TW201620192A - Non-aqueous electrolyte and non-aqueous electrolyte secondary cell - Google Patents

Abstract

The present invention provides a non-aqueous electrolyte having excellent overcharge prevention performance and being capable of maintaining low internal resistance and high electrical capacitance even after charging and discharging, and a non-aqueous electrolyte secondary cell in which the non-aqueous electrolyte is used. In particular, the present invention provides: a non-aqueous electrolyte in which a lithium salt is dissolved in an organic solvent, wherein the non-aqueous electrolyte is characterized by containing at least one compound represented by formula (1); and a non-aqueous electrolyte secondary cell in which the non-aqueous electrolyte is used. Formula (1) is described in detail in the description.

Description

Nonaqueous electrolyte and nonaqueous electrolyte secondary battery

The present invention relates to a nonaqueous electrolyte secondary battery, and more particularly to a nonaqueous electrolyte secondary battery comprising a nonaqueous electrolyte containing a specific compound.

A non-aqueous electrolyte secondary battery having a high voltage and a high energy density has been widely used as a power source with the spread of portable electronic devices such as portable computers, hand-held video cameras, and information terminals in recent years. Further, from the viewpoint of environmental issues, the utility model is being put into practical use of a battery car or a hybrid electric vehicle that uses electric power as a part of power.

In the nonaqueous electrolyte secondary battery, in order to improve the stability or electrical characteristics of the nonaqueous electrolyte secondary battery, various additives for the nonaqueous electrolyte are proposed. As such an additive, 1,3-propane sultone (for example, refer to Patent Document 1), vinyl ethylene carbonate (for example, see Patent Document 2), and ethylene carbonate (for example, refer to Patent Document 3), , 3-propane sultone, butane sultone (for example, refer to Patent Document 4), carbonic acid carbonate (for example, refer to Patent Document 5), vinyl ethylene carbonate (for example, see Patent Document 6), and the like. Carbonated vinyl ester is widely used because of its large effect. It is considered that these additives form a stable film called SEI (Solid Electrolyte Interface) on the surface of the anode, and the film covers the surface of the anode, thereby suppressing reductive decomposition of the electrolytic solution.

In the non-aqueous electrolyte secondary battery, if an excessive current is supplied due to an erroneous operation or the like, the battery is charged more than a specific voltage, and this phenomenon is called overcharging. Since the safety of the nonaqueous electrolyte secondary battery is remarkably lowered due to the excessively charged state, it is necessary to provide a mechanism for blocking the charging current when the specific voltage is exceeded. As a blocking charge One of the mechanisms of electric current uses an overcharge inhibitor such as cyclohexylbenzene. The overcharge inhibitor blocks the configuration of the current by generating a gas when the secondary battery reaches the voltage of the overcharged region and sensing the pressure sensor of the battery.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. SHO 63-102173

Patent Document 2: Japanese Patent Laid-Open No. Hei 4-87156

Patent Document 3: Japanese Patent Laid-Open No. Hei 5-74486

Patent Document 4: Japanese Patent Laid-Open No. Hei 10-50342

Patent Document 5: U.S. Patent No. 5,627,981

Patent Document 6: US Patent No. 6919145

Therefore, an object of the present invention is to provide a nonaqueous electrolyte which is excellent in overcharge suppression ability and which can maintain a small internal resistance and high capacitance even after charge and discharge, and a nonaqueous electrolyte secondary battery using the same.

The inventors of the present invention conducted intensive studies and found that the above object can be attained by using a nonaqueous electrolytic solution containing a compound having a specific structure, thereby completing the present invention.

In other words, the present invention provides a non-aqueous electrolyte solution obtained by dissolving a lithium salt in an organic solvent, and characterized in that it contains at least one compound represented by the following formula (1).

(wherein Ar represents a benzene ring or a naphthalene ring, and Z represents R ¹ OS(=O) ₂ -, R ¹² -S(=O) ₂ -, R ¹ OS(=O)- or R ¹² -S(= O)-, R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ² represents a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group or a mercapto group. , -SiR ⁹ R ¹⁰ R ¹¹ , a phosphoric acid group, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ¹² represents a halogen atom or a substituted or unsubstituted carbon atom number 1 to 20 a hydrocarbon group, a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group, a methyl group, a -SiR ⁹ R ¹⁰ substituted with a hydrocarbon group represented by R ¹ , R ² and R ¹² R ¹¹ or a phosphoric acid group, the alkylene group in the hydrocarbon group represented by R ¹ , R ² and R ¹² may also be through -O-, -CO-, -OCO-, -COO-, -O-CO-O-, -NR-, -S-, -SO-, -SO ₂ -, -NR-CO- or -CO-NR- is interrupted 1 to 3 times under non-adjacent conditions, and R represents a carbon number of 1 to 5 An aliphatic hydrocarbon group, in the case where R ² represents a hydrocarbon group, the site where R ² and Ar are bonded may also be through -O-, -CO-, -OCO-, -COO-, -O-CO-O-, -NR -, -S-, -NR-CO-, -C O-NR- or -N=interrupt, R ⁹ , R ¹⁰ and R ¹¹ represent a hydrocarbon group having 1 to 16 carbon atoms, and m and n each represent an integer of 1 or more, and when Ar represents a benzene ring, m+n 6 or less, when Ar represents a naphthalene ring, m+n is 10 or less, and when m is 2 or more, Z may be the same or different, and when n is 2 or more, R ² may be the same. Differentiating; wherein at least one of n R ² is a group represented by the following formula (2) or (3);

(wherein R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrocarbon group having a substituent or an unsubstituted carbon number of 1 to 18, and are represented by R ³ , R ⁴ , R ⁵ and R ⁶ The substituent to be substituted by a hydrocarbon group is a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group, a decyl group, a fluorenyl group, a -SiR ⁹ R ¹⁰ R ¹¹ or a phosphate group, and R ³ and R ⁴ The alkylene group in the hydrocarbon group represented by R ⁵ and R ⁶ may also be through -O-, -CO-, -OCO-, -COO-, -O-CO-O-, -NR-, -S-, -SO-, -SO ₂ -, -NR-CO- or -CO-NR- is interrupted 1~3 times under non-adjacent conditions, R represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ⁷ and R ⁸ independently represents a hydrogen atom, a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group, a decyl group, a fluorenyl group, a -SiR ⁹ R ¹⁰ R ¹¹ or a phosphate group, and R ⁹ and R ¹⁰ and R ¹¹ each independently represent a hydrocarbon group having 1 to 16 carbon atoms, wherein the general formulae (2) and (3) are in the range of 3 to 20 in terms of the total amount of the base).

Moreover, the present invention provides a nonaqueous electrolyte secondary battery comprising an anode capable of deintercalating lithium, a cathode containing a transition metal and lithium, and a nonaqueous electrolyte obtained by dissolving a lithium salt in an organic solvent. A nonaqueous electrolyte secondary battery characterized in that the nonaqueous electrolytic solution is the nonaqueous electrolytic solution described above.

Further, the present invention provides a compound represented by the following formula (1'),

(wherein Ar' represents a benzene ring or a naphthalene ring, and Z' represents R ^{1 '} OS(=O) ₂ -, R ^12' -S(=O) ₂ -, R ^{1 '} OS(=O)- or R ^12' -S(=O)-, R ^{1 '} represents a hydrocarbon group having 1 to 20 carbon atoms having a substituent, and R ^{2 '} represents a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group. , a mercapto group, -SiR ^9' R ^10' R ^{11 '} , a phosphate group, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ^12' represents a halogen atom or a carbon atom having a substituent a hydrocarbon group of 1 to 20, a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group, and a methyl group substituted for the hydrocarbon group represented by R ^{1 '} , R ^{2 '} and R ^{12 '} a group, -SiR ^9' R ^10' R ^{11 '} or a phosphate group, and the alkylene group in the hydrocarbon group represented by R ^{1 '} , R ^{2 '} and R ^{12 '} may also be -O-, -CO-, -OCO- , -COO-, -O-CO-O-, -NR'-, -S-, -SO-, -SO ₂ -, -NR'-CO- or -CO-NR'- in non-adjacent conditions The lower one is interrupted 1~3 times, and R' represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. When R ^{2 '} represents a hydrocarbon group, the portion where R ^{2 '} and Ar' are bonded may also pass through -O-, -CO. -, -OCO-, -COO-, -O-CO-O-, -NR'-, -S-, -NR'-CO-, -C O-NR'- or -N=interrupt, R ^9' , R ^10' and R ^{11 '} represent a hydrocarbon group having 1 to 16 carbon atoms, m' and n' each represent an integer of 1 or more, and Ar' represents a benzene ring. In the case of case, m'+n' is 6 or less, and when Ar' represents a naphthalene ring, m'+n' is 10 or less, and when m' is 2 or more, Z' may be the same or different. When n' is 2 or more, R ^{2 '} may be the same or different; when 2 or more, R ^{2 '} may be the same or different; wherein at least one of n' R ^{2 '} is lower a group represented by the formula (2') or (3');

(wherein R ^{3 '} , R ^{4 '} , R ^{5 '} and R ^{6 '} each independently represent a hydrocarbon group having a substituent or an unsubstituted carbon number of 1 to 18, for R ^{3 '} , R ^{4 '} , R ^a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group, a decyl group, a fluorenyl group, a -SiR ^9' R ^10' R substituted with a hydrocarbon group represented by ^5' and R ^{6' 11'} or a phosphate group, the alkyl group in the hydrocarbon group represented by R ^{3 '} , R ^{4 '} , R ^{5 '} and R ^{6 '} may also be through -O-, -CO-, -OCO-, -COO-, - O-CO-O-, -NR'-, -S-, -SO-, -SO ₂ -, -NR'-CO- or -CO-NR'- interrupt 1~3 times under non-adjacent conditions R' represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ^7' and R ^8' each independently represent a hydrogen atom, a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group, or a group An anthracenyl group, a fluorenyl group, a -SiR ^9' R ^{10 '} R ^{11 '} or a phosphate group, and R ^{9 '} , R ^{10 '} and R ^{11 '} each independently represent a hydrocarbon group having 1 to 16 carbon atoms, wherein the formula (2) ') and (3') are based on the total number of bases and the number of carbon atoms is in the range of 3 to 20.

According to the present invention, it is possible to provide a non-aqueous electrolyte which is excellent in overcharge inhibition ability by using a non-aqueous electrolyte solution containing a compound having a specific structure, and which can maintain a small internal resistance and a high capacitance even after charge and discharge. battery.

1‧‧‧ cathode

1a‧‧‧Cathode current collector

2‧‧‧Anode

2a‧‧‧Anode current collector

3‧‧‧ electrolyte

4‧‧‧ cathode casing

5‧‧‧Anode housing

6‧‧‧shims

7‧‧‧Separator

10‧‧‧Coin-type non-aqueous electrolyte secondary battery

10'‧‧‧Cylinder non-aqueous electrolyte secondary battery

11‧‧‧Anode

12‧‧‧Anode current collector

13‧‧‧ cathode

14‧‧‧ Cathode current collector

15‧‧‧ electrolyte

16‧‧‧Separator

17‧‧‧cathode terminal

18‧‧‧Anode terminal

19‧‧‧Anode plate

20‧‧‧Anode lead

21‧‧‧ cathode

22‧‧‧Cathode lead

23‧‧‧ housing

24‧‧‧Insulation board

25‧‧‧shims

26‧‧‧Safety valve

27‧‧‧PTC components

Fig. 1 is a longitudinal cross-sectional view showing an example of a structure of a coin battery of a nonaqueous electrolyte secondary battery of the present invention.

Fig. 2 is a schematic view showing a basic configuration of a cylindrical battery of the nonaqueous electrolyte secondary battery of the present invention.

Fig. 3 is a perspective view showing the internal structure of a cylindrical battery of the nonaqueous electrolyte secondary battery of the present invention in the form of a cross section.

Hereinafter, the nonaqueous electrolyte and the nonaqueous electrolyte secondary battery of the present invention are based on The preferred embodiment will be described in detail.

<Non-aqueous electrolyte>

The nonaqueous electrolytic solution (hereinafter also referred to as the nonaqueous electrolytic solution of the present invention) obtained by dissolving a lithium salt in an organic solvent used in the present invention will be described. The nonaqueous electrolytic solution of the present invention contains the compound represented by the above formula (1). Hereinafter, the compound will be described.

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , R ² and R ¹² in the formula (1) include saturated and unsaturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and carbon atoms. 6 to 20 aromatic hydrocarbon groups. Examples of the saturated and unsaturated hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 2-propynyl group, a butyl group, an isobutyl group, and a second butyl group. a saturated hydrocarbon group such as tributyl, pentyl, isopentyl, second pentyl, hexyl, 2-ethylhexyl, decyl, dodecyl, octadecyl, or the like, or a vinyl group, an ethynyl group, an allyl group An unsaturated hydrocarbon group such as a propargyl group, a 3-butenyl group, an isobutenyl group, a 3-butynyl group, a 4-pentenyl group or a 5-hexenyl group. Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, a cyclohexylphenyl group, a biphenyl group, a fluorenyl group, a 2'-phenyl-propylphenyl group, a benzyl group, and a naphthylmethyl group. Wait.

The alkyl group in the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , R ² and R ¹² (including the portion bonded to Ar in the case of R ² ) may also be subjected to -O-, -CO- , -OCO-, -COO-, -O-CO-O-, -NR-, -S-, -SO-, -SO ₂ -, -NR-CO-, -CO, -NR- or -N= It is interrupted 1 to 3 times under the condition of not adjacent, and R is an aliphatic hydrocarbon group having 1 to 5 carbon atoms.

In the case where the interrupted group contains a carbon atom, the number of carbon atoms including the number of carbon atoms in the interrupted group is 1 to 20.

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms in R include a saturated and unsaturated aliphatic hydrocarbon group having 1 to 5 carbon atoms in the description of R ¹ .

a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group, a mercapto group, a group substituted with a hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , R ² and R ¹² SiR ⁹ R ¹⁰ R ¹¹ or a phosphoric acid group, and R ⁹ , R ¹⁰ and R ¹¹ are a hydrocarbon group having 1 to 16 carbon atoms. Further, when the group to be substituted is a group containing a carbon atom, the number of carbon atoms including the number of carbon atoms to be substituted is 1 to 20.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Furthermore, all of the halogen atoms in this specification are identical thereto.

Examples of the aliphatic hydrocarbon group having 1 to 16 carbon atoms represented by R ⁹ , R ¹⁰ and R ¹¹ include the same groups as those having 1 to 16 carbon atoms in the description of R ¹ .

At least one of the n R ² in the formula (1) is a group represented by the above formula (2) or (3).

The hydrocarbon group having 1 to 18 carbon atoms represented by R ³ , R ⁴ , R ⁵ and R ⁶ in the formula (2) or (3), and the number of carbon atoms in the one described by R ¹ are 1 ~18 are the same base.

The alkylene group in the hydrocarbon group having 1 to 18 carbon atoms represented by R ³ , R ⁴ , R ⁵ and R ⁶ may also be through -O-, -CO-, -OCO-, -COO-, -O-CO. -O-, -NR-, -S-, -SO-, -SO ₂ -, -NR-CO-, -CO or -NR- is interrupted 1 to 3 times under non-adjacent conditions, R is a carbon atom An aliphatic hydrocarbon group of 1 to 5 carbon atoms.

In the case where the interrupted group contains a carbon atom, the number of carbon atoms including the number of carbon atoms in the interrupted group is 1 to 18.

a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group, a formazan group substituted with a hydrocarbon group having 1 to 18 carbon atoms represented by R ³ , R ⁴ , R ⁵ and R ⁶ a group, a fluorenyl group, a -SiR ⁹ R ¹⁰ R ¹¹ or a phosphate group, and R ⁹ , R ¹⁰ and R ¹¹ are a hydrocarbon group having 1 to 16 carbon atoms. Further, when the group to be substituted is a group containing a carbon atom, the number of carbon atoms including the number of carbon atoms to be substituted is 1 to 16.

In the general formula (1), examples of the substitution number and the substitution position of Z and R ² for Ar are as described in the following #1 to #7.

Further, in # 1 to # 7, when R ² in the general formula (2) or (3) the group represented by the set R ^2A, and in addition to the group R ^2B, reflected Z, R Examples of the number of substitutions and substitution positions of ^2A and R ^2B for Ar include the following #8 to #17.

[化2C]

In the compound represented by the above formula (1), at least one of the n R ² groups is a compound represented by the formula (2), and particularly, an isopropyl group, a second butyl group, and a second pentylene group. The compound is excellent as an overcharge inhibitor and is therefore preferred.

Further, preferred examples of the group (R ^2B ) other than the general formulae (2) and (3) in R ² include a halogen atom, an ester group, and a decylamino group.

Further, as Z, in the case where Z is R ¹ OS(=O) ₂ - or R ¹ OS(=O)-, R ¹ is a saturated or unsubstituted carbon atom number 1 to 6 saturated with a halogen atom. Or an unsaturated aliphatic hydrocarbon group (methyl, ethyl, propyl, isopropyl, 2-propynyl, butyl, isobutyl, t-butyl, tert-butyl, pentyl, isopentyl) , a second amyl, hexyl, vinyl, ethynyl, allyl, propargyl, 3-butenyl, isobutenyl, 3-butynyl, 4-pentenyl, 5-hexenyl or the Preferably, one of the groups is substituted by a halogen atom, etc., and in the case where Z is R ¹² -S(=O) ₂ - or R ¹² -S(=O)-, R ¹² is halogen. A saturated or unsaturated aliphatic hydrocarbon group having 1 to 6 carbon atoms (methyl, ethyl, propyl, isopropyl, 2-propynyl, butyl, iso) substituted or unsubstituted by a halogen atom. Butyl, t-butyl, tert-butyl, pentyl, isopentyl, second pentyl, hexyl, vinyl, ethynyl, allyl, propargyl, 3-butenyl, isobutenyl, 3-butynyl, 4-pentenyl, 5-hexenyl or a part of such a group taken through a halogen atom From, etc.) are preferred.

Specific examples of the compound represented by the above formula (1) include the compounds No. 1 to 23, but the present invention is not limited to these compounds.

[Chemical 3]

[Chemical 4]

The compound represented by the above formula (1) can be produced by sulfonating and esterifying an aromatic compound having a substituent.

In the non-aqueous electrolyte solution of the present invention, the compound represented by the above formula (1) may be used alone or in combination of two or more.

Further, in the non-aqueous electrolyte solution of the present invention, when the content of the compound represented by the above formula (1) is too small, sufficient effects cannot be exhibited, and in the case of too much, not only the amount of the compound is not commensurate with the compounding amount. The amount of the compound represented by the formula (1) is preferably 0.001 to 10% by mass in the non-aqueous electrolyte solution, and the amount of the compound represented by the formula (1) is preferably 0.001 to 10% by mass. Preferably, it is 0.01 to 8 mass%, and most preferably 0.1 to 5 mass%.

As the organic solvent to be used in the non-aqueous electrolyte solution of the present invention, one type or a combination of two or more types of the non-aqueous electrolyte solution can be used. Specifically, it can be cited as: saturation a cyclic carbonate compound, a saturated cyclic ester compound, an anthracene compound, an anthracene compound, a guanamine compound, a saturated chain carbonate compound, a chain ether compound, a cyclic ether compound, a saturated chain ester compound, and the like.

Among the above organic solvents, the saturated cyclic carbonate compound, the saturated cyclic ester compound, the sulfonium compound, the ruthenium compound, and the guanamine compound have a high relative dielectric constant, so that the dielectric constant of the nonaqueous electrolyte is increased. Particularly preferred is a saturated cyclic carbonate compound. Examples of such a saturated cyclic carbonate compound include ethylene carbonate, 1-fluoroethylene carbonate, 1,2-propylene diester, 1,3-propane carbonate, and carbonic acid. 1,2-butyl diester, 1,3-butyl dicarbonate, 1,1,-dimethylethylene carbonate, and the like. Examples of the saturated cyclic ester compound include γ-butyrolactone, γ-valerolactone, γ-caprolactone, δ-caprolactone, and δ-octanolactone. Examples of the above-mentioned fluorene compound include dimethyl hydrazine, diethyl hydrazine, dipropyl fluorene, diphenyl hydrazine, thiophene and the like. Examples of the hydrazine compound include dimethyl hydrazine, diethyl hydrazine, dipropyl hydrazine, diphenyl hydrazine, cyclobutyl hydrazine (also known as tetramethylene fluorene), and 3-methylcyclobutyl hydrazine. 3,4-Dimethylcyclobutanthene, 3,4-diphenylmethylcyclobutanthene, cyclobutenyl, 3-methylcyclobutene, 3-ethylcyclobutene, 3-bromo The cyclobutene oxime or the like is preferably cyclobutyl fluorene or tetramethylcyclobutyl fluorene. Examples of the above guanamine compound include N-methylpyrrolidone, dimethylformamide, and dimethylacetamide.

Among the above organic solvents, the saturated chain carbonate compound, the chain ether compound, the cyclic ether compound, and the saturated chain ester compound can reduce the viscosity of the nonaqueous electrolyte, and can improve the mobility of the electrolyte ions, etc., and can output density. The battery characteristics are excellent. Further, since it has a low viscosity, the performance of the nonaqueous electrolytic solution at a low temperature can be improved. Among them, a saturated chain carbonate compound is preferred. Examples of such a saturated chain carbonate compound include dimethyl carbonate (DMC, Dimethyl Carbonate), ethyl methyl carbonate (EMC, Ethyl Methyl Carbonate), and diethyl carbonate (DEC, Diethyl Carbonate). Ethyl butyl carbonate, methyl tertiary butyl carbonate, diisopropyl carbonate, t-butyl propyl carbonate, and the like. Examples of the chain ether compound or the cyclic ether compound include dimethoxyethane (DME), ethoxymethoxyethane, diethoxyethane, tetrahydrofuran, and dioxolane. ,two Alkane, 1,2-bis(methoxycarbonyloxy)ethane, 1,2-bis(ethoxycarbonyloxy)ethane, 1,2-bis(ethoxycarbonyloxy)propane, B Diol (trifluoroethyl)ether, propylene glycol bis(trifluoroethyl)ether, ethylene glycol bis(trifluoromethyl)ether, diethylene glycol bis(trifluoroethyl)ether, etc. Among them, dioxolane is preferred.

The saturated chain ester compound is preferably a monoester compound or a diester compound having a total carbon number of 2 to 8 in the molecule, and specific examples of the compound include methyl formate, ethyl formate, and methyl acetate. , ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethylacetate, trimethylacetic acid Ethyl ester, methyl malonate, ethyl malonate, methyl succinate, ethyl succinate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethylene glycol Diethyl hydrazine, propylene glycol diethyl hydrazine, etc., preferably methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, methyl propionate, and propionic acid Ethyl ester.

In addition to this, as the organic solvent, acetonitrile, propionitrile, nitromethane or the like can also be used.

As the lithium salt used in the nonaqueous electrolytic solution of the present invention, a previously known lithium salt can be used, and examples thereof include LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , and LiN (CF _{3 ).} SO ₂ ) ₂ , LiC(CF ₃ SO ₂ ) ₃ , LiB(CF ₃ SO ₃ ) ₄ , LiB(C ₂ O ₄ ) ₂ , LiBF ₂ (C ₂ O ₄ ), LiSbF ₆ , LiSiF ₅ , LiAlF ₄ , LiSCN, LiClO ₄ , LiCl, LiF, LiBr, LiI, LiAlF ₄ , LiAlCl ₄ , and derivatives thereof, among these, selected from LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiCF ₃ SO _{When one} or more of LiC(CF ₃ SO ₂ ) ₃ and a derivative of LiCF ₃ SO ₃ and a derivative of LiC(CF ₃ SO ₂ ) ₃ are used, the electrical properties are excellent. Preferably.

The lithium salt is preferably dissolved in the organic solvent in such a manner that the concentration in the nonaqueous electrolytic solution of the present invention is 0.1 to 3.0 mol/L, particularly 0.5 to 2.0 mol/L. If the lithium When the concentration of the salt is less than 0.1 mol/L, a sufficient current density may not be obtained, and if it is more than 3.0 mol/L, the stability of the nonaqueous electrolyte may be impaired. The lithium salt may be used in combination of two or more kinds of lithium salts.

The effect of adding the compound represented by the above formula (1) is an excessive charge suppression effect, but another excess charge inhibitor may be further added to the nonaqueous electrolyte of the present invention. Examples of the overcharge inhibitor include biphenyl, alkylbiphenyl, terphenyl, a partial hydride of terphenyl, cyclohexylbenzene, tert-butylbenzene, third amylbenzene, diphenyl ether, and An aromatic compound such as benzofuran; a partial fluoride of the above aromatic compound such as 2-fluorobiphenyl, o-cyclohexylfluorobenzene or p-cyclohexylfluorobenzene; 2,4-difluoroanisole, 2,5-di A fluorine-containing anisole compound such as fluoroanisole, 2,6-difluoroanisole or 3,5-difluoroanisole. Among them, preferred are biphenyl, alkylbiphenyl, terphenyl, diphenyl partial hydrogen, cyclohexylbenzene, tert-butylbenzene, third amylbenzene, diphenyl ether, dibenzofuran, and the like. Aromatic compound.

Further, a compound represented by the following formula (4) can also be preferably used.

(wherein R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrile group, a nitro group, An amine group, a carboxyl group, a hydroxyl group, a thiol group, a decyl group, a fluorenyl group, a -SiR ²⁹ R ³⁰ R ³¹ or a phosphate group, and an alkyl group in the group of an aliphatic hydrocarbon group having 1 to 20 carbon atoms (also included The benzene ring-bonded moiety can also be via -O-, -CO-, -OCO-, -COO-, -O-CO-O-, -NR ^a -, -S-, -SO-, -SO ₂ -, -NR ^a -CO- or -CO-NR ^a - is interrupted 1 to 3 times under non-adjacent conditions, R ^a represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ in the at least one represented by at least one carbon atom of a halogen atom, an aliphatic having 1 to 20 of the hydrocarbon group, R ²⁸ represents a p base ^{price, R 26, R 27, R} 29, R 30 and R ³¹ independently represents a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and p represents an integer of 1 to 3 ).

The aliphatic hydrocarbon group having 1 to 20 carbon atoms and the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ²¹ to R ²⁷ and R ²⁹ to R ³¹ in the above formula (4), and R ^a Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include the same groups as those described in the above formula (1).

Further, the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ²¹ to R ²⁶ and R ²⁹ to R ³¹ and the carbon number represented by R ²⁶ , R ²⁷ , R ²⁹ , R ³⁰ and R ³¹ are 6 The group in which the aromatic hydrocarbon group of -20 is substituted may be the same as those described in the above formula (1).

Specific examples of the compound represented by the above formula (4) include the following 4-1 to 4-4, but are not limited thereto.

In the case of adding another overcharge inhibitor, the amount thereof is not particularly limited, and is preferably from 1 to 500 parts by mass based on 100 parts by mass of the compound represented by the above formula (1).

Further, in order to impart flame retardancy, a halogen-based, phosphorus-based, and other flame retardant may be appropriately added to the non-aqueous electrolyte solution of the present invention. When the amount of the flame retardant added is too small, sufficient flame retarding effect cannot be exhibited, and in the case of too much, not only the incremental effect commensurate with the blending amount is obtained, but also the non-aqueous electrolyte is present. When the characteristics are adversely affected, the organic solvent constituting the nonaqueous electrolytic solution of the present invention is preferably from 1 to 50% by mass, and more preferably from 3 to 10% by mass.

The non-aqueous electrolyte of the present invention can also be used as a non-aqueous electrolyte of any one of a primary battery or a secondary battery, but is used as a non-aqueous electrolyte secondary battery constituting the present invention, particularly lithium ion two. The non-aqueous electrolyte of the secondary battery exerts the above effects.

<Non-aqueous electrolyte secondary battery>

The non-aqueous electrolyte secondary battery of the present invention comprises a lithium-decomposable anode, a cathode containing a transition metal and lithium, and a non-aqueous electrolyte obtained by dissolving a lithium salt in an organic solvent, and using the present invention The nonaqueous electrolyte is used as the nonaqueous electrolyte.

<anode>

The lithium capable of being detached from the anode used in the present invention is not particularly limited as long as lithium can be detached from the insertion, and is preferably as follows. In other words, the anode of the nonaqueous electrolyte secondary battery of the present invention can be obtained by applying a slurry of an anode active material and a binder by an organic solvent or water to a current collector and drying it. Those who are in the form of flakes may be provided with a conductive material as needed.

As the anode active material, natural graphite, artificial graphite, non-graphitizable carbon, easily graphitizable carbon, lithium, a lithium alloy, a tin alloy, a ruthenium alloy, ruthenium oxide, titanium oxide or the like can be used, but it is not limited thereto.

Examples of the binder for the anode include polyvinylidene fluoride and polytetrafluoroethylene. Ethylene, EPDM (Ethylene-Propylene-Diene Monomer, ethylene-propylene-diene terpolymer rubber), SBR (Styrene-Butadiene Rubber, styrene-butadiene rubber), NBR (nitrile butadiene rubber, nitrile rubber) , fluororubber, polyacrylic acid, etc., but is not limited to these. The amount of the binder to be used for the anode is preferably 0.001 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, even more preferably 0.01 to 2 parts by mass, per 100 parts by mass of the anode active material.

Examples of the solvent for slurrying of the anode include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, and acrylic acid. Methyl ester, diethyltriamine, N,N-dimethylaminopropylamine, polyethylene oxide, tetrahydrofuran, etc., but is not limited thereto. The amount of the solvent used is preferably 30 to 300 parts by mass, and more preferably 50 to 200 parts by mass, per 100 parts by mass of the anode active material.

Among the current collectors of the anode, copper, nickel, stainless steel, nickel-plated steel, or the like is usually used.

In addition, as the conductive material to be blended as needed, carbon black such as graphene or graphite, carbon black such as acetylene black or ketjen black, fine carbon particles such as needle coke, and the like, carbon nanofibers, etc. may be used, but Limited to these.

<cathode>

As a cathode containing a transition metal and lithium used in the present invention, similarly to a normal secondary battery, a slurry of a cathode active material, a binder, a conductive material, or the like by an organic solvent or water can be used. It is obtained by coating on a current collector and drying it to form a sheet. The cathode active material contains a transition metal and lithium, and preferably contains one type of transition metal and lithium. Examples thereof include a lithium transition metal composite oxide and a transition metal phosphate compound containing lithium, and these may be used in combination. . The transition metal of the lithium transition metal composite oxide is preferably vanadium, titanium, chromium, manganese, iron, cobalt, nickel, copper or the like. Specific examples of the lithium transition metal composite oxide include lithium cobalt composite oxide such as LiCoO ₂ , lithium nickel composite oxide such as LiNiO _{2 ,} and lithium manganese composite oxide such as LiMnO ₂ , LiMn ₂ O ₄ , and Li ₂ MnO ₃ . One part of the transition metal atom which becomes the main body of the lithium transition metal composite oxide is replaced by other metals such as aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, lithium, nickel, copper, zinc, magnesium, gallium, zirconium and the like. The winner and so on. Specific examples of the substituted composition include LiNi _0.5 Mn _0.5 O ₂ , LiNi _0.80 Co _0.17 Al _0.03 O ₂ , LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , and LiMn _1.8 Al _0.2 O. ₄ , LiMn _1.5 Ni _0.5 O ₄ and the like. The transition metal of the lithium-containing transition metal phosphate compound is preferably vanadium, titanium, manganese, iron, cobalt or nickel. Specific examples thereof include iron phosphates such as LiFePO ₄ and cobalt phosphates such as LiCoPO ₄ . One part of the transition metal atom which becomes the main body of the lithium transition metal phosphate compound is made of other metals such as aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, lithium, nickel, copper, zinc, magnesium, gallium, zirconium, hafnium and the like. Replace the founder and so on.

The binder as a cathode and the solvent for slurrying are the same as those of the above-mentioned anode. The amount of the binder to be used for the cathode is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, even more preferably 0.02 to 8 parts by mass, per 100 parts by mass of the cathode active material. The amount of the solvent used for the cathode is preferably 30 to 300 parts by mass, and more preferably 50 to 200 parts by mass, per 100 parts by mass of the cathode active material.

As the conductive material of the cathode, carbon black such as graphene or graphite, carbon black such as acetylene black or ketjen black, fine carbon particles such as needle coke, or the like, carbon nanofiber or the like can be used, but it is not limited thereto. . The amount of the conductive material used for the cathode is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the cathode active material.

As the current collector of the cathode, aluminum, stainless steel, nickel-plated steel or the like can be usually used.

In the non-aqueous electrolyte secondary battery of the present invention, a separator is preferably used between the cathode and the anode, and as the separator, a microporous membrane of a polymer which is generally used can be used without particular limitation. Examples of the film include a film containing polyethylene, polypropylene, polyvinylidene fluoride, polyvinylidene chloride, polyacrylonitrile, polypropylene decylamine, polytetrafluoroethylene, polyfluorene, and the like. Polyethers such as polyether oxime, polycarbonate, polyamide, polyamidiene, polyethylene oxide or polypropylene oxide, various celluloses such as carboxymethyl cellulose or hydroxypropyl cellulose, and poly Polymerization of (meth)acrylic acid and various esters thereof as a main component Or a derivative thereof, a copolymer or mixture of such. These films may be used singly or in the form of a multi-layer film by overlapping the films. Further, various additives may be used in the films, and the kind or content thereof is not particularly limited. Among the above-mentioned films, in the nonaqueous electrolyte secondary battery of the present invention, a film comprising polyethylene or polypropylene, polyvinylidene fluoride or polyfluorene can be preferably used.

These membranes are microporous in such a manner that the electrolyte penetrates and the ions are permeable. The method of the microporation includes a "phase separation method" in which a film is formed by microphase separation of a solution of a polymer compound and a solvent, and a solvent is extracted and removed, and a high draw ratio is obtained. After the molten polymer compound is extruded into a film and then heat-treated, the crystals are arranged in one direction, and a gap is formed between the crystals by stretching to realize a "stretching method" of porosification, and can be appropriately selected depending on the film to be used. .

In the non-aqueous electrolyte secondary battery of the present invention, a phenol-based antioxidant, a phosphorus-based antioxidant, or a thioether may be added to the cathode material, the non-aqueous electrolyte solution, and the separator to further improve safety. It is an antioxidant, a hindered amine compound, and the like.

The non-aqueous electrolyte secondary battery of the present invention having the above-described configuration is not particularly limited in shape, and can be formed into various shapes such as a coin shape, a cylindrical shape, and an angular shape. Fig. 1 is a view showing an example of a coin battery of the nonaqueous electrolyte secondary battery of the present invention, and Figs. 2 and 3 show an example of a cylindrical battery.

In the coin-type nonaqueous electrolyte secondary battery 10 shown in FIG. 1, 1 is a cathode capable of releasing lithium ions, 1a is a cathode current collector, and 2 is a lithium ion containing a storable and liberated release from the cathode. The anode of the carbonaceous material, 2a is the anode current collector, 3 is the non-aqueous electrolyte of the present invention, 4 is the cathode casing of stainless steel, 5 is the anode casing of stainless steel, 6 is the gasket of polypropylene, 7 is Polyethylene separator.

Further, in the cylindrical nonaqueous electrolyte secondary battery 10' shown in Figs. 2 and 3, 11 is an anode, 12 is an anode current collector, 13 is a cathode, 14 is a cathode current collector, and 15 is a Inventive non-aqueous electrolyte, 16 is a separator, 17 is a cathode terminal, 18 is an anode terminal, and 19 is an anode Plate, 20 is anode lead, 21 is cathode plate, 22 is cathode lead, 23 is housing, 24 is insulating plate, 25 is gasket, 26 is safety valve, 27 is PTC (Positive Temperature Coefficient) component .

<new compound>

The novel compound of the present invention is represented by the formula (1'), and in the compound represented by the formula (1) described in the above item of the "nonaqueous electrolyte", Z(Z') is R ¹ OS(=O) ₂ -, R ¹² -S(=O) ₂ -, R ¹ OS(=O)- or R ¹² -S(=O)- and R ¹ (R ^{1 '} ) is a substituent A hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms or a substituent having R ¹² (R ^{12 '} ) as a halogen atom or a substituent may belong to the novel compound.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ^{1 '} and R ^{12 '} may be exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ and R ¹² .

Further, a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group, a decyl group, a -SiR ^9' R ¹⁰ substituted with a hydrocarbon group represented by R ^{1 '} and R ^{12 ' '} R ^11' or phosphate group.

Formula (1 ') in the Ar' in the general formula (1) in the same Ar, Formula (1 ') in the R ^1' in the general formula (1), the R ^{1 'the} same as the general formula (1'R' is the same as R in the formula (1), and R ^9' , R ^10' and R ^11' in the formula (1') are respectively R ⁹ and R ¹⁰ in the formula (1) R ^{11 is the} same, and m' and n' in the formula (1') are the same as m and n in the formula (1), respectively.

It can be produced by the same method as the compound represented by the above formula (1).

Further, the novel compound of the present invention can be used for applications such as a surfactant and a precursor thereof in addition to the use as an additive for the above nonaqueous electrolyte.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. However, the present invention is not limited by the following examples and the like. In addition, the "parts" or "%" in the examples are based on the quality unless otherwise specified.

The following Synthesis Examples 1 to 3 are represented by the general formula (1) used in the nonaqueous electrolytic solution of the present invention. A synthetic example of a compound.

[Synthesis Example 1] Synthesis of Compound No. 9

Sodium hydride (3.20 g, 80.0 mmol) was added to the flask, dried under reduced pressure, and then replaced with argon gas. 20.0 mL of tetrahydrofuran was added, and 2-propanol (6.12 mL, 80.0 mmol) and 5.00 mL of tetrahydrofuran were slowly added dropwise under ice-cooling. Then, 2,4,6-triisopropylbenzenesulfonium chloride (9.692 g, 32.0 mmol) and 20.0 mL of tetrahydrofuran were added dropwise under ice cooling, and the mixture was stirred at room temperature for 3 hours. Next, 40.0 mL of distilled water and 40.0 mL of ethyl acetate were added to carry out oil-water separation, and further washed with 40.0 mL of distilled water twice. Anhydrous sodium sulfate was added to the obtained organic layer, filtered, and evaporated. The crude product was isolated by a medium pressure column (developing solvent, ethyl acetate:hexane = 19:1) to afford 6.77 g (yield 67.7%) of white solid. It was confirmed by ¹ H-NMR and IR that the obtained solid was a target. The data is shown in [Table 1].

[Synthesis Example 2] Synthesis of Compound No. 22

2,4,6-triisopropylbenzenesulfonium chloride (4.12 g, 13.6 mmol) was added to the flask, dried under reduced pressure, and then subjected to argon gas. 10.0 mL of tetrahydrofuran and triethylamine (4.74 mL, 34.0 mmol) were added, and 2,2,2-trifluoroethanol (2.43 mL, 34.0 mmol) was slowly added dropwise under ice-cooling. After stirring at 40 ° C for 1 hour and 30 minutes, 20.0 mL of distilled water and 20.0 mL of ethyl acetate were added to carry out oil-water separation, and further washed with 20.0 mL of distilled water twice. Anhydrous sodium sulfate was added to the obtained organic layer, filtered, and evaporated. The crude product was recrystallized (poor solvent, hexane) to afford 1.47 g (yield 29.3%) of white solid. It was confirmed by ¹ H-NMR and IR that the obtained solid was a target. The data is shown in [Table 1].

[Synthesis Example 3] Synthesis of Compound No. 23

2,4,6-triisopropylbenzenesulfonium chloride (5.30 g, 17.5 mmol), potassium fluoride (1.32 g, 22.8 mmol), 1, 4, 7, 10, 13, 16-six were added to the flask. Oxecyclooctadecane (0.25 g, 0.95 mmol) was dried under reduced pressure and then subjected to argon gas. 40.0 mL of acetonitrile was added and stirred overnight at room temperature. Next, 40 mL of distilled water was added to crystallize the solid. The obtained solid was separated by filtration to obtain a target of 4.05 g (yield: 81.0%) of white solid. It was confirmed by ¹ H-NMR and IR that the obtained solid was a target. The data is shown in [Table 1].

The following Example 1 and Comparative Examples 1 and 2 are examples of the nonaqueous electrolyte secondary battery of the present invention and comparative examples thereof.

[Examples 1 to 5 and Comparative Examples 1 and 2] Preparation and Evaluation of Nonaqueous Electrolyte Secondary Battery

In the examples and comparative examples, a nonaqueous electrolyte secondary battery (lithium secondary battery) was produced in the following production sequence.

<production order>

[Production of cathode]

90 parts by mass of LiMn ₂ O ₄ as an active material, 5 parts by mass of acetylene black as a conductive material, and 5 parts by mass of polyvinylidene fluoride (PVDF) as a binder, and then dispersed in The slurry was formed into 140 parts by mass of N-methyl-2-pyrrolidone (NMP, N-methyl-2-pyrrolidone). This slurry was applied onto an aluminum current collector, dried, and then subjected to press molding. Thereafter, the cathode was cut into a specific size to prepare a disk-shaped cathode.

[Production of anode]

97.0 parts by mass of artificial graphite as an active material, and 1.5 parts by mass of styrene butadiene rubber as a binder, and 1.5 parts by mass of carboxymethylcellulose as a tackifier, and dispersed in 120 parts by mass It is made into a slurry in water. This slurry was applied onto a copper negative electrode current collector, dried, and then subjected to press molding. Thereafter, the anode was cut into a specific size to prepare a disk-shaped anode.

[Preparation of electrolyte solution]

An electrolyte solution was prepared by dissolving LiPF ₆ at a concentration of 1 mol/L in a mixed solvent containing 30% by volume of ethylene carbonate, 40% by volume of methyl ethyl carbonate, and 30% by volume of dimethyl carbonate.

[Preparation of non-aqueous electrolyte]

The non-aqueous electrolyte solution of the present invention and the comparative non-aqueous electrolyte solution were prepared by dissolving the compound shown in [Table 1] as an electrolyte solution in the electrolyte solution at the stated ratio. Further, Comparative Compound 1 was cyclohexylbenzene and was produced by Tokyo Chemical Industry Co., Ltd.

Compound No. 4 was synthesized by referring to J. Chem. Soc., Perkin Trans. 1, 1980, (5), 1076-1079. Further, the number in ( ) in [Table 1] represents the concentration (% by mass) in the nonaqueous electrolytic solution.

[Battery assembly]

The obtained disk-shaped positive electrode and disk-shaped negative electrode were held in a casing via a polyethylene microporous film having a thickness of 25 μm. Thereafter, each of the non-aqueous electrolytes was injected into the casing, and the casing was sealed and sealed, and lithium secondary batteries (Φ20 mm and coin models having a thickness of 3.2 mm) of Examples 1 to 5 and Comparative Examples 1 and 2 were produced.

Using the lithium secondary batteries of Examples 1 to 5 and Comparative Examples 1 and 2, the initial discharge capacitance ratio and the overcharge resistance test were carried out by the following test methods. The results of these tests are shown in the following [Table 2]. In addition, the higher the discharge capacity ratio, the more excellent the initial characteristics of the nonaqueous electrolyte secondary battery, and the higher the value of the overcharge resistance, the more excellent the overcharge resistance.

<Discharge capacitance ratio test method>

The lithium secondary battery was placed in a thermostatic chamber at 20 ° C, and the following operation was performed 5 times: a constant current constant voltage charging was performed at a charging current of 0.3 mA/cm ² (corresponding to a current value of 0.2 C) up to 4.2 V to discharge A current of 0.3 mA/cm ² (corresponding to a current value of 0.2 C) was subjected to constant current discharge up to 3.0 V. Thereafter, a charging current of 0.3mA / cm ² constant current and voltage charge until 4.2V, at a discharge current of 0.3mA / cm ² constant current discharge until 3.0V. The discharge capacity measured in the sixth time was taken as the initial discharge capacitance of the battery, and the initial discharge capacity of Comparative Example 1 (without the addition of the electrolyte additive) was set to 100 to calculate the discharge-capacitance ratio (%). ).

Discharge-capacitance ratio (%) = [(initial discharge capacitance) / (initial discharge capacitance of Comparative Example 1)] × 100

<Overcharge resistance test>

The lithium secondary battery was placed in a thermostatic chamber at 20 ° C, and a constant current constant voltage charging was performed at a charging current of 0.3 mA/cm ² (corresponding to a current value of 0.2 C) until the capacitor was charged in an excessively charged state (5.5 V). (mAh/g). The capacitance of Comparative Example 1 (without adding an electrolyte additive) was calculated to be 100.

According to the above results, it is understood that the compound represented by the above formula (1) used in the nonaqueous electrolytic solution of the present invention can suppress the excess without lowering the battery characteristics (discharge capacity). The voltage rises during charging.

Claims (3)

A non-aqueous electrolyte solution obtained by dissolving a lithium salt in an organic solvent, characterized by containing at least one compound represented by the following formula (1), (wherein Ar represents a benzene ring or a naphthalene ring, and Z represents R ¹ OS(=O) ₂ -, R ¹² -S(=O) ₂ -, R ¹ OS(=O)- or R ¹² -S (= O)-, R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ² represents a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group or a mercapto group. , -SiR ⁹ R ¹⁰ R ¹¹ , a phosphoric acid group, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ¹² represents a halogen atom or a substituted or unsubstituted carbon atom number 1 to 20 a hydrocarbon group, a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group, a methyl group, a -SiR ⁹ R ¹⁰ substituted with a hydrocarbon group represented by R ¹ , R ² and R ¹² R ¹¹ or a phosphoric acid group, the alkylene group in the hydrocarbon group represented by R ¹ , R ² and R ¹² may also be through -O-, -CO-, -OCO-, -COO-, -O-CO-O-, -NR-, -S-, -SO-, -SO ₂ -, -NR-CO- or -CO-NR- is interrupted 1 to 3 times under non-adjacent conditions, and R represents a carbon number of 1 to 5 An aliphatic hydrocarbon group, in the case where R ² represents a hydrocarbon group, the site where R ² and Ar are bonded may also be through -O-, -CO-, -OCO-, -COO-, -O-CO-O-, -NR -, -S-, -NR-CO-, -CO -NR- or -N=interrupt, R ⁹ , R ¹⁰ and R ¹¹ represent a hydrocarbon group having 1 to 16 carbon atoms, and m and n each represent an integer of 1 or more, and when Ar represents a benzene ring, m+n is 6 or less, when Ar represents a naphthalene ring, m+n is 10 or less, and when m is 2 or more, Z may be the same or different, and when n is 2 or more, R ² may be the same or Different; wherein at least one of n R ² is a group represented by the following formula (2) or (3); (wherein R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrocarbon group having a substituent or an unsubstituted carbon number of 1 to 18, and are represented by R ³ , R ⁴ , R ⁵ and R ⁶ The substituent to be substituted by a hydrocarbon group is a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group, a decyl group, a fluorenyl group, a -SiR ⁹ R ¹⁰ R ¹¹ or a phosphate group, and R ³ and R ⁴ The alkylene group in the hydrocarbon group represented by R ⁵ and R ⁶ may also be through -O-, -CO-, -OCO-, -COO-, -O-CO-O-, -NR-, -S-, -SO-, -SO ₂ -, -NR-CO- or -CO-NR- is interrupted 1~3 times under non-adjacent conditions, R represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ⁷ and R ⁸ independently represents a hydrogen atom, a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group, a decyl group, a fluorenyl group, a -SiR ⁹ R ¹⁰ R ¹¹ or a phosphate group, and R ⁹ and R ¹⁰ and R ¹¹ each independently represent a hydrocarbon group having 1 to 16 carbon atoms, wherein the general formulae (2) and (3) are in the range of 3 to 20 in terms of the total amount of the base). A nonaqueous electrolyte secondary battery comprising: an anode capable of deintercalating lithium, a cathode containing a transition metal and lithium, and a nonaqueous electrolyte obtained by dissolving a lithium salt in an organic solvent, wherein: The nonaqueous electrolytic solution is the nonaqueous electrolytic solution of claim 1. a compound represented by the following formula (1'), (wherein Ar' represents a benzene ring or a naphthalene ring, and Z' represents R ^{1 '} OS(=O) ₂ -, R ^12' -S(=O) ₂ -, R ^{1 '} OS(=O)- or R ^12' -S(=O)-, R ^{1 '} represents a hydrocarbon group having 1 to 20 carbon atoms having a substituent, and R ^{2 '} represents a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group. , a mercapto group, -SiR ^9' R ^10' R ^{11 '} , a phosphate group, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ^12' represents a halogen atom or a carbon atom having a substituent a hydrocarbon group of 1 to 20, a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group, and a methyl group substituted for the hydrocarbon group represented by R ^{1 '} , R ^{2 '} and R ^{12 '} a group, -SiR ^9' R ^10' R ^{11 '} or a phosphate group, and the alkylene group in the hydrocarbon group represented by R ^{1 '} , R ^{2 '} and R ^{12 '} may also be -O-, -CO-, -OCO- , -COO-, -O-CO-O-, -NR'-, -S-, -SO-, -SO ₂ -, -NR'-CO- or -CO-NR'- in non-adjacent conditions The lower one is interrupted 1~3 times, and R' represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. When R ^{2 '} represents a hydrocarbon group, the portion where R ^{2 '} and Ar' are bonded may also pass through -O-, -CO. -, -OCO-, -COO-, -O-CO-O-, -NR'-, -S-, -NR'-CO-, -CO -NR'- or -N=interrupt, R ^9' , R ^10' and R ^{11 '} represent a hydrocarbon group having 1 to 16 carbon atoms, m' and n' each represent an integer of 1 or more, and Ar' represents a benzene ring. In the case where m'+n' is 6 or less, when Ar' represents a naphthalene ring, m'+n' is 10 or less, and when m' is 2 or more, Z' may be the same or different. When n' is 2 or more, R ^{2 '} may be the same or different; when 2 or more, R ^{2 '} may be the same or different; wherein at least one of n' R ^{2 '} is as follows a group represented by the formula (2') or (3')); (wherein R ^{3 '} , R ^{4 '} , R ^{5 '} and R ^{6 '} each independently represent a hydrocarbon group having a substituent or an unsubstituted carbon number of 1 to 18, for R ^{3 '} , R ^{4 '} , R ^a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group, a decyl group, a fluorenyl group, a -SiR ^9' R ^10' R substituted with a hydrocarbon group represented by ^5' and R ^{6' 11'} or a phosphate group, the alkylene group in the hydrocarbon group represented by R ^{3 '} , R ^{4 '} , R ^{5 '} and R ^{6 '} may also be -O-, -CO-, -OCO-, -COO-, - O-CO-O-, -NR'-, -S-, -SO-, -SO ₂ -, -NR'-CO- or -CO-NR'- non-adjacent conditions, interrupted 1~3 times, R' represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ^7' and R ^8' each independently represent a hydrogen atom, a halogen atom, a nitrile group, a nitro group, an amine group, a carboxyl group, a hydroxyl group, a thiol group, and a formazan group. a group, a fluorenyl group, a -SiR ^9' R ^10' R ^{11 '} or a phosphate group, and R ^{9 '} , R ^{10 '} and R ^{11 '} each independently represent a hydrocarbon group having 1 to 16 carbon atoms, wherein the formula (2' And (3') is based on the total number of bases and the number of carbon atoms is in the range of 3 to 20).