution is 0.001% by mass or more and 50% by mass or less. The present invention according to any one of claims 1 to 6, wherein the fluorine-containing cyclic carbonate is at least one selected from the group consisting of monofluoroethylene carbonate, 4,4-difluoroethylene carbonate and 4,5-difluoroethylene carbonate. The non-aqueous electrolyte solution described. The non-aqueous electrolytic solution according to claim 7, wherein the content of the fluorine-containing cyclic carbonate with respect to the total amount of the non-aqueous electrolytic solution is 0.001% by mass or more and 50% by mass or less. Sulfur-containing organic compounds, phosphorus-containing organic compounds, organic compounds having a cyano group other than the above formula (1), organic compounds having an isocyanate group, silicon-containing compounds, aromatic compounds, fluorine-free carboxylic acid esters, and a plurality of ether bonds. Contains at least one compound selected from the group consisting of a cyclic compound having an isocyanuric acid skeleton, a monofluorophosphate, a difluorophosphate, a borate, a oxalate and a fluorosulfonate. The non-aqueous electrolyte solution according to any one of claims 1 to 8. Sulfur-containing organic compounds, phosphorus-containing organic compounds, organic compounds having a cyano group other than the above formula (1), organic compounds having an isocyanate group, silicon-containing compounds, aromatic compounds, fluorine-free carboxylic acid esters, and a plurality of ether bonds. Non-aqueous electrolysis of at least one compound selected from the group consisting of a cyclic compound having an isocyanuric acid skeleton, a monofluorophosphate, a difluorophosphate, a borate, a oxalate and a fluorosulfonate. 9. Claim 9 in which the total content with respect to the total amount of the liquid is 0.001% by mass or more and 50% by mass or less.
The non-aqueous electrolyte solution described in 1. A power storage device comprising a negative electrode and a positive electrode, and the non-aqueous electrolyte solution according to any one of claims 1 to 10. The negative electrode has a negative electrode active material layer on a current collector, and the negative electrode active material layer is a simple substance metal of silicon, an alloy and a compound, a simple substance metal of tin, an alloy and a compound, a carbonaceous material, and a lithium titanium composite. The power storage device according to claim 11, which contains at least one selected from the group consisting of oxides. The positive electrode has a positive electrode active material layer on a current collector, and the positive electrode active material layer includes a lithium-cobalt composite oxide, a lithium-cobalt-nickel composite oxide, a lithium-manganese composite oxide, and a lithium-cobalt composite oxide. 11. 12. The power storage device according to 12.