WO2019016903A1

WO2019016903A1 - Nonaqueous electrolytic solution and electricity storage device using same

Info

Publication number: WO2019016903A1
Application number: PCT/JP2017/026151
Authority: WO
Inventors: 圭島本; 宏行瀬戸口; 洋輔佐藤
Original assignee: 宇部興産株式会社
Priority date: 2017-07-19
Filing date: 2017-07-19
Publication date: 2019-01-24

Abstract

Provided are: a nonaqueous electrolytic solution that is capable of having improved electrochemical characteristics in a wide temperature range, that has an electrolyte salt dissolved in a nonaqueous solvent, and that is characterized by containing an (2-oxo-1,3-dioxolan-4-yl)oxy compound represented by general formula (I); an electricity storage device; and a novel (2-oxo-1,3-dioxolan-4-yl)oxy compound. (In the formula, R1 represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, -OC(=O)-R4, -OS(=O)2-R5, or -OP(=O)(-R6)-R7. R2 and R3 each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and n represents an integer of 1-3. R4 represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or an alkoxycarbonyl group. R5 represents a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or an alkoxy group. R6 and R7 each independently represent a halogen atom, an alkoxy group, or an aryloxy group. In the case where n is 1, L1 represents -C(=O)-R4, -S(=O)2-R5 or -P(=O)(-R6)-R7. In the case where n is 2, L1 represents -C(=O)C(=O)-, -S(=O)2-, or -P(=O)(-R6)-. In the case where n is 3, L1 represents -P(=O)(-)2.)

Description

Non-aqueous electrolyte and storage device using the same

The present invention relates to a non-aqueous electrolyte capable of improving electrochemical characteristics in a wide temperature range, and an electricity storage device using the same.

In recent years, storage devices, particularly lithium secondary batteries, are widely used as power sources for small electronic devices such as mobile phones and laptop computers, as power sources for electric vehicles and power storage. Since these electronic devices and automobiles may be used in a wide temperature range such as midsummer high temperature or extremely cold low temperature, it is required to improve the electrochemical characteristics in a wide temperature range with good balance. .
In particular, in order to prevent global warming, it is urgent to reduce CO ₂ emissions, and among eco-friendly vehicles equipped with a storage device consisting of storage devices such as lithium secondary batteries and capacitors, hybrid electric vehicles ( Early deployment of plug-in hybrid electric vehicles (PHEVs) and battery electric vehicles (BEVs) is required. Due to the long travel distance of cars, they can be used in a wide temperature range from very hot areas in the tropics to extremely cold areas. Therefore, particularly these storage devices for vehicles are required to have no deterioration in electrochemical characteristics even when used in a wide temperature range from high temperature to low temperature.
In the present specification, the term lithium secondary battery is used as a concept including so-called lithium ion secondary battery.

A lithium secondary battery is mainly composed of a positive electrode and a negative electrode containing a material capable of absorbing and desorbing lithium ions, a lithium salt, and a non-aqueous electrolytic solution composed of a non-aqueous solvent, and ethylene carbonate (EC And carbonates such as propylene carbonate (PC) are used.
Further, as a negative electrode of a lithium secondary battery, metal lithium, a metal compound capable of inserting and extracting lithium ions (a single metal, a metal oxide, an alloy with lithium, etc.) and a carbon material are known. In particular, lithium secondary batteries using carbon materials capable of absorbing and desorbing lithium ions, such as coke, artificial graphite and natural graphite, have been widely put to practical use.

For example, a lithium secondary battery using a highly crystallized carbon material such as natural graphite or artificial graphite as a negative electrode material is a decomposed product generated by reduction decomposition of the solvent in the non-aqueous electrolyte on the surface of the negative electrode during charging. It has been found that gas deposits on the negative electrode surface and results in a decrease in cycling characteristics as it inhibits the desired electrochemical response of the cell. In addition, when the decomposition product of the non-aqueous solvent is accumulated, it is not possible to smoothly insert and extract lithium ions to the negative electrode, and the electrochemical characteristics in the case of using in a wide temperature range are easily deteriorated.
Furthermore, lithium secondary batteries using lithium metal or an alloy thereof, a metal simple substance such as tin or silicon, or a metal oxide as a negative electrode material have a high initial capacity, but pulverization proceeds during use as an electricity storage device. It is known that the reductive decomposition of the non-aqueous solvent occurs in an accelerated manner and the battery performance such as the battery capacity and the cycle characteristics is greatly reduced compared to the negative electrode of the carbon material. In addition, when pulverization of these negative electrode materials and decomposition products of non-aqueous solvent are accumulated, absorption and release of lithium ions to the negative electrode can not be performed smoothly, and the electrochemical characteristics are easily deteriorated when used in a wide temperature range. Become.

On the other hand, in a lithium secondary battery using, for example, LiCoO ₂ , LiMn ₂ O ₄ , LiNiO ₂ , LiFePO ₄ or the like as a positive electrode material, the positive electrode material and the non-aqueous electrolyte are used when the non-aqueous solvent in the non-aqueous electrolyte is charged. At the interface with the metal, decomposition products and gases generated by partial oxidation decomposition locally are deposited on the negative electrode surface to inhibit the desired electrochemical reaction of the battery, so the electricity when used also in a wide temperature range It has been found to cause a decrease in chemical properties.

As described above, the battery performance has been lowered by the movement of lithium ions being inhibited or the battery being swollen by decomposition products and gas when the non-aqueous electrolyte is decomposed on the positive electrode and the negative electrode. In spite of such circumstances, multifunctionalization of electronic devices equipped with lithium secondary batteries is in progress and power consumption is increasing. Therefore, the capacity of lithium secondary batteries is increasing, the density of the electrodes is increased, and the useless space volume in the batteries is reduced, and the volume occupied by the non-aqueous electrolyte in the batteries is small. It has become. Therefore, with the decomposition of a small amount of non-aqueous electrolyte, the electrochemical characteristics are likely to deteriorate when used in a wide temperature range.

Patent Document 1 discloses an electrolyte solution for a secondary battery containing an electrolyte salt and an electrolyte solvent, wherein the electrolyte solution contains a compound in which a cyclic carbonate group and a sulfonate group are linked via an alkylene group. There is. Patent Document 1 describes 1,3-dioxolane-2-onylmethyl allyl sulfonate as one of the compounds described above, and by adding to the electrolytic solution, the discharge capacity retention ratio after cycling of the battery is improved. It is supposed to be.

International Publication No. 2008/035928

The present invention provides a non-aqueous electrolyte capable of improving the electrochemical properties in a wide temperature range, a storage device using the same, and a novel (2-oxo-1,3-dioxolan-4-yl) oxy compound The purpose is

Patent Document 1 does not at all describe or suggest the effect of improving the low temperature discharge characteristics after high temperature storage.
As a result of examining the performance of the electrolytic solution of Patent Document 1 in detail, in the secondary battery using the electrolytic solution of Patent Document 1, cycle characteristics under high temperature, low temperature discharge characteristics after high temperature storage, etc. The fact is that no sufficient effect has been obtained for the problem of improving the electrochemical characteristics in a wide temperature range of.
Therefore, the present inventors have intensively studied to solve the above problems, and by containing a specific compound in a non-aqueous electrolyte in which an electrolyte salt is dissolved in a non-aqueous solvent, a wide temperature range can be obtained. The inventors have found that the electrochemical characteristics of a storage device, in particular, the lithium battery can be improved, and the present invention has been completed.

That is, the present invention provides the following (1), (2) and (3).
(1) A non-aqueous electrolytic solution in which an electrolyte salt is dissolved in a non-aqueous solvent, which is a (2-oxo-1,3-dioxolan-4-yl) oxy compound represented by the following general formula (I) Nonaqueous electrolyte characterized by containing.

(Wherein, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms , An aralkyl group having 7 to 13 carbon atoms, an aryl group having 6 to 12 carbon atoms, -OC (= O) -R ⁴ , -OS (= O) ₂ -R ⁵ , or -OP (= O) (-R ⁶ ) -R ⁷ R ² and R ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3.
R ⁴ represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, It represents an aryl group having 6 to 12 carbon atoms or an alkoxycarbonyl group having 2 to 6 carbon atoms. R ⁵ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or 7 to 13 carbon atoms It represents an aralkyl group, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R ⁶ and R ⁷ each independently represent a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms.
When n is 1, L ¹ represents -C (= O) -R ⁴ , -S (= O) ₂ -R ⁵ , or -P (= O) (-R ⁶ ) -R ⁷ and n When L is 2, L ¹ represents -C (= O) C (= O)-, -S (= O) _2- , or -P (= O) (-R ⁶ )-, and n is 3 , L ¹ represents -P (= O) (-) ₂ .
In addition, at least one hydrogen atom of the alkyl group, the aralkyl group, the aryl group, the alkoxycarbonyl group, the alkoxy group, and the aryloxy group may be substituted by a halogen atom. )

(2) A power storage device comprising a positive electrode, a negative electrode, and a non-aqueous electrolytic solution in which an electrolyte salt is dissolved in a non-aqueous solvent, wherein the non-aqueous electrolytic solution is the non-aqueous electrolytic solution according to (1) Power storage device characterized by.

(3) (2-Oxo-1,3-dioxolan-4-yl) oxy compounds represented by the following general formula (II).

(Wherein, R ⁸ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms , An aralkyl group having 7 to 13 carbon atoms, an aryl group having 6 to 12 carbon atoms, -OC (= O) -R ⁹ , -OS (= O) ₂ -R ⁵ , or -OP (= O) (-R ⁶ ) -R ⁷ R ² and R ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3.
R ⁵ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or 7 to 13 carbon atoms It represents an aralkyl group, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R ⁶ and R ⁷ each independently represent a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms. R ⁹ represents a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or 7 to 13 carbon atoms in which at least one hydrogen atom is substituted by a halogen atom And an aralkyl group, an aryl group having 6 to 12 carbon atoms, or an alkoxycarbonyl group having 2 to 6 carbon atoms.
When n is 1, L ² represents —C (= O) —R ⁹ , —S (= O) ₂ —R ⁵ , or —P (= O) (— R ⁶ ) —R ⁷ and n When L is 2, L ² represents -C (= O) C (= O)-, -S (= O) _2- , or -P (= O) (-R ⁶ )-, and n is 3 , L ² represents -P (= O) (-) ₂ .
In addition, at least one hydrogen atom of the alkyl group, the aralkyl group, the aryl group, the alkoxycarbonyl group, the alkoxy group, and the aryloxy group may be substituted by a halogen atom. )

The partial structure of -P (= O) (-) ₂ described in the present specification means a structure represented by the following general formula (III).

According to the present invention, a non-aqueous electrolyte capable of improving the electrochemical characteristics of a storage device over a wide temperature range, particularly the low temperature discharge characteristics after high temperature charge storage, a storage device such as a lithium secondary battery using the same, and a novel (2-oxo-1,3-dioxolan-4-yl) oxy compounds can be provided.

The present invention relates to a non-aqueous electrolytic solution and an electricity storage device using the same.

[Non-aqueous electrolyte]
The non-aqueous electrolytic solution of the present invention is a non-aqueous electrolytic solution in which an electrolyte salt is dissolved in a non-aqueous solvent, and is represented by the general formula (I) in the non-aqueous electrolytic solution (2-oxo-1, It is characterized by containing a 3-dioxolan-4-yl) oxy compound.

The reason why the non-aqueous electrolyte of the present invention can significantly improve the electrochemical characteristics of the storage device over a wide temperature range is not necessarily clear, but is considered as follows.
The compound used in the present invention is a cyclic carbonate in which a polar group is directly bonded to a ring without an alkylene group as described in the general formula (I). Therefore, the decomposition is more electrochemical than that of 1,3-dioxolane-2-onylmethyl allyl sulfonate, which is a compound in which the cyclic carbonate group described in Patent Document 1 and a sulfonate group as a polar group are linked via an alkylene group. Forming a dense and heat-resistant film on the positive electrode and the negative electrode. Therefore, it is considered that the electrochemical characteristics in a wide temperature range such as the low temperature discharge characteristics after high temperature charge storage can be improved.

[Compounds Represented by General Formula (I)]
The compound contained in the non-aqueous electrolytic solution of the present invention is a (2-oxo-1,3-dioxolan-4-yl) oxy compound represented by the following general formula (I).

Specific examples of R ¹ include halogen atoms such as hydrogen atom, fluorine atom, chlorine atom and bromine atom; methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group and n-hexyl group And straight-chain alkyl groups such as isopropyl group, sec-butyl group, 2-pentyl group, 3-pentyl group, tert-butyl group, tert-amyl group and the like branched alkyl groups; fluoromethyl group, difluoromethyl group Group, trifluoromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 3,3-difluoropropyl group Halogenated alkyl groups such as 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl and the like Cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc .; Vinyl group, 1-propen-1-yl group, 2-propen-1-yl group, 1-propen-2-yl group Group, 2-buten-1-yl group, 3-buten-1-yl group, 4-penten-1-yl group, 5-hexen-1-yl group, 1-propen-2-yl group, 1-butene Alkenyl groups such as -2-yl group and 2-methyl-2-propen-1-yl group; ethynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 4-heptynyl group, 1-methyl- Alkynyl groups such as 2-propynyl group, 1,1-dimethyl-2-propynyl group, 1-methyl-3-butynyl group, 1-methyl-4-heptynyl group; benzyl group, 4-methylbenzyl group, 4-tert - Aralkyl groups such as benzyl, 4-fluorobenzyl, 4-chlorobenzyl, 1-phenylethane-1-yl, 2-phenylethane-1-yl, 3-phenylpropan-1-yl and the like; phenyl Aryl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-tert-butylphenyl group; 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 4-fluoro-2-trifluoromethylphenyl group, 4-fluoro-3-trifluoromethylphenyl group, 2, 6-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 2,3,3, 5,6-tetrafluorophenyl group, halogenated aryl group such as perfluorophenyl, etc .; acetyloxy group, propionyloxy group, fluorosulfonyloxy group, methanesulfonyloxy group, vinylsulfonyloxy group, difluorophosphoryl group, dimethoxyphosphoryl group, Or diethoxy phosphoryl group and the like.

Among these, as R ¹ , hydrogen atom, fluorine atom, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, sec-butyl group, 2 -Pentyl group, tert-butyl group, tert-amyl group, trifluoromethyl group, 2-fluoroethyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group, vinyl group, 1-propen-1-yl group, 2-propene -1-yl group, 1-propen-2-yl group, ethynyl group, 2-propynyl group, 2-butynyl group, benzyl group, 4-methylbenzyl group, phenyl group, 4-methylphenyl group, acetyloxy group, Propionyloxy group, fluorosulfonyloxy group, methanesulfonyloxy group, vinylsulfonyloxy group, difluorophosphoryl group, dimethoxyphos Preferred is a lyl group or a diethoxy phosphoryl group, and a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an tert-butyl group, a trifluoromethyl group, a cyclopropyl group, a cyclohexyl group, a vinyl group 1-propen-1-yl group, 1-propen-2-yl group, ethynyl group, 2-propynyl group, phenyl group, 4-methylphenyl group, acetyloxy group, fluorosulfonyloxy group, methanesulfonyloxy group, A vinylsulfonyloxy group, a difluorophosphoryl group, a dimethoxyphosphoryl group or a diethoxyphosphoryl group is more preferable.

Specific examples of R ² and R ³ independently include halogen atoms such as hydrogen atom, fluorine atom, chlorine atom and bromine atom; methyl group, ethyl group, n-propyl group, n-butyl group, n- Straight-chain alkyl groups such as pentyl group and n-hexyl group; branched alkyl groups such as isopropyl group, sec-butyl group, 2-pentyl group, pentan-3-yl group, tert-butyl group and tert-amyl group Alkyl group; fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3-chloro Propyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropro And halogenated alkyl groups such as pill groups.
Among these, each of R ² and R ³ independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a sec-butyl group, or tert. -Butyl group or trifluoromethyl group is preferable, and a hydrogen atom, a fluorine atom or a methyl group is more preferable.

Specific examples of R ⁴ include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl; isopropyl and sec-butyl; Branched alkyl groups such as 2-pentyl group, 3-pentyl group, tert-butyl group, tert-amyl group; fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2, Halogenated alkyl groups such as 2,3,3,3-pentafluoropropyl group; cycloamides such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like Vinyl group, 1-propen-1-yl group, 2-propen-1-yl group, 2-buten-1-yl group, 3-buten-1-yl group, 4-penten-1-yl group And alkenyl groups such as 5-hexen-1-yl group, 1-propen-2-yl group, 1-buten-2-yl group, 2-methyl-2-propen-1-yl group; ethynyl group, 2- Propynyl group, 2-butynyl group, 3-butynyl group, 4-heptynyl group, 1-methyl-2-propynyl group, 1,1-dimethyl-2-propynyl group, 1-methyl-3-butynyl group, 1-methyl Alkynyl groups such as 4-pentynyl group; benzyl group, 4-methylbenzyl group, 1-phenylethane-1-yl group, 2-phenylethane-1-yl group, 3-phenylpropan-1-yl group, etc. Aralkyl group; phenyl group, 2-methyl Aryl groups such as hexyl group, 3-methylphenyl group, 4-methylphenyl group, 4-tert-butylphenyl group; 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-trifluoromethyl Phenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 4-fluoro-2-trifluoromethylphenyl group, 4-fluoro-3-trifluoromethylphenyl group, 2,6-difluorophenyl group Halogenated aryl groups such as 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, perfluorophenyl and the like; methoxycarbonyl group, ethoxycarbonyl group And the like.

Among these, as R ⁴ , methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, fluoromethyl group, chloromethyl group, trifluoromethyl group, 2-fluoroethyl group, cyclopropyl group , Cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, vinyl group, 1-propen-1-yl group, ethynyl group, 2-propynyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4 -Methylphenyl group, 4-fluorophenyl group, 4-trifluoromethylphenyl group, methoxycarbonyl group, or ethoxycarbonyl group is preferable, and methyl group, ethyl group, isopropyl group, trifluoromethyl group, cyclopropyl group, cyclohexyl group , Vinyl group, 1-propen-2-yl group, ethynyl group, Group, 4-fluorophenyl group, 4-trifluorophenyl group, a methoxycarbonyl group, or ethoxycarbonyl group are more preferable.

Specific examples of R ⁵ include halogen atoms such as fluorine atom, chlorine atom and bromine atom; straight lines such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group and n-hexyl group -Chain alkyl groups; branched alkyl groups such as isopropyl, sec-butyl, 2-pentyl and 3-pentyl; fluoromethyl, chloromethyl, trifluoromethyl and 2,2,2- Halogenated alkyl groups such as trifluoroethyl group and 1,1,2,2,3,3,4,4,4-nonafluorobutyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group Cycloalkyl groups such as hexyl group; alkenyl groups such as vinyl group, 1-propen-1-yl group, 2-propen-1-yl group; and alkynyl such as ethynyl group and 2-propynyl group Aralkyl groups such as benzyl group, 4-methylbenzyl group, 1-phenylethane-1-yl group, 2-phenylethane-1-yl group, 3-phenylpropan-1-yl group, etc .; phenyl group, 2- Aryl groups such as methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-tert-butylphenyl group, etc .; 2-fluorophenyl group, 2-chlorophenyl group, 2-bromophenyl group, 4-fluorophenyl group And halogenated aryl groups such as 4-chlorophenyl group and 4-trifluoromethylphenyl group; and alkoxy groups such as methoxy group and ethoxy group.
Among these, as R ⁵ , a fluorine atom, methyl group, ethyl group, n-propyl group, trifluoromethyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group, vinyl group, ethynyl group, phenyl group, 2-methyl group A phenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-fluorophenyl group, 4-trifluoromethylphenyl group, methoxy group or ethoxy group is preferable, and a fluorine atom, a methyl group, an ethyl group, a propyl group, Hexyl group, isopropyl group, trifluoromethyl group, cyclohexyl group, vinyl group, ethynyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-fluorophenyl group, 4-triphenyl group A fluoromethylphenyl group or a methoxy group is more preferable.

Specific examples of R ⁶ and R ⁷ are each independently a halogen atom such as fluorine atom, chlorine atom or bromine atom; methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentoxy group, straight-chain alkoxy groups such as n-hexyloxy group; branched alkoxy such as isopropoxy group, sec-butoxy group, 2-pentoxy group, pentan-3-yloxy group, tert-butoxy group, tert-amyloxy group and the like Group: 2-fluoroethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 3,3-difluoropropoxy group, 3,3 Halogen such as 3, 3-trifluoropropoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group Or phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 4-tert-butylphenoxy, 2-fluorophenoxy, 2-chlorophenoxy, 2-bromophenoxy Preferred are aryloxy groups such as 4-fluorophenoxy group, 4-chlorophenoxy group and 4-trifluoromethylphenoxy group.
Among them, R ⁶ and R ⁷ each independently represent a fluorine atom, chlorine atom, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, isopropoxy group, sec-butoxy group, tert-butoxy group Group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, phenoxy Group, 2-methyl phenoxy group, 3-methyl phenoxy group, 4-methyl phenoxy group, 2-fluoro phenoxy group 4- fluoro phenoxy group, or 4- trifluoromethyl phenoxy group is preferable, and a fluorine atom, a methoxy group, an ethoxy group , 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy or phenoxy is more preferred.

Specific examples of the compound represented by the general formula (I) are as follows.
(1) When n is 1 and L ¹ is —C (= O) —R ⁴ , the following compounds are preferably mentioned.

(2) When n is 2 and L ¹ is —C (-O) C (= O) —, the following compounds are preferably mentioned.

(3) In the case where n is 1 and L ¹ is —S (= O) ₂ —R ⁵ , the following compounds may preferably be mentioned.

(4) In the case where n is 2 and L ¹ is —S (= O) ₂ —, the following compounds may preferably be mentioned.

(5) In the case where n is 1 and L ¹ is -P (= O) (-R ⁶ ) -R ⁷ , the following compounds may preferably be mentioned.

(6) When n is 2 and L ¹ is -P (= O) (-R ⁶ )-, the following compounds are preferably mentioned.

(7) In the case where n is 3 and L ¹ is -P (= O) (-) ₂ , the following compounds may preferably be mentioned.

Among the above compounds, A1 to A10, A14 to A19, B1 to B3, C1 to C9, C11 to C20, C24 to C27, C32, C34 to C36, D1 to D3, E1 to E3, E5 to E8, E10 to E13. , E15, F1 to F3, F5 to F7, F9 to F11, and G1 to G3 are preferably at least one member selected from the group consisting of A1, A2, A4, A7, A8, A16 to A18. , B1, B2, C1 to C3, C7, C9, C11, C14, C17 to C19, C35, C36, D1, D2, E1, E2, E6, E7, E11, E12, F1, F2, F5, F6, F9 And more preferably one or more selected from the group consisting of compounds having the structural formulas of F 10, G 1, and G 2, 2-oxo-1,3-dioxolan-4-yl acetate ( Formula A1), 2-oxo-1,3-dioxolan-4-yl 2,2,2-trifluoroacetate (formula A4), 2-oxo-1,3-dioxolan-4-yl acrylate (formula A7), 2-oxo-1,3-dioxolan-4-yl methacrylate (structural formula A8), methyl (2-oxo-1,3-dioxolan-4-yl) oxalate (structural formula A16), ethyl (2-) Oxo-1,3-dioxolan-4-yl) oxalate (structural formula A17), bis (2-oxo-1,3-dioxolan-4-yl) oxalate (structural formula B1), 2-oxo-1,3-0. Dioxolan-4-yl sulfolofluoridate (structural formula C1), 2-oxo-1,3-dioxolan-4-yl methanesulfonate (structural formula C2), 2-oxo 1,3-dioxolan-4-yl trifluoromethanesulfonate (structural formula C7), 2-oxo-1,3-dioxolan-4-yl ethene sulfonate (structural formula C9), methyl (2-oxo-1,3-dioxolane 4-yl) sulfate (structural formula C17), 5-fluoro-2-oxo-1,3-dioxolan-4-yl methanesulfonate (structural formula C18), 5-methyl-2-oxo-1,3-dioxolane -4-yl methanesulfonate (structural formula C19), 2-oxo-1,3-dioxolane-4,5-diyl dimethanesulfonate (structural formula C35), bis (2-oxo-1,3-dioxolane-4-) Yl) sulfate (structural formula D1), 2-oxo-1,3-dioxolan-4-yl phosphorodifluoridate (structural formula E1), dimethyl (2-oxo-1,3-dioxolan-4-yl) phosphate (formula E6), and diethyl (2-oxo-1,3-dioxolan-4-yl) phosphate (formula E11) It is further preferable that one or more selected from the group consisting of

Among the above compounds, particularly preferred compounds are 2-oxo-1,3-dioxolan-4-yl acetate (structural formula A1), 2-oxo-1,3-dioxolan-4-yl 2,2,2-triacetate Fluoroacetate (Structural formula A4), 2-oxo-1,3-dioxolan-4-yl acrylate (Structural formula A7), 2-oxo-1,3-dioxolan-4-yl methacrylate (Structural formula A8), bis ( 2-oxo-1,3-dioxolan-4-yl) oxalate (structural formula B1), 2-oxo-1,3-dioxolan-4-yl sulfolofluoridate (structural formula C1), 2-oxo-1, 3-Dioxolan-4-yl methanesulfonate (structural formula C2), 2-oxo-1,3-dioxolan-4-yl trifluoromethanesulfonate Structural formula C7), 2-oxo-1,3-dioxolan-4-yl ethene sulfonate (structural formula C9), 5-fluoro-2-oxo-1,3-dioxolan-4-yl methanesulfonate (structural formula C18) , 5-methyl-2-oxo-1,3-dioxolan-4-yl methanesulfonate (structural formula C19), 2-oxo-1,3-dioxolan-4-yl phosphorodifluoridate (structural formula E1), dimethyl It is selected from the group consisting of (2-oxo-1,3-dioxolan-4-yl) phosphate (structural formula E6) and diethyl (2-oxo-1,3-dioxolan-4-yl) phosphate (structural formula E11) One or more.

The (2-oxo-1,3-dioxolan-4-yl) oxy derivative compound of the present invention can be synthesized by the following two methods, but is not limited to these methods.
(A) Method by the reaction of an alkyl halide and a potassium salt of carboxylic acid The above compound is obtained by reacting an alkyl halide and a potassium salt of carboxylic acid in a solvent by the method described in Chemische Berichte, 1970, 112 , 148. Can.
(B) Method by Reaction of Alkyl Halide and Silver Sulfate The above-mentioned compound can be obtained by reacting an alkyl halide and silver sulfonate in a solvent by the method described in Synthesis, 1971, 150.

In the non-aqueous electrolytic solution of the present invention, the content of the (2-oxo-1,3-dioxolan-4-yl) oxy compound represented by the above general formula (I) contained in the non-aqueous electrolytic solution is not particularly limited. The content is preferably 0.01 to 10% by mass in the water electrolyte. If the content is 10% by mass or less, there is little possibility that the film is excessively formed on the electrode and the low temperature characteristics are deteriorated, and if it is 0.01% by mass or more, the formation of the film is sufficient and a wide temperature The above range is preferable because the improvement effect of the electrochemical characteristics in the range is enhanced. The content is more preferably 0.05% by mass or more in the non-aqueous electrolyte, and still more preferably 0.1% by mass or more. Moreover, 5 mass% or less is more preferable, and, as for the upper limit, 3 mass% or less is still more preferable.

In the non-aqueous electrolyte solution of the present invention, the (2-oxo-1,3-dioxolan-4-yl) oxy compound represented by the above general formula (I) is described in the following non-aqueous solvent, electrolyte salt, and others. The combination of additives produces a unique effect that the electrochemical properties are synergistically improved over a wide temperature range.

[Non-aqueous solvent]
As a non-aqueous solvent used for the non-aqueous electrolyte solution of this invention, 1 type (s) or 2 or more types selected from the group which consists of cyclic carbonate, chain | strand-shaped ester, lactone, ether, and amide | amido are mentioned suitably. In order to synergistically improve the electrochemical properties over a wide temperature range, it is preferable to include a chain ester, more preferably to include a chain carbonate, and further to include both a cyclic carbonate and a chain ester. Preferably, both cyclic carbonate and linear carbonate are preferably included.
In addition, the term "linear ester" is used as a concept including linear carbonate and linear carboxylic acid ester.

<Cyclic carbonate>
The cyclic carbonates include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 4-fluoro-1,3-dioxolan-2-one (FEC), trans or Cis-4,5-difluoro-1,3-dioxolan-2-one (hereinafter collectively referred to as “DFEC”), vinylene carbonate (VC), vinyl ethylene carbonate (VEC), and 4-ethynyl-1 And 3-dioxolan-2-one (EEC), and ethylene carbonate (EC), propylene carbonate (PC), 4-fluoro-1,3-dioxolan-2-one (EC), and the like. FEC), vinylene carbonate (VC) and 4-ethynyl-1,3-dioxolane One or more members selected from the group consisting of 2-one is more preferred.

In addition, it is preferable to use at least one selected from cyclic carbonates having an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond or a fluorine atom, since the electrochemical characteristics in a high temperature environment are further improved. It is more preferable to include both a cyclic carbonate containing an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond and a cyclic carbonate having a fluorine atom. VC, VEC, or EEC is preferable as a cyclic carbonate having an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond, and FEC or DFEC is preferable as a cyclic carbonate having a fluorine atom.

(Content of cyclic carbonate)
The content of the cyclic carbonate having an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond is preferably 0.07% by volume or more, more preferably 0.2% by volume, relative to the total volume of the non-aqueous solvent. The upper limit is preferably 7% by volume or less, more preferably 4% by volume or less, and still more preferably 2.5% by volume or less. It is preferable that the content is in the above range, since the electrochemical characteristics in a wider temperature range can be increased without impairing the Li ion permeability.

The content of the cyclic carbonate having a fluorine atom is preferably 0.07% by volume or more, more preferably 4% by volume or more, still more preferably 6% by volume or more, based on the total volume of the non-aqueous solvent. The upper limit is preferably 35% by volume or less, more preferably 25% by volume or less, and further 15% by volume or less. It is preferable that the content is in the above range, since the electrochemical characteristics in a wider temperature range can be improved without deteriorating the Li ion permeability.

When the non-aqueous solvent contains both cyclic carbonate having unsaturated bond such as carbon-carbon double bond or carbon-carbon triple bond and cyclic carbonate having fluorine atom, carbon relative to the content of cyclic carbonate having fluorine atom The content of cyclic carbonate having an unsaturated bond such as a carbon double bond or a carbon-carbon triple bond is preferably 0.2% by volume or more, more preferably 3% by volume or more, still more preferably 7% by volume or more The upper limit thereof is preferably 40% by volume or less, more preferably 30% by volume or less, and further preferably 15% by volume or less. It is particularly preferable that the content is in the above range, since the electrochemical characteristics in a wider temperature range can be improved without impairing the Li ion permeability.

Also, when the non-aqueous solvent contains both ethylene carbonate and a cyclic carbonate having unsaturated bonds such as carbon-carbon double bonds or carbon-carbon triple bonds, the electrical properties over a wide temperature range of the film formed on the electrode The content of a cyclic carbonate having an unsaturated bond such as ethylene carbonate and a carbon-carbon double bond or a carbon-carbon triple bond is preferable with respect to the total volume of the non-aqueous solvent, since the chemical properties can be improved. Is 3% by volume or more, more preferably 5% by volume or more, still more preferably 7% by volume or more, and the upper limit thereof is preferably 45% by volume or less, more preferably 35% by volume or less, still more preferably 25% by volume % Or less.

These solvents may be used alone or in combination of two or more, since the effect of improving the electrochemical characteristics in a high temperature environment is further improved, which is preferable, and a combination of three or more is used. It is particularly preferred to Preferred combinations of these cyclic carbonates include EC and PC, EC and VC, PC and VC, VC and FEC, EC and FEC, PC and FEC, FEC and DFEC, EC and DFEC, PC and DFEC, VC and DFEC , VEC and DFEC, VC and EEC, EC and EEC, EC and PC and VC, EC and PC and FEC, EC and VC and FEC, EC and VC and VEC, EC and VC and EEC, EC and EEC and FEC, PC And VC and FEC, EC and VC and DFEC, PC and VC and DFEC, EC, PC and VC and FEC, or EC and PC and VC and DFEC, etc. are preferred. Among the combinations mentioned above, EC and VC, EC and FEC, PC and FEC, EC and PC and VC, EC and PC and FEC, EC and VC and FEC, EC and VC and EEC, EC and EEC and FEC, PC and More preferred is a combination of VC and FEC, or EC and PC, VC and FEC.

<Chain ester>
As the chain ester, one or more asymmetric chains selected from the group consisting of methyl ethyl carbonate (MEC), methyl propyl carbonate (MPC), methyl isopropyl carbonate (MIPC), methyl butyl carbonate and ethyl propyl carbonate Carbonates; one or more symmetrical linear carbonates selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate and dibutyl carbonate; methyl pivalate, ethyl pivalate, pivalate 1 or 2 or more chain | strand-shaped carboxylic acid S selected from the group which consists of pivalate esters, such as propyl, methyl propionate, an ethyl propionate, a propyl propionate, a methyl acetate, and ethyl acetate (EA) Le is preferably exemplified.

Among the above-mentioned chain esters, dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), methyl propyl carbonate (MPC), methyl isopropyl carbonate (MIPC), methyl butyl carbonate, methyl propionate, methyl propionate, methyl acetate and ethyl acetate (EA) The linear ester having a methyl group selected from the group consisting of is preferable, and in particular, a linear carbonate having a methyl group is preferable.

Further, from the viewpoint of improving the electrochemical characteristics under high voltage, it is preferable that at least one kind of chain ester in which at least one hydrogen atom is substituted by a fluorine atom is included.
Specific examples of chained esters in which at least one hydrogen atom is substituted with a fluorine atom include: 2,2-difluoroethyl acetate (DFEA), 2,2,2-trifluoroethyl acetate (TFEA), 2,2 -Difluoroethyl propionate, 2,2,2-trifluoroethyl propionate, methyl 2,2-difluoropropionate, methyl 2,2,2-trifluoropropionate, methyl (2,2-difluoroethyl) 1) At least one member selected from the group consisting of carbonate (MDFEC), methyl (2,2,2- trifluoroethyl) carbonate (MTFEC), and ethyl (2,2,2- trifluoroethyl) carbonate (ETFEC) Preferably it is mentioned.
Among them, 2,2,2-trifluoroethyl acetate (TFEA), 2,2-difluoroethyl acetate, methyl 2,2,2-trifluoropropionate, from the viewpoint of improving the electrochemical characteristics under high temperature environment. Consists of methyl (2,2-difluoroethyl) carbonate (MDFEC), methyl (2, 2, 2- trifluoroethyl) carbonate (MTFEC), and ethyl (2, 2, 2- trifluoroethyl) carbonate (ETFEC) One or more selected from the group are more preferable.

Moreover, when using a linear carbonate, it is preferable to use 2 or more types. Furthermore, it is more preferable that both symmetrical linear carbonate and asymmetric linear carbonate are contained, and it is further preferable that the content of symmetrical linear carbonate is larger than that of asymmetric linear carbonate.

(Content of linear ester)
The content of the linear ester is not particularly limited, but is preferably in the range of 60 to 90% by volume with respect to the total volume of the non-aqueous solvent. When the content is 60% by volume or more, the viscosity of the non-aqueous electrolyte does not become too high, and when it is 90% by volume or less, the electrical conductivity of the non-aqueous electrolyte decreases and the electrochemical characteristics in a wide temperature range Since it is less likely to decrease, the above range is preferable.

51 volume% or more is preferable, and, as for the ratio of the volume which symmetrical linear carbonate occupies in linear carbonate, 55 volume% or more is more preferable. As for the upper limit, 95 volume% or less is more preferable, and 85 volume% or less is still more preferable. It is particularly preferred that the symmetrical linear carbonate comprises dimethyl carbonate. Further, it is more preferable that the asymmetric linear carbonate has a methyl group, and methyl ethyl carbonate (MEC) is particularly preferable. In the above case, the electrochemical characteristics in a wider temperature range are improved, which is preferable.

The ratio of cyclic carbonate to linear ester is preferably 10/90 to 45/55, and more preferably 15/85 to 40/60, from the viewpoint of improving the electrochemical properties at high temperatures. Is more preferable, and 20/80 to 35/65 is even more preferable.

(Other non-aqueous solvents)
In the present invention, other nonaqueous solvents can be added in addition to the above-mentioned nonaqueous solvents.
Other nonaqueous solvents include cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, etc., chains such as 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, etc. 1 or 2 or more types selected from the group consisting of amidoethers, amides such as dimethylformamide, sulfones such as sulfolane, and lactones such as γ-butyrolactone (GBL), γ-valerolactone and α-angelica lactone Be
The above other non-aqueous solvents are usually used in combination to achieve appropriate physical properties. Examples of suitable combinations include combinations of cyclic carbonates and chained esters (especially chain carbonates) and lactones, combinations of cyclic carbonates and chained esters (especially chain carbonates) and ethers, etc. More preferred is a combination of a linear ester (especially a linear carbonate) and a lactone, and among the lactones, the use of γ-butyrolactone (GBL) is more preferred.
The content of the other non-aqueous solvent is usually 1% by volume or more, preferably 2% by volume or more, and usually 40% by volume or less, preferably 30% by volume or less, based on the total volume of the non-aqueous solvent Preferably it is 20 volume% or less.

(Other additives)
In order to improve the electrochemical properties over a wider temperature range, it is preferable to further add other additives to the non-aqueous electrolyte.
Specific examples of the other additives include the following compounds (A) to (I).

(A) One or more nitriles selected from the group consisting of acetonitrile, propionitrile, succinonitrile, glutaronitrile, adiponitrile, pimeronitrile, suberonitrile, and sebaconitrile.

(B) Cyclohexylbenzene, fluorocyclohexylbenzene compound (1-fluoro-2-cyclohexylbenzene, 1-fluoro-3-cyclohexylbenzene, 1-fluoro-4-cyclohexylbenzene), tert-butylbenzene, tert-amylbenzene, 1 Aromatic compounds having branched alkyl groups such as -fluoro-4-tert-butylbenzene, biphenyl, terphenyl (o-, m-, p-form), diphenyl ether, fluorobenzene, difluorobenzene (o-, m -, P-form), anisole, 2,4-difluoroanisole, partial hydride of terphenyl (1,2-dicyclohexylbenzene, 2-phenylbicyclohexyl, 1,2-diphenylcyclohexane, o-cyclohexylbiphenyl) Selected from the group Species or two or more aromatic compounds.

(C) Methyl isocyanate, ethyl isocyanate, butyl isocyanate, phenyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, 1,4-phenylene diisocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate One or two or more kinds of isocyanate compounds selected from the group.

(D) 2-propynyl methyl carbonate, acetic acid 2-propynyl, formic acid 2-propynyl, methacrylic acid 2-propynyl, methanesulfonic acid 2-propynyl, vinyl sulfonic acid 2-propynyl, 2- (methanesulfonyloxy) propionic acid Propynyl, di (2-propynyl) oxalate, methyl 2-propynyl oxalate, ethyl 2-propynyl oxalate, glutaric acid di (2-propynyl), 2-butyne-1,4-diyl dimethanesulfonate, 2- One or two or more triple bond-containing compounds selected from the group consisting of butyne-1,4-diyl diformate and 2,4-hexadiyne-1,6-diyl dimethanesulfonate.

(E) 1,3-propane sultone, 1,3-butane sultone, 2,4-butane sultone, 1,4-butane sultone, 1,3-propene sultone, 2,2-dioxide-1,2-oxathiolan-4-yl Acetone, or sultone such as 5,5-dimethyl-1,2-oxathiolan-4-one 2,2-dioxide, 4- (methylsulfonylmethyl) -1,3,2-dioxathiolane 2-oxide, ethylene sulfite, Hexahydrobenzo [1,3,2] dioxathiolane-2-oxide (also called 1,2-cyclohexanediol cyclic sulfite), 5-vinyl-hexahydro-1,3,2-benzodioxathiol-2-oxide Cyclic sulfite, butane-2,3-diyl dimethanesulfonate, butane-1 4-diyl dimethane sulfonate, dimethyl methane disulfonate, pentafluorophenyl methane sulfonate, sulfonic acid esters such as methylene methane disulfonate, divinyl sulfone, 1,2-bis (vinylsulfonyl) ethane, or bis (2-vinylsulfonylethyl) 1) One or two or more SOO group-containing compounds selected from the group consisting of chain S = O group-containing compounds such as vinyl sulfone compounds such as ethers.

(F) One or more cyclic acetal compounds selected from the group consisting of 1,3-dioxolane, 1,3-dioxane, and 1,3,5-trioxane.

(G) trimethyl phosphate, tributyl phosphate, trioctyl phosphate, tris (2,2,2-trifluoroethyl) phosphate, bis (2,2,2-trifluoroethyl) methyl phosphate, bis (phosphate) 2,2,2-Trifluoroethyl) ethyl, bis (2,2,2-trifluoroethyl) phosphate, 2,2-difluoroethyl, bis (2,2,2-trifluoroethyl) phosphate 2,2 , 3,3-tetrafluoropropyl, bis (2,2-difluoroethyl) phosphate 2,2,2-trifluoroethyl phosphate, bis (2,2,3,3-tetrafluoropropyl) phosphate 2,2,2, 2-trifluoroethyl, phosphoric acid (2,2,2-trifluoroethyl) (2,2,3,3-tetrafluoropropyl) methyl, phosphoric acid tris (1,1,1,3,3,3- Hexafluoro Loppan-2-yl), methyl methylene bisphosphonate, ethyl methylene bisphosphonate, methyl ethylene bisphosphonate, ethyl ethylene bisphosphonate, methyl butylene bisphosphonate, ethyl butylene bisphosphonate, methyl 2- (dimethylphosphoryl) acetate, ethyl 2- ( Dimethylphosphoryl) acetate, methyl 2- (diethylphosphoryl) acetate, ethyl 2- (diethylphosphoryl) acetate, 2-propynyl 2- (dimethylphosphoryl) acetate, 2-propynyl 2- (diethylphosphoryl) acetate, methyl 2- (dimethoxy) Phosphoryl) acetate, ethyl 2- (dimethoxyphosphoryl) acetate, methyl 2- (diethoxyphosphoryl) acetate, ethyl 2- (diethoxyphos 1) or 2 or more types of phosphorus content chosen from the group which consists of methyl arylphosphate, 2-propynyl 2- (dimethoxyphosphoryl) acetate, 2-propynyl 2- (diethoxyphosphoryl) acetate, and methyl pyrophosphate and ethyl pyrophosphate Compound.

(H) Linear carboxylic acid anhydrides such as acetic anhydride and propionic anhydride, succinic anhydride, maleic anhydride, 3-allyl succinic anhydride, glutaric anhydride, itaconic anhydride, and 3-sulfo-propionic anhydride Or one or more cyclic acid anhydrides selected from the group consisting of

(I) One or more cyclic phosphazene compounds selected from the group consisting of methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, and ethoxyheptafluorocyclotetraphosphazene.

Among the above, it is preferable to include at least one or more selected from the group consisting of (A) nitrile, (B) aromatic compound, and (C) isocyanate compound because the electrochemical characteristics in a much wider temperature range are improved.

Among the nitriles (A), one or more selected from the group consisting of succinonitrile, glutaronitrile, adiponitrile, and pimeronitrile are more preferable.
(B) Among aromatic compounds, one or two selected from biphenyl, terphenyl (o-, m-, p-form), fluorobenzene, cyclohexylbenzene, tert-butylbenzene, and tert-amylbenzene The above is more preferable, and one or more selected from the group consisting of biphenyl, o-terphenyl, fluorobenzene, cyclohexylbenzene and tert-amylbenzene are more preferable.
Among the isocyanate compounds (C), one or more selected from hexamethylene diisocyanate, octamethylene diisocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate are more preferable.

The content of the compounds (A) to (C) is preferably 0.01 to 7% by mass in the non-aqueous electrolyte. In this range, the coating is sufficiently formed without becoming too thick, and the electrochemical properties in a wider temperature range are enhanced. The content is more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and the upper limit thereof is 5% by mass or less in the non-aqueous electrolyte. Is more preferable, and 3% by mass or less is more preferable.

In addition, cyclic or chain-like S = O group-containing compounds selected from (D) triple bond-containing compounds, (E) sultones, cyclic sulfites, sulfonic acid esters, and vinyl sulfones (however, triple bond-containing compounds, and the aforementioned general compounds) (F) cyclic acetal compounds, (G) phosphorus-containing compounds, (H) cyclic acid anhydrides, or (I) cyclic phosphazene compounds, which do not include specific compounds represented by any of the formulas It is preferable because the electrochemical properties in the temperature range are improved.

(D) As the triple bond-containing compound, 2-propynyl methyl carbonate, 2-propynyl methacrylate, 2-propynyl methanesulfonic acid, 2-propynyl vinyl sulfonate, 2-propynyl 2- (methanesulfonyloxy) propionate, One or two or more selected from (2-propynyl) ogitalate, methyl 2-propynyl oxyallate, ethyl 2-propynyl oxygenate, and 2-butyne-1,4-diyl dimethanesulfonate are preferable, and methanesulfonic acid 2-propynyl is preferred. 1-type selected from the group consisting of vinylpropanoic acid 2-propynyl, 2- (methanesulfonyloxy) propionic acid 2-propynyl, di (2-propynyl) oxolate, and 2-butyne-1,4-diyl dimethanesulfonate Or two or more Preferred.
(E) Of the cyclic or chain-like S = O group-containing compounds, 1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone, 2,2-dioxide-1,2-oxathiolane-4 One or more selected from the group consisting of -yl acetate, ethylene sulfate, pentafluorophenyl methanesulfonate and divinyl sulfone are more preferable.
As the cyclic acetal compound (F), 1,3-dioxolane or 1,3-dioxane is preferable, and 1,3-dioxane is more preferable.

(G) As the phosphorus-containing compound, tris (2,2,2-trifluoroethyl) phosphate, tris (1,1,1,3,3,3-hexafluoropropan-2-yl) phosphate, methyl 2- (Dimethylphosphoryl) acetate, ethyl 2- (dimethylphosphoryl) acetate, methyl 2- (diethylphosphoryl) acetate, ethyl 2- (diethylphosphoryl) acetate, 2-propynyl 2- (dimethylphosphoryl) acetate, 2-propynyl 2 -(Diethylphosphoryl) acetate, methyl 2- (dimethoxyphosphoryl) acetate, ethyl 2- (dimethoxyphosphoryl) acetate, methyl 2- (diethoxyphosphoryl) acetate, ethyl 2- (diethoxyphosphoryl) acetate, 2-propynyl 2- (Dimet Preferred is cyphosphoryl) acetate or 2-propynyl 2- (diethoxyphosphoryl) acetate, and tris (2,2,2-trifluoroethyl) phosphate, tris (1,1,1,3,3,3-phosphate) Hexafluoropropan-2-yl), ethyl 2- (diethylphosphoryl) acetate, 2-propynyl 2- (dimethylphosphoryl) acetate, 2-propynyl 2- (diethylphosphoryl) acetate, ethyl 2- (diethoxyphosphoryl) acetate, More preferred is 2-propynyl 2- (dimethoxyphosphoryl) acetate or 2-propynyl 2- (diethoxyphosphoryl) acetate.

As the cyclic acid anhydride (H), succinic anhydride, maleic anhydride or 3-allyl succinic anhydride is preferable, and succinic anhydride or 3-allyl succinic anhydride is more preferable.
(I) The cyclic phosphazene compound is preferably a cyclic phosphazene compound such as methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene or phenoxypentafluorocyclotriphosphazene, and is preferably methoxypentafluorocyclotriphosphazene or ethoxypentafluorocyclo Triphosphazene is more preferred.

The content of the compounds (D) to (I) is preferably 0.001 to 5% by mass in the non-aqueous electrolyte. In this range, the coating is sufficiently formed without becoming too thick, and the electrochemical properties in a wider temperature range are enhanced. The content is more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and the upper limit thereof is 3% by mass or less in the non-aqueous electrolytic solution. Is more preferable, and 2% by mass or less is more preferable.

(Lithium salt)
Further, in order to improve the electrochemical characteristics in a wider temperature range, a lithium salt having an oxalic acid structure, a lithium salt having a phosphoric acid structure, and a lithium salt having an S = O group are further added to the non-aqueous electrolytic solution. It is preferable to include one or more lithium salts selected from among the above.
Specific examples of the lithium salt include lithium bis (oxalato) borate [LiBOB], lithium difluoro (oxalato) borate [LiDFOB], lithium tetrafluoro (oxalato) phosphate [LiTFOP], lithium difluorobis (oxalato) phosphate [LiDFOP], etc. Lithium salt having an oxalic acid structure, lithium salt having a phosphoric acid structure such as lithium difluorophosphate [LiPO ₂ F ₂ ] or lithium fluorophosphate [Li ₂ PO ₃ F], lithium trifluoro ((methanesulfonyl) oxy) borate [LiTFMSB], lithium pentafluoro ((methanesulfonyl) oxy) phosphate [LiPFMSP], lithium methyl sulfate [LMS], lithium ethyl sulfate Preparative [LES], lithium 2,2,2-trifluoroethyl sulfate [LFES], lithium fluoro sulfate _[FSO 3 Li], and lithium bis (fluorosulfonyl) imide _{_{[LiN (SO 2 F) 2;}} LiFSI ] such as 1 type, or 2 or more types selected from the group which consists of lithium salt which has S = O group are mentioned suitably.
Among these, it is more preferable to include a lithium salt selected from the group consisting of LiBOB, LiDFOB, LiTFOP, LiDFOP, LiPO ₂ F ₂ , LiTFMSB, LMS, LES, LFES, FSO ₃ Li, and LiFSI, LiDFOP, LiPO It is more preferable to include a lithium salt selected from the group consisting of ₂ F ₂ , LES, and LiFSI.

The total content of the lithium salt in the non-aqueous solvent is preferably 0.001 M or more and 0.5 M or less. Within this range, the effect of improving the electrochemical characteristics in a wide temperature range is further exhibited. Preferably it is 0.01 M or more, More preferably, it is 0.03 M or more, More preferably, it is 0.04 M or more. The upper limit thereof is preferably 0.4 M or less, more preferably 0.2 M or less. Here, M represents mol / L.

(Electrolyte salt)
As an electrolyte salt used for this invention, the following lithium salt is mentioned suitably.
As lithium salts, inorganic lithium salts such as LiPF ₆ , LiBF ₄ , LiClO ₄ , LiPO ₂ F ₂ , LiN (SO ₂ F) ₂ , LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) _{_{_{_{2, LiCF 3 SO 3, LiC}}}} (SO 2 CF 3) 3, LiPF 4 (CF 3) 2, LiPF 3 (C 2 F 5) 3, LiPF 3 (CF 3) 3, LiPF 3 (iso-C 3 F ₇ ) ₃ , lithium salts containing a linear fluorinated alkyl group such as LiPF ₅ (iso-C ₃ F ₇ ), (CF ₂ ) ₂ (SO ₂ ) ₂ NLi, (CF ₂ ) ₃ (SO ₂ ) One or two or more selected from the group consisting of lithium salts having a cyclic fluorinated alkylene chain such as ₂ NLi, and the like are preferably mentioned. Among _{_{them, LiPF 6, LiBF 4, LiPO}} 2 F 2, LiN (SO 2 F) 2, LiN (SO 2 CF 3) 2, and _{_{_{LiN (SO 2 C 2 F 5}}} ) 1 kind or 2 selected from ₂ The species is more preferable, and LiPF ₆ is more preferable.

The concentration of the electrolyte salt is preferably 0.3 M or more, more preferably 0.7 M or more, and still more preferably 1.1 M or more, in the non-aqueous electrolyte. The upper limit thereof is preferably 2.5 M or less, more preferably 2.0 M or less, and still more preferably 1.6 M or less.
In addition, preferable combinations of these electrolyte salts include LiPF ₆ and at least one lithium selected from LiBF ₄ , LiN (SO ₂ CF ₃ ) ₂ , and LiN (SO ₂ F) ₂ [LiFSI]. It is preferred that the salt be contained in the non-aqueous electrolyte.
If the proportion of lithium salt other than LiPF _{6 in the} non-aqueous solvent is 0.001 M or more, the effect of improving the electrochemical characteristics in a wide temperature range is easily exhibited, and if it is 1.0 M or less, the wide temperature range It is preferable because there is little concern that the improvement effect of the electrochemical characteristics in The content of lithium salt other than LiPF ₆ is preferably 0.01 M or more, more preferably 0.03 M or more, still more preferably 0.04 M or more, and the upper limit thereof is preferably 0.8 M or less, more preferably It is 0.6 M or less, more preferably 0.4 M or less.

[Production of Nonaqueous Electrolyte]
The non-aqueous electrolytic solution of the present invention can be obtained, for example, by mixing the above-mentioned non-aqueous solvent, adding to the above-mentioned electrolytic salt and the above-mentioned non-aqueous electrolytic solution, It can be obtained by adding a 3-dioxolan-4-yl) oxy compound.
Under the present circumstances, it is preferable to refine | purify previously and to use the said compound added to the non-aqueous solvent and non-aqueous electrolyte to be used as much as possible as much as possible, as much as possible.

The non-aqueous electrolyte solution of the present invention can be used in the following first to fourth electricity storage devices, and as the non-aqueous electrolyte, not only liquid ones but also gelled ones can be used. Furthermore, the non-aqueous electrolytic solution of the present invention can also be used for solid polymer electrolytes. Above all, it is preferable to use as a first storage battery device (that is, for lithium battery) or a fourth storage battery device (that is, for lithium ion capacitor) that uses lithium salt for electrolyte salt. It is more preferable to use for lithium secondary batteries.

[First power storage device (lithium battery)]
The lithium battery, which is the first electricity storage device, is a general term for lithium primary batteries and lithium secondary batteries, and the term lithium secondary battery is used as a concept including so-called lithium ion secondary batteries.
The lithium battery of the present invention comprises a positive electrode, a negative electrode, and the non-aqueous electrolytic solution in which an electrolyte salt is dissolved in a non-aqueous solvent. The constituent members such as the positive electrode and the negative electrode other than the non-aqueous electrolyte can be used without particular limitation.
For example, as a positive electrode active material of a positive electrode for a lithium secondary battery, a composite metal oxide with lithium containing one or more selected from the group consisting of cobalt, manganese, and nickel is used. These positive electrode active materials can be used singly or in combination of two or more.
As such lithium composite metal oxides, for example, LiCoO ₂ , LiCo _{1 -x} M _x O ₂ (where M is Sn, Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn, and One or more elements selected from Cu, 0.001 ≦ x ≦ 0.05), LiMn ₂ O ₄ , LiNiO ₂ , LiCo _1-x Ni _x O ₂ (0.01 <x <1), LiCo _1/3 Ni _1/3 Mn _1/3 O ₂ , LiNi _0.5 Mn _0.3 Co _0.2 O ₂ , LiNi _0.8 Mn _0.1 Co _0.1 O ₂ , LiNi _0.8 Co _0.15 Al _0.05 O ₂ , LiNi _1/2 Mn _3/2 O ₄ , solid solution of Li ₂ MnO ₃ and LiMO ₂ (M is a transition metal such as Co, Ni, Mn, Fe, etc.), and LiNi consisting of _1/2 Mn _3/2 O ₄ More 1 or more are suitably exemplified chosen, or two or more is more preferable. Further, LiCoO ₂ and LiMn ₂ O ₄ , LiCoO ₂ and LiNiO ₂ , and LiMn ₂ O ₄ and LiNiO ₂ may be used in combination.

When a lithium composite metal oxide that operates at a high charge voltage is used, generally, the electrochemical characteristics are likely to be degraded in a high temperature environment due to a reaction with an electrolyte during charge, but in the lithium secondary battery according to the present invention The deterioration of these electrochemical properties can be suppressed.
In particular, when a positive electrode active material containing Ni is used, the non-aqueous solvent is generally decomposed on the surface of the positive electrode by the catalytic action of Ni, and the resistance of the battery tends to increase. In particular, the electrochemical characteristics in a high temperature environment tend to be deteriorated, but the lithium secondary battery according to the present invention is preferable because the deterioration of these electrochemical characteristics can be suppressed. In particular, the above effect is remarkable when the positive electrode active material in which the ratio of the atomic concentration of Ni to the atomic concentration of all transition metal elements in the positive electrode active material exceeds 10 atomic% is preferable, and 20 atomic% or more is more preferable. And 30 atomic% or more is particularly preferable. Specifically, LiCo _1/3 Ni _1/3 Mn _1/3 O ₂ , LiNi _0.5 Mn _0.3 Co _0.2 O ₂ , LiNi _0.8 Mn _0.1 Co _0.1 O ₂ , One or more selected from the group consisting of LiNi _1/2 Mn _3/2 O ₄ and LiNi _0.8 Co _0.15 Al _0.05 O ₂ is preferably mentioned.

Furthermore, a lithium-containing olivine-type phosphate can also be used as the positive electrode active material. Particularly preferred is a lithium-containing olivine-type phosphate containing one or more selected from the group consisting of iron, cobalt, nickel and manganese. Specific examples thereof include one or more selected from LiFePO ₄ , LiCoPO ₄ , LiNiPO ₄ , LiMnPO ₄ , and LiFe _1-x Mn _x PO ₄ (0.1 <x <0.9). .
Some of these lithium-containing olivine-type phosphates may be substituted with other elements, and some of iron, cobalt, nickel and manganese may be replaced with Co, Mn, Ni, Mg, Al, B, Ti, V, Nb Alternatively, it may be substituted with one or more elements selected from Cu, Zn, Mo, Ca, Sr, W, and Zr, or may be coated with a compound or carbon material containing these other elements. Among these, LiFePO ₄ or LiMnPO ₄ is preferred.
The lithium-containing olivine-type phosphate can also be used, for example, as a mixture with the above-mentioned positive electrode active material.
The lithium-containing olivine-type phosphate forms a stable phosphoric acid (PO ₄ ) structure and is excellent in thermal stability at the time of charging, so that it can improve the electrochemical characteristics in a wide temperature range.

As the positive electrode for lithium primary _{_{_{_{battery, CuO, Cu 2 O, Ag}}}} 2 O, Ag 2 CrO 4, CuS, CuSO 4, TiO 2, TiS 2, SiO 2, SnO, V 2 O 5, V 6 O 12 , VO _x , Nb ₂ O ₅ , Bi ₂ O ₃ , Bi ₂ Pb ₂ O ₅ , Sb ₂ O ₃ , CrO ₃ , Cr ₂ O ₃ , MoO ₃ , WO ₃ , SeO ₂ , MnO ₂ , Mn ₂ O ₃ Oxides or chalcogen compounds of one or more metal elements such as Fe ₂ O ₃ , FeO, Fe ₃ O ₄ , Ni ₂ O ₃ , NiO, CoO ₃ , CoO etc., sulfur such as SO ₂ , SOCl ₂ etc. compounds of the general formula (CF _x) fluorocarbon (graphite fluoride) represented by _n, and the like. Among these, MnO ₂ , V ₂ O ₅ , fluorinated graphite and the like are preferable.

The conductive agent of the positive electrode is not particularly limited as long as it is an electron conductive material which does not cause a chemical change. For example, graphite such as natural graphite (scalate graphite etc.), artificial graphite etc., carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black or thermal black etc. may be mentioned. In addition, graphite and carbon black may be appropriately mixed and used. The amount of the conductive agent added to the positive electrode mixture is preferably 1 to 10% by mass, and more preferably 2 to 5% by mass.

The positive electrode includes the above-mentioned positive electrode active material as a conductive agent such as acetylene black and carbon black, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), copolymer of styrene and butadiene (SBR), acrylonitrile and butadiene Mixed with a binder such as copolymer (NBR), carboxymethyl cellulose (CMC), ethylene propylene diene terpolymer, etc., added with a high boiling point solvent such as 1-methyl-2-pyrrolidone and kneaded to prepare a positive electrode mixture Then, the positive electrode mixture is applied to an aluminum foil of a current collector, a stainless steel lath plate, etc., dried and pressure-molded, and then under a vacuum at a temperature of about 50 ° C. to 250 ° C. for about 2 hours. It can be produced by heat treatment.
The density of the part except the collector of the positive electrode is usually at 1.5 g / cm ³ or more, for further increasing the capacity of the battery, it is preferably 2 g / cm ³ or more, more preferably, 3 g / cm ³ It is the above, More preferably, it is 3.6 g / cm ³ or more. The upper limit thereof is preferably 4 g / cm ³ or less.

As a negative electrode active material of a negative electrode for a lithium secondary battery, lithium metal, a lithium alloy, and a carbon material capable of inserting and extracting lithium ions (graphitizable carbon, and the spacing of the (002) plane is 0. 0). Non-graphitizable carbon of 37 nm or more, Graphite with an (002) plane spacing of 0.34 nm or less, etc., tin (single body), tin compound, silicon (single body), silicon compound, Li ₄ Ti ₅ O _{12 and the} like 1 type, or 2 or more types selected from the group which consists of a lithium titanate compound etc. are preferable.
Among these, it is more preferable to use a highly crystalline carbon material such as artificial graphite or natural graphite in the ability to absorb and release lithium ions, and the lattice spacing (d ₀₀₂ ) of the lattice plane ( ₀₀₂ ) is 0. It is further preferred to use a carbon material having a graphitic crystal structure of 340 nm (nanometers) or less, in particular 0.335 to 0.337 nm.

In particular, it repeatedly applies mechanical actions such as compressive force, frictional force, and shear force to artificial graphite particles having a massive structure in which a plurality of flat graphite particles are aggregated or bonded non-parallel to each other, and scaly natural graphite particles, It is preferable to use spheroidized graphite particles.
Graphite obtained by X-ray diffraction measurement of a negative electrode sheet when pressure molding is performed such that the density of the portion of the negative electrode excluding the current collector is 1.5 g / cm ³ or more by such spheroidizing treatment of the graphite particles When the ratio I (110) / I (004) of the peak intensity I (110) of the (110) plane to the peak intensity I (004) of the (004) plane becomes 0.01 or more in a wider temperature range It is preferable because the electrochemical characteristics are improved, and is preferably 0.05 or more, and more preferably 0.1 or more. In addition, excessive treatment may lower crystallinity and decrease the discharge capacity of the battery. Therefore, the upper limit of the peak intensity ratio I (110) / I (004) is preferably 0.5 or less, and 0. 0. 3 or less is more preferable.
In addition, it is preferable that the highly crystalline carbon material (core material) is coated with a carbon material having a lower crystallinity than the core material, because the electrochemical characteristics in a wide temperature range are further improved. The crystallinity of the coated carbon material can be confirmed by transmission electron microscopy (TEM).
The use of a highly crystalline carbon material generally tends to react with the non-aqueous electrolyte during charging and to lower the electrochemical properties at low or high temperatures by increasing the interfacial resistance, but the lithium according to the present invention The secondary battery has good electrochemical characteristics in a wide temperature range.

In addition, metal compounds capable of inserting and extracting lithium ions as the negative electrode active material include Si, Ge, Sn, Pb, P, Sb, Bi, Al, Ga, In, Ti, Mn, Fe, Co, Ni, Examples thereof include compounds containing at least one metal element such as Cu, Zn, Ag, Mg, Sr, or Ba. These metal compounds may be used in any form such as an alloy, an oxide, a nitride, a sulfide, a boride, an alloy with lithium, or any of an alloy, an oxide, an alloy with an oxide or lithium. It is preferable because it can increase the capacity. Among them, one containing at least one element selected from the group consisting of Si, Ge and Sn is preferable, and one containing at least one element selected from Si and Sn is more preferable because the capacity of the battery can be increased.

The negative electrode is kneaded using the same conductive agent, binder and high boiling point solvent as in the preparation of the above positive electrode to form a negative electrode mixture, and this negative electrode mixture is then applied to copper foil of the current collector and the like. After drying and pressure molding, it can be manufactured by heat treatment at a temperature of about 50 ° C. to 250 ° C. for about 2 hours under vacuum.
The density of the part excluding the current collector of the negative electrode is usually 1.1 g / cm ³ or more, and is preferably 1.5 g / cm ³ or more, more preferably 1.7 g to further increase the capacity of the battery. / cm ³ or more, the upper limit is preferably 2 g / cm ³ or less.

Moreover, lithium metal or a lithium alloy is mentioned as a negative electrode active material for lithium primary batteries.

The structure of the lithium battery is not particularly limited, and a coin battery, a cylindrical battery, a prismatic battery, a laminate battery or the like having a single layer or multilayer separator can be applied.
The battery separator is not particularly limited, but a microporous film, woven fabric, non-woven fabric, etc. of a single layer or laminated layer of polyolefin such as polypropylene, polyethylene, ethylene-propylene copolymer, etc. can be used.
As a laminate of polyolefin, a laminate of polyethylene and polypropylene is preferable, and a three-layer structure of polypropylene / polyethylene / polypropylene is more preferable.
The thickness of the separator is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and the upper limit thereof is 30 μm or less, preferably 20 μm or less, more preferably 15 μm or less.

The lithium secondary battery according to the present invention is excellent in electrochemical characteristics in a wide temperature range even when the charge termination voltage is 4.2 V or more, particularly 4.3 V or more, and further, the characteristics are excellent even at 4.4 V or more is there. The discharge termination voltage can be usually 2.8 V or more, and further 2.5 V or more, but the lithium secondary battery in the present invention can be 2.0 V or more. Although the current value is not particularly limited, it is usually used in the range of 0.1 to 30C. In addition, the lithium battery in the present invention can be charged and discharged at -40 to 100 ° C, preferably -10 to 80 ° C.

In the present invention, as a measure to increase the internal pressure of the lithium battery, a method of providing a safety valve on the battery cover or making a notch in a member such as a battery can or a gasket can also be adopted. In addition, as a safety measure against overcharge, a current blocking mechanism that senses the internal pressure of the battery and cuts off the current can be provided on the battery cover.

[Second power storage device (electric double layer capacitor)]
The second electricity storage device of the present invention is an electricity storage device that contains the non-aqueous electrolyte solution of the present invention and stores energy using the electric double layer capacity at the interface between the electrolyte solution and the electrode. One example of the present invention is an electric double layer capacitor. The most typical electrode active material used for this storage device is activated carbon. The bilayer capacity increases approximately in proportion to the surface area.

[Third power storage device]
The third electricity storage device of the present invention is an electricity storage device that includes the non-aqueous electrolyte solution of the present invention and stores energy using the electrode doping / dedoping reaction. Examples of the electrode active material used in the electricity storage device include metal oxides such as ruthenium oxide, iridium oxide, tungsten oxide, molybdenum oxide and copper oxide, and π-conjugated polymers such as polyacene and polythiophene derivatives. Capacitors using these electrode active materials can store energy associated with electrode doping / de-doping reactions.

[Fourth electricity storage device (lithium ion capacitor)]
A fourth electricity storage device of the present invention is an electricity storage device that includes the non-aqueous electrolyte solution of the present invention and stores energy using intercalation of lithium ions to a carbon material such as graphite which is a negative electrode. It is called a lithium ion capacitor (LIC). Examples of the positive electrode include those using an electric double layer between an activated carbon electrode and an electrolytic solution, and those using a doping / dedoping reaction of a π-conjugated polymer electrode. The electrolyte includes lithium salts such as at least LiPF _6.

The (2-oxo-1,3-dioxolan-4-yl) oxy derivative compound which is a novel compound of the present invention is represented by the following general formula (II).

In formula (II), the same meaning as ^{^{^{R 2, R 3, R 5}}} , R 6, and ^{R 7} in the substituent ^{^{^{R 2, R 3, R 5}}} , R 6, and ^{R 7} of the general formula (I) .

Specific examples of R ⁸ include halogen atoms such as hydrogen atom, fluorine atom, chlorine atom and bromine atom; methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and the like Straight-chain alkyl groups of: branched alkyl groups such as isopropyl group, sec-butyl group, 2-pentyl group, 3-pentyl group, tert-butyl group, tert-amyl group, etc .; fluoromethyl group, difluoromethyl group , Trifluoromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 3,3-difluoropropyl group And halogenated alkyl groups such as 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group; Cycloalkyl groups such as chloropropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl; vinyl, 1-propen-1-yl, 2-propen-1-yl, 2-buten-1-yl Group, 3-buten-1-yl group, 4-penten-1-yl group, 5-hexen-1-yl group, 1-propen-2-yl group, 1-buten-2-yl group, 2-methyl Alkenyl groups such as -2-propen-1-yl group; ethynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 4-heptynyl group, 1-methyl-2-propynyl group, 1,1- Alkynyl groups such as dimethyl-2-propynyl group, 1-methyl-3-butynyl group, 1-methyl-4-heptynyl group; benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group; 4-fluoro Aralkyl groups such as benzyl group, 4-chlorobenzyl group, 1-phenylethane-1-yl group, 2-phenylethane-1-yl group, 3-phenylpropan-1-yl group, etc .; phenyl group, 2-methylphenyl Group, aryl group such as 3-methylphenyl group, 4-methylphenyl group, 4-tert-butylphenyl group, etc .; 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-trifluoromethylphenyl group Group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 4-fluoro-2-trifluoromethylphenyl group, 4-fluoro-3-trifluoromethylphenyl group, 2,6-difluorophenyl group, 3,5-Difluorophenyl, 2,4,6-trifluorophenyl, 2,3,5,6-tetrafluoropheny Preferred examples include a halogenated aryl group such as a fluoro group, perfluorophenyl and the like; a fluorosulfonyloxy group, a methanesulfonyloxy group, a vinylsulfonyloxy group, a difluorophosphoryl group, a dimethoxyphosphoryl group or a diethoxyphosphoryl group.

Among these, hydrogen atom, fluorine atom, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, sec-butyl group, 2-pentyl group, tert -Butyl group, tert-amyl group, trifluoromethyl group, 2-fluoroethyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group, vinyl group, 1-propen-1-yl group, 2-propen-1-yl group 1-propen-2-yl group, ethynyl group, 2-propynyl group, 2-butynyl group, benzyl group, 4-methylbenzyl group, phenyl group, 4-methylphenyl group, fluorosulfonyloxy group, methanesulfonyloxy group , A vinylsulfonyloxy group, a difluorophosphoryl group, a dimethoxyphosphoryl group or a diethoxyphosphoryl group is preferable, and hydrogen , Fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, trifluoromethyl group, cyclopropyl group, cyclohexyl group, vinyl group, 1-propen-1-yl group, 1- Propen-2-yl group, ethynyl group, 2-propynyl group, phenyl group, 4-methylphenyl group, fluorosulfonyloxy group, methanesulfonyloxy group, vinylsulfonyloxy group, difluorophosphoryl group, dimethoxyphosphoryl group, or diethoxy A phosphoryl group is more preferred.

R ⁹ is a fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group Halogenated alkyl groups such as 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group; cyclopropyl group, Cycloalkyl groups such as cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl; ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 4-heptynyl, 1-methyl-2-propynyl, Alkynyl groups such as 1,1-dimethyl-2-propynyl group, 1-methyl-3-butynyl group, 1-methyl-4-pentynyl group; Aralkyl groups such as benzyl group, 4-methylbenzyl group, 1-phenylethane-1-yl group, 2-phenylethane-1-yl group, 3-phenylpropan-1-yl group, etc .; phenyl group, 2-methylphenyl Group, aryl group such as 3-methylphenyl group, 4-methylphenyl group, 4-tert-butylphenyl group, etc .; 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-trifluoromethylphenyl group Group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 4-fluoro-2-trifluoromethylphenyl group, 4-fluoro-3-trifluoromethylphenyl group, 2,6-difluorophenyl group, 3,5-Difluorophenyl group, 2,4,6-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group Group, halogenated aryl group perfluorophenyl, and the like; a methoxycarbonyl group, an alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group are preferably exemplified.

Among these, fluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, ethynyl group, 2-propynyl group, phenyl group, 2-methyl group A phenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-fluorophenyl group, 4-trifluoromethylphenyl group, methoxycarbonyl group or ethoxycarbonyl group is preferable, and a trifluoromethyl group, cyclopropyl group, cyclohexyl A group, ethynyl group, phenyl group, 4-fluorophenyl group, 4-trifluorophenyl group, methoxycarbonyl group or ethoxycarbonyl group is more preferable.

Specific compounds represented by the general formula (II) are the same as described and preferred in the specific compounds of the general formula (I) except for compounds having a structural formula of A1 to A3, A7 to A8, or A20. It is.

Hereinafter, although the example of the electrolyte solution using the compound of this invention is shown, this invention is not limited to these examples.

Synthesis Example 1 [Synthesis of 2-oxo-1,3-dioxolan-4-yl acetate (Structural Formula A1)]
0.3 g (5.2 mmol) of potassium fluoride is suspended in 20 ml of acetonitrile, and 3.0 g (24.5 mmol) of 4-chloro-1,3-dixolan-2-one, 1.6 g of acetic acid 26.6 mmol) and 3.2 g (31.6 mmol) of triethylamine were added and stirred at room temperature under a nitrogen stream. The mixture was cooled to room temperature, filtered, and the filtrate was concentrated under reduced pressure. The residue is isolated by silica gel column chromatography (eluent: n-hexane / ethyl acetate (7: 1)) to obtain the desired 2-oxo-1,3-dioxolan-4-yl acetate 1.5 g (yield) 42%) was obtained as an oil. The obtained 2-oxo-1,3-dioxolan-4-yl acetate was subjected to measurement of ¹ H-NMR spectrum to confirm its structure. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ = 6.72 (dd, 1 H, J = 5.6, 1.9 Hz), 4.63 (dd, 1 H, J = 10.1, 5.6 Hz), 4.42 (dd, 1 H, J = 10.1, 1.9 Hz), 2.18 (s, 3 H)

Synthesis Example 2 [Synthesis of Bis (2-oxo-1,3-dioxolan-4-yl) oxalate (Structural Formula B1)]
By a method similar to Synthesis Example 1, the target bis (2-oxo-1,3-dioxolan-4-yl) was obtained as a white solid. The ¹ H-NMR spectrum of the obtained bis (2-oxo-1,3-dioxolan-4-yl) oxalate was measured to confirm its structure. The results are shown below.
¹ H-NMR (400 MHz, DMSO-d6) δ = 6.79-6.75 (m, 2 H), 4. 85-4. 79 (m, 2 H), 4. 66 (dd, 2 H, J = 10.3, 1.8 Hz)

Synthesis Example 3 [Synthesis of 2-oxo-1,3-dioxolan-4-yl methanesulfonate (Structural Formula C2)]
6.09 g (30.0 mmol) of silver methanesulfonate is suspended in 10 ml of dichloromethane, 3.06 g (25.0 mmol) of 4-chloro-1,3-dixolan-2-one is added with stirring, and a nitrogen stream is produced. The mixture was heated to reflux for 6.5 hours. It cooled to room temperature and the silver chloride produced | generated by filtration was removed. The filtrate is concentrated under reduced pressure, diethyl ether is added to the residue, and filtration is performed to obtain 2.00 g (yield 44%) of the target 2-oxo-1,3-dioxolan-4-yl methanesulfonate as a white solid. The The obtained 2-oxo-1,3-dioxolan-4-yl methanesulfonate was subjected to measurement of ¹ H-NMR spectrum to confirm its structure. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ = 6.52 (dd, 1 H, J = 5.7, 1.9 Hz), 4.71 (dd, 1 H, J = 10.5, 5.7 Hz), 4.55 (dd, 1 H, J = 10.5, 1.9 Hz), 3.33 (s, 3 H)

Synthesis Example 4 [Synthesis of 2-oxo-1,3-dioxolan-4-yl 2,2,2-trifluoroacetate (Structural Formula A4)]
In the synthesis example 3, silver methanesulfonate is changed to silver trifluoroacetate, and in the same manner as in the synthesis example 3, the target 2-oxo-1,3-dioxolan-4-yl 2,2,2-trifluoroacetate Was obtained as a colorless oil. The ¹ H-NMR spectrum of the obtained 2-oxo-1,3-dioxolan-4-yl 2,2,2-trifluoroacetate was measured to confirm its structure. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ = 6.81 (dd, 1 H, J = 5.5, 1.6 Hz), 4.76 (dd, 1 H, J = 11.0, 5.5 Hz), 4.61 dd, 1 H, J = 11.0, 1.6 Hz)

Synthesis Example 5 [Synthesis of 2-oxo-1,3-dioxolan-4-yl ethene sulfonate (structural formula C9)]
By a method similar to Synthesis Example 3, the target 2-oxo-1,3-dioxolan-4-yl ethene sulfonate was obtained as a white solid. The obtained 2-oxo-1,3-dioxolan-4-yl ethene sulfonate was subjected to measurement of ¹ H-NMR spectrum to confirm its structure. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ = 6.69 (dd, 1 H, J = 16.5, 9.7 Hz), 6.54 (dd, 1 H, J = 16.5, 0.8 Hz), 6.47 (dd, 1 H, J = 5.6, 1.8 Hz), 6.27 (dd, 1H, J = 9.7, 0.8 Hz), 4.69 (dd, 1 H, J = 10.5, 5.6 Hz), 4.55 (dd, 1 H, J = 10.5, 1.8 Hz)

Synthesis Example 6 Synthesis of Dimethyl (2-oxo-1,3-dioxolan-4-yl) phosphate (Structural Formula E6)]
A solution of 0.83 g (6.6 mmol) of dimethyl phosphate in 10 ml of acetonitrile was mixed with 0.97 g (7.9 mmol) of 4-chloro-1,3-dixolan-2-one and 1.99 g (8.6 mmol) of silver acetate. In addition, the mixture was heated to reflux for 2 hours under a nitrogen stream. After cooling to room temperature, the reaction solution was filtered, diethyl ether and water were added thereto to separate it, and the organic phase was washed with saturated brine. After drying over magnesium sulfate, the solution was concentrated under reduced pressure. The target dimethyl (2-oxo-1,3-dioxolan-4-yl) is obtained by isolating the residue by silica gel column chromatography (eluent: n-hexane / ethyl acetate (1: 1 to 1: 4)). 0.72 g (50% yield) of phosphate was obtained as an oil. The obtained dimethyl (2-oxo-1,3-dioxolan-4-yl) phosphate was subjected to measurement of ¹ H-NMR spectrum to confirm its structure. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ = 6.35 (m, 1 H), 4.62 (m, 1 H), 4.46 (dd, 1 H, J = 10.2, 2.0 Hz), 3.87 (d, 3 H, J = 6.8 Hz ), 3.84 (d, 3H, J = 6.8 Hz)

Synthesis Example 7 Synthesis of Diethyl (2-oxo-1,3-dioxolan-4-yl) phosphate (Structural Formula E11)]
In Synthesis Example 6, dimethyl phosphate was changed to diethyl phosphate, and in the same manner as in Synthesis Example 6, the target diethyl (2-oxo-1,3-dioxolan-4-yl) phosphate was obtained as a white solid. The obtained diethyl (2-oxo-1,3-dioxolan-4-yl) phosphate was subjected to measurement of ¹ H-NMR spectrum to confirm its structure. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ = 6.35 (m, 1 H), 4.61 (m, 1 H), 4.44 (dd, 1 H, J = 10.4, 1.8 Hz) 4.19 (m, 4 H), 1.37 (m, 1 6H)

Examples 1 to 24 and Comparative Examples 1 to 2
[Fabrication of lithium ion secondary battery]
LiNi _0.33 Mn _0.33 Co _0.34 O ₂ 94% by mass, acetylene black (conductive agent) 3% by mass are mixed, and 3% by mass of polyvinylidene fluoride (binding agent) in advance is 1-methyl-2- The mixture was added to a solution dissolved in pyrrolidone and mixed to prepare a positive electrode mixture paste. The positive electrode material mixture paste was applied to one side of an aluminum foil (current collector), dried and pressurized, and cut into a predetermined size to prepare a strip-shaped positive electrode sheet. The density of the portion of the positive electrode excluding the current collector was 3.6 g / cm ³ .
In addition, 10% by mass of silicon (simple substance), 80% by mass of artificial graphite (d ₀₀₂ = 0.335 nm, negative electrode active material), and 5% by mass of acetylene black (conductive agent) are mixed, and polyvinylidene fluoride (binding agent) is made in advance. A negative electrode mixture paste was prepared by adding 5% by mass to a solution in which 1% by mass was dissolved in 1-methyl-2-pyrrolidone and mixing. The negative electrode material mixture paste was applied to one side of a copper foil (current collector), dried and pressurized, and cut into a predetermined size to prepare a negative electrode sheet. The density of the part except the current collector of the negative electrode was 1.5 g / cm ³ . As a result of X-ray diffraction measurement using this electrode sheet, the peak intensity I of the (110) plane of the graphite crystal and the ratio of the peak intensity I (004) of the (004) plane [I (110) / I (004) ) Was 0.1.
The obtained positive electrode sheet, microporous polyethylene film separator, and negative electrode sheet were laminated in this order, and the non-aqueous electrolytic solution of the composition shown in Table 1 and Table 2 was added to prepare a laminate type battery.

[Discharge capacity maintenance rate after high temperature cycle]
Using the battery fabricated by the above method, the battery is charged to a final voltage of 4.25 V for 3 hours at a constant current of 1 C and a constant voltage in a thermostatic chamber at 55 ° C., and then a discharge voltage of 3.0 V under a constant current of 1 C The discharging up to 1 cycle was repeated until this reached 300 cycles.
And the discharge capacity maintenance factor after a cycle was calculated | required by the following formula.
Discharge capacity retention rate (%) = (discharge capacity at 300th cycle / discharge capacity at 1st cycle) × 100

[Discharge capacity maintenance rate after high temperature charge storage]
<Initial discharge capacity>
Using the laminate type battery produced by the above method, charge the battery to a final voltage of 4.35 V for 3 hours with a constant current of 1 C and a constant voltage in a 25 ° C. thermostat, and lower the temperature of the thermostat to -20 ° C. The battery was discharged to a final voltage of 2.75 V under a constant current of 1 C to obtain an initial discharge capacity of −20 ° C.
<High temperature charge storage test>
Next, this laminate type battery was charged to a final voltage of 4.35 V for 3 hours with a constant current and constant voltage of 1 C in a constant temperature bath at 65 ° C., and was stored for 7 days while being held at 4.35 V. Then, it was put in a thermostat at 25 ° C., and was discharged to a final voltage of 2.75 V under a constant current of 1 C.
<Discharge capacity after high temperature charge storage>
Thereafter, the discharge capacity at −20 ° C. after high-temperature (65 ° C.) charge storage was determined in the same manner as in the measurement of the initial discharge capacity.
<-20 ° C discharge capacity maintenance rate after high temperature (65 ° C) charge storage>
The −20 ° C. discharge capacity retention rate after high-temperature charge storage was determined by the following equation.
-20 ° C discharge capacity retention rate (%) after high temperature charge storage = (−20 ° C discharge capacity after high temperature charge storage / initial -20 ° C discharge capacity) × 100
Further, the production conditions of the battery and the battery characteristics are shown in Tables 1 to 3.

Example 25 and Comparative Example 3
A positive electrode sheet was produced using lithium nickel manganate (LiNi _1/2 Mn _3/2 O ₄ , positive electrode active material) in place of the positive electrode active material used in Example 1 and Comparative Example 1.
94% by mass of LiNi _1/2 Mn _3/2 O ₄ coated with amorphous carbon and 3% by mass of acetylene black (conductive agent) are mixed, and 3% by mass of polyvinylidene fluoride (binding agent) is mixed in advance. The solution was added to a solution dissolved in methyl-2-pyrrolidone and mixed to prepare a positive electrode mixture paste. This positive electrode material mixture paste was applied on one side of an aluminum foil (current collector), dried, pressurized and cut into a predetermined size to prepare a positive electrode sheet, and the charge termination voltage at the time of battery evaluation. A laminate type battery was produced in the same manner as in Example 4 and Comparative Example 1 except that the discharge termination voltage was set to 2.7 V, and the battery evaluation was performed. The results are shown in Table 4.

Examples 26, 27 and Comparative Example 4
A negative electrode sheet was produced using lithium titanate (Li ₄ Ti ₅ O ₁₂ , a negative electrode active material) in place of the negative electrode active material used in Example 4 and Comparative Example 1.
80% by mass of lithium titanate and 15% by mass of acetylene black (conductive agent) are mixed, and 5% by mass of polyvinylidene fluoride (binder) is added to a solution previously dissolved in 1-methyl-2-pyrrolidone The mixture was mixed to prepare a negative electrode mixture paste. The negative electrode material mixture paste was applied to one side of a copper foil (current collector), dried, pressurized and cut into a predetermined size to prepare a negative electrode sheet, and the charge termination voltage at the time of battery evaluation. In the same manner as in Example 1 and Comparative Example 1, except that the voltage of the discharge was 2.8 V and the discharge end voltage was 1.2 V, and the composition of the non-aqueous electrolyte was changed to a predetermined one, a laminate type battery was produced. The battery was evaluated. The results are shown in Table 5.

In each of the lithium secondary batteries of Examples 1 to 24 above, the compounds described in Comparative Example 1 and Patent Document 1 when the compound represented by General Formula (I) is not added to the non-aqueous electrolyte of the present invention The high temperature cycle characteristics and the high temperature, high voltage storage characteristics are improved as compared with the lithium secondary battery of Comparative Example 2 in the case of adding. From the above, it can be seen that the effect of using the electricity storage device of the present invention at a high voltage is an effect unique to the case where the compound represented by general formula (I) is contained in the non-aqueous electrolyte.
Further, from the comparison of Example 25 and Comparative Example 3, the same applies to the case where lithium titanate is used for the negative electrode and the case where lithium titanate is used for the negative electrode from the comparison of Examples 26 to 27 and Comparative Example 4 Effect is seen.
Therefore, it is clear that the effect of the present invention is not dependent on a specific positive electrode or negative electrode.

Furthermore, the non-aqueous electrolyte of the present invention also has the effect of improving the discharge characteristics of the lithium primary battery in a wide temperature range.

By using the non-aqueous electrolytic solution of the present invention, it is possible to obtain an electricity storage device having excellent electrochemical characteristics in a wide temperature range. In particular, when used as a non-aqueous electrolyte for storage devices such as lithium secondary batteries mounted in hybrid electric vehicles, plug-in hybrid electric vehicles, battery electric vehicles, etc., the electric storage devices whose electrochemical characteristics are unlikely to deteriorate over a wide temperature range You can get
In addition, the novel compounds of the present invention, due to their special structures, are generally used as materials for electrolyte applications, heat resistant applications, etc. in the fields of general chemistry, in particular in the fields of organic chemistry, electrochemistry, biochemistry and polymer chemistry. Are useful as intermediate materials such as electronic materials and polymer materials, or as battery materials.

Claims

A non-aqueous electrolytic solution in which an electrolyte salt is dissolved in a non-aqueous solvent, and containing a (2-oxo-1,3-dioxolan-4-yl) oxy compound represented by the following general formula (I) Non-aqueous electrolyte characterized by

(Wherein, R 1 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms , An aralkyl group having 7 to 13 carbon atoms, an aryl group having 6 to 12 carbon atoms, -OC (= O) -R 4 , -OS (= O) 2 -R 5 , or -OP (= O) (-R 6 ) -R 7 R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3.
R 4 represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, It represents an aryl group having 6 to 12 carbon atoms or an alkoxycarbonyl group having 2 to 6 carbon atoms. R 5 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or 7 to 13 carbon atoms It represents an aralkyl group, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R 6 and R 7 each independently represent a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms.
When n is 1, L 1 represents -C (= O) -R 4 , -S (= O) 2 -R 5 , or -P (= O) (-R 6 ) -R 7 and n When L is 2, L 1 represents -C (= O) C (= O)-, -S (= O) 2- , or -P (= O) (-R 6 )-, and n is 3 , L 1 represents -P (= O) (-) 2 .
In addition, at least one hydrogen atom of the alkyl group, the aralkyl group, the aryl group, the alkoxycarbonyl group, the alkoxy group, and the aryloxy group may be substituted by a halogen atom. )
The compound represented by the general formula (I) is 2-oxo-1,3-dioxolan-4-yl acetate, 2-oxo-1,3-dioxolan-4-yl 2,2,2-trifluoroacetate, 2-oxo-1,3-dioxolan-4-yl acrylate, 2-oxo-1,3-dioxolan-4-yl methacrylate, methyl (2-oxo-1,3-dioxolan-4-yl) oxalate, ethyl ( 2-oxo-1,3-dioxolan-4-yl) oxalate, bis (2-oxo-1,3-dioxolan-4-yl) oxalate, 2-oxo-1,3-dioxolan-4-yl sulfolofluor Date, 2-oxo-1,3-dioxolan-4-yl methanesulfonate, 2-oxo-1,3-dioxolan-4-yl trif Oromethane sulfonate, 2-oxo-1,3-dioxolan-4-yl ethene sulfonate, methyl (2-oxo-1,3-dioxolan-4-yl) sulfate, 5-fluoro-2-oxo-1,3- Dioxolan-4-yl methanesulfonate, 5-methyl-2-oxo-1,3-dioxolan-4-yl methanesulfonate, 2-oxo-1,3-dioxolane-4,5-diyl dimethanesulfonate, bis (2 -Oxo-1,3-dioxolan-4-yl) sulfate, 2-oxo-1,3-dioxolan-4-yl phosphorodifluoridate, dimethyl (2-oxo-1,3-dioxolan-4-yl) phosphate And diethyl (2-oxo-1,3-dioxolan-4-yl) phosphate Non-aqueous electrolyte according to claim 1 is at least one selected.
The non-aqueous electrolytic solution according to claim 1 or 2, wherein the non-aqueous solvent comprises cyclic carbonate and linear ester.
One or at least one cyclic carbonate selected from the group consisting of ethylene carbonate, propylene carbonate, 4-fluoro-1,3-dioxolan-2-one, vinylene carbonate, and 4-ethynyl-1,3-dioxolan-2-one The non-aqueous electrolyte according to claim 3, comprising two or more.
The non-aqueous electrolytic solution according to claim 3, comprising both symmetrical linear carbonate and asymmetric linear carbonate as the linear ester, wherein the symmetrical linear carbonate is contained more than the asymmetric linear carbonate.
One or more asymmetric linear carbonates selected from the group consisting of methyl ethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, methyl butyl carbonate, and ethyl propyl carbonate; 1 or 2 types of symmetrical linear carbonates selected from the group consisting of propyl carbonate and dibutyl carbonate; methyl pivalate, ethyl pivalate, propyl pivalate, methyl propionate, ethyl propionate, propyl propionate, methyl acetate The non-aqueous electrolytic solution according to claim 3, comprising one or more selected from one or more chain carboxylic acid esters selected from the group consisting of and ethyl acetate.
Furthermore, 2,2,2-trifluoroethyl acetate, 2,2-difluoroethyl acetate, methyl 2,2,2-trifluoropropionate, methyl (2,2-difluoroethyl) carbonate, methyl (2,2,2 The non-aqueous electrolytic solution according to claim 6, comprising one or more selected from the group consisting of 2-tolyloroethyl) carbonate and ethyl (2,2,2-tolyloroethyl) carbonate.
Furthermore, it includes one or more lithium salts selected from the group consisting of lithium salts having an oxalic acid structure, lithium salts having a phosphoric acid structure, and lithium salts having an S = O group, and the total content thereof is 0. The non-aqueous electrolytic solution according to any one of claims 1 to 7, which is at least 001 mol / L and at most 0.5 mol / L.
Lithium salt is lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium tetrafluoro (oxalato) phosphate, lithium difluorobis (oxalato) phosphate, lithium difluorophosphate, lithium trifluoro ((methanesulfonyl) oxy) borate, 8. The method according to claim 8, wherein one or more selected from the group consisting of lithium methyl sulfate, lithium ethyl sulfate, lithium 2,2,2-trifluoroethyl sulfate, lithium fluorosulfate, and lithium bis (fluorosulfonyl) imide. Nonaqueous electrolyte as described in.
Electrolyte salt, LiPF 6, LiBF 4, LiPO 2 F 2, LiN (SO 2 F) 2, LiN (SO 2 CF 3) 2, and LiN (SO 2 C 2 F 5 ) 1 kind or 2 selected from 2 The non-aqueous electrolyte according to any one of claims 1 to 9, which is at least a species.
The non-aqueous electrolyte according to any one of claims 1 to 10, which is for a storage device.
A storage device comprising a positive electrode, a negative electrode, and a non-aqueous electrolytic solution in which an electrolyte salt is dissolved in a non-aqueous solvent, wherein the non-aqueous electrolytic solution is the non-aqueous electrolytic solution according to claim 1. Storage device.
The positive electrode is selected from the group consisting of iron, cobalt, nickel and manganese, and a composite metal oxide with lithium containing one or more selected from the group consisting of cobalt, manganese and nickel as a positive electrode active material The electricity storage device according to claim 12, comprising a lithium-containing olivine-type phosphate containing one or more of the following.
The negative electrode is selected from the group consisting of lithium metal, lithium alloy, a carbon material capable of inserting and extracting lithium ions as a negative electrode active material, tin, a tin compound, silicon, a silicon compound, and a lithium titanate compound 1 The electricity storage device according to claim 12, comprising a species or two or more species.
(2-Oxo-1,3-dioxolan-4-yl) oxy compound represented by the following general formula (II).

(Wherein, R 8 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms , An aralkyl group having 7 to 13 carbon atoms, an aryl group having 6 to 12 carbon atoms, -OC (= O) -R 9 , -OS (= O) 2 -R 5 , or -OP (= O) (-R 6 ) -R 7 R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3.
R 5 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or 7 to 13 carbon atoms It represents an aralkyl group, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R 6 and R 7 each independently represent a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms. R 9 represents a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or 7 to 13 carbon atoms in which at least one hydrogen atom is substituted by a halogen atom And an aralkyl group, an aryl group having 6 to 12 carbon atoms, or an alkoxycarbonyl group having 2 to 6 carbon atoms.
When n is 1, L 2 represents —C (= O) —R 9 , —S (= O) 2 —R 5 , or —P (= O) (— R 6 ) —R 7 and n When L is 2, L 2 represents -C (= O) C (= O)-, -S (= O) 2- , or -P (= O) (-R 6 )-, and n is 3 , L 2 represents -P (= O) (-) 2 .
In addition, at least one hydrogen atom of the alkyl group, the aralkyl group, the aryl group, the alkoxycarbonyl group, the alkoxy group, and the aryloxy group may be substituted by a halogen atom. )