JP2018163867A - Nonaqueous electrolyte and energy device employing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-aqueous electrolyte solution which is excellent in charge/discharge efficiency and rate characteristics after a high temperature storage durability test and further reduces gas generation after a high temperature storage durability test in an energy device, and an energy device using this non-aqueous electrolyte solution. I will provide a. A non-aqueous electrolyte solution for an energy device having a positive electrode and a negative electrode, the non-aqueous electrolyte solution containing an electrolyte and a non-aqueous solvent, a fluorine-containing cyclic carbonate, and a compound represented by the formula (1). According to the non-aqueous electrolytic solution characterized by containing. (In the formula, R1 is an unsaturated hydrocarbon group having 3 to 12 carbon atoms which may have a substituent having at least one carbon-carbon unsaturated bond, and R2 is a fat having 2 to 10 carbon atoms. Group hydrocarbon group.) [Selection diagram] None

Description

  The present invention relates to a non-aqueous electrolyte and an energy 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 capacities for batteries used for the main power source and backup power source, such as nickel cadmium batteries and nickel Energy devices such as lithium ion secondary batteries having a higher energy density than hydrogen batteries have attracted attention.
As an electrolytic solution of the lithium ion secondary battery, an electrolyte such as LiPF ₆ , LiBF ₄ , LiN (CF ₃ SO ₂ ) ₂ , LiCF ₃ (CF ₂ ) ₃ SO ₃ is used as a high dielectric constant such as ethylene carbonate or propylene carbonate. A typical example is a non-aqueous electrolyte solution dissolved in a mixed solvent of a solvent and a low-viscosity solvent such as dimethyl carbonate, diethyl carbonate, or ethyl methyl carbonate.

  Carbonaceous materials that can occlude and release lithium ions are mainly used as negative electrode active materials for lithium ion secondary batteries, and natural graphite, artificial graphite, amorphous carbon, etc. are typical examples. Can be mentioned. Furthermore, metal or alloy negative electrodes using silicon, tin or the like for increasing the capacity are also known. As the positive electrode active material, a transition metal composite oxide capable of mainly occluding and releasing lithium ions is used, and representative examples of the transition metal include cobalt, nickel, manganese, iron and the like.

  Such a lithium ion secondary battery uses a highly active positive electrode and negative electrode, and it is known that the charge / discharge capacity decreases due to a side reaction between the electrode and the electrolyte, improving battery characteristics. 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 alkyl nitrile is added.
Patent Document 2 proposes a technique for improving the high-temperature storage characteristics of a battery and the permeability of the electrolytic solution into a separator by using an electrolytic solution to which a long-chain alkyl nitrile is added.
In Patent Document 3, an electrolyte solution is prepared by mixing ethylene carbonate, a chain carbonate ester, a cyclic carbonate ester having at least one carbon-carbon unsaturated bond, and a nitrile compound in a specific ratio and using it as a solvent for the electrolyte solution. Techniques for improving the ionic conductivity of these have been proposed.
Patent Document 4 discloses a technique for improving the charge / discharge efficiency of a battery by using an electrolytic solution to which a nitrile compound having a carbon-carbon unsaturated bond is added, thereby suppressing the decomposition reaction of the electrolytic solution on the negative electrode. Has been proposed.
Patent Documents 5 and 6 propose techniques for suppressing swelling during battery high-temperature storage by using an electrolytic solution to which a nitrile compound having a carbon-carbon unsaturated bond is added.
Patent Document 7 proposes a technique for suppressing a reductive decomposition reaction of a solvent that occurs when a highly crystalline carbon such as graphite is used for a negative electrode by using an electrolytic solution to which a compound having a cyanoethoxy group is added. Yes.
Non-Patent Document 1 proposes a technique in which a protective film is formed on a negative electrode by using a propylene carbonate-containing electrolytic solution to which allyl cyanide is added, and side reactions at the negative electrode due to propylene carbonate can be suppressed.

JP-A-10-189008 JP 2011-003364 A JP 2004-303437 A JP 2003-86248 A Chinese Patent Application No. 102738511 US Patent Application Publication No. 2014/0356734 JP 2000-243444 A

Ionics, 2013, 19, 1099-1103.

  The nitrile compounds described in Patent Documents 1 to 7 and Non-Patent Document 1 have a problem that the reduction side reaction also proceeds on the negative electrode, and the effect of improving battery characteristics is insufficient. In addition, 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 high temperature storage durability test of the battery is insufficient.

  The present invention has been made to solve the above problems, and in an energy device, it is excellent in charge and discharge efficiency and rate characteristics after a high temperature storage durability test, and further reduces gas generation after a high temperature storage durability test. It is an object of the present invention to provide a non-aqueous electrolyte solution that can be produced and an energy 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 problem can be solved by including a specific nitrile in the electrolytic solution, and have completed the present invention. . The summary of the aspect of the present invention is as follows.

  (A) A nonaqueous electrolytic solution of an energy device including a positive electrode and a negative electrode, wherein the nonaqueous electrolytic solution contains a fluorine-containing cyclic carbonate and a compound represented by the formula (1) together with the electrolyte and the nonaqueous solvent. A non-aqueous electrolyte characterized by that.

(Where
R ¹ is an unsaturated hydrocarbon group having 3 to 12 carbon atoms which may have a substituent having at least one carbon-carbon unsaturated bond, and R ² is an aliphatic carbon atom having 2 to 10 carbon atoms. It is a hydrogen group. )

(B) The nonaqueous electrolytic solution according to (a), wherein the unsaturated hydrocarbon group of R ¹ has at least one carbon-carbon double bond in the formula (1).

(C) In the formula (1), the unsaturated hydrocarbon group of R ¹ is an aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond, described in (a) or (b) Non-aqueous electrolyte. (D) The non-aqueous electrolyte solution according to any one of (a) to (c), wherein R ² in the formula (1) is an alkylene group having 2 to 10 carbon atoms.
(E) The content of the compound represented by the formula (1) with respect to the total amount of the electrolytic solution is 0.001% by mass or more and 10% by mass or less, according to any one of (a) to (d). Aqueous electrolyte.

(F) 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, (a) to (e) The non-aqueous electrolyte solution as described in any one.
(G) The non-aqueous electrolyte solution according to (f), wherein the content of the fluorine-containing cyclic carbonate 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.

(H) Further, a cyclic carbonate having a carbon-carbon unsaturated bond, 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 a silicon-containing compound , Aromatic compounds, fluorine-free carboxylic acid esters, cyclic compounds having a plurality of ether bonds, compounds having an isocyanuric acid skeleton, monofluorophosphates, difluorophosphates, borates, oxalates and fluorosulfonic acids The non-aqueous electrolyte solution according to any one of (a) to (g), which contains at least one compound selected from the group consisting of salts.
(I) a cyclic carbonate having a carbon-carbon unsaturated bond, 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, a silicon-containing compound, an aromatic Group compounds, fluorine-free carboxylic acid esters, cyclic compounds having a plurality of ether bonds, compounds having an isocyanuric acid skeleton, monofluorophosphates, difluorophosphates, borates, oxalates and fluorosulfonates The non-aqueous electrolyte solution according to (h), wherein the total content of at least one compound selected from the group consisting of 0.001% by mass to 50% by mass with respect to the total amount of the non-aqueous electrolyte solution.

(J) An energy device comprising a negative electrode and a positive electrode capable of inserting and extracting lithium ions, and the non-aqueous electrolyte solution according to any one of (a) to (i).
(K) The negative electrode has a negative electrode active material layer on a current collector, and the negative electrode active material layer includes a silicon simple metal, an alloy and a compound, tin simple metal, an alloy and a compound, a carbonaceous material, and The energy device according to (j), containing at least one selected from the group consisting of lithium titanium composite oxides.
(L) 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, Containing at least one selected from the group consisting of lithium-cobalt-manganese composite oxide, lithium-nickel composite oxide, lithium-nickel-manganese composite oxide, and lithium-cobalt-nickel-manganese composite oxide, An energy device according to j) or (k).

  ADVANTAGE OF THE INVENTION According to this invention, the nonaqueous electrolyte solution for implement | achieving the energy device which was excellent in the charge / discharge efficiency and rate characteristic after a high temperature storage durability test, and also reduced the gas generation after a high temperature storage durability test can be provided. Thereby, size reduction, high performance, and high safety of the energy device can be achieved.

  In the energy device manufactured using the non-aqueous electrolyte solution of the present invention, the charge / discharge efficiency and rate characteristics after the high temperature storage durability test are improved, and the action / principle of reducing the gas generation after the high temperature storage durability test is Although it is not clear, it is thought as follows. However, the present invention is not limited to the operations and principles described below.

Usually, the nitrile compounds represented by Patent Documents 1 to 3 have a cyano group coordinated to the metal oxide in the positive electrode active material, thereby suppressing the oxidative decomposition of the non-aqueous electrolyte and after the high temperature storage durability test. This brings about an improvement effect of reducing gas generation. However, since these nitrile compounds have a small binding energy to the metal oxide and are easily detached during the durability test, the effect of suppressing the oxidation reaction of the non-aqueous electrolyte was small. Furthermore, since the compound having a cyano group has low reduction resistance, the reduction side reaction proceeds remarkably on the negative electrode. As a result, the charge / discharge efficiency after the durability test is reduced, which leads to a capacity loss of the energy device.

  In addition, a compound having a carbon-carbon unsaturated bond at the α-position with respect to a cyano group represented by Patent Document 4 improves battery characteristics by coordinating the cyano group to a metal oxide in the positive electrode active material. Bring. However, since the carbon-carbon unsaturated bond and the electron-withdrawing cyano group are close to each other in the molecule, the reduction resistance at the negative electrode is lowered, and the reduction side reaction on the negative electrode proceeds significantly. End up. As a result, the charge / discharge efficiency after the durability test is reduced, which leads to a capacity loss of the energy device.

  Furthermore, the nitrile compound having a carbon-carbon unsaturated bond represented by Patent Documents 5 and 6 and Non-Patent Document 1 is similar to the above alkyl nitrile because the cyano group acts on the metal oxide in the positive electrode active material. In addition, by-product gas is suppressed, and battery characteristics are improved. Moreover, a negative electrode protective film is formed by the reaction of a carbon-carbon unsaturated bond, and the battery characteristic is improved. However, since the reduction reactivity of the carbon-carbon unsaturated bond is high due to the electron withdrawing effect of the nitrile group, the reduction side reaction on the negative electrode cannot be suppressed. Discharge efficiency is reduced, leading to a capacity loss of the energy device.

  Moreover, the compound which has a cyanoethoxy group shown by patent document 8 brings about the improvement of a battery characteristic by suppressing the reductive decomposition reaction on a negative electrode. However, Patent Document 8 does not describe the action of the compound having a cyanoethoxy group on the positive electrode, and the charge / discharge efficiency and rate characteristics after the high-temperature storage durability test caused by the positive electrode oxidative decomposition, which is the subject of the present invention, There is no suggestion of gas generation after the storage durability test.

  In the nonaqueous electrolytic solution of the present invention, the compound represented by the formula (1) has ether oxygen and a cyano group present via an aliphatic hydrocarbon group. Therefore, chelate coordination can be performed on the metal oxide of the positive electrode using ether oxygen and a cyano group, and the bond energy with the metal oxide is increased. As a result, it is possible to stably protect the metal oxide of the positive electrode, suppress oxidative decomposition of the non-aqueous electrolyte, and suppress side reactions at the interface between the positive electrode and the electrolyte represented by gas generation, Battery characteristics are improved. In addition, by stably coordinating to the metal oxide of the positive electrode, the amount of reduction reaction at the negative electrode is reduced, so that it also has the function of suppressing unnecessary capacity reduction at the negative electrode. Furthermore, since the compound represented by Formula (1) has a carbon-carbon unsaturated bond, a negative electrode protective film can be effectively formed even if it undergoes a reduction reaction at the negative electrode. In addition, since the carbon-carbon unsaturated bond and the cyano group exist via ether oxygen, the electron withdrawing effect of the cyano group on the carbon-carbon unsaturated bond is suppressed, and the reduction reactivity of the carbon-carbon unsaturated bond is reduced. It is suitably maintained. As a result, an excessive negative electrode reaction is suppressed, and charge / discharge efficiency after the durability test is improved. Furthermore, since ether oxygen has high polarity, the compound represented by the formula (1) can also interact effectively with cations in the non-aqueous electrolyte. As a result, since the movement of cations during charging and discharging is improved, the compound represented by the formula (1) also has an effect of improving the rate characteristics of the energy device. Therefore, by using the compound represented by the formula (1), the charge / discharge efficiency and rate characteristics after the high-temperature storage endurance test are improved without deteriorating the characteristics of the energy device, and further, the gas generation after the high-temperature storage endurance test. Can be reduced.

Furthermore, by allowing the fluorine-containing cyclic carbonate to coexist in the non-aqueous electrolyte solution, the compound represented by the formula (1) or the reductive decomposition product of the fluorine-containing cyclic carbonate interacts with each other, thereby producing a high-quality composite. A protective coating can be formed. As a result, side reactions on the negative electrode can be suppressed, and the battery characteristics after the durability test can be further improved.

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

1. Non-aqueous electrolyte The non-aqueous electrolyte of the present invention is a non-aqueous electrolyte of an energy device including a positive electrode and a negative electrode. It contains the compound represented by these, It is characterized by the above-mentioned.

1-1-1. Compound Represented by Formula (1) The non-aqueous electrolyte solution of the present invention contains a compound represented by formula (1). In the compound represented by the formula (1), the cis-trans isomer and the optical isomer cannot be distinguished from each other, and any of the isomers alone or a mixture thereof can be applied.

(Where
R ¹ is an unsaturated hydrocarbon group having 3 to 12 carbon atoms which may have a substituent having at least one carbon-carbon unsaturated bond, and R ² is an aliphatic carbon atom having 2 to 10 carbon atoms. It is a hydrogen group.

R ¹ in the formula (1) has at least one carbon-carbon unsaturated bond, and is not particularly limited as long as it is an unsaturated hydrocarbon group having 3 to 12 carbon atoms. Good. This R ¹ is an unsaturated hydrocarbon group having at least one carbon-carbon double bond or an unsaturated hydrocarbon group having at least one carbon-carbon triple bond, preferably at least one carbon -An unsaturated hydrocarbon group having a carbon double bond.

More specifically, as R ¹ , the unsaturated hydrocarbon group includes an aliphatic unsaturated chain hydrocarbon group having at least one carbon-carbon double bond and an aliphatic group having at least one carbon-carbon triple bond. Saturated chain hydrocarbon group, aromatic hydrocarbon group having at least one aromatic ring is preferable, aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond, aromatic having at least one aromatic ring A hydrocarbon group is more preferable, and an aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond is more preferable. It is preferable for R ^{1 to} be these unsaturated hydrocarbon groups because a negative electrode protective film can be effectively formed and an excessive negative electrode reaction can be suppressed.

Furthermore, the unsaturated hydrocarbon group of R ¹ in the formula (1) is an unsaturated hydrocarbon group having no substituent other than the hydrocarbon group, or an unsaturated hydrocarbon group in which a part of H is substituted with F. Preferably, an unsaturated hydrocarbon group having no substituent other than the hydrocarbon group is more preferable. When R ¹ is a group such as these, chelate coordination to the positive electrode metal oxide using ether oxygen and a cyano group is not hindered, so that coordination to the positive electrode can be performed more effectively, and high temperature storage durability It is easy to obtain the effect of the present invention such as reduction of gas generation after the test, and it is easy to obtain the effect of improving the rate characteristics because the interaction with the cation is not hindered. Is also preferable because it can be improved.

In addition, the number of carbon atoms in the unsaturated hydrocarbon group ^{R 1} in the formula (1) is 3 to 12, more preferably from 3 to 9, 3 to 7 are more preferred. If carbon number is this range, it is excellent in the solubility with respect to the electrolyte solution of the compound represented by Formula (1).

なお、＊はエーテル酸素との結合部位を表す。以下も同様である。 Specific examples of R ¹ in formula (1) include the following.
<< aliphatic unsaturated chain hydrocarbon group having at least one carbon-carbon double bond >>

Note that * represents a bonding site with ether oxygen. The same applies to the following.

≪芳香環を少なくとも１つ有する芳香族炭化水素基≫

<< aliphatic unsaturated chain hydrocarbon group having at least one carbon-carbon triple bond >>

<< Aromatic hydrocarbon group having at least one aromatic ring >>

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

Examples of the compound represented by the formula (1) include the following compounds.
<< When R ¹ is an aliphatic unsaturated chain hydrocarbon group having at least one carbon-carbon double bond >>

<< When R ¹ is an aliphatic unsaturated chain hydrocarbon group having at least one carbon-carbon triple bond >>

<< When R ¹ is an aromatic hydrocarbon group having at least one aromatic ring >>

Among these, the following compounds are preferable from the viewpoint of solubility in an electrolytic solution and ease of production.

Among these, the following compounds are more preferable from the viewpoint of easy coordination to the positive electrode metal and high coordination bond energy.

The following compounds are most preferable because of the low side reaction in the energy device.

  The compound represented by Formula (1) may be used independently or may use 2 or more types together. In the total amount (100% by mass) of the non-aqueous electrolyte solution, the amount of the compound represented by the formula (1) (total amount in the case of two or more) is not particularly limited in order to exhibit the effect of the present invention. , Preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.1% by mass or more, particularly preferably 0.3% by mass or more, and most preferably 0.6% by mass. In addition, it is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, particularly preferably 1.5% by mass or less, and most preferably 1.0% by mass or less. is there. Within this range, it is easy to control charge / discharge efficiency, rate characteristics, gas generation and rate characteristics after the durability test, initial charge / discharge efficiency and rate characteristics, continuous charge capacity, low temperature characteristics, cycle characteristics, and the like.

1-1-2. Fluorine-containing cyclic carbonate The nonaqueous electrolytic solution of the present invention further contains a fluorine-containing cyclic carbonate in addition to the compound of the general formula (1). The fluorine-containing cyclic carbonate is not particularly limited as long as it has a cyclic carbonate structure and contains a fluorine atom.

  Examples of the fluorine-containing cyclic carbonate include a fluorinated product of a cyclic carbonate having an alkylene group having 2 to 6 carbon atoms, and derivatives thereof. For example, a fluorinated product of ethylene carbonate (hereinafter referred to as “fluorinated ethylene carbonate”) And derivatives thereof. Examples of the fluorinated derivative of ethylene carbonate include fluorinated ethylene carbonate substituted with an alkyl group (for example, an alkyl group having 1 to 4 carbon atoms). Of these, fluorinated ethylene carbonate having 1 to 8 fluorine atoms and derivatives thereof are preferred.

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

Examples of the fluorinated ethylene carbonate having 1 to 8 fluorine atoms and derivatives thereof 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 Carbonate, 4- (trifluoromethyl) -ethylene carbonate, 4- (fluoromethyl) -4-fluoroethylene carbonate, 4- (fluoromethyl) -5-fluoroethylene carbonate, 4-fluoro-4,5- Methyl ethylene carbonate, 4,5-difluoro-4,5-dimethylethylene carbonate, 4,4-difluoro-5,5-dimethylethylene carbonate. Among these, monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, and 4,5-difluoroethylene carbonate are preferable because they give high ionic conductivity to the electrolyte and easily form a stable interface protective film.

  A fluorinated cyclic carbonate may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. The amount of the fluorinated cyclic carbonate (total amount in the case of 2 or more types) is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.1% in 100% by mass of the electrolyte. % 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 10% by mass or less, more preferably 7% by mass. Hereinafter, it is more preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably 2% by mass or less. In addition, when fluorinated cyclic carbonate is used as the non-aqueous solvent, the amount is 100% by volume in the non-aqueous solvent, preferably 1% by volume or more, more preferably 5% by volume or more, and still more preferably 10% by volume or more. Moreover, it is preferably 50% by volume or less, more preferably 35% by volume or less, and 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 sometimes referred to as “fluorinated unsaturated cyclic carbonate”) may be used. If the fluorine number which a fluorinated unsaturated cyclic carbonate has is one or more, it will not restrict | limit in particular. The number of fluorines can be 6 or less, preferably 4 or less, and more preferably 1 or 2.

Examples of the fluorinated unsaturated cyclic carbonate include fluorinated vinylene carbonate derivatives, fluorinated ethylene carbonate derivatives substituted with an aromatic ring or a substituent having a carbon-carbon double bond.
Fluorinated vinylene carbonate derivatives include 4-fluoro vinylene carbonate, 4-fluoro-5-methyl vinylene carbonate, 4-fluoro-5-phenyl vinylene carbonate, 4-fluoro-5-vinyl vinylene carbonate, 4-allyl-5- A fluoro vinylene carbonate etc. are mentioned.

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, 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-diflu B-4,5-diallylethylene carbonate, 4-fluoro-4-phenylethylene carbonate, 4-fluoro-5-phenylethylene carbonate, 4,4-difluoro-5-phenylethylene carbonate, 4,5-difluoro-4- Examples thereof include phenylethylene carbonate.

  Among these, as fluorinated unsaturated cyclic carbonate, 4-fluoro vinylene carbonate, 4-fluoro-5-methyl vinylene carbonate, 4-fluoro-5-vinyl vinylene carbonate, 4-allyl-5-fluoro vinylene 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 form a stable interface protective coating This is preferable.

  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. If it is this range, it will be easy to ensure the solubility of the fluorinated cyclic carbonate with respect to a non-aqueous electrolyte solution, and the effect of this invention will be easy to be expressed. The production method of the fluorinated unsaturated cyclic carbonate is not particularly limited, and can be produced by arbitrarily selecting a known method. The molecular weight is more preferably 100 or more, and more preferably 200 or less.

  A fluorinated unsaturated cyclic carbonate may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the fluorinated unsaturated cyclic carbonate (the total amount in the case of two or more) is 100% by mass of the electrolytic solution, preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0. 0.1% 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. If it is within this range, the energy device is likely to exhibit a sufficient cycle characteristics improvement effect, and it is easy to avoid a situation in which the high temperature storage characteristics are deteriorated, the amount of gas generation is increased, and the discharge capacity maintenance rate is reduced. .

  The mass ratio of the compound represented by the formula (1) and the fluorine-containing cyclic carbonate is such that the compound represented by the formula (1): the fluorine-containing cyclic carbonate is 1: 100 or more, preferably 10: 100 or more, more preferably 20: 100 or more, further preferably 25: 100 or more, and can be 10000: 100 or less, preferably 500: 100 or less, more preferably 300: 100 or less, and still more preferably 100 : 100 or less, particularly preferably 75: 100 or less, and most preferably 50: 100 or less. If it is this range, a battery characteristic, especially a durable characteristic can be improved significantly. Although this principle is not clear, it is considered that the side reaction of the additive on the electrode can be minimized by mixing at this ratio.

In addition, the method in particular of mix | blending the compound represented by Formula (1) and a fluorine-containing cyclic carbonate with the electrolyte solution of this invention is not restrict | limited. In addition to the method of directly adding the compound represented by the formula (1) and the fluorine-containing cyclic carbonate to the electrolytic solution, the compound represented by the formula (1) and the fluorine-containing cyclic carbonate are chemically reacted in the battery or in the electrolytic solution. The method of generating by is mentioned. As a method for generating the compound represented by the formula (1) and the fluorine-containing cyclic carbonate by a chemical reaction, it is generated by adding a compound other than these compounds and oxidizing or hydrolyzing battery components such as an electrolytic solution. The method of letting it be mentioned. Furthermore, a method of generating a battery by applying an electrical load such as charge / discharge is also mentioned.

  Further, when the compound represented by the formula (1) and the fluorine-containing cyclic carbonate are contained in a non-aqueous electrolyte and actually used for the production of an energy device, the battery is disassembled and the non-aqueous electrolyte is extracted again. In many cases, the content thereof is significantly reduced. Therefore, what can be detected even in a very small amount of the compound represented by the formula (1) and the fluorine-containing cyclic carbonate from the non-aqueous electrolyte extracted from the battery is considered to be included in the present invention. In addition, when the compound represented by the formula (1) and the fluorine-containing cyclic carbonate are actually used for the production of an energy device as a non-aqueous electrolyte solution, the non-aqueous electrolyte solution disassembled and taken out again has the formula ( Even when the compound represented by 1) and the fluorine-containing cyclic carbonate are contained in a very small amount, they are often detected on the positive electrode, the negative electrode, or the separator, which are other components of the energy device. Therefore, when the compound represented by the formula (1) and the fluorine-containing cyclic carbonate are detected from the positive electrode, the negative electrode, and the separator, it can be assumed that the total amount is contained in the nonaqueous electrolytic solution. Under this assumption, it is preferable that the compound represented by the formula (1) and the fluorine-containing cyclic carbonate are contained so as to be in the range shown above.

  1-2. A cyclic carbonate having a carbon-carbon unsaturated bond, 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, a silicon-containing compound, an aromatic compound, Fluorine-free carboxylic acid ester, cyclic compound having a plurality of ether bonds and compound having isocyanuric acid skeleton, monofluorophosphate, difluorophosphate, borate, oxalate and fluorosulfonate

  The aspect of the present invention is an organic compound having a cyano group other than a cyclic carbonate having a carbon-carbon unsaturated bond, a sulfur-containing organic compound, a phosphorus-containing organic compound, and a compound represented by the formula (1). Compound, organic compound having isocyanate group, silicon-containing compound, aromatic compound, fluorine-free carboxylic acid ester, cyclic compound having a plurality of ether bonds and compound having isocyanuric acid skeleton, monofluorophosphate, difluorophosphate And at least one compound selected from the group consisting of borate, oxalate and fluorosulfonate (compound of group (II)). It is because the side reaction on the positive / negative electrode which can cause the compound represented by Formula (1) can be efficiently suppressed by using these together.

  Among them, a cyclic carbonate having a carbon-carbon unsaturated bond, 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 plurality of At least one compound selected from the group consisting of cyclic compounds having an ether bond is preferable because it forms a good composite film on the negative electrode, and the initial battery characteristics and the battery characteristics after the durability test are improved in a balanced manner. -At least 1 type of compound chosen from the group which consists of the cyclic carbonate which has a carbon unsaturated bond, the organic compound which has cyano groups other than Formula (1), an aromatic compound, and a fluorine-free carboxylic acid ester is more preferable. The reason is that these compounds that form a relatively low molecular weight film on the negative electrode efficiently suppress degradation due to side reactions of the compound represented by formula (1) because the formed negative electrode film is dense. It can be mentioned. In this way, side reactions can be effectively suppressed, resistance increase can be suppressed, volume changes can be suppressed by suppressing side reactions during initial and high temperature durability, safety after high temperature durability can be ensured, and rate characteristics can be improved. .

The method for blending the compound of group (II) into the electrolytic solution of the present invention is not particularly limited. In addition to the method of directly adding the above compound to the electrolytic solution, a method of generating a compound of group (II) in the battery or in the electrolytic solution can be mentioned. Examples of the method for generating the compound of group (II) include a method in which a compound other than these compounds is added to generate a battery component such as an electrolytic solution by oxidation or hydrolysis. Furthermore, a method of generating a battery by applying an electrical load such as charge / discharge is also mentioned.

  In addition, when the compound of group (II) is contained in a non-aqueous electrolyte solution and actually used for production of an energy device, the content in the non-aqueous electrolyte solution is remarkably increased even if the battery is disassembled and the non-aqueous electrolyte solution is extracted again. In many cases, it is decreasing. Accordingly, it is considered that the present invention includes a non-aqueous electrolyte extracted from a battery that can detect even a very small amount of the compound of group (II). In addition, when the compound of group (II) is actually used for the production of an energy device as a non-aqueous electrolyte, only a very small amount of the compound of group (II) is present in the non-aqueous electrolyte obtained by disassembling the battery and extracting it again. Even if it is not contained, it is often detected on the positive electrode, the negative electrode, or the separator, which is another component of the energy device. Therefore, when a compound of group (II) is detected from the positive electrode, the negative electrode, and the separator, it can be assumed that the total amount is contained in the non-aqueous electrolyte. Under this assumption, it is preferable that the compound of the group (II) is included in a range described later.

  Below, the compound of the (II) group is demonstrated. However, regarding monofluorophosphate, difluorophosphate, borate, oxalate and fluorosulfonate, the description in “1-3. Electrolyte” is applied. Moreover, regarding the compound represented by Formula (1) combined with the said compound, the previous description regarding the compound represented by Formula (1) is applied including an illustration and a preferable example. Moreover, in the aspect containing a certain compound, the compound other than that in the said compound may be contained.

1-2-1. Cyclic carbonate having a carbon-carbon unsaturated bond Cyclic carbonate having a carbon-carbon unsaturated bond (not including fluorine atoms, hereinafter may be referred to as “unsaturated cyclic carbonate”) is carbon. As long as it is a cyclic carbonate having a carbon double bond or carbon-carbon triple bond, any unsaturated carbonate can be used, but a cyclic carbonate having a carbon-carbon double bond is preferred. . In the present invention, the cyclic carbonate having an aromatic ring is also included in the unsaturated cyclic carbonate.

  Examples of unsaturated cyclic carbonates include vinylene carbonates, aromatic rings, ethylene carbonates substituted with a substituent having a carbon-carbon double bond or carbon-carbon triple bond, phenyl carbonates, vinyl carbonates, allyl carbonates, Catechol carbonates etc. are mentioned.

  As vinylene carbonates, vinylene carbonate, methyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, phenyl vinylene carbonate, 4,5-diphenyl vinylene carbonate, vinyl vinylene carbonate, 4,5-divinyl vinylene carbonate, allyl vinylene carbonate, 4 , 5-diallyl vinylene carbonate and the like.

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, 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-ethynylethylene carbonate, phenylethylene carbonate, 4,5-diphenylethylene carbonate, 4-phenyl-5-vinylethylene carbonate, 4-allyl-5-phenylethylene carbonate,
Examples include allyl ethylene carbonate, 4,5-diallyl ethylene carbonate, 4-methyl-5-allyl ethylene carbonate.

  Among these, preferable unsaturated cyclic carbonates to be used in combination are vinylene carbonate, methyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, vinyl vinylene carbonate, 4,5-vinyl vinylene carbonate, allyl vinylene carbonate, 4, 5-diallyl vinylene carbonate, vinyl ethylene carbonate, 4,5-divinyl ethylene carbonate, 4-methyl-5-vinyl ethylene carbonate, allyl ethylene carbonate, 4,5-diallyl ethylene carbonate, 4-methyl-5-allyl ethylene carbonate, 4-allyl-5-vinylethylene carbonate, ethynylethylene carbonate, 4,5-diethynylethylene carbonate, 4-methyl-5-ethynylethylene carbonate Include 4-vinyl-5-ethynyl-ethylene carbonate. In addition, vinylene carbonate, vinyl ethylene carbonate, and ethynyl ethylene carbonate are preferable because they form a more stable interface protective film, vinylene carbonate and vinyl ethylene carbonate are more preferable, and vinylene carbonate is more preferable.

  The molecular weight of the unsaturated cyclic carbonate is not particularly limited and is arbitrary as long as the effects of the present invention are not significantly impaired. The molecular weight is preferably 80 or more, more preferably 85 or more, and preferably 250 or less, more preferably 150 or less. If it is this range, it will be easy to ensure the solubility of the unsaturated cyclic carbonate with respect to a non-aqueous electrolyte solution, and the effect of this invention will fully be expressed easily. The production method of the unsaturated cyclic carbonate is not particularly limited, and can be produced by arbitrarily selecting a known method.

  An unsaturated cyclic carbonate may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and a ratio. Moreover, the compounding quantity of unsaturated cyclic carbonate is not restrict | limited in particular, As long as the effect of this invention is not impaired remarkably, it is arbitrary. The compounding amount of the unsaturated cyclic carbonate can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, in 100% by mass of the non-aqueous electrolyte solution. It is 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 or less, still more preferably 3% by mass or less, and particularly preferably 2% by mass. It is below mass%. Within this range, it is easy for the energy device to exhibit a sufficient cycle characteristics improvement effect, and it is easy to avoid a situation where the high temperature storage characteristics deteriorate, the amount of gas generation increases, and the discharge capacity retention rate decreases. .

  The mass ratio of the compound represented by the above formula (1) and the cyclic carbonate having a carbon-carbon unsaturated bond (the total amount in the case of two or more) is the compound represented by the formula (1): carbon-carbon unsaturated. The cyclic carbonate having a saturated bond can be 1: 100 or more, preferably 10: 100 or more, more preferably 20: 100 or more, still more preferably 25: 100 or more, and 10000: 100 or less. Preferably, it is 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. If it is this range, a battery characteristic, especially a durable characteristic can be improved significantly. Although this principle is not clear, it is considered that the side reaction of the additive on the electrode can be minimized by mixing at this ratio.

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 100% by mass of the electrolytic solution, preferably 0.002% by mass or more, more preferably 0.0%.
2 mass% or more, more preferably 0.2 mass% or more, particularly preferably 0.4 mass% or more, preferably 20 mass% or less, more preferably 10 mass% or less, still more preferably 8 mass%. % Or less, particularly preferably 6% by mass or less. Within this range, an effective composite film with the compound represented by the formula (1) is formed, the energy device tends to exhibit a sufficient cycle characteristic improving effect, and the high-temperature storage characteristic is lowered. It is easy to avoid a situation in which the amount of gas generation increases and the discharge capacity maintenance rate decreases.

  The mass ratio of the compound represented by the formula (1) to the total of 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. The total of the cyclic carbonate having a bond and the fluorine-containing cyclic carbonate can be 1: 200 or more, preferably 10: 200 or more, more preferably 10: 100 or more, still more preferably 20: 100 or more, and 10,000 : 100 or less, preferably 500: 100 or less, 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. If it is this range, a battery characteristic, especially a durable characteristic can be improved significantly. Although this principle is not clear, it is considered that the side reaction of the additive on the electrode can be minimized by mixing at this ratio.

1-2-2. 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 preferably an organic compound having an S═O group in the molecule. Examples of the compound include a chain sulfonate ester, a cyclic sulfonate 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 included in “1-2-2. Sulfur-containing organic compounds”, but are included in “1-3-4. .

In the electrolytic solution of the present invention, by using the compound represented by the formula (1) and the sulfur-containing organic compound in combination, durability characteristics can be improved in a battery using this electrolytic solution.
Among these, a chain sulfonate ester, a cyclic sulfonate ester, a chain sulfate ester, a cyclic sulfate ester, a chain sulfite ester and a cyclic sulfite ester are preferable, and a compound having an S (= O) ₂ group is more preferable. A chain sulfonate ester and a cyclic sulfonate ester are preferable, and a cyclic sulfonate ester is particularly preferable.
Examples of the sulfur-containing organic compound include the following.

≪Chain sulfonate ester≫
Fluorosulfonic acid esters such as methyl fluorosulfonate and ethyl fluorosulfonate;
Methyl methanesulfonate, ethyl methanesulfonate, 2-propynyl methanesulfonate, 3-butynyl methanesulfonate, busulfan, methyl 2- (methanesulfonyloxy) propionate, ethyl 2- (methanesulfonyloxy) propionate, 2- (Methanesulfonyloxy) propionate 2-propynyl, 2- (methanesulfonyloxy) propionate 3-butynyl, methanesulfonyloxyacetate methyl, methanesulfonyloxyacetate ethyl, methanesulfonyloxyacetate 2-propynyl and methanesulfonyloxyacetate 3- Methanesulfonic acid esters such as butynyl;
Methyl vinyl sulfonate, ethyl vinyl sulfonate, allyl vinyl sulfonate, propargyl vinyl sulfonate, methyl allyl sulfonate, ethyl allyl sulfonate, allyl sulfonate, propargyl allyl sulfonate and 1,2-bis (vinyl sulfonyloxy) ) Alkenyl sulfonic acid esters such as ethane;
Methanedisulfonic acid methoxycarbonylmethyl, methanedisulfonic acid ethoxycarbonylmethyl, methanedisulfonic acid 1-methoxycarbonylethyl, methanedisulfonic acid 1-
Ethoxycarbonylethyl, 1,2-ethanedisulfonic acid methoxycarbonylmethyl, 1,2-ethanedisulfonic acid ethoxycarbonylmethyl, 1,2-ethanedisulfonic acid 1-methoxycarbonylethyl, 1,2-ethanedisulfonic acid 1-ethoxycarbonyl Ethyl, 1,3-propanedisulfonic acid methoxycarbonylmethyl, 1,3-propanedisulfonic acid ethoxycarbonylmethyl, 1,3-propanedisulfonic acid 1-methoxycarbonylethyl, 1,3-propanedisulfonic acid 1-ethoxycarbonylethyl, 1,3-butanedisulfonic acid methoxycarbonylmethyl, 1,3-butanedisulfonic acid ethoxycarbonylmethyl, 1,3-butanedisulfonic acid 1-methoxycarbonylethyl, 1,3-butanedisulfonic acid 1-ethoxycarbonyl Alkyl disulfonic acid esters, such as Boniruechiru;

≪Cyclic sulfonate ester≫
1,3-propane sultone, 1-fluoro-1,3-propane sultone, 2-fluoro-1,3-propane sultone, 3-fluoro-1,3-propane sultone, 1-methyl-1,3-propane sultone 2-methyl-1,3-propane sultone, 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-propene-1,3-sultone, 2-methyl-2-propene-1,3-sultone, 3 -Sultone compounds such as methyl-2-propene-1,3-sultone, 1,4-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-oxathiazol-2,2-dioxide 5H-1,2,3-oxathiazol-2,2-dioxide, 1,2,4-oxathiazolidine-2,2-dioxide, 1,2,5-oxathiazolidine-2,2-dioxide, 1, 2,3-oxathiazinane-2,2-dioxide, 3-methyl-1,2,3-oxathiazinane-2,2-dioxide, 5,6-dihydro-1,2,3-oxathiazine-2,2-dioxide and Nitrogen-containing compounds such as 1,2,4-oxathiazinane-2,2-dioxide.

  1,2,3-oxathiaphoslane-2,2-dioxide, 3-methyl-1,2,3-oxathiaphoslane-2,2-dioxide, 3-methyl-1,2,3-oxathi Aphoslane-2,2,3-trioxide, 3-methoxy-1,2,3-oxathiaphoslane-2,2,3-trioxide, 1,2,4-oxathiaphoslane-2,2-dioxide 1,2,5-oxathiaphoslane-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-oxathiaphosphie Down-dioxide, 1,2,5-oxathiazolium phosphinothricin Nan-2,2-dioxide and 1,2,6-oxa-thia phosphinothricin Nan -2,2-containing phosphorus compounds such as dioxide.

≪Chain sulfate ester≫
Dialkyl sulfate compounds such as dimethyl sulfate, ethyl methyl sulfate and diethyl sulfate.

≪Cyclic sulfate ester≫
1,2-ethylene sulfate, 1,2-propylene sulfate, 1,3-propylene sulfate, 1,2-butylene sulfate, 1,3-butylene sulfate, 1,4-butylene sulfate, 1, Alkylene sulfate compounds such as 2-pentylene sulfate, 1,3-pentylene sulfate, 1,4-pentylene sulfate, and 1,5-pentylene sulfate.

≪Chainous sulfite ester≫
Dialkyl sulfite compounds such as dimethyl sulfite, ethyl methyl sulfite and diethyl sulfite.

≪Cyclic sulfite ester≫
1,2-ethylene sulfite, 1,2-propylene sulfite, 1,3-propylene sulfite, 1,2-butylene sulfite, 1,3-butylene sulfite, 1,4-butylene sulfite, 1, Alkylene sulfite compounds such as 2-pentylenesulfite, 1,3-pentylenesulfite, 1,4-pentylenesulfite and 1,5-pentylenesulfite.

  Of these, methyl 2- (methanesulfonyloxy) propionate, ethyl 2- (methanesulfonyloxy) propionate, 2-propynyl 2- (methanesulfonyloxy) propionate, 1-methoxycarbonylethyl propanedisulfonate, propanedisulfone 1-ethoxycarbonylethyl acid, 1-methoxycarbonylethyl butanedisulfonate, 1-ethoxycarbonylethyl butanedisulfonate, 1,3-propane sultone, 1-propene-1,3-sultone, 1,4-butane sultone, 1, 2-Ethylene sulfate, 1,2-ethylene sulfite, methyl methanesulfonate, and ethyl methanesulfonate are preferred from the viewpoint of improving the initial efficiency, and 1-methoxycarbonylethyl propanedisulfonate, 1-ethanepropanedisulfonate is preferable. Xicarbonylethyl, 1-methoxycarbonylethyl butanedisulfonate, 1-ethoxycarbonylethyl butanedisulfonate, 1,3-propane sultone, 1-propene-1,3-sultone, 1,2-ethylene sulfate, 1,2 -Ethylene sulfite is more preferable, and 1,3-propane sultone and 1-propene-1,3-sultone are more preferable.

A sulfur containing organic compound may be used individually by 1 type, and may have 2 or more types together by arbitrary combinations and ratios.
The content of the sulfur-containing organic compound (the total amount in the case of two or more types) can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably in 100% by mass of the electrolytic solution. 0.1% by mass or more, particularly preferably 0.3% by mass or more, particularly preferably 0.6% by mass or more, and can be 10% by mass or less, preferably 5% by mass or less, More preferably, it is 3 mass% or less, More preferably, it is 2 mass% or less, Especially preferably, it is 1.5 mass% or less, Most preferably, it is 1.0 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 formula (1) and the sulfur-containing organic compound is such that the compound represented by the formula (1): sulfur-containing organic compound is 1: 100 or more, preferably 10: 100 or more, more preferably 20: 100 or more, further preferably 25: 100 or more, and can be 10000: 100 or less, preferably 500: 100 or less, more preferably 300: 100 or less, and still more preferably 100 : 100 or less, particularly preferably 75: 100 or less, and most preferably 50: 100 or less. If it is this range, a battery characteristic, especially a durable characteristic can be improved significantly. Although this principle is not clear, it is considered that the side reaction of the additive on the electrode can be minimized by mixing at this ratio.

1-2-3. 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 electrolytic solution of the present invention containing a phosphorus-containing organic compound can improve durability characteristics.

As a phosphorus containing organic compound, phosphoric acid ester, phosphonic acid ester, phosphinic acid ester, and phosphorous acid ester are preferable, More preferably, they are phosphoric acid ester and phosphonic acid ester, More preferably, they are phosphonic acid ester.
Examples of the phosphorus-containing organic compound include the following.

≪Phosphate ester≫
Has vinyl groups such as dimethyl vinyl phosphate, diethyl vinyl phosphate, dipropyl vinyl phosphate, dibutyl vinyl phosphate, dipentyl vinyl phosphate, methyl divinyl phosphate, ethyl divinyl phosphate, propyl divinyl phosphate, butyl divinyl phosphate, pentyl divinyl phosphate and trivinyl phosphate Compound;
Allyl groups such as allyl dimethyl phosphate, allyl diethyl phosphate, allyl dipropyl phosphate, allyl dibutyl phosphate, allyl dipentyl phosphate, diallyl methyl phosphate, diallyl ethyl phosphate, diallyl propyl phosphate, diallyl butyl phosphate, diallyl pentyl phosphate and triallyl phosphate Compound;
Propargyl dimethyl phosphate, propargyl diethyl phosphate, propargyl dipropyl phosphate, propargyl dibutyl phosphate, propargyl dipentyl phosphate, dipropargyl methyl phosphate, dipropargyl ethyl phosphate, dipropargyl propyl phosphate, dipropargyl butyl phosphate, dipropargyl pentyl phosphate propyl phosphate A compound having a propargyl group of
2-acryloyloxymethyl dimethyl phosphate, 2-acryloyloxymethyl diethyl phosphate, 2-acryloyloxymethyl dipropyl phosphate, 2-acryloyloxymethyl dibutyl phosphate, 2-acryloyloxymethyl dipentyl phosphate, bis (2-acryloyloxymethyl) methyl Phosphate, bis (2-acryloyloxymethyl) ethyl phosphate, bis (2-acryloyloxymethyl) propyl phosphate, bis (2-acryloyloxymethyl) butyl phosphate, bis (2-acryloyloxymethyl) pentyl phosphate and tris (2- (Acryloyloxymethyl) phosphate compound having a 2-acryloyloxymethyl group;
2-acryloyloxyethyl dimethyl phosphate, 2-acryloyloxyethyl diethyl phosphate, 2-acryloyloxyethyl dipropyl phosphate, 2-acryloyloxyethyl dibutyl phosphate, 2-acryloyloxyethyl dipentyl 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) pentyl phosphate and tris (2- (Acryloyloxyethyl) phosphate (phosphonate)
Trimethyl phosphonoformate, methyl diethyl phosphonoformate, methyl dipropyl phosphonoformate, methyl dibutyl phosphonoformate, triethyl phosphonoformate, ethyl dimethylphosphonoformate, ethyl dipropyl phosphonoformate, ethyl Dibutyl phosphonoformate, tripropyl phosphonoformate, propyl dimethylphosphonoformate, propyl diethylphosphonoformate, propyl dibutylphosphonoformate, tributyl phosphonoformate, butyl dimethylphosphonoformate, butyl diethylphospho Noformate, butyl dipropylphosphonoformate, methyl bis (2,2,2-trifluoroethyl) phosphonoformate, ethyl bis (2 2,2-trifluoroethyl) phosphonoformate, propyl bis (2,2,2-trifluoroethyl) phosphonoformate, butyl bis (2,2,2-trifluoroethyl) phosphonoformate, trimethyl Phosphoacetate, methyl diethyl phosphonoacetate, methyl dipropyl phosphonoacetate, methyl dibutyl phosphonoacetate, triethyl phosphonoacetate, ethyl dimethylphosphonoacetate, ethyl dipropylphosphonoacetate, ethyl dibutylphosphonoacetate, tripropyl phospho No acetate, propyl dimethyl phosphono acetate, propyl diethyl phosphono acetate, propyl dibutyl phosphono acetate, tributyl phosphono acetate, butyl dimethyl phosphono acetate Butyl diethylphosphonoacetate, butyl dipropylphosphonoacetate, methyl bis (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-propynyl diethylphosphonoacetate, 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- (diethylphosphono) propionate, butyl 3- (dipropylphosphono) propionate, methyl 3- (bis (2,2,2-trifluoroethyl) phosphono) propionate, ethyl 3- (bis (2,2,2) 2-Trifluo Roethyl) phosphono) propionate, propyl 3- (bis (2,2,2-trifluoroethyl) phosphono) propionate, butyl 3- (bis (2,2,2-trifluoroethyl) phosphono) propionate, trimethyl 4-phospho Nobtilate, methyl 4- (diethylphosphono) butyrate, methyl 4- (dipropylphosphono) butyrate, methyl 4- (dibutylphosphono) butyrate, triethyl 4-phosphonobutyrate, ethyl 4- (dimethylphosphono ) Butyrate, ethyl 4- (dipropylphosphono) butyrate, ethyl 4- (dibutylphosphono) butyrate, tripropyl 4-phosphonobutyrate, propyl 4- (dimethylphosphono) butyrate, propyl 4- (diethylphosphono) ) Butyrate, Propyl 4- (Dibu Ruhosuhono) butyrate, tributyl 4-phosphono butyrate, butyl 4- (dimethyl phosphono) butyrate, butyl 4- (diethylphosphono) butyrate, butyl 4- (dipropyl phosphonomethyl) butyrate and the like.

Among these, from the viewpoint of improving battery characteristics, triallyl phosphate and tris (2-acryloyloxyethyl) phosphate, trimethyl phosphonoacetate, triethyl phosphonoacetate, 2-propynyl dimethylphosphonoacetate, 2-propynyl diethylphosphonoacetate Is preferred.

A phosphorus containing organic compound may be used individually by 1 type, and may have 2 or more types together by arbitrary combinations and ratios.
The content of the phosphorus-containing organic compound (the total amount in the case of two or more) can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably in 100% by mass of the electrolytic solution. 0.1% by mass or more, more preferably 0.4% by mass or more, particularly preferably 0.6% by mass or more, and can be 10% by mass or less, preferably 5% by mass or less, more preferably Is 3% by mass or less, more preferably 2% by mass or less, particularly preferably 1.2% by mass or less, and most preferably 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 formula (1) and the phosphorus-containing organic compound is such that the compound represented by the formula (1): phosphorus-containing organic compound is 1: 100 or more, preferably 10: 100 or more, more preferably 20: 100 or more, further preferably 25: 100 or more, and can be 10000: 100 or less, preferably 500: 100 or less, more preferably 300: 100 or less, and still more preferably 100 : 100 or less, particularly preferably 75: 100 or less, and most preferably 50: 100 or less. If it is this range, a battery characteristic, especially a durable characteristic can be improved significantly. Although this principle is not clear, it is considered that the side reaction of the additive on the electrode can be minimized by mixing at this ratio.

1-2-4. Organic compound having cyano group other than formula (1) The organic compound having a cyano group other than formula (1) may be an organic compound other than formula (1) having at least one cyano group in the molecule. Although not particularly limited, compounds represented by formula (2-4-1), formula (2-4-2) and formula (2-4-3) are preferred, and formula (2-4-2) is more preferred. 4-2) and a compound represented by formula (2-4-3), and more preferably a compound represented by formula (2-4-2). In addition, when the organic compound which has cyano groups other than Formula (1) is also a cyclic compound which has a some ether bond, you may belong to the cyclic compound which has a some ether bond.
In the electrolytic solution of the present invention, the combined use of the compound represented by the formula (1) and the organic compound having a cyano group other than the formula (1) improves the durability characteristics in a battery using the electrolytic solution. be able to.

1-2-4-1. Compound represented by formula (2-4-1) A ¹ -CN (2-4-1)
(In the formula, A ¹ represents a hydrocarbon group having 2 to 20 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, preferably 310 or less, more preferably 185 or less, and further preferably 155 or less. If it is this range, it will be easy to ensure the solubility of the compound represented by Formula (2-4-1) with respect to a non-aqueous electrolyte solution, and the effect of this invention will be easy to be expressed. The method for producing the compound represented by the formula (2-4-1) is not particularly limited, and can be produced by arbitrarily selecting a known method.

In the formula (2-4-1), examples of the hydrocarbon group having 2 to 20 carbon atoms include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and the like. An ethyl group, an n-propyl group, an iso-propyl group, and the like. 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 group, decyl group Group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and other alkyl groups; vinyl group, 1-propenyl group, isopropenyl group, 1- Alkenyl groups such as butenyl and 1-pentenyl groups; ethynyl groups, 1-propynyl groups, 1-butynyl groups and 1-pentynyl groups Alkynyl groups such as groups; phenyl group, tolyl group, ethylphenyl group, n-propylphenyl group, i-propylphenyl group, n-butylphenyl group, sec-butylphenyl group, i-butylphenyl group, tert-butylphenyl Group, trifluoromethylphenyl group, xylyl group, benzyl group, phenethyl group, methoxyphenyl group, ethoxyphenyl group, aryl group such as trifluoromethoxyphenyl group, and the like are preferable.

Of these, a straight chain or branched alkyl group having 2 to 15 carbon atoms and an alkenyl group having 2 to 4 carbon atoms are more preferable from the viewpoint that the ratio of the cyano group to the whole molecule is large and the effect of improving battery characteristics is high. Further, a linear or branched alkyl group having 2 to 12 carbon atoms is more preferable, and a linear or branched alkyl group having 4 to 11 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, cyclopentanecarboro. Nitrile, cyclohexanecarbonitrile, acrylonitrile, methacrylonitrile, crotononitrile, 3-methylcrotononitrile, 2-methyl-2-butenenitryl, 2-pentenenitrile, 2-methyl-2-pentenenitrile, 3-methyl -2-pentenenitrile, 2-hexenenitrile and the like.

Among these, pentanenitrile, octanenitrile, decanenitrile, dodecanenitrile and crotononitrile are preferable from the viewpoint of the stability of the compound, battery characteristics and production, pentanenitrile, decanenitrile, dodecanenitrile and crotononitrile are more preferable, Pentanenitrile, decanenitrile and crotononitrile are preferred.
As the compound represented by the formula (2-4-1), one type may be used alone, or two or more types may be used in any combination and ratio. The amount of the compound represented by the formula (2-4-1) (the total amount in the case of two or more types) can be 0.001% by mass or more in 100% by mass of the non-aqueous electrolyte solution, preferably It can be 0.01% by mass or more, more preferably 0.1% by mass or more, and 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 2% by mass. Hereinafter, it is 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.

1-2-4-2. Compound represented by formula (2-4-2) NC-A ² -CN (2-4-2)
(In the formula, A ² has 1 to 10 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. Organic group.)
The organic group having 1 to 10 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 a carbon atom and In addition to an organic group composed of a hydrogen atom, an organic group that may contain a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, or a halogen atom is included. In the organic group which may contain a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom or a halogen atom, a part of the skeleton carbon atom in the group composed of the carbon atom and the hydrogen atom is substituted with these atoms. Or an organic group having a substituent 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, and still more preferably 135 or less. If it is this range, it will be easy to ensure the solubility of the compound represented by Formula (2-4-2) with respect to a non-aqueous electrolyte solution, and the effect of this invention will be easy to be expressed. The method for producing the compound represented by the formula (2-4-2) is not particularly limited, and can be produced by arbitrarily selecting a known method.

As A ² in the compound represented by the formula (2-4-2), 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 , Arylene group or derivative thereof, carbonyl group or derivative thereof, sulfonyl group or derivative thereof, sulfinyl group or derivative thereof, phosphonyl group or derivative thereof, phosphinyl group or derivative thereof, amide group or derivative thereof, imide group or derivative thereof, ether Groups or derivatives thereof, thioether groups or derivatives thereof, borinic acid groups or derivatives thereof, borane groups or derivatives thereof, and the like.

Among these, 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 is preferable. A ² is more preferably an alkylene group having 2 to 5 carbon atoms which may have a substituent.
Examples of the compound represented by the formula (2-4-2) include malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimonitrile, suberonitrile, azeronitrile, sebacononitrile, undecandinitrile, dodecandinitrile, methylmalononitrile, ethylmalononitrile. Nitrile, 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-dicyanodeca 1,2-didianobenzene, 1,3-dicyanobenzene, 1,4-dicyanobenzene, 3,3 ′-(ethylenedioxy) dipropionitrile, 3,3 ′-(ethylenedithio) dipropionitrile, and 3,9-bis (2-cyanoethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like can be mentioned.

  Among these, malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimeonitrile, suberonitrile, azeronitrile, sebacononitrile, undecandinitrile, dodecandinitrile and 3,9-bis (2-cyanoethyl) -2,4,8,10 -Tetraoxaspiro [5,5] undecane and fumaronitrile are preferred from the viewpoint of improving high-temperature storage durability characteristics. Furthermore, succinonitrile, glutaronitrile, adiponitrile, pimonitrile, suberonitrile, glutaronitrile and 3,9-bis (2-cyanoethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane are The effect of improving the high-temperature storage durability is particularly excellent, and the deterioration due to side reaction at the electrode is small, so that it is more preferable. Usually, in dinitrile compounds, the smaller the molecular weight, the larger the proportion of cyano groups in one molecule and the higher the viscosity of the molecule, while the higher the molecular weight, the higher the boiling point of the compound. Therefore, succinosuccinonitrile, glutaronitrile, adiponitrile, and pimelonitrile are more preferable from the viewpoint of improving working 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 any combination and ratio. The amount of the compound represented by the formula (2-4-2) (the total amount in the case of two or more types) can be 0.001% by mass or more in 100% by mass of the electrolytic solution, and preferably is 0.00. 01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.3% by mass or more, and can be 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass. It is contained at a concentration of not more than mass%. When the above range is satisfied, effects such as output characteristics, load characteristics, low temperature characteristics, cycle characteristics, and high temperature storage characteristics are further improved.
1-2-4-3. Compound represented by formula (2-4-3)

(In the formula, A ³ is a carbon atom having 1 to 12 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. (It is an organic group, and n ⁴³ is an integer of 0 or more and 5 or less.)
An organic group having 1 to 12 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 a carbon atom. And an organic group which may contain a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom or a halogen atom in addition to an organic group composed of a hydrogen atom. In the organic group which may contain a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom or a halogen atom, a part of the skeleton carbon atom in the group composed of the carbon atom and the hydrogen atom is substituted with these atoms. Or an organic group having a substituent 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.
In addition, A ³ is preferably an organic group having 1 to 12 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, and a sulfur atom. More preferably, it is an organic group having 1 to 12 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 carbon atom, hydrogen atom, nitrogen atom, oxygen atom, sulfur atom, phosphorus atom and halogen atom.
Substituents include halogen atoms; unsubstituted or halogen-substituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups; isocyanato groups; alkoxycarbonyloxy groups; acyl groups; carboxyl groups; alkoxycarbonyl groups; An alkylsulfonyl group; an alkoxysulfonyl group; a dialkoxyphosphantriyl group; a dialkoxyphosphoryl group and a dialkoxyphosphoryloxy group, 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 still 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 Below, more preferably 6 or less.
Examples of the aliphatic hydrocarbon group, in response to n ^43, alkanetriyl, alkanetetrayl groups, alkane pen tile group, alkanetetrayl groups, alkene tri-yl group, alkene tetrayl group, alkene pen tile group, alkene Examples thereof include a tetrayl group, an alkyne triyl group, an alkyne tetrayl group, an alkyne pentile group, and an alkyne tetrayl group.

Of these, saturated hydrocarbon groups such as alkanetriyl groups, alkanetetrayl groups, alkanepentyl groups, and alkanetetrayl groups are more preferred, and alkanetriyl groups are more preferred.
Furthermore, the compound represented by the formula (2-4-3) is more preferably a compound represented by the formula (2-4-3 ′).

(Wherein, ^{A 4} and ^{A 5} are as defined in the above ^{A 3.)}
The above A ⁴ and A ⁵ are more preferably a hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
As the hydrocarbon group, 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, propynylene group, 1-butynylene group, 2-butynylene group, 1-pentynylene group, 2-pentynylene group and the like.

Among 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.
A ⁴ and A ⁵ are preferably not the same as each other but different.
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, further preferably 150 or more, preferably 450 or less, more preferably 300 or less, and further preferably 250 or less. If it is this range, it will be easy to ensure the solubility of the compound represented by Formula (2-4-3) with respect to a non-aqueous electrolyte solution, and the effect of this invention will be easy to be expressed. The method for producing the compound represented by the formula (2-4-3) is not particularly limited, and can be produced by arbitrarily selecting a known method.
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 the storage characteristics.

  The amount of the compound represented by the formula (2-4-3) (the total amount in the case of 2 or more types) can be 0.001% by mass or more in 100% by mass of the electrolytic solution, and preferably is 0.00. 01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.3% by mass or more, and can be 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass. It is contained at a concentration of not more than mass%, particularly preferably not more than 2 mass%. 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 organic compound which has cyano groups other than Formula (1) may be used individually by 1 type, and may have 2 or more types together by arbitrary combinations and ratios.
The mass ratio of the compound represented by the formula (1) and 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). Can be 1: 100 or more, preferably 10: 100 or more, more preferably 20: 100 or more, still more preferably 25: 100 or more, and 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. If it is this range, a battery characteristic, especially a durable characteristic can be improved significantly. Although this principle is not clear, it is considered that the side reaction of the additive on the electrode can be minimized by mixing at this ratio.

1-2-5. 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 preferably 1 or more in one molecule. 4 or less, more preferably 2 or more and 3 or less, and still more preferably 2.
In the electrolytic solution of the present invention, by using the compound represented by the formula (1) and the compound having an isocyanate group in combination, durability characteristics can be improved in a battery using this electrolytic solution.

Examples of the organic compound having an isocyanate group include the following.
Isocyanate groups such as 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, phenyl isocyanate, fluorophenyl isocyanate An organic compound having one of the following:
Monomethylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanate Natopropane, 1,4-diisocyanato-2-butene, 1,4-diisocyanato-2-fluorobutane, 1,4-diisocyanato-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 (isocyanato) Methyl) 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 (methylisocyanate), bicyclo [2.2.1] heptane-2,6-diylbis (methylisocyanate), isophorone diisocyanate, carbonyl diisocyanate, 1,4-diisocyanatobutane-1,4- It has two isocyanate groups such as dione, 1,5-diisocyanatopentane-1,5-dione, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. Organic compounds; and the like.

Among 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 (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-trimethylhexamethyle Organic compounds having two isocyanate groups such as diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate are preferred from the viewpoint of improving the storage characteristics, and hexamethylene diisocyanate and 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'-Gii Cyanate, bicyclo [2.2.1] heptane-2,5-diyl bis (methyl isocyanate), bicyclo [2.2.1] heptane-2,6-diyl bis (methyl isocyanate) are more preferred.

  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 obtained by adding a polyhydric alcohol thereto. Examples thereof include biuret, isocyanurate, adduct, and bifunctional type modified polyisocyanate represented by the basic structures of formulas (2-5-1) to (2-5-4).

(In the formula, R ^{51 to} R ⁵⁴ and R ⁵⁴ ′ are independently a divalent hydrocarbon group (for example, a tetramethylene group or a hexamethylene group), and R ⁵³ ′ is independently a trivalent group. Hydrocarbon group.)
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 enhance storage stability. Examples of the blocking agent include alcohols, phenols, organic amines, oximes, and lactams. Specific examples include n-butanol, phenol, tributylamine, diethylethanolamine, methyl ethyl ketoxime, and ε-caprolactam. Etc.

Metal catalysts such as dibutyltin dilaurate and amines such as 1,8-diazabicyclo [5.4.0] undecene-7 are used for the purpose of promoting a reaction based on an organic compound having an isocyanate group and obtaining a higher effect. It is also preferable to use a system catalyst or the like in combination.
The organic compound which has an isocyanate group may be used individually by 1 type, and may have 2 or more types together by arbitrary combinations and ratios.

  The amount of the organic compound having an isocyanate group (the total amount in the case of two or more) can be 0.001% by mass or more, preferably 0.1% by mass or more, more preferably in 100% by mass of the electrolytic solution. Is 0.3% 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. 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 formula (1) and the organic compound having an isocyanate group is such that the compound represented by the formula (1): the organic compound having an isocyanate group is 1: 100 or more, Preferably it is 10: 100 or more, more preferably 20: 100 or more, still more preferably 25: 100 or more, and can be 10000: 100 or less, preferably 500: 100 or less, more preferably 300: 100 or less, More preferably, it is 100: 100 or less, particularly preferably 75: 100 or less, and most preferably 50: 100 or less. If it is this range, a battery characteristic, especially a durable characteristic can be improved significantly. Although this principle is not clear, it is considered that the side reaction of the additive on the electrode can be minimized by mixing at this ratio.

1-2-6. 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 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.
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 (tripropylsilyl), Tris phosphate (triphenylsilyl), Tris phosphate (trimethoxysilyl), Phosphoric acid Phosphoric acid compounds such as tris (triethoxysilyl), tris (triphenoxysilyl) phosphate, tris (dimethylvinylsilyl) phosphate and tris (diethylvinylsilyl) phosphate;
Tris phosphite (trimethylsilyl), Tris phosphite (triethylsilyl), Tris phosphite (tripropylsilyl), Tris phosphite (triphenylsilyl), Tris phosphite (trimethoxysilyl), Phosphorous acid Phosphite compounds such as tris (triethoxysilyl), tris phosphite (triphenoxysilyl), tris phosphite (dimethylvinylsilyl) and tris phosphite (diethylvinylsilyl);
Sulfonic acid compounds such as trimethylsilyl methanesulfonate and trimethylsilyl tetrafluoromethanesulfonate;
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;
Etc.

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

In addition, these silicon containing compounds may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
The silicon-containing compound (the total amount in the case of two or more) can be 0.001% by mass or more, preferably 0.1% by mass or more, more preferably 0.3% by mass in 100% by mass of the electrolytic solution. % Or more, and can be 10% by mass or less, preferably 5% by mass or less, more 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 formula (1) and the silicon-containing compound (the total amount in the case of two or more) is 1: 100 or more of the compound represented by the formula (1): silicon-containing compound. Preferably 10: 100 or more, more preferably 20: 100 or more, further preferably 25: 100 or more, and 10000: 100 or less, preferably 500: 100 or less, more preferably 300 : 100 or less, more preferably 100: 100 or less, particularly preferably 75: 100 or less, and most preferably 50: 100 or less. If it is this range, a battery characteristic, especially a durable characteristic can be improved significantly. Although this principle is not clear, it is considered that the side reaction of the additive on the electrode can be minimized by mixing at this ratio.

1-2-7. Aromatic compounds (excluding compounds represented by formula (1))
The electrolytic solution of the present invention can contain an aromatic compound. The aromatic compound is not particularly limited as long as it is an organic compound having at least one aromatic ring in the molecule, but is preferably represented by formulas (2-7-1) and (2-7-2). It is an aromatic compound represented.
1-2-7-1. Aromatic compound represented by formula (2-7-1)

(In the formula, the substituent X ⁷¹ represents a halogen atom, a halogen atom or an organic group which may have a hetero atom. The organic group which may have a hetero atom is a group having 1 to 12 carbon atoms. A linear or branched or cyclic saturated hydrocarbon group, a group having a carboxylate structure, a group having a carbonate structure (excluding a fluorine-containing cyclic carbonate), a group having a phosphorus atom, a group having a sulfur atom, And a group having a silicon atom, and each substituent may be further substituted with a halogen atom, a hydrocarbon group, an aromatic group, a halogen-containing hydrocarbon group, a halogen-containing aromatic group, or the like. The number n ^{71 of} X ⁷¹ is 1 or more and 6 or less, and when it has a plurality of substituents, each substituent may be the same or different, and may form a ring.
Among these, a linear, branched or 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 group having a straight chain, branched chain or cyclic saturated hydrocarbon group having 3 to 12 carbon atoms and a carboxylate structure.

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

  Examples of the organic group having no hetero atom include linear, branched, and cyclic saturated hydrocarbon groups having 3 to 12 carbon atoms. The linear and branched groups include those having a ring structure. It is. Specific examples of linear, branched, and cyclic saturated hydrocarbon groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and pentyl. Group, tert-pentyl group, cyclopentyl group, cyclohexyl group, 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, and a silicon atom. Examples of the group having an oxygen atom include a group having a carboxylic ester structure and a group having a carbonate structure. Examples of those having a sulfur atom include groups having a sulfonate structure. Examples of those having a phosphorus atom include a group having a phosphate ester structure, a group having a phosphonate ester structure, and the like. Examples of the group having a silicon atom include a group having a silicon-carbon structure.

Examples of the aromatic compound represented by the formula (2-7-1) include the following.
As ^X71 being a halogen atom or an organic group which may have a halogen atom, chlorobenzene, fluorobenzene, difluorobenzene, trifluorobenzene, tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene, benzotrifluoride, etc. And preferred are fluorobenzene and hexafluorobenzene. More preferred is fluorobenzene.

As ^X71 is a hydrocarbon group having 1 to 12 carbon atoms,
2,2-diphenylpropane, 1,4-diphenylcyclohexane, cyclopentylbenzene, cyclohexylbenzene, cis-1-propyl-4-phenylcyclohexane, trans-1-propyl-4-phenylcyclohexane, cis-1-butyl-4- Phenylcyclohexane, trans-1-butyl-4-phenylcyclohexane, propylbenzene, butylbenzene, tert-butylbenzene, tert-amylbenzene, and the like, preferably 2,2-diphenylpropane, 1,4-diphenylcyclohexane, Cyclopentylbenzene, cyclohexylbenzene, cis-1-propyl-4-phenylcyclohexane, trans-1-propyl-4-phenylcyclohexane, cis-1-butyl-4-phenylcyclohexa , 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, and tert-amylbenzene, and more preferable examples include cyclohexylbenzene, tert-butylbenzene, and tert-amylbenzene.

As ^X71 is a group having a carboxylate structure,
Phenyl acetate, benzyl acetate, 2-phenylethyl acetate, 3-phenylpropyl acetate, 4-phenylbutyl acetate, phenyl propionate, benzyl propionate, 2-phenylethyl propionate, 3-phenylpropyl propionate, 4-propionate 4- Phenyl butyl, phenyl butyrate, benzyl butyrate, 2-phenylethyl butyrate, 3-phenylpropyl butyrate, 4-phenylbutyl butyrate, methyl phenylacetate, ethyl phenylacetate, propylphenylacetate, butylphenylacetate, phenylphenylacetate, phenylphenylacetate 2-phenylethyl phenylacetate, 3-phenylpropyl phenylacetate, 4-phenylbutyl phenylacetate, methyl 2,2-dimethyl-phenylacetate, ethyl 2,2-dimethyl-phenylacetate, 2,2-dimethyl-phenyl Propyl nyl acetate, 2,2-dimethyl-phenyl acetate butyl, 2,2-dimethyl-phenyl acetate phenyl, 2,2-dimethyl-phenyl acetate benzyl, 2,2-dimethyl-phenyl acetate 2-phenylethyl, 2,2 -3-phenylpropyl dimethyl-phenylacetate, 4-phenylbutyl 2,2-dimethyl-phenylacetate, methyl 3-phenylpropionate, ethyl 3-phenylpropionate, propyl 3-phenylpropionate, butyl 3-phenylpropionate , Phenyl 3-phenylpropionate, benzyl 3-phenylpropionate, 2-phenylethyl 3-phenylpropionate, 3-phenylpropyl 3-phenylpropionate, 4-phenylbutyl 3-phenylpropionate, methyl 4-phenylbutyrate 4-phenylbutyric acid ethyl Propyl 4-phenylbutyrate, butyl 4-phenylbutyrate, phenyl 4-phenylbutyrate, benzyl 4-phenylbutyrate, 2-phenylethyl 4-phenylbutyrate, 3-phenylpropyl 4-phenylbutyrate, 4-phenylbutyrate Butyl, methyl 5-phenyl valerate, ethyl 5-phenyl valerate, propyl 5-phenyl valerate, butyl 5-phenyl valerate, phenyl 5-phenyl valerate, benzyl 5-phenyl valerate, 5-phenyl valerate 2 -Phenylethyl, 3-phenylpropyl 5-phenylvalerate, 4-phenylbutyl 5-phenylvalerate, methyl 1-phenylcyclopentanecarboxylate, ethyl 1-phenylcyclopentanecarboxylate, propyl 1-phenylcyclopentanecarboxylate 1-phenylcyclopentanecarboxylic acid buty 1-phenylcyclopentanecarboxylic acid phenyl, 1-phenylcyclopentanecarboxylic acid benzyl, 1-phenylcyclopentanecarboxylic acid 2-phenylethyl, 1-phenylcyclopentanecarboxylic acid 3-phenylpropyl, 1-phenylcyclopentanecarboxylic acid 4-phenylbutyl acid, 2,2-bis (4-acetoxyphenyl) propane, and the like, preferably 2-phenylethyl acetate, 3-phenylpropyl acetate, 4-phenylbutyl acetate, 2-phenylethyl propionate 3-phenylpropyl propionate, 4-phenylbutyl propionate, 2-phenylethyl butyrate, 3-phenylpropyl butyrate, 4-phenylbutyl butyrate, methyl phenylacetate, ethyl phenylacetate, propylphenylacetate, butylphenylacetate, 2-phenylethyl phenylacetate, 3-phenylpropyl phenylacetate, 4-phenylbutyl phenylacetate, methyl 2,2-dimethyl-phenylacetate, ethyl 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, Methyl 3-phenylpropionate, ethyl 3-phenylpropionate, propyl 3-phenylpropionate, butyl 3-phenylpropionate, 2-phenylethyl 3-phenylpropionate, 3-phenylpropyl 3-phenylpropionate, 3- 4-phenylbutyl phenylpropionate Methyl 4-phenylbutyrate, ethyl 4-phenylbutyrate, propyl 4-phenylbutyrate, butyl 4-phenylbutyrate, 2-phenylethyl 4-phenylbutyrate, 3-phenylpropyl 4-phenylbutyrate, 4-phenylbutyl 4-phenylbutyrate Methyl 5-phenylvalerate, ethyl 5-phenylvalerate, propyl 5-phenylvalerate, butyl 5-phenylvalerate, 2-phenylethyl 5-phenylvalerate, 3-phenylpropyl 5-phenylvalerate, 5 4-phenylbutyl phenylvalerate, methyl 1-phenylcyclopentanecarboxylate, ethyl 1-phenylcyclopentanecarboxylate, propyl 1-phenylcyclopentanecarboxylate, butyl 1-phenylcyclopentanecarboxylate, 1-phenylcyclopentane 2-phenylethyl carboxylate, 1 -3-phenylpropyl phenylcyclopentanecarboxylate, more preferably 2-phenylethyl acetate, 3-phenylpropyl acetate, methyl phenylacetate, ethyl phenylacetate, 2-phenylethyl phenylacetate, 3-phenylpropyl phenylacetate 2,2-dimethyl-phenylacetic acid methyl, 2,2-dimethyl-phenylacetic acid ethyl, 2,2-dimethyl-phenylacetic acid 2-phenylethyl, 2,2-dimethyl-phenylacetic acid 3-phenylpropyl, 3-phenylpropoxy Methyl onate, ethyl 3-phenylpropionate, 2-phenylethyl 3-phenylpropionate, 3-phenylpropyl 3-phenylpropionate, methyl 5-phenylvalerate, ethyl 5-phenylvalerate, 5-phenylvalerate 2-phenylethyl, 5-pheny 3-phenylpropyl valerate, methyl 1-phenylcyclopentanecarboxylate, ethyl 1-phenylcyclopentanecarboxylate, 2-phenylethyl 1-phenylcyclopentanecarboxylate, 3-phenylpropyl 1-phenylcyclopentanecarboxylate And more preferably 2-phenylethyl acetate, 3-phenylpropyl acetate, methyl phenylacetate, ethyl phenylacetate, 2-phenylethyl phenylacetate, 3-phenylpropyl phenylacetate, methyl 2,2-dimethyl-phenylacetate, 2 1,2-dimethyl-phenylacetic acid ethyl, 2,2-dimethyl-phenylacetic acid 2-phenylethyl, 2,2-dimethyl-phenylacetic acid 3-phenylpropyl, methyl 3-phenylpropionate, ethyl 3-phenylpropionate, 3 -Phenylp 2-phenylethyl pionate, 3-phenylpropyl 3-phenylpropionate, methyl 5-phenylvalerate, ethyl 5-phenylvalerate, 2-phenylethyl 5-phenylvalerate, 3-phenylpropyl 5-phenylvalerate 1-phenylcyclopentanecarboxylic acid methyl, 1-phenylcyclopentanecarboxylic acid ethyl, 1-phenylcyclopentanecarboxylic acid 2-phenylethyl, 1-phenylcyclopentanecarboxylic acid 3-phenylpropyl.

As 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-tert-butylphenyl) carbonate, 4-tert-butylphenylmethyl carbonate, 4-tert-butylphenylethyl carbonate, bis (4-tert-butylphenyl) carbonate, benzyl And methyl carbonate, benzyl ethyl carbonate, dibenzyl carbonate and the like, preferably 2,2-bis (4-methoxycarbonyloxyphenyl) propane, , 1,1-bis (4-methoxycarbonyloxyphenyl) cyclohexane body, diphenyl carbonate, methyl phenyl carbonate, more preferably diphenyl carbonate, methyl phenyl carbonate, more preferably, and the like methyl phenyl carbonate.

As ^X71 is a group having a sulfonate structure,
Examples include methyl phenyl sulfonate, ethyl phenyl sulfonate, diphenyl sulfonate, phenyl methyl sulfonate, 2-tert-butyl phenyl methyl sulfonate, 4-tert-butyl phenyl methyl sulfonate, cyclohexyl phenyl methyl sulfonate, and the like, preferably methyl phenyl sulfonate, diphenyl sulfonate 2-tert-butylphenylmethylsulfonate, 4-tert-butylphenylmethylsulfonate, cyclohexylphenylmethylsulfonate, more preferably methylphenylsulfonate, 2-tert-butylphenylmethylsulfonate, 4-tert-butylphenylmethylsulfonate Cyclohexyl phenyl methyl sulfonate.

As ^X71 is a group having a silicon-carbon structure,
Examples include trimethylphenylsilane, diphenylsilane, diphenyltetramethyldisilane, and the like, preferably trimethylphenylsilane.
As ^X71 is a group having a phosphate 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-cyclohexylphenyl) phosphate, tris (4-cyclohexylphenyl) phosphate, diethyl (4 -Methylbenzyl) phosphonate and the like, preferably triphenyl phosphate, tris (2-tert-butylphenyl) phosphate, tris (3-tert-butylpheny). ) 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-cyclohexylphenyl) phosphate, tris (4-cyclohexylphenyl) phosphate, more preferably tris (2-tert-butylphenyl) phosphate, tris (4-tert-butylphenyl) Phosphate, tris (2-cyclohexylphenyl) phosphate, tris (4-cyclohexylphenyl) phosphate.

As X ⁷¹ is a group having a phosphonic acid 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, Dimethylbenzylphosphonate, diethylbenzylphosphonate, Methyl- (4-fluorobenzyl) phosphonate, diethyl- (4-fluorobenzyl) phosphonate, more preferably dimethylphenylphosphonate, diethylphenylphosphonate, dimethylbenzylphosphonate, diethylbenzylphosphonate, dimethyl- (4-fluorobenzyl) phosphonate , Diethyl- (4-fluorobenzyl) phosphonate.

The aromatic compound represented by the formula (2-7-1) includes a fluorinated product of the aromatic compound. In particular,
Partially fluorinated compounds having hydrocarbon groups such as trifluoromethylbenzene, 2-fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, trifluoromethylbenzene, o-cyclohexylfluorobenzene, p-cyclohexylfluorobenzene; 2- Partially fluorinated products of carboxylic acid ester structures 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, partially fluorinated compounds having an ether structure such as 4-trifluoromethoxyanisole, etc. Preferably a partially fluorinated product having a hydrocarbon group such as trifluoromethylbenzene, 2-fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, o-cyclohexylfluorobenzene, p-cyclohexylfluorobenzene; 2-fluorophenylacetate , Partially fluorinated compounds having a carboxylic acid ester structure such as 4-fluorophenylacetate; ether structures such as trifluoromethoxybenzene 2-fluoroanisole, 4-fluoroanisole, 2,4-difluoroanisole, 4-trifluoromethoxyanisole A partially fluorinated compound having a hydrocarbon group, more preferably a partially fluorinated compound having a hydrocarbon group such as 2-fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, etc .; Partially fluorinated products of carboxylic acid ester structures such as phenyl acetate and 4-fluorophenyl acetate; trifluoromethoxybenzene, 2-fluoroanisole, 4-fluoroanisole, 2,4-difluoroanisole, 4-trifluoromethoxyanisole, etc. These are partially fluorinated compounds having an ether structure.

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

(Wherein R ^{11 to} R ¹⁵ are each independently hydrogen, halogen, or an unsubstituted or halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁶ and R ¹⁷ are independently carbon atoms. It is a hydrocarbon group having a number of 1 or more and 12 or less, and at least two of R ^{11 to} R ¹⁷ may be combined to form a ring, provided that the formula (2-7-2) is (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 to 20 carbon atoms.
(B) The total number of carbon atoms of R ^{11 to} R ¹⁷ is 3 or more and 20 or less, satisfying at least one condition)
It is an aromatic compound represented by these. If at least two of R ¹¹ to R ¹⁷ but that together form a ^ring, it is preferred that two of R 11 ^{to R 17} form a ring together.

R ¹⁶ and R ¹⁷ are each independently a hydrocarbon group having 1 to 12 carbon atoms (for example, an alkyl group or an aryl group), and R ¹⁶ and R ¹⁷ are combined to form a ring (for example, a hydrocarbon group). A cyclic group) may be formed. From the viewpoint of improving the initial efficiency, solubility and storage characteristics, R ¹⁶ and R ¹⁷ are preferably hydrocarbon groups having 1 to 12 carbon atoms, or hydrocarbons formed by combining R ¹⁶ and R ¹⁷ together. A cyclic group, more preferably a methyl group, an ethyl group, a propyl group, a butyl group, a tert-butyl group, or a hydrocarbon group formed by combining R ¹⁶ and R ¹⁷ together 5 -8-membered cyclic group, more preferably a methyl group, an ethyl group, a cyclohexyl group formed by combining R ¹⁶ and R ¹⁷ and a cyclopentyl group, and most preferably a methyl group, an ethyl group, R A cyclohexyl group formed by combining ¹⁶ and R ¹⁷ together.

R ^{11 to} R ¹⁵ are independently hydrogen, halogen, or an unsubstituted or halogen-substituted hydrocarbon group having 1 to 20 carbon atoms (for example, an alkyl group, an aryl group, and an aralkyl group). They may be joined together to form a ring (for example, a cyclic group which is a hydrocarbon group). From the viewpoint of improving initial efficiency, solubility and storage characteristics, hydrogen, fluorine, unsubstituted or halogen-substituted hydrocarbon group having 1 to 12 carbon atoms is preferable, and hydrogen, fluorine, unsubstituted or fluorine-substituted is more preferable. A hydrocarbon group having 1 to 10 carbon atoms, more 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, nonafluoro tert-butyl group, 1-methyl-1-phenyl-ethyl group, 1-ethyl-1-phenyl-propyl group, particularly preferably hydrogen, fluorine, tert-butyl group, 1-methyl-1-phenyl-ethyl group, most preferably hydrogen, tert-butyl group, 1-methyl-1- Eniru - an ethyl group.

Any one of R ^{11 to} R ¹⁵ may be combined with R ¹⁶ to form a ring (for example, a cyclic group that is a hydrocarbon group). Preferably, R ¹¹ and R ¹⁶ are combined to form a ring (for example, a cyclic group that is a hydrocarbon group). In this case, R ¹⁷ is preferably an alkyl group. Examples of compounds in which R ¹⁷ is a methyl group and R ¹¹ and R ¹⁶ are combined to form a ring include 1-phenyl-1,3,3-trimethylindane, 2,3-dihydro-1,3-dimethyl-1- (2-methyl-2-phenylpropyl) -3-phenyl-1H-indane and the like.

Formula (2-7-2) is represented by (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 to 20 carbon atoms.
(B) The total number of carbon atoms of R ^{11 to} R ¹⁷ is 3 or more and 20 or less.
Satisfies at least one of the conditions.

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 electrolyte, B) is preferably satisfied. Formula (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 to 20 carbon atoms, a ring is formed even if the other is a hydrogen atom You may do 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, and still more preferably. 1 or 2, most preferably 1.

As for (B), if the total number of carbon atoms of R ^{11 to} R ¹⁷ is 3 or more and 20 or less, at least two of R ^{11 to} R ¹⁷ may be combined to form a ring. In the case where at least two of R ^{11 to} R ¹⁷ are combined to form a ring, in calculating the total number of carbon atoms, carbon that does not correspond to R ^{11 to} R ¹⁷ among the carbons forming the ring (R for ¹¹ to R ^15, carbon atoms constituting the benzene ring to which they are ^attached, for ^{R 16} and ^{R 17,} carbon atoms in the benzyl position) is set to be not counted. The total number of carbon atoms is preferably 3 or more and 14 or less, more preferably 3 or more and 10 or less, from the viewpoint of solubility in the electrolytic solution. For example, compounds in which R ¹⁷ is a methyl group and R ¹¹ and R ¹⁶ are combined to form a ring include 1-phenyl-1,3,3-trimethylindane, 2,3-dihydro-1,3-dimethyl Examples include -1- (2-methyl-2-phenylpropyl) -3-phenyl-1H-indane, which satisfies the condition (B).

Examples of the aromatic compound represented by the formula (2-7-2) include the following.
R ¹⁶ and R ¹⁷ are each independently a hydrocarbon group having 1 to 20 carbon atoms (provided that
R ¹⁶ and R ^{17 have} a total of 3 to 20 carbon atoms), and compounds in which R ^{11 to} R ¹⁵ are hydrogen (satisfy (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 are combined to form a ring, and R ^{11 to} R ¹⁵ are hydrogen (satisfying (B)).
1,1-diphenylcyclohexane, 1,1-diphenylcyclopentane, 1,1-diphenyl-4-methylcyclohexane.
The following compounds may be used (they may be overlapped with the above-exemplified compounds, but will be represented by a structural formula).

A compound in which at least one of R ^{11 to} R ¹⁵ is a halogen or an unsubstituted or halogen-substituted hydrocarbon group having 1 to 20 carbon atoms (satisfies (A)).
1,3-bis (1-methyl-1-phenylethyl) -benzene, 1,4-bis (1-methyl-1-phenylethyl) -benzene.
The following compounds may be used (they may be overlapped with the above-exemplified compounds, but will be represented by a structural formula).

R ¹⁷ is a hydrocarbon group having 1 to 20 carbon atoms (for example, an alkyl group having 1 to 20 carbon atoms, preferably a methyl group), and R ¹¹ and R ¹⁶ together form a ring. Compound (which satisfies (B)).
1-phenyl-1,3,3-trimethylindane.
The following compounds may be used (they may be overlapped with the above-exemplified compounds, but will be represented by a structural formula).

Among these, from the viewpoint of reducing properties 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 can also be mentioned as preferable ones (they may be overlapped with the above-mentioned preferable compounds, but will be represented by the structural formula).

More preferred is
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-trimethylindane.
The following compounds may also be mentioned as more preferable ones (they may be overlapped with the more preferable compounds described above, but will be represented 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-trimethylindane.
The following compounds are also mentioned as more preferable ones (they may be overlapped with the above-mentioned more preferable compounds, but will be shown by the structural formula).

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

  Most preferred is a 1-phenyl-1,3,3-trimethylindane compound, which is represented by the following structural formula.

  An aromatic compound may be used independently or may use 2 or more types together. In the total amount of the non-aqueous electrolyte solution (100% by mass), the amount of aromatic compound (total amount in the case of two or more types) can be 0.001% by mass or more, preferably 0.01% by mass or more, More preferably 0.05 mass% or more, still more preferably 0.1 mass% or more, still more preferably 0.4 mass% or more, and can be 10 mass% or less, preferably 8 mass% or less. More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less, Most preferably, it is 2.5 mass% or less. By being in the said range, the effect of this invention is easy to express and the resistance increase of a battery can be prevented.

  The mass ratio of the compound represented by the formula (1) and the aromatic compound (the total amount in the case of two or more) is 1: 100 or more of the compound represented by the formula (1): aromatic compound. Preferably 10: 100 or more, more preferably 20: 100 or more, further preferably 25: 100 or more, and 10000: 100 or less, preferably 500: 100 or less, more preferably 300 : 100 or less, more preferably 100: 100 or less, particularly preferably 75: 100 or less, and most preferably 50: 100 or less. If it is this range, a battery characteristic, especially a durable characteristic can be improved significantly. Although this principle is not clear, it is considered that the side reaction of the additive on the electrode can be minimized by mixing at this ratio.

1-2-8. Fluorine-free carboxylic acid ester The electrolyte solution of the present invention may contain a fluorine-free carboxylic acid ester. In the electrolytic solution of the present invention, durability characteristics can be improved by using a compound represented by the formula (1) and a fluorine-free carboxylic acid ester in combination. 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, more preferably a fluorine-free carboxylic acid ester. It is a saturated chain carboxylic acid ester. The total number of carbon atoms of the fluorine-free chain carboxylic acid ester is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, preferably 7 or less, more preferably 6 or less, still more preferably 5 or less. It is.

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-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate, tert-butyl butyrate, methyl isobutyrate, ethyl isobutyrate, iso N-propyl butyrate, isopropyl isobutyrate, n-butyl isobutyrate, isobutyl isobutyrate, tert-butyl isobutyrate, methyl valerate, ethyl valerate, n-propyl valerate, isopropyl valerate, n-butyl valerate, Isobutyl valerate, valerate-ter -Butyl, methyl hydroangelate, ethyl hydroangelate, n-propyl hydroangelate, isopropyl hydroangelate, n-butyl hydroangelate, isobutyl hydroangelate, tert-butyl hydroangelate, methyl isovalerate, Ethyl isovalerate, n-propyl isovalerate, isopropyl isovalerate, n-butyl isovalerate, isobutyl isovalerate, isotert-butyl isovalerate, methyl pivalate, ethyl pivalate, n-propyl pivalate , Saturated carboxylic acid esters such as isopropyl pivalate, n-butyl pivalate, isobutyl pivalate, tert-butyl pivalate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, acrylic acid n-butyl, a Isobutyl toluate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, methyl crotonate, Ethyl crotonate, n-propyl crotonate, isopropyl crotonate, n-butyl crotonate, isobutyl crotonate, tert-butyl crotonate, methyl 3-butenoate, ethyl 3-butenoate, n-propyl 3-butenoate Isopropyl 3-butenoate, n-butyl 3-butenoate, isobutyl 3-butenoate, tert-butyl 3-butenoate, methyl 4-pentenoate, ethyl 4-pentenoate, n-propyl 4-pentenoate, Isopropyl 4-pentenoate, n-pentenoic acid n -Butyl, 4-butyl pentenoate, 4-tert-butyl 4-pentenoate, methyl 3-pentenoate, ethyl 3-pentenoate, n-propyl 3-pentenoate, isopropyl 3-pentenoate, n-pentenoic acid n- Butyl, 3-butyl pentenoate, tert-butyl 3-pentenoate, methyl 2-pentenoate, ethyl 2-pentenoate, n-propyl 2-pentenoate, isopropyl 2-pentenoate, n-butyl 2-pentenoate , 2-butyl pentenoate, 2-tert-butyl 2-pentenoate, methyl 2-propinate, ethyl 2-propinate, n-propyl 2-propinate, isopropyl 2-propanoate, n-butyl 2-propinate, 2-isopropanoate, 2-tert-butyl 2-propanoate, methyl 3-butyrate, ethyl 3-butyrate N-propyl 3-butyrate, isopropyl 3-butyrate, n-butyl 3-butyrate, isobutyl 3-butyrate, 3-tert-butyl butyrate, methyl 2-butyrate, ethyl 2-butyrate, 2 -N-propyl butyrate, isopropyl 2-butyrate, n-butyl 2-butyrate, isobutyl 2-butyrate, 2-tert-butyl butyrate, methyl 4-pentynoate, ethyl 4-pentynoate, 4- N-propyl pentinate, isopropyl 4-pentynoate, n-butyl 4-pentynoate, isobutyl 4-pentynoate, 4-tert-butyl 4-pentynoate, methyl 3-pentynoate, ethyl 3-pentynoate, 3-pentyne N-propyl acid, isopropyl 3-pentynoate, n-butyl 3-pentynoate, isobutyl 3-pentynoate, 3-pentynoic acid-ter -Butyl, 2-pentynoic acid methyl, 2-pentynoic acid ethyl, 2-pentynoic acid n-propyl, 2-pentynoic acid isopropyl, 2-pentynoic acid n-butyl, 2-pentynoic acid isobutyl, 2-pentynoic acid Unsaturated chain carboxylic acid esters such as butyl.

  Among these, since there are few side reactions at the negative electrode, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, 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, ethyl pivalate, n-propyl pivalate, N-Butyl pivalate is preferable, and from the viewpoint of improving ionic conductivity due to a decrease in electrolyte viscosity, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl propionate, ethyl propionate, n-propionate Propyl, n-butyl propionate is more preferred, methyl propionate, ethyl propionate, n-propionate Propyl, n- butyl propionate are more preferable, and ethyl propionate, propionic acid n- propyl particularly preferred.

The fluorine-free carboxylic acid ester may be used alone or in combination of two or more in any combination and ratio.
The amount of the fluorine-free carboxylic acid ester (the total amount in the case of two or more) can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably in 100% by mass of the electrolytic solution. Is 0.1% by mass or more, more preferably 0.3% by mass or more, particularly preferably 0.6% by mass or more, and can be 10% by mass or less, preferably 5% by mass or less, More preferably, it is 3 mass% or less, More preferably, it is 2 mass% or less, Most preferably, it is 1 mass% or less. Within such a range, increase in negative electrode resistance is suppressed, and output characteristics, load characteristics, low temperature characteristics, cycle characteristics, and high temperature storage characteristics can be easily controlled.

  The mass ratio of the compound represented by the above formula (1) and the fluorine-free carboxylic acid ester is such that the compound represented by the formula (1): the fluorine-free carboxylic acid ester is 1: 100 or more, Preferably it is 10: 100 or more, more preferably 20: 100 or more, still more preferably 25: 100 or more, and can be 10000: 100 or less, preferably 500: 100 or less, more preferably 300: 100 or less, More preferably, it is 100: 100 or less, particularly preferably 75: 100 or less, and most preferably 50: 100 or less. If it is this range, a battery characteristic, especially a durable characteristic can be improved significantly. Although this principle is not clear, it is considered that the side reaction of the additive on the electrode can be minimized by mixing at this ratio.

1-2-9. Cyclic compound having a plurality of ether bonds The cyclic compound having a plurality of ether bonds is not particularly limited as long as it is a cyclic compound having a plurality of ether bonds in the molecule, but is preferably represented by formula (2-10). It is a compound. The cyclic compound having a plurality of ether bonds contributes to improvement of the high-temperature storage characteristics of the battery. In the electrolytic solution of the present invention, this electrolytic solution is used in combination with the compound represented by the formula (1). In the battery using the battery, durability characteristics can be improved.

(In the formula, A ^{15 to} A ²⁰ independently represent a hydrogen atom, a fluorine atom, or a hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. N ¹⁰¹ is 1 to 4 inclusive. And when n ¹⁰¹ is an integer of 2 or more, the plurality of A ¹⁷ and A ¹⁸ may be the same or different.)
Two members 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. Among these, preferably 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, an acyloxy group, which may be substituted with a halogen atom, an alkoxy group or a fluorine atom. More preferably an alkyl group, a cyano group and an ether group which are not substituted with a fluorine atom.

In formula (2-10), n ¹⁰¹ is preferably an integer of 1 or more, 3 or less, more preferably an integer of 1 or more and 2 or less, and even more preferably n ¹⁰¹ is 2.
The hydrocarbon group having 1 to 5 carbon atoms in A ^{15 to} A ²⁰ is a monovalent hydrocarbon group such as an alkyl group, an alkenyl group, an alkynyl group, and an aryl group;
And divalent hydrocarbon groups such as an alkylene group, an alkenylene group, an alkynylene group, and an arylene group. 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-pentyl group, neopentyl An alkyl group having 1 to 5 carbon atoms such as a group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group;
Vinyl group, 1-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 An alkenyl group having 2 to 5 carbon atoms, such as a group;
Carbon 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 and 4-pentynyl group An alkynyl group having a number of 2 or more and 5 or less;
Alkylene groups having 1 to 5 carbon atoms, such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group;
An alkenylene group having 2 to 5 carbon atoms, such as a vinylene group, 1-propenylene group, 2-propenylene group, 1-butenylene group, 2-butenylene group, 1-pentenylene group, 2-pentenylene group;
Examples thereof include alkynylene groups having 2 to 5 carbon atoms such as ethynylene group, propynylene group, 1-butynylene group, 2-butynylene group, 1-pentynylene group and 2-pentynylene group. Of these, 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 is preferable, and an ethylene group, a trimethylene group, a tetramethylene group, and a pentane are more preferable. An alkylene group having 2 to 5 carbon atoms, such as a methylene group, and more preferably an alkylene group having 3 to 5 carbon atoms, such as a trimethylene group, a tetramethylene group, and a pentamethylene group.

The hydrogen atom, fluorine atom, or hydrocarbon group having 1 to 5 carbon atoms in A ^{15 to} A ²⁰ is a group in which a hydrogen atom, a fluorine atom, or the above substituent is combined with the hydrocarbon group having 1 to 5 carbon atoms. Preferably, it is a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms which does not have a substituent, and an alkylene group having an ether structure in which 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.

  Among these,

Etc. are preferred.

Is more preferable.

  The cyclic compound which has a some ether bond may be used individually by 1 type, and may have 2 or more types by arbitrary combinations and ratios. The amount of the cyclic compound having a plurality of ether bonds (the total amount in the case of two or more types) can be 0.001% by mass or more, preferably 0.01% by mass or more, in 100% by mass of the electrolytic solution. More preferably, it is 0.1% by mass or more, particularly preferably 0.3% 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, and further Preferably it is 2 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 formula (1) and the cyclic compound having a plurality of ether bonds (the total amount in the case of two or more) is the compound represented by the formula (1): having a plurality of ether bonds The cyclic compound can be 1: 100 or more, preferably 10: 100 or more, more preferably 20: 100 or more, still more preferably 25: 100 or more, and 10000: 100 or less, preferably Is 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. If it is this range, a battery characteristic, especially a durable characteristic can be improved significantly. Although this principle is not clear, it is considered that the side reaction of the additive on the electrode can be minimized by mixing at this ratio.

1-2-10. Compound having an isocyanuric acid skeleton The compound having an isocyanuric acid skeleton is not particularly limited as long as it is an organic compound having at least one isocyanuric acid skeleton in the molecule. A battery using the electrolytic solution of the present invention containing a compound having an isocyanuric acid skeleton can improve durability characteristics.
Examples of the compound having an isocyanuric acid skeleton include compounds having the following structure.

Preferably, the compound of the following structures is mentioned.

  More preferably, the compound of the following structures is mentioned.

  Particularly preferred are compounds having the following structures.

  Most preferably, the compound of the following structure is mentioned.

  Among these most preferable compounds, compounds having the following structure are preferable from the viewpoint of the ability to form a negative electrode film.

  There is no restriction | limiting in particular also in a manufacturing method regarding the compound which has an isocyanuric acid frame | skeleton, It is possible to select and manufacture a well-known method arbitrarily.

  The compound represented by the compound having an isocyanuric acid skeleton may be used alone or in combination of two or more in any combination and ratio. The amount of the compound having an isocyanuric acid skeleton (total amount in the case of two or more types) can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably in 100% by mass of the electrolytic solution. It can be 0.1% by mass or more, more preferably 0.2% 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, and still more preferably 2%. % By mass or less, particularly preferably 1% by mass or less, and most preferably 0.5% by mass or less. When it is within the above range, inhibition of the electrode reaction due to the reduction product covering the negative electrode surface excessively is prevented. In addition, since the action at the electrode interface proceeds more suitably, the battery characteristics can be optimized.

  The mass ratio of the compound represented by the formula (1) and the compound having an isocyanuric acid skeleton may be 1: 100 or more for the compound represented by the formula (1): the compound having an isocyanuric acid skeleton, Preferably it is 10: 100 or more, more preferably 20: 100 or more, still more preferably 25: 100 or more, and can be 10000: 100 or less, preferably 500: 100 or less, more preferably 300: 100 or less, More preferably, it is 100: 100 or less, particularly preferably 75: 100 or less, and most preferably 50: 100 or less. If it is this range, a battery characteristic, especially a durable characteristic can be improved significantly. Although this principle is not clear, it is considered that the side reaction of the additive on the electrode can be minimized by mixing at this ratio.

1-3. Electrolyte There is no restriction | limiting in particular in electrolyte, What is well-known as electrolyte can be used arbitrarily. In the case of a lithium secondary battery, a lithium salt is usually used. Specifically, inorganic lithium salts such as LiPF ₆ , LiBF _4, LiClO ₄ , LiAlF ₄ , LiSbF ₆ , LiTaF ₆ , LiWF ₇ ; lithium tungstates such as LiWOF ₅ ; HCO ₂ Li, CH ₃ CO ₂ Li, _{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
Carboxylic acid lithium 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 Sulfonic acid lithium salts such as CF ₂ CF ₂ SO ₃ Li, CF ₃ CF ₂ CF ₂ CF ₂ SO ₃ Li; 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 SO ₂ ) ₂ , lithium cyclic 1,2-perfluoroethanedisulfonylimide, lithium cyclic 1,3-par fluoropropane _{disulfonylimide, LiN (CF 3 SO 2)} (C 4 F 9 SO 2) lithium imide salts such as; LiC (FSO _{2 3, LiC (CF 3 SO 2} ) 3, LiC (C 2 F 5 SO 2) 3 , etc. Richiumumechido salts; lithium bis (Maronato) borate, lithium such as lithium difluoro (Maronato) borate (Maronato) borates; lithium tris Lithium (malonate) phosphate salts such as (malonate) phosphate, lithium difluorobis (malonate) phosphate, lithium tetrafluoro (malonate) phosphate; other, LiPF ₄ (CF ₃ ) ₂ , LiPF ₄ (C ₂ F ₅ ) ₂ , LiPF ₄ (CF ₃ SO ₂ ) ₂ , LiPF ₄ (C ₂ F ₅ SO ₂ ) ₂ , 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 Fluorine-containing organic lithium salts such as SO ₂ ) ₂ and LiBF ₂ (C ₂ F ₅ SO ₂ ) ₂ ; lithium oxalatoborate salts such as lithium difluorooxalatoborate and lithium bis (oxalato) borate;
And lithium oxalate phosphate salts such as lithium tetrafluorooxalato phosphate, lithium difluorobis (oxalato) phosphate, lithium tris (oxalato) phosphate; and the like.

Among these, LiPF ₆ , LiSbF ₆ , LiTaF ₆ , FSO ₃ Li, CF ₃ SO 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-perfluoropropane disulfonylimide, LiC (FSO ₂ ) ₃ , LiC (CF ₃ SO ₂ ) ₃ , LiC (C ₂ F ₅ SO ₂ ) ₃ , LiBF ₃ CF ₃ , LiBF ₃ C ₂ F ₅ , LiPF ₃ (CF ₃ ) ₃ , LiPF ₃ (C ₂ F ₅ ) _3, lithium difluorooxalatoborate , Lithium bis (oxalato) borate, lithium difluorobis (oxalato) phosphate, etc. Sex and high-rate discharge characteristics, high-temperature storage characteristics, from the viewpoint of an effect of improving the cycle characteristics and the like. LiPF ₆ , FSO ₃ Li, LiN (FSO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , lithium difluorooxalatoborate, lithium bis (oxalato) borate, lithium difluorobis (oxalato) phosphate are more preferable, and LiPF ₆ , FSO ₃ Li, LiN (FSO ₂ ) ₂ , lithium bis (oxalato) borate is more preferable from the viewpoint of further improving output characteristics, high-rate charge / discharge characteristics, high-temperature storage characteristics, cycle characteristics, etc. From the viewpoint of redox stability, LiPF ₆ is most preferable. In particular, LiPF ₆ decomposes in the system to produce Lewis acid PF ₅ and causes deterioration of electrolyte stability, electrolyte physical properties, and battery characteristics. Therefore, by using together with the compound represented by the formula (1), it is possible to exhibit excellent characteristics as an electrolyte while suppressing 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 electrolytic solution is not particularly limited in order to exhibit the effects of the present invention, but is usually 0.00. 043 or more, preferably 0.050 or more, more preferably 0.075 or more, further preferably 0.080 or more, particularly preferably 0.100 or more, usually 0.935 or less, preferably 0.850 or less. More preferably, it is 0.760 or less, More preferably, it is 0.300 or less, Most preferably, it is 0.200 or less. If it is this range, a battery characteristic, especially a continuous charge durability characteristic can be improved remarkably. Although this principle is not clear, it is considered that mixing at this ratio facilitates efficient complex formation with the decomposition product 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
) Represents a value obtained by dividing the molar content of the compound represented by) by the molar content of the electrolyte, and is an index representing the number of molecules of the compound represented by the formula (1) for one molecule of the electrolyte.

  The concentration of these electrolytes in the non-aqueous electrolyte solution is not particularly limited as long as the effects of the present invention are not impaired, but the electric conductivity of the electrolyte solution is in a good range, and good battery performance is ensured. In view of this, the total molar concentration of lithium in the non-aqueous electrolyte is preferably 0.25 mol / L or more, more preferably 0.5 mol / L or more, still more preferably 1.1 mol / L or more, and preferably Is 3.0 mol / L or less, more preferably 2.5 mol / L or less, and still more preferably 2.0 mol / L or less. If it is this range, since there is not too little lithium which is a charged particle and a viscosity can be made into an appropriate range, it will become easy to ensure favorable electrical conductivity.

  When two or more electrolytes are used in combination, at least one of them is preferably a salt selected from the group consisting of monofluorophosphate, difluorophosphate, borate, oxalate and fluorosulfonate. More preferably, it is a salt selected from the group consisting of 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.

The electrolyte preferably contains at least one selected from the group consisting of monofluorophosphates, difluorophosphates, borates, oxalates and fluorosulfonates and at least one of the other salts. . 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 , LiN (C ₂ F ₅ SO ₂ ) ₂ , lithium cyclic 1,2-perfluoroethanedisulfonylimide, lithium cyclic 1,3-perfluoropropane disulfonylimide, LiC (FSO ₂ ) ₃ , LiC (CF ₃ SO ₂ ) ₃ , LiC (C ₂ F ₅ SO ₂ ) ₃ , LiBF ₃ CF ₃ , LiBF ₃ C ₂ F ₅ , LiPF ₃ (CF ₃ ) ₃ , and LiPF ₃ (C ₂ F ₅ ) ₃ are preferable, and LiPF ₆ is more preferable. The other salt may 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 viscosity of the electrolytic solution. Or less, preferably 15% by mass or less, more preferably 10% by mass or less.

1-3-1. Monofluorophosphate, difluorophosphate Monofluorophosphate and difluorophosphate are not particularly limited as long as each has at least one monofluorophosphate or difluorophosphate structure in the molecule. In the electrolytic solution of the present invention, by using a compound represented by the above formula (1) and at least one selected from monofluorophosphate and difluorophosphate, in a battery using this electrolytic solution, Durability characteristics can be improved.

The counter cation in the monofluorophosphate and difluorophosphate is not particularly limited, and lithium, sodium, potassium, magnesium, calcium, NR ¹²¹ R ¹²² R ¹²³ R ¹²⁴ (wherein R ^{121 to} R ¹²⁴ are independently And ammonium represented by a hydrogen atom or an organic group having 1 to 12 carbon atoms. The organic group having 1 to 12 carbon atoms represented by R ^{121 to} R ¹²⁴ of ammonium is not particularly limited. And a cycloalkyl group, an aryl group optionally substituted with a halogen atom or an alkyl group, a nitrogen atom-containing heterocyclic group optionally having a substituent, and the like. Among these, R ^{121 to} R ¹²⁴ are preferably independently a hydrogen atom, an alkyl group, a cycloalkyl group, a nitrogen atom-containing heterocyclic group, or the like. As a counter cation, lithium, sodium, and potassium are preferable, and lithium is particularly preferable.

  Examples of monofluorophosphate and difluorophosphate include lithium monofluorophosphate, sodium monofluorophosphate, potassium monofluorophosphate, lithium difluorophosphate, sodium difluorophosphate, and potassium difluorophosphate. Lithium monofluorophosphate and lithium difluorophosphate are preferred, and lithium difluorophosphate is more preferred. Monofluorophosphate and difluorophosphate may be used alone or in combination of two or more in any combination and ratio.

  The amount of one or more selected from monofluorophosphate and difluorophosphate (the total amount in the case of two or more) can be 0.001% by mass or more, preferably 0.01% by mass or more. More preferably, it is 0.1% by mass or more, more 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. Hereinafter, it is more preferably 2% by mass or less, further 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 the compound represented by the above formula (1) and one or more selected from monofluorophosphate and difluorophosphate (total amount in the case of two or more) is represented by formula (1). Compound: monofluorophosphate and difluorophosphate are preferably 1:99 to 99: 1, more preferably 10:90 to 90:10, and particularly preferably 20:80 to 80:20. Within this range, the intended characteristics can be improved without degrading other battery characteristics.

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, what corresponds to oxalate is 1-3-2. Not borate, but will be described later 1-3-3. Included in oxalate. In the electrolytic solution of the present invention, by using the compound represented by the formula (1) and a borate in combination, durability characteristics can be improved in a battery using this electrolytic solution.

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

As the borate, a lithium salt is preferable, and a lithium borate salt can also be suitably 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. Among these, LiBF ₄ is more preferable because it has an effect of improving initial charge / discharge efficiency, high-temperature cycle characteristics, and the like. A borate may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of borate (total amount in the case of two or more types) can be 0.05% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably. Is 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, more preferably 2.0% by mass or less, and particularly preferably 1.0% by mass or less. Within this range, side reactions of the battery negative electrode are suppressed and resistance is hardly increased.

The mass ratio of the compound represented by the above formula (1) and 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 preferable, and 20:80 to 80:20 is particularly preferable. Within this range, side reactions on the positive and negative electrodes in the battery are suppressed, and the resistance of the battery is difficult to increase.

Moreover, when borate and LiPF ₆ are used as the electrolyte, the ratio of the molar content of borate to the molar content of LiPF ₆ in the non-aqueous electrolyte is preferably 0.001 or more and 12 or less. 01-1.1 are more preferable, 0.01-1.0 are still more preferable, and 0.01-0.7 are more preferable. Within this range, side reactions on the positive and negative electrodes in the battery are suppressed, and the charge / discharge 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 electrolytic solution of the present invention, by using the compound represented by the formula (1) and oxalate in combination, durability characteristics can be improved in a battery using this electrolytic solution.

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

(In the formula, M ¹ is an element selected from the group consisting of Group 1, 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 halogen, an alkyl group having 1 to 11 carbon atoms and a halogen-substituted alkyl group having 1 to 11 carbon atoms,
a and b are positive integers;
c is 0 or a positive integer;
d is an integer of 1-3. )
M ¹ is preferably lithium, sodium, potassium, magnesium, or calcium, and particularly preferably lithium, from the viewpoint of battery characteristics when the electrolytic solution of the present invention is used for a lithium secondary battery.

M ² is particularly preferably boron or phosphorus from the viewpoint 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, tert-butyl group, and the like. A trifluoromethyl group is preferred.

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

  One oxalate may be used alone, or two or more oxalates may be used in any combination and ratio.

  The amount of oxalate (the total amount in the case of two or more types) 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. Is 0.3% 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% 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) and the oxalate is preferably 1:99 to 99: 1 for the compound represented by the formula (1): oxalate, and 10:90 to 90: 10 is more preferable, and 20:80 to 80:20 is particularly preferable. Within this range, side reactions on the positive and negative electrodes of the battery are suppressed in a balanced manner, and the battery characteristics are easily improved.

1-3-4. Fluorosulfonate The fluorosulfonate is not particularly limited as long as it is a salt having at least one fluorosulfonic acid structure in the molecule. In the electrolytic solution of the present invention, by using the compound represented by the above formula (1) and the fluorosulfonate together, durability characteristics can be improved in a battery using this electrolytic solution.

The counter cation in the fluorosulfonate is not particularly limited, and lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, and NR ¹³¹ R ¹³² R ¹³³ R ¹³⁴ (wherein R ^{131 to} R ¹³⁴ are And each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms. The organic group having 1 to 12 carbon atoms represented by R ^{131 to} R ¹³⁴ of the ammonium is not particularly limited. A cycloalkyl group that may be substituted, an aryl group that may be substituted with a halogen atom or an alkyl group, a nitrogen-containing heterocyclic group that may have a substituent, and the like. Among these, R ^{131 to} R ¹³⁴ are each independently preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a nitrogen atom-containing heterocyclic group, or the like. As a 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 lithium fluorosulfonate is preferable. An imide salt having a fluorosulfonic acid structure such as lithium bis (fluorosulfonyl) imide can also be used as the fluorosulfonic acid salt.

A fluorosulfonate may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
The content of fluorosulfonate (total amount in the case of two or more) can be 0.05% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, More preferably, it is 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, Preferably it is 2 mass% or less, Most preferably, it is 1 mass% or less. Within this range, there are few side reactions in the battery and resistance is hardly increased.

  The mass ratio of the compound represented by the formula (1) and the fluorosulfonate is preferably 1:99 to 99: 1, preferably 10:90 to 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 high temperature durability characteristics are unlikely to deteriorate.

1-4. Nonaqueous solvent There is no restriction | limiting in particular about the nonaqueous solvent in this invention, It is possible to use a well-known organic solvent. Specific examples include cyclic carbonates (excluding fluorine-containing cyclic carbonates), chain carbonates, cyclic and chain carboxylic acid esters, ether compounds, and sulfone compounds.
In this specification, the volume of the non-aqueous solvent is a measured value at 25 ° C., but the measured value at the melting point is used for a solid at 25 ° C. such as ethylene carbonate.

1-4-1. Cyclic carbonate (excluding fluorine-containing cyclic carbonate)
Examples of the cyclic carbonate include cyclic carbonates 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. Among these, ethylene carbonate and propylene carbonate are particularly preferable from the viewpoint of improving battery characteristics resulting from an improvement in the degree of lithium ion dissociation.
A cyclic carbonate may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The blending amount of the cyclic carbonate is not particularly limited and is arbitrary as long as the effects of the present invention are not significantly impaired. However, the blending amount in the case of using one kind alone is 5% by volume or more in 100% by volume of the non-aqueous solvent. More preferably, it is 10 volume% or more. By setting this range, it is possible to avoid a decrease in electrical conductivity resulting from a decrease in the dielectric constant of the non-aqueous electrolyte, and to make the energy device's large current discharge characteristics, stability to the negative electrode, and cycle characteristics favorable. . Moreover, it is 95 volume% or less, More preferably, it is 90 volume% or less, More preferably, it is 85 volume% or less. By setting it as this range, it becomes easy to make the viscosity of a non-aqueous electrolyte solution into an appropriate range, to suppress a decrease in ion conductivity, and to make the load characteristics of the energy device into 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 dialkyl carbonate having 3 to 7 carbon atoms is more preferable.
Examples of the chain carbonate include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, n-propyl isopropyl carbonate, ethyl methyl carbonate, methyl n-propyl carbonate, n-butyl methyl carbonate, isobutyl methyl carbonate, tert -Butyl methyl carbonate, ethyl-n-propyl carbonate, n-butyl ethyl carbonate, isobutyl ethyl carbonate, tert-butyl ethyl carbonate and the like.

Among them, dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, n-propyl isopropyl carbonate, ethyl methyl carbonate, and methyl n-propyl carbonate are preferable, and dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate are particularly preferable. is there.
Further, chain carbonates having a fluorine atom (hereinafter sometimes referred to as “fluorinated chain carbonate”) can also be suitably 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 may be bonded to different carbons.
Examples of the fluorinated chain carbonate include fluorinated dimethyl carbonate and derivatives thereof, fluorinated ethyl methyl carbonate and derivatives thereof, and fluorinated diethyl carbonate and derivatives thereof.

Fluorinated dimethyl carbonate and derivatives thereof include fluoromethyl methyl carbonate, difluoromethyl methyl carbonate, trifluoromethyl methyl carbonate, bis (fluoromethyl) carbonate, bis (difluoro) methyl carbonate, bis (trifluoromethyl) carbonate, and the like. It is done.
Fluorinated ethyl methyl carbonate and derivatives thereof include 2-fluoroethyl methyl carbonate, ethyl fluoromethyl carbonate, 2,2-difluoroethyl methyl carbonate, 2-fluoroethyl fluoromethyl carbonate, ethyl difluoromethyl carbonate, 2,2,2 -Trifluoroethyl methyl carbonate, 2,2-difluoroethyl fluoromethyl carbonate, 2-fluoroethyl difluoromethyl carbonate, ethyl trifluoromethyl carbonate, etc. are mentioned.

  Fluorinated diethyl carbonate and its derivatives include ethyl- (2-fluoroethyl) carbonate, ethyl- (2,2-difluoroethyl) carbonate, bis (2-fluoroethyl) carbonate, 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 include 2,2-trifluoroethyl-2 ′, 2′-difluoroethyl carbonate, bis (2,2,2-trifluoroethyl) carbonate, and the like.

  A chain carbonate may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. The blending amount of the chain carbonate is preferably 5% by volume or more, more preferably 10% by volume or more, and further preferably 15% by volume or more in 100% by volume of the non-aqueous solvent. By setting the lower limit in this manner, the viscosity of the non-aqueous electrolyte solution is set in an appropriate range, the decrease in ionic conductivity is suppressed, and the high current discharge characteristics of the energy device are easily set in a favorable range. Further, the chain carbonate is preferably 90% by volume or less, more preferably 85% by volume or less, in 100% by volume of the nonaqueous solvent. By setting the upper limit in this way, it is easy to avoid a decrease in electrical conductivity due to a decrease in dielectric constant of the non-aqueous electrolyte and to set the large current discharge characteristics of the energy device within a favorable range.

1-4-3. Cyclic and linear carboxylic acid esters As the cyclic carboxylic acid esters, those having 3 to 12 carbon atoms are preferable.
Specific examples include gamma butyrolactone, gamma valerolactone, gamma caprolactone, epsilon caprolactone, and the like. Among these, gamma butyrolactone is particularly preferable from the viewpoint of improving battery characteristics resulting from an improvement in the degree of lithium ion dissociation.

A cyclic carboxylic acid ester may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
The amount of the cyclic carboxylic acid ester is usually 5% by volume or more, more preferably 10% by volume or more, in 100% by volume of the non-aqueous solvent. If it is this range, it will become easy to improve the electrical conductivity of a non-aqueous electrolyte, and to improve the large current discharge characteristic of an energy device. Moreover, the compounding quantity of cyclic carboxylic acid ester becomes like this. Preferably it is 50 volume% or less, More preferably, it is 40 volume% or less. By setting the upper limit in this way, the viscosity of the non-aqueous electrolyte solution is set to an appropriate range, a decrease in electrical conductivity is avoided, an increase in negative electrode resistance is suppressed, and the large current discharge characteristics of the energy device are in a favorable range. And it will be easier.

  Examples of the chain carboxylic acid ester include those described in “1-2-8. Fluorine-free carboxylic acid ester”.

  The blending amount when the chain carboxylic acid ester is used as the non-aqueous solvent is 100% by volume in the non-aqueous solvent, preferably 1% by volume or more, more preferably 5% by volume or more, still more preferably 10% by volume or more, and even more. Preferably it is 20 volume% or more, and can be made to contain by 50 volume% or less, More preferably, it is 45 volume% or less, More preferably, it is 40 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 charge / discharge rate characteristics of the non-aqueous electrolyte secondary battery are easily improved. Moreover, increase in negative electrode resistance is suppressed, and the input / output characteristics and charge / discharge rate characteristics of the non-aqueous electrolyte secondary battery are easily set in a favorable range.

  In addition, when using chain | strand-shaped carboxylic acid ester as a nonaqueous solvent, Preferably it is combined use with a cyclic carbonate, More preferably, it is combined use of a cyclic carbonate and a chain carbonate.

  For example, when a cyclic carbonate and a 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 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 40% by volume or less. Is 50% by volume or less. Further, when a cyclic carbonate, a chain carbonate, and a chain carboxylate 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, usually 45% by volume or less, preferably 40% by volume or less, and the content of the chain carbonate is usually 25% by volume or more, preferably 30% by volume or more, and usually 84% by volume or less. , Preferably it is 80 volume% or less. By making the content within the above range, while lowering the low temperature deposition temperature of the electrolyte, the viscosity of the nonaqueous electrolytic solution is also lowered to improve the ionic conductivity, and even higher input / output can be obtained even at a low temperature, Further, it is preferable from the viewpoint of further reducing battery swelling.

1-4-4. Ether compound As the ether compound, a chain ether having 3 to 10 carbon atoms and a cyclic ether having 3 to 6 carbon atoms in which part of hydrogen may be substituted with fluorine is preferable.
As the 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-tetrafluoroethyl) ether, ethyl-n-propyl ether, ethyl (3-Fluoro-n-propyl) ether, ethyl (3,3,3-trifluoro-n-propyl) ether, ethyl (2,2,3,3-teto Fluoro-n-propyl) ether, ethyl (2,2,3,3,3-pentafluoro-n-propyl) ether, 2-fluoroethyl-n-propylether, (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-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-tetrafluoroethyl) (3,3,3-trifluoro-n-propyl) ether, (1,1,2,2-tetrafluoroethyl) (2,2,3,3-tetrafluoro -N-propyl) ether, (1,1,2,2-tetrafluoroethyl) (2,2,3,3,3-pentafluoro-n-propyl) ether, di-n-propyl ether, (n- Propyl) (3-fluoro (Ro-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) ether ) (2, 2, 3, 3- Trifluoro-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-tri Fluoroethoxy) methanemethoxy (1,1,2,2-tetrafluoroethoxy) methane, diethoxymethane, ethoxy (2-fluoroethoxy) methane, ethoxy (2,2 2-trifluoroethoxy) methane, ethoxy (1,1,2,2-tetrafluoroethoxy) methane, di (2-fluoroethoxy) methane, (2-fluoroethoxy) (2,2,2-trifluoroethoxy) Methane, (2-fluoroethoxy) (1,1,2,2-tetrafluoroethoxy) methanedi (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 Ci (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 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 solvating ability to lithium ions and improve ion dissociation. Of these, dimethoxymethane, diethoxymethane, and ethoxymethoxymethane are preferable because they have low viscosity and give high ionic conductivity.

An ether type compound may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
The compounding amount of the ether compound is usually in 100% by volume of the non-aqueous solvent, preferably 5% by volume or more, more preferably 10% by volume or more, further preferably 15% by volume or more, and preferably 70% by volume or less. More preferably, it is 60 volume% or less, More preferably, it is 50 volume% or less. If it is this range, it is easy to ensure the improvement effect of the lithium ion dissociation degree of chain ether, and the improvement of the ionic conductivity derived from a viscosity fall. It is easy to avoid a situation where the capacity is reduced due to co-insertion.

1-4-5. Sulfone compound As the sulfone 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 trimethylene sulfones, tetramethylene sulfones and hexamethylene sulfones which are monosulfone compounds;
Examples include disulfone compounds such as trimethylene disulfones, tetramethylene disulfones, and hexamethylene disulfones.

Among these, from the viewpoint of dielectric constant and viscosity, tetramethylene sulfones, tetramethylene disulfones, hexamethylene sulfones, and hexamethylene disulfones are more preferable, and tetramethylene sulfones (sulfolanes) are particularly preferable.
As the sulfolanes, sulfolane and / or sulfolane derivatives (hereinafter sometimes referred to as “sulfolanes” including sulfolane) are preferable. The sulfolane derivative is preferably one in which one or more hydrogen atoms bonded to the carbon atoms constituting the sulfolane ring are substituted with a fluorine atom or an alkyl group.

  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-methylsulfolane, 3-fluoro-3-methylsulfolane, 3-fluoro-2-methylsulfolane, 4-fluoro-3-methyl Sulfolane, 4-fluoro-2-methylsulfolane, 5-fluoro-3-methylsulfolane, 5-fluoro-2-methylsulfolane, 2-fluoromethylsulfolane, 3-fluoromethylsulfolane, 2-difluoromethylsulfolane, 3-difluoro Methyl sulfolane, 2- Trifluoromethylsulfolane, 3-trifluoromethylsulfolane, 2-fluoro-3- (trifluoromethyl) sulfolane, 3-fluoro-3- (trifluoromethyl) sulfolane, 4-fluoro-3- (trifluoromethyl) sulfolane , 5-fluoro-3- (trifluoromethyl) sulfolane and the like are preferable in terms of high ionic conductivity and high input / output characteristics.

In addition, as the chain sulfone having 2 to 6 carbon atoms,
Dimethylsulfone, ethylmethylsulfone, diethylsulfone, n-propylmethylsulfone, n-propylethylsulfone, di-n-propylsulfone, isopropylmethylsulfone, isopropylethylsulfone, diisopropylsulfone, n-butylmethylsulfone, n-butylethyl Sulfone, tert-butylmethylsulfone, tert-butylethylsulfone, monofluoromethylmethylsulfone, difluoromethylmethylsulfone, trifluoromethylmethylsulfone, monofluoroethylmethylsulfone, difluoroethylmethylsulfone, trifluoroethylmethylsulfone, pentafluoro Ethyl methyl 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, tri Fluoromethyl-n-propylsulfone, fluoromethylisopropylsulfone, difluoromethylisopropylsulfone, trifluoromethylisopropylsulfone, trifluoroethyl-n-propylsulfone, trifluoroethylisopropylsulfone, pentafluoroethyl-n-propylsulfone, pentafluoro Ethyl isopropyl sulfone, trifluoroethyl-n-butyl sulfone, trifluoroethyl-tert-butyl sulfone, pen Trifluoroethyl -n- butyl sulfone, pentafluoroethyl -tert- butyl sulfone, and the like.

  Among them, dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, n-propyl methyl sulfone, isopropyl methyl sulfone, n-butyl methyl sulfone, tert-butyl methyl sulfone, monofluoromethyl methyl sulfone, difluoromethyl methyl sulfone, trifluoromethyl methyl sulfone , Monofluoroethyl methyl sulfone, difluoroethyl methyl sulfone, trifluoroethyl methyl sulfone, pentafluoroethyl methyl sulfone, ethyl monofluoromethyl sulfone, ethyl difluoromethyl sulfone, ethyl trifluoromethyl sulfone, ethyl trifluoroethyl sulfone, ethyl pentafluoro Ethyl sulfone, trifluoromethyl-n-propyl sulfone, trifluoromethyl isopropyl sulfone Trifluoroethyl-n-butylsulfone, trifluoroethyl-tert-butylsulfone, trifluoromethyl-n-butylsulfone, trifluoromethyl-tert-butylsulfone, etc. have high ionic conductivity and high input / output characteristics. preferable.

A sulfone compound may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
The compounding amount of the sulfone compound is usually 0.3% by volume or more, more preferably 1% by volume or more, still more preferably 5% by volume or more in 100% by volume of the non-aqueous solvent, and preferably 40%. Volume% or less, More preferably, it is 35 volume% or less, More preferably, it is 30 volume% or less. Within this range, durability improvement effects such as cycle characteristics and storage characteristics can be easily obtained, and the viscosity of the non-aqueous electrolyte can be set within an appropriate range to prevent a decrease in electrical conductivity, and energy can be avoided. When charging / discharging a device at a high current density, it is easy to avoid a situation in which the charge / discharge capacity retention rate is reduced.

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 thereof may be used in any combination and ratio.
For example, as a preferable combination of the non-aqueous solvent, a combination mainly composed of a cyclic carbonate (excluding a fluorine-containing cyclic carbonate) and a chain carbonate can be given.

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 with respect to the total is preferably 5% by volume or more, more preferably 10% by volume or more, and 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 high-temperature storage characteristics (particularly, the remaining capacity and high-load discharge capacity after high-temperature storage) of a battery produced using the non-aqueous solvent may be improved.
For example, as a preferable combination of a cyclic carbonate and a chain carbonate,
Ethylene carbonate and dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and ethyl methyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and ethyl methyl carbonate, ethylene carbonate and diethyl carbonate and ethyl methyl carbonate, ethylene carbonate And dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.

  Among the combinations of cyclic carbonates and chain carbonates, those containing asymmetrical chain alkyl carbonates as chain carbonates are more preferred, especially ethylene carbonate, dimethyl carbonate and ethyl methyl 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 ethyl methyl carbonate are preferred because of a good balance between cycle characteristics and large current discharge characteristics.

  Among these, the asymmetric chain carbonate is preferably ethyl methyl carbonate, and the alkyl group of the chain carbonate preferably has 1 to 2 carbon atoms.

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

  In the case of containing propylene carbonate, the volume ratio of ethylene carbonate to propylene carbonate is preferably 99: 1 to 40:60, particularly preferably 95: 5 to 50:50. Furthermore, the proportion of propylene carbonate in the entire non-aqueous solvent is preferably 0.1% by volume or more, more preferably 1% by volume or more, still more 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 improved while maintaining the combination characteristics of ethylene carbonate and chain carbonate.

  When dimethyl carbonate is contained in the non-aqueous solvent, the proportion of dimethyl carbonate in the total non-aqueous solvent is preferably 10% by volume or more, more preferably 20% by volume or more, and even more preferably 25% by volume or more. Preferably it is 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, it contains dimethyl carbonate and ethyl methyl carbonate, and by increasing the content ratio of dimethyl carbonate from the content ratio of ethyl methyl carbonate, it is possible to maintain the electric conductivity of the electrolyte solution, but the battery characteristics after high-temperature storage May improve.

  The volume ratio of dimethyl carbonate to ethyl methyl carbonate in all non-aqueous solvents (dimethyl carbonate / ethyl methyl carbonate) is 1.1 or more in terms of improving the electric conductivity of the electrolyte and improving the battery characteristics after storage. Is preferably 1.5 or more, more preferably 2.5 or more. The volume ratio (dimethyl carbonate / ethyl methyl carbonate) is preferably 40 or less, more preferably 20 or less, still more preferably 10 or less, and particularly preferably 8 or less, from the viewpoint of improving battery characteristics at low temperatures.

  In the combination of the above cyclic carbonate (excluding fluorine-containing cyclic carbonate) and chain carbonate, cyclic carboxylic acid esters, chain carboxylic acid esters, cyclic ethers, chain ethers, sulfur-containing compounds Other solvents such as an organic solvent, a phosphorus-containing organic solvent, and an aromatic fluorine-containing solvent may be mixed.

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

1-5-1. Other auxiliary agents Known other auxiliary agents can be used in the electrolytic 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 Carboxylic anhydrides such as itaconic acid, diglycolic anhydride, cyclohexanedicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride and phenylsuccinic anhydride; 3,9-divinyl-2,4,8,10-tetra Spiro compounds such as oxaspiro [5.5] undecane; sulfur-containing compounds such as N, N-dimethylmethanesulfonamide, N, N-diethylmethanesulfonamide; trimethyl phosphite, triethyl phosphite, triphosphite Phenyl, trimethyl phosphate, triethyl phosphate, lithium Phosphorus compounds such as triphenyl acid, methyl dimethylphosphinate, ethyl diethylphosphinate, trimethylphosphine oxide, triethylphosphine oxide; 1-methyl-2-pyrrolidinone, 1-methyl-2-piperidone, 3-methyl-2-oxazolidinone , 1,3-dimethyl-2-imidazolidinone and nitrogen-containing compounds such as N-methylsuccinimide; hydrocarbon compounds such as heptane, octane, nonane, decane, cycloheptane; 2-propynyl 2- (diethoxyphosphoryl) acetate 1-methyl-2-propynyl 2- (diethoxyphosphoryl) acetate, 1,1-dimethyl-2-propynyl 2- (diethoxyphosphoryl) acetate, pentafluorophenyl methanesulfonate, pentafluorophenyl trifluoromethyl Sulfonate, pentafluorophenyl acetate, pentafluorophenyl trifluoroacetate, methyl pentafluorophenyl carbonate, 2-propynyl 2- (methanesulfonyloxy) propionate, 2-methyl 2- (methanesulfonyloxy) propionate, 2- ( Methanesulfonyloxy) propionic acid 2-ethyl, methanesulfonyloxyacetic acid 2-propynyl, methanesulfonyloxyacetic acid 2-methyl, methanesulfonyloxyacetic acid 2-ethyl, lithium ethyl methyloxycarbonylphosphonate, lithium ethyl ethyloxycarbonylphosphonate, lithium ethyl 2-propynyloxycarbonylphosphonate, lithium ethyl 1-methyl-2-propynyloxycarbonylphosphonate, lithium ethyl 1,1 Dimethyl-2-propynyloxycarbonylphosphonate, lithium methyl sulfate, lithium ethyl sulfate, lithium 2-propynyl sulfate, lithium 1-methyl-2-propynyl sulfate, lithium 1,1-dimethyl-2-propynyl sulfate, lithium 2,2, 2-trifluoroethyl sulfate, methyl trimethylsilyl sulfate, ethyl trimethylsilyl sulfate, 2-propynyl trimethylsilyl sulfate, dilithium ethylene disulfate, 2-butyne-1,4-diyl dimethanesulfonate, 2-butyne-1,4-diyl diethanesulfonate 2-butyne-1,4-diyl diformate, 2-butyne-1,4-diyl diacetate, 2-butyne-1,4-dii Didipropionate, 4-hexadiyne-1,6-diyl dimethanesulfonate, 2-propynyl methanesulfonate, 1-methyl-2-propynyl methanesulfonate, 1,1-dimethyl-2-propynyl methanesulfonate, 2-propynyl ethanesulfonate, 2-propynyl vinyl sulfonate, methyl 2-propynyl carbonate, ethyl 2-propynyl carbonate, bis (2-propynyl) carbonate, methyl 2-propynyl oxalate, ethyl 2-propynyl oxalate, bis (2-propynyl) oxalate, 2-propynyl acetate , 2-propynyl formate, 2-propynyl methacrylate, di (2-propynyl) glutarate, 2,2-dioxide-1,2-oxathiolan-4-yl Tate, 2,2-dioxide-1,2-oxathiolan-4-yl propionate, 5-methyl-1,2-oxathiolan-4-one 2,2-dioxide, 5,5-dimethyl-1,2-oxathiolane- 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 succinic anhydride, 2- (1-penten-3-yl) succinic anhydride, 2- (1-hexen-3-yl) anhydride Succinic acid, 2- (1-hepten-3-yl) succinic anhydride, 2- (1-octene-3- Succinic anhydride, 2- (1-nonen-3-yl) succinic anhydride, 2- (3-buten-2-yl) succinic anhydride, 2- (2-methylallyl) succinic anhydride, 2- ( 3-methyl-3-buten-2-yl) succinic anhydride and the like. These may be used alone or in combination of two or more. By adding these auxiliaries, capacity maintenance characteristics and cycle characteristics after high temperature storage can be improved.

  The blending amount of other auxiliary agents 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 or more and 5% by mass or less in 100% by mass of the non-aqueous electrolyte solution. Within this range, the effects of other auxiliaries can be sufficiently exhibited, and it is easy to avoid a situation in which battery characteristics such as high-load discharge characteristics deteriorate. The blending amount of other auxiliaries is more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, more preferably 3% by mass or less, still more preferably 1% by mass or less. .

2. Energy Device Using Non-aqueous Electrolyte Solution An energy device using the non-aqueous electrolyte solution of the present invention includes a positive electrode, a negative electrode, a non-aqueous electrolyte solution together with an electrolyte and a non-aqueous solvent, a fluorine-containing cyclic carbonate, a formula (1 And a compound represented by the formula:

  The energy device using the non-aqueous electrolyte 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. Are preferred, lithium batteries and lithium ion capacitors are more preferred, and lithium batteries are even more preferred. The non-aqueous electrolyte used in these energy devices is preferably a so-called gel electrolyte that is pseudo-solidified with a polymer, a filler, or the like.

2-1. Lithium Battery A lithium battery using the non-aqueous electrolyte of the present invention is provided with a current collector and a positive electrode having a positive electrode active material layer provided on the current collector, and on the current collector and the current collector. The negative electrode has a negative electrode active material layer and can absorb and release ions, and the non-aqueous electrolyte solution of the present invention described above. In addition, the lithium battery in this invention is a general term for a lithium primary battery and a lithium secondary battery.

<2-1-1. Battery configuration>
The configuration of the lithium battery of the present invention is the same as that of conventionally known lithium batteries except for the above-described non-aqueous electrolyte solution of the present invention. Usually, a positive electrode and a negative electrode are laminated via a porous film (separator) impregnated with the non-aqueous electrolyte solution of the present invention, and these are 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 shape, a square shape, a laminate shape, a coin shape, a large size, and the like.

2-1-2. Non-aqueous electrolyte solution The non-aqueous electrolyte solution of the present invention described above is used as the non-aqueous electrolyte solution. In addition, in the range which does not deviate from the meaning of this invention, it is also possible to mix | blend and use other nonaqueous electrolyte solutions with respect to the nonaqueous electrolyte solution of this invention.

2-1-3. Negative electrode The negative electrode has a negative electrode active material layer on a 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 battery is not particularly limited as long as it can electrochemically release lithium ions. Specific examples thereof include 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 materials, lithium-containing metal composite oxide materials, and the like. These may be used individually by 1 type, and may be used together combining 2 or more types arbitrarily.

<Negative electrode active material>
Examples of the negative electrode active material include carbonaceous materials, alloy 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 material and an artificial graphite material at least once in the range of 400 to 3200 ° C;
(3) a carbonaceous material in which the negative electrode active material layer is made of carbonaceous materials having at least two or more different crystallinities and / or has an interface in contact with the different crystalline carbonaceous materials,
(4) A carbonaceous material in which the negative electrode active material layer is made of carbonaceous materials having at least two or more different orientations and / or has an interface in contact with the carbonaceous materials having different orientations,
Is preferably a good balance between initial irreversible capacity and high current density charge / discharge characteristics. Moreover, the carbonaceous materials (1) to (4) may be used alone or in combination of two or more in any combination and ratio.

  As the artificial carbonaceous material and artificial graphite material of (2) above, natural graphite, coal-based coke, petroleum-based coke, coal-based pitch, petroleum-based pitch, and those obtained by oxidizing these pitches, needle coke, pitch coke, and Carbon materials that are partially graphitized, furnace black, acetylene black, organic pyrolysis products such as pitch-based carbon fibers, carbonizable organic materials and their carbides, or carbonizable organic materials are benzene, toluene, xylene, quinoline And a solution dissolved in a low-molecular organic solvent such as n-hexane, and carbides thereof.

  As an alloy material used as the negative electrode active material, as long as lithium can be occluded / released, lithium alone, simple metals and alloys forming lithium alloys, or oxides, carbides, nitrides, silicides, sulfides thereof Any of compounds such as products or phosphides may be used and is not particularly limited. The single metal and alloy forming the lithium alloy are preferably materials containing group 13 and group 14 metal / metalloid elements (that is, excluding carbon), more preferably aluminum, silicon and tin (hereinafter referred to as “ Simple metals) and alloys or compounds containing these atoms (sometimes abbreviated as “specific metal elements”). These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  As a negative electrode active material having at least one kind of atom selected from a specific metal element, a metal simple substance of any one specific metal element, an alloy composed of two or more specific metal elements, one type or two or more specific types Alloys composed of metal elements and one or more other metal elements, as well as compounds containing one or more specific metal elements, and oxides, carbides, nitrides and silicides of the compounds And composite compounds such as sulfides or phosphides. By using these simple metals, alloys or metal compounds as the negative electrode active material, the capacity of the battery can be increased.

  In addition, a compound in which these complex compounds are complexly bonded to several kinds of elements such as a simple metal, an alloy, or a nonmetallic element is also included. 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, 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 operate as a negative electrode, and a nonmetallic element may be used. it can.

  Among these negative electrode active materials, since the capacity per unit mass is large when a battery is formed, any one simple metal of a specific metal element, an alloy of two or more specific metal elements, oxidation of a specific metal element In particular, silicon and / or tin metal simple substance, alloy, oxide, carbide, nitride and the like are 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 occlude 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 sometimes 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 energy devices because the output resistance is greatly reduced.

In addition, lithium or titanium of the lithium titanium composite oxide is at least selected from the group consisting of other metal elements such as Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb. Those substituted with one element are also preferred.
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 upon doping and dedoping of lithium ions is stable.

_{Li x Ti y M z O 4} (A)
[In the formula (A), M represents at least one element selected from the group consisting of Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn 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 of a good balance of battery performance.
Particularly preferred representative compositions of the above compounds are Li _4/3 Ti _5/3 O ₄ in (a), Li ₁ Ti ₂ O ₄ in (b), and Li _4/5 Ti _11/5 O in (c). ₄ . As for the structure of Z ≠ 0, for example, Li _4/3 Ti _4/3 Al _1/3 O ₄ is preferable.

<Physical properties of carbonaceous materials>
When using a carbonaceous material as a negative electrode active material, it is desirable to have the following physical properties.

(X-ray parameters)
The d value (interlayer distance) of the lattice plane (002 plane) determined by X-ray diffraction by the Gakushin method of carbonaceous materials is preferably 0.335 nm or more, and is usually 0.360 nm or less. 350 nm or less is preferable, and 0.345 nm or less is more preferable. Further, the crystallite size (Lc) of the carbonaceous material obtained 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 diameter of the carbonaceous material is a volume-based average particle diameter (median diameter) determined 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 7 μm. The above is particularly preferable, and is usually 100 μm or less, preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 25 μm or less.

If the volume-based average particle size is below the above range, the irreversible capacity may increase, leading to loss of initial battery capacity. On the other hand, when the above range is exceeded, when an electrode is produced by coating, an uneven coating surface tends to be formed, which may be undesirable in the battery production process.
The volume-based average particle size is measured by dispersing carbon powder in a 0.2% by weight aqueous solution (about 10 mL) of polyoxyethylene (20) sorbitan monolaurate, which is a surfactant, and laser diffraction / scattering particle size distribution. This is carried out using a meter (LA-700 manufactured by Horiba, Ltd.).

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

Further, the Raman half-width in the vicinity of 1580 cm ^{−1 of the} 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, and 80 cm ⁻¹ or less. Preferably, 60 cm ⁻¹ or less is more preferable, and 40 cm ⁻¹ or less is particularly preferable.

The Raman R value and the Raman half width are indices indicating 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 through charge and discharge. It is preferable that the crystallinity is such that the sites between the layers are not lost, that is, the charge acceptability is not lowered. In the case where the density of the negative electrode is increased by press after applying to the current collector, it is preferable to take account of this because crystals tend to be oriented in a direction parallel to the electrode plate. When the Raman R value or the Raman half width is in the above range, a suitable film can be formed on the negative electrode surface to improve the storage characteristics, cycle characteristics, and load characteristics, and the efficiency associated with the reaction with the nonaqueous electrolyte solution Reduction and gas generation can be suppressed.

The measurement of the Raman spectrum, using a Raman spectrometer (manufactured by JASCO Corporation Raman spectrometer), the sample is naturally dropped into the measurement cell and filled, and while irradiating the sample surface in the cell with argon ion laser light, This is done by rotating the cell in a plane perpendicular to the laser beam. The resulting Raman spectrum, the intensity IA of a peak PA around 1580 cm ^-1, and measuring the intensity IB of the peak PB around 1360 cm ^-1, and calculates the intensity ratio R (R = IB / IA) .

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

(BET specific surface area)
BET specific surface area of the carbonaceous material is a value of the measured specific surface area using the BET method is usually 0.1 m ² · ^{g -1} or more, 0.7 m ² · ^{g -1} or more, 1. 0 m ² · ^{g -1} or more, and particularly preferably 1.5 m ² · ^{g -1} or more, generally not more than 100 m ² · ^{g -1,} preferably ^{25 m} 2 · ^{g -1} or less, 15 m ² · g ^-1 more preferably less, ^{10 m} 2 · ^{g -1} or less are especially preferred.

When the value of the BET specific surface area is in the above range, precipitation of lithium on the electrode surface can be suppressed, while gas generation due to reaction with the non-aqueous electrolyte can be suppressed.
The specific surface area was measured by the BET method using a surface area meter (a fully automated surface area measuring device manufactured by Okura Riken), preliminarily drying the sample at 350 ° C. for 15 minutes under nitrogen flow, Using a nitrogen helium mixed gas accurately prepared so that the value of the relative pressure is 0.3, the nitrogen adsorption BET one-point method by the gas flow method is used.

(Roundness)
When the circularity is measured as the degree of the sphere of the carbonaceous material, it is preferably within the following range. The circularity is defined as “circularity = (peripheral length of an equivalent circle having the same area as the particle projection shape) / (actual perimeter of the particle projection shape)”, and is theoretical when the circularity is 1. Become a true sphere. The circularity of the particles having a particle size of 3 to 40 μm in the range of the carbonaceous material is desirably closer to 1, and is preferably 0.1 or more, more 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 the high current density charge / discharge characteristics are larger, the filling property is improved and the resistance between the particles can be suppressed as the circularity is larger, 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 a sample was dispersed in a 0.2% by mass aqueous solution (about 50 mL) of polyoxyethylene (20) sorbitan monolaurate as a surfactant, and irradiated with 28 kHz ultrasonic waves at an output of 60 W for 1 minute. The detection range is specified as 0.6 to 400 μm, and the particle size is measured in the range of 3 to 40 μm.

The method for improving the circularity is not particularly limited, but a sphere-shaped sphere is preferable because the shape of the interparticle void when the electrode body is formed is preferable. Examples of spheroidizing treatment include a method of mechanically approaching a sphere by applying a shearing force and a compressive force, a mechanical / physical processing method of granulating a plurality of fine particles by the binder or the adhesive force of the particles themselves, etc. Is mentioned.

(Tap density)
The tap density of the carbonaceous material is usually 0.1 g · cm ⁻³ or more, preferably 0.5 g · cm ⁻³ or more, more preferably 0.7 g · cm ⁻³ or more, and more preferably 1 g · cm ⁻³ or more. Particularly preferable, 2 g · cm ⁻³ or less is preferable, 1.8 g · cm ⁻³ or less is more preferable, and 1.6 g · cm ⁻³ or less is particularly preferable. When the tap density is in the above range, battery capacity can be ensured and increase in resistance between particles can be suppressed.

The tap density is measured by passing through a sieve having an opening of 300 μm, dropping the sample onto a 20 cm ³ tapping cell and filling the sample to the upper end surface of the cell, and then measuring a powder density measuring device (for example, manufactured by Seishin Enterprise Co., Ltd.). Using a tap denser, tapping with a stroke length of 10 mm is performed 1000 times, and the tap density is calculated 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, more preferably 0.015 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 value of the orientation ratio of the carbonaceous material.

The orientation ratio is measured by X-ray diffraction after pressure-molding the sample. Set the molding obtained by filling 0.47 g of the sample into a molding machine with a diameter of 17 mm and compressing it with 58.8 MN · m ^{-2 so} that it is flush with the surface of the sample holder for measurement. X-ray diffraction is measured. From the (110) diffraction and (004) diffraction peak intensities of the obtained carbon, a ratio represented by (110) diffraction peak intensity / (004) diffraction peak intensity is calculated.

The X-ray diffraction measurement conditions are as follows. “2θ” indicates a diffraction angle.
・ Target: Cu (Kα ray) graphite monochromator ・ Slit:
Divergence slit = 0.5 degree Light receiving slit = 0.15 mm
Scattering slit = 0.5 degree / measurement range and step angle / measurement time:
(110) plane: 75 degrees ≦ 2θ ≦ 80 degrees 1 degree / 60 seconds (004) plane: 52 degrees ≦ 2θ ≦ 57 degrees 1 degree / 60 seconds

(Aspect ratio (powder))
The aspect ratio of the carbonaceous material is usually 1 or more and usually 10 or less, preferably 8 or less, and more preferably 5 or less. Within the above range, streaking during electrode plate formation is suppressed, 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 value of the aspect ratio of the carbonaceous material.

  The aspect ratio is measured by magnifying and observing the carbonaceous material particles with a scanning electron microscope. Carbonaceous material particles when three-dimensional observation is performed by selecting arbitrary 50 graphite particles fixed to the end face of a metal having a thickness of 50 μm or less and rotating and tilting the stage on which the sample is fixed. The longest diameter A and the shortest diameter B orthogonal thereto are measured, and the average value of A / B is obtained.

<Configuration and production method of negative electrode>
Any known method can be used for producing the electrode as long as the effects of the present invention are not significantly impaired. For example, it is formed by adding a binder, a solvent, and, if necessary, a thickener, a conductive material, a filler, etc. to a negative electrode active material to form a slurry, which is applied to a current collector, dried and then pressed. Can do.
In the case of using an alloy-based material, a method of forming a thin film layer (negative electrode active material layer) containing the above-described negative electrode active material by a technique such as vapor deposition, sputtering, or plating is also used.

(Current collector)
As the current collector for holding the negative electrode active material, a known material can be arbitrarily used. Examples of the current collector for the negative electrode include metal materials such as aluminum, copper, nickel, stainless steel, and nickel-plated steel. Copper is particularly preferable from the viewpoint of ease of processing and cost.
In addition, the shape of the current collector may be, for example, a metal foil, a metal cylinder, a metal coil, a metal plate, a metal thin film, an expanded metal, a punch metal, a foam metal, or the like when the current collector is a metal material. Among them, a metal thin film is preferable, and 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, and both 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 handling properties.

(Thickness ratio 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 “(the thickness of the negative electrode active material layer on one side immediately before the nonaqueous electrolyte injection) / (thickness of the current collector)” However, 150 or less is preferable, 20 or less is more preferable, 10 or less is particularly preferable, 0.1 or more is 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 in the above range, battery capacity can be secured and heat generation of the current collector during high current density charge / discharge can be suppressed.

(Binder)
The binder for binding the negative electrode active material is not particularly limited as long as it is a material that is stable with respect to the non-aqueous electrolyte solution and the solvent used in manufacturing the electrode.
Specific examples include resin polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, polyimide, cellulose, and nitrocellulose; SBR (styrene butadiene rubber), isoprene rubber, butadiene rubber, fluorine rubber, NBR (Acrylonitrile / butadiene rubber), rubbery polymers such as ethylene / propylene rubber; styrene / butadiene / styrene block copolymer or hydrogenated product thereof; EPDM (ethylene / propylene / diene terpolymer), styrene / ethylene・ Thermoplastic elastomeric polymers such as butadiene / styrene copolymer, styrene / isoprene / styrene block copolymer or hydrogenated products thereof; syndiotactic-1,2-polybutadiene, polyvinyl acetate Soft resinous polymers such as ethylene / vinyl acetate copolymer, propylene / α-olefin copolymer; polyvinylidene fluoride, polytetrafluoroethylene, fluorinated polyvinylidene fluoride, polytetrafluoroethylene / ethylene copolymer, etc. Fluoropolymers; polymer compositions having ionic conductivity of alkali metal ions (especially lithium ions). These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios.

  The ratio of the binder to the negative electrode active material is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 0.6% by mass or more, and preferably 20% by mass or less, 15% by mass. The following is more preferable, 10 mass% or less is still more preferable, and 8 mass% or less is especially 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 as a 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 0 .6% by mass or more is more preferable, and is usually 5% by mass or less, preferably 3% by mass or less, and more preferably 2% by mass or less. Moreover, when the main component contains a fluorine-based polymer typified by polyvinylidene fluoride, the ratio to the negative electrode active material is usually 1% by mass or more, preferably 2% by mass or more, and more preferably 3% by mass or more. Preferably, it is usually 15% by mass or less, preferably 10% by mass or less, and more preferably 8% by mass or less.

(Slurry forming solvent)
The solvent for forming the slurry is not 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 conductive material used as necessary. Alternatively, either an aqueous solvent or an organic solvent may be used.
Examples of the aqueous solvent include water and alcohol. Examples of the organic solvent include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N, N- Examples 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 add a dispersant or the like in addition to the thickener and slurry it using a latex such as SBR. In addition, these solvents may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and a ratio.

(Thickener)
A thickener is usually used to adjust the viscosity of the slurry. The thickener is not particularly limited, and specific examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios.

  Furthermore, when using a thickener, the ratio of the thickener to the negative electrode active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.6% by mass or more, Moreover, it is 5 mass% or less normally, 3 mass% or less is preferable, and 2 mass% or less is still more preferable. When the ratio of the thickener to the negative electrode active material is in the above range, it is possible to suppress a decrease in battery capacity and an increase in resistance, and it is possible to ensure good coatability.

(Electrode density)
The electrode structure when the negative electrode active material is made into an electrode is not particularly limited, but the density of the negative electrode active material present on the current collector is preferably 1 g · cm ⁻³ or more, and 1.2 g · cm ⁻³ or more. but more preferably, particularly preferably 1.3 g · ^{cm -3} or more, preferably 2.2 g · ^{cm -3} or less, more preferably 2.1 g · ^{cm -3} or less, 2.0 g · ^{cm -3} or less Further preferred is 1.9 g · cm ⁻³ or less. When the density of the negative electrode active material existing on the current collector is in the above range, the negative electrode active material particles are prevented from being destroyed, and an increase in initial irreversible capacity or to the vicinity of the current collector / negative electrode active material interface. While the deterioration of the high current density charge / discharge characteristics due to the reduced permeability of the non-aqueous electrolyte solution can be suppressed, the decrease in battery capacity and the increase in resistance can be suppressed.

(Thickness of negative electrode plate)
The thickness of the negative electrode plate is designed according to the positive electrode plate used, and is not particularly limited. , More preferably 30 μm or more, and usually 300 μm or less, preferably 280 μm
m or less, more preferably 250 μm or less.

(Surface coating of negative electrode plate)
Moreover, you may use what adhered the substance of the composition different from this to the surface of the said negative electrode plate. Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate And sulfates such as aluminum sulfate and carbonates such as lithium carbonate, calcium carbonate and magnesium carbonate.

2-1-4. Positive electrode The positive electrode has a positive electrode active material layer on a 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 for 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). For example, lithium and at least one transition metal Substances containing are preferred. Specific examples include lithium transition metal composite oxides and lithium-containing transition metal phosphate compounds. These may be used individually by 1 type, and may be used together combining 2 or more types arbitrarily.

V, Ti, Cr, Mn, Fe, Co, Ni, Cu, etc. are preferable as the transition metal of the lithium transition metal composite oxide. Specific examples include lithium-cobalt composite oxides such as LiCoO ₂ and LiNiO ₂ . Lithium / nickel composite oxide, LiMnO ₂ , LiMn ₂ O ₄ , Li ₂ MnO _{4 and} other lithium / manganese composite oxides, LiNi _1/3 Mn _1/3 Co _1/3 O ₂ , LiNi _0.5 Mn _{0. 3} Co _0.2 O _{2 and} other lithium / nickel / manganese / cobalt composite oxides, and some of the transition metal atoms that are the main components of these lithium transition metal composite oxides are Na, K, B, F, Al, Ti , V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Si, Nb, Mo, Sn, W, etc. That. As the substituted ones, LiNi _0.5 Mn _0.5 O ₂ , 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 , LiMn _1.5 Ni _0.5 O _{4 and the} like.

As the transition metal of the lithium-containing transition metal phosphate compound, V, Ti, Cr, Mn, Fe, Co, Ni, Cu and the like are preferable, and specific examples include LiFePO ₄ , Li ₃ Fe ₂ (PO 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 components 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.

In addition, it is preferable to include lithium phosphate in the positive electrode active material because continuous charge characteristics are improved. Although there is no restriction | limiting in the use of lithium phosphate, It is preferable to mix and use said positive electrode active material and lithium phosphate. The lower limit of the amount of lithium phosphate to be used is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass with respect to the total of the positive electrode active material and lithium phosphate. %, And the upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less.

(Surface coating)
Moreover, you may use what the substance of the composition different from this adhered to the surface of the said positive electrode active material. Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate And sulfates such as aluminum sulfate, carbonates such as lithium carbonate, calcium carbonate, and magnesium carbonate, and carbon.

  For example, these surface adhering substances are dissolved or suspended in a solvent, impregnated and added to the positive electrode active material, and dried. After the surface adhering substance precursor is dissolved or suspended in a solvent and impregnated and added to the positive electrode active material, It can be made to adhere to the surface of the positive electrode active material by a method of reacting by heating or the like, a method of adding to the positive electrode active material precursor and firing simultaneously. In addition, when making carbon adhere, the method of making carbonaceous adhere mechanically later in the form of activated carbon etc. can also be used, for example.

The amount of the surface adhering substance is, by mass, with respect to the positive electrode active material, preferably 0.1 ppm or more, more preferably 1 ppm or more, still more preferably 10 ppm or more, and the upper limit, preferably 20% or less, more preferably as the lower limit. Is used at 10% or less, more preferably 5% or less. The surface adhering substance can suppress the oxidation reaction of the electrolyte solution on the surface of the positive electrode active material and can improve the battery life. However, when the amount of the adhering quantity is too small, the effect is not sufficiently manifested. If it is too high, the resistance may increase in order to inhibit the entry and exit of lithium ions.
In the present invention, a material having a composition different from that 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 a lump shape, a polyhedron shape, a sphere shape, an oval sphere shape, a plate shape, a needle shape, and a column shape as conventionally used. Moreover, primary particles may aggregate 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 g / cm ³ or more, and further 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 and the necessary amount of the conductive material and the binder necessary for forming the positive electrode active material layer can be suppressed. As a result, the filling rate of the positive electrode active material and the battery Capacity can be secured. By using a complex oxide powder having a high tap density, a high-density positive electrode active material layer can be formed. In general, the tap density is preferably as high as possible, and there is no particular upper limit. However, the tap density is preferably 4.0 g / cm ³ or less, more preferably 3.7 g / cm ³ or less, and still more preferably 3.5 g / cm ³ or less. When it is within the above range, it is possible to suppress a decrease in load characteristics.
In the present invention, the tap density is defined as the powder packing density (tap density) g / cc when 5 to 10 g of the positive electrode active material powder is put in a 10 ml glass measuring cylinder and tapped 200 times with a stroke of about 20 mm. Ask.

(Median diameter d50)
The median diameter d50 of the positive electrode active material particles (secondary particle diameter when primary particles are aggregated to form secondary particles) is preferably 0.3 μm or more, more preferably 0.5 μm or more, and even more preferably. 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 battery performance degradation can be suppressed. On the other hand, when producing a positive electrode for a battery, that is, when an active material, a conductive material, a binder, etc. are slurried with a solvent and applied in a thin film form Problems such as streaking can be prevented. Here, by mixing two or more positive electrode active materials having different median diameters d50, it is possible to further improve the filling property at the time of producing the positive electrode. In the present invention, the median diameter d50 is measured by a known laser diffraction / scattering particle size distribution measuring device. When LA-920 manufactured by HORIBA is used as a particle size distribution meter, a 0.1% by mass sodium hexametaphosphate aqueous solution is used as a dispersion medium for measurement, and a measurement refractive index of 1.24 is set after ultrasonic dispersion for 5 minutes. Measured.

(Average primary particle size)
When 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, and still more preferably 0.8. The upper limit is preferably 5 μm or less, more preferably 4 μm or less, still more preferably 3 μm or less, and most preferably 2 μm or less. When it is in the above range, powder filling property and specific surface area can be secured and deterioration of battery performance can be suppressed, while reversibility of charge and discharge can be secured by obtaining appropriate crystallinity. . In the present invention, the primary particle diameter is measured by observation using a scanning electron microscope (SEM). Specifically, in a photograph at 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 obtained by taking the average value. It is done.

(BET specific surface area)
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, further preferably 0.3 m ² / g or more, the upper limit is ^{50 m} 2 / g below , 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 secured and the applicability of the positive electrode active material can be kept good. In the present invention, the BET specific surface area is determined by using a surface area meter (for example, a fully automatic surface area measuring device manufactured by Okura Riken), preliminarily drying the sample at 150 ° C. for 30 minutes under nitrogen flow, and then atmospheric pressure. It is defined by a value measured by a nitrogen adsorption BET one-point method using a gas flow method using a nitrogen-helium mixed gas accurately prepared so that the value of the relative pressure of nitrogen to 0.3 is 0.3.

(Method for producing positive electrode active material)
As a manufacturing method of the positive electrode active material, a general method is used as a manufacturing method of the inorganic compound. In particular, various methods are conceivable for producing a spherical or elliptical active material. For example, a transition metal raw material is dissolved or ground and dispersed in a solvent such as water, and the pH is adjusted while stirring. And a spherical precursor is prepared and recovered, dried as necessary, and then added with a Li source such as LiOH, Li ₂ CO ₃ , LiNO _{3 and the} like, and then fired at a high temperature to obtain an active material. .

For the production of the positive electrode, the positive electrode active material may be used alone, or one or more of the different compositions may be used in any combination or ratio. As a preferable combination in this case, a combination of LiCoO ₂ and LiMn ₂ O ₄ such as LiNi _0.33 Co _0.33 Mn _0.33 O ₂ or a part of this Mn substituted with another transition metal or the like Or a combination with LiCoO ₂ or a part of this Co substituted with another transition metal or the like.

<Configuration and manufacturing method of positive electrode>
The structure 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. Manufacture of the positive electrode using a positive electrode active material can be performed by a conventional method. That is, a positive electrode active material and a binder, and if necessary, a conductive material and a thickener mixed in a dry form are pressure-bonded to a positive electrode current collector, or these materials are liquid media A positive electrode can be obtained by forming a positive electrode active material layer on the current collector by applying it to a positive electrode current collector and drying it as a slurry by dissolving or dispersing in a slurry.

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. Moreover, an upper limit becomes like this. Preferably it is 99 mass% or less, More preferably, it is 98 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. The positive electrode active material layer obtained by coating and 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. 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, and even more preferably at 2.2 g / cm ³ or more, the upper limit is preferably 5 g / cm ^{It is 3} or less, more preferably 4.5 g / cm ³ or less, and 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)
A known conductive material can be arbitrarily used as the conductive material. 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; and carbon materials such as amorphous carbon such as needle coke. In addition, these may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. The conductive material is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more in the positive electrode active material layer, and the upper limit is usually 50% by mass or less, preferably It is used so as to contain 30% by mass or less, more preferably 15% by mass or less. Sufficient electrical conductivity and battery capacity can be ensured within the above range.

(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 that can be dissolved or dispersed in the liquid medium used during electrode production may be used. , Polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polyimide, aromatic polyamide, cellulose, nitrocellulose, and other resin polymers; SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), fluororubber, isoprene rubber , Rubber polymers such as butadiene rubber and ethylene-propylene rubber; styrene / butadiene / styrene block copolymer or hydrogenated product thereof, EPDM (ethylene / propylene / diene terpolymer), styrene / ethylene / butadiene / Ethylene copolymer, styrene Thermoplastic elastomeric polymer such as isoprene / styrene block copolymer or hydrogenated product thereof; syndiotactic-1,2-polybutadiene, polyvinyl acetate, ethylene / vinyl acetate copolymer, propylene / α-olefin copolymer Soft resinous polymers such as polymers; Fluoropolymers such as polyvinylidene fluoride (PVdF), polytetrafluoroethylene, fluorinated polyvinylidene fluoride, polytetrafluoroethylene / ethylene copolymers; alkali metal ions (especially lithium ions) And a polymer composition having ion conductivity. In addition, these substances may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

The ratio 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 1.5% by mass or more, and the upper limit is usually 80% by mass or less, preferably Is 60% by mass or less, more preferably 40% by mass or less, and most preferably 10% by mass or less. When the ratio of the binder is too low, the positive electrode active material cannot be sufficiently retained and the positive electrode has insufficient mechanical strength, which may deteriorate battery performance such as cycle characteristics. On the other hand, if it is too high, battery capacity and conductivity may be reduced.

(Slurry forming solvent)
The solvent for forming the slurry is not particularly limited as long as it is a solvent that can dissolve or disperse the positive electrode active material, the conductive material, the binder, and the thickener used as necessary. However, either an aqueous solvent or an organic solvent may be used. Examples of the aqueous medium include water and a mixed medium of alcohol and water. 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; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; Esters such as methyl acetate and methyl acrylate; Amines such as diethylenetriamine and N, N-dimethylaminopropylamine; Ethers such as diethyl ether, propylene oxide and tetrahydrofuran (THF); N-methylpyrrolidone (NMP) and dimethyl Examples include amides such as formamide and dimethylacetamide; aprotic polar solvents such as hexamethylphosphalamide and dimethyl sulfoxide.

  In particular, when an aqueous medium is used, it is preferable to make a slurry using a thickener and a latex such as styrene-butadiene rubber (SBR). A thickener is usually used to adjust the viscosity of the slurry. The thickener is not particularly limited, and specific examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios. 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. The upper limit is 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less. When it is in 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 a known material can be arbitrarily used. Specific examples include metal materials such as aluminum, stainless steel, nickel plating, titanium, and tantalum; and carbon materials such as carbon cloth and carbon paper. Of these, metal materials, particularly aluminum, are preferred.

  Examples of the shape of the current collector include metal foil, metal cylinder, metal coil, metal plate, metal thin film, expanded metal, punch metal, and foam metal in the case of a metal material. A thin film, a carbon cylinder, etc. are mentioned. Of these, metal thin films are preferred. In addition, you may form a thin film suitably in mesh shape. Although the thickness of the thin film is arbitrary, 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, it is 50 μm or less.

  Moreover, it is also preferable from the viewpoint of reducing the electronic contact resistance between the current collector and the positive electrode active material layer that a conductive additive is applied to the surface of the current collector. Examples of the conductive assistant include noble metals such as carbon, 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 electrolyte injection) / (thickness of the current collector) is 20 The lower limit is 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. Above this range, the current collector may generate heat due to Joule heat during high current density charge / discharge. Within the above range, heat generation of the current collector during high current density charge / discharge can be suppressed, and battery capacity can be secured.

(Electrode area)
When using the electrolytic solution of the present invention, 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 increasing the stability at high output and high temperature. Specifically, the sum of the electrode areas of the positive electrode with respect to the surface area of the exterior of the secondary battery is preferably 15 times or more, more preferably 40 times or more. The outer surface area of the outer case is the total area obtained by calculation from the vertical, horizontal, and thickness dimensions of the case part filled with the power generation element excluding the protruding part of the terminal in the case of a 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 geometric 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 current collector foil. , The sum of the areas where each surface is calculated separately.

(Thickness of positive 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 composite layer obtained by subtracting the metal foil thickness of the core material is preferably as a 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.

(Positive electrode surface coating)
Moreover, you may use what adhered the substance of the composition different from this to the surface of the said positive electrode plate. Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate And sulfates such as aluminum sulfate, carbonates such as lithium carbonate, calcium carbonate, and magnesium carbonate, and carbon.

2-1-5. Separator Normally, a separator is interposed between the positive electrode and the negative electrode in order to prevent a short circuit. In this case, the 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, a resin, glass fiber, inorganic material, etc., which is formed of a material that is stable with respect to the electrolytic solution of the present invention, is used, and it is preferable to use a porous sheet or a nonwoven fabric-like material excellent in liquid retention. .

  As materials for the resin and glass fiber separator, polyolefins such as polyethylene and polypropylene, aromatic polyamides, polytetrafluoroethylene, polyethersulfone, glass filters and the like can be used. Of these, glass filters and polyolefins are preferred, polyolefins are more preferred, and polypropylenes are particularly preferred. One of these materials may be used alone, or two or more of these materials may be used in any combination and ratio, or those laminated may be used. A specific example of a laminate of two or more kinds in any combination includes 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, more preferably 8 μm or more, and usually 50 μm or less, preferably 40 μm or less, more preferably 30 μm or less. Within the above range, insulation and mechanical strength can be secured, while battery performance such as rate characteristics and energy density can be secured.
Furthermore, when a porous material such as a porous sheet or nonwoven fabric is used as the separator, the porosity of the separator is arbitrary, but is usually 20% or more, preferably 35% or more, more preferably 45% or more, Moreover, it is 90% or less normally, 85% or less is preferable and 75% or less is still more preferable. When the porosity is in the above range, insulation and mechanical strength can be secured, while film resistance can be suppressed and good rate characteristics can be obtained.

  Moreover, although the average pore diameter of a separator is also arbitrary, it is 0.5 micrometer or less normally, 0.2 micrometer or less is preferable, and it is 0.05 micrometer or more normally. If the average pore diameter exceeds the above range, a short circuit tends to occur. When the average pore diameter is in the above range, the film resistance can be suppressed and good rate characteristics can be obtained while preventing a short circuit. On the other hand, as inorganic materials, 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 having a particle shape or fiber shape are used. .

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

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 interposed through the separator, and a structure in which the positive electrode plate and the negative electrode plate are wound in a spiral shape through the separator. Either is acceptable. The ratio of the mass of the electrode group to the internal volume of the battery (hereinafter referred to as the electrode group occupation ratio) is usually 40% or more, preferably 50% or more, and usually 90% or less, preferably 80% or less. . When the electrode group occupancy is in the above range, the battery capacity can be secured, the charge / discharge repeatability and the high temperature storage accompanying the increase in internal pressure are suppressed, and further the operation of the gas release valve is prevented. Can do.

<Current collection structure>
The current collecting structure is not particularly limited, but is preferably a structure that reduces the resistance of the wiring portion and the joint portion. In the case where the electrode group has the above laminated structure, a structure formed by bundling the metal core portions of the electrode layers and welding them to the terminals is preferably used. When the area of one electrode increases, the internal resistance increases. Therefore, it is also preferable to provide a plurality of terminals in the electrode to reduce the resistance. When the electrode group has the winding structure described above, the internal resistance can be lowered by providing a plurality of lead structures for the positive electrode and the negative electrode, respectively, and bundling the terminals.

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

In an exterior case using metals, the metal is welded together by laser welding, resistance welding, or ultrasonic welding to form a sealed sealed structure, or a caulking structure using the above metals via a resin gasket. Things. Examples of the outer case using the laminate film include a case where a resin-sealed structure is formed by heat-sealing resin layers. In order to improve sealing performance, a resin different from the resin used for the laminate film may be interposed between the resin layers. In particular, when a resin layer is heat-sealed through a current collecting terminal to form a sealed structure, a metal and a resin are joined, so that a resin having a polar group or a modified group having a polar group introduced as an intervening resin is used. Resins are preferably used. The shape of the exterior body is also arbitrary, and may be any of a cylindrical shape, a square shape, a laminate shape, a coin shape, a large size, and the like.

<Protective element>
As a protective element, PTC (Positive Temperature Coefficient) whose resistance increases when abnormal heat generation or excessive current flows, temperature fuse, thermistor, shuts off the current flowing through the circuit due to sudden increase in battery internal pressure or internal temperature at abnormal heat generation A valve (current cutoff valve) or the like can be used. It is preferable to select a protective element that does not operate under normal use at a high current, and it is more preferable that the protective element is designed 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. For the electrolyte, a non-aqueous electrolyte solution in which a magnesium salt, calcium salt, aluminum salt or the like is dissolved in a non-aqueous solvent so as to give the same element as the reactive active material species of the negative electrode, that is, magnesium ion, calcium ion, and aluminum ion. And 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), A non-aqueous electrolyte solution for a valent cation battery can be prepared.

<2-3. Metal-air battery>
For the negative electrode, metals such as zinc, lithium, sodium, magnesium, aluminum, calcium, and compounds containing these metals are used. Since the positive electrode active material is oxygen, a porous gas diffusion electrode is used for the positive electrode. The porous material is preferably carbon. In the electrolyte, lithium salt, sodium salt, magnesium salt, aluminum salt, calcium salt, etc. are dissolved in a non-aqueous solvent to give the same element as the negative electrode active material species, that is, lithium, sodium, magnesium, aluminum, calcium, etc. A non-aqueous electrolyte, and 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. By making it, the non-aqueous electrolyte solution for metal air batteries 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 (beryllium, magnesium and alkaline earth metal) and helium, and the s-block metal secondary battery is the s-block element. -Represents a secondary battery using a block metal as a negative electrode and / or an electrolyte. Specific examples of the s-block metal secondary battery other than the above include lithium-sulfur batteries, sodium-sulfur batteries, and sodium-ion batteries that use sulfur for the positive electrode.

<2-5. Lithium ion capacitor>
A material capable of forming an electric double layer is used for the positive electrode, and a material capable of inserting and extracting lithium ions is used for the negative electrode. Activated carbon is preferred as the positive electrode material. Moreover, as a negative electrode material, a carbonaceous material is preferable. The non-aqueous electrolyte 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 electrolyte.

<2-6. Electric Double Layer Capacitor>
A material capable of forming an electric double layer is used for 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 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 electrolyte.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.
The structure of the compound represented by formula (1) used in this example is shown below.

  Moreover, the structure of the other used compound is shown below.

<Example 1-1 and Comparative Examples 1-1 to 1-4>
[Example 1-1]
[Preparation of non-aqueous electrolyte]
LiPF _{6 as} an electrolyte in a mixed solvent (mixing volume ratio EC: EMC: DEC = 3: 4: 3) composed of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and diethyl carbonate (DEC) under a dry argon atmosphere. Was dissolved at a rate of 1.2 mol / L. And vinylene carbonate (VC) 2.0 mass% and monofluoroethylene carbonate (MFEC) 2.0 mass% were mix | blended, and it was set as the basic electrolyte solution. Furthermore, 0.50 mass% of compound (1-1) was mix | blended with respect to the basic electrolyte solution, and the non-aqueous electrolyte solution of Example 1-1 was prepared.

[Production of positive electrode]
97% by mass of lithium cobaltate (LiCoO ₂ ) as a positive electrode active material, 1.5% by mass of acetylene black as a conductive material, and 1.5% by mass of polyvinylidene fluoride (PVdF) as a binder, N-methylpyrrolidone In a solvent, the mixture was slurried by mixing with a disperser. This was uniformly applied on both sides of a 15 μm thick aluminum foil, dried, and then pressed to obtain a positive electrode.

[Production of negative electrode]
Natural graphite powder as negative electrode active material, aqueous dispersion of sodium carboxymethylcellulose as thickener (carboxymethylcellulose sodium concentration 1 mass%), aqueous dispersion of styrene butadiene rubber as binder (concentration of styrene butadiene rubber 50 mass%) ) And mixed with a disperser to form a slurry. This slurry was uniformly applied to one side of a 10 μm thick copper foil, dried, and then pressed to obtain a negative electrode. In addition, in the negative electrode after drying, it produced so that it might become the mass ratio of natural graphite: carboxymethylcellulose sodium: styrene-butadiene rubber = 98: 1: 1.

[Production of lithium secondary battery]
The above positive electrode, negative electrode, and polypropylene separator were laminated in the order of the negative electrode, separator, positive electrode, separator, and negative electrode to produce a battery element. After inserting this battery element into a bag made of a laminate film in which both surfaces of aluminum (thickness 40 μm) are coated with a resin layer while projecting positive and negative terminals, a non-aqueous electrolyte solution is injected into the bag, Vacuum sealing was performed to produce a sheet-like lithium secondary battery.

[Initial charge / discharge test]
The lithium secondary battery was charged under constant pressure at 25 ° C. with a current corresponding to 0.05 C for 6 hours, and then discharged at a constant current of 0.2 C to 3.0 V. Furthermore, after a constant current-constant voltage charge (also referred to as “CC-CV charge”) (0.05 C cut) to 4.1 V with a current corresponding to 0.2 C, it was left under conditions of 45 ° C. and 72 hours. . Then, it discharged to 3.0V with a constant current of 0.2C. Next, after CC-CV charge (0.05 C cut) to 4.4 V at 0.2 C, the battery was discharged again to 3.0 V at 0.2 C to stabilize the initial battery characteristics. Here, 1C represents a current value for discharging the reference capacity of the battery in one hour, and for example, 0.2C represents a current value of 1/5 thereof.

[High-temperature storage durability test (charge / discharge efficiency after storage, rate characteristics after storage, amount of stored gas)]
The lithium secondary battery that had been initially charged and discharged was CC-CV charged at 0.05C up to 4.4V (cut at 0.05C) at 25 ° C, then immersed in an ethanol bath. The battery volume was determined. Thereafter, high temperature storage was performed at 85 ° C. for 1 day. The sufficiently cooled battery was immersed in an ethanol bath to measure the volume, and the amount of change from the battery volume before storage was taken as the storage gas amount. Next, a constant current was discharged to 3.0 V at 0.2 C at 25 ° C. After that, CC-CV charge (0.05C cut) to 4.4V at a constant current of 0.2C at 25 ° C, and then discharged again to 3.0V at 0.2C, and this was made a recovery 0.2C capacity . Furthermore, after CC-CV charge (0.05C cut) to 4.4V at 0.2C, it discharged to 3.0V at 1.0C, and this was made into recovery 1.0C capacity. The charge / discharge efficiency at this time was defined as the charge / discharge efficiency after storage, the ratio of the recovery 1.0C capacity to the recovery 0.2C capacity was determined, and this was defined as the post-storage rate characteristic (%).

    An initial charge / discharge test and a high-temperature storage durability test were performed using the lithium secondary battery produced above. The evaluation results are shown in Table 1 as relative values when Comparative Example 1-1 is 100.0%. The same applies to the following.

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

[Comparative Example 1-2]
In the electrolyte solution of Example 1-1, the compound (1-1) was not used, but instead the compound (2
-1) A lithium secondary battery was produced in the same manner as in Example 1-1 except that 0.36% by mass was used, and the above evaluation was performed. In addition, the compound (1-1) added in Example 1-1 and the compound (2-1) added in Comparative Example 1-2 are equivalent substance amounts.

[Comparative Example 1-3]
In the electrolytic solution of Example 1-1, the lithium secondary solution was obtained in the same manner as in Example 1-1 except that the compound (1-1) was not used and 0.76% by mass of the compound (2-2) was used instead. A battery was prepared and evaluated as described above. In addition, the compound (1-1) added in Example 1-1 and the compound (2-2) added in Comparative Example 1-3 are equivalent substance amounts.

From Table 1, when the non-aqueous electrolyte solution of Example 1-1 according to the present invention is used, charging after storage is performed as compared with the case where the compound represented by Formula (1) is not added (Comparative Example 1-1). Efficiency and post-storage rate characteristics are improved and the amount of stored gas is reduced. That is, it was suggested that by adding the compound represented by the formula (1), the decomposition of the nonaqueous electrolytic solution was suppressed, and the electrochemical side reaction on the electrode of the decomposition product was suppressed.
In addition, when a compound not included in the range of the formula (1) is used (Comparative Examples 1-2 and 1-2), the storage gas amount is reduced, but the improvement effect is small. The rate characteristics after storage are also inferior to those of Example 1-1. Therefore, it is clear that the battery using the non-aqueous electrolyte according to the present invention has superior characteristics.

  According to the non-aqueous electrolyte of the present invention, the charge / discharge efficiency and rate characteristics after the high-temperature storage durability test of the energy device containing the non-aqueous electrolyte can be improved, and further, the gas generation after the high-temperature storage durability test can be reduced. It is. Therefore, the non-aqueous electrolyte solution and energy device of the present invention can be used for various known applications. Specific examples include notebook computers, pen input computers, mobile computers, electronic book players, mobile phones, mobile faxes, mobile copy, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, minidiscs, etc. , Walkie Talkie, Electronic Notebook, Calculator, Memory Card, Portable Tape Recorder, Radio, Backup Power Supply, Motor, Car, Motorcycle, Motorbike, Bicycle, Lighting Equipment, Toy, Game Equipment, Clock, Electric Tool, Strobe, Camera, Home Backup power source, office backup power source, load leveling power source, natural energy storage power source and the like.

Claims (12)

A nonaqueous electrolytic solution for an energy device including a positive electrode and a negative electrode, wherein the nonaqueous electrolytic solution contains a fluorine-containing cyclic carbonate and a compound represented by the formula (1) together with the electrolyte and the nonaqueous solvent. Non-aqueous electrolyte.

(Where
R ¹ is an unsaturated hydrocarbon group having 3 to 12 carbon atoms which may have a substituent having at least one carbon-carbon unsaturated bond, and R ² is an aliphatic carbon atom having 2 to 10 carbon atoms. It is a hydrogen group. ) The non-aqueous electrolyte solution according to claim 1, wherein the unsaturated hydrocarbon group of R ¹ has at least one carbon-carbon double bond in the formula (1). The non-aqueous electrolyte solution according to claim 1 or 2, wherein the unsaturated hydrocarbon group of R ^{1 in} the formula (1) is an aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. . Wherein in formula (1), R ² is an alkylene group having 2 to 10 carbon atoms, a non-aqueous electrolyte solution according to any one of claims 1-3.   The non-aqueous electrolyte solution according to any one of claims 1 to 4, wherein the content of the compound represented by the formula (1) with respect to the total amount of the electrolyte solution is 0.001 mass% or more and 10 mass% or less.   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 described.   The non-aqueous electrolyte solution according to claim 6, wherein the content of the fluorine-containing cyclic carbonate 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.   Furthermore, a cyclic carbonate having a carbon-carbon unsaturated bond, 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, a silicon-containing compound, an aromatic Compound, fluorine-free carboxylic acid ester, cyclic compound having a plurality of ether bonds, compound having isocyanuric acid skeleton, monofluorophosphate, difluorophosphate, borate, oxalate and fluorosulfonate The non-aqueous electrolyte solution of any one of Claims 1-7 containing the at least 1 sort (s) of compound chosen from a group. A cyclic carbonate having a carbon-carbon unsaturated bond, 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, a silicon-containing compound, an aromatic compound, Fluorine-free carboxylic acid ester, cyclic compound having a plurality of ether bonds, compound having isocyanuric acid skeleton, monofluorophosphate, difluorophosphate, borate, oxalate and fluorosulfonate The total content of at least one selected compound with respect to the total amount of the non-aqueous electrolyte solution is 0.
The nonaqueous electrolytic solution according to claim 8, wherein the content is 001 mass% or more and 50 mass% or less.   The energy device containing the negative electrode and positive electrode which can occlude / release lithium ion, and the non-aqueous electrolyte solution of any one of Claims 1-9.   The negative electrode has a negative electrode active material layer on a current collector, and the negative electrode active material layer includes a silicon simple metal, an alloy and a compound, a tin simple metal, an alloy and a compound, a carbonaceous material, and a lithium titanium composite. The energy device according to claim 10, comprising 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. -Containing at least one selected from the group consisting of manganese composite oxide, lithium-nickel composite oxide, lithium-nickel-manganese composite oxide, and lithium-cobalt-nickel-manganese composite oxide The energy device according to 11.