Non-aqueous electrolyte, and non-aqueous electrolyte battery

Abstract

Provided is a non-aqueous electrolyte containing: a solute; a non-aqueous organic solvent; at least one compound selected from the group consisting of compounds represented by general formula (1-1) in the description and compounds represented by general formula (1-2) in the description; and a compound represented by general formula (2). Also provided is a non-aqueous electrolyte battery using the same.

Description

Non-aqueous electrolyte and non-aqueous electrolyte battery

[0001] This disclosure relates to non-aqueous electrolytes and non-aqueous electrolyte batteries.

[0002] To date, various battery components, including the active materials of the positive and negative electrodes, have been considered as means to improve 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. Patent Document 1 describes a secondary battery comprising a positive electrode and a negative electrode capable of adsorbing and releasing electrode reactants, and an electrolyte containing a solvent and an electrolyte salt, wherein the solvent contains a specific sulfone compound, the positive electrode has a positive electrode active material layer in a part of the positive electrode current collector, and the negative electrode has a negative electrode active material layer in a region of the negative electrode current collector facing the positive electrode active material layer and in a region facing the positive electrode current collector, and an insulating member is disposed in at least the region where the positive electrode current collector and the negative electrode active material layer face each other. Patent Document 2 describes a non-aqueous electrolyte containing a silane compound having a specific structure and a fluorine-containing compound having a specific structure, and a non-aqueous electrolyte battery using the same.

[0003] Japanese Patent Publication No. 2010-165549 Japanese Patent Publication No. 2016-157679

[0004] However, it has been found that the non-aqueous electrolytes described in Patent Documents 1 and 2 have room for improvement in their high-temperature storage characteristics (the rate at which discharge capacity is maintained when a non-aqueous electrolyte battery is stored at high temperatures). The purpose of this disclosure is to provide a non-aqueous electrolyte that can improve high-temperature storage characteristics when used in a non-aqueous electrolyte battery, and a non-aqueous electrolyte battery using the same.

[0005] The above problem can be solved with the following configuration.

[0006] <1> A non-aqueous electrolyte containing (I) a solute, (II) a non-aqueous organic solvent, (III) at least one compound selected from the group consisting of compounds represented by the following general formula (1-1) and compounds represented by the following general formula (1-2), and (IV) a compound represented by the following general formula (2).

[0007]

[0008] [In general formula (1-1), R １ represents an alkylene group having 1 to 5 carbon atoms or an alkenylene group having 2 to 5 carbon atoms. In general formula (1-2), R ２ , R ３ , R ４ , and R ５ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms. ]

[0009]

[0010] [In general formula (2), M ｎ＋ represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and n represents an integer equal to the valence of the corresponding cation. X represents a sulfur atom or a phosphorus atom. When X represents a sulfur atom, m represents 2 and R ９ does not exist. When X represents a phosphorus atom, m represents 1. R ６ to R ９ each independently represent a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an 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 cycloalkyloxy 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, or an aryloxy group having 6 to 10 carbon atoms. When there are a plurality of R ６ to R ９ , they may be the same or different. ] <2> R in the general formula (1-1) １The non-aqueous electrolyte according to <1>, wherein R in the general formula (1-2) represents a methylene group, an ethylene group, a fluoroethylene group, a 1,2-difluoroethylene group, a 1,1,2,2-tetrafluoroethylene group, an ethenyl group, a 1,2-difluoroethenyl group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1-(trifluoromethyl)ethylene group, a trimethylene group, a 1-butene group, a 1,3-butadiene group, a 2-methyltrimethylene group, a 2-fluorotrimethylene group, a 1,2-dimethyltrimethylene group, a 1-butene-3-yne group, a 1-pentene group, a 1,4-pentadiene group, a 1-pentene-4-yne group, or a 1-butene-3-methyl group. <3> R in the general formula (1-2) ２ , R ３ , R ４ , and R ５ The non-aqueous electrolyte according to <1> or <2>, wherein each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, an ethenyl group, an ethynyl group, a 2-propyl group, a 1-methylethenyl group, or a methoxy group. <4> The R in the general formula (2) ６ ~R ９ A non-aqueous electrolyte according to any one of <1> to <3>, wherein at least one of represents a fluorine atom. <5> M in the general formula (2) ｎ＋ A non-aqueous electrolyte according to any one of <1> to <4>, wherein (I) represents lithium ions or sodium ions. <6> A non-aqueous electrolyte according to any one of <1> to <5>, wherein the concentration of (III) is 0.01 to 5% by mass relative to the total amount of non-aqueous electrolyte. <7> A non-aqueous electrolyte according to any one of <1> to <6>, wherein the concentration of (IV) is 0.01 to 5% by mass relative to the total amount of non-aqueous electrolyte. <8> (I) is LiPF ６ LiBF ４ LiSbF ６ LiAsF ６ LiClO ４ , LiN (SO ２ F) ２ LiAlO ２ LiAlCl ４ A non-aqueous electrolyte according to any one of <1> to <7>, wherein at least one is selected from the group consisting of , LiCl, and LiI. <9> The above (I) is NaPF ６、!BF ４ 、!? ６ 、!... ６ 、!!|, ４ 、!??(3-) ２ F) ２ 、!?... ２ 、!!!, ４A non-aqueous electrolyte according to any one of <1> to <8>, wherein (II) is at least one selected from the group consisting of NaCl and NaI. <10> A non-aqueous electrolyte according to any one of <1> to <9>, wherein (II) comprises at least one selected from the group consisting of cyclic esters, linear esters, cyclic ethers, linear ethers, sulfone compounds, sulfoxide compounds and ionic liquids. <11> A non-aqueous electrolyte according to <10>, wherein the cyclic ester comprises a cyclic carbonate. <12> A non-aqueous electrolyte according to <11>, wherein the cyclic carbonate comprises at least one selected from the group consisting of ethylene carbonate and propylene carbonate. <13> A non-aqueous electrolyte according to any one of <10> to <12>, wherein the linear ester comprises a linear carbonate. <14> The non-aqueous electrolyte according to <13>, wherein the chain carbonate comprises at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate. <15> Furthermore, cyclohexylbenzene, cyclohexylfluorobenzene, biphenyl, 2-fluorobiphenyl, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, fluorobenzene, difluoroanisole, vinylene carbonate, oligomer of vinylene carbonate (number average molecular weight in terms of polystyrene is 170 to 5000), vinylethylene carbonate, divinylethylene carbonate, fluoroethylene carbonate, ethynylethylene carbonate, trans-difluoroethylene carbonate, methylpropargyl carbonate, ethylpropargyl carbonate - Carbonate, dipropargyl carbonate, dimethylvinylene carbonate, dimethyl dicarbonate, bis(1,1,1,3,3,3-hexafluoro-1-propyl) carbonate, bis(2,2,2-trifluoroethyl) carbonate, 1,6-diisocyanatohexane, maleic anhydride, succinic anhydride, 1,4-dioxan-2,6-dione, glutaric anhydride, methanedisulfonic anhydride, 1,3-propanesultone, 1,3-propensultone, 1,4-butanesultone, 2,4-butanesultone, 1,3,2-dioxathiolan-2,2-dioxide, 4-propyl-1,32-Dioxathiolane-2,2-dioxide, methylene methane disulfonate, dimethyl methane disulfonate, trimethylene methane disulfonate, methyl methanesulfonate, methanesulfonyl fluoride, ethenesulfonyl fluoride, 1,2-ethane disulfonic anhydride, methanesulfonic anhydride, N,N'-carbonyl bis(N-methylsulfamoyl fluoride), difluoro(picolinato)borate, phenyl difluorophosphate, tripropargyl Sulfate, tetrafluoro(picolinato) phosphate, (ethoxy)pentafluorocyclotriphosphazene, succinonitrile, methyldifluorovinylsilane, methylfluorodivinylsilane, dimethyldivinylsilane, trivinylmethylsilane, trivinylfluorosilane, tetravinylsilane, tris(trimethylsilyl)borate, tris(trimethylsilyl) phosphate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-Hexafluoroisopropyl)disiloxane, fluorosulfonate, trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutanesulfonate, monomethyl sulfate, monoethyl sulfate, bis(trifluoromethanesulfonyl)imide, bis(pentafluoroethanesulfonyl)imide, (trifluoromethanesulfonyl)(nonafluorobutanesulfonyl)imide, (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide, (trifluoromethanesulfonyl)(fluorosulfonyl)imide, (pentafluoroethanesulfonyl)(fluorosulfonyl) A non-aqueous electrolyte according to any one of <1> to <14>, comprising at least one selected from nyl)imide salt, monofluorophosphate, difluorophosphate, tetrafluoro(malonato)phosphate, tris(oxalato)phosphate, difluorobis(oxalato)phosphate, tetrafluorooxalatophosphate, bis(oxalato)borate, difluorooxalatoborate, difluoro(malonato)borate, tris(trifluoromethanesulfonyl)methide salt, tris(fluorosulfonyl)methide salt, acrylate, methacrylate, nitrate, nitrite, hexafluoroisopropanol, and trifluoroethanol. <16> 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 <15>. <17> A method for manufacturing a non-aqueous electrolyte battery, comprising the step of injecting the non-aqueous electrolyte according to any one of <1> to <15>.

[0011] According to this disclosure, it is possible to provide a non-aqueous electrolyte that can improve high-temperature storage characteristics when used in a non-aqueous electrolyte battery, and a non-aqueous electrolyte battery using the same.

[0012] In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively.

[0013] The following is a detailed description of this disclosure, but the description of the constituent elements described below is an example of an embodiment of this disclosure and is not limited to these specific contents.

[0014] 1. Regarding the non-aqueous electrolyte, the non-aqueous electrolyte of this disclosure contains (I) a solute, (II) a non-aqueous organic solvent, (III) at least one compound selected from the group consisting of compounds represented by the following general formula (1-1) and compounds represented by the following general formula (1-2), and (IV) a compound represented by the following general formula (2).

[0015]

[0016] [In general formula (1-1), R １ R represents an alkylene group having 1 to 5 carbon atoms, or an alkenylene group having 2 to 5 carbon atoms. In general formula (1-2), R ２ , R ３ , R ４ , and R ５ Each of these independently represents a hydrogen atom, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms.

[0017]

[0018] [In general formula (2), M ｎ＋ represents an alkali metal cation, alkaline earth metal cation, or onium cation, and n represents an integer equal to the valency of the corresponding cation. X represents a sulfur atom or a phosphorus atom. If X represents a sulfur atom, m represents 2, and R ９ It does not exist. If X represents a phosphorus atom, then m represents 1. R ６ ~R ９ Each of these independently represents a fluorine atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C2-C10 alkenyl group, a C2-C10 alkenyloxy group, a C2-C10 alkynyl group, a C2-C10 alkynyloxy group, a C3-C10 cycloalkyl group, a C3-C10 cycloalkyloxy group, a C3-C10 cycloalkenyl group, a C3-C10 cycloalkenyloxy group, a C6-C10 aryl group, or a C6-C10 aryloxy group. ６ ~R ９ If there are multiple instances, they may be the same or different.

[0019] <Regarding (I) Solute> The (I) solute (also referred to as "(I)") contained in the non-aqueous electrolyte of this disclosure will be described below. The (I) solute can be any type of solute that has been conventionally used in the field of such non-aqueous electrolytes, without any particular limitations. Such a solute is preferably an ionic salt consisting of a pair of any cation and anion, and any type of solute can be used without particular limitations, as long as it exists in an ionic state as a cation and anion in a non-aqueous organic solvent. For example, such a 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, hexafluoroantimonate anion, hexafluoroarsenate anion, perchlorate anion, bis(fluorosulfonyl)imide anion, aluminate anion, tetrachloroaluminate anion, chloride ion, and iodide ion. Specifically, LiPF ６ LiBF ４ LiSbF ６ LiAsF ６ LiClO ４ , 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 NaN(SO ２ F) ２ NaAlO ２ NaAlCl ４ At least one selected from the group consisting of NaCl and NaI can be preferably listed.

[0020] 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 ions, sodium ions, potassium ions, magnesium ions, and quaternary ammonium cations, and that the anion be at least one selected from the group consisting of hexafluorophosphate anions, tetrafluoroborate anions, and bis(fluorosulfonyl)imide anions.

[0021] The non-aqueous electrolyte of this disclosure may be (I) used as a single compound alone, or two or more compounds may be mixed in any combination and ratio according to the application.

[0022] There are no particular restrictions on the concentration of (I) relative to the total amount of non-aqueous electrolyte. For example, the lower limit of the concentration of (I) may be 0.5 mol / L or higher, 0.7 mol / L or higher, or 0.9 mol / L or higher. The upper limit of the concentration of (I) may be 5 mol / L or lower, 4 mol / L or lower, or 2 mol / L or lower. A concentration of 0.5 mol / L or higher is preferable because it does not easily reduce ionic conductivity, and the cycle characteristics and output characteristics of the non-aqueous electrolyte battery do not easily deteriorate. On the other hand, a concentration of 5 mol / L or lower is preferable because it does not easily increase the viscosity of the non-aqueous electrolyte and does not easily reduce ionic conductivity. When two or more types of (I) are used, it is preferable that the total concentration of those solutes is within the above range.

[0023] The temperature at which (I) is dissolved in (II) a non-aqueous organic solvent is not particularly limited, but may be -20 to 80°C or 0 to 60°C. Furthermore, the cation of the solute is more preferably lithium ions when used in lithium-ion battery applications, and more preferably sodium ions when used in sodium-ion battery applications.

[0024] <Regarding (II) Non-Aqueous Organic Solvents> The (II) non-aqueous organic solvents (also referred to as "(II)") contained in the non-aqueous electrolyte of this disclosure will be described below. The type of (II) non-aqueous organic solvent is not particularly limited, and any non-aqueous organic solvent can be used. Such non-aqueous organic solvents preferably contain at least one selected from the group consisting of cyclic esters, linear esters, cyclic ethers, linear ethers, sulfone compounds, sulfoxide compounds, amide compounds, nitrile compounds, and ionic liquids, and more preferably contain at least one selected from the group consisting of cyclic esters, linear esters, cyclic ethers, linear ethers, sulfone compounds, sulfoxide compounds, and ionic liquids. Note that cyclic carbonates are a sub-concept of cyclic esters, and linear carbonates are a sub-concept of linear esters. Specific examples of (II) non-aqueous organic solvents include the following non-aqueous organic solvents. Examples of cyclic esters include cyclic carbonates such as propylene carbonate (hereinafter sometimes referred to as "PC"), ethylene carbonate (hereinafter sometimes referred to as "EC"), and butylene carbonate, as well as γ-butyrolactone and γ-valerolactone. Examples of chain esters include diethyl carbonate (hereinafter sometimes referred to as "DEC"), dimethyl carbonate (hereinafter sometimes referred to as "DMC"), ethyl methyl carbonate (hereinafter sometimes referred to as "EMC"), methyl propyl carbonate, ethyl propyl carbonate, methyl butyl carbonate, 2,2,2-trifluoroethyl methyl carbonate, 2,2,2-trifluoroethyl ethyl carbonate, and 2,2,2-trifluoroethyl propyl carbonate. Examples include linear carbonates such as carbonates, 1,1,1,3,3,3-hexafluoro-1-propylmethyl carbonate, 1,1,1,3,3,3-hexafluoro-1-propylethyl carbonate, and 1,1,1,3,3,3-hexafluoro-1-propylpropyl carbonate, as well as methyl acetate, ethyl acetate, methyl propionate, ethyl propionate (hereinafter sometimes referred to as "EP"), methyl 2-fluoropropionate, and ethyl 2-fluoropropionate.Examples of cyclic ethers include tetrahydrofuran, 2-methyltetrahydrofuran, furan, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, 1,3-dioxolane, and trioxane. Examples of linear ethers include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dimethoxymethane, trimethoxymethane, 1,2-dimethoxyethane, diethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. Other examples include sulfone compounds such as dimethyl sulfoxide and sulfolane, sulfoxide compounds, N,N-dimethylformamide, acetonitrile, and propionitrile. Ionic liquids can also be mentioned.

[0025] The cyclic ester may contain a cyclic carbonate, and the cyclic carbonate may contain at least one selected from the group consisting of ethylene carbonate and propylene carbonate.

[0026] The linear ester may contain a linear carbonate, and the linear carbonate may contain at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.

[0027] The cyclic ether may include at least one selected from the group consisting of tetrahydrofuran, 2-methyltetrahydrofuran, furan, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, 1,3-dioxolane, and trioxane.

[0028] The chain-like ether may include at least one selected from the group consisting of diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dimethoxymethane, trimethoxymethane, 1,2-dimethoxyethane, diethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.

[0029] The non-aqueous electrolyte of this disclosure may be (II) a single compound alone, or two or more compounds may be mixed in any combination and ratio depending on the application. Among these, it is particularly preferable to include at least one selected from the group consisting of PC, EC, DEC, DMC, and EMC, from the viewpoint of electrochemical stability with respect to oxidation and reduction and chemical stability with respect to heat and reaction with the solute.

[0030] Furthermore, it is preferable to include, for example, one or more cyclic carbonates with high dielectric constants and one or more chain carbonates or chain esters with low liquid viscosity as the non-aqueous organic solvent, because this increases the ionic conductivity of the electrolyte. Specifically, the following combinations are more preferable. (1) Combination of EC and EMC, (2) Combination of EC and DEC, (3) Combination of EC, DMC and EMC, (4) Combination of EC, DEC and EMC, (5) Combination of EC, EMC and EP, (6) Combination of PC and DEC, (7) Combination of PC and EMC, (8) Combination of PC and EP, (9) Combination of PC, DMC and EMC, (10) Combination of PC, DEC and EMC, (11) Combination of PC, DEC and EP, (12) Combination of PC, EC and EMC, (13) Combination of PC, EC, DMC and EMC, (14) Combination of PC, EC, DEC and EMC, (15) Combination of PC, EC, EMC and EP

[0031] The concentration of the non-aqueous organic solvent in this disclosure is not particularly limited as long as it functions as a non-aqueous organic solvent, but it may be, for example, 40 to 99% by mass, preferably 50 to 95% by mass, and particularly preferably 70 to 93% by mass, based on the total amount (100% by mass) of the non-aqueous electrolyte.

[0032] The content of the cyclic carbonate is not particularly limited and is arbitrary as long as it does not significantly impair the effects of this disclosure. However, when using one type alone, the content may be 3% by volume or more, and more preferably 5% by volume or more, in 100% by volume of the non-aqueous organic solvent. By setting it within this range, a decrease in electrical conductivity due to a decrease in the dielectric constant of the non-aqueous electrolyte is avoided, and it becomes easier to achieve good high-current discharge characteristics, stability to the negative electrode, and cycle characteristics of the non-aqueous electrolyte battery. Alternatively, it may be 90% by volume or less, preferably 85% by volume or less, and more preferably 80% by volume or less. By setting it within this range, the viscosity of the non-aqueous electrolyte is set within an appropriate range, a decrease in ionic conductivity is suppressed, and consequently it becomes easier to achieve good load characteristics of the non-aqueous electrolyte battery.

[0033] Furthermore, cyclic carbonates can be used in any combination of two or more types. One preferred combination is ethylene carbonate and propylene carbonate. In this case, the volume ratio of ethylene carbonate to propylene carbonate is preferably 99:1 to 40:60, and particularly preferably 95:5 to 50:50. Moreover, the amount of propylene carbonate in the total non-aqueous organic solvent is not particularly limited and is arbitrary as long as it does not significantly impair the effects of this disclosure, but it may be 1% by volume or more, preferably 2% by volume or more, more preferably 3% by volume or more, also 30% by volume or less, preferably 25% by volume or less, and more preferably 20% by volume or less. Including propylene carbonate within this range is preferable because, for example, when combining ethylene carbonate with dialkyl carbonates, the low-temperature characteristics are further improved while maintaining the characteristics of the combination of ethylene carbonate and dialkyl carbonates.

[0034] The chain-like ester may be used alone, or two or more may be used in any combination and ratio. The content of the chain-like ester is not particularly limited, but may be 15% by volume or more, preferably 20% by volume or more, more preferably 25% by volume or more, or 90% by volume or less, preferably 85% by volume or less, and more preferably 80% by volume or less, based on 100% by volume of the non-aqueous organic solvent. By setting the content of the chain-like ester within the above range, the viscosity of the non-aqueous electrolyte can be set to an appropriate range, the decrease in ionic conductivity can be suppressed, and consequently, the input / output characteristics and charge / discharge rate characteristics of the non-aqueous electrolyte battery can be set to a favorable range. In addition, a decrease in electrical conductivity due to a decrease in the dielectric constant of the non-aqueous electrolyte can be avoided, and the input / output characteristics and charge / discharge rate characteristics of the non-aqueous electrolyte battery can be set to a favorable range. Furthermore, by combining a specific chain-like ester with ethylene carbonate in a specific content, the battery performance can be significantly improved.

[0035] For example, when dimethyl carbonate, ethyl methyl carbonate, or a mixture of dimethyl carbonate and ethyl methyl carbonate is selected as a specific chain ester, the content of ethylene carbonate is not particularly limited and is arbitrary as long as it does not significantly impair the effects of this disclosure, but it may be 5% by volume or more, preferably 10% by volume or more, also 45% by volume or less, and preferably 40% by volume or less. The content of dimethyl carbonate may be 20% by volume or more, preferably 30% by volume or more, also 50% by volume or less, and preferably 45% by volume or less. The content of ethyl methyl carbonate may be 20% by volume or more, preferably 30% by volume or more, also 50% by volume or less, and preferably 45% by volume or less. By setting the content within the above ranges, the low-temperature deposition temperature of the electrolyte is reduced, the viscosity of the non-aqueous electrolyte is also reduced, the ionic conductivity is improved, and it becomes easier to obtain high input and output even at low temperatures.

[0036] The content of the chain ether is not particularly limited and is arbitrary as long as it does not significantly impair the effects of this disclosure. However, it may be 1% by volume or more, preferably 2% by volume or more, more preferably 3% by volume or more, or 30% by volume or less, preferably 25% by volume or less, and more preferably 20% by volume or less, per 100% by volume of non-aqueous organic solvent. If the content of the chain ether is within the above range, for example, in the case of a lithium-ion battery in which the cation is mainly lithium, it is easy to ensure the effect of improving ionic conductivity due to the improved degree of lithium ion dissociation of the chain ether and the decrease in viscosity. Furthermore, when the negative electrode active material is a carbonaceous material, the phenomenon of co-insertion of the chain ether together with lithium ions can be suppressed, making it easier to set the input / output characteristics and charge / discharge rate characteristics within an appropriate range.

[0037] The content of the sulfone compound is not particularly limited and is arbitrary as long as it does not significantly impair the effects of the present disclosure. However, it may be 0.3% by volume or more, preferably 0.5% by volume or more, more preferably 1% by volume or more, or 40% by volume or less, preferably 35% by volume or less, and more preferably 30% by volume or less, based on 100% by volume of the non-aqueous organic solvent. If the content of the sulfone compound is within the above range, it is easier to obtain effects that improve durability such as cycle characteristics and storage characteristics, and it is also possible to set the viscosity of the non-aqueous electrolyte within an appropriate range, avoid a decrease in electrical conductivity, and make it easier to set the input / output characteristics and charge / discharge rate characteristics of the non-aqueous electrolyte battery within an appropriate range.

[0038] <Regarding at least one compound selected from the group consisting of compounds represented by general formula (1-1) and compounds represented by general formula (1-2) (III)> The at least one compound selected from the group consisting of compounds represented by general formula (1-1) and compounds represented by general formula (1-2) (also referred to as "(III)") that is included in the non-aqueous electrolyte of this disclosure will be described below.

[0039]

[0040] [In general formula (1-1), R １R represents an alkylene group having 1 to 5 carbon atoms, or an alkenylene group having 2 to 5 carbon atoms. In general formula (1-2), R ２ , R ３ , R ４ , and R ５ Each of these independently represents a hydrogen atom, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms.

[0041] R in general formula (1-1) １ R represents an alkylene group with 1 to 5 carbon atoms, or an alkenylene group with 2 to 5 carbon atoms. １ The alkylene group having 1 to 5 carbon atoms and the alkenylene group having 2 to 5 carbon atoms represented by may have one or more substituents. Examples of substituents include alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, hydroxyl groups, amino groups, nitro groups, cyano groups, carboxyl groups, trifluoromethyl groups, difluoromethyl groups, and groups formed by combining at least two of these.

[0042] R １ The alkylene group represented by has 1 to 5 carbon atoms, and may be 2 to 5 or 2 to 4 carbon atoms. １ The number of carbon atoms in the alkenylene group represented by R is 2 to 5, and may also be 2 to 4. １ The number of carbon atoms in the alkylene group and alkenylene group represented by the formula includes the number of carbon atoms of the substituents if the alkylene group and alkenylene group have substituents.

[0043] R １Preferably, represents a methylene group, an ethylene group, a fluoroethylene group, a 1,2-difluoroethylene group, a 1,1,2,2-tetrafluoroethylene group, an ethenyl group, a 1,2-difluoroethenyl group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1-(trifluoromethyl)ethylene group, a trimethylene group, a 1-butene group, a 1,3-butadiene group, a 2-methyltrimethylene group, a 2-fluorotrimethylene group, a 1,2-dimethyltrimethylene group, a 1-buten-3-yne group, a 1-pentene group, a 1,4-pentadiene group, a 1-penten-4-yne group, or a 1-buten-3-methyl group.

[0044] Specific examples of compounds represented by general formula (1-1) are shown below, but are not limited to these.

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052] The compound represented by general formula (1-1) may be at least one selected from the group consisting of (1-1-1), (1-1-2), (1-1-3), (1-1-4), (1-1-5), (1-1-6), (1-1-7), (1-1-9), (1-1-10), (1-1-17), (1-1-18), (1-1-22), (1-1-23), (1-1-24), (1-1-25), (1-1-26), (1-1-27), and (1-1-28), or at least one selected from the group consisting of (1-1-1), (1-1-3), (1-1-6), and (1-1-7), or it may be (1-1-1).

[0053] R in general formula (1-2) ２ , R ３ , R ４, and R ５ each independently represents a hydrogen atom, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms. R ２ , R ３ , R ４ , and R ５ The alkoxy group having 1 to 4 carbon atoms, the alkyl group having 1 to 4 carbon atoms, the alkenyl group having 2 to 4 carbon atoms, and the alkynyl group represented by R

[0054] may have one or more substituents. Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxy group, an amino group, a nitro group, a cyano group, a carboxy group, a trifluoromethyl group, a difluoromethyl group, and a group formed by combining at least two of these. ２ , R ３ , R ４ , and R ５ The alkoxy group represented by has 1 to 4 carbon atoms, may have 1 to 3 carbon atoms, or may have 1 or 2 carbon atoms. R ２ , R ３ , R ４ , and R ５ The alkyl group represented by has 1 to 4 carbon atoms, may have 1 to 3 carbon atoms, or may have 1 or 2 carbon atoms. R ２ , R ３ , R ４ , and R ５ The alkenyl group represented by has 2 to 4 carbon atoms, or may have 2 to 3 carbon atoms. R ２ , R ３ , R ４ , and R ５ The alkynyl group represented by has 2 to 4 carbon atoms, or may have 2 to 3 carbon atoms. R ２ , R ３ , R ４ , and R ５ The number of carbon atoms of the alkoxy group, alkyl group, alkenyl group, and alkynyl group represented by is the sum including the number of carbon atoms of the substituent when the alkoxy group, alkyl group, alkenyl group, and alkynyl group have substituents.

[0055] R ２ , R ３ , R ４ , and R ５ Preferably, each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, an ethenyl group, an ethynyl group, a 2-propyl group, a 1-methylethenyl group, or a methoxy group.

[0056] Specific examples of compounds represented by general formula (1-2) are shown below, but are not limited to these.

[0057]

[0058]

[0059]

[0060]

[0061] The compound represented by general formula (1-2) may be at least one selected from the group consisting of (1-2-1), (1-2-2), (1-2-3), (1-2-4), (1-2-6), (1-2-8), (1-2-12), and (1-2-13), or it may be at least one selected from the group consisting of (1-2-1), (1-2-2), (1-2-3), (1-2-12), and (1-2-13), or it may be (1-2-1).

[0062] The non-aqueous electrolyte of this disclosure may be used as (III) by using one compound alone, or by mixing two or more compounds in any combination and ratio according to the application. (III) is the above (1-1-1), (1-1-2), (1-1-3), (1-1-4), (1-1-5), (1-1-6), (1-1-7), (1-1-9), (1-1-10), (1-1-17), (1-1-18), (1-1-22), (1-1-23), (1-1-24), (1-1-25), (1-1-26), (1-1-27), (1-1-28), (1-2-1), (1-2-2), (1-2-3), (1-2-4), (1-2-6) It may be at least one selected from the group consisting of (1-2-8), (1-2-12), and (1-2-13), and it may be at least one selected from the group consisting of (1-1-1), (1-1-3), (1-1-6), (1-1-7), (1-2-1), (1-2-2), (1-2-3), (1-2-12), and (1-2-13), and it may be at least one selected from the group consisting of (1-1-1) and (1-2-1).

[0063] In the non-aqueous electrolyte of this disclosure, the content of (III) relative to the total amount of the non-aqueous electrolyte (also referred to as "concentration of (III)") may be 0.01 to 10% by mass or 0.01 to 5% by mass. The lower limit of the concentration of (III) may be 0.05% by mass or more or 0.2% by mass or more. The upper limit of the concentration of (III) may be 4% by mass or less, 3% by mass or less or 2% by mass or less.

[0064] <(IV) Compound represented by general formula (2)> The compound represented by general formula (2) (also referred to as "(IV)") contained in the non-aqueous electrolyte of this disclosure will be described below.

[0065]

[0066] [In general formula (2), M ｎ＋ represents an alkali metal cation, alkaline earth metal cation, or onium cation, and n represents an integer equal to the valency of the corresponding cation. X represents a sulfur atom or a phosphorus atom. If X represents a sulfur atom, m represents 2, and R９ It does not exist. If X represents a phosphorus atom, then m represents 1. R ６ ~R ９ Each of these independently represents a fluorine atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C2-C10 alkenyl group, a C2-C10 alkenyloxy group, a C2-C10 alkynyl group, a C2-C10 alkynyloxy group, a C3-C10 cycloalkyl group, a C3-C10 cycloalkyloxy group, a C3-C10 cycloalkenyl group, a C3-C10 cycloalkenyloxy group, a C6-C10 aryl group, or a C6-C10 aryloxy group. ６ ~R ９ If there are multiple instances, they may be the same or different.

[0067] When X in general formula (2) represents a sulfur atom, the compound represented by general formula (2) is the compound represented by general formula (2a) below. When X in general formula (2) represents a phosphorus atom, the compound represented by general formula (2) is the compound represented by general formula (2b) below.

[0068]

[0069] [In general formulas (2a) and (2b), M ｎ＋ R represents an alkali metal cation, alkaline earth metal cation, or onium cation, and n represents an integer equal to the valency of the corresponding cation. ６ ~R ９ Each of these independently represents a fluorine atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C2-C10 alkenyl group, a C2-C10 alkenyloxy group, a C2-C10 alkynyl group, a C2-C10 alkynyloxy group, a C3-C10 cycloalkyl group, a C3-C10 cycloalkyloxy group, a C3-C10 cycloalkenyl group, a C3-C10 cycloalkenyloxy group, a C6-C10 aryl group, or a C6-C10 aryloxy group. ６ ~R ９ If there are multiple instances, they may be the same or different.

[0070] R ６ ~R９ The alkyl group having 1 to 10 carbon atoms represented by may be linear or branched. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, and n-pentyl groups. The alkyl group may have 1 to 8 carbon atoms or 1 to 6 carbon atoms.

[0071] R ６ ~R ９ The alkoxy group, represented by , having 1 to 10 carbon atoms, may be linear or branched. Examples of alkoxy groups include methoxy groups and ethoxy groups. The alkoxy group may have 1 to 8 carbon atoms or 1 to 6 carbon atoms.

[0072] R ６ ~R ９ The alkenyl group, represented by , having 2 to 10 carbon atoms, may be linear or branched. Examples of alkenyl groups include the ethenyl group and the allyl group. The alkenyl group may have 2 to 8 carbon atoms or 2 to 6 carbon atoms.

[0073] R ６ ~R ９ The alkenyloxy group having 2 to 10 carbon atoms, represented by , may be linear or branched. Examples of alkenyloxy groups include ethenyloxy groups and allyloxy groups. The number of carbon atoms in the alkenyloxy group may be 2 to 8 or 2 to 6.

[0074] R ６ ~R ９ The alkynyl group, represented by , having 2 to 10 carbon atoms, may be linear or branched. Examples of alkynyl groups include the ethynyl group. The alkynyl group may have 2 to 8 carbon atoms or 2 to 6 carbon atoms.

[0075] R ６ ~R ９ The alkynyloxy group having 2 to 10 carbon atoms, represented by , may be linear or branched. Examples of alkynyloxy groups include the ethynyloxy group. The number of carbon atoms in the alkynyloxy group may be 2 to 8 or 2 to 6.

[0076] R ６ ~R ９ Examples of cycloalkyl groups having 3 to 10 carbon atoms, as represented by , include cyclopentyl groups and cyclohexyl groups. The number of carbon atoms in the cycloalkyl group may be 3 to 8 or 3 to 6.

[0077] R ６ ~R ９ Examples of cycloalkyloxy groups having 3 to 10 carbon atoms, as represented by , include cyclopentyloxy and cyclohexyloxy. The number of carbon atoms in the cycloalkyloxy group may be 3 to 8 or 3 to 6.

[0078] R ６ ~R ９ Examples of cycloalkenyl groups having 3 to 10 carbon atoms, as represented by the formula, include cyclopentenyl and cyclohexenyl groups. The number of carbon atoms in the cycloalkenyl group may be 3 to 8 or 3 to 6.

[0079] R ６ ~R ９ Examples of cycloalkenyloxy groups having 3 to 10 carbon atoms, as represented by , include cyclopentenyloxy groups and cyclohexenyloxy groups. The number of carbon atoms in the cycloalkenyloxy group may be 3 to 8 or 3 to 6.

[0080] R ６ ~R ９ Examples of aryl groups having 6 to 10 carbon atoms represented by this formula include phenyl groups and naphthyl groups.

[0081] R ６ ~R ９ Examples of aryloxy groups having 6 to 10 carbon atoms represented by this formula include phenyloxy groups and naphthyloxy groups.

[0082] R ６ ~R ９The alkyl groups, alkoxy groups, alkenyl groups, alkenyloxy groups, alkynyl groups, alkynyloxy groups, cycloalkyl groups, cycloalkyloxy groups, cycloalkenyl groups, cycloalkenyloxy groups, aryl groups, and aryloxy groups represented by may have one or more substituents. Examples of substituents include alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, hydroxyl groups, amino groups, nitro groups, cyano groups, carboxyl groups, trifluoromethyl groups, difluoromethyl groups, and groups formed by combining at least two of these.

[0083] R ６ ~R ９ The number of carbon atoms in the alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy, cycloalkyl, cycloalkyloxy, cycloalkenyl, cycloalkenyloxy, aryl, and aryloxy groups represented by includes the number of carbon atoms of the substituents if the alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy, cycloalkyl, cycloalkyloxy, cycloalkenyl, cycloalkenyloxy, aryl, and aryloxy groups have substituents.

[0084] R ６ ~R ９ Preferably, at least one of them represents a fluorine atom. ６ ~R ９ It is more preferable that the majority of these atoms are fluorine atoms, and most preferably that all of them are fluorine atoms.

[0085] R ６ ~R ９ If there are multiple items, they may be the same or different.

[0086] M ｎ＋ M represents alkali metal cations, alkaline earth metal cations, protons, tetraalkylammonium cations, tetraalkylphosphonium cations, or onium cations. ｎ＋ Preferably, represents lithium ions or sodium ions.

[0087] n represents an integer equal to the valency of the corresponding cation. For example, M ｎ＋ When n represents a lithium ion or a sodium ion, n represents 1.

[0088] M of compounds represented by general formula (2) ｎ＋ Other specific examples of anions are shown below, but are not limited to these. Me represents a methyl group, and Et represents an ethyl group.

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099] The compound represented by general formula (2) may be at least one Li salt or Na salt selected from the group consisting of (2-1), (2-3), (2-4), (2-7), (2-19), and (2-20), or at least one Li salt or Na salt selected from the group consisting of (2-1), (2-3), (2-4), (2-7), and (2-19), or at least one Li salt or Na salt selected from the group consisting of (2-1) and (2-19).

[0100] The non-aqueous electrolyte of this disclosure may be used as (IV) by using one compound alone, or by mixing two or more compounds in any combination and ratio according to the application.

[0101] In the non-aqueous electrolyte of this disclosure, the content of (IV) relative to the total amount of the non-aqueous electrolyte (also referred to as "concentration of (IV)") may be 0.01 to 10% by mass or 0.01 to 5% by mass. The lower limit of the concentration of (IV) may be 0.05% by mass or more or 0.2% by mass or more. The upper limit of the concentration of (IV) may be 5% by mass or less, 4% by mass or less or 3% by mass or less.

[0102] <Regarding other components that may be included> The non-aqueous electrolyte of this disclosure is composed of the above components as basic components, but the non-aqueous electrolyte of this disclosure may contain the components described below (hereinafter also referred to as "other components that may be included" or "other components") in any combination and ratio, as long as the gist of this disclosure is not impaired. As other components, for example, other additives that are commonly used in this art may be added in any ratio.

[0103] Other components include, for example, aromatic compounds such as cyclohexylbenzene, cyclohexylfluorobenzene, biphenyl, 2-fluorobiphenyl, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, fluorobenzene, and difluoroanisole; vinylene carbonate (hereinafter sometimes referred to as "VC"), vinylene carbonate oligomers (number average molecular weight in polystyrene terms of 170 to 5000); vinylethylene carbonate, divinylethylene carbonate, fluoroethylene carbonate (hereinafter sometimes referred to as "FEC"), ethynylethylene carbonate, trans-difluoroethylene carbonate, methylpropargyl carbonate, ethylpropargyl carbonate, dipropargyl carbonate, dimethylvinylene carbonate, dimethyl dicarbonate, bis(1,1,1,3,3,3-hexafluoro-1-propyl) carbonate, and bis(2,2,2 Carbonate compounds such as trifluoroethyl carbonate, isocyanate compounds such as 1,6-diisocyanatohexane, maleic anhydride, succinic anhydride, 1,4-dioxan-2,6-dione, glutaric anhydride, methanedisulfonic anhydride, 1,2-ethanedisulfonic anhydride, methanesulfonic anhydride, organic acid anhydrides such as 1,3-propanedisulfonic anhydride, 1,3-propanesultone, 1,3-propensultone, 1,4-butanesultone, 2, 4-Butanesultone, 1,3,2-Dioxathiolane-2,2-Dioxide, 4-Propyl-1,3,2-Dioxathiolane-2,2-Dioxide, 1,3-Dithiolane-1,1,3,3-Tetraoxide, 1,3-Dithiane-1,1,3,3-Tetraoxide, Methylenemethanedisulfate, Dimethylenemethanedisulfate, Trimethylenemethanedisulfate, Methyl methanesulfonate, Methanesulfonyl fluoride, Ethenesulfonyl fluoride, N,Sulfonic acid ester compounds such as N'-carbonylbis(N-methylsulfamoylfluoride) and sulfonyl compounds, boric acid ester compounds such as difluoro(picolinato)borate, phosphate ester compounds such as phenyl difluorophosphate, trippropargyl phosphate, and tetrafluoro(picolinato)phosphate, phosphazene compounds such as (ethoxy)pentafluorocyclotriphosphazene, nitrile compounds such as succinonitrile, silane compounds such as methyldifluorovinylsilane, methylfluorodivinylsilane, dimethyldivinylsilane, trivinylmethylsilane, trivinylfluorosilane, tetravinylsilane, tris(trimethylsilyl)borate, and tris(trimethylsilyl)phosphate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,Siloxane compounds such as 3-hexafluoroisopropyl)disiloxane, sulfonates such as fluorosulfonates, trifluoromethanesulfonates, pentafluoroethanesulfonates, and nonafluorobutanesulfonates (preferably fluorosulfonates and trifluoromethanesulfonates), monoalkyl sulfates such as monomethyl sulfate and monoethyl sulfate, bis(trifluoromethanesulfonyl)imide salts, bis(pentafluoroethanesulfonyl)imide salts, (trifluoromethanesulfonyl)(nonafluorobutanesulfonyl)imide salts, (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide salts, (trifluoromethanesulfonyl)(fluorosulfonyl)imide salts, (fluorosulfonyl)(lithium carbonyloxymethanesulfonate)imide salts (preferably bis(trifluoromethanesulfonyl)imide salts Examples include imide salts such as (trifluoromethanesulfonyl)(fluorosulfonyl)imide salts, or imide compounds in which a hydrogen atom is bonded to a nitrogen atom instead of a cation in the above imide salts, phosphates such as monofluorophosphates, difluorophosphates, tetrafluoro(malonato)phosphates, tris(oxalato)phosphates, difluorobis(oxalato)phosphates, and tetrafluorooxalatophosphates, borates such as bis(oxalato)borates, difluorooxalatoborates, and difluoro(malonato)borates, methide salts such as tris(trifluoromethanesulfonyl)methide salts and tris(fluorosulfonyl)methide salts, carboxylates such as acrylates and methacrylates, inorganic salts such as nitrates and nitrites, and fluorine-containing alcohols such as hexafluoroisopropanol and trifluoroethanol. The cation in the above salts may be an alkali metal ion, an alkaline earth metal ion, or a quaternary ammonium compound.

[0104] Furthermore, the non-aqueous electrolyte of this disclosure may further contain the following compounds in order to improve the cycle capacity maintenance rate and gas generation during cycle testing.

[0105]

[0106] The non-aqueous electrolyte of this disclosure further includes cyclohexylbenzene, cyclohexylfluorobenzene, biphenyl, 2-fluorobiphenyl, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, fluorobenzene, difluoroanisole, vinylene carbonate, oligomers of vinylene carbonate (number average molecular weight in polystyrene terms of 170 to 5000), vinylethylene carbonate, divinylethylene carbonate, fluoroethylene carbonate, ethynylethylene carbonate, and trans-difluoro Ethylene carbonate, methylpropargyl carbonate, ethylpropargyl carbonate, dipropargyl carbonate, dimethylvinylene carbonate, dimethyl dicarbonate, bis(1,1,1,3,3,3-hexafluoro-1-propyl) carbonate, bis(2,2,2-trifluoroethyl) carbonate, 1,6-diisocyanatohexane, maleic anhydride, succinic anhydride, 1,4-dioxan-2,6-dione, glutaric anhydride, methanedisulfonic anhydride, 1,3-propanesultone, 1,3-propensul Ton, 1,4-butanesultone, 2,4-butanesultone, 1,3,2-dioxathiolan-2,2-dioxide, 4-propyl-1,3,2-dioxathiolan-2,2-dioxide, methylene methanedisulfonate, dimethylene methanedisulfonate, trimethylene methanedisulfonate, methyl methanesulfonate, methanesulfonyl fluoride, ethenesulfonyl fluoride, 1,2-ethanedisulfonic anhydride, methanesulfonic anhydride, N,N'-carbonylbis(N-methylsulfamoyl fluoride), difluoro(pico Linat (borate), phenyl difluorophosphate, trippropargyl phosphate, tetrafluoro(picolinat) phosphate, (ethoxy)pentafluorocyclotriphosphazene, succinonitrile, methyldifluorovinylsilane, methylfluorodivinylsilane, dimethyldivinylsilane, trivinylmethylsilane, trivinylfluorosilane, tetravinylsilane, tris(trimethylsilyl)borate, tris(trimethylsilyl)phosphate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-Hexafluoroisopropyl)disiloxane, fluorosulfonate, trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutanesulfonate, monomethyl sulfate, monoethyl sulfate, bis(trifluoromethanesulfonyl)imide, bis(pentafluoroethanesulfonyl)imide, (trifluoromethanesulfonyl)(nonafluorobutanesulfonyl)imide, (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide, (trifluoromethanesulfonyl)(fluorosulfonyl)imide, (pentafluoroethanesulfonyl It is preferable to contain at least one selected from (fluorosulfonyl)imide salt, monofluorophosphate, difluorophosphate, tetrafluoro(malonato)phosphate, tris(oxalato)phosphate, difluorobis(oxalato)phosphate, tetrafluorooxalatophosphate, bis(oxalato)borate, difluorooxalatoborate, difluoro(malonato)borate, tris(trifluoromethanesulfonyl)methide salt, tris(fluorosulfonyl)methide salt, acrylate, methacrylate, nitrate, nitrite, hexafluoroisopropanol, and trifluoroethanol.

[0107] By including the above-mentioned other components in the non-aqueous electrolyte of this disclosure, at least one of the overcharge prevention effect, negative electrode film formation effect, and positive electrode protection effect may be enhanced.

[0108] Furthermore, as is the case when used in non-aqueous electrolyte batteries called lithium polymer batteries, the electrolyte for non-aqueous electrolyte batteries can be pseudo-solidified using a gelling agent or crosslinking polymer. Examples of the polymers mentioned above include polymers having polyethylene oxide as the main chain or side chain, homopolymers or copolymers of polyvinylidene fluoride, methacrylate polymers, and polyacrylonitrile.

[0109] If the non-aqueous electrolyte of this disclosure contains other components, the content of these other components may be 0.01% by mass or more and 10% by mass or less based on the total amount of the non-aqueous electrolyte. Of the above other components, the content of fluoroethylene carbonate may be 0.01% by mass or more and 55% by mass or less based on the total amount of the non-aqueous electrolyte.

[0110] Furthermore, the content of bis(trifluoromethanesulfonyl)imide salts, trifluoromethanesulfonates, and nonafluorobutanesulfonates relative to the total amount of the non-aqueous electrolyte may be 0.01% by mass or more and 20% by mass or less.

[0111] Furthermore, the content of bis(1,1,1,3,3,3-hexafluoro-1-propyl) carbonate and bis(2,2,2-trifluoroethyl) carbonate relative to the total amount of the non-aqueous electrolyte may be 0.1% by mass or more and 70% by mass or less.

[0112] Furthermore, if the above-mentioned other components are ionic salts, the cations are more preferably lithium ions when used in lithium-ion battery applications, and more preferably sodium ions when used in sodium-ion battery applications.

[0113] The non-aqueous electrolyte of this disclosure may use multiple types of solutes (such as lithium salts and sodium salts) and salt compounds of the other components, depending on the required characteristics, so that the total number of alkali metal salts is four or more. Alternatively, the total number of alkali metal salts may be five or more.

[0114] The non-aqueous electrolyte of this disclosure is suitably used in non-aqueous electrolyte batteries (preferably non-aqueous electrolyte secondary batteries).

[0115] The non-aqueous electrolyte of this disclosure may contain, as (III), at least one selected from the group consisting of (1-1-1) and (1-2-1), and as (IV), at least one Li salt or Na salt selected from the group consisting of (2-1), (2-3), (2-4), (2-7), (2-19), and (2-20). In this case, the concentration of (III) may be 0.01 to 10% by mass, 0.01 to 5% by mass, or 0.01 to 2% by mass. In this case, the concentration of (IV) may be 0.01 to 10% by mass, 0.01 to 5% by mass, or 0.01 to 2.5% by mass. The non-aqueous electrolyte of this disclosure may further contain, in addition to the above composition, at least one selected from the group consisting of VC, tetravinylsilane, lithium fluorosulfonate, lithium bis(fluorosulfonyl)imide, lithium difluorophosphate, lithium difluorobis(oxalato)phosphate, lithium tetrafluorooxalatophosphate, lithium bis(oxalato)borate, lithium difluorooxalatoborate, sodium fluorosulfonate, sodium bis(fluorosulfonyl)imide, sodium difluorophosphate, sodium difluorobis(oxalato)phosphate, sodium tetrafluorooxalatophosphate, sodium difluorooxalatoborate, and fluoroethylene carbonate. In this case, the content (concentration) of the other components other than fluoroethylene carbonate may be 0.01% by mass or more and 10% by mass or less, 0.01 to 5% by mass or 0.01 to 4% by mass, based on the total amount of the non-aqueous electrolyte. Furthermore, if the non-aqueous electrolyte of this disclosure contains fluoroethylene carbonate as another component, the content (concentration) of fluoroethylene carbonate may be 0.01% by mass or more and 55% by mass or less, 0.01 to 35% by mass, 0.01 to 20% by mass, or 0.01 to 10% by mass, based on the total amount of the non-aqueous electrolyte.

[0116] The non-aqueous electrolyte of this disclosure may contain, as (III), at least one selected from the group consisting of (1-1-1) and (1-2-1), and as (IV), at least one Li salt or Na salt selected from the group consisting of (2-1), (2-3), (2-4), (2-7), and (2-19). In this case, the concentration of (III) may be 0.01 to 10% by mass, 0.01 to 5% by mass, or 0.01 to 2% by mass. In this case, the concentration of (IV) may be 0.01 to 10% by mass, 0.01 to 5% by mass, or 0.01 to 2.5% by mass. The non-aqueous electrolyte of this disclosure may further contain, in addition to the above composition, at least one selected from the group consisting of VC, tetravinylsilane, lithium fluorosulfonate, lithium bis(fluorosulfonyl)imide, lithium difluorophosphate, lithium difluorobis(oxalato)phosphate, lithium tetrafluorooxalatophosphate, lithium bis(oxalato)borate, lithium difluorooxalatoborate, sodium fluorosulfonate, sodium bis(fluorosulfonyl)imide, sodium difluorophosphate, sodium difluorobis(oxalato)phosphate, sodium tetrafluorooxalatophosphate, sodium difluorooxalatoborate, and fluoroethylene carbonate. In this case, the content (concentration) of the other components other than fluoroethylene carbonate may be 0.01% by mass or more and 10% by mass or less, 0.01 to 5% by mass or 0.01 to 4% by mass, based on the total amount of the non-aqueous electrolyte. Furthermore, if the non-aqueous electrolyte of this disclosure contains fluoroethylene carbonate as another component, the content (concentration) of fluoroethylene carbonate may be 0.01% by mass or more and 55% by mass or less, 0.01 to 35% by mass, 0.01 to 20% by mass, or 0.01 to 10% by mass, based on the total amount of the non-aqueous electrolyte.

[0117] The non-aqueous electrolyte of this disclosure may contain, as (III), at least one selected from the group consisting of (1-1-1) and (1-2-1), and as (IV), at least one Li salt or Na salt selected from the group consisting of (2-1), (2-3), (2-4), and (2-19). In this case, the concentration of (III) may be 0.01 to 10% by mass, 0.01 to 5% by mass, or 0.01 to 2% by mass. In this case, the concentration of (IV) may be 0.01 to 10% by mass, 0.01 to 5% by mass, or 0.01 to 2.5% by mass. The non-aqueous electrolyte of this disclosure may further contain, in addition to the above composition, at least one selected from the group consisting of VC, tetravinylsilane, lithium fluorosulfonate, lithium bis(fluorosulfonyl)imide, lithium difluorophosphate, lithium difluorobis(oxalato)phosphate, lithium tetrafluorooxalatophosphate, lithium bis(oxalato)borate, lithium difluorooxalatoborate, sodium fluorosulfonate, sodium bis(fluorosulfonyl)imide, sodium difluorophosphate, sodium difluorobis(oxalato)phosphate, sodium tetrafluorooxalatophosphate, sodium difluorooxalatoborate, and fluoroethylene carbonate. In this case, the content (concentration) of the other components other than fluoroethylene carbonate may be 0.01% by mass or more and 10% by mass or less, 0.01 to 5% by mass or 0.01 to 4% by mass, based on the total amount of the non-aqueous electrolyte. Furthermore, if the non-aqueous electrolyte of this disclosure contains fluoroethylene carbonate as another component, the content (concentration) of fluoroethylene carbonate may be 0.01% by mass or more and 55% by mass or less, 0.01 to 35% by mass, 0.01 to 20% by mass, or 0.01 to 10% by mass, based on the total amount of the non-aqueous electrolyte.

[0118] The non-aqueous electrolyte of this disclosure may contain, as (III), at least one selected from the group consisting of (1-1-1) and (1-2-1), and as (IV), at least one Li salt or Na salt selected from the group consisting of (2-1) and (2-19). In this case, the concentration of (III) may be 0.01 to 10% by mass, 0.01 to 5% by mass, or 0.01 to 2% by mass. In this case, the concentration of (IV) may be 0.01 to 10% by mass, 0.01 to 5% by mass, or 0.01 to 2.5% by mass. The non-aqueous electrolyte of this disclosure may further contain, in addition to the above composition, at least one selected from the group consisting of VC, tetravinylsilane, lithium fluorosulfonate, lithium bis(fluorosulfonyl)imide, lithium difluorophosphate, lithium difluorobis(oxalato)phosphate, lithium tetrafluorooxalatophosphate, lithium bis(oxalato)borate, lithium difluorooxalatoborate, sodium fluorosulfonate, sodium bis(fluorosulfonyl)imide, sodium difluorophosphate, sodium difluorobis(oxalato)phosphate, sodium tetrafluorooxalatophosphate, sodium difluorooxalatoborate, and fluoroethylene carbonate. In this case, the content (concentration) of the other components other than fluoroethylene carbonate may be 0.01% by mass or more and 10% by mass or less, 0.01 to 5% by mass or 0.01 to 4% by mass, based on the total amount of the non-aqueous electrolyte. Furthermore, if the non-aqueous electrolyte of this disclosure contains fluoroethylene carbonate as another component, the content (concentration) of fluoroethylene carbonate may be 0.01% by mass or more and 55% by mass or less, 0.01 to 35% by mass, 0.01 to 20% by mass, or 0.01 to 10% by mass, based on the total amount of the non-aqueous electrolyte.

[0119] 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. It may also include a separator, an outer casing, etc. Alternatively, a solid electrolyte may be used as a medium for impregnating the non-aqueous electrolyte instead of a separator. Preferably, the non-aqueous electrolyte battery of this disclosure comprises at least a positive electrode, a negative electrode, a separator, and the non-aqueous electrolyte of this disclosure. Preferably, the non-aqueous electrolyte battery of this disclosure is a non-aqueous electrolyte secondary battery.

[0120] [Negative electrode] The negative electrode is not particularly limited, but a material that allows reversible insertion and removal of alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions, may be used.

[0121] [Negative Electrode Active Material] For example, in the case of a lithium-ion battery in which the cation is mainly lithium, the negative electrode active material constituting the negative electrode is one that can be doped and dedoped with lithium ions, and includes, for example, carbon materials such as artificial graphite and natural graphite with a d value of 0.340 nm or less on the lattice plane (002) in X-ray diffraction, carbon materials such as hard carbon with a d value of 0.340 nm or more on the lattice plane (002) in X-ray diffraction, lithium metal, lithium metal and other metals (for example, an alloy of lithium metal with one or more metals selected from Si, Sn, and Al, an alloy of lithium metal with an alloy containing one or more metals selected from Si, Sn, and Al, etc.), intermetallic compounds of lithium metal and other metals, metal oxides (for example, oxides of one or more metals selected from Si, Sn, and Al, lithium titanium oxide, etc.), metal nitrides, tin (elementary), tin compounds, activated carbon, and conductive polymers, containing at least one of these. Furthermore, a negative electrode active material containing Si and / or Si metal oxide and a carbon material can be preferably cited. The above Si is silicon metal. The Si metal oxide may also be a compound represented as SiOx (where x is a value between 0.5 and 1.5). The total content of Si and / or Si metal oxide in the negative electrode active material may be 0.1 to 50% by mass, preferably 0.1 to 30% by mass, when the total amount of Si and / or Si metal oxide and carbon material in the negative electrode active material is considered to be 100% by mass. Graphite is preferred as the carbon material, and various types of artificial graphite, natural graphite, and hard carbon (non-graphitizable carbon) can be used. Graphite exhibits very little change in its crystal structure during lithium absorption and release, resulting in high energy density and excellent cycle characteristics. The graphite may be fibrous, spherical, granular, or flaky. Amorphous carbon or graphite coated with amorphous carbon is more preferable because it reduces the reactivity between the material surface and the electrolyte. These negative electrode active materials can be used individually or in combination of two or more types.

[0122] For example, in the case of a sodium-ion battery in which the cation is mainly sodium, the negative electrode active material that constitutes the negative electrode may be sodium metal, alloys of sodium metal and other metals such as tin, intermetallic compounds of sodium metal and other metals, 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.

[0123] [Negative Electrode Current Collector] The negative electrode has a negative electrode current collector. For example, copper, stainless steel, nickel, titanium, or alloys thereof can be used as the negative electrode current collector. In addition, aluminum or its alloys can be used in sodium-ion batteries.

[0124] [Negative Electrode Active Material Layer] The negative electrode is formed by creating a negative electrode active material layer on at least one surface of the negative electrode current collector. The negative electrode active material layer is composed of, for example, the aforementioned negative electrode active material, a binder, and a conductive agent as needed. Examples of binders include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, styrene-butadiene rubber (hereinafter also referred to as "SBR"), carboxymethylcellulose, methylcellulose, cellulose phthalate acetate, hydroxypropylmethylcellulose, polyvinyl alcohol, and polyimide. Examples of conductive agents include acetylene black, Ketjen black, furnace black, carbon fiber, graphite, fluorinated graphite, and other carbon materials.

[0125] [Positive electrode] The positive electrode is not particularly limited, but a material that allows reversible insertion and removal of alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions, may be used.

[0126] [Positive electrode active material] For example, if the cation is lithium, the positive electrode material (positive electrode active material) is LiCoO ２ LiNiO ２ LiMnO ２ LiMn ２ O ４ Li[Ni １／３ Mn １／３ Co １／３ ]O ２ , Li[Ni ０．４５ Mn ０．３５ Co ０．２ ]O ２ , Li[Ni ０．５ Mn ０．３ Co ０．２ ]O ２ , Li[Ni ０．６ Mn ０．２ Co ０．２ ]O ２ , Li[Ni ０．８ Mn ０．１ Co ０．１ ]O ２ (Hereafter, it may be referred to as "NCM811"), Li [Ni ０．４９ Mn ０．３ Co ０．２ Zr ０．０１ ]O ２ , Li[Ni ０．４９ Mn ０．３ Co ０．２ Mg ０．０１ ]O ２ LiNi ０．８ Co ０．２ O ２ LiNi ０．８５ Co ０．１０ Al ０．０５ O ２ LiNi ０．８７ Co ０．１０ Al ０．０３ O ２ LiNi ０．９０ Co ０．０７ Al ０．０３ O ２ LiNi０．６ Co ０．３ Al ０．１ O ２ LiNi ０．５ Mn １．５ O ４ LiNi ０．５ Mn ０．５ O ２ LiNi ０．１ Mn １．９ O ４ LiCo ０．５ Mn ０．５ O ２ , 0.5[LiNi ０．５ Mn ０．５ O ２ ]・0.5[Li ２ MnO ３ ], 0.5[LiNi １／３ Co １／３ Mn １／３ O ２ ]・0.5[Li ２ MnO ３ ], 0.5[LiNi ０．３７５ Co ０．２５ Mn ０．３７５ O ２ ]・0.5[Li ２ MnO ３ ], 0.5[LiNi ０．３７５ Co ０．１２５ Fe ０．１２５ Mn ０．３７５ O ２ ]・0.5[Li ２ MnO ３ ], 0.45[LiNi ０．３７５ Co ０．２５ Mn ０．３７５ O ２ ]・0.10[Li ２ TiO ３ ]・0.45[Li ２ MnO ３ Examples include olivine. α M ００１ PO ４ Compounds represented by (0 < α ≤ 1) may also be used. ００１ is at least one element selected from the group consisting of Mn, Fe, Co, or Ni. ００１From the viewpoint of battery capacity and cycle characteristics, it is preferable that the mixture contains Fe, Mn, or both Fe and Mn, and more preferably Fe or both Fe and Mn. ００１ A portion of it can be substituted with other elements such as Mg, Al, Ti, V, Cr, Zr, etc. Furthermore, the olivine-type cathode active material may have one or more elements selected from the group consisting of B, C, N, F, Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, Zn, Zr, and W present on part or all of its particle surface, either as individual elements or compounds thereof. Specifically, LiFePO ４ LiCoPO ４ LiMnPO ４ LiNiPO ４ LiFe ０．５ Mn ０．５ PO ４ LiFe ０．４ Mn ０．６ PO ４ LiFe ０．３ Mn ０．７ PO ４ LiFe ０．５ Mn ０．４ Mg ０．１ PO ４ LiFe ０．５ Mn ０．４５ Zr ０．０５ PO ４ Examples include phosphate compounds of transition metals such as TiO. ２ , V ２ O ５ MoO ３ Oxides such as TiS ２ FeS, MoS ２ Sulfides such as those mentioned above, or conductive polymers such as polyacetylene, poly(p-phenylene), polyaniline, and polypyrrole, activated carbon, radical-generating polymers, carbon materials, etc. may also be used.

[0127] For example, if the cation is sodium, the positive electrode material (positive electrode active material) would be NaCrO ２ NaFe ０．５ Co ０．５ O ２ NaFe ０．４ Mn ０．３ Ni ０．３ O２ NaNi ０．５ Ti ０．３ Mn ０．２ O ２ NaNi １／３ Ti １／３ Mn １／３ O ２ NaNi ０．３３ Ti ０．３３ Mn ０．１６ Mg ０．１７ O ２ Na ２／３ Ni １／３ Ti １／６ Mn １／２ O ２ Na ２／３ Ni １／３ Mn ２／３ O ２ Sodium-containing transition metal composite oxides such as, mixtures of multiple transition metals such as Co, Mn, and Ni in these sodium-containing transition metal composite oxides, and in which some of the transition metals in these sodium-containing transition metal composite oxides are replaced with other metals, NaFePO ４ NaVPO ４ F, Na ３ V ２ (PO ４ ) ３ Na ２ Fe ２ (SO ４ ) ３ Polyanionic compounds such as, composition formula Na β M ００２ γ [Fe(CN)] ６ ] δ The sodium salt of the Prussian blue analog represented by (M ００２ = Represents Cr, Mn, Fe, Co, Ni, Cu, or Zn, with 0 ≤ β ≤ 2, 0.5 ≤ γ ≤ 1.5, 0.5 ≤ δ ≤ 1.5), TiO ２ , V ２ O ５ MoO ３ Oxides such as TiS ２ FeS, MoS ２ Sulfides such as those mentioned above, or conductive polymers such as polyacetylene, poly(p-phenylene), polyaniline, and polypyrrole, activated carbon, radical-generating polymers, carbon materials, etc. may also be used.

[0128] [Positive electrode current collector] The positive electrode has a positive electrode current collector. As the positive electrode current collector, for example, aluminum, stainless steel, nickel, titanium, or alloys thereof can be used.

[0129] [Positive Electrode Active Material Layer] The positive electrode is formed by creating a positive electrode active material layer on at least one surface of the positive electrode current collector. The positive electrode active material layer is composed of, for example, the positive electrode active material described above, a binder, and a conductive agent as needed. The binder is the same as described in [Negative Electrode Active Material Layer]. As the conductive agent, carbon materials such as acetylene black, Ketjen black, furnace black, carbon fiber, graphite (granular graphite or flake graphite), and fluorinated graphite can be used. In the positive electrode, it is preferable to use acetylene black or Ketjen black with low crystallinity.

[0130] [Method for manufacturing electrodes (positive and negative electrodes)] Electrodes can be obtained, for example, by dispersing and kneading an active material, a binder, and optionally a conductive agent in predetermined proportions in a solvent such as N-methyl-2-pyrrolidone (hereinafter sometimes referred to as "NMP") or water, applying the resulting paste to a current collector, and drying it to form an active material layer. It is preferable to compress the obtained electrodes using a method such as a roll press to adjust them to an electrode of appropriate density.

[0131] [Separator] The non-aqueous electrolyte battery of this disclosure may be equipped with a separator. As a separator to prevent contact between the positive electrode and the negative electrode, for example, nonwoven fabrics or porous sheets made of polyolefins such as polypropylene and polyethylene, cellulose, paper, glass fiber, etc. are used. These films are preferably microporous so that the electrolyte can permeate and ions can easily pass through. As a polyolefin separator, for example, a microporous polymer film such as a porous polyolefin film can be used, which electrically insulates the positive electrode and the negative electrode and allows lithium ions to pass through. Specific examples of porous polyolefin films include, for example, a porous polyethylene film alone, or a porous polyethylene film and a porous polypropylene film layered together to form a multilayer film. Also, a composite film of a porous polyethylene film and a polypropylene film can be used. The non-aqueous electrolyte of this disclosure may be impregnated into the above separator and held therein. There are no particular restrictions on the impregnation method, and it may be carried out by known methods. Specifically, impregnation can be achieved by pouring electrolyte into a battery that consists of a positive electrode, a separator, and a negative electrode.

[0132] [Outer casing] Suitable outer casings for the non-aqueous electrolyte battery of this disclosure include, for example, coin-type, cylindrical, or rectangular metal cans, as well as laminated outer casings. Suitable metal can materials include, for example, nickel-plated steel, stainless steel, nickel-plated stainless steel, aluminum or its alloys, nickel, titanium, etc. Suitable laminated outer casings include, for example, aluminum laminate film, SUS laminate film, silica-coated polypropylene, polyethylene laminate film, etc.

[0133] The configuration of the non-aqueous electrolyte battery according to this embodiment is not particularly limited, but for example, it can be configured such that electrode elements with a positive electrode and a negative electrode facing each other and a non-aqueous electrolyte are enclosed in an outer casing. The shape of the non-aqueous electrolyte battery is not particularly limited, but an electrochemical device in the shape of a coin, cylinder, prismatic, or aluminum laminate sheet can be assembled from the above elements.

[0134] 3. Method for Manufacturing a Non-Aqueous Electrolyte Battery The method for manufacturing a non-aqueous electrolyte battery according to this disclosure includes a step of injecting the non-aqueous electrolyte described above. There are no particular restrictions on the method of injection, and conventional methods can be used. For example, vacuum injection is one example.

[0135] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to such examples.

[0136] [Preparation of Non-Aqueous Electrolyte] <Example 1-1> (Preparation of Non-Aqueous Electrolyte 1-1) A mixed solvent of ethylene carbonate (hereinafter also referred to as "EC"), dimethyl carbonate (hereinafter also referred to as "DMC"), and ethyl methyl carbonate (hereinafter also referred to as "EMC") in a volume ratio of 3:3:4 was used as the non-aqueous organic solvent, and lithium hexafluorophosphate (hereinafter also referred to as "LiPF") was added to the solvent as the solute. ６ (Also written as ") was dissolved to a concentration of 1.0 mol / L, the compound represented by the above formula (1-1-1) as (III) to a concentration of 0.3% by mass relative to the total amount of non-aqueous electrolyte, and further, the compound containing the anion and lithium ion represented by the above formula (2-1) (lithium salt) as (IV) to a concentration of 0.5% by mass relative to the total amount of non-aqueous electrolyte, thereby obtaining non-aqueous electrolyte 1-1. The above preparations were carried out while maintaining the liquid temperature at 25°C.

[0137] <Examples 1-2 to 1-16> (Preparation of Non-Aqueous Electrolytes 1-2 to 1-16) Non-aqueous electrolytes 1-2 to 1-16 were prepared by dissolving the components in the same manner as the preparation of non-aqueous electrolyte 1-1, except that the type of (III), the concentration of (III), the type of (IV), and the concentration of (IV) were changed as shown in Tables 1 to 3. For (IV), compounds containing anions and lithium ions (lithium salts) as listed in the table were used.

[0138] <Comparative Examples 1-1 to 1-21> (Preparation of Comparative Non-Aqueous Electrolytes 1-1 to 1-21) Comparative non-aqueous electrolytes 1-1 to 1-21 were prepared by dissolving the compounds in the same procedure as for the preparation of non-aqueous electrolyte 1-1, except that the type of (III), the concentration of (III), the type of (IV), and the concentration of (IV) were changed as shown in Tables 1 to 3. In the table, "-" means that no compound was added. Also, in the table, "PRS" means that 1,3-propensultone (hereinafter referred to as "PRS") was used as a comparative compound instead of (III).

[0139]

[0140] <Examples 2-1 to 2-4, Comparative Examples 2-1 to 2-2> (Preparation of Non-Aqueous Electrolytes 2-1 to 2-4 and Comparative Non-Aqueous Electrolytes 2-1 to 2-2) Non-aqueous electrolytes 2-1 to 2-4 were obtained in the same manner as the preparation of non-aqueous electrolyte 1-3, except that the types of (III) and (IV) were changed as shown in Table 4, and vinylene carbonate (hereinafter also referred to as "VC") was added as another component and dissolved. Comparative non-aqueous electrolytes 2-1 to 2-2 were obtained by dissolving them in the same procedure as the preparation of non-aqueous electrolytes 2-1 to 2-2, except that PRS was used as the comparative compound instead of (III).

[0141] <Examples 3-1 to 3-4, Comparative Examples 3-1 to 3-2> to <Examples 10-1 to 10-4, Comparative Examples 10-1 to 10-2> Except for changing the types and concentrations of other components as shown in Table 4, the non-aqueous electrolytes and comparative non-aqueous electrolytes listed in the table were prepared by dissolving in the same procedure as for non-aqueous electrolytes 2-1 to 2-4 and comparative non-aqueous electrolytes 2-1 to 2-2. Note that "TV-Si" means tetravinylsilane, "FS" means lithium fluorosulfonate, "FSI" means lithium bis(fluorosulfonyl)imide, "DFP" means lithium difluorophosphate, "DFBOP" means lithium difluorobis(oxalato)phosphate, "TFOP" means lithium tetrafluorooxalatophosphate, "BOB" means lithium bis(oxalato)borate, and "DFOB" means lithium difluorooxalatoborate.

[0142] <Examples 11-1 to 11-16, Comparative Examples 11-1 to 11-21> Except that a mixed solvent of EC, DMC, and EMC in a volume ratio of 3:3:4 was used as the non-aqueous organic solvent, and fluoroethylene carbonate (hereinafter also referred to as "FEC") was added to the solvent as another component to a total of 5% by mass, the non-aqueous electrolytes and comparative non-aqueous electrolytes described in Tables 5 to 7 were prepared by dissolving in the same manner as the preparation of the non-aqueous electrolytes described in Tables 1 to 3.

[0143] <Examples 12-1 to 12-4, Comparative Examples 12-1 to 12-2> to <Examples 20-1 to 20-4, Comparative Examples 20-1 to 20-2> As shown in Table 8, the non-aqueous electrolytes and comparative non-aqueous electrolytes listed in Table 8 were prepared by dissolving them in the same manner as the preparation of non-aqueous electrolytes 11-3 to 11-4, 11-11 to 11-12, and comparative non-aqueous electrolytes 11-19 and 11-21, except that other components were added.

[0144] <Example 21-1> (Preparation of Non-Aqueous Electrolyte 21-1) EC, propylene carbonate (hereinafter also referred to as "PC"), FEC, and EMC were mixed and dissolved in a volume ratio of 2:1:0.2:6.8 to obtain a solution of a non-aqueous organic solvent and other components. Sodium hexafluorophosphate (hereinafter referred to as "NaPF") was added to the solution as a solute. ６Non-aqueous electrolyte 21-1 was prepared by dissolving (also written as ") to a concentration of 1.0 mol / L, the compound represented by the above formula (1-1-1) as (III) to a concentration of 0.3% by mass relative to the total amount of non-aqueous electrolyte, and further dissolving the compound (sodium salt) containing the anion and sodium ion represented by the above formula (2-1) as (IV) to a concentration of 0.5% by mass relative to the total amount of non-aqueous electrolyte. The above preparation was carried out while maintaining the liquid temperature at 25°C.

[0145] <Examples 21-2 to 21-16, Comparative Examples 21-1 to 21-21> Except for changing the types and concentrations of (III) and (IV) as shown in Tables 9 to 11, using PRS as a comparative compound instead of (III), and changing the concentration of PRS, non-aqueous electrolytes 21-2 to 21-16 and comparative non-aqueous electrolytes 21-1 to 21-21 were prepared by dissolving in the same procedure as for the preparation of non-aqueous electrolyte 21-1. For (IV), a compound (sodium salt) containing the anion and sodium ion listed in the table was used.

[0146] <Examples 22-1 to 22-4, Comparative Examples 22-1 to 22-2> to <Examples 29-1 to 29-4, Comparative Examples 29-1 to 29-2> As shown in Table 12, the non-aqueous electrolytes and comparative non-aqueous electrolytes listed in Table 12 were prepared by dissolving the components in the same manner as in the preparation of non-aqueous electrolytes 21-3 to 21-4, 21-11 to 21-12, and comparative non-aqueous electrolytes 21-19 and 21-21, except that other components were added. Note that "Na-FS" means sodium fluorosulfonate, "Na-FSI" means sodium bis(fluorosulfonyl)imide, "Na-DFP" means sodium difluorophosphate, "Na-DFBOP" means sodium difluorobis(oxalato)phosphate, "Na-TFOP" means sodium tetrafluorooxalatophosphate, and "Na-DFOB" means sodium difluorooxalatoborate.

[0147] [Fabrication of Non-Aqueous Electrolyte Batteries] (Fabrication of NCM622 Positive Electrode) LiNi ０．６ Co ０．２ Mn ０．２ O ２A cathode composite paste was prepared by mixing 90.0% by mass of powder with 5.0% by mass of polyvinylidene fluoride (hereinafter also referred to as "PVDF") as a binder and 5.0% by mass of acetylene black as a conductive material, and then adding N-methyl-2-pyrrolidone (hereinafter also referred to as "NMP"). This paste was applied to both sides of aluminum foil (A1085), dried, and pressurized, and then punched out to a 4cm x 5cm rectangle to obtain a test NCM622 cathode.

[0148] (Fabrication of NCM811 positive electrode) LiNi ０．８ Mn ０．１ Co ０．１ O ２ A cathode composite paste was prepared by mixing 92.0% by mass of powder with 3.5% by mass of PVDF as a binder and 4.5% by mass of acetylene black as a conductive material, and then adding NMP. This paste was applied to both sides of aluminum foil (A1085), dried, and pressurized, and then punched out to a 4cm x 5cm rectangle to obtain a test NCM811 cathode.

[0149] (Sodium-ion battery positive electrode: NaNi) ０．５ Ti ０．３ Mn ０．２ O ２ Fabrication of the positive electrode (NTM532 positive electrode) NaNi as the positive electrode active material ０．５ Ti ０．３ Mn ０．２ O ２ A positive electrode composite paste was prepared by mixing 90.0% by mass of [the substance] with 5.0% by mass of acetylene black as a conductive agent and 5.0% by mass of PVDF as a binder, and then adding NMP as a solvent. This paste was applied to both sides of aluminum foil (A1085), dried, and pressed, and then punched out to 4 cm x 5 cm to obtain test NaNi [the substance]. ０．５ Ti ０．３ Mn ０．２ O ２ The positive electrode was obtained.

[0150] (Preparation of Natural Graphite Anode) A negative electrode mixture paste was prepared by mixing 92.0% by mass of natural graphite powder, 3.0% by mass of conductive material (Denka, HS-100), 2.0% by mass of carbon nanofiber (Showa Denko, VGCF), 2.0% by mass of styrene-butadiene rubber (hereinafter sometimes referred to as "SBR"), 1.0% by mass of carboxymethylcellulose (hereinafter sometimes referred to as "CMC"), and water. This paste was applied to copper foil, dried, and then punched out to 4.5 cm x 5.5 cm to obtain a test natural graphite anode.

[0151] (Preparation of silicon-containing graphite anode) A negative electrode composite paste was prepared by mixing 85.0% by mass of artificial graphite powder with 7.0% by mass of nanosilicon, 3.0% by mass of conductive material (Denka, HS-100), 2.0% by mass of carbon nanofiber (Showa Denko, VGCF), 2.0% by mass of SBR, 1.0% by mass of CMC, and water. This paste was applied to copper foil, dried, and then punched out to 4.5 cm x 5.5 cm to obtain a test silicon-containing graphite anode.

[0152] (Preparation of hard carbon anode) 90.0% by mass of hard carbon powder (Carbotron P, manufactured by Kureha Corporation) and 10.0% by mass of PVDF as a binder were mixed, and NMP was added as a solvent to prepare an anode composite paste. This paste was applied to aluminum foil (A1085), dried, and pressed, and then punched out to 4.5 cm x 5.5 cm to obtain a test hard carbon anode.

[0153] (Fabrication of Non-Aqueous Electrolyte Batteries) In an argon atmosphere with a dew point of -50°C or lower, terminals were welded to the NCM622 positive electrode as described above. Then, the positive electrode was sandwiched between two polyethylene separators (5 cm x 6 cm) on both sides, and further sandwiched on the outside by two natural graphite negative electrodes with terminals welded to them in advance, so that the negative electrode active material surface faced the positive electrode active material surface. These were then placed in an aluminum laminate bag with an opening on one side, and after vacuum injection of the non-aqueous electrolyte, the opening was sealed with heat to produce aluminum laminate type non-aqueous electrolyte batteries (lithium-ion batteries) according to the examples and comparative examples in Tables 1 to 4.

[0154] Furthermore, in the examples and comparative examples shown in Tables 5 to 8, non-aqueous electrolyte batteries (lithium-ion batteries) were similarly fabricated using NCM811 as the positive electrode and silicon-containing graphite as the negative electrode.

[0155] Furthermore, in the examples and comparative examples shown in Tables 9 to 12, NaNi was used as the positive electrode. ０．５ Ti ０．３ Mn ０．２ O ２ A non-aqueous electrolyte battery (sodium-ion battery) was similarly fabricated using an NTM532 positive electrode and a hard carbon negative electrode.

[0156] [Evaluation] <Initial Charge / Discharge Test: Lithium-ion Battery> First, the fabricated cells were conditioned at an ambient temperature of 25°C under the following conditions. Specifically, as an initial charge / discharge test, the cells were charged with a constant current and voltage at a maximum charge voltage of 4.2V and 5mA, discharged with a constant current of 10mA until the discharge termination voltage reached 2.5V, and then the charge / discharge cycle was repeated three times, with the cells being charged with a constant current and voltage at a maximum charge voltage of 4.2V and 10mA, and discharged with a constant current of 10mA until the discharge termination voltage reached 2.5V. The discharge capacity from the third cycle was defined as the initial discharge capacity.

[0157] <Initial Charge / Discharge Test: Sodium-Ion Battery> First, the fabricated cells were conditioned at an ambient temperature of 25°C under the following conditions. Specifically, as an initial charge / discharge test, the cells were charged with a constant current and voltage at a maximum charge voltage of 4.1V and 5mA, then discharged with a constant current of 10mA until the discharge termination voltage reached 1.5V. This charge / discharge cycle was repeated three times, followed by charging with a constant current and voltage at a maximum charge voltage of 4.1V and 10mA, and then discharged with a constant current of 10mA until the discharge termination voltage reached 1.5V. The discharge capacity from the third cycle was defined as the initial discharge capacity.

[0158] <Initial Resistance: Lithium-ion Battery> After the initial charge-discharge test described above was performed on a non-aqueous electrolyte battery, it was charged at a constant current and voltage of 10mA to the maximum charge voltage of 4.2V at an ambient temperature of 25°C, and then the AC impedance was measured at an ambient temperature of -20°C.

[0159] <Initial Resistance: Sodium-ion Battery> The evaluation was the same as for the lithium-ion battery, except that the maximum charging voltage was changed to 4.1V.

[0160] <High-Temperature Storage Test (80°C): Lithium-ion Battery> The non-aqueous electrolyte battery, after the initial resistance measurement described above, was left at an ambient temperature of 80°C for 10 days. After that, it was left to stand for 4 hours at a 25°C environment, and then a constant current discharge of 10mA was performed until the discharge termination voltage reached 2.5V. Furthermore, it was charged at a constant current and constant voltage of 4.2V and 10mA, and then a constant current discharge of 10mA was performed until the discharge termination voltage reached 2.5V. The discharge capacity was defined as the discharge capacity after the high-temperature storage test.

[0161] <High-temperature storage test (80°C): Sodium-ion battery> The evaluation was the same as for lithium-ion batteries, except that the maximum charge voltage was changed to 4.1V and the discharge termination voltage to 1.5V.

[0162] <Capacity retention rate after high-temperature storage test: Lithium-ion batteries> The capacity retention rate after the high-temperature storage test was calculated using the following formula. A higher value indicates better high-temperature storage characteristics. Capacity retention rate after high-temperature storage test (%) = (Discharge capacity after high-temperature storage test / Initial discharge capacity) × 100

[0163] <Capacity retention rate after high-temperature storage test: Sodium-ion battery> Evaluated in the same way as lithium-ion batteries. A higher value indicates better high-temperature storage characteristics.

[0164] The results are shown in Tables 1 to 12 below. In the tables, "Initial resistance (relative value)" represents the initial resistance, and "Discharge capacity retention rate after high-temperature storage (relative value)" represents the high-temperature storage characteristics (capacity retention rate after high-temperature storage test). The initial resistance and high-temperature storage characteristics values ​​in each table are relative values, with the comparative example value listed at the top of each table set to 100.

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177] From the results shown in the table above, the following can be seen: The non-aqueous electrolyte of the example can improve the high-temperature storage characteristics of the non-aqueous electrolyte battery compared to the comparative non-aqueous electrolyte that does not contain at least one of (III) and (IV). The non-aqueous electrolyte of the example can improve the high-temperature storage characteristics when used in a non-aqueous electrolyte battery compared to the comparative non-aqueous electrolyte that uses PRS instead of (III). Even when the non-aqueous electrolyte contains other components, the non-aqueous electrolyte of the example can improve the high-temperature storage characteristics when used in a non-aqueous electrolyte battery compared to the comparative non-aqueous electrolyte that uses PRS instead of (III). From Tables 4, 8 and 12, when the non-aqueous electrolyte contains other components, the initial resistance tends to be higher, but the non-aqueous electrolyte of the example can suppress the increase in initial resistance compared to the comparative non-aqueous electrolyte.

[0178] According to this disclosure, it is possible to provide a non-aqueous electrolyte that can improve high-temperature storage characteristics when used in a non-aqueous electrolyte battery, and a non-aqueous electrolyte battery using the same.

[0179] 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. 2024-225401, filed on 20 December 2024, the contents of which are incorporated herein by reference.

Claims

1. A non-aqueous electrolyte containing (I) a solute, (II) a non-aqueous organic solvent, (III) at least one compound selected from the group consisting of a compound represented by the following general formula (1-1) and a compound represented by the following general formula (1-2), and (IV) a compound represented by the following general formula (2). [In general formula (1-1), R ６ , ９ represents an alkylene group having 1 to 5 carbon atoms or an alkenylene group having 2 to 5 carbon atoms. In general formula (1-2), R ２ , R ３ , R ４ , and R ５ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms.] [In general formula (2), M ｎ＋ represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and n represents an integer equal to the valence of the corresponding cation. X represents a sulfur atom or a phosphorus atom. When X represents a sulfur atom, m represents 2 and R ９ does not exist. When X represents a phosphorus atom, m represents 1. R ６ to R ９ each independently represent a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an 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 cycloalkyloxy 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, or an aryloxy group having 6 to 10 carbon atoms. When there are a plurality of R ６ to R ９ , they may be the same or different.] 2. R in the general formula (1-1) １ The non-aqueous electrolyte according to claim 1, wherein is a methylene group, an ethylene group, a fluoroethylene group, a 1,2-difluoroethylene group, a 1,1,2,2-tetrafluoroethylene group, an ethenyl group, a 1,2-difluoroethenyl group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1-(trifluoromethyl)ethylene group, a trimethylene group, a 1-butene group, a 1,3-butadiene group, a 2-methyltrimethylene group, a 2-fluorotrimethylene group, a 1,2-dimethyltrimethylene group, a 1-buten-3-yne group, a 1-pentene group, a 1,4-pentadiene group, a 1-penten-4-yne group, or a 1-buten-3-methyl group.

3. R ​​in the general formula (1-2) ２ , R ３ , R ４ , and R ５ The non-aqueous electrolyte according to claim 1, wherein each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, an ethenyl group, an ethynyl group, a 2-propyl group, a 1-methylethenyl group, or a methoxy group.

4. R in the general formula (2) ６ ~R ９ The non-aqueous electrolyte according to claim 1, wherein at least one of the atoms represents a fluorine atom.

5. M in the general formula (2) ｎ＋ The non-aqueous electrolyte according to claim 1, wherein represents lithium ions or sodium ions.

6. The non-aqueous electrolyte according to claim 1, wherein the concentration of (III) is 0.01 to 5% by mass relative to the total amount of the non-aqueous electrolyte.

7. The non-aqueous electrolyte according to claim 1, wherein the concentration of (IV) is 0.01 to 5% by mass relative to the total amount of the non-aqueous electrolyte.

8. The above (I) is LiPF ６ LiBF ４ LiSbF ６ LiAsF ６ LiClO ４ , LiN (SO ２ F) ２ LiAlO ２ LiAlCl ４ The non-aqueous electrolyte according to claim 1, wherein at least one is selected from the group consisting of , LiCl, and LiI.

9. The above (I) is NaPF ６ NaBF ４ NaSbF ６ NaAsF ６ NaClO ４ 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.

10. The non-aqueous electrolyte according to claim 1, wherein (II) comprises at least one selected from the group consisting of cyclic esters, linear esters, cyclic ethers, linear ethers, sulfone compounds, sulfoxide compounds, and ionic liquids.

11. The non-aqueous electrolyte according to claim 10, wherein the cyclic ester comprises a cyclic carbonate.

12. The non-aqueous electrolyte according to claim 11, wherein the cyclic carbonate comprises at least one selected from the group consisting of ethylene carbonate and propylene carbonate.

13. The non-aqueous electrolyte according to claim 10, wherein the chain-like ester comprises a chain-like carbonate.

14. The non-aqueous electrolyte according to claim 13, wherein the chain-like carbonate comprises at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.

15. Furthermore, cyclohexylbenzene, cyclohexylfluorobenzene, biphenyl, 2-fluorobiphenyl, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, fluorobenzene, difluoroanisole, vinylene carbonate, oligomers of vinylene carbonate (number-average molecular weight in polystyrene terms of 170-5000), vinylethylene carbonate, divinylethylene carbonate, fluoroethylene carbonate, ethynylethylene carbonate, trans-difluoro Ethylene carbonate, methylpropargyl carbonate, ethylpropargyl carbonate, dipropargyl carbonate, dimethylvinylene carbonate, dimethyl dicarbonate, bis(1,1,1,3,3,3-hexafluoro-1-propyl) carbonate, bis(2,2,2-trifluoroethyl) carbonate, 1,6-diisocyanatohexane, maleic anhydride, succinic anhydride, 1,4-dioxan-2,6-dione, glutaric anhydride, methanedisulfonic anhydride, 1,3-propanesult N, 1,3-propensultone, 1,4-butanesultone, 2,4-butanesultone, 1,3,2-dioxathiolan-2,2-dioxide, 4-propyl-1,3,2-dioxathiolan-2,2-dioxide, methylene methane disulfonate, dimethyl methane disulfonate, trimethylene methane disulfonate, methyl methanesulfonate, methanesulfonyl fluoride, ethenesulfonyl fluoride, 1,2-ethane disulfonic anhydride, methanesulfonic anhydride, N,N'-carbonyl bis(N-methyl Sulfamoyl fluoride), difluoro(picolinato) borate, phenyl difluorophosphate, trippropargyl phosphate, tetrafluoro(picolinato) phosphate, (ethoxy)pentafluorocyclotriphosphazene, succinonitrile, methyldifluorovinylsilane, methylfluorodivinylsilane, dimethyldivinylsilane, trivinylmethylsilane, trivinylfluorosilane, tetravinylsilane, tris(trimethylsilyl) borate, tris(trimethylsilyl) phosphate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-Hexafluoroisopropyl)disiloxane, fluorosulfonates, trifluoromethanesulfonates, pentafluoroethanesulfonates, nonafluorobutanesulfonates, monomethyl sulfate, monoethyl sulfate, bis(trifluoromethanesulfonyl)imide, bis The non-aqueous electrolyte according to claim 1, comprising at least one selected from (pentafluoroethanesulfonyl)imide salt, (trifluoromethanesulfonyl)(nonafluorobutanesulfonyl)imide salt, (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide salt, (trifluoromethanesulfonyl)(fluorosulfonyl)imide salt, (pentafluoroethanesulfonyl)(fluorosulfonyl)imide salt, monofluorophosphate, difluorophosphate, tetrafluoro(malonato) phosphate, tris(oxalato) phosphate, difluorobis(oxalato) phosphate, tetrafluorooxalato phosphate, bis(oxalato) borate, difluorooxalatoborate, difluoro(malonato) borate, tris(trifluoromethanesulfonyl)methide salt, tris(fluorosulfonyl)methide salt, acrylate, methacrylate, nitrate, nitrite, hexafluoroisopropanol, and trifluoroethanol.

16. 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 15.

17. A method for manufacturing a non-aqueous electrolyte battery, comprising the step of injecting a non-aqueous electrolyte according to any one of claims 1 to 15.

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