Nonaqueous electrolyte solution and nonaqueous electrolyte battery

Abstract

A nonaqueous electrolyte solution containing (I) a compound represented by general formula (1) set forth in the description, (II) at least one compound selected from the group consisting of compounds (2)-(5) set forth in the description, (III) a solute, and (IV) a nonaqueous organic solvent; and a nonaqueous electrolyte battery including the nonaqueous electrolyte solution.

Description

Non-aqueous electrolyte and non-aqueous electrolyte battery

[0001] The present disclosure relates to a non-aqueous electrolyte and a non-aqueous electrolyte battery.

[0002] In recent years, there has been a rapid increase in demand for high-capacity, high-power, and high-energy-density batteries that can be installed as auxiliary power sources for electric vehicles, hybrid vehicles, and fuel cell vehicles, as well as for energy storage systems for small, high-energy-density applications such as information-related devices and communication devices, i.e., personal computers, video cameras, digital cameras, mobile phones, and smartphones. There is also a growing demand for batteries that can be used for long periods of time in energy storage systems for large, power applications such as power storage. Non-aqueous electrolyte batteries, such as lithium secondary batteries, have been actively developed as candidates for these various energy storage systems. Non-aqueous electrolyte batteries typically include a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte.

[0003] Patent Document 1 proposes improving charge / discharge efficiency and cycle characteristics by using a sulfonic acid anhydride in an electrolyte. Patent Document 2 proposes improving cycle characteristics and low-temperature characteristics by using a silicon compound in an electrolyte. Patent Document 3 proposes improving storage characteristics by using a nonaqueous electrolyte containing lithium bisfluorosulfonylimide as a solute. Patent Document 4 proposes suppressing self-discharge and improving storage characteristics after charging by using lithium monofluorophosphate or lithium difluorophosphate in an electrolyte. Patent Document 5 proposes maintaining high input / output and impedance characteristics even after durability testing by using a nonaqueous electrolyte containing a fluorosulfonate. Patent Document 6 proposes suppressing decomposition on a carbon anode as charge / discharge cycles progress by using a nonaqueous electrolyte containing a cyclic sulfate.

[0004] Japanese Patent No. 4379567 Japanese Patent No. 3497812 Japanese Patent No. 4847675 Japanese Patent No. 3439085 Japanese Patent No. 5353923 Japanese Patent No. 3760540

[0005] As described above, Patent Document 1 proposes that the charge / discharge efficiency and cycle characteristics of a secondary battery be improved by using an electrolyte solution containing a sulfonic acid anhydride. However, the present inventors have found through their studies that the secondary battery described in Patent Document 1 has a problem in that it has high initial resistance.

[0006] The present disclosure has been made in view of the above circumstances, and aims to provide a nonaqueous electrolyte that can reduce the initial resistance of a nonaqueous electrolyte battery, and a nonaqueous electrolyte battery with low initial resistance.

[0007] As a result of extensive research to solve these problems, the present inventors have found that a nonaqueous electrolyte battery with low initial resistance can be provided by incorporating a specific sulfonic acid anhydride and a specific compound into a nonaqueous electrolyte solution containing a nonaqueous organic solvent and a solute. Specifically, the above problems can be solved by the following configuration.

[0008] [1] A non-aqueous electrolyte solution containing: (I) a compound represented by the following general formula (1); (II) at least one compound selected from the group consisting of the following compounds (2) to (5); (III) a solute; and (IV) a non-aqueous organic solvent.

[0009]

[0010] In general formula (1), R １ represents an alkylene group having 1 to 6 carbon atoms. An oxygen atom may be contained between the carbon atom-carbon atom bond in the alkylene group. Any hydrogen atom in the alkylene group may be substituted with a halogen atom. Compound (2): At least one compound selected from the group consisting of compounds represented by the following general formula (2-A), compounds represented by the following general formula (2-B), and compounds represented by the following general formula (2-C):

[0011]

[0012] In general formula (2-A), R ２１ and R ２２each independently represents an organic group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, or a fluorine atom. Any hydrogen atom in the organic group may be substituted with a fluorine atom. An oxygen atom may be contained between the carbon atom-carbon atom bond in the organic group. M １ ｍ＋ is a proton, a metal cation, or an onium cation. m represents the valence of the corresponding cation. However, the compound represented by general formula (2-A) contains at least one P—F bond. In general formula (2-B), X ２１ represents an organic group selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, cycloalkenyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkenyloxy groups having 2 to 10 carbon atoms, alkynyloxy groups having 2 to 10 carbon atoms, cycloalkoxy groups having 3 to 10 carbon atoms, cycloalkenyloxy groups having 3 to 10 carbon atoms, and aryloxy groups having 6 to 10 carbon atoms, or a fluorine atom. Any hydrogen atom in the organic group may be substituted with a fluorine atom. An oxygen atom may be contained between the carbon atom-carbon atom bond in the organic group. However, the organic group contains at least one fluorine atom. M １ ｍ＋ is a proton, a metal cation, or an onium cation. m represents the valence of the corresponding cation. ２２ ~X ２５each independently represents an organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, or a fluorine atom. Any hydrogen atom in the organic group may be substituted with a fluorine atom. An oxygen atom may be contained between the carbon atom-carbon atom bond in the organic group. However, the organic group contains at least one fluorine atom. M １ ｍ＋ is a proton, a metal cation, or an onium cation. m represents the valence of the corresponding cation. However, the compound represented by general formula (2-C) contains at least one B—F bond. Compound (3): A compound represented by the following general formula (3).

[0013]

[0014] In general formula (3), R ３１ represents a group having a carbon-carbon unsaturated bond. ３１ may be the same or different. ３２ represents a fluorine atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may have at least one of a fluorine atom and an oxygen atom. ３２ If there are multiple R ３２ may be the same or different. v represents an integer of 2 to 4. Compound (4): A compound represented by the following general formula (4).

[0015]

[0016] In general formula (4), R ４１ and R ４２each independently represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Any hydrogen atom in the alkenyl group and the aryl group may be substituted with a halogen atom. n4 is 0 or 1. Compound (5): A compound represented by the following general formula (5).

[0017]

[0018] In general formula (5), R ５０ ~R ５３ each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. n51 represents an integer from 1 to 3. [2] The nonaqueous electrolyte solution according to [1], wherein the content of (I) relative to the total amount of the nonaqueous electrolyte solution is 0.01% by mass or more and 10% by mass or less. [3] The nonaqueous electrolyte solution according to [1] or [2], wherein the content of (II) relative to the total amount of the nonaqueous electrolyte solution is 0.01% by mass or more and 10% by mass or less. [4] The nonaqueous electrolyte solution according to any one of [1] to [3], wherein the compound represented by general formula (1) is at least one compound selected from the group consisting of 1,2-ethanedisulfonic acid anhydride and 1,3-propanedisulfonic acid anhydride. [5] The nonaqueous electrolyte solution according to any one of [1] to [4], wherein the compound (2) is at least one compound selected from the group consisting of lithium difluorophosphate, lithium fluorosulfonate, lithium trifluoromethanesulfonate, and lithium tetrafluoroborate. [6] The nonaqueous electrolyte solution according to any one of [1] to [5], wherein the compound (3) is at least one compound selected from the group consisting of trivinylmethylsilane, trivinylfluorosilane, and tetravinylsilane. [7] The nonaqueous electrolyte solution according to any one of [1] to [6], wherein the compound (4) is at least one compound selected from the group consisting of 1,3,2-dioxathiolane-2,2-dioxide and 1,3,2-dioxathiane-2,2-dioxide. [8] The nonaqueous electrolyte solution according to any one of [1] to [6], wherein the compound (III) is LiPF ６ , LiSbF ６ , LiAsF ６ , LiClO ４, LiN(CF ３ SO ２ ) ２ , LiN(FSO ２ ) ２ , LiN (POF ２ ) ２ , LiCF ３ SO ３ , LiC ４ F ９ SO ３ , LiAlO ２ , LiAlCl ４ , LiCl and LiI, or NaPF ６ , NaSbF ６ , NaAsF ６ , NaClO ４ , NaN(CF ３ SO ２ ) ２ , NaN(FSO ２ ) ２ , NaN(POF ２ ) ２ , NaCF ３ SO ３ , NaC ４ F ９ SO ３ , NaAlO ２ , NaAlCl ４The nonaqueous electrolyte solution according to any one of [1] to [7], wherein (IV) is at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds, and ionic liquids.

[10] The nonaqueous electrolyte solution according to [9], wherein the cyclic ester is a cyclic carbonate.

[11] The nonaqueous electrolyte solution according to

[10] , wherein the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate.

[12] The nonaqueous electrolyte solution according to [9], wherein the chain ester is a chain carbonate.

[13] The nonaqueous electrolyte solution according to

[12] , wherein the chain carbonate is at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.

[14] A nonaqueous electrolyte battery comprising at least a positive electrode, a negative electrode, a separator, and the nonaqueous electrolyte solution according to any one of [1] to

[13] .

[0019] According to the present disclosure, it is possible to provide a nonaqueous electrolyte that can reduce the initial resistance of a nonaqueous electrolyte battery, and a nonaqueous electrolyte battery with low initial resistance.

[0020] In this specification, the word "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0021] The present disclosure will be described in detail below, but the following description of the constituent elements is an example of an embodiment of the present disclosure, and the present disclosure is not limited to these specific contents.

[0022] 1. Regarding the Non-Aqueous Electrolyte The non-aqueous electrolyte of the present disclosure is a non-aqueous electrolyte containing: (I) a compound represented by the following general formula (1); (II) at least one compound selected from the group consisting of the following compounds (2) to (5); (III) a solute; and (IV) a non-aqueous organic solvent.

[0023]

[0024] In general formula (1), R １ represents an alkylene group having 1 to 6 carbon atoms. The alkylene group may contain an oxygen atom between the carbon atom-carbon atom bond. Any hydrogen atom in the alkylene group may be substituted with a halogen atom.

[0025] Compound (2): At least one compound selected from the group consisting of a compound represented by the following general formula (2-A), a compound represented by the following general formula (2-B), and a compound represented by the following general formula (2-C):

[0026]

[0027] In general formula (2-A), R ２１ and R ２２ each independently represents an organic group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, or a fluorine atom. Any hydrogen atom in the organic group may be substituted with a fluorine atom. An oxygen atom may be contained between the carbon atom-carbon atom bond in the organic group. M １ ｍ＋ is a proton, a metal cation, or an onium cation, and m represents the valence of the corresponding cation. However, the compound represented by general formula (2-A) contains at least one P—F bond.

[0028] In general formula (2-B), X ２１represents an organic group selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, cycloalkenyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkenyloxy groups having 2 to 10 carbon atoms, alkynyloxy groups having 2 to 10 carbon atoms, cycloalkoxy groups having 3 to 10 carbon atoms, cycloalkenyloxy groups having 3 to 10 carbon atoms, and aryloxy groups having 6 to 10 carbon atoms, or a fluorine atom. Any hydrogen atom in the organic group may be substituted with a fluorine atom. An oxygen atom may be contained between the carbon atom-carbon atom bond in the organic group. However, the organic group contains at least one fluorine atom. M １ ｍ＋ is a proton, a metal cation or an onium cation, and m represents the valence of the corresponding cation.

[0029] In general formula (2-C), X ２２ ~X ２５ each independently represents an organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, or a fluorine atom. Any hydrogen atom in the organic group may be substituted with a fluorine atom. An oxygen atom may be contained between the carbon atom-carbon atom bond in the organic group. However, the organic group contains at least one fluorine atom. M １ ｍ＋ is a proton, a metal cation, or an onium cation, and m represents the valence of the corresponding cation. However, the compound represented by general formula (2-C) contains at least one B—F bond.

[0030] Compound (3): A compound represented by the following general formula (3).

[0031]

[0032] In general formula (3), R ３１ represents a group having a carbon-carbon unsaturated bond. ３１ may be the same or different. ３２ represents a fluorine atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may have at least one of a fluorine atom and an oxygen atom. ３２ If there are multiple R ３２ may be the same or different, and v represents an integer of 2 to 4.

[0033] Compound (4): A compound represented by the following general formula (4).

[0034]

[0035] In general formula (4), R ４１ and R ４２ each independently represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Any hydrogen atom in the alkenyl group and the aryl group may be substituted with a halogen atom. n4 is 0 or 1.

[0036] Compound (5): A compound represented by the following general formula (5).

[0037]

[0038] In general formula (5), R ５０ ~R ５３ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. n51 represents an integer of 1 to 3.

[0039] (I) Compound Represented by General Formula (1) The compound (I) represented by general formula (1) (also referred to as "(I)") contained in the nonaqueous electrolyte solution of the present disclosure will be described. In general formula (1), R １ The alkylene group having 1 to 6 carbon atoms represented by the formula (R) may be linear or branched. １Examples of R include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, and an n-hexylene group. １ An oxygen atom may be contained between the carbon atom-carbon atom bond in the alkylene group having 1 to 6 carbon atoms represented by the formula: １ Any hydrogen atom in the alkylene group having 1 to 6 carbon atoms represented by the formula (R) may be substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.). １ preferably represents an alkylene group having 2 to 3 carbon atoms.

[0040] (I) is preferably at least one compound selected from the group consisting of 1,2-ethanedisulfonic anhydride and 1,3-propanedisulfonic anhydride.

[0041] In the nonaqueous electrolyte solution of the present disclosure, one type of compound may be used alone as (I), or two or more types of compounds may be mixed in any combination and ratio depending on the application.

[0042] The compound represented by formula (1) can be produced by various methods.

[0043] In the nonaqueous electrolyte solution of the present disclosure, the content of (I) (also referred to as the "concentration of (I)") relative to the total amount of the nonaqueous electrolyte solution may be 0.01% by mass or more and 10% by mass or less. The lower limit of the concentration of (I) may be 0.08% by mass or more, 0.3% by mass or more, or 0.8% by mass or more. The upper limit of the concentration of (I) may be 8% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, or 1.5% by mass or less.

[0044] (II) At least one compound selected from the group consisting of compounds (2) to (5) The nonaqueous electrolyte solution of the present disclosure contains (II) at least one compound selected from the group consisting of compounds (2) to (5) (also referred to as “(II)”).

[0045] Compound (2) is at least one compound selected from the group consisting of compounds represented by the following general formula (2-A), compounds represented by the following general formula (2-B), and compounds represented by the following general formula (2-C):

[0046]

[0047] In general formula (2-A), R ２１ and R ２２ each independently represents an organic group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, or a fluorine atom. Any hydrogen atom in the organic group may be substituted with a fluorine atom. An oxygen atom may be contained between the carbon atom-carbon atom bond in the organic group. M １ ｍ＋ is a proton, a metal cation, or an onium cation, and m represents the valence of the corresponding cation. However, the compound represented by general formula (2-A) contains at least one P—F bond.

[0048] In general formula (2-B), X ２１ represents an organic group selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, cycloalkenyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkenyloxy groups having 2 to 10 carbon atoms, alkynyloxy groups having 2 to 10 carbon atoms, cycloalkoxy groups having 3 to 10 carbon atoms, cycloalkenyloxy groups having 3 to 10 carbon atoms, and aryloxy groups having 6 to 10 carbon atoms, or a fluorine atom. Any hydrogen atom in the organic group may be substituted with a fluorine atom. An oxygen atom may be contained between the carbon atom-carbon atom bond in the organic group. However, the organic group contains at least one fluorine atom. M １ ｍ＋ is a proton, a metal cation or an onium cation, and m represents the valence of the corresponding cation.

[0049] In general formula (2-C), X ２２ ~X ２５ each independently represents an organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, or a fluorine atom. Any hydrogen atom in the organic group may be substituted with a fluorine atom. An oxygen atom may be contained between the carbon atom-carbon atom bond in the organic group. However, the organic group contains at least one fluorine atom. M １ ｍ＋ is a proton, a metal cation, or an onium cation, and m represents the valence of the corresponding cation. However, the compound represented by general formula (2-C) contains at least one B—F bond.

[0050] In general formula (2-A), R ２１ and R ２２ each independently represents an organic group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, or a fluorine atom. Any hydrogen atom in the organic group may be substituted with a fluorine atom. M １ ｍ＋ is a proton, a metal cation, or an onium cation. m represents the valence of the corresponding cation. However, the compound represented by general formula (2-A) contains at least one P—F bond. In general formula (2-B), X ２１represents an organic group selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, cycloalkenyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkenyloxy groups having 2 to 10 carbon atoms, alkynyloxy groups having 2 to 10 carbon atoms, cycloalkoxy groups having 3 to 10 carbon atoms, cycloalkenyloxy groups having 3 to 10 carbon atoms, and aryloxy groups having 6 to 10 carbon atoms, or a fluorine atom, provided that the organic group contains at least one fluorine atom. M １ ｍ＋ is a proton, a metal cation, or an onium cation. m represents the valence of the corresponding cation. ２２ ~X ２５ each independently represents an organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, or a fluorine atom, provided that the organic group contains at least one fluorine atom. １ ｍ＋ is a proton, a metal cation, or an onium cation, and m represents the valence of the corresponding cation. However, the compound represented by general formula (2-C) contains at least one B—F bond.

[0051] In general formula (2-A), R ２１ and R ２２The alkoxy group represented by the formula (I) may be linear or branched. Any hydrogen atom in the alkoxy group may be substituted with a fluorine atom. An oxygen atom may be contained between a carbon atom-carbon atom bond in the alkoxy group. Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms and fluorine-containing alkoxy groups, such as a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, trifluoromethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 1,1,1-trifluoroisopropoxy group, and 1,1,1,3,3,3-hexafluoroisopropoxy group.

[0052] R ２１ and R ２２ The alkenyloxy group represented by the formula (I) may be linear or branched. Any hydrogen atom in the alkenyloxy group may be substituted with a fluorine atom. An oxygen atom may be contained between the carbon-carbon bond in the alkenyloxy group. In addition to the carbon-carbon double bond, the alkenyloxy group may also have an unsaturated bond other than the carbon-carbon double bond. Examples of the alkenyloxy group include alkenyloxy groups having 2 to 10 carbon atoms, such as vinyloxy group, 1-propenyloxy group, 2-propenyloxy group, isopropenyloxy group, 2-butenyloxy group, 3-butenyloxy group, and 1,3-butadienyloxy group, as well as fluorine-containing alkenyloxy groups.

[0053] R ２１ and R ２２The alkynyloxy group represented by the formula (I) may be linear or branched. Any hydrogen atom in the alkynyloxy group may be substituted with a fluorine atom. An oxygen atom may be contained between the carbon-carbon bond in the alkynyloxy group. In addition to the carbon-carbon triple bond, the alkynyloxy group may also have an unsaturated bond other than the carbon-carbon triple bond. Examples of the alkynyloxy group include alkynyloxy groups having 2 to 10 carbon atoms, such as an ethynyloxy group, a 2-propynyloxy group, and a 1,1-dimethyl-2-propynyloxy group, as well as fluorine-containing alkynyloxy groups.

[0054] R ２１ and R ２２ Any hydrogen atom in the cycloalkoxy group represented by the formula (I) may be substituted with at least one of an alkyl group and a fluorine atom. An oxygen atom may be contained between the carbon atom-carbon atom bond in the cycloalkoxy group. Examples of the cycloalkoxy group include cycloalkoxy groups having 3 to 10 carbon atoms, such as a cyclopentyloxy group and a cyclohexyloxy group, and fluorine-containing cycloalkoxy groups.

[0055] R ２１ and R ２２ Any hydrogen atom in the cycloalkenyloxy group represented by the formula (I) may be substituted with at least one of an alkyl group and a fluorine atom. An oxygen atom may be contained between the carbon atom-carbon atom bond in the cycloalkenyloxy group. Examples of the cycloalkenyloxy group include cycloalkenyloxy groups having 3 to 10 carbon atoms, such as a cyclopentenyloxy group and a cyclohexenyloxy group, and fluorine-containing cycloalkenyloxy groups.

[0056] R ２１ and R ２２ Any hydrogen atom of the aryloxy group represented by the formula (I) may be substituted with at least one of an alkyl group and a fluorine atom. Examples of the aryloxy group include aryloxy groups having 6 to 10 carbon atoms, such as a phenyloxy group, a tolyloxy group, and a xylyloxy group, and fluorine-containing aryloxy groups.

[0057] However, the compound represented by the general formula (2-A) contains at least one P—F bond. ２１ and m R ２２ Preferably, at least one of represents a fluorine atom.

[0058] R ２１ and R ２２ are each independently a fluorine atom or an alkoxy group having a fluorine atom, since the strong electron-withdrawing property improves the degree of ionic dissociation, thereby increasing the ionic conductivity in a solution or a composition. ２１ and R ２２ When R is a fluorine atom, the anion size becomes small, which improves the mobility, resulting in a very high ionic conductivity in a solution or a composition, and this is more preferable. ２１ and R ２２ Each of the groups preferably has 6 or less carbon atoms. When the number of carbon atoms is 6 or less, the ionic conductivity tends to be relatively high, which is preferable.

[0059] In general formula (2-A), M １ ｍ＋ represents a proton, a metal cation, or an onium cation. There are no particular limitations on the type of the cation, and various cations can be selected from the above, as long as they do not impair the performance of the nonaqueous electrolyte and nonaqueous electrolyte battery of the present disclosure.

[0060] M １ ｍ＋ When M represents a metal cation, examples of the metal cation include alkali metal cations such as lithium ion, sodium ion, potassium ion, rubidium ion, and cesium ion, alkaline earth metal cations such as magnesium ion, calcium ion, and barium ion, silver ion, copper ion, and iron ion. １ ｍ＋ When represents an onium cation, examples of the onium cation include onium cations such as tetraalkylammonium, tetraalkylphosphonium, and imidazolium derivatives. m represents the valence of the corresponding cation, and may be 1 to 3, or may be 1 or 2.

[0061] M１ ｍ＋ In particular, from the viewpoint of helping ion conduction in a non-aqueous electrolyte battery, lithium ions, sodium ions, potassium ions, tetramethylammonium ions, tetraethylammonium ions, tetrabutylphosphonium ions, etc. are preferred. １ ｍ＋ When used in a lithium ion battery, the charge carrier is more preferably a lithium ion, and when used in a sodium ion battery, the charge carrier is more preferably a sodium ion.

[0062] Specific examples of the anion structure of the compound represented by formula (2-A) are shown below, but are not limited to these.

[0063]

[0064] In general formula (2-B), X ２１ The alkyl group represented by the formula (I) may be linear or branched. Any hydrogen atom in the alkyl group may be substituted with a fluorine atom. An oxygen atom may be contained between a carbon atom-carbon atom bond in the alkyl group. However, the alkyl group contains at least one fluorine atom. Examples of the alkyl group include fluorine-containing alkyl groups having 1 to 10 carbon atoms, such as a trifluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3-tetrafluoropropyl group, and a 1,1,1,3,3,3-hexafluoroisopropyl group.

[0065] X ２１ The alkenyl group represented by the formula (I) may be linear or branched. Any hydrogen atom in the alkenyl group may be substituted with a fluorine atom. An oxygen atom may be present between a carbon-carbon bond in the alkenyl group. In addition to the carbon-carbon double bond, the alkenyl group may also have an unsaturated bond other than the carbon-carbon double bond. However, the alkenyl group contains at least one fluorine atom.

[0066] X ２１The alkynyl group represented by the formula (I) may be linear or branched. Any hydrogen atom in the alkynyl group may be substituted with a fluorine atom. An oxygen atom may be present between the carbon-carbon bonds in the alkynyl group. In addition to the carbon-carbon triple bond, the alkynyl group may also have an unsaturated bond other than the carbon-carbon triple bond. However, the alkynyl group contains at least one fluorine atom.

[0067] X ２１ Any hydrogen atom in the cycloalkyl group represented by the formula (I) may be substituted with at least one of an alkyl group and a fluorine atom. The cycloalkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. However, the cycloalkyl group contains at least one fluorine atom.

[0068] X ２１ Any hydrogen atom in the cycloalkenyl group represented by the formula (I) may be substituted with at least one alkyl group or fluorine atom. The cycloalkenyl group may contain an oxygen atom between the carbon atom-carbon atom bond. However, the cycloalkenyl group contains at least one fluorine atom.

[0069] X ２１ Any hydrogen atom of the aryl group represented by the formula (I) may be substituted with at least one of an alkyl group and a fluorine atom, provided that the aryl group contains at least one fluorine atom.

[0070] X ２１ The alkoxy group represented by the formula (I) may be linear or branched. Any hydrogen atom in the alkoxy group may be substituted with a fluorine atom. An oxygen atom may be contained between the carbon atom-carbon atom bond in the alkoxy group. However, the alkoxy group contains at least one fluorine atom. Examples of the alkoxy group include fluorine-containing alkoxy groups having 1 to 10 carbon atoms, such as a trifluoromethoxy group, a 2,2-difluoroethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 1,1,1-trifluoroisopropoxy group, and a 1,1,1,3,3,3-hexafluoroisopropoxy group.

[0071] X ２１The alkenyloxy group represented by the formula (I) may be linear or branched. Any hydrogen atom in the alkenyloxy group may be substituted with a fluorine atom. An oxygen atom may be contained between the carbon-carbon bond in the alkenyloxy group. In addition to the carbon-carbon double bond, the alkenyloxy group may also contain an unsaturated bond other than the carbon-carbon double bond. However, the alkenyloxy group contains at least one fluorine atom.

[0072] X ２１ The alkynyloxy group represented by the formula (I) may be linear or branched. Any hydrogen atom in the alkynyloxy group may be substituted with a fluorine atom. An oxygen atom may be contained between the carbon-carbon bond in the alkynyloxy group. In addition to the carbon-carbon triple bond, the alkynyloxy group may also contain an unsaturated bond other than the carbon-carbon triple bond. However, the alkynyloxy group contains at least one fluorine atom.

[0073] X ２１ Any hydrogen atom in the cycloalkoxy group represented by the formula (I) may be substituted with at least one alkyl group or fluorine atom. The cycloalkoxy group may contain an oxygen atom between the carbon atom-carbon atom bond. However, the cycloalkoxy group contains at least one fluorine atom.

[0074] X ２１ Any hydrogen atom in the cycloalkenyloxy group represented by the formula (I) may be substituted with at least one alkyl group or fluorine atom. The cycloalkenyloxy group may contain an oxygen atom between the carbon atom-carbon atom bond. However, the cycloalkenyloxy group contains at least one fluorine atom.

[0075] X ２１ Any hydrogen atom of the aryloxy group represented by the formula (I) may be substituted with at least one of an alkyl group and a fluorine atom, provided that the aryloxy group contains at least one fluorine atom.

[0076] In general formula (2-B), X ２１When the group is an alkyl group or an alkoxy group, the internal resistance tends to be relatively small when a film is formed on an electrode, which is preferable.

[0077] In general formula (2-B), X ２１ When X is a fluorine atom, the degree of ionic dissociation is improved due to its strong electron-withdrawing property, and therefore the ionic conductivity in a solution or a composition is increased, which is preferable. ２１ When X is a fluorine atom, the anion size becomes small, which improves the mobility, resulting in a very high ionic conductivity in a solution or a composition, which is preferable. ２１ When the number of carbon atoms is 6 or less, the ionic conductivity tends to be relatively high, so it is preferable, the number of carbon atoms is more preferably 1 to 4, and the number of carbon atoms is still more preferably 1 to 3. Specific examples include a trifluoromethyl group, a trifluoromethoxy group, and a trifluoroethoxy group, and a trifluoromethyl group having a small anion size is particularly preferable.

[0078] M in general formula (2-B) １ ｍ＋ The explanation, specific examples and preferred ranges of m and m are respectively described in the above-mentioned formula (2-A) M １ ｍ＋ and the same for m.

[0079] Specific examples of the anion structure of the compound represented by formula (2-B) are shown below, but are not limited to these.

[0080]

[0081] X in general formula (2-C) ２２ ~X ２５ The explanation, specific examples and preferred ranges of X in the general formula (2-B) are as follows: ２１ It is the same as that for the X ２２ ~X ２５ is more preferably an alkyl group having a fluorine atom or a fluorine atom, and particularly preferably a fluorine atom. １ ｍ＋The explanation, specific examples and preferred ranges of m and m are respectively described in the above-mentioned formula (2-A) M １ ｍ＋ and the same for m.

[0082] Specific examples of the anion structure of the compound represented by formula (2-C) are shown below, but are not limited to these.

[0083]

[0084] Compound (2) is preferably at least one compound selected from the group consisting of difluorophosphates, fluorosulfonates, trifluoromethanesulfonates, and tetrafluoroborates, and more preferably at least one compound selected from the group consisting of lithium difluorophosphate, lithium fluorosulfonate, lithium trifluoromethanesulfonate, and lithium tetrafluoroborate.

[0085] The compound (3) is a compound represented by the following general formula (3).

[0086]

[0087] In general formula (3), R ３１ represents a group having a carbon-carbon unsaturated bond. ３１ may be the same or different. ３２ represents a fluorine atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may have at least one of a fluorine atom and an oxygen atom. ３２ If there are multiple R ３２ may be the same or different, and v represents an integer of 2 to 4.

[0088] R ３１Examples of the group having a carbon-carbon unsaturated bond represented by the formula (I) include alkenyl groups having 2 to 8 carbon atoms, such as vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, and 1,3-butadienyl, or alkenyloxy groups derived from these groups; alkynyl groups having 2 to 8 carbon atoms, such as ethynyl, 2-propynyl, and 1,1-dimethyl-2-propynyl, or alkynyloxy groups derived from these groups; and aryl groups having 6 to 12 carbon atoms, such as phenyl, tolyl, and xylyl, or aryloxy groups derived from these groups. The above groups may also contain fluorine atoms and oxygen atoms. Among these, groups containing a carbon-carbon unsaturated bond having 6 or less carbon atoms are preferred. When the number of carbon atoms is 6 or less, the resistance tends to be low when a film is formed on an electrode. R ３１ The group having a carbon-carbon unsaturated bond represented by the formula (I) is preferably a group selected from the group consisting of a vinyl group, an allyl group, a 1-propenyl group, an ethynyl group, and a 2-propynyl group.

[0089] R ３２ The alkyl group represented by the formula (I) may be linear or branched. Any hydrogen atom in the alkyl group may be substituted with a fluorine atom. An oxygen atom may be contained between a carbon atom-carbon atom bond in the alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, and a pentyl group. Furthermore, the above groups may have at least one of a fluorine atom and an oxygen atom.

[0090] R ３２ is a group selected from the group consisting of a fluorine atom, a methyl group, an ethyl group, a propyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,1-trifluoroisopropyl group, and a 1,1,1,3,3,3-hexafluoroisopropyl group, the initial resistance when a film is formed on an electrode tends to be smaller, and as a result, this is preferable from the viewpoint of output characteristics.

[0091] In formula (3), v represents an integer of 2 to 4, preferably 3 or 4, and particularly preferably 4.

[0092] Specific examples of the compound represented by formula (3) are shown below, but the invention is not limited to these.

[0093]

[0094] The compound (3) is preferably at least one compound selected from the group consisting of trivinylmethylsilane, trivinylfluorosilane, and tetravinylsilane.

[0095] The compound (4) is a compound represented by the following general formula (4).

[0096]

[0097] In general formula (4), R ４１ and R ４２ each independently represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Any hydrogen atom in the alkenyl group and the aryl group may be substituted with a halogen atom. n4 is 0 or 1.

[0098] R ４１ and R ４２ Examples of the alkyl group represented by R include a methyl group and an ethyl group. ４１ and R ４２ The alkenyl group represented by may be linear or branched. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, and a 1,3-butadienyl group. ４１ and R ４２ Any hydrogen atom of the aryl group represented by may be substituted with an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group.

[0099] At least one of the hydrogen atoms in the alkenyl group and aryl group may be substituted with a halogen atom, such as a fluorine atom, a bromine atom, or an iodine atom, with a fluorine atom being preferred.

[0100] R ４１ and R４２ preferably represents a hydrogen atom. When n4 is 0, R ４１ and the carbon atom to which R is bonded ４２ is bonded to the carbon atom to which it is bonded by a single bond.

[0101] The compound (4) is preferably at least one compound selected from the group consisting of 1,3,2-dioxathiolane-2,2-dioxide and 1,3,2-dioxathiane-2,2-dioxide.

[0102] Specific examples of the compound represented by formula (4) are shown below, but the invention is not limited to these.

[0103]

[0104] The compound (5) is a compound represented by the following general formula (5).

[0105]

[0106] In general formula (5), R ５０ ~R ５３ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. n51 represents an integer of 1 to 3.

[0107] In general formula (5), R ５０ ~R ５３ The alkyl group represented by the formula (I) may be linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a pentyl group.

[0108] R ５０ ~R ５３ The fluoroalkyl group represented by the formula (I) may be linear or branched. Examples of the fluoroalkyl group include a trifluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3-tetrafluoropropyl group, and a 1,1,1,3,3,3-hexafluoroisopropyl group.

[0109] R ５０ ~R５３ is preferably a hydrogen atom, a fluorine atom or a trifluoromethyl group, more preferably a hydrogen atom.

[0110] In the general formula (5), n51 represents an integer of 1 to 3, may be 1 or 2, and is preferably 1.

[0111] Examples of compound (5) include 1,3-propene sultone (1-propene-1,3-sultone), 1,4-butene sultone, 2,4-pentene sultone, 3,5-pentene sultone, 1-fluoro-1,3-propene sultone, 1-trifluoromethyl-1,3-propene sultone, 1,1,1-trifluoro-2,4-butene sultone, 1,4-butene sultone, and 1,5-pentene sultone.

[0112] Compound (5) is preferably 1-propene 1,3-sultone.

[0113] In the nonaqueous electrolyte solution of the present disclosure, as (II), one type of compound may be used alone, or two or more types of compounds may be mixed in any combination and in any ratio depending on the application.

[0114] In the nonaqueous electrolyte solution of the present disclosure, the content of (II) (also referred to as the "concentration of (II)") relative to the total amount of the nonaqueous electrolyte solution may be 0.01% by mass or more and 10% by mass or less. The lower limit of the concentration of (II) may be 0.08% by mass or more, 0.1% by mass or more, or 0.2% by mass or more. The upper limit of the concentration of (II) may be 8% by mass or less, 6% by mass or less, or 5% by mass or less.

[0115] (III) Solute The (III) solute (also referred to as "(III)") contained in the nonaqueous electrolyte solution of the present disclosure will be described. The (III) solute is not particularly limited, and may be, for example, LiPF ６ , LiSbF ６ , LiAsF ６ , LiClO ４ , LiN(CF ３ SO ２ ) ２ , LiN(FSO ２ ) ２, LiN (POF ２ ) ２ , LiCF ３ SO ３ , LiC ４ F ９ SO ３ , LiAlO ２ , LiAlCl ４ , LiCl and LiI, or NaPF ６ , NaSbF ６ , NaAsF ６ , NaClO ４ , NaN(CF ３ SO ２ ) ２ , NaN(FSO ２ ) ２ , NaN(POF ２ ) ２ , NaCF ３ SO ３ , NaC ４ F ９ SO ３ , NaAlO ２ , NaAlCl ４ , NaCl, and NaI.

[0116] In the nonaqueous electrolyte solution of the present disclosure, as (III), one type of compound may be used alone, or two or more types of compounds may be mixed in any combination and ratio depending on the application.

[0117] The concentration of (III) relative to the total amount of the nonaqueous electrolyte is not particularly limited. For example, the lower limit of the concentration of (III) may be 0.5 mol / L or more, 0.7 mol / L or more, or 0.9 mol / L or more. The upper limit of the concentration of (III) may be 2.5 mol / L or less, 2 mol / L or less, or 1.5 mol / L or less. When two or more types of (III) are used, it is preferable that the total concentration of these solutes is in the above-mentioned range.

[0118] The liquid temperature when (III) is dissolved in (IV) the nonaqueous organic solvent is not particularly limited, but may be from -20 to 80°C or from 0 to 60°C.

[0119] (IV) Non-aqueous Organic Solvent The non-aqueous organic solvent (IV) (also referred to as "(IV)") contained in the non-aqueous electrolyte solution of the present disclosure will be described. The type of non-aqueous organic solvent (IV) is not particularly limited, and any non-aqueous organic solvent can be used. Specific examples of the non-aqueous organic solvent (IV) include the following non-aqueous organic solvents. Examples of cyclic esters include cyclic carbonates such as propylene carbonate (hereinafter sometimes referred to as "PC"), ethylene carbonate (hereinafter sometimes referred to as "EC"), fluoroethylene carbonate (hereinafter sometimes referred to as "FEC"), and butylene carbonate, as well as γ-butyrolactone and γ-valerolactone. Note that when the content of the FEC relative to the total amount of the non-aqueous electrolyte solution is 10.0% by mass or less, it is defined as an "other additive" as described below. Examples of chain esters include chain carbonates such as diethyl carbonate (hereinafter sometimes referred to as "DEC"), dimethyl carbonate (hereinafter sometimes referred to as "DMC"), ethyl methyl carbonate (hereinafter sometimes referred to as "EMC"), and methyl propyl carbonate, as well as methyl acetate, methyl propionate, and ethyl propionate (hereinafter sometimes referred to as "EP"). Examples of cyclic ethers include tetrahydrofuran, 2-methyltetrahydrofuran, and dioxane. Examples of chain ethers include dimethoxyethane and diethyl ether. Other examples include sulfone compounds and sulfoxide compounds such as dimethyl sulfoxide and sulfolane. Ionic liquids and the like can also be used.

[0120] (IV) The nonaqueous organic solvent may contain at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds, and ionic liquids.

[0121] The cyclic ester is a cyclic carbonate, and the cyclic carbonate may be at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate.

[0122] The chain ester is a chain carbonate, and the chain carbonate may be at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.

[0123] In the nonaqueous electrolyte solution of the present disclosure, one type of compound may be used alone as (IV), or two or more types of compounds may be mixed in any combination and ratio depending on the application.

[0124] The content of the cyclic carbonate is not particularly limited and may be any content as long as it does not significantly impair the effects of the present disclosure. However, when one type is used alone, the content may be 3 vol% or more, more preferably 5 vol% or more, based on 100 vol% of the nonaqueous organic solvent. By setting the content within this range, a decrease in electrical conductivity due to a decrease in the dielectric constant of the nonaqueous electrolyte can be avoided, and the large-current discharge characteristics, stability with respect to the negative electrode, and cycle characteristics of the nonaqueous electrolyte battery can be easily maintained within good ranges. The content may also be 90 vol% or less, preferably 85 vol% or less, and more preferably 80 vol% or less. Setting the content within this range allows the viscosity of the nonaqueous electrolyte to be within an appropriate range, suppresses a decrease in ionic conductivity, and ultimately facilitates the load characteristics of the nonaqueous electrolyte battery to be easily maintained within good ranges.

[0125] Additionally, any combination of two or more cyclic carbonates can be used. One preferred combination is a combination of ethylene carbonate and propylene carbonate. In this case, the volume ratio of ethylene carbonate to propylene carbonate is preferably 99:1 to 40:60, and particularly preferably 95:5 to 50:50. Furthermore, the amount of propylene carbonate relative to the total nonaqueous organic solvent is not particularly limited and may be any amount as long as it does not significantly impair the effects of the present disclosure. However, it may be 1% by volume or more, preferably 2% by volume or more, more preferably 3% by volume or more, or 30% by volume or less, preferably 25% by volume or less, and more preferably 20% by volume or less. The inclusion of propylene carbonate within this range is preferred because it maintains the properties of the combination of ethylene carbonate and dialkyl carbonates while providing even more excellent low-temperature properties.

[0126] The chain ester may be used alone or in any combination and ratio of two or more. The content of the chain ester is not particularly limited, but may be 15% by volume or more, preferably 20% by volume or more, and more preferably 25% by volume or more, based on 100% by volume of the nonaqueous organic solvent. It may also be 90% by volume or less, preferably 85% by volume or less, and more preferably 80% by volume or less. By setting the content of the chain ester within the above range, the viscosity of the nonaqueous electrolyte can be set to an appropriate range, a decrease in ionic conductivity can be suppressed, and the input / output characteristics and charge / discharge rate characteristics of the nonaqueous electrolyte battery can be easily set to good ranges. Furthermore, a decrease in electrical conductivity due to a decrease in the dielectric constant of the nonaqueous electrolyte can be avoided, and the input / output characteristics and charge / discharge rate characteristics of the nonaqueous electrolyte battery can be easily set to good ranges. Furthermore, by combining a specific chain ester with a specific amount of ethylene carbonate, battery performance can be significantly improved.

[0127] For example, when dimethyl carbonate and ethyl methyl carbonate are selected as the specific chain esters, the content of ethylene carbonate is not particularly limited and may be any content as long as it does not significantly impair the effects of the present disclosure, but may be 5% by volume or more, preferably 10% by volume or more, or 45% by volume or less, preferably 40% by volume or less. The content of dimethyl carbonate may be 20% by volume or more, preferably 30% by volume or more, or 50% by volume or less, preferably 45% by volume or less. The content of ethyl methyl carbonate may be 20% by volume or more, preferably 30% by volume or more, or 50% by volume or less, preferably 45% by volume or less. By setting the content within the above range, the low-temperature deposition temperature of the electrolyte is lowered, while also reducing the viscosity of the nonaqueous electrolyte, improving ionic conductivity and allowing high input / output even at low temperatures.

[0128] The content of the chain ether is not particularly limited and may be any amount as long as it does not significantly impair the effects of the present disclosure. It may be 1% by volume or more, preferably 2% by volume or more, more preferably 3% by volume or more, or 30% by volume or less, preferably 25% by volume or less, more preferably 20% by volume or less, based on 100% by volume of the nonaqueous organic solvent. When the content of the chain ether is within the above range, it is easy to ensure the effect of improving the degree of lithium ion dissociation of the chain ether and improving ionic conductivity due to reduced viscosity. Furthermore, when the negative electrode active material is a carbonaceous material, the phenomenon of co-insertion of the chain ether with lithium ions can be suppressed, thereby allowing the input / output characteristics and charge / discharge rate characteristics to be within appropriate ranges.

[0129] The content of the sulfone compound is not particularly limited and may be any content as long as it does not significantly impair the effects of the present disclosure, but may be 0.3 vol% or more, preferably 0.5 vol% or more, more preferably 1 vol% or more, or 40 vol% or less, preferably 35 vol% or less, more preferably 30 vol% or less, relative to 100 vol% of the nonaqueous organic solvent. If the content of the sulfone compound is within the above range, it is easy to obtain an effect of improving durability such as cycle characteristics and storage characteristics, and it is also possible to keep the viscosity of the nonaqueous electrolyte within an appropriate range, avoid a decrease in electrical conductivity, and keep the input / output characteristics and charge / discharge rate characteristics of the nonaqueous electrolyte battery within appropriate ranges.

[0130] Other Additives: The above is a description of the basic configuration of the nonaqueous electrolyte solution of the present disclosure, but additives that are commonly used in the nonaqueous electrolyte solution of the present disclosure may be added in any ratio as long as the gist of the present disclosure is not impaired. When the nonaqueous electrolyte solution of the present disclosure contains other additives, the content of the other additives may be 0.01% by mass or more and 10% by mass or less with respect to the total amount of the nonaqueous electrolyte solution.

[0131] Specific examples of other additives include vinylene carbonate (hereinafter sometimes referred to as "VC"), vinylene carbonate oligomer (having a number average molecular weight of 170 to 5000 in terms of polystyrene), fluoroethylene carbonate, trans-difluoroethylene carbonate, 1,6-diisocyanatohexane, ethynylethylene carbonate, 1,3-propane sultone (hereinafter sometimes referred to as "1,3-PS"), methylenemethane disulfonate, methanesulfonyl fluoride, Examples of such additives include tris(trimethylsilyl)borate, (ethoxy)pentafluorocyclotriphosphazene, tetrafluoro(picolinato)phosphate, difluoro(picolinato)borate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-hexafluoroisopropyl)disiloxane, t-butylbenzene, t-amylbenzene, fluorobenzene, cyclohexylbenzene, biphenyl, difluoroanisole, dimethylvinylene carbonate, and nitrates. By incorporating the above-mentioned additives into the nonaqueous electrolyte solution of the present disclosure, at least one of the overcharge prevention effect, the negative electrode film formation effect, and the positive electrode protection effect may be enhanced.

[0132] The nonaqueous electrolyte of the present disclosure is suitable for use in nonaqueous electrolyte batteries (preferably nonaqueous electrolyte secondary batteries).

[0133] 2. Regarding the Non-Aqueous Electrolyte Battery The non-aqueous electrolyte battery of the present disclosure includes at least the non-aqueous electrolyte of the present disclosure, a negative electrode, and a positive electrode. It may also include a separator, an exterior body, and the like. The non-aqueous electrolyte battery of the present disclosure preferably includes at least a positive electrode, a negative electrode, a separator, and the non-aqueous electrolyte of the present disclosure. The non-aqueous electrolyte battery of the present disclosure is preferably a non-aqueous electrolyte secondary battery.

[0134] The negative electrode is not particularly limited, but may be made of a material that allows reversible insertion and desorption of alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions.

[0135] For example, in the case of a lithium-ion secondary battery in which the cation is mainly lithium, the negative electrode active material constituting the negative electrode is capable of doping and dedoping lithium ions. For example, carbon materials having a d value of the (002) lattice plane in X-ray diffraction of 0.340 nm or less, carbon materials having a d value of the (002) lattice plane in X-ray diffraction of more than 0.340 nm, oxides of one or more metals selected from Si, Sn, and Al, alloys containing one or more metals selected from Si, Sn, and Al, or alloys of these metals or alloys with lithium, and lithium titanium oxide. These negative electrode active materials can be used alone or in combination of two or more. Lithium metal, metal nitrides, tin compounds, conductive polymers, etc. may also be used.

[0136] For example, in the case of a sodium-ion secondary battery in which the cation is primarily sodium, the negative electrode active material constituting the negative electrode may be sodium metal, an alloy of sodium metal with other metals such as tin, an intermetallic compound of sodium metal with other metals, various carbon materials such as hard carbon, metal oxides such as titanium oxide, metal nitrides, tin (simple substance), tin compounds, activated carbon, conductive polymers, etc. In addition to these, phosphorus (simple substance) such as red phosphorus and black phosphorus, phosphorus compounds such as Co—P, Cu—P, Sn—P, Ge—P, and Mo—P, antimony (simple substance), antimony compounds such as Sb / C and Bi—Sb, etc., may also be used. These negative electrode active materials may be used alone or in combination of two or more types.

[0137] The positive electrode is not particularly limited, but may be made of a material that allows reversible insertion and desorption of alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions.

[0138] For example, when the cation is lithium, the positive electrode material is LiCoO ２ , LiNiO ２ , LiMnO ２ , LiMn ２ O ４Lithium-containing transition metal composite oxides such as those described above, in which a plurality of transition metals such as Co, Mn, and Ni are mixed, those in which a part of the transition metal in the lithium-containing transition metal composite oxide is replaced with a metal other than the transition metal, and LiFePO , which is called olivine. ４ , LiCoPO ４ , LiMnPO ４ transition metal phosphate compounds such as TiO ２ , V ２ O ５ , MoO ３ oxides such as TiS ２ Alternatively, sulfides such as FeS, conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole, activated carbon, radical-generating polymers, carbon materials, and the like may be used.

[0139] For example, when the cation is sodium, the positive electrode material (positive electrode active material) is NaCrO ２ , NaFe ０．５ Co ０．５ O ２ , NaFe ０．４ Mn ０．３ Ni ０．３ O ２ , NaNi ０．５ Ti ０．３ Mn ０．２ O ２ , NaNi １／３ Ti １／３ Mn １／３ O ２ , NaNi ０．３３ Ti ０．３３ Mn ０．１６ Mg ０．１７ O ２ , Na ２／３ Ni １／３ Ti １／６ Mn １／２ O ２ , Na ２／３ Ni １／３ Mn ２／３ O ２sodium-containing transition metal composite oxides such as those described above, in which a plurality of transition metals such as Co, Mn, and Ni are mixed, sodium-containing transition metal composite oxides in which a part of the transition metal is replaced with a metal other than the transition metal, NaFePO ４ , NaVPO ４ F, Na ３ V ２ (P.O. ４ ) ３ , Na ２ Fe ２ (SO ４ ) ３ Polyanion type compounds such as those of the formula Na ａ M ｂ [Fe(CN) ６ ] ｃ (M=Cr, Mn, Fe, Co, Ni, Cu, or Zn, and 0≦a≦2, 0.5≦b≦1.5, 0.5≦c≦1.5), TiO ２ , V ２ O ５ , MoO ３ oxides such as TiS ２ Alternatively, sulfides such as FeS, conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole, activated carbon, radical-generating polymers, carbon materials, and the like may be used.

[0140] The positive electrode and negative electrode materials may contain, as a conductive material, acetylene black, ketjen black, carbon fiber, or graphite, and as a binder, polytetrafluoroethylene, polyvinylidene fluoride, SBR resin, or the like, and may further contain an electrode sheet formed into a sheet.

[0141] As a separator for preventing contact between the positive electrode and the negative electrode, a nonwoven fabric or porous sheet made of polypropylene, polyethylene, paper, glass fiber, or the like may be used.

[0142] The above elements are assembled into an electrochemical device having a coin-like, cylindrical, rectangular, aluminum laminate sheet, or other shape.

[0143] The present disclosure will be specifically described below using examples, but the present disclosure is not limited to such examples.

[0144] [Examples 1-1 to 1-67, Comparative Examples 1-1 to 1-37] <Preparation of Non-Aqueous Electrolyte> In a glove box with a dew point of −60° C. or less, EC, EMC, and DMC were mixed as (IV) in a volume ratio of EC:EMC:DMC=25:50:25. Thereafter, while maintaining the internal temperature at 40° C. or less, LiPF as (III) was added under stirring. ６ The non-aqueous electrolyte solution of Comparative Example 1-1 was prepared by adding and dissolving the compound (1-1) as (I) so that the concentration was 0.5% by mass relative to the total amount of the non-aqueous electrolyte solution, and stirring for 1 hour. In addition, as shown in Tables 1 to 4, the type and concentration of (I) were changed, the type and concentration of (II) were changed, and the type and concentration of other additives were changed. The non-aqueous electrolyte solutions of each Example and Comparative Example were prepared in the same manner as the non-aqueous electrolyte solution of Comparative Example 1-1.

[0145] The compounds used in the examples and comparative examples are shown below. Only the compound numbers are shown in the tables. (1-1): 1,2-ethanedisulfonic anhydride (1-2): 1,3-propanedisulfonic anhydride (2-1): Lithium difluorophosphate (2-2): Lithium fluorosulfonate (2-3): Lithium tetrafluoroborate (3-1): Trivinylmethylsilane (3-2): Trivinylfluorosilane (3-3): Tetravinylsilane (4-1): 1,3,2-dioxathiolane-2,2-dioxide (5-1): 1-propene-1,3-sultone (1-R): 2,1,3-benzoxadithiol-1,1,3,3-tetraoxide (3-R): Trimethylvinylsilane

[0146] (Preparation of NCM811 positive electrode) LiNi ０．８ Mn ０．１ Co ０．１ O ２92.0% by mass of the powder was mixed with 3.5% by mass of polyvinylidene fluoride (hereinafter also referred to as "PVDF") as a binder and 4.5% by mass of acetylene black as a conductive material, and further N-methyl-2-pyrrolidone (hereinafter also referred to as "NMP") was added to the LiNi 0.8 Mn 0.1 Co 0.1 O ２ The paste was applied to both sides of an aluminum foil (A1085), dried, pressed, and punched into a 4 cm × 5 cm piece to obtain a test NCM811 positive electrode.

[0147] (Preparation of Natural Graphite Negative Electrode) 97.0% by mass of natural graphite powder, 2.0% by mass of styrene-butadiene rubber as a binder, 1.0% by mass of sodium carboxymethyl cellulose, and water were mixed to prepare a negative electrode composite paste. This paste was applied to one side of copper foil, dried, pressed, and then punched out to a size of 4.5 cm x 5.5 cm to obtain a test natural graphite negative electrode.

[0148] (Preparation of silicon-containing graphite negative electrode) 85.0% by mass of artificial graphite powder, 7.0% by mass of nanosilicon, 3.0% by mass of conductive material (HS-100 manufactured by Denka), 2.0% by mass of carbon nanofiber (VGCF manufactured by Showa Denko), 2.0% by mass of styrene butadiene rubber (hereinafter also referred to as "SBR"), 1.0% by mass of sodium carboxymethyl cellulose (hereinafter also referred to as "CMC") and water were mixed to prepare a negative electrode composite paste. This paste was applied to copper foil, dried, pressed, and then punched out to 4.5 cm x 5.5 cm to obtain a test silicon-containing graphite negative electrode.

[0149] (Preparation of non-aqueous electrolyte batteries listed in Tables 1 to 4) In an argon atmosphere with a dew point of −50° C. or lower, a terminal was welded to the aforementioned NCM811 positive electrode, and then the electrode was sandwiched between two polyethylene separators (5 cm × 6 cm). The outer surface of the separator was further sandwiched between two natural graphite negative electrodes with terminals previously welded, with the negative electrode active material surface facing the positive electrode active material surface. These were then placed in an aluminum laminate bag with an opening on one side, and the non-aqueous electrolyte prepared above was vacuum-injected into the bag. The opening was then heat-sealed to prepare aluminum laminate-type non-aqueous electrolyte batteries of the examples and comparative examples listed in Tables 1 to 4 below.

[0150] (Evaluation of Nonaqueous Electrolyte Battery) - Initial Charge / Discharge - The fabricated nonaqueous electrolyte battery was placed in a thermostatic chamber at 25°C and connected to a charge / discharge device in this state. Current density: 0.38 mA / cm ２ After maintaining 4.2 V for 1 hour, the battery was charged at a current density of 0.38 mA / cm ２ The battery was discharged at 100 V to 2.5 V. This was defined as one charge / discharge cycle, and a total of three charge / discharge cycles were performed to stabilize the battery. The discharge capacity at the third cycle was defined as the initial charge / discharge capacity.

[0151] <Initial resistance> 25℃, 0.38mA / cm after initial charge / discharge ２ The battery was charged to 4.2 V, and the resistance value (initial resistance) was measured by impedance measurement.

[0152] <High-temperature storage characteristics> The nonaqueous electrolyte battery after the initial charge and discharge was charged at an upper limit voltage of 4.2 V and a current of 0.38 mA / cm ２ After that, the battery was taken out of the charge / discharge device maintained at 25°C, placed in a thermostatic chamber at 60°C, and stored for 14 days. Thereafter, the battery was placed in a charge / discharge device maintained at 25°C, and charged at 0.38 mA / cm until the discharge cut-off voltage reached 2.5 V. ２ After discharge, the cell was evaluated for deterioration based on the discharge capacity retention rate after storage. ２ After charging to 4.2 V, the current density was 0.38 mA / cm ２ The capacity obtained at this time was defined as the discharge capacity after storage at 60° C. The discharge capacity retention rate after storage at 60° C. was calculated using the following formula.

[0153] (Discharge capacity retention rate after storage at 60°C) Discharge capacity retention rate after storage at 60°C (%) = (discharge capacity after storage at 60°C / initial charge / discharge capacity) x 100

[0154] (Resistance value after storage at 60°C) Next, at 25°C, 0.38 mA / cm ２ The battery was charged to 4.2 V, and the resistance value (resistance value after storage at 60° C.) was measured by impedance measurement.

[0155] In the following Tables 1 to 4, the initial resistance value represents a relative value when Comparative Example 1-1 is set to 100, "E1" represents the discharge capacity retention rate after storage at 60°C (a relative value when Comparative Example 1-1 is set to 100), and "E2" represents the resistance value after storage at 60°C (a relative value when Comparative Example 1-1 is set to 100).

[0156]

[0157]

[0158]

[0159]

[0160] Tables 1 to 4 show that when compared under conditions where the type and concentration of (II) are the same and the types and concentrations of other additives are the same, the nonaqueous electrolyte batteries containing the nonaqueous electrolytes of the Examples have lower initial resistance than the nonaqueous electrolyte batteries containing the corresponding nonaqueous electrolytes of the Comparative Examples. It is also clear that the nonaqueous electrolyte batteries containing the nonaqueous electrolytes of the Examples have higher E1 and lower E2 than the nonaqueous electrolyte batteries containing the nonaqueous electrolytes of the Comparative Examples. It is also clear that when the concentration of (I) is 0.01% by mass or more and 10% by mass or less, the initial resistance is easily reduced, and when the concentration is 0.1% by mass or more and 1.5% by mass or less, the initial resistance is lowest. It is also clear that the nonaqueous electrolyte batteries containing the nonaqueous electrolytes of the Examples have higher E1 and lower E2 than the nonaqueous electrolyte batteries containing the corresponding nonaqueous electrolytes of the Comparative Examples. Focusing on the type of (I), a comparison between Examples 1-4 and 1-17 in Table 1 shows that (I-1) has a greater effect on reducing initial resistance than (I-2). When attention is paid to the type of compound (2), it is understood that the magnitude of the effect of reducing the initial resistance is (2-3)>(2-1)>(2-2) from the comparison of Example 1-3, Example 1-13, and Example 1-15, the comparison of Example 1-4, Example 1-14, and Example 1-16, the comparison of Example 1-17, Example 1-18, and Example 1-19, and the comparison of Example 1-20, Example 1-21, and Example 1-22 in Table 1. When attention is paid to the type of compound (3), it is understood that the magnitude of the effect of reducing the initial resistance is (3-1) ≒ (3-3)>(3-2) from the comparison of Example 1-23, Example 1-25, and Example 1-29 in Table 2, the comparison of Example 1-24, Example 1-26, and Example 1-30, and the comparison of Example 1-39, Example 1-40, and Example 1-41.

[0161] [Examples 2-1 to 2-59, Comparative Examples 2-1 to 2-28] <Preparation of Non-Aqueous Electrolyte> In a glove box with a dew point of −60° C. or less, EC, EMC, and DMC were mixed as (IV) in a volume ratio of EC:EMC:DMC=25:50:25. Thereafter, while maintaining the internal temperature at 40° C. or less, LiPF as (III) was added with stirring. ６The non-aqueous electrolyte solution was dissolved to a concentration of 1.0 mol / L relative to the total amount of the non-aqueous electrolyte, and the compound (1-1) was dissolved as (I) to a concentration of 0.5% by mass relative to the total amount of the non-aqueous electrolyte, and other additives were added and dissolved to concentrations of 5.0% by mass and 2.0% by mass, respectively, relative to the total amount of the non-aqueous electrolyte, and the non-aqueous electrolyte solution of Comparative Example 2-1 was prepared by stirring for 1 hour. Further, as shown in Tables 5 to 10, changing the type and concentration of (I), changing the type and concentration of (II), and changing the type and concentration of other additives, except for changing the non-aqueous electrolyte solution of Comparative Example 2-1, the non-aqueous electrolyte solutions of each Example and Comparative Example were prepared in the same manner.

[0162] (Preparation of non-aqueous electrolyte batteries listed in Tables 5 to 10) In an argon atmosphere with a dew point of −50° C. or less, a terminal was welded to the aforementioned NCM811 positive electrode, and then the electrode was sandwiched between two polyethylene separators (5 cm × 6 cm). The outer surface of the separator was further sandwiched between two silicon-containing graphite negative electrodes with terminals previously welded, with the negative electrode active material surface facing the positive electrode active material surface. These were then placed in an aluminum laminate bag with an opening on one side, and the non-aqueous electrolyte prepared above was vacuum-injected into the bag. The opening was then heat-sealed to prepare aluminum laminate-type non-aqueous electrolyte batteries of the examples and comparative examples listed in Tables 5 to 10 below.

[0163] (Evaluation of Nonaqueous Electrolyte Battery) - Initial Charge / Discharge - The fabricated nonaqueous electrolyte battery was placed in a thermostatic chamber at 25°C and connected to a charge / discharge device in this state. Current density: 0.38 mA / cm ２ After maintaining 4.2 V for 1 hour, the battery was charged at a current density of 0.38 mA / cm ２ This was counted as one charge-discharge cycle, and a total of three charge-discharge cycles were carried out to stabilize the battery.

[0164] <Initial resistance> 25℃, 0.38mA / cm after initial charge / discharge ２ The battery was charged to 4.2 V, and the resistance value (initial resistance) was measured by impedance measurement.

[0165] <Cycle characteristic test at 25° C.> A charge / discharge test was carried out at an ambient temperature of 25° C. to evaluate the cycle characteristics. Charging was performed up to 4.2 V and discharging was performed up to 2.5 V, and the current density was 1.9 mA / cm ２ The charge-discharge cycle was repeated at 25°C. The deterioration of the cell was evaluated based on the discharge capacity retention rate after 200 cycles. The discharge capacity retention rate after 200 cycles was calculated using the following formula. The discharge capacity at the first cycle in the cycle characteristic test at an ambient temperature of 25°C was defined as the initial discharge capacity.

[0166] (Discharge capacity retention rate after 200 cycles) Discharge capacity retention rate after 200 cycles (%) = (discharge capacity after 200 cycles / initial discharge capacity) x 100

[0167] (Resistance value after 200 cycles) The nonaqueous electrolyte battery after the cycle characteristic test was subjected to a test at 25°C and 0.38 mA / cm ２ The battery was charged to 4.2 V at 100 V, and the resistance value (resistance value after 200 cycles) was measured by impedance measurement.

[0168] In the following Tables 5 to 10, the initial resistance value represents a relative value when Comparative Example 2-1 is set to 100, "E3" represents the discharge capacity retention rate after the cycle characteristic test at 25°C (a relative value when Comparative Example 2-1 is set to 100), and "E4" represents the resistance value after the cycle characteristic test at 25°C (a relative value when Comparative Example 2-1 is set to 100).

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175] Tables 5 to 10 show that the nonaqueous electrolyte batteries containing the nonaqueous electrolytes of the Examples have lower initial resistance than the nonaqueous electrolyte batteries containing the corresponding comparative examples. Furthermore, the nonaqueous electrolyte batteries containing the nonaqueous electrolytes of the Examples have larger E3 and smaller E4 than the nonaqueous electrolyte batteries containing the corresponding comparative examples. Focusing on the type of (I), a comparison of Example 2-4 with Example 2-17 in Table 6 shows that (1-1) has a greater effect of reducing initial resistance than (1-2). Focusing on the type of compound (2), a comparison of Example 2-3 with Example 2-13 and Example 2-15, a comparison of Example 2-4 with Example 2-14 and Example 2-16, and a comparison of Example 2-17 with Example 2-18 and Example 2-19 in Table 6 shows that the magnitude of the effect of reducing initial resistance is (2-3) > (2-1) > (2-2).

[0176] According to the present disclosure, it is possible to provide a nonaqueous electrolyte that can reduce the initial resistance of a nonaqueous electrolyte battery, and a nonaqueous electrolyte battery with low initial resistance.

[0177] Although the present disclosure has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present disclosure. This application is based on a Japanese patent application (Patent Application No. 2023-123780) filed on July 28, 2023, the contents of which are incorporated herein by reference.

Claims

1. A non-aqueous electrolyte solution containing: (I) a compound represented by the following general formula (1); (II) at least one compound selected from the group consisting of the following compounds (2) to (5); (III) a solute; and (IV) a non-aqueous organic solvent. In general formula (1), R １ represents an alkylene group having 1 to 6 carbon atoms. An oxygen atom may be contained between the carbon atom-carbon atom bond in the alkylene group. Any hydrogen atom in the alkylene group may be substituted with a halogen atom. Compound (2): At least one compound selected from the group consisting of compounds represented by the following general formula (2-A), compounds represented by the following general formula (2-B), and compounds represented by the following general formula (2-C). In general formula (2-A), R ２１ and R ２２ each independently represents an organic group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, or a fluorine atom. Any hydrogen atom in the organic group may be substituted with a fluorine atom. An oxygen atom may be contained between the carbon-carbon bonds in the organic group. １ ｍ＋ is a proton, a metal cation or an onium cation. m represents the valence of the corresponding cation. However, the compound represented by the general formula (2-A) contains at least one P—F bond. In the general formula (2-B), X ２１ represents an organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, or a fluorine atom. Any hydrogen atom in the organic group may be substituted with a fluorine atom. An oxygen atom may be contained between a carbon-carbon bond in the organic group. However, the organic group contains at least one fluorine atom. １ ｍ＋ In the general formula (2-C), X is a proton, a metal cation, or an onium cation. m represents the valence of the corresponding cation. ２２ ~X ２５ each independently represents an organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, or a fluorine atom. Any hydrogen atom in the organic group may be substituted with a fluorine atom. An oxygen atom may be contained between a carbon-carbon bond in the organic group. However, the organic group contains at least one fluorine atom. １ ｍ＋ is a proton, a metal cation or an onium cation. m represents the valence of the corresponding cation. However, the compound represented by general formula (2-C) contains at least one B—F bond. Compound (3): A compound represented by the following general formula (3). In general formula (3), R ３１ represents a group having a carbon-carbon unsaturated bond. ３１ may be the same or different. ３２ R represents a fluorine atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may have at least one of a fluorine atom and an oxygen atom. ３２ When there are multiple R ３２ may be the same or different, and v represents an integer of 2 to 4. Compound (4): A compound represented by the following general formula (4). In general formula (4), R ４１ and R ４２ each independently represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Any hydrogen atom in the alkenyl group and the aryl group may be substituted with a halogen atom. n4 is 0 or 1. Compound (5): A compound represented by the following general formula (5). In general formula (5), R ５０ ~R ５３ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. n51 represents an integer of 1 to 3.

2. The nonaqueous electrolyte according to claim 1, wherein the content of said (I) is 0.01% by mass or more and 10% by mass or less relative to the total amount of said nonaqueous electrolyte.

3. The non-aqueous electrolyte according to claim 1 or 2, wherein the content of said (II) is 0.01 mass % or more and 10 mass % or less relative to the total amount of said non-aqueous electrolyte.

4. The nonaqueous electrolyte according to claim 1 or 2, wherein the compound represented by general formula (1) is at least one compound selected from the group consisting of 1,2-ethanedisulfonic anhydride and 1,3-propanedisulfonic anhydride.

5. The nonaqueous electrolyte according to claim 1 or 2, wherein the compound (2) is at least one compound selected from the group consisting of lithium difluorophosphate, lithium fluorosulfonate, lithium trifluoromethanesulfonate, and lithium tetrafluoroborate.

6. The nonaqueous electrolyte according to claim 1 or 2, wherein the compound (3) is at least one compound selected from the group consisting of trivinylmethylsilane, trivinylfluorosilane, and tetravinylsilane.

7. The nonaqueous electrolyte according to claim 1 or 2, wherein the compound (4) is at least one compound selected from the group consisting of 1,3,2-dioxathiolane-2,2-dioxide and 1,3,2-dioxathiane-2,2-dioxide.

8. The above (III) is LiPF ６ , LiSbF ６ , LiAsF ６ , LiClO ４ , LiN(CF ３ SO ２ ) ２ , LiN(FSO ２ ) ２ , LiN(POF ２ ) ２ , LiCF ３ SO ３ , LiC ４ F ９ SO ３ , LiAlO ２ , LiAlCl ４ At least one selected from the group consisting of LiCl and LiI, or NaPF ６ , NaSbF ６ , NaAsF ６ , NaClO ４ , NaN(CF ３ SO ２ ) ２ , NaN(FSO ２ ) ２ , NaN(POF ２ ) ２ , NaCF ３ SO ３ , NaC ４ F ９ SO ３ , NaAlO ２ , NaAlCl ４ 3. The nonaqueous electrolyte according to claim 1, wherein the nonaqueous electrolyte is at least one selected from the group consisting of NaCl and NaI.

9. The nonaqueous electrolyte according to claim 1 or 2, wherein the (IV) contains at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds, and ionic liquids.

10. The nonaqueous electrolyte according to claim 9, wherein the cyclic ester is a cyclic carbonate.

11. The nonaqueous electrolyte according to claim 10, wherein the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate.

12. The nonaqueous electrolyte according to claim 9, wherein the chain ester is a chain carbonate.

13. The nonaqueous electrolyte according to claim 12, wherein the chain carbonate is at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate and methyl propyl carbonate.

14. A nonaqueous electrolyte battery comprising at least a positive electrode, a negative electrode, a separator, and the nonaqueous electrolyte according to claim 1 or 2.

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