Non-aqueous electrolyte, non-aqueous electrolyte battery, and compound

Abstract

The present invention provides a nonaqueous electrolyte solution comprising: (I) at least one compound selected from the group consisting of compounds represented by general formula (1) in the description (for example, compounds represented by formula (1a)) and compounds represented by general formula (2) (for example, compounds represented by formula (2a)); (II) a solute; and (III) a nonaqueous organic solvent. Thus, provided are a nonaqueous electrolyte solution that has a low initial resistance value, a nonaqueous electrolyte battery, and a compound that can be suitably used in the nonaqueous electrolyte solution.

Description

[Technical Field]

[0001] The present disclosure relates to non-aqueous electrolytes, non-aqueous electrolyte batteries, and compounds. [Background technology]

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

[0003] For example, Patent Document 1 discloses a nonaqueous electrolyte solution for lithium batteries that can be used to construct lithium batteries with excellent battery characteristics such as cycle characteristics, battery capacity, storage characteristics, and conductivity. The nonaqueous electrolyte solution is characterized in that the nonaqueous electrolyte solution has an electrolyte dissolved in a nonaqueous solvent and further contains a pyrrolidone derivative.

[0004] Furthermore, Patent Document 2 shows that by adding a nitrogen-containing heterocyclic compound such as pyrrolidone, oxazolidinone, or imidazolidinone to a nonaqueous electrolyte solution, a nonaqueous electrolyte secondary battery can be obtained that has excellent charge / discharge efficiency and capacity retention characteristics over a wide temperature range. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2009-224281 [Patent Document 2] Japanese Patent No. 5109213 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the inventors of the present invention have found that the addition of these five-membered ring compounds having an amide group increases the internal resistance, and that the effect of improving the initial input / output characteristics is small or nonexistent. Thus, there is still room for further investigation into the resistance characteristics, particularly the initial resistance characteristics.

[0007] The present disclosure has been made in view of the above circumstances, and aims to provide a nonaqueous electrolyte and a nonaqueous electrolyte battery that can reduce the initial resistance of the battery, and also aims to provide a compound that can be suitably used in the nonaqueous electrolyte. [Means for solving the problem]

[0008] In view of the above problem, the present inventors have conducted extensive research and have found that The inventors have found that a nonaqueous electrolyte battery having a low initial resistance can be obtained by using a nonaqueous electrolyte containing (I) at least one selected from the group consisting of a compound represented by the general formula (1) described below and a compound represented by the general formula (2) described below (hereinafter, sometimes referred to as "component (I)"), (II) a solute (hereinafter, sometimes referred to as "component (II)"), and (III) a nonaqueous organic solvent (hereinafter, sometimes referred to as "component (III)"). This solves the above-mentioned problem.

[0009] That is, the present inventors have found that the above problems can be solved by the following configuration.

[0010] [1] A non-aqueous electrolyte solution containing (I) at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2), (II) a solute, and (III) a non-aqueous organic solvent:

[0011] [ka]

[0012] [In the general formula (1), X represents CH2, NH, O, S, or SO2; Y represents CH or N; Z represents CH2, O, or NR 5 Represents R 5 represents a hydrogen atom, an alkali metal cation, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. R 5 When represents an alkali metal cation, the nitrogen atom in Z and R 5 The bond with represents an ionic bond. R 1 is PO(R f )2 or SO2R f Represents R f represents a halogen atom or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. R f If there are multiple R f may be the same or different. R 3 and R 4 are each independently a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between a carbon atom-carbon atom bond. Any hydrogen atom in the alkyl group may be substituted with a fluorine atom.

[0013] [ka]

[0014] [In the general formula (2), Y and Y' each independently represent CH or N. Z and Z' each independently represent CH, O, or NR 5 Represents R 5represents a hydrogen atom, an alkali metal cation, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. R 5 When represents an alkali metal cation, the nitrogen atoms in Z and Z' and R 5 The bond with represents an ionic bond. R 1 and R 2 are each independently, PO(R f )2 or SO2R f Represents R f represents a halogen atom or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. R f If there are multiple R f may be the same or different. R 3 and R 4 are each independently a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between a carbon atom-carbon atom bond. Any hydrogen atom in the alkyl group may be substituted with a fluorine atom.

[0015] [2] R in the general formula (1) 1 represents POF2 or SO2F. [3] R in the general formula (2) 1 and R 2 each independently represents POF2 or SO2F. [4] In the general formula (1), Z is NR 5 wherein R represents 5represents a hydrogen atom, a lithium ion, a sodium ion, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms. [5] In the general formula (2), Z and Z′ are each independently NR 5 wherein R represents 5 each independently represent a hydrogen atom, a lithium ion, a sodium ion, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms. [6] 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、 The nonaqueous electrolyte according to any one of [1] to [5], which is at least one selected from the group consisting of NaAlO2, NaAlCl4, NaCl, and NaI. [7] The non-aqueous electrolyte solution according to any one of [1] to [6], wherein the non-aqueous organic solvent 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. [8] The non-aqueous electrolyte solution according to [7], wherein the non-aqueous organic solvent contains a cyclic ester, and the cyclic ester is a cyclic carbonate. [9] The nonaqueous electrolyte solution according to [8], wherein the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate.

[10] The non-aqueous electrolyte solution according to [7], wherein the non-aqueous organic solvent contains a chain ester, and the chain ester is a chain carbonate.

[11] The nonaqueous electrolyte solution according to

[10] , 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.

[12] The nonaqueous electrolyte solution according to any one of [1] to

[11] , wherein the content of (I) is 0.01 to 10.0 mass % relative to the total amount of (I), (II), and (III).

[13] Furthermore, vinylene carbonate, bis(oxalato)borate, difluorooxalatoborate, difluorobis(oxalato)phosphate, tetrafluorooxalatophosphate, (difluorophosphoryl)(fluorosulfonyl)imide salt, difluorophosphate, fluorosulfonate, 1,3-propene sultone, 1,3-propane sultone, 1,6-diisocyanatohexane, ethynylethylene carbonate, 1,3,2-dioxathiolane-2,2-dioxide, 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, methylenemethane disulfonate, 1,2 The non-aqueous electrolyte solution according to any one of [1] to

[12] , which contains at least one selected from the group consisting of ethanedisulfonic anhydride, methanesulfonyl fluoride, tris(trimethylsilyl)borate, (ethoxy)pentafluorocyclotriphosphazene, lithium tetrafluoro(malonato)phosphate, tetrafluoro(picolinato)phosphate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-hexafluoroisopropyl)disiloxane, t-butylbenzene, t-amylbenzene, fluorobenzene, and cyclohexylbenzene.

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

[13] .

[15] A compound represented by the following general formula (1) or the following general formula (2).

[0016] [ka]

[0017] [In the general formula (1), X represents CH2, NH, O, S, or SO2; Y represents CH or N; Z represents CH2, O, or NR 5 Represents R 5 represents a hydrogen atom, an alkali metal cation, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. R 5 When represents an alkali metal cation, the nitrogen atom in Z and R 5 The bond with represents an ionic bond. R 1 represents POF2 or SO2F. R 3 and R 4 are each independently a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between a carbon atom-carbon atom bond. Any hydrogen atom in the alkyl group may be substituted with a fluorine atom.

[0018] [ka]

[0019] [In the general formula (2), Y and Y' each independently represent CH or N. Z and Z' each independently represent CH, O, or NR 5 Represents R 5 represents a hydrogen atom, an alkali metal cation, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. R 5 When represents an alkali metal cation, the nitrogen atoms in Z and Z' and R 5 The bond with represents an ionic bond. R1 and R 2 each independently represents POF2 or SO2F. R 3 and R 4 are each independently a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between a carbon atom-carbon atom bond. Any hydrogen atom in the alkyl group may be substituted with a fluorine atom. [Effects of the Invention]

[0020] According to the present disclosure, it is possible to provide a nonaqueous electrolyte and a nonaqueous electrolyte battery capable of reducing the initial resistance value, and also to provide a compound that can be suitably used in the nonaqueous electrolyte. DETAILED DESCRIPTION OF THE INVENTION

[0021] The configurations and combinations thereof in the following embodiments are examples, and additions, substitutions, and other modifications of the configurations are possible without departing from the spirit of the present disclosure. Furthermore, the present disclosure is not limited to the embodiments, but is limited only by the claims.

[0022] In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0023] In this specification, the initial resistance value refers to the resistance value of a nonaqueous electrolyte battery immediately after the first charge-discharge cycle performed for battery stabilization, specifically, the resistance value measured by the first impedance measurement after three cycles of charge-discharge cycles for battery stabilization.

[0024] [1. Non-aqueous electrolyte] The nonaqueous electrolyte solution of the present disclosure is a nonaqueous electrolyte solution containing (I) at least one selected from the group consisting of a compound represented by the above general formula (1) and a compound represented by the above general formula (2), (II) a solute, and (III) a nonaqueous organic solvent.

[0025] <About ingredient (I)> The non-aqueous electrolyte solution of the present disclosure contains, as component (I), at least one selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (2). When a nonaqueous electrolyte containing the above-mentioned component (I) is used in a nonaqueous electrolyte battery (e.g., a lithium-ion secondary battery or a sodium-ion secondary battery), component (I) decomposes on at least one of the positive electrode and the negative electrode, forming a coating with high cation conductivity on the surface of at least one of the positive electrode and the negative electrode. This coating is thought to suppress direct contact between the nonaqueous organic solvent or the solute and the electrode active material, thereby reducing the cation dissociation energy of the solute. The inventors believe that this results in a reduction in the initial resistance of the nonaqueous electrolyte battery.

[0026] The compound represented by general formula (1) will be described below. X represents CH2, NH, O, S or SO2. Y represents CH or N. Z represents CH2, O or NR 5 Represents.

[0027] X is preferably CH2 or O. Y is preferably N. Z is NR 5 It is preferable that:

[0028] R 5 represents a hydrogen atom, an alkali metal cation, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. R 5 When represents an alkali metal cation, the nitrogen atom in Z and R 5 The bond with represents an ionic bond.

[0029] R 5is preferably a hydrogen atom, an alkali metal cation, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, more preferably a hydrogen atom, a lithium ion, a sodium ion, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, and even more preferably a hydrogen atom, a lithium ion, a sodium ion, or a methyl group.

[0030] R 1 is PO(R f )2 or SO2R f Represents.

[0031] R f represents a halogen atom or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms. f If there are multiple R f may be the same or different.

[0032] R f When represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, etc.

[0033] The alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. Specific examples of the alkyl group containing an oxygen atom between the carbon atom-carbon atom bond include a 2-methoxyethyl group and a 2-ethoxyethyl group.

[0034] Any hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the alkyl group in which any hydrogen atom is substituted with a fluorine atom include a trifluoromethyl group, a difluoromethyl group, a fluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-difluoroethyl group, a 2-fluoroethyl group, a 3-fluoropropyl group, a 3,3,3-trifluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, and a hexafluoroisopropyl group.

[0035] R 1 is preferably POF2 or SO2F, more preferably SO2F.

[0036] R 3 and R 4 each independently represents a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms.

[0037] R 3 and R 4 When represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, etc.

[0038] The alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. Specific examples of the alkyl group containing an oxygen atom between the carbon atom-carbon atom bond include a 2-methoxyethyl group and a 2-ethoxyethyl group.

[0039] Any hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the alkyl group in which any hydrogen atom is substituted with a fluorine atom include a trifluoromethyl group, a difluoromethyl group, a fluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-difluoroethyl group, a 2-fluoroethyl group, a 3-fluoropropyl group, a 3,3,3-trifluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, and a hexafluoroisopropyl group.

[0040] The alkyl group is preferably an alkyl group having 6 or less carbon atoms, since this reduces the resistance when a coating is formed on an electrode. The alkyl group is more preferably an alkyl group having 4 or less carbon atoms, and is particularly preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, or tert-butyl group.

[0041] R 3 and R 4 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0042] Specifically, the compound represented by general formula (1) is preferably at least one selected from the group consisting of compounds represented by the following formulas (1a) to (1r). More preferably, it is at least one selected from the group consisting of a compound represented by formula (1a) (also referred to as compound (1a)), a compound represented by formula (1b) (also referred to as compound (1b)), a compound represented by formula (1c) (also referred to as compound (1c)), a compound represented by formula (1e) (also referred to as compound (1e)), and a compound represented by formula (1f) (also referred to as compound (1f)), even more preferably at least one selected from the group consisting of compound (1a) and compound (1e), and particularly preferably compound (1a).

[0043] [ka]

[0044] [ka]

[0045] The compound represented by general formula (2) will be explained below. Y and Y' each independently represent CH or N. Z and Z' each independently represent CH, O, or NR 5 Represents.

[0046] It is preferred that both Y and Y' are N. Z and Z' are both NR 5 It is preferable that:

[0047] R 5 represents a hydrogen atom, an alkali metal cation, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. R 5 When represents an alkali metal cation, the nitrogen atom in Z and R 5 The bond with represents an ionic bond.

[0048] R 5 is preferably a hydrogen atom, an alkali metal cation, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, more preferably a hydrogen atom, a lithium ion, a sodium ion, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, and even more preferably a hydrogen atom, a lithium ion, a sodium ion, or a methyl group.

[0049] R 1 and R 2 are each independently, PO(R f )2 or SO2R f Represents.

[0050] R f represents a halogen atom or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms. f If there are multiple R f may be the same or different.

[0051] R f When represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, etc.

[0052] The alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. Specific examples of the alkyl group containing an oxygen atom between the carbon atom-carbon atom bond include a 2-methoxyethyl group and a 2-ethoxyethyl group.

[0053] Any hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the alkyl group in which any hydrogen atom is substituted with a fluorine atom include a trifluoromethyl group, a difluoromethyl group, a fluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-difluoroethyl group, a 2-fluoroethyl group, a 3-fluoropropyl group, a 3,3,3-trifluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, and a hexafluoroisopropyl group.

[0054] R 1 and R 2 are each independently preferably POF2 or SO2F, and R 1 and R 2 It is more preferable that both are SO2F.

[0055] R 3 and R 4each independently represents a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms.

[0056] R 3 and R 4 When represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, etc.

[0057] The alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. Specific examples of the alkyl group containing an oxygen atom between the carbon atom-carbon atom bond include a 2-methoxyethyl group and a 2-ethoxyethyl group.

[0058] Any hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the alkyl group in which any hydrogen atom is substituted with a fluorine atom include a trifluoromethyl group, a difluoromethyl group, a fluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-difluoroethyl group, a 2-fluoroethyl group, a 3-fluoropropyl group, a 3,3,3-trifluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, and a hexafluoroisopropyl group.

[0059] The alkyl group is preferably an alkyl group having 6 or less carbon atoms, since this reduces the resistance when a coating is formed on an electrode. The alkyl group is more preferably an alkyl group having 4 or less carbon atoms, and is particularly preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, or tert-butyl group.

[0060] R 3 and R 4are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0061] Specifically, the compound represented by general formula (2) is preferably at least one selected from the group consisting of compounds represented by the following formulas (2a) to (2r). More preferably, it is at least one selected from the group consisting of a compound represented by formula (2a) (also referred to as compound (2a)), a compound represented by formula (2d) (also referred to as compound (2d)), a compound represented by formula (2f) (also referred to as compound (2f)), a compound represented by formula (2h) (also referred to as compound (2h)), a compound represented by formula (2l) (also referred to as compound (2l)), and a compound represented by formula (2p) (also referred to as compound (2p)), and even more preferably it is at least one selected from the group consisting of compound (2a) and compound (2d), and particularly preferably compound (2a).

[0062] [ka]

[0063] [ka]

[0064] In the nonaqueous electrolyte solution of the present disclosure, the total amount of component (I) (hereinafter also referred to as "the concentration of (I)") relative to the total amount (100% by mass) of components (I), (II), and (III) 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, and even more preferably 2.0% by mass or less. By setting the concentration of (I) to 0.01% by mass or more, the effect of suppressing an increase in the initial resistance of a nonaqueous electrolyte battery using the nonaqueous electrolyte can be easily achieved, while by setting the concentration of (I) to 10.0% by mass or less, the increase in viscosity of the nonaqueous electrolyte can be suppressed, making it easier to achieve the effect of suppressing an increase in the resistance of a nonaqueous electrolyte battery using the nonaqueous electrolyte.

[0065] In the nonaqueous electrolyte solution of the present disclosure, as component (I), 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.

[0066] The compound represented by formula (1) can be produced by various methods, and the production method is not particularly limited. For example, it can be obtained by reacting 2-pyrrolidone or 2-oxazolidone with fluorosulfonyl isocyanate or difluorophosphoryl isocyanate, followed by reaction with lithium hydride or dialkyl sulfate. The compound represented by formula (2) can be produced by various methods, and the production method is not particularly limited. For example, it can be obtained by reacting 2-imidazolidinone with fluorosulfonyl isocyanate or difluorophosphoryl isocyanate, followed by reaction with lithium hydride or dialkyl sulfate.

[0067] In addition, in the above general formula (1), R 1 represents POF2 or SO2F, or a compound represented by the general formula (2) above, 1 and R 2 and each independently represents POF2 or SO2F. The above compound is suitably used as an additive in a non-aqueous electrolyte.

[0068] <(II) Solute> The nonaqueous electrolyte of the present disclosure contains a solute. The solute is not particularly limited, but is preferably an ionic salt, more preferably an ionic salt containing fluorine.

[0069] 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 a hexafluorophosphate anion, a tetrafluoroborate anion, a perchlorate anion, a hexafluoroarsenate anion, a hexafluoroantimonate anion, a trifluoromethanesulfonate anion, a bis(trifluoromethanesulfonyl)imide anion, a bis(pentafluoroethanesulfonyl)imide anion, a (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide anion, a bis(fluorosulfonyl)imide anion, a (trifluoromethanesulfonyl)(fluorosulfonyl)imide anion, a (pentafluoroethanesulfonyl)(fluorosulfonyl)imide anion, and a tris(trifluoromethanesulfonyl)methide anion.

[0070] 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 preferably at least one selected from the group consisting of NaAlO2, NaAlCl4, NaCl, and NaI.

[0071] These solutes may be used singly or in any combination and ratio of two or more depending on the application. In particular, in consideration of the energy density, output characteristics, lifespan, etc. of the non-aqueous electrolyte battery, it is preferable that the cation is at least one selected from the group consisting of lithium, sodium, potassium, magnesium, and quaternary ammonium, and the anion is at least one selected from the group consisting of hexafluorophosphate anion, tetrafluoroborate anion, bis(trifluoromethanesulfonyl)imide anion, and bis(fluorosulfonyl)imide anion.

[0072] The total amount of solutes in the nonaqueous electrolyte solution of the present 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. By setting the solute concentration to 0.5 mol / L or more, it is possible to suppress a decrease in ionic conductivity, which would otherwise cause a decrease in the cycle characteristics and output characteristics of the nonaqueous electrolyte battery. By setting the solute concentration to 5.0 mol / L or less, it is possible to suppress a decrease in ionic conductivity, which would otherwise cause a decrease in the cycle characteristics and output characteristics of the nonaqueous electrolyte battery, which would otherwise cause a increase in the viscosity of the nonaqueous electrolyte.

[0073] <(III) Non-aqueous organic solvents> The type of nonaqueous organic solvent used in the nonaqueous electrolyte solution of the present disclosure is not particularly limited, and any nonaqueous organic solvent can be used. The non-aqueous organic solvent is preferably at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, chain 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 , 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. In the present disclosure, an ionic liquid having a salt structure may be used as the nonaqueous organic solvent.

[0074] It is preferable that the non-aqueous organic solvent is at least one selected from the group consisting of cyclic esters and chain esters, since this will result in excellent input / output characteristics at low temperatures. Furthermore, it is preferable that the non-aqueous organic solvent is at least one selected from the group consisting of cyclic carbonates and chain carbonates, since this provides excellent cycle characteristics at high temperatures.

[0075] It is preferable that the non-aqueous organic solvent contains a cyclic ester, and the cyclic ester is a cyclic carbonate. Specific examples of the cyclic carbonate include EC, PC, butylene carbonate, FEC, etc., and among these, at least one selected from the group consisting of EC, PC, and FEC is preferred.

[0076] It is also preferable that the non-aqueous organic solvent contains a chain ester, and the chain ester is a chain carbonate. Specific examples of the chain carbonate include EMC, DMC, DEC, methyl propyl carbonate, ethyl propyl carbonate, 2,2,2-trifluoroethyl methyl carbonate, 2,2,2-trifluoroethyl ethyl carbonate, 1,1,1,3,3,3-hexafluoro-1-propyl methyl carbonate, and 1,1,1,3,3,3-hexafluoro-1-propyl ethyl carbonate, and among these, at least one selected from the group consisting of EMC, DMC, DEC, and methyl propyl carbonate is preferred.

[0077] Specific examples of the ester include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, and ethyl 2-fluoropropionate.

[0078] <Other additives> As long as the gist of the present disclosure is not impaired, additive components generally used in the nonaqueous electrolyte solution of the present disclosure may be further added in any ratio. Specific examples of other 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, methyl propargyl carbonate, ethyl propargyl carbonate, dipropargyl carbonate, maleic anhydride, succinic anhydride, propane sultone, 1,3-propane sultone, 1,3-propene sultone, butane sultone, 1,3,2-dioxathiolane-2,2-dioxide, 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, methylenemethane disulfonate, dimethylmethane disulfonate, trimethylenemethane disulfonate, 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 an overcharge prevention effect, a negative electrode film forming effect, or a positive electrode protection effect 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.

[0079] The nonaqueous electrolyte of the present disclosure may be any of vinylene carbonate, bis(oxalato)borate, difluorooxalatoborate, difluorobis(oxalato)phosphate, tetrafluorooxalatophosphate, (difluorophosphoryl)(fluorosulfonyl)imide salt, difluorophosphate, fluorosulfonate, 1,3-propene sultone, 1,3-propane sultone, 1,6-diisocyanatohexane, ethynylethylene carbonate, 1,3,2-dioxathiolane-2,2-dioxide, 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, methyl The non-aqueous electrolyte may contain at least one additive selected from the group consisting of methylmethane disulfonate, 1,2-ethane disulfonic anhydride, methanesulfonyl fluoride, tris(trimethylsilyl)borate, (ethoxy)pentafluorocyclotriphosphazene, lithium tetrafluoro(malonato)phosphate, tetrafluoro(picolinato)phosphate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-hexafluoroisopropyl)disiloxane, t-butylbenzene, t-amylbenzene, fluorobenzene, and cyclohexylbenzene. The content of the additive 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.

[0080] The nonaqueous electrolyte solution of the present disclosure may contain a compound represented by the following general formula (3) as another additive.

[0081] [ka]

[0082] [In general formula (3), R 6 ~R 8are each independently an organic group selected from a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms or a branched alkoxy group having 3 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 the organic group may also contain a fluorine atom, an oxygen atom, or an unsaturated bond. 6 ~R 8 At least one of the groups is a fluorine atom. M m+ is an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m is an integer equal to the valence of the corresponding cation.

[0083] When the compound represented by general formula (3) (salt having an imide anion) has at least one PF bond or SF bond, excellent low-temperature properties can be obtained. The more PF bonds or SF bonds there are in the salt having an imide anion, the more the low-temperature properties can be improved, which is preferable. In the salt having an imide anion represented by general formula (3), R 6 ~R 8 It is more preferable that all of the groups are fluorine atoms.

[0084] In addition, in the salt having the imide anion represented by the above general formula (3), R 6 ~R 8 at least one of which is a fluorine atom, R 6 ~R 8 At least one of these is preferably a compound selected from hydrocarbon groups having 6 or less carbon atoms which may contain a fluorine atom.

[0085] In addition, in the salt having the imide anion represented by the above general formula (3), R 6 ~R 8 at least one of which is a fluorine atom, R 6 ~R 8 at least one of which is a compound 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.

[0086] Counter cation M of the salt having the imide anion represented by the general formula (3) m+ is preferably selected from the group consisting of lithium ions, sodium ions, potassium ions, and tetraalkylammonium ions.

[0087] In addition, in the general formula (3), R 6 ~R 8 Examples of the alkyl group and alkoxy group represented by the formula (I) include alkyl groups and fluorine-containing alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl 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, as well as alkoxy groups derived from these groups.

[0088] Examples of the alkenyl group and alkenyloxy group include alkenyl groups having 2 to 10 carbon atoms, such as vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, and 1,3-butadienyl group, as well as fluorine-containing alkenyl groups, and alkenyloxy groups derived from these groups.

[0089] Examples of the alkynyl group and alkynyloxy group include alkynyl groups having 2 to 10 carbon atoms, such as ethynyl, 2-propynyl, and 1,1-dimethyl-2-propynyl, as well as fluorine-containing alkynyl groups, and alkynyloxy groups derived from these groups.

[0090] Examples of the cycloalkyl group and cycloalkoxy group include cycloalkyl groups and fluorine-containing cycloalkyl groups having 3 to 10 carbon atoms, such as a cyclopentyl group and a cyclohexyl group, and cycloalkoxy groups derived from these groups.

[0091] Examples of the cycloalkenyl group and cycloalkenyloxy group include cycloalkenyl groups having 3 to 10 carbon atoms, such as cyclopentenyl and cyclohexenyl groups, and fluorine-containing cycloalkenyl groups, as well as cycloalkenyloxy groups derived from these groups.

[0092] Examples of the aryl group and aryloxy group include aryl groups and fluorine-containing aryl groups having 6 to 10 carbon atoms, such as phenyl, tolyl, and xylyl, and aryloxy groups derived from these groups.

[0093] Specific examples and synthesis methods of salts having an imide anion represented by the above general formula (3) include those described in WO 2017 / 111143.

[0094] The content of the other additives in the non-aqueous electrolyte is preferably 0.01 mass % or more and 8.0 mass % or less relative to the total amount of the non-aqueous electrolyte.

[0095] Furthermore, the ionic salts listed as solutes can exert a negative electrode film forming effect and a positive electrode protecting effect as "other additives" when their content in the nonaqueous electrolyte is less than 0.5 mol / L, which is the lower limit of the preferred solute concentration. In this case, the content in the nonaqueous electrolyte is preferably 0.01% by mass to 5.0% by mass. In this case, examples of the ionic salt include, when the nonaqueous electrolyte battery is a lithium ion battery, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium (trifluoromethanesulfonyl)(fluorosulfonyl)imide; and when the nonaqueous electrolyte battery is a sodium ion battery, examples of the ionic salt include sodium hexafluorophosphate, sodium tetrafluoroborate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, sodium bis(fluorosulfonyl)imide, and sodium (trifluoromethanesulfonyl)(fluorosulfonyl)imide.

[0096] Furthermore, alkali metal salts other than the above solutes may be used as additives. Specific examples include carboxylates such as lithium acrylate, sodium acrylate, lithium methacrylate, and sodium methacrylate, and sulfates such as lithium methyl sulfate, sodium methyl sulfate, lithium ethyl sulfate, and sodium ethyl sulfate.

[0097] From the viewpoint of improving the durability (life) of the battery, when the nonaqueous electrolyte battery is a lithium ion battery, the nonaqueous electrolyte solution of the present disclosure preferably contains, among the above-mentioned other additives, 0.01 to 5.0 mass% of 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-propene sultone, 1,3-propane sultone, 1,3,2-dioxathiolane-2,2-dioxide, and 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, relative to the total amount of the nonaqueous electrolyte solution. When the non-aqueous electrolyte battery is a sodium ion battery, it is preferable that the non-aqueous electrolyte contain 0.01 to 5.0 mass % of 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-propene sultone, 1,3-propane sultone, 1,3,2-dioxathiolane-2,2-dioxide, and 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, relative to the total amount of the non-aqueous electrolyte.

[0098] The nonaqueous electrolyte solution of the present disclosure may also contain a polymer, and may be used after being quasi-solidified with a gelling agent or crosslinked polymer, as in the case of a nonaqueous electrolyte battery known as a polymer battery. Polymer solid electrolytes also include those containing a nonaqueous organic solvent as a plasticizer.

[0099] The polymer is not particularly limited as long as it is an aprotic polymer that can dissolve the compound represented by general formula (1) or (2), the solute, and other additives. Examples include polymers having polyethylene oxide in the main chain or side chain, homopolymers or copolymers of polyvinylidene fluoride, methacrylic acid ester polymers, and polyacrylonitrile. When a plasticizer is added to these polymers, aprotic nonaqueous organic solvents are preferred among the nonaqueous organic solvents listed above.

[0100] [2. Non-aqueous electrolyte battery] The nonaqueous electrolyte battery of the present disclosure includes at least the nonaqueous electrolyte of the present disclosure, a negative electrode, and a positive electrode, and preferably further includes a separator, an exterior body, and the like.

[0101] The negative electrode is not particularly limited, but it is preferable to use a material that can reversibly insert and extract alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions.

[0102] For example, in the case of a lithium-ion secondary battery in which the cation is primarily lithium, the negative electrode active material constituting the negative electrode is one capable of doping and dedoping lithium ions. Examples include carbon materials having a d value of 0.340 nm or less in the (002) lattice plane in X-ray diffraction, carbon materials having a d value of more than 0.340 nm in the (002) lattice plane in X-ray diffraction, oxides of one or more metals selected from Si, Sn, and Al, alloys containing one or more metals selected from Si, Sn, and Al, alloys of these metals or alloys with lithium, and lithium titanium oxide. These negative electrode active materials can be used alone or in combination. Lithium metal, metal nitrides, tin compounds, conductive polymers, etc. may also be used.

[0103] For example, in the case of a sodium-ion secondary battery in which the cation is primarily sodium, examples of the negative electrode active material that constitutes the negative electrode include sodium metal, alloys of sodium metal with other metals such as tin, intermetallic compounds, various carbon materials such as hard carbon, metal oxides such as titanium oxide, metal nitrides, tin (element), tin compounds, activated carbon, and conductive polymers. Other examples include phosphorus (element) such as red phosphorus and black phosphorus, phosphorus compounds such as Co-P, Cu-P, Sn-P, Ge-P, and Mo-P, antimony (element), and antimony compounds such as Sb / C and Bi-Sb. These negative electrode active materials may be used alone or in combination.

[0104] The positive electrode is not particularly limited, but it is preferable to use a material that allows reversible insertion and desorption of alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions.

[0105] For example, when the cation is lithium, examples of the positive electrode material that can be used include lithium-containing transition metal composite oxides such as LiCoO2, LiNiO2, LiMnO2, and LiMn2O4; mixtures of these lithium-containing transition metal composite oxides with multiple transition metals such as Co, Mn, and Ni; lithium-containing transition metal composite oxides in which a portion of the transition metal has been substituted with a metal other than the transition metal; transition metal phosphate compounds called olivine, such as LiFePO4, LiCoPO4, and LiMnPO4; oxides such as TiO2, V2O5, and MoO3; sulfides such as TiS2 and FeS; conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole; activated carbon; radical-generating polymers; and carbon materials.

[0106] For example, if the cation is sodium, the positive electrode material (positive electrode active material) is NaCrO2, 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, NaNi1 / 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, sodium-containing transition metal composite oxides in which part of the transition metal has been replaced with a metal other than the transition metal, polyanion compounds such as NaFePO4, NaVPO4F, Na3V2(PO4)3, and Na2Fe2(SO4)3, and compounds with the formula Na a M b [Fe(CN)6] c Examples of materials that can be used include sodium salts of Prussian blue analogues represented by the following formula (where M=Cr, Mn, Fe, Co, Ni, Cu, or Zn; 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, conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole, activated carbon, radical-generating polymers, and carbon materials.

[0107] The positive and negative electrode materials may contain conductive materials such as acetylene black, ketjen black, carbon fiber, or graphite, and binders such as polytetrafluoroethylene, polyvinylidene fluoride, or SBR resin, and may be molded into sheets to form electrode sheets.

[0108] 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 is used.

[0109] The above elements are assembled into an electrochemical device having a coin-like, cylindrical, rectangular, aluminum laminate sheet, or other shape. [Example]

[0110] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these descriptions in any way.

[0111] <Synthesis Example 1> A 50 ml recovery flask was charged with 7.0 g of EMC and 0.6 g of 2-pyrrolidone, followed by slow addition of 1.0 g of fluorosulfonyl isocyanate. After the internal temperature had dropped to 25°C, 0.06 g of lithium hydride was added. After the foaming had ceased, the mixture was concentrated to give 1.4 g of compound (1a) (recovery rate: 94%). 1 H NMR(CD3CN) σ H 3.78, 2.52 ppm, 19 F NMR(CD3CN) σ F 49.0 ppm.

[0112] <Synthesis Example 2> A 50 ml recovery flask was charged with 7.0 g of EMC and 0.6 g of 2-imidazolidinone, followed by slow addition of 1.0 g of fluorosulfonyl isocyanate. After the internal temperature had dropped to 25°C, 0.06 g of lithium hydride was added. After the bubbling had ceased, the mixture was concentrated to give 1.4 g of compound (1 g) (recovery rate: 92%). 1 H NMR(CD3CN) σ H 3.78, 3.34 ppm, 19 F NMR(CD3CN) σ F 52.7 ppm.

[0113] The synthesis of compounds (1a) and (1g) has been described here, but compounds (1c), (1e), (1f), and (1i) used in the examples described later were also obtained by the same method as above, except that the corresponding starting materials were changed.

[0114] <Synthesis Example 3> A 50 ml recovery flask was charged with 7.0 g of EMC and 0.6 g of 2-imidazolidinone, followed by slow addition of 2.0 g of fluorosulfonyl isocyanate. After the internal temperature had dropped to 25°C, 0.12 g of lithium hydride was added. After the foaming had ceased, the mixture was concentrated to give 2.3 g of compound (2a) (95% recovery). 1 H NMR(CD3CN) σ H 3.76 ppm, 19 F NMR(CD3CN) σ F 49.3 ppm.

[0115] Here, the synthesis of compound (2a) was described, but compounds (2d), (2l), and (2p) used in the examples described later were also obtained by the same method as above, except that the corresponding starting materials were changed.

[0116] [Preparation of non-aqueous electrolyte solutions in examples and comparative examples] <Comparative Example 1-1> (Preparation of LiPF6 solution) In a glove box with a dew point of -60°C or less, EC, FEC, EMC, and DMC were mixed in a volume ratio of EC:FEC:EMC:DMC = 2:1:3:4 (component (III)). Then, while maintaining the internal temperature at 40°C or less, LiPF (component (II)) was added in an amount to give a concentration of 1.0 mol / L, and the mixture was stirred to completely dissolve, yielding a LiPF solution. This was designated comparative nonaqueous electrolyte 1-1.

[0117] <Example 1-1> (Preparation of non-aqueous electrolyte 1-1) In a glove box with a dew point of −60° C. or less, EC, FEC, EMC, and DMC were mixed in a volume ratio of EC:FEC:EMC:DMC=2:1:3:4 (component (III)). Then, while maintaining the internal temperature at 40° C. or less, LiPF (component (II)) was added in an amount to give a concentration of 1.0 mol / L, and compound (1a) (component (I)) corresponding to the compound represented by general formula (1) was added so as to give a concentration of 0.5 mass% relative to the total amount of components (I), (II), and (III). The mixture was stirred for 1 hour to dissolve, thereby preparing nonaqueous electrolyte 1-1 of Example 1-1.

[0118] <Examples 1-2 to 1-8, Comparative Examples 1-2 to 1-5> (Preparation of non-aqueous electrolytes 1-2 to 1-8 and comparative non-aqueous electrolytes 1-2 to 1-5) Non-aqueous electrolyte solutions 1-2 to 1-8 and comparative non-aqueous electrolyte solutions 1-2 to 1-5 were obtained in the same manner as in the preparation of non-aqueous electrolyte solution 1-1, except that the type and amount of component (I) (or comparative compound) were changed as shown in Table 1.

[0119] <Examples 2-1 and 2-2, Comparative Examples 2-1 to 2-3> (Preparation of nonaqueous electrolytes 2-1, 2-2, and comparative nonaqueous electrolytes 2-1 to 2-3) Furthermore, as another additive, vinylene carbonate was added and dissolved to the concentration shown in Table 2. Non-aqueous electrolyte solutions 2-1, 2-2, and comparative non-aqueous electrolyte solutions 2-1 to 2-3 were obtained in the same manner as in the preparation of non-aqueous electrolyte solutions 1-2, 1-6, and comparative non-aqueous electrolyte solutions 1-1, 1-3, and 1-5, respectively.

[0120] <Examples 3-1 and 3-2, Comparative Examples 3-1 to 3-3> (Preparation of nonaqueous electrolytes 3-1, 3-2, and comparative nonaqueous electrolytes 3-1 to 3-3) Non-aqueous electrolyte solutions 3-1, 3-2, and comparative non-aqueous electrolyte solutions 3-1 to 3-3 were obtained in the same manner as non-aqueous electrolyte solutions 2-1, 2-2, and comparative non-aqueous electrolyte solutions 2-1 to 2-3, except that vinylene carbonate was changed to lithium bis(oxalato)borate.

[0121] <Examples 4-1 and 4-2, Comparative Examples 4-1 to 4-3> (Preparation of nonaqueous electrolytes 4-1, 4-2, and comparative nonaqueous electrolytes 4-1 to 4-3) Non-aqueous electrolytes 4-1, 4-2, and comparative non-aqueous electrolytes 4-1 to 4-3 were obtained in the same manner as in the preparation of non-aqueous electrolytes 2-1, 2-2, and comparative non-aqueous electrolytes 2-1 to 2-3, except that vinylene carbonate was changed to lithium difluorobis(oxalato)phosphate.

[0122] <Examples 5-1 and 5-2, Comparative Examples 5-1 to 5-3> (Preparation of nonaqueous electrolytes 5-1, 5-2, and comparative nonaqueous electrolytes 5-1 to 5-3) Non-aqueous electrolytes 5-1, 5-2, and comparative non-aqueous electrolytes 5-1 to 5-3 were obtained in the same manner as non-aqueous electrolytes 2-1, 2-2, and comparative non-aqueous electrolytes 2-1 to 2-3, except that vinylene carbonate was changed to lithium tetrafluorooxalatophosphate.

[0123] <Examples 6-1 and 6-2, Comparative Examples 6-1 to 6-3> (Preparation of nonaqueous electrolytes 6-1, 6-2, and comparative nonaqueous electrolytes 6-1 to 6-3) Non-aqueous electrolytes 6-1, 6-2, and comparative non-aqueous electrolytes 6-1 to 6-3 were obtained in the same manner as non-aqueous electrolytes 2-1, 2-2, and comparative non-aqueous electrolytes 2-1 to 2-3, except that lithium bis(fluorosulfonyl)imide was used instead of vinylene carbonate.

[0124] <Examples 7-1 and 7-2, Comparative Examples 7-1 to 7-3> (Preparation of nonaqueous electrolytes 7-1, 7-2, and comparative nonaqueous electrolytes 7-1 to 7-3) Non-aqueous electrolytes 7-1, 7-2, and comparative non-aqueous electrolytes 7-1 to 7-3 were obtained in the same manner as non-aqueous electrolytes 2-1, 2-2, and comparative non-aqueous electrolytes 2-1 to 2-3, except that vinylene carbonate was changed to lithium difluorophosphate.

[0125] <Examples 8-1 to 8-10, Comparative Examples 8-1 to 8-3> (Preparation of non-aqueous electrolytes 8-1 to 8-10 and comparative non-aqueous electrolytes 8-1 to 8-3) As another additive, lithium fluorosulfonate was added and dissolved to a concentration shown in Table 8, and the type and amount of component (I) (or comparative compound) added were changed as shown in Table 8. Non-aqueous electrolyte solutions 8-1 to 8-10 and comparative non-aqueous electrolyte solutions 8-1 to 8-3 were obtained in the same manner as in the preparation of non-aqueous electrolyte solution 1-1.

[0126] In Tables 1 to 8 below, MP represents N-methylpyrrolidone, DMI represents 1,3-dimethylimidazolidinone, VC represents vinylene carbonate, BOB represents lithium bis(oxalato)borate, DFBOP represents lithium difluorobis(oxalato)phosphate, TFOP represents lithium tetrafluorooxalatophosphate, FSI represents lithium bis(fluorosulfonyl)imide, DFP represents lithium difluorophosphate, and FS represents lithium fluorosulfonate.

[0127] In the following Tables 1 to 8, the amount of component (I) (or comparative compound) added represents the concentration relative to the total amount of component (I) (or comparative compound), component (II), and component (III). The amount of other additives added represents the concentration relative to the total amount of component (I) (or comparative compound), component (II), component (III), and the other additive.

[0128] [Fabrication of non-aqueous electrolyte battery] (Preparation of NCM622 cathode) LiNi 0.6 Co 0.2 Mn 0.2 A positive electrode paste was prepared by mixing 90% O2 powder with 5% polyvinylidene fluoride (PVDF) as a binder and 5% acetylene black as a conductive material, and then adding N-methyl-2-pyrrolidone. This paste was applied to both sides of aluminum foil (A1085), dried, pressed, and then punched out to a 4 x 5 cm piece to obtain a test NCM622 positive electrode.

[0129] (Preparation of NCM811 positive electrode) LiNi 0.8 Co 0.1 Mn 0.1 A positive electrode paste was prepared by mixing 92.0% by weight of O2 powder with 3.5% by weight of polyvinylidene fluoride as a binder and 4.5% by weight of acetylene black as a conductive material, and then adding N-methyl-2-pyrrolidone. This paste was applied to both sides of aluminum foil (A1085), dried, pressed, and then punched out to a 4 x 5 cm piece to obtain a test NCM811 positive electrode.

[0130] (Production of artificial graphite negative electrode) A negative electrode composite paste was prepared by mixing 90% by mass of artificial graphite powder, 5% by mass of PVDF as a binder, and 5% by mass of acetylene black as a conductive material. This paste was applied to one side of copper foil, dried, pressed, and then punched out to a 4 x 5 cm piece to obtain a test artificial graphite negative electrode.

[0131] (Preparation of silicon-containing graphite negative electrode) A negative electrode composite paste was prepared by mixing 85% by mass of artificial graphite powder, 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 carboxymethyl cellulose, and water. This paste was applied to one side of copper foil, dried, pressed, and then punched out to a 4 x 5 cm piece to obtain a silicon-containing graphite negative electrode for testing.

[0132] (Fabrication of non-aqueous electrolyte battery) In an argon atmosphere with a dew point of -50°C or less, a terminal was welded to the above-mentioned NCM622 positive electrode, and then the electrode was sandwiched between two polyethylene separators (5 x 6 cm). The outer surface of the separator was then sandwiched between two artificial graphite negative electrodes with terminals previously welded, with the negative electrode active material facing the positive electrode active material. The resulting assembly was then placed in an aluminum-laminated bag with an opening on one side. After vacuum-injecting the nonaqueous electrolyte, the opening was heat-sealed to produce aluminum-laminated nonaqueous electrolyte batteries for the Examples and Comparative Examples. The nonaqueous electrolytes used were those listed in Tables 1 to 8. Further, in Examples 9-1 to 9-8, Comparative Examples 9-1 to 9-5, Examples 10-1 to 10-2, Comparative Examples 10-1 to 10-3, Examples 11-1 to 11-2, Comparative Examples 11-1 to 11-3, Examples 12-1 to 12-2, Comparative Examples 12-1 to 12-3, Examples 13-1 to 13-2, Comparative Examples 13-1 to 13-3, Examples 14-1 to 14-2, Comparative Examples 14-1 to 14-3, Examples 15-1 to 15-2, Comparative Examples 15-1 to 15-3, Examples 16-1 to 16-10, and Comparative Examples 16-1 to 16-3, NCM811 was used as the positive electrode and silicon-containing graphite was used as the negative electrode to prepare a non-aqueous electrolyte battery in the same manner. Note that the non-aqueous electrolytes listed in Tables 9 to 16 were used.

[0133] 〔evaluation〕 -Initial charge / discharge- The fabricated non-aqueous electrolyte battery was placed in a thermostatic chamber at 25°C and connected to a charge / discharge device in that state. It was charged to 4.3 V at 3 mA. After maintaining 4.3 V for 1 hour, it was discharged to 2.7 V at 6 mA. This constitutes one charge / discharge cycle, and a total of three charge / discharge cycles were performed to stabilize the battery.

[0134] <Initial resistance measurement> After the initial charge and discharge, the battery was charged at 25°C and 6 mA up to 4.3 V, and the resistance value was measured by impedance measurement.

[0135] In each of Tables 1 to 16, the initial resistance value of comparative examples (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, and Comparative Example 16-1 in Table 16) using comparative nonaqueous electrolytes to which neither component (I) nor comparative compounds was added was set to 100, and the evaluation results of the initial resistance of each example and comparative example are shown as relative values.

[0136]

Table 1

[0137]

Table 2

[0138]

Table 3

[0139]

Table 4

[0140]

Table 5

[0141]

Table 6

[0142]

Table 7

[0143]

Table 8

[0144]

Table 9

[0145]

Table 10

[0146]

Table 11

[0147] [Table 12]

[0148] [Table 13]

[0149] [Table 14]

[0150] [Table 15]

[0151] [Table 16]

[0152] As is clear from Tables 1 to 16, the nonaqueous electrolyte batteries using the nonaqueous electrolyte containing the component (I) of the present disclosure have low initial resistance and are excellent. [Industrial Applicability]

[0153] According to the present disclosure, it is possible to provide a nonaqueous electrolyte and a nonaqueous electrolyte battery capable of reducing the initial resistance value, and also to provide a compound that can be suitably used in the nonaqueous electrolyte.

[0154] 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 disclosure. This application is based on a Japanese patent application (Patent Application No. 2021-016941) filed on February 4, 2021, the contents of which are incorporated herein by reference.

Claims

1. (I) At least one selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2): (II) a solute, and (III) Non-aqueous organic solvent A non-aqueous electrolyte containing 【Chemical 1】 [In the general formula (1), X is CH ２ , NH, O, S or SO ２ Y represents CH or N. Z represents CH ２ , O or NR ５ Represents R ５ represents a hydrogen atom, an alkali metal cation, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. R ５ represents an alkali metal cation, the nitrogen atom in Z and R ５ The bond with represents an ionic bond. R １ is PO(R ｆ ) ２ or SO ２ R ｆ Represents R ｆ represents a halogen atom or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. ｆ If there are multiple R ｆ may be the same or different. R ３ and R ４ each independently represents a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and an oxygen atom may be contained between a carbon atom-carbon atom bond in the alkyl group. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. 【Chemistry 2】 [In the general formula (2), Y and Y′ each independently represent CH or N. Z and Z′ each independently represent CH ２ , O or NR ５ Represents R ５ represents a hydrogen atom, an alkali metal cation, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. R ５ represents an alkali metal cation, the nitrogen atoms in Z and Z′ and R ５ The bond with represents an ionic bond. R １ and R ２ are each independently PO(R ｆ ) ２ or SO ２ R ｆ Represents R ｆ represents a halogen atom or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. R ｆ If there are multiple R ｆ may be the same or different. R ３ and R ４ each independently represents a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and an oxygen atom may be contained between a carbon atom-carbon atom bond in the alkyl group. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom.

2. R in the general formula (1) １ However, POF ２ or SO ２ The non-aqueous electrolyte according to claim 1 , wherein F represents an elemental element.

3. R in the general formula (2) １ and R ２ However, each independently, POF ２ or SO ２ The non-aqueous electrolyte solution according to claim 1 or 2, wherein F is present.

4. In the general formula (1), Z is NR ５ wherein R ５ represents a hydrogen atom, a lithium ion, a sodium ion, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms.

5. In the general formula (2), Z and Z′ are each independently NR ５ wherein R ５ each independently represent a hydrogen atom, a lithium ion, a sodium ion, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms.

6. 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 , 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 6. The non-aqueous electrolyte solution according to claim 1, wherein the non-aqueous electrolyte solution is at least one selected from the group consisting of NaCl, NaCl, and NaI.

7. The nonaqueous electrolytic solution according to any one of claims 1 to 6, wherein the nonaqueous organic solvent is at least one selected from the group consisting of a cyclic ester, a chain ester, a cyclic ether, a chain ether, a sulfone compound, a sulfoxide compound, and an ionic liquid.

8. The non-aqueous electrolyte solution according to claim 7 , wherein the non-aqueous organic solvent contains a cyclic ester, and the cyclic ester is a cyclic carbonate.

9. 9. The nonaqueous electrolyte solution according to claim 8, wherein the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate.

10. 8. The non-aqueous electrolyte solution according to claim 7, wherein the non-aqueous organic solvent contains a chain ester, and the chain ester is a chain carbonate.

11. 11. The nonaqueous electrolyte solution according to claim 10, 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.

12. The nonaqueous electrolyte solution according to any one of claims 1 to 11, wherein the content of (I) is 0.01 to 10.0 mass% relative to the total amount of (I), (II), and (III).

13. Further, vinylene carbonate, bis(oxalato)borate, difluorooxalatoborate, difluorobis(oxalato)phosphate, tetrafluorooxalatophosphate, (difluorophosphoryl)(fluorosulfonyl)imide salt, difluorophosphate, fluorosulfonate, 1,3-propene sultone, 1,3-propane sultone, 1,6-diisocyanatohexane, ethynylethylene carbonate, 1,3,2-dioxathiolane-2,2-dioxide, 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, methylenemethane disulfonate, 1, The non-aqueous electrolyte solution according to any one of claims 1 to 12, comprising at least one selected from the group consisting of 2-ethanedisulfonic anhydride, methanesulfonyl fluoride, tris(trimethylsilyl)borate, (ethoxy)pentafluorocyclotriphosphazene, lithium tetrafluoro(malonato)phosphate, tetrafluoro(picolinato)phosphate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-hexafluoroisopropyl)disiloxane, t-butylbenzene, t-amylbenzene, fluorobenzene, and cyclohexylbenzene.

14. A non-aqueous electrolyte battery comprising at least a positive electrode, a negative electrode, a separator, and the non-aqueous electrolyte according to any one of claims 1 to 13.

15. A compound represented by the following general formula (1) or the following general formula (2): 【Chemistry 3】 [In the general formula (1), X is CH ２ , NH, O, S or SO ２ Y represents CH or N. Z represents CH ２ , O or NR ５ Represents R ５ represents a hydrogen atom, an alkali metal cation, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. R ５ represents an alkali metal cation, the nitrogen atom in Z and R ５ The bond with represents an ionic bond. R １ is POF ２ or SO ２ Represents F. R ３ and R ４ each independently represents a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and an oxygen atom may be contained between a carbon atom-carbon atom bond in the alkyl group. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. 【Chemistry 4】 [In the general formula (2), Y and Y′ each independently represent CH or N. Z and Z′ each independently represent CH ２ , O or NR ５ Represents R ５ represents a hydrogen atom, an alkali metal cation, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and the alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. R ５ represents an alkali metal cation, the nitrogen atoms in Z and Z′ and R ５ The bond with represents an ionic bond. R １ and R ２ are each independently a POF ２ or SO ２ Represents F. R ３ and R ４ each independently represents a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, and an oxygen atom may be contained between a carbon atom-carbon atom bond in the alkyl group. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom.

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