Non-aqueous electrolytes, non-aqueous electrolyte batteries, compounds and additives for non-aqueous electrolytes

Abstract

The present invention provides: a non-aqueous electrolytic solution including (I) a compound represented by general formula (1) described in the description (for example, a compound represented by the following formula (a-1)), (II) a solute, and (III) a non-aqueous organic solvent; a non-aqueous electrolytic solution and a non-aqueous electrolyte battery that are capable of improving a high-temperature cycle characteristic and suppressing the resistance increase of the battery because of the compound represented by general formula (1) and an additive for the non-aqueous electrolytic solution; and a compound and an additive for a non-aqueous electrolytic solution that can be suitably used for the non-aqueous electrolytic solution.

Description

[Technical Field]

[0001] This disclosure relates to non-aqueous electrolytes, non-aqueous electrolyte batteries, compounds, and additives for non-aqueous electrolytes. [Background technology]

[0002] To date, various battery components, including the active materials of the positive and negative electrodes, have been optimized as a means of improving the durability of non-aqueous electrolyte batteries, such as their cycle characteristics and high-temperature storage characteristics. Non-aqueous electrolyte-related technologies are no exception, and it has been proposed to suppress degradation caused by the decomposition of the non-aqueous electrolyte on the surface of the active positive and negative electrodes using various additives.

[0003] For example, Patent Document 1 describes that incorporating a hydroxyalkyl sulfonate into the negative electrode improves cycle characteristics and suppresses gas generation at high temperatures. Patent Document 2 discloses a non-aqueous electrolyte for lithium batteries in which gas generation and self-discharge reactions during high-temperature storage are suppressed by the combined addition of hydroxyalkyl sulfonic acid and sulfonic acid ester. Furthermore, Patent Document 3 describes that by adding a sulfonic acid having urethane bonds and polymerizable unsaturated bonds to the electrolyte, excellent output characteristics and long-term cycle characteristics can be obtained, and an effect of suppressing electrode resistance can be obtained. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent No. 5262085 [Patent Document 2] Japanese Patent No. 5815118 [Patent Document 3] Japanese Patent No. 6165162 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, the Disclosers' investigation revealed that when these sulfonic acids or sulfonates are added, there is room for improvement in the effect of improving the cycle characteristics at high temperatures and the effect of suppressing resistance increase.

[0006] This disclosure has been made in view of the above circumstances and aims to provide a non-aqueous electrolyte and a non-aqueous electrolyte battery that can improve high-temperature cycle characteristics and suppress the increase in battery resistance. It also aims to provide compounds and additives for non-aqueous electrolytes that can be suitably used with the above non-aqueous electrolyte. [Means for solving the problem]

[0007] In light of the aforementioned problems, the Disclosing Parties conducted extensive research and discovered that a non-aqueous electrolyte battery with improved high-temperature cycle characteristics and suppression of resistance increase can be obtained by using a non-aqueous electrolyte containing (I) a compound represented by the general formula (1) described below (hereinafter sometimes referred to as "component (I)"), (II) a solute (hereinafter sometimes referred to as "component (II)"), and (III) a non-aqueous organic solvent (hereinafter sometimes referred to as "component (III)"), thereby solving the above-mentioned problems.

[0008] In other words, the Disclosers have found that the above problem can be solved by the following configuration.

[0009] [1] (I) Compounds represented by the following general formula (1), (II) Solute, and (III) Non-aqueous organic solvents A non-aqueous electrolyte containing [a specific component].

[0010] [ka]

[0011] [In general formula (1), A represents an organic group selected from the group consisting of a linear alkylene group having 1 to 8 carbon atoms or a branched alkylene group having 2 to 8 carbon atoms, and a linear alkenylene group having 2 to 8 carbon atoms or a branched alkenylene group having 3 to 8 carbon atoms. At least one hydrogen atom in the organic group may be substituted with a fluorine atom, and an oxygen atom may also be present in the organic group. B represents an oxygen atom or NR a , and R a represents a hydrogen atom, or 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, and an aryl group having 6 to 10 carbon atoms. At least one hydrogen atom in the organic group may be substituted with a halogen atom. M1 and M2 each independently represent a hydrogen atom, a metal cation, or an onium cation. When M1 and M2 represent a metal cation or an onium cation, the bond between the oxygen atom and M1 and the bond between the nitrogen atom and M2 in the general formula (1) represent an ionic bond. X is -S(=O)2-R b、 or -P(=O)-R c R d , and R b to R d each independently represent a fluorine atom, or 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. At least one hydrogen atom in the organic group may be substituted with a fluorine atom, and at least one of an oxygen atom and an unsaturated bond may also be present in the organic group. Also, R c and R dThey can also be bonded together to form a cyclic structure. n is an integer between 1 and 4. [2] In the general formula (1) above, X is -S(=O)²-R b Represents the above R b The non-aqueous electrolyte described in [1], where is a fluorine atom. [3] The non-aqueous electrolyte according to [1] or [2], wherein A in the general formula (1) represents a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 2 to 4 carbon atoms. [4] The solute is at least one selected from the group consisting of LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, LiC4F9SO3, LiN(SO2F)2, LiAlO2, LiAlCl4, LiCl, and LiI, or NaPF6, NaBF4, NaSbF6, NaAsF6, NaClO4, NaCF3SO3, NaC4F9SO3, NaN(SO2F) 2、 A non-aqueous electrolyte according to any one of [1] to [3], which is at least one selected from the group consisting of NaAlO2, NaAlCl4, NaCl, and NaI. [5] The nonaqueous electrolyte according to any one of [1] to [4], wherein the nonaqueous organic solvent is at least one selected from the group consisting of cyclic esters, linear esters, cyclic ethers, linear ethers, sulfone compounds, sulfoxide compounds, and ionic liquids. [6] The non-aqueous electrolyte according to [5], wherein the non-aqueous organic solvent contains a cyclic ester, and the cyclic ester is a cyclic carbonate. [7] The non-aqueous electrolyte according to [6], wherein the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate. [8] The non-aqueous electrolyte according to [5], wherein the non-aqueous organic solvent contains a linear ester, and the linear ester is a linear carbonate. [9] The non-aqueous electrolyte according to [8], wherein the chain-like carbonate is at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.

[10] The non-aqueous electrolyte according to any one of [1] to [9], wherein the content of (I) relative to the total amount of the non-aqueous electrolyte is 0.01 to 5.0% by mass.

[11] Furthermore, vinylene carbonate, bis(oxalato)borate, difluorooxalatoborate, difluorobis(oxalato)phosphate, tetrafluorooxalatophosphate, (difluorophosphoryl)(fluorosulfonyl)imide salt, difluorophosphate, fluorosulfonate, 1,3-propensultone, 1,3-propanesultone, 1,6-diisocyanatohexane, ethynylethylene carbonate, 1,3,2-dioxathiolan-2,2-dioxide, 4-propyl-1,3,2-dioxathiolan-2,2-dioxide, methylenemethanedisulfonate, 1,2- A non-aqueous electrolyte according to any one of [1] to

[10] , comprising at least one selected from ethanedisulfonic acid anhydride, methanesulfonyl fluoride, tris(trimethylsilyl)borate, (ethoxy)pentafluorocyclotriphosphazene, tetrafluoro(malonato) phosphate, tetrafluoro(picolinato) phosphate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-hexafluoroisopropyl)disiloxane, tetravinylsilane, t-butylbenzene, t-amylbenzene, fluorobenzene, and cyclohexylbenzene.

[12] A non-aqueous electrolyte battery comprising at least a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte as described in any one of [1] to

[11] .

[13] A compound represented by the following general formula (1).

[0012] [ka]

[0013] [In general formula (1), A represents an organic group selected from the group consisting of linear alkylene groups having 1 to 8 carbon atoms or branched alkylene groups having 2 to 8 carbon atoms, and linear alkenylene groups having 2 to 8 carbon atoms or branched alkenylene groups having 3 to 8 carbon atoms. At least one hydrogen atom in the organic group may be substituted with a fluorine atom, and an oxygen atom may also be present in the organic group. B is an oxygen atom or NR a Represents R a represents a hydrogen atom, or 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, and an aryl group having 6 to 10 carbon atoms. At least one of the hydrogen atoms in the organic group may be substituted with a halogen atom. M1 and M2 each independently represent a hydrogen atom, a metal cation, or an onium cation. When M1 and M2 represent a metal cation or an onium cation, the bond between the oxygen atom and M1, and the bond between the nitrogen atom and M2 in general formula (1) represent ionic bonds. X is -S(=O)2-R b、 or -P(=O)-R c R d Represents R b ~R d Each of these independently represents a fluorine atom, or 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. At least one hydrogen atom in the organic group may be substituted with a fluorine atom, and at least one oxygen atom and an unsaturated bond may be present in the organic group.c and R d They can also be bonded together to form a cyclic structure. n is an integer between 1 and 4.

[14] In the general formula (1) above, X is -S(=O)²-R b Represents the above R b The compound described in

[13] , where is a fluorine atom.

[15] The compound according to

[13] or

[14] , wherein A in the general formula (1) represents a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 2 to 4 carbon atoms.

[16] An additive for non-aqueous electrolytes represented by the following general formula (1).

[0014] [ka]

[0015] [In general formula (1), A represents an organic group selected from the group consisting of linear alkylene groups having 1 to 8 carbon atoms or branched alkylene groups having 2 to 8 carbon atoms, and linear alkenylene groups having 2 to 8 carbon atoms or branched alkenylene groups having 3 to 8 carbon atoms. At least one hydrogen atom in the organic group may be substituted with a fluorine atom, and an oxygen atom may also be present in the organic group. B is an oxygen atom or NR a Represents R a represents a hydrogen atom, or 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, and an aryl group having 6 to 10 carbon atoms. At least one of the hydrogen atoms in the organic group may be substituted with a halogen atom. M1 and M2 each independently represent a hydrogen atom, a metal cation, or an onium cation. When M1 and M2 represent a metal cation or an onium cation, the bond between the oxygen atom and M1, and the bond between the nitrogen atom and M2 in general formula (1) represent ionic bonds. X is -S(=O)2-R b、 or -P(=O)-R c R d Represents R b ~R d Each of these independently represents a fluorine atom, or 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. At least one hydrogen atom in the organic group may be substituted with a fluorine atom, and at least one oxygen atom and an unsaturated bond may be present in the organic group. c and R d They can also be bonded together to form a cyclic structure. n is an integer between 1 and 4.

[17] In the general formula (1) above, X is -S(=O)²-R b Represents the above R b The additive for non-aqueous electrolytes described in

[16] , wherein represents a fluorine atom.

[18] The additive for non-aqueous electrolytes according to

[16] or

[17] , wherein A in the general formula (1) represents a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 2 to 4 carbon atoms. [Effects of the Invention]

[0016] This disclosure provides a non-aqueous electrolyte and a non-aqueous electrolyte battery that can improve high-temperature cycle characteristics and suppress the increase in battery resistance. Furthermore, it provides compounds and additives suitable for use in the above-mentioned non-aqueous electrolyte. [Modes for carrying out the invention]

[0017] The configurations and combinations thereof in the following embodiments are examples, and additions, substitutions, and other modifications are possible without departing from the spirit of the Disclosure. Furthermore, this Disclosure is not limited by the embodiments, but is limited only by the claims.

[0018] In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively.

[0019] [1. Non-aqueous electrolyte] The non-aqueous electrolyte of this disclosure is a non-aqueous electrolyte containing (I) a compound represented by the general formula (1) above, (II) a solute, and (III) a non-aqueous organic solvent.

[0020] <About ingredient (I)> The non-aqueous electrolyte of this disclosure contains a compound represented by general formula (1), which is component (I). When a non-aqueous electrolyte containing component (I) is used in a non-aqueous electrolyte battery (e.g., a lithium-ion secondary battery or a sodium-ion secondary battery), component (I) decomposes at least on either the positive or negative electrode, forming a film with good cation conductivity on at least one of the positive or negative electrode surfaces. This film is thought to suppress direct contact between the non-aqueous organic solvent or solute and the electrode active material, thereby reducing the cation dissociation energy of the solute. As a result, the disclosers estimate that this improves the high-temperature cycle characteristics of the non-aqueous electrolyte battery and suppresses the increase in battery resistance.

[0021] The following describes compounds represented by general formula (1).

[0022] [ka]

[0023] [In general formula (1), A represents an organic group selected from the group consisting of linear alkylene groups having 1 to 8 carbon atoms or branched alkylene groups having 2 to 8 carbon atoms, and linear alkenylene groups having 2 to 8 carbon atoms or branched alkenylene groups having 3 to 8 carbon atoms. At least one hydrogen atom in the organic group may be substituted with a fluorine atom, and an oxygen atom may also be present in the organic group. B is an oxygen atom or NR a Represents R a represents a hydrogen atom, or 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, and an aryl group having 6 to 10 carbon atoms. At least one of the hydrogen atoms in the organic group may be substituted with a halogen atom. M1 and M2 each independently represent a hydrogen atom, a metal cation, or an onium cation. When M1 and M2 represent a metal cation or an onium cation, the bond between the oxygen atom and M1, and the bond between the nitrogen atom and M2 in general formula (1) represent ionic bonds. X is -S(=O)2-R b、 or -P(=O)-R c R d Represents R b ~R d Each of these independently represents a fluorine atom, or 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. At least one hydrogen atom in the organic group may be substituted with a fluorine atom, and at least one oxygen atom and an unsaturated bond may be present in the organic group. c and R dThey can also be bonded together to form a cyclic structure. n is an integer between 1 and 4.

[0024] In general formula (1), A represents an organic group selected from the group consisting of linear alkylene groups having 1 to 8 carbon atoms or branched alkylene groups having 2 to 8 carbon atoms, and linear alkenylene groups having 2 to 8 carbon atoms or branched alkenylene groups having 3 to 8 carbon atoms.

[0025] Specific examples of cases where A represents a linear alkylene group having 1 to 8 carbon atoms or a branched alkylene group having 2 to 8 carbon atoms include methylene group, methylmethylene group, ethylmethylene group, ethylene group, methylethylene group, ethylethylene group, n-propylethylene group, i-propylethylene group, n-butylethylene group, i-butylethylene group, tert-butylethylene group, n-propylene group, i-propylene group, n-butylene group, 1-methylpropylene group, 2-methylpropylene group, tert-butylene group, n-pentylene group, i-pentylene group, 1,1-dimethylpropylene group, 1-methylbutylene group, 1,1-dimethylbutylene group, n-hexylene group, etc. As the alkylene group, a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 2 to 4 carbon atoms is preferred.

[0026] Specific examples of cases where A represents a linear alkenylene group having 2 to 8 carbon atoms or a branched alkenylene group having 3 to 8 carbon atoms include vinylene, propenylene, 1-butenylene, 2-butenylene, butadienylene, pentenylene, hexenylene, heptenylene, and octenylene groups. As the alkenylene group, a linear alkenylene group having 2 to 4 carbon atoms or a branched alkenylene group having 3 to 4 carbon atoms is preferred.

[0027] Any hydrogen atom in the above organic group represented by A may be substituted with a fluorine atom. Examples of organic groups in which any hydrogen atom is substituted with a fluorine atom include the -CF2- group, -CHF- group, -CH2CF2- group, -CH2CHF- group, -CH2CH2CHF- group, -CH2CH2CF2- group, -CH2CF2CF2- group, -CF2CF2CF2- group, -CF=CF- group, -CF=CH- group, etc.

[0028] Oxygen atoms may be present in the above organic group. For example, oxygen atoms may be present between carbon atoms in the above organic group. Specific examples of cases where an oxygen atom is included between carbon atoms in the above organic group include, for example, the -CH2CH2-O-CH2- group and the -CH2CH2-O-CH2CH2- group.

[0029] A is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 2 to 4 carbon atoms, more preferably an unsubstituted linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 2 to 4 carbon atoms, and more preferably a methylene group, a methylmethylene group, an ethylene group, an n-propylene group, or an i-propylene group.

[0030] In general formula (1), B is an oxygen atom or NR a Represents R a This represents an organic group selected from the group consisting of a hydrogen atom or 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, and an aryl group having 6 to 10 carbon atoms.

[0031] R a However, examples of alkyl groups with 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, and n-decanyl group. Ra However, examples of alkenyl groups with 2 to 10 carbon atoms include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, and 1,3-butadienyl groups. R a However, when the alkynyl group has 2 to 10 carbon atoms, examples of alkynyl groups include the ethynyl group, the 2-propynyl group, and the 1,1-dimethyl-2-propynyl group. R a However, examples of cycloalkyl groups with 3 to 10 carbon atoms include cyclopentyl groups and cyclohexyl groups. R a However, when the cycloalkenyl group has 3 to 10 carbon atoms, examples of cycloalkenyl groups include the cyclopentenyl group and the cyclohexenyl group. R a However, when the aryl group has 6 to 10 carbon atoms, examples of aryl groups include the phenyl group, tolyl group, and xylyl group.

[0032] At least one of the hydrogen atoms in the above organic group may be substituted with a halogen atom. Examples of halogen atoms include fluorine, bromine, and iodine atoms, with fluorine being preferred.

[0033] R a It is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, or an isopropyl group, and even more preferably a methyl group.

[0034] B is preferably an oxygen atom, NH, N(CH3), N(CH2CH3), or N(CH(CH3)2), more preferably an oxygen atom or N(CH3), and even more preferably an oxygen atom.

[0035] In general formula (1), M1 and M2 each independently represent a hydrogen atom, a metal cation, or an onium cation. When M1 and M2 represent a metal cation or an onium cation, the bond between the oxygen atom and M1, and the bond between the nitrogen atom and M2 in general formula (1) represent ionic bonds.

[0036] Examples of metal cations when M1 and M2 represent metal cations include alkali metal cations such as lithium ions, sodium ions, and potassium ions. Examples of onium cations when M1 and M2 represent onium cations include tetraalkylammonium ions.

[0037] M1 preferably represents a metal cation; more preferably a lithium ion when used in lithium-ion battery applications, and more preferably a sodium ion when used in sodium-ion battery applications. M2 preferably represents a hydrogen atom or a metal cation. When used in lithium-ion battery applications, it is more preferably a lithium ion, and when used in sodium-ion battery applications, it is more preferably a sodium ion.

[0038] In general formula (1), X is -S(=O)²-R b、 or -P(=O)-R c R d Represents R b ~R d Each of these independently represents a fluorine atom, or 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.

[0039] R b ~R d Specific examples of alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkynyl groups with 2 to 10 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, cycloalkenyl groups with 3 to 10 carbon atoms, and aryl groups with 6 to 10 carbon atoms represented by the above R a Examples include 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, and aryl groups having 6 to 10 carbon atoms. R b ~R d However, when representing an alkoxy group with 1 to 10 carbon atoms, the alkyl group included in the alkoxy group is R b ~R d Examples include alkyl groups with 1 to 10 carbon atoms represented by . R b ~R d However, when representing an alkenyloxy group with 2 to 10 carbon atoms, the alkenyl group included in the alkenyloxy group is R b ~R d Examples include alkenyl groups with 2 to 10 carbon atoms represented by . R b ~R d However, when representing an alkynyloxy group with 2 to 10 carbon atoms, the alkynyl group included in the alkynyloxy group is R b ~R d Examples include alkynyl groups with 2 to 10 carbon atoms represented by . R b ~R d However, when referring to a cycloalkoxy group with 3 to 10 carbon atoms, the cycloalkyl group included in the cycloalkoxy group is R b ~R d Examples include cycloalkyl groups with 3 to 10 carbon atoms represented by . R b ~R dWhen representing a cycloalkenyloxy group with 3 to 10 carbon atoms, examples of the cycloalkenyl group contained in the cycloalkenyloxy group include the cycloalkenyl group represented by R b ~R d which represents a cycloalkenyl group with 3 to 10 carbon atoms. R b ~R d When representing an aryloxy group with 6 to 10 carbon atoms, examples of the aryl group contained in the aryloxy group include the aryl group represented by R b ~R d which represents an aryl group with 6 to 10 carbon atoms.

[0040] R b ~R d Any hydrogen atom of the above organic group may be substituted with a fluorine atom. Examples of the organic group in which any hydrogen atom is substituted with a fluorine atom include, for example, trifluoromethyl group, difluoromethyl group, fluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-difluoroethyl group, 2-fluoroethyl group, 3-fluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, hexafluoroisopropyl group, -CF=CF2 group, -CF=CH2 group, etc.

[0041] An oxygen atom may also be present in the above organic group. For example, an oxygen atom may be included between carbon-carbon bonds in the above organic group. Specific examples of the case where an oxygen atom is included between carbon-carbon bonds in the above organic group include, for example, -CH2CH2-O-CH3 group, -CH2CH2-O-CH2CH3 group, etc.

[0042] The above R c and R d can also be bonded to have a cyclic structure. The cyclic structure formed by R c and R d together with a phosphorus atom is preferably a 5- or 6-membered ring, and more preferably a 5-membered ring.

[0043] X represents -S(=O)2-R b When it represents b R

[0044] X represents -P(=O)-R c R d When it represents c and R d each independently preferably represents a fluorine atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, more preferably represents a fluorine atom or an alkoxy group having 1 to 3 carbon atoms, and even more preferably is a fluorine atom or a methoxy group. R c and R d represent an alkoxy group having 1 or 2 carbon atoms and combine to form a 5-membered or 6-membered ring together with the phosphorus atom, which is also preferable.

[0045] X represents -S(=O)2-R b and b it is most preferable that R represents a fluorine atom

[0046] n represents an integer of 1 to 4, preferably 1 to 3, and more preferably 1 or 2.

[0047] When n represents 1, the compound represented by the general formula (1) is a compound represented by the following general formula (1-1).

[0048] [In the general formula (1-1), A, B, X, M1 and M2 respectively represent the same meanings as A, B, X, M1 and M2 in the general formula (1).]​​​​​​​

[0050] Specific examples of compounds represented by general formula (1) are shown below, but are not limited to these.

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] In the non-aqueous electrolyte of this disclosure, the content of component (I) (hereinafter also referred to as "concentration of (I)") relative to the total amount of the non-aqueous electrolyte (100% by mass) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. The upper limit of the concentration of (I) is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, even more preferably 4.0% by mass or less, and particularly preferably 2.5% by mass or less. By setting the concentration of (I) to 0.01% by mass or higher, it is easier to obtain an improvement in the cycle characteristics of a non-aqueous electrolyte battery using the non-aqueous electrolyte. On the other hand, by setting the concentration of (I) to 10.0% by mass or lower, the viscosity increase of the non-aqueous electrolyte can be suppressed, and it becomes easier to obtain an effect of suppressing the resistance increase of a non-aqueous electrolyte battery using the non-aqueous electrolyte. The content of component (I) relative to the total amount of the non-aqueous electrolyte is preferably 0.01 to 5.0% by mass.

[0058] The non-aqueous electrolyte of this disclosure may use one compound alone as component (I), or it may be used by mixing two or more compounds in any combination and ratio according to the application.

[0059] Compounds represented by general formula (1) can be produced by various methods. The production method is not particularly limited. For example, it can be obtained by reacting 2-hydroxyethanesulfonate or hydroxymethanesulfonate with fluorosulfonyl isocyanate, and then reacting it with lithium hydride.

[0060] This disclosure also relates to compounds represented by the general formula (1) described above. The above compound is suitably used as an additive in non-aqueous electrolytes. That is, this disclosure also relates to an additive for non-aqueous electrolytes represented by the above general formula (1).

[0061] (II) Regarding solutes The non-aqueous electrolyte of this disclosure contains a solute. The solute is not particularly limited, but it is preferably an ionic salt, and more preferably an ionic salt containing fluorine.

[0062] The solute is preferably an ionic salt consisting of a pair of at least one cation selected from the group consisting of alkali metal ions such as lithium ions and sodium ions, alkaline earth metal ions, and quaternary ammonium, and at least one anion selected from the group consisting of hexafluorophosphate anion, tetrafluoroborate anion, perchlorate anion, hexafluoroarsenate anion, hexafluoroantimonate anion, trifluoromethanesulfonate anion, bis(trifluoromethanesulfonyl)imide anion, bis(pentafluoroethanesulfonyl)imide anion, (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide anion, bis(fluorosulfonyl)imide anion, (trifluoromethanesulfonyl)(fluorosulfonyl)imide anion, (pentafluoroethanesulfonyl)(fluorosulfonyl)imide anion, and tris(trifluoromethanesulfonyl)methide anion.

[0063] The solute is at least one selected from the group consisting of LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, LiC4F9SO3, LiN(SO2F)2, LiAlO2, LiAlCl4, LiCl, and LiI, or NaPF6, NaBF4, NaSbF6, NaAsF6, NaClO4, NaCF3SO3, NaC4F9SO3, NaN(SO2F) 2、 It is preferable that it be at least one selected from the group consisting of NaAlO2, NaAlCl4, NaCl, and NaI.

[0064] These solutes may be used individually, or two or more may be mixed in any combination and ratio according to the application. In particular, considering the energy density, output characteristics, and lifespan of the non-aqueous electrolyte battery, it is preferable that the cation be at least one selected from the group consisting of lithium, sodium, potassium, magnesium, and quaternary ammonium, and the anion be at least one selected from the group consisting of hexafluorophosphate anion, tetrafluoroborate anion, bis(trifluoromethanesulfonyl)imide anion, and bis(fluorosulfonyl)imide anion.

[0065] The total amount of solute in the non-aqueous electrolyte of this disclosure (hereinafter also referred to as "solute concentration") is not particularly limited, but the lower limit is preferably 0.5 mol / L or more, more preferably 0.7 mol / L or more, and even more preferably 0.9 mol / L or more. The upper limit of the solute concentration is preferably 5.0 mol / L or less, more preferably 4.0 mol / L or less, and even more preferably 2.0 mol / L or less. Setting the solute concentration to 0.5 mol / L or more can suppress the decrease in cycle characteristics and output characteristics of the non-aqueous electrolyte battery due to a decrease in ionic conductivity, and setting it to 5.0 mol / L or less can suppress the decrease in ionic conductivity and the decrease in cycle characteristics and output characteristics of the non-aqueous electrolyte battery due to an increase in the viscosity of the non-aqueous electrolyte.

[0066] <(III) Regarding non-aqueous organic solvents> The type of non-aqueous organic solvent used in the non-aqueous electrolyte of this disclosure is not particularly limited, and any non-aqueous organic solvent can be used. The non-aqueous organic solvent is preferably at least one selected from the group consisting of cyclic esters, linear esters, cyclic ethers, linear ethers, sulfone compounds, sulfoxide compounds, and ionic liquids. Specifically, ethyl methyl carbonate (hereinafter also referred to as "EMC"), dimethyl carbonate (hereinafter also referred to as "DMC"), diethyl carbonate (hereinafter also referred to as "DEC"), methyl propyl carbonate, ethyl propyl carbonate, methyl butyl carbonate, 2,2,2-trifluoroethyl methyl carbonate, 2,2,2-trifluoroethyl ethyl carbonate, 2,2,2-trifluoroethyl propyl carbonate, bis(2,2,2-trifluoroethyl) carbonate, 1,1,1,3,3,3-hexafluoro-1-propyl methyl carbonate, 1,1,1,3,3,3-hexafluoro-1-propyl ethyl carbonate, 1,1,1,3,3,3-hexafluoro-1-propyl propyl carbonate, bis(1,1,1,3,3,3-hexafluoro-1-propyl) carbonate Preferably, it is at least one selected from the group consisting of ethylene carbonate (hereinafter also referred to as "EC"), propylene carbonate (hereinafter also referred to as "PC"), butylene carbonate, fluoroethylene carbonate (hereinafter also referred to as "FEC"), difluoroethylene carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, ethyl 2-fluoropropionate, diethyl ether, dibutyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, furan, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, N,N-dimethylformamide, acetonitrile, propionitrile, dimethyl sulfoxide, sulfolane, γ-butyrolactone, and γ-valerolactone. Furthermore, in this disclosure, an ionic liquid that adopts a salt structure may be used as the non-aqueous organic solvent.

[0067] It is preferable that the non-aqueous organic solvent is at least one selected from the group consisting of cyclic esters and linear esters, as this provides excellent input / output characteristics at low temperatures. Furthermore, the non-aqueous organic solvent is preferably at least one selected from the group consisting of cyclic carbonates and linear carbonates, as this provides excellent cycling characteristics at high temperatures.

[0068] The non-aqueous organic solvent preferably contains a cyclic ester, and the cyclic ester is preferably a cyclic carbonate. Specific examples of the above-mentioned cyclic carbonates include EC, PC, butylene carbonate, and FEC, and it is preferable that at least one is selected from the group consisting of EC, PC, and FEC.

[0069] It is also preferable that the non-aqueous organic solvent contains a linear ester, and that the linear ester is a linear carbonate. Specific examples of the above-mentioned linear carbonates include EMC, DMC, DEC, methylpropyl carbonate, ethylpropyl carbonate, 2,2,2-trifluoroethylmethyl carbonate, 2,2,2-trifluoroethylethyl carbonate, 1,1,1,3,3,3-hexafluoro-1-propylmethyl carbonate, and 1,1,1,3,3,3-hexafluoro-1-propylethyl carbonate, among others, and it is preferable that at least one is selected from the group consisting of EMC, DMC, DEC, and methylpropyl carbonate.

[0070] Furthermore, specific examples of the above esters include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, and ethyl 2-fluoropropionate.

[0071] <About other additives> Insofar as it does not impair the essence of this disclosure, additives commonly used in the non-aqueous electrolytes of this disclosure may be added in any proportion. Other specific examples of additives include cyclohexylbenzene, cyclohexylfluorobenzene, fluorobenzene, biphenyl, difluoroanisole, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, 2-fluorobiphenyl, vinylene carbonate, dimethylvinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate, trans-difluoroethylene carbonate, methylpropargyl carbonate, ethylpropargyl carbonate, dipropargyl carbonate, maleic anhydride, succinic anhydride, propanesultone, 1,3-propanesultone, 1,3-propensultone, butanesultone, 1,3,2-dioxathiolan-2,2-dioxide, 4-propyl-1,3,2-dioxathiolan-2,2-dioxide, methylenemethanedisulfate, dimethylmethanedisulfate, trimethylenemethanedisulfate, methyl methanesulfonate, 1,6-Diisocyanatohexane, tris(trimethylsilyl)borate, succinonitrile, (ethoxy)pentafluorocyclotriphosphazene, lithium difluorobis(oxalato)phosphate, sodium difluorobis(oxalato)phosphate, potassium difluorobis(oxalato)phosphate, lithium difluorooxalatoborate, sodium difluorooxalatoborate, potassium difluorooxalatoborate, lithium bis(oxalato)borate, sodium bis(oxalato)borate, potassium bis(oxalato)borate, lithium tetrafluorooxalatophosphate, sodium tetrafluorooxalatophosphate, potassium tetrafluorooxalatophosphate, tris(oxalato)phosphate Examples of compounds that have overcharge prevention effects, negative electrode film formation effects, and positive electrode protection effects include lithium, sodium tris(oxalato)phosphate, potassium tris(oxalato)phosphate, lithium difluorophosphate, sodium difluorophosphate, potassium difluorophosphate, lithium monofluorophosphate, sodium monofluorophosphate, potassium monofluorophosphate, lithium fluorosulfonate, sodium fluorosulfonate, potassium fluorosulfonate, lithium bis(difluorophosphoryl)imide, sodium bis(difluorophosphoryl)imide, potassium bis(difluorophosphoryl)imide, methanesulfonyl fluoride, ethenesulfonyl fluoride, and phenyl difluorophosphate.

[0072] Furthermore, the non-aqueous electrolyte of this disclosure includes vinylene carbonate, bis(oxalato)borate, difluorooxalatoborate, difluorobis(oxalato)phosphate, tetrafluorooxalatophosphate, (difluorophosphoryl)(fluorosulfonyl)imide salt, difluorophosphate, fluorosulfonate, 1,3-propensultone, 1,3-propanesultone, 1,6-diisocyanatohexane, ethynylethylene carbonate, 1,3,2-dioxathiolan-2,2-dioxide, 4-propyl-1,3,2-dioxathiolan-2,2-dioxide, and methylene. The solution may contain at least one selected from methanedisulfonate, 1,2-ethanedisulfonic anhydride, methanesulfonyl fluoride, tris(trimethylsilyl)borate, (ethoxy)pentafluorocyclotriphosphazene, tetrafluoro(malonato) phosphate, tetrafluoro(picolinato) phosphate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-hexafluoroisopropyl)disiloxane, tetravinylsilane, t-butylbenzene, t-amylbenzene, fluorobenzene, and cyclohexylbenzene. The content of the above additives in the non-aqueous electrolyte is preferably 0.01% by mass or more and 5.0% by mass or less, based on the total amount of the non-aqueous electrolyte.

[0073] The non-aqueous electrolyte of this disclosure may also contain, as other additives, a compound represented by the following general formula (3).

[0074] [ka]

[0075] [In general formula (3), R 6 ~R 8Each of these is an organic group independently selected from a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and a fluorine atom, an oxygen atom, or an unsaturated bond may be present in the organic group. However, R 6 ~R 8 At least one of them is a fluorine atom. M m+ [where m is an alkali metal cation, alkaline earth metal cation, or onium cation, and m is an integer equal to the valency of the corresponding cation.]

[0076] When a compound represented by general formula (3) (a salt having an imido anion) has at least one PF bond or SF bond, excellent low-temperature properties can be obtained. The more PF bonds or SF bonds in the salt having the imido anion, the better the low-temperature properties can be further improved, and is therefore preferable. In the salt having the imido anion represented by general formula (3), R 6 ~R 8 It is even more preferable if the compound consists entirely of fluorine atoms.

[0077] Furthermore, in a salt having an imido anion represented by the above general formula (3), R 6 ~R 8 At least one of them is a fluorine atom, R 6 ~R 8 It is preferable that at least one of these compounds is selected from hydrocarbon groups having 6 or fewer carbon atoms, which may contain a fluorine atom.

[0078] Furthermore, in a salt having an imido anion represented by the above general formula (3), R6 ~R 8 At least one of them is a fluorine atom, R 6 ~R 8 Preferably, at least one of the compounds is selected from a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a 2-propynyl group, a 2-propynyloxy group, a phenyl group, a phenyloxy group, a 2,2-difluoroethyl group, a 2,2-difluoroethyloxy group, a 2,2,2-trifluoroethyl group, a 2,2,2-trifluoroethyloxy group, a 2,2,3,3-tetrafluoropropyl group, a 2,2,3,3-tetrafluoropropyloxy group, a 1,1,1,3,3,3-hexafluoroisopropyl group, and a 1,1,1,3,3,3-hexafluoroisopropyloxy group.

[0079] The countercation M of the salt having the imido anion represented by the general formula (3) above m+ However, it is preferable that the ions be selected from the group consisting of lithium ions, sodium ions, potassium ions, and tetraalkylammonium ions.

[0080] Furthermore, in the above general formula (3), R 6 ~R 8 Examples of alkyl and alkoxy groups represented by include alkyl groups and fluorine-containing alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-butyl group, 3-butyl group, pentyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, and 1,1,1,3,3,3-hexafluoroisopropyl group, as well as alkoxy groups derived from these groups.

[0081] Examples of alkenyl groups and alkenyloxy groups include alkenyl groups with 2 to 10 carbon atoms, such as vinyl groups, allyl groups, 1-propenyl groups, isopropenyl groups, 2-butenyl groups, and 1,3-butadienyl groups, as well as fluorine-containing alkenyl groups and alkenyloxy groups derived from these groups.

[0082] Examples of alkynyl groups and alkynyloxy groups include alkynyl groups with 2 to 10 carbon atoms, such as ethynyl, 2-propynyl, and 1,1-dimethyl-2-propynyl groups, as well as fluorine-containing alkynyl groups and alkynyloxy groups derived from these groups.

[0083] Examples of cycloalkyl and cycloalkoxy groups include cycloalkyl groups with 3 to 10 carbon atoms, such as cyclopentyl and cyclohexyl groups, as well as fluorine-containing cycloalkyl groups and cycloalkoxy groups derived from these groups.

[0084] Examples of cycloalkenyl groups and cycloalkenyloxy groups include cycloalkenyl groups with 3 to 10 carbon atoms, such as cyclopentenyl and cyclohexenyl groups, as well as fluorine-containing cycloalkenyl groups and cycloalkenyloxy groups derived from these groups.

[0085] Examples of aryl groups and aryloxy groups include aryl groups with 6 to 10 carbon atoms, such as phenyl groups, tolyl groups, and xylyl groups, as well as fluorine-containing aryl groups and aryloxy groups derived from these groups.

[0086] Specific examples and synthesis methods of salts having the imide anion represented by the above general formula (3) are described in International Publication No. 2017 / 111143.

[0087] The content of the other additives in the non-aqueous electrolyte is preferably 0.01% by mass or more and 8.0% by mass or less, relative to the total amount of the non-aqueous electrolyte.

[0088] Furthermore, when the ionic salt listed as the solute is present in a non-aqueous electrolyte at a concentration lower than 0.5 mol / L, which is the lower limit of the solute's preferred concentration, it can act as an "other additive" and exhibit negative electrode film formation and positive electrode protection effects. In this case, the content in the non-aqueous electrolyte is preferably between 0.01% and 5.0% by mass. Examples of ionic salts in this case include, for example, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium (trifluoromethanesulfonyl)(fluorosulfonyl)imide when the non-aqueous electrolyte battery is a lithium-ion battery, and sodium hexafluorophosphate, sodium tetrafluoroborate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, sodium bis(fluorosulfonyl)imide, and sodium (trifluoromethanesulfonyl)(fluorosulfonyl)imide when the non-aqueous electrolyte battery is a sodium-ion battery.

[0089] Furthermore, alkali metal salts other than the solutes mentioned above may be used as additives. Specifically, examples include carboxylates such as lithium acrylate, sodium acrylate, lithium methacrylate, and sodium methacrylate, as well as sulfate esters such as lithium methyl sulfate, sodium methyl sulfate, lithium ethyl sulfate, and sodium ethyl sulfate.

[0090] In the non-aqueous electrolyte of this disclosure, from the viewpoint of improving the durability (lifespan) of the battery, if the non-aqueous electrolyte battery is a lithium-ion battery, it is preferable that at least one selected from vinylene carbonate, fluoroethylene carbonate, lithium bis(oxalato)borate, lithium difluorooxalatoborate, lithium difluorobis(oxalato)phosphate, lithium tetrafluorooxalatophosphate, lithium bis(fluorosulfonyl)imide, lithium (difluorophosphoryl)(fluorosulfonyl)imide, lithium difluorophosphate, lithium fluorosulfonate, 1,3-propensultone, 1,3-propanesultone, 1,3,2-dioxathiolan-2,2-dioxide, and 4-propyl-1,3,2-dioxathiolan-2,2-dioxide is contained in 0.01 to 5.0% by mass of the total amount of the non-aqueous electrolyte. In the case of a non-aqueous electrolyte battery, it is preferable that at least one selected from vinylene carbonate, fluoroethylene carbonate, sodium bis(oxalato)borate, sodium difluorooxalatoborate, sodium difluorobis(oxalato)phosphate, sodium tetrafluorooxalatophosphate, sodium bis(fluorosulfonyl)imide, sodium (difluorophosphoryl)(fluorosulfonyl)imide, sodium difluorophosphate, sodium fluorosulfonate, 1,3-propensultone, 1,3-propanesultone, 1,3,2-dioxathiolan-2,2-dioxide, and 4-propyl-1,3,2-dioxathiolan-2,2-dioxide be included in 0.01 to 5.0% by mass relative to the total amount of the non-aqueous electrolyte.

[0091] Furthermore, the non-aqueous electrolyte of this disclosure may also contain polymers, and it is possible to use the non-aqueous electrolyte in a pseudo-solid state with a gelling agent or crosslinked polymer, as is the case when used in non-aqueous electrolyte batteries called polymer batteries. Polymer solid electrolytes may also include those containing a non-aqueous organic solvent as a plasticizer.

[0092] The polymer described above is not particularly limited as long as it is an aprotic polymer capable of dissolving the compound represented by the general formula (1), the solute, and the other additives described above. Examples include polymers having polyethylene oxide as the main chain or side chain, homopolymers or copolymers of polyvinylidene fluoride, methacrylate polymers, and polyacrylonitrile. When a plasticizer is added to these polymers, an aprotic nonaqueous organic solvent is preferred among the nonaqueous organic solvents described above.

[0093] [2. Non-aqueous electrolyte battery] The non-aqueous electrolyte battery of this disclosure comprises at least the non-aqueous electrolyte of this disclosure, a negative electrode, and a positive electrode. Furthermore, it is preferable to include a separator, an outer casing, etc.

[0094] While not particularly limited, it is preferable to use a material that allows for the reversible insertion and removal of alkali metal ions, such as lithium ions and sodium ions, or alkaline earth metal ions, as the negative electrode.

[0095] 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 can be one that is capable of doping and dedoping with lithium ions. Examples include carbon materials with a d value of 0.340 nm or less at the lattice plane (002 plane) in X-ray diffraction, carbon materials with a d value of 0.340 nm or more at the lattice plane (002 plane) in X-ray diffraction, oxides of one or more metals selected from Si, Sn, and Al, one or more metals selected from Si, Sn, and Al or alloys containing these metals or alloys with lithium, and materials containing at least one selected from lithium titanium oxide. These negative electrode active materials can be used individually or in combination of two or more. In addition, lithium metal, metal nitrides, tin compounds, conductive polymers, etc. may also be used.

[0096] For example, in the case of a sodium-ion secondary battery in which the cation is mainly sodium, the negative electrode active material that constitutes the negative electrode can be sodium metal, alloys of sodium metal with other metals such as tin, intermetallic compounds, various carbon materials including hard carbon, metal oxides such as titanium oxide, metal nitrides, elemental tin, tin compounds, activated carbon, conductive polymers, etc. In addition to these, elemental phosphorus such as red phosphorus and black phosphorus, phosphorus compounds such as Co-P, Cu-P, Sn-P, Ge-P, and Mo-P, elemental antimony, antimony compounds such as Sb / C and Bi-Sb, etc. These negative electrode active materials may be used individually or in combination of two or more types.

[0097] While not particularly limited, it is preferable to use a material that allows for the reversible insertion and removal of alkali metal ions, such as lithium ions and sodium ions, or alkaline earth metal ions, as the positive electrode.

[0098] For example, when the cation is lithium, lithium-containing transition metal composite oxides such as LiCoO2, LiNiO2, LiMnO2, and LiMn2O4 are used as positive electrode materials; these lithium-containing transition metal composite oxides contain a mixture of multiple transition metals such as Co, Mn, and Ni; these lithium-containing transition metal composite oxides have some of their transition metals replaced by other metals; phosphate compounds of transition metals called olivine, such as LiFePO4, LiCoPO4, and LiMnPO4; oxides such as TiO2, V2O5, and MoO3; sulfides such as TiS2 and FeS; or conductive polymers such as polyacetylene, poly(p-phenylene), polyaniline, and polypyrrole; activated carbon; polymers that generate radicals; and carbon materials. Specifically, Li[Ax 1 / 3 Mn 1 / 3 Co 1 / 3 ]O2, Li[Ni 0.45 Mn 0.35 Co 0.2 ]O2, Li[Ni 0.5 Mn 0.3 Co 0.2 ]O2, Li[Ni 0.6 Mn 0.2 Co 0.2 ]O2, Li[Ni 0.8 Mn 0.1 Co 0.1 ]O2, Li[Ni 0.49 Mn 0.3 Co 0.2 Zr 0.01 ]O2, Li[Ni 0.49 Mn 0.3 Co 0.2 Mg 0.01 ]O2, LiNi 0.8 Co 0.2 O2, LiLiLi 0.85 Co 0.10 Al 0.05 O2, LiLiLi 0.87 Co 0.10 Al 0.03 O2, LiLiLi 0.90 Co 0.07 Al 0.03 O2, LiLiLi 0.6 Co 0.3 Al 0.1 O 2、 LiMn 1.5 Ni0.5 Examples include O4.

[0099] For example, if the cation is sodium, the positive electrode material (positive electrode active material) could be NaCrO2 or NaFe 0.5 Co 0.5 O2, NaFe 0.4 Mn 0.3 Ni 0.3 O2, NaNi 0.5 Ti 0.3 Mn 0.2 O2, NaNi 1 / 3 Ti 1 / 3 Mn 1 / 3 O2, NaNi 0.33 Ti 0.33 Mn 0.16 Mg 0.17 O2, Na 2 / 3 Ni 1 / 3 Ti 1 / 6 Mn 1 / 2 O2, Na 2 / 3 Ni 1 / 3 Mn 2 / 3 Sodium-containing transition metal composite oxides such as O2, mixtures of multiple transition metals such as Co, Mn, and Ni in these sodium-containing transition metal composite oxides, and cases in which some of the transition metals in these sodium-containing transition metal composite oxides are substituted with other metals, polyanionic compounds such as NaFePO4, NaVPO4F, Na3V2(PO4)3, and Na2Fe2(SO4)3, and composition formula Na a M b [Fe(CN)6] c Sodium salts of Prussian blue analogs represented by (M = Cr, Mn, Fe, Co, Ni, Cu, or Zn, with 0 ≤ a ≤ 2, 0.5 ≤ b ≤ 1.5, 0.5 ≤ c ≤ 1.5), oxides such as TiO2, V2O5, and MoO3, sulfides such as TiS2 and FeS, or conductive polymers such as polyacetylene, poly(p-phenylene), polyaniline, and polypyrrole, activated carbon, radical-generating polymers, and carbon materials are used.

[0100] For the positive and negative electrode materials, conductive materials such as acetylene black, Ketjen black, carbon fiber, or graphite, and binders such as polytetrafluoroethylene, polyvinylidene fluoride, or SBR resin can be added, and electrode sheets molded into a sheet shape can be used.

[0101] Nonwoven fabrics or porous sheets made of polypropylene, polyethylene, paper, or glass fiber are used as separators to prevent contact between the positive and negative electrodes.

[0102] From these elements, electrochemical devices in shapes such as coin-shaped, cylindrical, rectangular, or aluminum laminate sheet can be assembled. [Examples]

[0103] The present disclosure will be further described below with reference to examples, but the present disclosure is not limited in any way to these examples.

[0104] <Synthesis Example-1> Synthesis of compound (a-1)

[0105] [ka]

[0106] 100 g of acetonitrile (MeCN) and 1.2 g of lithium hydroxymethanesulfonate were placed in a 50 ml round-bottom flask, and then 1.7 g of chlorosulfonyl isocyanate was slowly added. After the internal temperature had cooled to room temperature, 0.5 g of sodium fluoride was added. The reaction mixture was filtered and concentrated to obtain 2.0 g of compound (a-1) (recovery rate 76%). 1 1H NMR (CD3CN) σ H 11.49, 4.88 ppm, 19 F NMR (CD3CN) σ F 51.0 ppm.

[0107] <Synthesis Example-2> Synthesis of compound (a-2)

[0108] [ka]

[0109] 100g of MeCN and 1.3g of Li 2-hydroxyethanesulfonic acid were placed in a 50ml round-bottom flask, and then 1.5g of fluorosulfonyl isocyanate was slowly added. After the internal temperature had cooled to room temperature, 0.08g of lithium hydride was added. After the foaming subsided, concentration was performed to obtain 2.5g of compound (a-2) (95% recovery rate). 1 1H NMR (CD3CN) σ H 4.38, 3.26 ppm, 19 F NMR (CD3CN) σ F 49.1 ppm.

[0110] <Synthesis Example-3> Synthesis of compound (a-3)

[0111] [ka]

[0112] 100g of MeCN and 1.3g of Li 1-hydroxyethanesulfonic acid were placed in a 50ml round-bottom flask, and then 1.5g of fluorosulfonyl isocyanate was slowly added. After the internal temperature had cooled to room temperature, 0.08g of lithium hydride was added. After the foaming subsided, concentration was performed to obtain 2.4g of compound (a-3) (92% recovery rate). 1 1H NMR (CD3CN) σ H 5.43, 1.48 ppm, 19 F NMR (CD3CN) σ F 49.0 ppm.

[0113] <Synthesis Example-4> Synthesis of compound (a-4)

[0114] [ka]

[0115] 100g of MeCN and 1.9g of Li 6-hydroxyhexanesulfonic acid were placed in a 50ml round-bottom flask, and then 1.5g of fluorosulfonyl isocyanate was slowly added. After the internal temperature had cooled to room temperature, 0.08g of lithium hydride was added. After the foaming subsided, concentration was performed to obtain 2.9g of compound (a-4) (90% recovery rate). 1 1H NMR (CD3CN) σ H 4.45, 3.31, 1.57―0.94, ppm, 19 F NMR (CD3CN) σ F 49.3 ppm.

[0116] <Synthesis Example-5> Synthesis of compound (a-5)

[0117] [ka]

[0118] 100 g of MeCN and 1.6 g of Li 2,3-dihydrocypropanesulfonic acid were placed in a 50 ml round-bottom flask, and then 1.5 g of fluorosulfonyl isocyanate was slowly added. After the internal temperature had cooled to room temperature, 0.08 g of lithium hydride was added. After the foaming subsided, concentration was performed to obtain 3.4 g of compound (a-5) (80% recovery). 1 1H NMR (CD3CN) σ H 5.38, 4.55, 4.43, 4.10, 3.40, 3.21ppm, 19 F NMR (CD3CN) σ F 51.6, 51.1 ppm.

[0119] Furthermore, compounds a-1(Na) to a-5(Na) were obtained by subjecting the above compounds (a-1) to (a-5) to cation exchange reactions, respectively. Compounds a-1(Na) to a-5(Na) can also be obtained by reacting the corresponding sodium hydroxyalkanesulfonate with fluorosulfonyl isocyanate as a starting material and then neutralizing with sodium hydride.

[0120] [ka]

[0121] [Preparation of non-aqueous electrolytes in the examples and comparative examples] <Comparative Example 1-1> (Preparation of LiPF6 solution) In a glove box with a dew point of -60°C or lower, EC, FEC, EMC, and DMC were mixed in a volume ratio of EC:FEC:EMC:DMC = 25:5:45:25 (component (III)). Then, while maintaining the internal temperature below 40°C, an amount of LiPF6 (component (II)) to a concentration of 1.0 mol / L was added and stirred to completely dissolve the LiPF6 solution. This was obtained. This was designated as comparative non-aqueous electrolyte 1-1.

[0122] <Example 1-1> (Preparation of non-aqueous electrolyte 1-1) In a glove box with a dew point of -60°C or lower, EC, FEC, EMC, and DMC were mixed in a volume ratio of EC:FEC:EMC:DMC = 25:5:45:25 (component (III)). Then, while maintaining the internal temperature below 40°C, an amount of LiPF6 (component (II)) to a concentration of 1.0 mol / L was added, and compound (a-1) (component (I)), which corresponds to the compound represented by general formula (1), was added to a concentration of 0.05% by mass relative to the total volume of the non-aqueous electrolyte. The mixture was then stirred for 1 hour to dissolve it, thereby preparing non-aqueous electrolyte 1-1 of Example 1-1.

[0123] <Examples 1-2 to 1-15, Comparative Examples 1-2, 1-3> (Preparation of non-aqueous electrolytes 1-2 to 1-15 and comparative non-aqueous electrolytes 1-2 and 1-3) Non-aqueous electrolytes 1-2 to 1-15, comparative non-aqueous electrolytes 1-2, and 1-3 were obtained in the same manner as the preparation of non-aqueous electrolyte 1-1, except that the type and content of component (I) (or comparative compound) were changed as shown in Table 1. Compound (X) was purchased from Tokyo Chemical Industry Co., Ltd. (product code H0597). Compound (Y) was synthesized by the same method as disclosed in WO2014 / 073378.

[0124] The structures of compounds (X) and (Y) used in the comparative example are shown below.

[0125] [ka]

[0126] <Examples 2-1 to 2-3, Comparative Examples 2-1 to 2-3> (Preparation of non-aqueous electrolytes 2-1 to 2-3 and comparative non-aqueous electrolytes 2-1 to 2-3) Furthermore, non-aqueous electrolytes 2-1 to 2-3 and comparative non-aqueous electrolytes 2-1 to 2-3 were obtained in the same manner as the preparations of non-aqueous electrolytes 1-4, 1-9, 1-11 and comparative non-aqueous electrolytes 1-1 to 1-3, except that vinylene carbonate (VC) was added as an additional additive to the concentrations shown in Table 2 and dissolved.

[0127] <Examples 3-1 to 3-3, Comparative Examples 3-1 to 3-3> (Preparation of non-aqueous electrolytes 3-1 to 3-3 and comparative non-aqueous electrolytes 3-1 to 3-3) Non-aqueous electrolytes 3-1 to 3-3 and comparative non-aqueous electrolytes 3-1 to 3-3 were obtained in the same manner as the preparations of non-aqueous electrolytes 2-1 to 2-3 and comparative non-aqueous electrolytes 2-1 to 2-3, except that VC was replaced with lithium bis(oxalato)borate (BOB).

[0128] <Examples 4-1 to 4-3, Comparative Examples 4-1 to 4-3> (Preparation of non-aqueous electrolytes 4-1 to 4-3 and comparative non-aqueous electrolytes 4-1 to 4-3) Non-aqueous electrolytes 4-1 to 4-3 and comparative non-aqueous electrolytes 4-1 to 4-3 were obtained in the same manner as the preparations of non-aqueous electrolytes 2-1 to 2-3 and comparative non-aqueous electrolytes 2-1 to 2-3, except that VC was replaced with lithium difluorobis(oxalato)phosphate (DFBOP).

[0129] <Examples 5-1 to 5-3, Comparative Examples 5-1 to 5-3> (Preparation of non-aqueous electrolytes 5-1 to 5-3 and comparative non-aqueous electrolytes 5-1 to 5-3) Non-aqueous electrolytes 5-1 to 5-3 and comparative non-aqueous electrolytes 5-1 to 5-3 were obtained in the same manner as the preparations of non-aqueous electrolytes 2-1 to 2-3 and comparative non-aqueous electrolytes 2-1 to 2-3, except that VC was replaced with lithium tetrafluorooxalathrate (TFOP).

[0130] <Examples 6-1 to 6-3, Comparative Examples 6-1 to 6-3> (Preparation of non-aqueous electrolytes 6-1 to 6-3 and comparative non-aqueous electrolytes 6-1 to 6-3) Non-aqueous electrolytes 6-1 to 6-3 and comparative non-aqueous electrolytes 6-1 to 6-3 were obtained in the same manner as the preparations of non-aqueous electrolytes 2-1 to 2-3 and comparative non-aqueous electrolytes 2-1 to 2-3, except that VC was replaced with bis(fluorosulfonyl)imide lithium (FSI).

[0131] <Examples 7-1 to 7-3, Comparative Examples 7-1 to 7-3> (Preparation of non-aqueous electrolytes 7-1 to 7-3 and comparative non-aqueous electrolytes 7-1 to 7-3) Non-aqueous electrolytes 7-1 to 7-3 and comparative non-aqueous electrolytes 7-1 to 7-3 were obtained in the same manner as the preparations of non-aqueous electrolytes 2-1 to 2-3 and comparative non-aqueous electrolytes 2-1 to 2-3, except that VC was replaced with lithium difluorophosphate (DFP).

[0132] <Examples 8-1 to 8-3, Comparative Examples 8-1 to 8-3> (Preparation of non-aqueous electrolytes 8-1 to 8-3 and comparative non-aqueous electrolytes 8-1 to 8-3) Non-aqueous electrolytes 8-1 to 8-3 and comparative non-aqueous electrolytes 8-1 to 8-3 were obtained in the same manner as the preparation of non-aqueous electrolytes 2-1 to 2-3 and comparative non-aqueous electrolytes 2-1 to 2-3, except that VC was replaced with lithium fluorosulfonate (FS).

[0133] <Example 17-1> (Preparation of non-aqueous electrolyte 9-1) In a glove box with a dew point of -60°C or lower, PC, EC, FEC, and EMC were mixed in a volume ratio of PC:EC:FEC:EMC = 20:10:2:68 (component (III)). Then, while maintaining the internal temperature below 40°C, an amount of NaPF6 (component (II)) to a concentration of 1.0 mol / L was added, and compound (a-1(Na)) (component (I)), which corresponds to the compound represented by general formula (1), was added to a concentration of 0.5% by mass relative to the total volume of the non-aqueous electrolyte. The mixture was then stirred for 1 hour to dissolve it, thereby preparing the non-aqueous electrolyte 9-1 of Example 17-1.

[0134] <Examples 17-2 to 17-10, Comparative Examples 17-1, 17-2> (Preparation of non-aqueous electrolytes 9-2 to 9-10 and comparative non-aqueous electrolytes 9-1 and 9-2) Non-aqueous electrolytes 9-2 to 9-15, comparative non-aqueous electrolytes 9-1, and 9-2 were obtained in the same manner as the preparation of non-aqueous electrolyte 9-1, except that the type and content of component (I) (or comparative compound) were changed as shown in Table 17.

[0135] <Examples 18-1 to 18-3, Comparative Examples 18-1 to 18-2> (Preparation of non-aqueous electrolytes 10-1 to 10-3 and comparative non-aqueous electrolytes 10-1 to 10-2) Furthermore, non-aqueous electrolytes 10-1 to 10-3 and comparative non-aqueous electrolytes 10-1 to 10-2 were obtained in the same manner as the preparation of non-aqueous electrolytes 9-1, 9-3, 9-5 and comparative non-aqueous electrolytes 9-1 to 9-2, except that VC was added as another additive to the concentration shown in Table 18 and dissolved.

[0136] <Examples 19-1 to 19-3, Comparative Examples 19-1 to 19-2> (Preparation of non-aqueous electrolytes 11-1 to 11-3 and comparative non-aqueous electrolytes 11-1 to 11-2) Except for replacing VC with sodium fluorosulfate (NaSO3F) and adding and dissolving it to the concentrations shown in Table 19, non-aqueous electrolytes 11-1 to 11-3 and comparative non-aqueous electrolytes 11-1 to 11-2 were prepared in the same manner as the preparations for non-aqueous electrolytes 10-1 to 10-3 and comparative non-aqueous electrolytes 11-1 to 11-2.

[0137] <Examples 20-1 to 20-3, Comparative Examples 20-1 to 20-2> (Preparation of non-aqueous electrolytes 12-1 to 12-3 and comparative non-aqueous electrolytes 12-1 to 12-2) Except for replacing VC with sodium tetrafluorooxalathrate (TFOP-Na) and adding and dissolving it to the concentrations shown in Table 20, non-aqueous electrolytes 12-1 to 12-3 and comparative non-aqueous electrolytes 12-1 to 12-2 were prepared in the same manner as for non-aqueous electrolytes 10-1 to 10-3 and comparative non-aqueous electrolytes 12-1 to 12-2.

[0138] <Examples 21-1 to 21-3, Comparative Examples 21-1 to 21-2> (Preparation of non-aqueous electrolytes 13-1 to 13-3 and comparative non-aqueous electrolytes 13-1 to 13-2) Except for replacing VC with sodium difluorophosphate (DFP-Na) and adding and dissolving it to the concentrations shown in Table 21, non-aqueous electrolytes 13-1 to 13-3 and comparative non-aqueous electrolytes 13-1 to 13-2 were obtained in the same manner as the preparation of non-aqueous electrolytes 10-1 to 10-3 and comparative non-aqueous electrolytes 13-1 to 13-2.

[0139] In Tables 1 to 21 below, the content of component (I) (or comparative compound) represents the concentration relative to the total volume of the non-aqueous electrolyte. The content of other additives also represents the concentration relative to the total volume of the non-aqueous electrolyte.

[0140] [Construction of a non-aqueous electrolyte battery] (Lithium-ion battery positive electrode: Fabrication of NCM622 positive electrode) LiNi 0.6 Co0.2 Mn 0.2 90 mass% of MnO₂, 5 mass% of acetylene black as a conductive agent, and 5 mass% of polyvinylidene fluoride (hereinafter also referred to as PVDF) as a binder were mixed, and further N-methyl-2-pyrrolidone as a solvent was added to be 55 mass% based on the total mass of the positive electrode active material, the conductive agent, and the binder, and a slurry solution was prepared. This slurry solution was applied onto an aluminum foil which is a positive electrode current collector and dried at 150 °C for 12 hours, thereby obtaining a test NCM622 positive electrode with a positive electrode active material layer formed on the current collector.

[0141] (Fabrication of Lithium-Ion Battery Positive Electrode: NCM811 Positive Electrode) As the positive electrode active material, LiNi 0.8 Co 0.1 Mn 0.1 92 mass% of LiNiCoMnO₂, 4.5 mass% of acetylene black as a conductive agent, and 3.5 mass% of PVDF as a binder were mixed, and further N-methyl-2-pyrrolidone as a solvent was added to be 55 mass% based on the total mass of the positive electrode active material, the conductive agent, and the binder, and a slurry solution was prepared. This slurry solution was applied onto an aluminum foil which is a positive electrode current collector and dried at 150 °C for 12 hours, thereby obtaining a test NCM811 positive electrode with a positive electrode active material layer formed on the current collector.

[0142] (Sodium-Ion Battery Positive Electrode: Fabrication of NaNi 0.5 Ti 0.3 Mn 0.2 O₂ Positive Electrode) As the positive electrode active material, NaNi 0.5 Ti 0.3 Mn 0.2 90 mass% of NaNiTiMnO₂, 5 mass% of acetylene black as a conductive agent, and 5 mass% of PVDF as a binder were mixed, and further N-methyl-2-pyrrolidone as a solvent was added to be 50 mass% based on the total mass of the positive electrode active material, the conductive agent, and the binder, and a slurry solution was prepared. This slurry solution was applied onto an aluminum foil which is a positive electrode current collector and dried at 150 °C for 12 hours, thereby obtaining a test NaNi 0.5 Ti0.3 Mn 0.2 An O2 positive electrode was obtained.

[0143] (Fabrication of natural graphite anodes) A slurry solution was prepared by mixing 92% by mass of natural graphite powder, 3% by mass of conductive material (HS-100, manufactured by Denka Co., Ltd.), 2% by mass of carbon nanofiber (VGCF, manufactured by Showa Denko Corporation), 2% by mass of styrene-butadiene rubber, 1% by mass of carboxymethylcellulose sodium, and water. This slurry solution was applied to a copper foil, which served as the negative electrode current collector, and dried at 100°C for 12 hours to obtain a test natural graphite negative electrode with a negative electrode active material layer formed on the current collector.

[0144] (Fabrication of silicon-containing graphite anode) A slurry solution was prepared by mixing 85% by mass of artificial graphite powder with 7% by mass of nanosilicon, 3% by mass of conductive material (HS-100), 2% by mass of carbon nanofiber (VGCF), 2% by mass of styrene-butadiene rubber, 1% by mass of sodium carboxymethylcellulose, and water. This slurry solution was applied to a copper foil, which served as the negative electrode current collector, and dried at 100°C for 12 hours to obtain a test silicon-containing graphite negative electrode with a negative electrode active material layer formed on the current collector.

[0145] (Fabrication of hard carbon anodes) A slurry solution was prepared by mixing 90% by mass of hard carbon powder (Carbotron P, manufactured by Kureha Corporation) as the negative electrode active material with 10% by mass of PVDF as a binder, and then adding N-methylpyrrolidone as a solvent in an amount of 50% by mass relative to the total mass of the negative electrode active material and binder. This slurry solution was applied to an aluminum foil negative electrode current collector and dried at 150°C for 12 hours to obtain a test hard carbon negative electrode with a negative electrode active material layer formed on the current collector.

[0146] (Construction of non-aqueous electrolyte batteries) In an argon atmosphere with a dew point of -50°C or lower, a test NCM622 positive electrode and a test natural graphite negative electrode were placed via a polyethylene separator impregnated with a test electrolyte, and a non-aqueous electrolyte battery (lithium-ion battery) with an aluminum laminate casing was assembled. The non-aqueous electrolytes used were those listed in Tables 1 to 8. Furthermore, in Examples 9-1 to 9-15, Comparative Examples 9-1 to 9-3, Examples 10-1 to 10-3, Comparative Examples 10-1 to 10-3, Examples 11-1 to 11-3, Comparative Examples 11-1 to 11-3, Examples 12-1 to 12-3, Comparative Examples 12-1 to 12-3, Examples 13-1 to 13-3, Comparative Examples 13-1 to 13-3, Examples 14-1 to 14-3, Comparative Examples 14-1 to 14-3, Examples 15-1 to 15-3, Comparative Examples 15-1 to 15-3, Examples 16-1 to 16-3, and Comparative Examples 16-1 to 16-3, non-aqueous electrolyte batteries (lithium-ion batteries) were similarly prepared using NCM811 as the positive electrode and silicon-containing graphite as the negative electrode. The non-aqueous electrolytes used were those listed in Tables 9 to 16. Furthermore, in Examples 17-1 to 17-10, Comparative Examples 17-1 to 17-2, Examples 18-1 to 18-3, Comparative Examples 18-1 to 18-2, Examples 19-1 to 19-3, Comparative Examples 19-1 to 19-2, Examples 20-1 to 20-3, Comparative Examples 20-1 to 20-2, Examples 21-1 to 21-3, and Comparative Examples 21-1 to 21-2, NaNi was used as the positive electrode. 0.5 Ti 0.3 Mn 0.2 A non-aqueous electrolyte battery (sodium-ion battery) was similarly constructed using O2 as the positive electrode and a hard carbon negative electrode. The non-aqueous electrolytes used were those listed in Tables 17-21.

[0147] 〔evaluation〕 -Lithium-ion batteries: Initial charging and discharging- The fabricated non-aqueous electrolyte battery was placed in a 25°C constant temperature bath and connected to a charge / discharge device. It was charged at 3mA until it reached 4.3V. After maintaining 4.3V for 1 hour, it was discharged at 6mA until it reached 2.5V. This constituted one charge / discharge cycle, and a total of three charge / discharge cycles were performed to stabilize the battery.

[0148] -Sodium-ion batteries: Initial charging and discharging- The fabricated non-aqueous electrolyte battery was placed in a 25°C constant temperature bath and connected to a charge / discharge device. It was charged at 3mA until it reached 4.1V. After maintaining 4.1V for 1 hour, it was discharged at 6mA until it reached 1.5V. This constituted one charge / discharge cycle, and a total of three charge / discharge cycles were performed to stabilize the battery.

[0149] [Lithium-ion batteries: High-temperature cycle performance evaluation] The non-aqueous electrolyte batteries, stabilized by the initial charge-discharge process described above, were subjected to charge-discharge tests at an ambient temperature of 60°C to evaluate their high-temperature cycle characteristics. With a maximum charge voltage of 4.3V and a minimum discharge voltage of 2.5V, charge-discharge cycles were repeated using a constant current-constant voltage method at a current of 30mA. The degree of degradation of the non-aqueous electrolyte batteries was evaluated by the discharge capacity retention rate at 700 cycles in the charge-discharge test at an ambient temperature of 60°C. The "high-temperature cycle discharge capacity retention rate," expressed as the discharge capacity retention rate at 700 cycles, was calculated using the following formula. The discharge capacity of the first cycle in the charge-discharge test at an ambient temperature of 60°C was defined as the initial discharge capacity. High-temperature cycle retention rate (%) = (Discharge capacity at 700 cycles / Initial discharge capacity) × 100

[0150] [Sodium-ion batteries: High-temperature cycle performance evaluation] Aside from changing the maximum charge voltage to 4.1V and the minimum discharge voltage to 1.5V, the evaluation was the same as for lithium-ion batteries.

[0151] [Lithium-ion battery: Resistance measurement after high-temperature cycle test] After the high-temperature cycle test described above, the non-aqueous electrolyte battery was charged to 4.3V at 25°C and 6mA, and then its resistance was measured by impedance measurement in a -20°C environment.

[0152] [Sodium-ion battery: Resistance measurement after high-temperature cycle test] Aside from changing the charging voltage to 4.1V, the evaluation was the same as for lithium-ion batteries.

[0153] In each of Tables 1 to 21, the value of the resistance after the high-temperature cycle test and the discharge capacity maintenance rate after the high-temperature cycle of the comparative example (Comparative Example 1-1 in Table 1, Comparative Example 2-1 in Table 2, Comparative Example 3-1 in Table 3, Comparative Example 4-1 in Table 4, Comparative Example 5-1 in Table 5, Comparative Example 6-1 in Table 6, Comparative Example 7-1 in Table 7, Comparative Example 8-1 in Table 8, Comparative Example 9-1 in Table 9, Comparative Example 10-1 in Table 10, Comparative Example 11-1 in Table 11, Comparative Example 12-1 in Table 12, Comparative Example 13-1 in Table 13, Comparative Example 14-1 in Table 14, Comparative Example 15-1 in Table 15, Comparative Example 16-1 in Table 16, Comparative Example 17-1 in Table 17, Comparative Example 18-1 in Table 18, Comparative Example 19-1 in Table 19, Comparative Example 20-1 in Table 20, Comparative Example 21-1 in Table 21) using a comparative non-aqueous electrolyte to which neither Component (I) nor the comparative compound was added were each set to 100, and the evaluation results of each Example and Comparative Example are shown as relative values.

[0154]

Table 1

[0155]

Table 2

[0156]

Table 3

[0157]

Table 4

[0158]

Table 5

[0159]

Table 6

[0160] Table 7

[0161] Table 8

[0162] Table 9

[0163] Table 10

[0164] Table 11

[0165] Table 12

[0166] Table 13

[0167] Table 14

[0168] Table 15

[0169] Table 16

[0170] [Table 17]

[0171] [Table 18]

[0172] [Table 19]

[0173] [Table 20]

[0174] [Table 21]

[0175] As is clear from Tables 1-21, a non-aqueous electrolyte battery using a non-aqueous electrolyte containing component (I) of this disclosure exhibits excellent high-temperature cycle characteristics and can suppress the increase in battery resistance. [Industrial applicability]

[0176] This disclosure provides a non-aqueous electrolyte and a non-aqueous electrolyte battery that can improve high-temperature cycle characteristics and suppress the increase in battery resistance. Furthermore, it provides compounds and additives suitable for use in the above-mentioned non-aqueous electrolyte.

[0177] Although this 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 this disclosure. This application is based on Japanese Patent Application No. 2021-162010 filed on September 30, 2021, the contents of which are incorporated herein by reference.

Claims

1. (I) Compounds represented by the following general formula (1), (II) Solute, and (III) Non-aqueous organic solvents A non-aqueous electrolyte containing [a specific component]. 【Chemistry 1】 [In general formula (1), A represents an organic group selected from the group consisting of linear alkylene groups having 1 to 8 carbon atoms or branched alkylene groups having 2 to 8 carbon atoms, and linear alkenylene groups having 2 to 8 carbon atoms or branched alkenylene groups having 3 to 8 carbon atoms. At least one hydrogen atom in the organic group may be substituted with a fluorine atom, and an oxygen atom may also be present in the organic group. B is an oxygen atom or NR ａ Represents R ａ represents a hydrogen atom, or 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, and an aryl group having 6 to 10 carbon atoms. At least one of the hydrogen atoms in the organic group may be substituted with a halogen atom. M １ and M ２ Each of these independently represents a hydrogen atom, a metal cation, or an onium cation. １ and M ２ When represents a metal cation or an onium cation, the oxygen atom in general formula (1) and M １ Bonding with, and nitrogen atom and M ２ The bond between them represents an ionic bond. X is -S(=O) ２ -R ｂ、 or -P(=O)-R ｃ R ｄ represents, and R ｂ to R ｄ each independently represents an organic group selected from the group consisting of a fluorine atom, 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. At least one of the hydrogen atoms in the organic group may be substituted with a fluorine atom, and at least one of an oxygen atom and an unsaturated bond may be present in the organic group. Also, R ｃ and R ｄ can combine to have a cyclic structure. n is an integer between 1 and 4.

2. In the general formula (1) above, X is -S (=O) ２ -R ｂ Represents the above R ｂ The non-aqueous electrolyte according to claim 1, wherein represents a fluorine atom.

3. The non-aqueous electrolyte according to claim 1, wherein A in the general formula (1) represents a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 2 to 4 carbon atoms.

4. The solute is LiPF ６ LiBF ４ LiSbF ６ LiAsF ６ LiClO ４ LiCF ３ SO ３ LiC ４ F ９ SO ３ , LiN (SO ２ F) ２ LiAlO ２ LiAlCl ４ At least one selected from the group consisting of , LiCl, and LiI, or NaPF ６ NaBF ４ NaSbF ６ NaAsF ６ NaClO ４ NaCF ３ SO ３ NaC ４ F ９ SO ３ NaN(SO ２ F) ２、 NaAlO ２ NaAlCl ４ The non-aqueous electrolyte according to claim 1, wherein at least one selected from the group consisting of , NaCl, and NaI.

5. The nonaqueous electrolyte according to claim 1, wherein the nonaqueous organic solvent is at least one selected from the group consisting of cyclic esters, linear esters, cyclic ethers, linear ethers, sulfone compounds, sulfoxide compounds, and ionic liquids.

6. The non-aqueous electrolyte according to claim 5, wherein the non-aqueous organic solvent contains a cyclic ester, and the cyclic ester is a cyclic carbonate.

7. The non-aqueous electrolyte according to claim 6, wherein the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate.

8. The non-aqueous electrolyte according to claim 5, wherein the non-aqueous organic solvent contains a linear ester, and the linear ester is a linear carbonate.

9. The non-aqueous electrolyte according to claim 8, wherein the chain-like carbonate is at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.

10. The non-aqueous electrolyte according to claim 1, wherein the content of (I) relative to the total amount of the non-aqueous electrolyte is 0.01 to 5.0% by mass.

11. Furthermore, vinylene carbonate, bis(oxalato)borate, difluorooxalatoborate, difluorobis(oxalato)phosphate, tetrafluorooxalatophosphate, (difluorophosphoryl)(fluorosulfonyl)imide salt, difluorophosphate, fluorosulfonate, 1,3-propensultone, 1,6-diisocyanatohexane, ethynylethylene carbonate, 1,3,2-dioxathiolan-2,2-dioxide, 4-propyl-1,3,2-dioxathiolan-2,2-dioxide, methylenemethanedisulfonate The non-aqueous electrolyte according to claim 1, comprising at least one selected from 1,2-ethanedisulfonic anhydride, methanesulfonyl fluoride, tris(trimethylsilyl)borate, (ethoxy)pentafluorocyclotriphosphazene, tetrafluoro(malonato) phosphate, tetrafluoro(picolinato) phosphate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-hexafluoroisopropyl)disiloxane, tetravinylsilane, t-butylbenzene, t-amylbenzene, fluorobenzene, and cyclohexylbenzene.

12. A non-aqueous electrolyte battery comprising at least a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte according to any one of claims 1 to 11.

13. A compound represented by the following general formula (1). 【Chemistry 2】 [In general formula (1), A represents an organic group selected from the group consisting of linear alkylene groups having 1 to 8 carbon atoms or branched alkylene groups having 2 to 8 carbon atoms, and linear alkenylene groups having 2 to 8 carbon atoms or branched alkenylene groups having 3 to 8 carbon atoms. At least one hydrogen atom in the organic group may be substituted with a fluorine atom, and an oxygen atom may also be present in the organic group. B is an oxygen atom or NR ａ Represents R ａ represents a hydrogen atom, or 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, and an aryl group having 6 to 10 carbon atoms. At least one of the hydrogen atoms in the organic group may be substituted with a halogen atom. M １ and M ２ Each of these independently represents a hydrogen atom, a metal cation, or an onium cation. １ and M ２ When represents a metal cation or an onium cation, the oxygen atom in general formula (1) and M １ Bonding with, and nitrogen atom and M ２ The bond between them represents an ionic bond. X is -S (=O) ２ -R ｂ、 or -P(=O)-R ｃ R ｄ Represents R ｂ ~R ｄ Each of these independently represents a fluorine atom, or 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. At least one hydrogen atom in the organic group may be substituted with a fluorine atom, and at least one oxygen atom and an unsaturated bond may be present in the organic group. ｃ and R ｄ They can also be bonded together to form a cyclic structure. n is an integer between 1 and 4.

14. In the general formula (1) above, X is -S (=O) ２ -R ｂ Represents the above R ｂ The compound according to claim 13, wherein represents a fluorine atom.

15. The compound according to claim 13 or 14, wherein A in the general formula (1) represents a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 2 to 4 carbon atoms.

16. An additive for non-aqueous electrolytes represented by the following general formula (1). 【Transformation 3】 [In general formula (1), A represents an organic group selected from the group consisting of linear alkylene groups having 1 to 8 carbon atoms or branched alkylene groups having 2 to 8 carbon atoms, and linear alkenylene groups having 2 to 8 carbon atoms or branched alkenylene groups having 3 to 8 carbon atoms. At least one hydrogen atom in the organic group may be substituted with a fluorine atom, and an oxygen atom may also be present in the organic group. B is an oxygen atom or NR ａ Represents R ａ represents a hydrogen atom, or 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, and an aryl group having 6 to 10 carbon atoms. At least one of the hydrogen atoms in the organic group may be substituted with a halogen atom. M １ and M ２ Each of these independently represents a hydrogen atom, a metal cation, or an onium cation. １ and M ２ When represents a metal cation or an onium cation, the oxygen atom in general formula (1) and M １ Bonding with, and nitrogen atom and M ２ The bond between them represents an ionic bond. X is -S (=O) ２ -R ｂ、 or -P(=O)-R ｃ R ｄ Represents R ｂ ~R ｄ Each of these independently represents a fluorine atom, or 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. At least one hydrogen atom in the organic group may be substituted with a fluorine atom, and at least one oxygen atom and an unsaturated bond may be present in the organic group. ｃ and R ｄ They can also be bonded together to form a cyclic structure. n is an integer between 1 and 4.

17. In the general formula (1) above, X is -S (=O) ２ -R ｂ Represents the above R ｂ The additive for non-aqueous electrolyte according to claim 16, wherein represents a fluorine atom.

18. The additive for non-aqueous electrolyte according to claim 16 or 17, wherein A in the general formula (1) represents a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 2 to 4 carbon atoms.

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