JP2017168347A - Nonaqueous electrolyte solution for power storage device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a nonaqueous electrolyte solution for a power storage device, which enables the decrease in electric resistance and which is superior in cycle characteristics; and a power storage device.SOLUTION: A nonaqueous electrolyte solution for a power storage device comprises an electrolyte dissolved in a nonaqueous solvent, and one or more compounds selected from a group consisting of organic sulfone compounds represented by the formulas (1) and (2) below, provided that the electrolyte is a lithium salt soluble in the nonaqueous solvent. R-SO-X-Y-OR(1) (where Ris e.g. an alkyl group with 1-6 carbon atoms; Ris e.g. an alkyl group with 1-6 carbon atoms; X is e.g. a phenylene group; Y is a carbonyl group or sulfonyl group; m and n are 0 or 1-3; and m+n≥2); and (CH=CH-SO-X)-Y(OR)-(Z-SO-CH=CH)(2) (where X, Y and Z are e.g. a phenylene group; R is e.g. a hydrogen atom; m, n, p, q and t are 0 or 1-4; p+q≥1; and m+n≥1).SELECTED DRAWING: None

Description

  The present invention relates to a nonaqueous electrolytic solution for an electricity storage device such as a lithium ion secondary battery.

  In recent years, with the widespread use of various portable electronic devices such as portable electronic terminals typified by mobile phones and notebook computers, secondary batteries play an important role as their power source. Examples of these secondary batteries include lead-acid batteries, aqueous batteries such as nickel / cadmium batteries, and nonaqueous electrolyte batteries. Among them, the non-aqueous electrolyte secondary battery composed of a positive electrode and a negative electrode that can occlude and release lithium and a non-aqueous electrolyte has high voltage, high energy density, excellent safety, and environmental problems. Thus, it has various advantages compared to other secondary batteries.

  As non-aqueous electrolyte secondary batteries currently in practical use, for example, a composite oxide of lithium and a transition metal is used as a positive electrode active material, and a material capable of doping and dedoping lithium is used as a negative electrode active material. Lithium ion secondary battery. In the negative electrode active material of a lithium ion secondary battery, a carbon material is mentioned as a material which has the outstanding cycling characteristics. Among carbon materials, graphite material is expected as a material that can improve the energy density per unit volume.

Further, in order to improve the characteristics of the lithium ion secondary battery, not only the characteristics of the negative electrode / positive electrode but also the characteristics of the non-aqueous electrolyte responsible for transferring lithium ions are required. As such a non-aqueous electrolyte, a lithium salt such as LiBF ₄ , LiPF ₆ , LiClO ₄ , LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ CF ₂ CF ₃ ) ₂ was mixed in an aprotic organic solvent. A non-aqueous solution is used (Non-Patent Document 1). Carbonates are known as typical examples of aprotic organic solvents, and the use of various carbonate compounds such as ethylene carbonate, propylene carbonate, and dimethyl carbonate has been proposed (Patent Documents 1 and 2).

On the other hand, as the electrolyte of the non-aqueous electrolyte, the non-aqueous electrolyte in which LiBF ₄ , LiPF ₆ or the like is dissolved has high conductivity indicating the transfer of lithium ions, and the oxidative decomposition voltage such as LiBF ₄ or LiPF _{6 is used.} Therefore, the lithium ion secondary battery is known to be stable at a high voltage, which contributes to the extraction of the high voltage and high energy density characteristics of the lithium ion secondary battery.

  On the other hand, when using a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery as each power source, the electrical resistance of the non-aqueous electrolyte is lowered to increase the conductivity of lithium ions, and Even after repeated charging and discharging, there is a need for a long life that suppresses a decrease in battery capacity and maintains a high capacity, so-called cycle characteristics.

In order to achieve such an object, various proposals have conventionally been made for non-aqueous electrolytes to specify the structure of a lithium salt that is an electrolyte or to add a specific compound.
For example, Patent Document 3 includes adding a vinylsulfone derivative having a specific structure to a non-aqueous electrolyte, and Patent Document 4 includes lithium salts other than a bifunctional lithium salt having a specific structure. It is known to add a lithium salt having no boron atom.
However, conventional non-aqueous electrolytes are not always satisfactory, including the cost, and further techniques are required for non-aqueous electrolytes for power storage devices.

JP-A-4-184872 Japanese Patent Laid-Open No. 10-27625 JP 11-329494 A Japanese Patent Laid-Open No. 2014-22334

  The present invention improves the solubility of the electrolyte in the non-aqueous electrolyte, lowers the electrical resistance of the non-aqueous electrolyte, and maintains a high capacity even after repeated many times of charging and discharging, so-called cycle It is an object of the present invention to provide a nonaqueous electrolytic solution for an electricity storage device such as a lithium ion secondary battery having improved characteristics, and an electricity storage device using the nonaqueous electrolyte.

  As a result of various researches, the present inventors have found that the nonaqueous electrolytic solution containing the organic sulfone compound represented by the following formula (1) or the organic sulfone compound represented by the formula (2) has the above-mentioned purpose. Found to be effective for achievement. That is, such an organic sulfone compound not only increases the solubility of the lithium electrolyte in the non-aqueous electrolyte and decreases the electric resistance of the non-aqueous electrolyte, but also maintains a high capacity even after repeated charging and discharging. It has been found that so-called cycle characteristics are improved.

The present invention is based on the above new findings and has the following gist.
(1) A nonaqueous electrolytic solution for an electricity storage device obtained by dissolving an electrolyte in a nonaqueous solvent, wherein the electrolyte is a lithium salt dissolved in the nonaqueous solvent and is represented by the following formula (1) A nonaqueous electrolytic solution for an electricity storage device, comprising at least one selected from the group consisting of a sulfone compound and an organic sulfone compound represented by formula (2).

_{R 1 -SO 2 -X m -Y n} -OR 2 (1)

(R ₁ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a phenyl group, or a halogen atom. R ₂ is an alkyl group having 1 to 6 carbon atoms or a carbon number. 2 to 6 alkenyl group, phenyl group or silyl group, X is a phenylene group or an alkylene group having 1 to 6 carbon atoms, Y is a carbonyl group or a sulfonyl group, m and n are Each independently represents an integer of 0 or 1 to 3, and m + n ≧ 2.

_{(CH 2 = CH-SO 2} -X m) p -Y (OR) t - (Z n -SO 2 -CH = CH 2) q (2)

(X, Y, and Z are each independently a phenylene group or an alkylene group having 1 to 4 carbon atoms. R is a hydrogen atom, a phenyl group, or an alkyl group having 1 to 6 carbon atoms. M, n, p, q, and t are each independently 0 or an integer of 1 to 4, and p + q ≧ 1 and m + n ≧ 1.)
(2) The nonaqueous electrolytic solution for an electricity storage device according to (1), wherein R _{1 in the} formula (1) is a fluorine atom or an alkyl group substituted with a fluorine atom.
(3) The nonaqueous electrolytic solution for an electricity storage device according to (1) or (2), wherein X in the formula (1) is an alkylene group substituted with a fluorine atom.
(4) The nonaqueous electrolytic solution for an electricity storage device according to any one of (1) to (3), wherein R _{2 in the} formula (1) is a silyl group.
(5) The nonaqueous electrolytic solution for an electricity storage device according to (1), wherein p + q ≧ 2 in Formula (2).

(6) The organic sulfone compound represented by the formula (1) is methyl methanesulfonyl acetate, ethyl methanesulfonyl acetate, methyl ethanesulfonyl acetate, difluoro (fluorosulfonyl) acetate methyldifluoro (fluorosulfonyl) acetate trimethylsilyl, difluoro (fluoro The nonaqueous electrolytic solution for an electricity storage device according to any one of the above (1) to (5), which is trimethylsilylmethyl sulfonyl acetate, trimethylsilyl difluoro (fluorosulfonyl) sulfonate, or trimethylsilylmethyl difluoro (fluorosulfonyl) sulfonate.
(7) The organic sulfone compound represented by the formula (2) is 1,2-bis (vinylsulfonylacetamido) ethane, tetrakis (vinylsulfonylmethyl) methane, 1,2-bis (vinylsulfonyl) propane-2- The nonaqueous electrolytic solution for an electricity storage device according to any one of (1) to (5), which is diol or 1,2-bis (vinylsulfonylmethyl) benzene.
(8) The nonaqueous electrolytic solution for an electricity storage device according to any one of (1) to (7), containing 0.0001 to 10% by mass of the organic sulfone compound.
(9) The nonaqueous electrolytic solution for an electricity storage device according to any one of (1) to (8), wherein the nonaqueous solvent contains a chain carbonate ester, a saturated cyclic carbonate ester, and an unsaturated cyclic carbonate ester.
(10) The content of the chain carbonate ester, the saturated cyclic carbonate ester, and the unsaturated cyclic carbonate ester is 30 to 80% by mass, 10 to 50% by mass, and 0.01 to 5% by mass, respectively. The nonaqueous electrolyte for electrical storage devices as described in said (9).

(11) The lithium salt is LiPF ₆ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (FSO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiN (CF _{3 SO 2) (C 2 F 5} SO 2), and one of _{LiN (CF 3 SO 2) (} C 4 F 9 SO 2) above is from one or more selected the group consisting of (1) - (10) A nonaqueous electrolytic solution for an electricity storage device according to 1.
(12) Further, 1 selected from the group consisting of a sulfur-containing compound (excluding the organic sulfone compound represented by the formula (1) or formula (2)), a cyclic acid anhydride, a carboxylic acid compound, and a boron-containing compound. The nonaqueous electrolytic solution for an electricity storage device according to any one of the above (1) to (11), which contains at least one kind of additive.
(13) An electricity storage device using the nonaqueous electrolytic solution according to any one of (1) to (12).
(14) The livestock device according to (13), wherein the electricity storage device is a lithium ion secondary battery.

  The nonaqueous electrolytic solution of the present invention not only lowers the electrical resistance of the nonaqueous electrolytic solution by increasing the solubility of the lithium electrolyte in the nonaqueous electrolytic solution, but also maintains a high capacity even after repeated charging and discharging. In addition, so-called cycle characteristics are improved. For this reason, the nonaqueous electrolyte for electrical storage devices, such as a lithium ion secondary battery excellent in the favorable initial characteristic and cycling characteristics, is provided.

<Nonaqueous solvent>
As the nonaqueous solvent used in the nonaqueous electrolytic solution of the present invention, various solvents can be used. For example, an aprotic polar solvent is preferable. Specific examples thereof are ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, trifluoromethylethylene carbonate, fluoroethylene carbonate. , Cyclic carbonates such as 4,5-difluoroethylene carbonate; lactones such as γ-ptyrolactone and γ-valerolactone; cyclic sulfones such as sulfolane; cyclic ethers such as tetrahydrofuran and dioxane; ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, methylpropyl carbonate, Methyl isopropyl carbonate, dipropyl carbonate, methyl butyl carbonate, dibutyl carbonate, ethyl propyl carbonate -Chain carbonates such as boronate and methyl trifluoroethyl carbonate; Nitriles such as acetonitrile; Chain ethers such as dimethyl ether; Chain carboxylic acid esters such as methyl propionate; Chain glycol ethers such as dimethoxyethane; , 2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (CF ₂ HCF ₂ CH ₂ OCF ₂ CF ₂ H), 1,1,2,2-tetrafluoroethyl-2,2,3 , 3,3-pentafluoropropyl ether (CF ₃ CF ₂ CH ₂ OCF ₂ CF ₂ H), ethoxy-2,2,2-trifluoroethoxy-ethane (CF ₃ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ ) Fluorine-substituted ethers such as These can be used individually by 1 type or in combination of 2 or more types.

  As the non-aqueous solvent, it is more preferable to use a carbonate-based solvent such as cyclic carbonate and chain carbonate from the viewpoint of ion conductivity. It is more preferable to use a combination of a cyclic carbonate and a chain carbonate as the carbonate solvent. Among the above, the cyclic carbonate is preferably ethylene carbonate, propylene carbonate, or fluoroethylene carbonate. As the chain carbonate, among the above, ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate is preferable. In the case of using a carbonate-based solvent, another non-aqueous solvent such as a nitrile compound or a sulfone compound can be further added as necessary from the viewpoint of improving battery physical properties.

  As the nonaqueous solvent, in the present invention, it is particularly preferable to contain a chain carbonate ester, a saturated cyclic carbonate ester, and an unsaturated cyclic carbonate ester. In the case of containing these three kinds of carbonates, it is particularly preferable since the effects of the present invention are exhibited. In the nonaqueous solvent used in the present invention, the chain carbonate ester, the saturated cyclic carbonate ester, and the unsaturated cyclic carbonate ester are 30 to 80% by mass, 10 to 50% by mass, respectively. And 0.01 to 5% by mass, and 50 to 70% by mass, 20 to 30% by mass, and 0.1 to 2% by mass are more preferable.

When the amount of chain carbonate is less than 30% by mass, the viscosity of the electrolytic solution increases, and in addition, it solidifies at a low temperature, so that sufficient characteristics cannot be obtained. On the other hand, when it is more than 80% by mass, the dissociation / solubility of the lithium salt is lowered, and the ionic conductivity of the electrolytic solution is lowered. When the saturated cyclic carbonate is less than 10% by mass, the dissociation / solubility of the lithium salt is lowered, and the ionic conductivity of the electrolytic solution is lowered. On the other hand, when the amount is more than 50% by mass, the viscosity of the electrolytic solution increases and further solidifies at a low temperature, so that sufficient characteristics cannot be obtained.
On the other hand, when the unsaturated cyclic carbonate is less than 0.01% by mass, a good film is not formed on the surface of the negative electrode, so that the cycle characteristics are deteriorated. On the other hand, when the amount is more than 5% by mass, for example, the electrolyte solution is likely to generate gas during high-temperature storage, and the pressure in the battery is increased, which is not preferable in practice.

  Examples of the chain carbonate used in the present invention include a chain carbonate having 3 to 9 carbon atoms in total. Specifically, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, n-propyl isopropyl carbonate, di-n-butyl carbonate, di-t-butyl carbonate, n-butyl isobutyl carbonate , N-butyl-t-butyl carbonate, isobutyl-t-butyl carbonate, ethyl methyl carbonate, methyl-n-propyl carbonate, n-butyl methyl carbonate, isobutyl methyl carbonate, t-butyl methyl carbonate, ethyl-n-propyl carbonate , N-butyl ethyl carbonate, isobutyl ethyl carbonate, t-butyl ethyl carbonate, n-butyl-n-propyl carbonate, isobutyl-n Propyl carbonate, t- butyl -n- propyl carbonate, n- butyl isopropyl carbonate, isobutyl isopropyl carbonate, and t-butyl isopropyl carbonate. Among these, dimethyl carbonate, diethyl carbonate or methyl ethyl carbonate is preferable, but is not particularly limited. Two or more of these chain carbonates may be mixed.

  Examples of the saturated cyclic carbonate used in the present invention include ethylene carbonate, propylene carbonate, butylene carbonate, and fluoroethylene carbonate. Among these, ethylene carbonate, propylene carbonate, or fluoroethylene carbonate is more preferable. By using propylene carbonate, a stable non-aqueous electrolyte can be provided in a wide temperature range. Two or more of these saturated cyclic carbonates may be mixed.

Examples of the unsaturated cyclic carbonate used in the present invention include vinylene carbonate derivatives represented by the following general formula (I).

In the general formula (I), R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms that may contain a halogen atom. Among these, R ₁ and R ₂ are preferably hydrogen atoms (the compound of formula (I) is vinylene carbonate).

  Specific examples of the vinylene carbonate derivative include vinylene carbonate, fluorovinylene carbonate, methyl vinylene carbonate, fluoromethyl vinylene carbonate, ethyl vinylene carbonate, propyl vinylene carbonate, butyl vinylene carbonate, dimethyl vinylene carbonate, diethyl vinylene carbonate, dipropyl vinylene carbonate, etc. However, it is not limited to these.

Among these compounds, vinylene carbonate is effective and advantageous in terms of cost. In addition, the said vinylene carbonate derivative can also be used individually by 1 type or in mixture.
Another unsaturated cyclic carbonate used in the present invention includes alkenyl ethylene carbonate represented by the following general formula (II).

In the above formula (II), R _{3 to} R ₆ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms that may contain a halogen atom, or a group having 2 to 12 carbon atoms. An alkenyl group, at least one of which is an alkenyl group having 2 to 12 carbon atoms. Of these, alkenyl ethylene carbonate in which one of R _{3 to} R ₆ is a vinyl group and the remainder is a hydrogen atom (the compound of formula (II) is 4-vinyl ethylene carbonate) is preferable.

  Specific examples of the alkenyl ethylene carbonate include 4-vinyl ethylene carbonate, 4-vinyl-4-methyl ethylene carbonate, 4-vinyl-4-ethyl ethylene carbonate, 4-vinyl-4-n-propyl ethylene carbonate, and the like. It is done.

  The non-aqueous solvent used in the present invention may contain various other solvents in addition to the above components. Examples of these various other solvents include cyclic carboxylic acid esters, chain esters having 3 to 9 carbon atoms, and chain ethers having 3 to 6 carbon atoms. These other various solvents are preferably contained in the nonaqueous electrolytic solution in an amount of 0.2 to 10% by mass, particularly preferably 0.5 to 5% by mass.

  Among cyclic carboxylic acid esters, examples of the lactone compound having 3 to 9 carbon atoms include γ-butyrolactone, γ-valerolactone, γ-caprolactone, and ε-caprolactone. Among these, γ-butyrolactone or γ-valerolactone is more preferable, but it is not particularly limited. Two or more of these cyclic carboxylic acid esters may be mixed.

  Examples of the chain ester having 3 to 9 carbon atoms include methyl acetate, ethyl acetate, acetic acid-n-propyl, acetic acid-isopropyl, acetic acid-n-butyl, acetic acid isobutyl, acetic acid-t-butyl, methyl propionate, Mention may be made of ethyl propionate, propionate-n-propyl, propionate-isopropyl, propionate-n-butyl, propionate isobutyl, propionate-t-butyl. Of these, ethyl acetate, methyl propionate or ethyl propionate is preferred.

  Examples of the chain ether having 3 to 6 carbon atoms include dimethoxymethane, dimethoxyethane, diethoxymethane, diethoxyethane, ethoxymethoxymethane, and ethoxymethoxyethane. Of these, dimethoxyethane or diethoxyethane can be more preferred.

  Further, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, dioxolane, 4-methyldioxolane, N, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dioxane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene and the like can be used. .

<Lithium salt>
A lithium salt is used as the solute of the nonaqueous electrolytic solution of the present invention. The lithium salt is not particularly limited as long as it can be dissolved in the non-aqueous solvent. Specific examples thereof are as follows, for example.
(A) Inorganic lithium salt:
LiPF _6, LiAsF _6, inorganic fluoride salts LiBF ₄ or the _{like, LiClO 4, LiBrO 4, LiIO} 4, perhalogenate etc. like.
(B) Organic lithium salt:
Organic sulfonates such as LiCF ₃ SO ₃ , LiN (FSO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂₎ perfluoroalkylsulfonic acid imide salts such as, _LiC (CF 3 _{SO 2)} perfluoroalkylsulfonic acid methide salts such as _{3, LiPF (CF 3) 5} , LiPF 2 (CF 3) 4, LiPF 3 (CF ₃ ) ₃ , LiPF ₂ (C ₂ F ₅ ) ₄ , LiPF ₃ (C ₂ F ₅ ) ₃ , LiPF (n-C ₃ F ₇ ) ₅ , LiPF ₂ (n-C ₃ F ₇ ) ₄ , LiPF ₃ ( _{n-C 3 F 7) 3} , LiPF (iso-C 3 F 7) 5, LiPF 2 (iso-C 3 F 7) 4, LiPF 3 (iso-C 3 F 7) 3, LiB (CF 3 _{4, LiBF (CF 3) 3} , LiBF 2 (CF 3) 2, LiBF 3 (CF 3), LiB (C 2 F 5) 4, LiBF (C 2 F 5) 3, LiBF 2 (C 2 F 5) ₂ , LiBF ₃ (C ₂ F ₅ ), LiB (n—C ₃ F ₇ ) ₄ , LiBF (n—C ₃ F ₇ ) ₃ , LiBF ₂ (n—C ₃ F ₇ ) ₂ , LiBF ₃ (n— _{C 3 F 7), LiB (} iso-C 3 F 7) 4, LiBF (iso-C 3 F 7) 3, LiBF 2 (iso-C 3 F 7) 2, LiBF 3 (iso-C 3 F 7) Inorganic fluoride salt fluorophosphate in which some fluorine atoms are substituted with a perfluoroalkyl group, and fluorine-containing organic lithium salt of perfluoroalkyl.

In the present invention, among the above, LiPF ₆ , LiBF ₄ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) (C ₂ F ₅ SO ₂ ) LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ) is more preferable. Two or more of these lithium salts may be mixed.

  The concentration of the lithium salt, which is the solute of the nonaqueous electrolytic solution of the present invention, is preferably 0.5 to 3 mol / liter, particularly 0.7 to 2 mol / liter. If this concentration is too low, the ionic conductivity of the non-aqueous electrolyte becomes insufficient due to an absolute concentration shortage. If the concentration is too high, the ionic conductivity decreases due to an increase in viscosity, and problems such as easy precipitation at low temperatures occur, which is not preferable because the performance of the nonaqueous electrolyte battery decreases.

<Organic sulfone compound>
The organic sulfone compound represented by the following formula (1) and the organic sulfone compound represented by the formula (2) are added to the nonaqueous electrolytic solution of the present invention.

_{R 1 -SO 2 -X m -Y n} -OR 2 (1)

R ₁ , R ₂ , X, Y, m, and n in the above formula (1) are as described above.
Among these, R ₁ is preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom. R ₂ is preferably an alkyl group having 1 to 3 carbon atoms or a silyl group. X is preferably an alkylene group having 1 to 3 carbon atoms. Y is preferably a carbonyl group or a sulfonyl group. M and n are 0 or an integer of 1 to 3, and preferably n ≧ 1.
In the formula (1), when R ₁ , R ₂ and X are an alkyl group, an alkenyl group, a phenyl group, an alkylene group, a phenylene group or a silyl group, the hydrogen atom of these groups is a halogen atom , An alkyl group, a phenyl group, a hydroxyl group, or an alkoxy group may be optionally substituted.

_{(CH 2 = CH-SO 2} -X m) p -Y (OR) t - (Z n -SO 2 -CH = CH 2) q (2)

In the above formula (2), X, Y, Z, R, m, n, p, q, and t are as described above.
Among these, X is preferably an alkylene group having 1 to 2 carbon atoms. Y is preferably an alkylene group having 1 to 2 carbon atoms. Z is preferably an alkylene group having 1 to 2 carbon atoms. R is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Moreover, m and n are preferably integers of 1 to 2. p and q are 0 or an integer of 1 to 4, and preferably p + q ≧ 3. t is preferably 0 or an integer of 1 to 2.
In addition, when X, Y, and R in Formula (2) are an alkyl group, an alkylene group, a phenyl group, or a phenylene group, the hydrogen atom that these groups have is a halogen atom, an alkyl group, a phenyl group, a hydroxyl group Or optionally substituted with an alkoxy group.

Specific examples of the organic sulfone compound represented by the above formula (1) include methyl methanesulfonyl acetate, ethyl methanesulfonyl acetate, methyl ethanesulfonyl acetate, methyl difluoro (fluorosulfonyl) acetate, or trimethylsilyl difluoro (fluorosulfonyl) acetate, Trifluorosilyl methyl difluoro (fluorosulfonyl) acetate, methyl methylsulfonylmethanesulfonate, ethyl methylsulfonylmethanesulfonate, methyl difluoromethane (fluorosulfonyl) sulfonate, trimethylsilyldifluoro (fluorosulfonyl) sulfonate difluoro (fluorosulfonyl) sulfonate Examples thereof include trimethylsilyl and trifluorosilylmethyl difluoro (fluorosulfonyl) sulfonate.
Of these, methyl methanesulfonyl acetate, ethyl methanesulfonyl acetate, methyl difluoro (fluorosulfonyl) acetate, trimethylsilyl difluoro (fluorosulfonyl) acetate, trimethylsilylmethyl difluoro (fluorosulfonyl) acetate, methyl methylsulfonylmethanesulfonate, difluoromethane (fluoro Preference is given to methyl sulfonyl) sulfonate, trimethylsilyl difluoro (fluorosulfonyl) sulfonate, or trimethylsilylmethyl difluoro (fluorosulfonyl) sulfonate.

  Specific examples of the organic sulfone compound represented by the above formula (2) include 1,2-bis (vinylsulfonylacetamido) ethane, tetrakis (vinylsulfonylmethyl) methane, 1,2-bis (vinylsulfonyl). Propane-2-diol, 1,2-bis (vinylsulfonylmethyl) benzene and the like can be mentioned. Of these, 1,2-bis (vinylsulfonylacetamido) ethane or tetrakis (vinylsulfonylmethyl) methane is preferable.

  The content of the organic sulfone compound represented by formula (1) or formula (2) in the nonaqueous electrolytic solution of the present invention is preferably 0.0001 to 10% by mass, more preferably 0.001 to 2% by mass, Most preferably, it is 0.01-1 mass%. When the content is less than 0.0001% by mass, the resistance reduction effect is reduced. On the other hand, when it exceeds 10 mass%, film resistance becomes high and life performance deteriorates, which is not preferable.

<Second additive substance>
In the nonaqueous electrolytic solution of the present invention, a second additive substance may be contained in addition to the specific organic sulfone compound for the purpose of improving the life performance and resistance performance of the electricity storage device. The second additive substance includes a sulfur-containing compound (excluding the organic sulfone compound represented by the formula (1) or formula (2)), a cyclic acid anhydride, a carboxylic acid compound, and a boron-containing compound. One or more compounds selected from the above can be used.
Examples of the sulfur-containing compound include 1,3-propane sultone (PS), propene sultone, ethylene sulfite, 1,4-butane sultone, methyl methanesulfonate, ethyl methanesulfonate, dimethyl methanedisulfonate, diethyl methanedisulfonate, Dipropyl methanedisulfonate, bis (trifluoromethyl) methanedisulfonate, bis (trimethylsilyl) methanedisulfonate, methylenemethanedisulfonic acid, ethylene methanedisulfonate, propylenemethanemethanesulfonate, methyleneethylenedisulfonate, ethyleneethylenedisulfonate, ethanedisulfone Dimethyl acid, Diethyl ethanedisulfonate, Bis (trifluoromethyl) ethanedisulfonate, Bis (trimethylsilyl) ethanedisulfonate, Dimethylpropanedisulfonate , Diethyl propanedisulfonate, methylene propanedisulfonate, ethylene propanedisulfonate, dimethyl 1,5-naphthalenedisulfonate, dimethyl butanedisulfonate, diethyl butanedisulfonate, 5-vinyl-hexahydro 1,3,2-benzodioxathiol -2-oxide, 1,4-butanediol dimethanesulfonate, 1,3-butanediol dimethanesulfonate, N, N-dimethylmethanesulfonamide, N, N-diethylmethanesulfonamide, divinylsulfone, 1,2- Bis (vinyl sulfonyl) methane etc. are mentioned.

  Examples of the cyclic acid anhydride include glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, succinic anhydride, diglycolic anhydride, cyclohexanedicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride 4-cyclohexene-1,2-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phenylsuccinic anhydride, 2- Phenylglutaric anhydride, phthalic anhydride, pyromellitic anhydride, fluorosuccinic anhydride, carboxylic anhydrides such as tetrafluorosuccinic anhydride, trifluoromethanesulfonic anhydride, 1,2-ethanedisulfonic anhydride 1,3-propanedisulfonic anhydride, 1,4-butanedisulfonic anhydride, 1,2- Zendisulfonic anhydride, tetrafluoro-1,2-ethanedisulfonic anhydride, hexafluoro-1,3-propanedisulfonic anhydride, octafluoro-1,4-butanedisulfonic anhydride, 3-fluoro-1 , 2-benzenedisulfonic anhydride, 4-fluoro-1,2-benzenedisulfonic anhydride, 3,4,5,6-tetrafluoro-1,2-benzenedisulfonic anhydride, and the like.

Examples of the carboxylic acid compound include lithium oxalate, lithium malonate, lithium difluoromalonate, lithium succinate, lithium tetrafluorosuccinate, lithium adipate, lithium glutarate, lithium acetonedicarboxylate, lithium 2-oxobutyrate, and oxal. Lithium acetate, lithium 2-oxoglutarate, lithium acetoacetate, 3-oxocyclobutanecarboxylic acid, 3-oxocyclopentanecarboxylic acid, lithium 2-oxovalerate, lithium pyruvate, lithium glyoxylate, 3,3-dimethyl-2 -Lithium oxobutyrate, lithium 2-hydroxypropionate, 2-methyl lithium lactate, lithium tartrate, lithium cyanoacetate, lithium 2-mercaptopropionate, lithium methylenebis (thioglycolate) thiosuccinate, 3- (methylthio) propiate Lithium phosphate, 3,3'-thiodipropionic lithium, lithium dithiodiglycolic acid, lithium 2,2'-thio diglycolic acid, 2,4-lithium-dicarboxylic acid, lithium acetylthio acetate.
Examples of the boron-containing compound include LiBF ₂ (C ₂ O ₄ ), LiB (C ₂ O ₄ ) ₂ , LiBF ₂ (CO ₂ CH ₂ CO ₂ ), LiB (CO ₂ CH ₂ CO ₂ ) ₂ , LiB (CO ₂ CF ₂ CO ₂ ) ₂ , LiBF ₂ (CO ₂ CF ₂ CO ₂ ), LiBF ₃ (CO ₂ CH ₃ ), LiBF ₃ (CO ₂ CF ₃ ), LiBF ₂ (CO ₂ CH ₃ ) ₂ , LiBF ₂ ( _{CO 2 CF 3) 2, LiBF} (CO 2 CH 3) 3, LiBF (CO 2 CF 3) 3, LiB (CO 2 CH 3) 4, LiB (CO 2 CF 3) 4, Li 2 B 2 O 7, li ₂ B ₂ O ₄ and the like.
As said 2nd additive substance, each 1 type may be used independently and 2 or more types may be used together. In addition, when the second additive substance is added to the aqueous electrolyte, the content of the second additive substance in the non-aqueous electrolyte is preferably 0.01 to 5% by mass, although it varies depending on the second additive substance. More preferably, the content is 0.1 to 2% by mass.

<Power storage device>
The nonaqueous electrolytic solution of the present invention can be used in various power storage devices such as lithium ion secondary batteries, electric double layer capacitors, hybrid batteries in which one of the positive electrode and the negative electrode is a battery and the other is a double layer. A typical example of the lithium ion secondary battery will be described below.
As the negative electrode active material constituting the negative electrode, carbon materials capable of doping / de-doping lithium ions, metallic lithium, lithium-containing alloys, silicon capable of being alloyed with lithium, silicon alloys, tin, Tin alloy, tin oxide capable of doping / de-doping lithium ions, silicon oxide, transition metal oxide capable of doping / de-doping lithium ions, doping / desorption of lithium ions Any of the transition metal nitrogen compounds which can be doped, or a mixture thereof can be used. The negative electrode generally has a configuration in which a negative electrode active material is formed on a current collector such as a copper foil or expanded metal.
In order to improve the adhesion of the negative electrode active material to the current collector, it may contain, for example, a polyvinylidene fluoride binder, a latex binder, etc., and carbon black, amorphous whisker carbon, etc. as a conductive aid. In addition, it may be used.

As the carbon material constituting the negative electrode active material, for example, pyrolytic carbons, cokes (pitch coke, needle coke, petroleum coke, etc.), graphites, organic polymer compound fired bodies (phenol resin, furan resin, etc.) are suitable. And carbonized by firing at a suitable temperature), carbon fiber, activated carbon and the like. The carbon material may be graphitized.
As the carbon material, a carbon material having a (002) plane interval (d002) measured by X-ray diffraction method of 0.340 nm or less is preferable, and graphite having a true density of 1.70 g / cm ³ or more is preferably used. A highly crystalline carbon material having similar properties is desirable. When such a carbon material is used, the energy density of the nonaqueous electrolyte battery can be increased.

Further, those containing boron in the carbon material, those coated with a metal such as gold, platinum, silver, copper, Sn, Si (for example, boric acid-containing carbon material), or coated with amorphous carbon (Eg, magnesium salt-coated carbon material, calcium salt-coated carbon material, etc.) can be used. One type of these carbon materials may be used, or two or more types may be used in combination as appropriate.
Silicon, silicon alloy, tin, tin alloy that can be alloyed with lithium, tin oxide that can be doped / undoped with lithium ions, silicon oxide, transition metals that can be doped / undoped with lithium ions In the case of using an oxide or the like, any of these is a preferable material because it has a higher theoretical capacity per weight than the above-described carbon material.

On the other hand, the positive electrode active material constituting the positive electrode can be formed from various materials that can be charged and discharged. Examples thereof include lithium-containing transition metal oxides, lithium-containing transition metal composite oxides using one or more transition metals, transition metal oxides, transition metal sulfides, metal oxides, and olivine-type metal lithium salts. For _example, in _{LiCoO 2, LiNiO 2, LiMn 2} O 4, LixMO 2 such as LiMnO ₂ (where, M is one or more transition metals, x is different according to the charge and discharge state of the battery, usually 0.05 ≦ x ≦ 1.20), a composite oxide of lithium and one or more transition metals (lithium transition metal composite oxide), one of transition metal atoms that are the main components of these lithium transition metal composite oxides Metal composite oxide in which part is replaced with other metals such as Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Si, Yb, FeS ₂ , TiS ₂ , chalcogenides of transition elements such as V ₂ 0 ₅ , MoO ₃ , and MoS _2, or polymers such as polyacetylene and polypyrrole can be used. Among these, materials such as a lithium transition metal composite oxide capable of doping and dedoping Li or a metal composite oxide in which a part of the transition metal atom is substituted with another metal are preferable.

  In addition, a material in which a substance having a composition different from that of the substance constituting the main cathode active material is attached to the surface of the cathode active material can be used. Surface adhering substances include oxides such as 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, Examples thereof include sulfates such as calcium sulfate and aluminum sulfate; carbonates such as lithium carbonate, calcium carbonate and magnesium carbonate.

  The positive electrode generally has a configuration in which a positive electrode active material is formed on a current collector such as an aluminum, titanium, or stainless steel foil, or an expanded metal. In order to improve the adhesion of the positive electrode active material to the current collector, for example, to improve the electron conductivity in the positive electrode such as polyvinylidene fluoride binder and latex binder, carbon black, amorphous whisker, graphite Etc. may be contained.

  The separator is preferably a membrane that electrically insulates the positive electrode from the negative electrode and is permeable to lithium ions. For example, a porous membrane such as a microporous polymer film is used. As the microporous polymer film, a porous polyolefin film is particularly preferable, and specifically, a porous polyethylene film, a porous polypropylene film, or a multilayer film of a porous polyethylene film and a polypropylene film is preferable. Furthermore, a polymer electrolyte can be used as the separator. As the polymer electrolyte, for example, a polymer material in which a lithium salt is dissolved, a polymer material swollen with an electrolytic solution, and the like can be used, but the polymer electrolyte is not limited thereto.

The non-aqueous electrolyte of the present invention may be used for the purpose of obtaining a polymer electrolyte by swelling a polymer substance with the non-aqueous electrolyte, or a separator having a combination of a porous polyolefin film and a polymer electrolyte. A non-aqueous electrolyte may be soaked in the liquid.
The shape of the lithium ion secondary battery using the non-aqueous electrolyte of the present invention is not particularly limited, and may be various shapes such as a cylindrical shape, a square shape, an aluminum laminate type, a coin shape, and a button shape. it can.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples, and can be modified within the scope of the present invention.

[Example of A series]
<Preparation of electrolytes 1-1 to 1-9>
As a reference electrolyte solution 1-1, a mixed solvent of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and fluoroethylene carbonate (FEC) (mass ratio 35: 62: 3) was used, and 1 mol / liter of LiPF ₆ was used as a lithium salt. It was prepared by dissolving to a concentration of 1 liter.
Next, a predetermined amount of the compounds shown in Table 1 was added to the reference electrolyte solution 1-1 so that the total mass was 100, thereby preparing electrolyte solutions 1-2 to 1-9. The addition amount (%) in Table 1 is mass% relative to the total mass (100 mass%) of the reference electrolyte solution 1-1 and the compound.

<Preparation of electrolytic solutions 2-1 to 2-5>
As a reference electrolyte, a mixed solvent of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and fluoroethylene carbonate (FEC) (mass ratio 35: 62: 3), and LiPF ₆ as a lithium salt at a concentration of 1 mol / liter Then, 0.75% by mass of trifluorosilyl difluoro (fluorosulfonyl) acetate was added to the reference electrolyte 1-1 (99.25% by mass) and dissolved.
Next, a predetermined amount of the compounds shown in Table 2 was added to the reference electrolyte solution so that the total mass was 100 to prepare electrolyte solutions 2-1 to 2-5. The addition amount (%) of the second additive in Table 2 is mass% with respect to the total mass (100 mass%) of the reference electrolyte solution 1-1 and the compound.

<Production of battery>
Separator with a thickness of 23 μm (F23DHA, manufactured by Toray Battery Separator Film Fuel Chemical Co., Ltd.), a positive electrode formed by applying a positive electrode mixture to an aluminum current collector and a negative electrode formed by applying a negative electrode mixture to a copper current collector The flat wound electrode group wound through the case was housed in a case to produce a battery cell having a rectangular parallelepiped shape of 30 mm long × 30 mm wide × 2.0 mm thick. Using this battery cell, a battery was prepared according to the following procedure.
The positive electrode is made of 5% by mass of polyvinylidene fluoride as a binder, 4% by mass of acetylene black as a conductive agent, and a positive electrode active material LiNi _0.5 Mn ₀ that is a composite oxide powder of lithium-nickel-manganese-cobalt. _.3 Co _0.2 O ₂ 91% by mass of N-methylpyrrolidone was added to a positive electrode mixture prepared to prepare a paste, which was applied to both sides of an aluminum foil current collector having a thickness of 18 μm. Then, after removing the solvent by drying, it was produced by rolling with a roll press.

  The negative electrode is a slurry prepared by mixing 95.8% by mass of artificial graphitizable carbon powder, 2.0% by mass of styrene butadiene rubber (SBR) as a binder and 2.2% by mass of carboxymethyl cellulose and using water as a dispersion medium. The slurry was applied to both sides of a copper foil having a thickness of 12 μm, and the solvent was dried and removed, followed by rolling with a roll press. A polyethylene microporous membrane was used for the separator.

Using the battery cell produced above, a battery was produced in the following procedure.
a. 0.55 g of various electrolytes were weighed, poured into the injection port of the battery cell, and after reducing the pressure, the injection port was sealed.
b. In a state where the sealed battery cell was maintained in a 45 ° C. atmosphere, the battery cell was charged at 8 mA up to 4.2 V, and then discharged at 8 mA up to 3.0 V.
c. The internal gas of the battery cell discharged to 3.0 V was removed under reduced pressure to produce a battery.

<Battery evaluation>
About the battery produced above, the charge / discharge characteristic was measured as follows.
a. Resistance evaluation: Charged to SOC (State of Charge) 50% at 25 ° C, and discharged for 10 seconds at 0.2C, 0.5C, 1.0C, and 2.0C, respectively, in each environment. The DC resistance value was determined.
b. Capacity maintenance rate After charging to 4.2 V at a 1 C rate in an atmosphere at 25 ° C., the battery was discharged to 3.0 V at a 1 C rate in the same atmosphere, and the discharge capacity value was taken as the initial capacity value. Next, 300 times were repeated under the same conditions, and the discharge capacity value at the 300th time was taken as the capacity value after the cycle. The capacity retention rate was determined from the initial capacity value and the capacity value after the cycle using the following formula.
Capacity retention rate (%) = (capacity value after cycle / initial capacity value) × 100 (1)

<Examples 1-8>
Using the electrolytic solutions 1-1 to 1-8 shown in Table 1, laminate batteries of Examples 1 to 8 and Comparative Example 1 were manufactured using the above battery manufacturing procedure, and at 25 ° C. in an atmosphere. The initial resistance value was determined and the result is shown in Table 3.
Next, in an atmosphere of 25 ° C., charging up to 4.2 V and discharging up to 3.0 V at a 1 C rate were repeated 300 times, and the capacity retention rate was obtained from the initial capacity value and the discharge capacity value after 300 cycles. Thereafter, the DC resistance value after the cycle was determined in the same manner. The results are shown in Table 3.

表３に示すように、有機スルホン化合物を添加することで直流抵抗を大幅に減少させるとともに、サイクル後の直流抵抗も小さく抑制できる。また、同時にサイクル後の容量維持率の向上効果がある。

As shown in Table 3, by adding the organic sulfone compound, the direct current resistance can be greatly reduced, and the direct current resistance after the cycle can be reduced. At the same time, there is an effect of improving the capacity maintenance rate after the cycle.

<Examples 9 to 13>
Using the electrolytic solutions 2-1 to 2-5 shown in Table 2, using the above battery production procedure, laminate batteries of Examples 9 to 13 were produced. The resistance increase rate and capacity retention rate after cycling were determined. The results are shown in Table 4.

  As shown in Table 4, by using the organic sulfone compound and the second additive, the direct current resistance increase rate is significantly suppressed, and the cycle capacity maintenance rate is also greatly improved.

[Example of B series]
<Preparation of electrolytes 1-1 to 1-6>
As a reference electrolyte solution 1-1, a mixed solvent of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and fluoroethylene carbonate (FEC) (mass ratio 35: 62: 3) was used, and 1 mol / liter of LiPF ₆ was used as a lithium salt. It was prepared by dissolving to a concentration of 1 liter.
Next, a predetermined amount of the compounds shown in Table 5 was added to the reference electrolyte solution 1-1 so that the total mass was 100, thereby preparing electrolyte solutions 1-2 to 1-6. The addition amount (%) in the second of Table 5 is mass% with respect to the total mass (100 mass%) of the reference electrolyte 1-1 and the compound.

<Preparation of electrolytic solutions 2-1 to 2-7>
As a reference electrolyte, a mixed solvent of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and fluoroethylene carbonate (FEC) (mass ratio 35: 62: 3), and LiPF ₆ as a lithium salt at a concentration of 1 mol / liter Then, tetrakis (vinylsulfonylmethyl) methane was added and dissolved in 0.75% by mass with respect to the reference electrolyte 1-1 (99.25% by mass).
Next, a predetermined amount of the compounds shown in Table 6 was added to the reference electrolyte solution 2-1 so that the total mass was 100, thereby preparing electrolyte solutions 2-1 to 2-7. The addition amount (%) in Table 6 is mass% relative to the total mass (100 mass%) of the reference electrolyte solution 1-1 and the compound.

<Production of battery>
A battery was produced in the same procedure using the battery cell produced in the same manner as in [A Series Examples].
<Battery evaluation>
About the battery produced above, it carried out similarly to the case in [A series Example], and evaluated charging / discharging characteristic by calculating | requiring resistance evaluation, resistance increase rate (%), and capacity | capacitance maintenance factor (%).

<Examples 1 to 12>
Using the electrolytic solutions 1-1 to 1-6 shown in Table 5 and 2-1 to 2-7 shown in Table 6 above, in the same manner as the battery manufacturing procedure in the above [A Series Examples] The laminated batteries of Examples 1 to 12 and Comparative Example 1 were prepared, and the initial resistance value was determined at 25 ° C. in an atmosphere.
Next, in an atmosphere of 45 ° C., charging up to 4.2 V and discharging up to 3.0 V at a 1 C rate was repeated 300 times, and the capacity retention rate was obtained from the initial capacity value and the discharge capacity value after 300 cycles. Thereafter, the DC resistance value after the cycle was determined in the same manner. The results are shown in Table 7.

  As shown in Table 7, it was confirmed that the increase in DC resistance was significantly suppressed by adding an organic sulfone compound. At the same time, the cycle capacity retention rate is improved. Furthermore, when combined with other additives, there is a further improvement in capacity retention and an improvement in DC resistance.

<Examples 13 to 17 and Comparative Example 2>
Using the electrolyte solutions 1-1 to 1-6 shown in Table 5 above, 0.55 g of various electrolyte solutions were weighed, injected into the injection port of the battery cell, and after reducing the pressure, the injection port was sealed. did.
In the state which kept the sealed battery cell in 45 degreeC atmosphere, after charging at 4.4 mA to 4.4V, it discharged at 8 mA to 3.0V. The internal gas of the battery cell discharged to 3.0 V was removed under reduced pressure, and the laminated batteries of Examples 13 to 17 and Comparative Example 2 were produced.
In the atmosphere of 45 ° C, the manufactured laminated battery was repeatedly charged up to 4.35V at 1C rate and discharged up to 3.0V 300 times, and the capacity retention rate was calculated from the initial capacity value and the discharge capacity value after 300 cycles. Asked. The results are shown in Table 8.

  As shown in Table 8, by adding the organic sulfone compound, the cycle capacity retention rate was significantly improved in the high voltage charge / discharge of 4.35V.

  The non-aqueous electrolyte for power storage devices of the present invention is widely used for power storage devices such as power supplies for various consumer devices such as mobile phones and laptop computers, power supplies for industrial equipment, storage batteries, and power supplies for automobiles.

Claims (18)

A nonaqueous electrolytic solution for an electricity storage device obtained by dissolving an electrolyte in a nonaqueous solvent, wherein the electrolyte is a lithium salt dissolved in the nonaqueous solvent, and an organic sulfone compound represented by the following formula (1): A nonaqueous electrolytic solution for an electricity storage device, comprising at least one selected from the group consisting of an organic sulfone compound represented by formula (2).

_{R 1 -SO 2 -X m -Y n} -OR 2 (1)

(R ₁ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a phenyl group, or a halogen atom. R ₂ is an alkyl group having 1 to 6 carbon atoms or a carbon number. 2 to 6 alkenyl group, phenyl group or silyl group, X is a phenylene group or an alkylene group having 1 to 6 carbon atoms, Y is a carbonyl group or a sulfonyl group, m and n are Each independently represents an integer of 0 or 1 to 3, and m + n ≧ 2.

_{(CH 2 = CH-SO 2} -X m) p -Y (OR) t - (Z n -SO 2 -CH = CH 2) q (2)

(X, Y, and Z are each independently a phenylene group or an alkylene group having 1 to 4 carbon atoms. R is a hydrogen atom, a phenyl group, or an alkyl group having 1 to 6 carbon atoms. M, n, p, q, and t are each independently 0 or an integer of 1 to 4, and p + q ≧ 1 and m + n ≧ 1.) The nonaqueous electrolytic solution for an electricity storage device according to claim 1, wherein R _{1 in} formula (1) is a fluorine atom or an alkyl group substituted with a fluorine atom.   The nonaqueous electrolytic solution for an electricity storage device according to claim 1, wherein X in the formula (1) is an alkylene group substituted with a fluorine atom. R < ₂ > of Formula (1) is a silyl group, The nonaqueous electrolyte solution for electrical storage devices of any one of Claims 1-3.   The nonaqueous electrolytic solution for an electricity storage device according to claim 1, wherein in formula (2), p + q ≧ 2.   The organic sulfone compound represented by the formula (1) is methyl methanesulfonyl acetate, ethyl methanesulfonyl acetate, methyl ethanesulfonyl acetate, methyl difluoro (fluorosulfonyl) acetate, trimethylsilyl difluoro (fluorosulfonyl) acetate, difluoro (fluorosulfonyl) The nonaqueous electrolytic solution for an electricity storage device according to any one of claims 1 to 5, which is trimethylsilylmethyl acetate, trimethylsilyl difluoro (fluorosulfonyl) sulfonate, or trimethylsilylmethyl difluoro (fluorosulfonyl) sulfonate.   The organic sulfone compound represented by the formula (2) is 1,2-bis (vinylsulfonylacetamido) ethane, tetrakis (vinylsulfonylmethyl) methane, 1,2-bis (vinylsulfonyl) propane-2-diol, or The nonaqueous electrolytic solution for an electricity storage device according to any one of claims 1 to 5, which is 1,2-bis (vinylsulfonylmethyl) benzene.   The non-aqueous electrolyte for electrical storage devices of any one of Claims 1-7 which contains the said organic sulfone compound 0.0001-10 mass%.   The nonaqueous electrolytic solution for an electricity storage device according to any one of claims 1 to 8, wherein the nonaqueous solvent contains a chain carbonate ester, a saturated cyclic carbonate ester, and an unsaturated cyclic carbonate ester.   The chain carbonate ester, saturated cyclic carbonate ester, and unsaturated cyclic carbonate ester content are 30 to 80% by mass, 10 to 50% by mass, and 0.01 to 5% by mass, respectively. Non-aqueous electrolyte for electricity storage devices. The lithium salt is LiPF ₆ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (FSO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ). _{(C 2 F 5 SO 2)} , and _{LiN (CF} 3 SO ₂₎ in any one of claims 1 to 10 _{(C 4} F 9 SO ₂₎ is at least one lithium salt selected from the group consisting of The non-aqueous electrolyte for electrical storage devices of description.   Further, at least one selected from the group consisting of sulfur-containing compounds (excluding the organic sulfone compounds represented by the formula (1) or formula (2)), cyclic acid anhydrides, carboxylic acid compounds, and boron-containing compounds. The non-aqueous electrolyte for electrical storage devices of any one of Claims 1-11 containing an additive.   The sulfur-containing compound is 1,3-propane sultone (PS), propene sultone, ethylene sulfite, 1,4-butane sultone, methyl methanesulfonate, ethyl methanesulfonate, dimethyl methanedisulfonate, diethyl methanedisulfonate, methane Dipropyl disulfonate, bis (trifluoromethyl) methane disulfonate, bis (trimethylsilyl) methane disulfonate, methylene methane disulfonic acid, ethylene methane disulfonate, propylene methane disulfonate, methylene ethylene disulfonate, ethylene ethylene disulfonate, ethane disulfonic acid Dimethyl, diethyl ethanedisulfonate, bis (trifluoromethyl) ethanedisulfonate, bis (trimethylsilyl) ethanedisulfonate, dimethyl propanedisulfonate, Diethyl pandisulfonate, methylene propanedisulfonate, ethylene propanedisulfonate, dimethyl 1,5-naphthalenedisulfonate, dimethyl butanedisulfonate, diethyl butanedisulfonate, 5-vinyl-hexahydro1,3,2-benzodioxathiol 2-oxide, 1,4-butanediol dimethanesulfonate, 1,3-butanediol dimethanesulfonate, N, N-dimethylmethanesulfonamide, N, N-diethylmethanesulfonamide, divinylsulfone, 1,2-bis The nonaqueous electrolytic solution for an electricity storage device according to claim 12, which is at least one selected from the group consisting of (vinylsulfonyl) methane.   The carboxylic acid compound is lithium oxalate, lithium malonate, lithium difluoromalonate, lithium succinate, lithium tetrafluorosuccinate, lithium adipate, lithium glutarate, lithium acetonedicarboxylate, lithium 2-oxobutyrate, oxalacetic acid Lithium, lithium 2-oxoglutarate, lithium acetoacetate, 3-oxocyclobutanecarboxylic acid, 3-oxocyclopentanecarboxylic acid, lithium 2-oxovalerate, lithium pyruvate, lithium glyoxylate, 3,3-dimethyl-2- Lithium oxobutyrate, lithium 2-hydroxypropionate, lithium 2-methyl lactate, lithium tartrate, lithium cyanoacetate, lithium 2-mercaptopropionate, lithium methylenebis (thioglycolate) thiodisuccinate, 3- (methylthio) propionic acid Selected from the group consisting of lithium, lithium 3,3'-thiodipropionate, lithium dithiodiglycolate, lithium 2,2'-thiodiglycolate, lithium thiazolidine-2,4-dicarboxylate, and lithium acetylthioacetate The nonaqueous electrolytic solution for an electricity storage device according to claim 12, which is at least one kind.   The cyclic acid anhydride is glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, succinic anhydride, diglycolic anhydride, cyclohexanedicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride. 4-cyclohexene-1,2-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phenylsuccinic anhydride, 2-phenyl Glutaric anhydride, phthalic anhydride, pyromellitic anhydride, fluorosuccinic anhydride, carboxylic anhydrides such as tetrafluorosuccinic anhydride, 1,2-ethanedisulfonic anhydride, 1,3-propanedisulfonic acid Anhydride, 1,4-butanedisulfonic anhydride, 1,2-benzenedisulfonic anhydride, tetrafluoro 1,2-ethanedisulfonic anhydride, hexafluoro-1,3-propanedisulfonic anhydride, octafluoro-1,4-butanedisulfonic anhydride, 3-fluoro-1,2-benzenedisulfonic anhydride, 13. It is at least one selected from the group consisting of 4-fluoro-1,2-benzenedisulfonic anhydride and 3,4,5,6-tetrafluoro-1,2-benzenedisulfonic anhydride. The non-aqueous electrolyte for electrical storage devices of description. The boron-containing compound is LiBF ₂ (C ₂ O ₄ ), LiB (C ₂ O ₄ ) ₂ , LiBF ₂ (CO ₂ CH ₂ CO ₂ ), LiB (CO ₂ CH ₂ CO ₂ ) ₂ , LiB (CO _2). CF ₂ CO ₂ ) ₂ , LiBF ₂ (CO ₂ CF ₂ CO ₂ ), LiBF ₃ (CO ₂ CH ₃ ), LiBF ₃ (CO ₂ CF ₃ ), LiBF ₂ (CO ₂ CH ₃ ) ₂ , LiBF ₂ (CO _{2 CF 3) 2, LiBF (} CO 2 CH 3) 3, LiBF (CO 2 CF 3) 3, LiB (CO 2 CH 3) 4, LiB (CO 2 CF 3) 4, Li 2 B 2 O 7 and, The nonaqueous electrolytic solution for an electricity storage device according to claim 12, which is at least one selected from the group consisting of Li ₂ B ₂ O ₄ .   The electrical storage device which uses the non-aqueous electrolyte of any one of Claims 1-16.   The livestock device according to claim 17, wherein the electricity storage device is a lithium secondary battery.