Nonaqueous electrolyte, nonaqueous electrolyte battery, method for manufacturing nonaqueous electrolyte battery, compound, and method for producing compound

Abstract

Provided are: a nonaqueous electrolyte containing (I) a solute, (II) a nonaqueous organic solvent, and (III) a compound represented by general formula (1) described in the specification; a nonaqueous electrolyte battery comprising at least a positive electrode, a negative electrode, and the nonaqueous electrolyte; a method for manufacturing the nonaqueous electrolyte battery, the method comprising a step for injecting the nonaqueous electrolyte; a compound represented by general formula (1) described in the specification; and a method for producing a compound represented by general formula (1A) described in the specification.

Description

Non-aqueous electrolyte, non-aqueous electrolyte battery, method for manufacturing non-aqueous electrolyte battery, compound, and method for manufacturing compound

[0001] The present disclosure relates to a nonaqueous electrolyte, a nonaqueous electrolyte battery, a method for manufacturing a nonaqueous electrolyte battery, a compound, and a method for manufacturing the compound.

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

[0003] For example, Patent Document 1 discloses a nonaqueous electrolyte for lithium batteries to which a phosphonic acid compound is added as a nonaqueous electrolyte that improves cycle characteristics and storage characteristics. Patent Document 2 discloses a nonaqueous electrolyte to which a specific phosphate ester compound having a double bond is added as a nonaqueous electrolyte that suppresses gas generation and has excellent cycle characteristics.

[0004] Japanese Patent No. 5181754 Japanese Patent Application Laid-Open No. 2015-43298

[0005] However, the inventors have conducted studies and found that the addition of these phosphonic acid compounds and phosphate ester compounds does not sufficiently suppress gas generation during high-temperature storage tests, and further improvement is necessary.

[0006] The present disclosure has been made in view of the above circumstances, and aims to provide a nonaqueous electrolyte, a nonaqueous electrolyte battery, and a method for manufacturing a nonaqueous electrolyte battery that significantly suppress gas generation during a high-temperature storage test. It also aims to provide a compound that can be suitably used in the nonaqueous electrolyte, and a method for manufacturing the compound.

[0007] As a result of extensive research to solve these problems, the present inventors have found that when a nonaqueous electrolyte containing a phosphonic acid compound having a specific structure is used in a nonaqueous electrolyte battery, gas generation during a high-temperature storage test can be significantly suppressed, and have arrived at the present invention.

[0008] That is, the present invention is as follows.

[0009] [1] A non-aqueous electrolyte solution containing: (I) a solute; (II) a non-aqueous organic solvent; and (III) a compound represented by the following general formula (1):

[0010]

[0011] [In general formula (1), R represents an alkenyl group or an alkynyl group, and X represents an alkylene group, an alkenylene group, an alkynylene group, or an arylene group.]

[0012] [2] The nonaqueous electrolyte solution according to [1], wherein R in the compound represented by general formula (1) is an allyl group or a 2-propynyl group. [3] The nonaqueous electrolyte solution according to [1] or [2], wherein X in the compound represented by general formula (1) is an alkylene group. [4] The nonaqueous electrolyte solution according to any one of [1] to [3], wherein the content of the compound represented by general formula (1) with respect to the total amount of the nonaqueous electrolyte is 0.005% by mass to 5.0% by mass.

[0013] [5] The (I) is LiPF ６ , LiBF ４ , LiSbF ６ , LiAsF ６ , LiClO ４ , LiN(SO ２ F) ２ , LiAlO ２ , LiAlCl ４ [6] The nonaqueous electrolyte solution according to any one of [1] to [4], wherein (I) is at least one selected from the group consisting of NaPF 6, LiCl 6, and LiI 6. ６ , NaBF ４ , NaSbF ６ , NaAsF ６ , NaClO ４ , NaN(SO ２ F) ２ , NaAlO ２ , NaAlCl ４ 5. The nonaqueous electrolyte solution according to any one of [1] to [4], wherein the nonaqueous electrolyte solution is at least one selected from the group consisting of NaCl, NaI, and NaI.

[0014] [7] The nonaqueous electrolyte according to any one of [1] to [6], wherein (II) comprises at least one selected from the group consisting of a cyclic ester, a chain ester, a cyclic ether, a chain ether, a sulfone compound, a sulfoxide compound, and an ionic liquid. [8] The nonaqueous electrolyte according to [7], wherein the cyclic ester comprises a cyclic carbonate. [9] The nonaqueous electrolyte according to [8], wherein the cyclic carbonate comprises at least one selected from the group consisting of ethylene carbonate and propylene carbonate.

[10] The nonaqueous electrolyte according to [7], wherein the chain ester comprises a chain carbonate.

[0015]

[11] The nonaqueous electrolyte according to

[10] , 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.

[12] The nonaqueous electrolyte according to [7], wherein the cyclic ether comprises 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.

[13] The nonaqueous electrolyte according to [7], wherein the chain ether comprises 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.

[0016]

[14] Further, cyclohexylbenzene, cyclohexylfluorobenzene, biphenyl, 2-fluorobiphenyl, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, fluorobenzene, difluoroanisole, vinylene carbonate, vinylene carbonate oligomers (having a number average molecular weight of 170 to 5000 in terms of polystyrene), vinylethylene carbonate, divinylethylene carbonate, fluoroethylene carbonate, ethynylethylene carbonate, trans-difluoroethylene carbonate ester, methyl propargyl carbonate, ethyl propargyl 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-dioxane-2,6-dione, glutaric anhydride, methanedisulfonic anhydride, 1,3-propane sultone, 1,3-propene sultone, 1, 4-butane sultone, 2,4-butane sultone, 1,3,2-dioxathiolane-2,2-dioxide, 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, methylenemethane disulfonate, dimethylenemethane disulfonate, trimethylenemethane disulfonate, methyl methanesulfonate, methanesulfonyl fluoride, ethenesulfonyl fluoride, 1,2-ethanedisulfonic anhydride, methanesulfonic anhydride, N,N'-carbonylbis(N-methylsulfamoyl fluoride), difluoro(picolinic acid) tris(trimethylsilyl)borate, phenyl difluorophosphate, tripropargyl 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, fluorosulfonate, trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutanesulfonate, monomethyl sulfate, monoethyl sulfate, bis(trifluoromethanesulfonyl)imide salt, bis(pentafluoroethanesulfonyl)imide salt, (trifluoromethanesulfonyl)(nonafluorobutanesulfonyl)imide salt, (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide salt, (trifluoromethanesulfonyl)(fluorosulfonyl)imide salt, (pentafluoroethanesulfonyl)(fluorosulfonyl)imide salt, (difluorophosphoryl)(fluorosulfonyl)imide salt, (difluoro The non-aqueous electrolyte solution according to any one of [1] to

[13] , containing at least one selected from the group consisting of bis(difluorophosphoryl)(trifluoromethanesulfonyl)imide salts, bis(difluorophosphoryl)imide salts, monofluorophosphates, difluorophosphates, tetrafluoro(malonato)phosphates, tris(oxalato)phosphates, difluorobis(oxalato)phosphates, tetrafluorooxalatophosphates, bis(oxalato)borate salts, difluorooxalatoborate salts, difluoro(malonato)borate salts, tris(trifluoromethanesulfonyl)methide salts, tris(fluorosulfonyl)methide salts, acrylates, methacrylates, nitrates, nitrites, hexafluoroisopropanol, and trifluoroethanol.

[0017]

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

[14] .

[16] A method for producing a nonaqueous electrolyte battery, comprising the step of injecting the nonaqueous electrolyte solution according to any one of [1] to

[14] .

[0018]

[17] A compound represented by the following general formula (1):

[0019]

[0020] [In general formula (1), R is an alkenyl group or an alkynyl group, and X is an alkylene group, an alkenylene group, an alkynylene group, or an arylene group.]

[18] The compound according to

[17] , wherein R in the compound represented by general formula (1) is an allyl group or a 2-propynyl group.

[19] The compound according to

[17] or

[18] , wherein X in the compound represented by general formula (1) is an alkylene group.

[0021]

[20] A method for producing a compound represented by the following general formula (1A), comprising a step of reacting a compound represented by the following general formula (2) with a compound represented by the following general formula (3):

[0022]

[0023] R １１ are each independently an alkenyl group or an alkynyl group. A is a halogen atom. Q is a single bond, an alkylene group, an alkenylene group, an alkynylene group, or an arylene group. R １２ is a hydrogen atom or a monovalent substituent.

[0024] The present disclosure provides a nonaqueous electrolyte that can significantly suppress gas generation during a high-temperature storage test when used in a nonaqueous electrolyte battery, a nonaqueous electrolyte battery, and a method for manufacturing the nonaqueous electrolyte battery. It also provides a compound that is suitably used in the nonaqueous electrolyte, and a method for manufacturing the compound.

[0025] In this specification, the word "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0026] The present disclosure will be described in detail below, but the following description of the constituent elements is an example of an embodiment of the present disclosure, and the present disclosure is not limited to these specific contents.

[0027] 1. Regarding the Non-Aqueous Electrolyte The non-aqueous electrolyte of the present disclosure contains (I) a solute, (II) a non-aqueous organic solvent, and (III) a compound represented by the above general formula (1).

[0028] When a nonaqueous electrolyte containing (III) is used in a nonaqueous electrolyte battery (e.g., a lithium ion secondary battery or a sodium ion secondary battery), (III) decomposes at least on either the positive electrode or the negative electrode, and a polymerization reaction proceeds from the alkenyl or alkynyl group portion of R in the compound represented by general formula (1), forming a strong, heat-resistant coating. Therefore, it is believed that decomposition of the solvent, which is a gas generation source, can be suppressed without the coating becoming brittle during a high-temperature storage test. The inventors estimate that, as a result, gas generation during a high-temperature storage test can be significantly suppressed.

[0029] <Regarding (I) Solute> The solute (I) (also referred to as "(I)") contained in the nonaqueous electrolyte solution of the present disclosure will be described. The solute (I) can be any of various solutes that have been conventionally used in the field of such nonaqueous electrolyte solutions, without any particular limitations. Such a solute is preferably an ionic salt consisting of any pair of cation and anion. Various solutes can be used without any particular limitations as long as they exist in an ionic state as a cation and an anion in a nonaqueous organic solvent. 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 , LiCl, and LiI, or NaPF６ , 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 mentioned.

[0030] In particular, in consideration of the energy density, output characteristics, life, and the like of the nonaqueous electrolyte battery, it is preferable that the cation is 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 is at least one selected from the group consisting of hexafluorophosphate anions, tetrafluoroborate anions, and bis(fluorosulfonyl)imide anions.

[0031] In the nonaqueous electrolyte solution of the present disclosure, as (I), one type of compound may be used alone, or two or more types of compounds may be mixed in any combination and ratio depending on the application.

[0032] The concentration of (I) relative to the total amount of the nonaqueous electrolyte is not particularly limited. For example, the lower limit of the concentration of (I) may be 0.5 mol / L or more, 0.7 mol / L or more, or 0.9 mol / L or more. The upper limit of the concentration of (I) may be 5 mol / L or less, 4 mol / L or less, or 2 mol / L or less. A concentration of 0.5 mol / L or more is preferable because the ionic conductivity is less likely to decrease, and the cycle characteristics and output characteristics of the nonaqueous electrolyte battery are less likely to decrease. On the other hand, a concentration of 5 mol / L or less is preferable because the viscosity of the nonaqueous electrolyte is less likely to increase, and the ionic conductivity is less likely to decrease. Note that when two or more types of (I) are used, it is preferable that the total concentration of these solutes is in the above-mentioned range.

[0033] The temperature of the solution when (I) is dissolved in (II) the nonaqueous 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 a lithium ion when used in a lithium ion battery, and more preferably a sodium ion when used in a sodium ion battery.

[0034] <Regarding (II) Non-aqueous Organic Solvent> The non-aqueous organic solvent (II) (also referred to as "(II)") contained in the non-aqueous electrolyte solution of the present disclosure will be described. The type of non-aqueous organic solvent (II) is not particularly limited, and any non-aqueous organic solvent can be used. Such non-aqueous organic solvent preferably contains at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds, amide compounds, nitrile compounds, and ionic liquids, and more preferably contains at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds, and ionic liquids. Note that cyclic carbonates are a sub-concept of cyclic esters, and chain carbonates are a sub-concept of chain esters. Specific examples of the non-aqueous organic solvent (II) 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. In addition to chain carbonates such as 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, 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 chain 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 and sulfoxide compounds such as dimethyl sulfoxide and sulfolane, N,N-dimethylformamide, acetonitrile, and propionitrile. Other examples include ionic liquids.

[0035] (II) The nonaqueous organic solvent may contain at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds, and ionic liquids.

[0036] The cyclic ester may include a cyclic carbonate, and the cyclic carbonate may include at least one selected from the group consisting of ethylene carbonate and propylene carbonate.

[0037] The chain ester may include a chain carbonate, and the chain carbonate may include at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.

[0038] 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.

[0039] The chain 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.

[0040] The nonaqueous electrolyte solution of the present disclosure may use one type of compound alone as (II), or two or more types of compounds may be mixed in any combination and ratio depending on the application. Among these, from the viewpoints of electrochemical stability against oxidation-reduction and chemical stability related to heat and reactions with the solute, it is particularly preferable to include at least one selected from the group consisting of PC, EC, DEC, DMC, and EMC.

[0041] Furthermore, it is preferable that the nonaqueous organic solvent contains, for example, one or more cyclic carbonates having a high dielectric constant and one or more chain carbonates or chain esters having a low liquid viscosity, since this increases the ionic conductivity of the electrolyte solution. Specifically, it is more preferable to use a nonaqueous organic solvent containing the following combinations: (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

[0042] The concentration of the nonaqueous organic solvent in the present disclosure is not particularly limited as long as it functions as a nonaqueous organic solvent, but may be, for example, 40 to 99 mass %, preferably 50 to 95 mass %, and particularly preferably 70 to 93 mass %, relative to the total amount (100 mass %) of the nonaqueous electrolyte solution.

[0043] The content of the cyclic carbonate is not particularly limited and may be any content as long as it does not significantly impair the effects of the present disclosure. However, when one type is used alone, the content may be 3 vol% or more, more preferably 5 vol% or more, based on 100 vol% of the nonaqueous organic solvent. By setting the content within this range, a decrease in electrical conductivity due to a decrease in the dielectric constant of the nonaqueous electrolyte can be avoided, and the large-current discharge characteristics, stability with respect to the negative electrode, and cycle characteristics of the nonaqueous electrolyte battery can be easily maintained within good ranges. The content may also be 90 vol% or less, preferably 85 vol% or less, and more preferably 80 vol% or less. Setting the content within this range allows the viscosity of the nonaqueous electrolyte to be within an appropriate range, suppresses a decrease in ionic conductivity, and ultimately facilitates the load characteristics of the nonaqueous electrolyte battery to be easily maintained within good ranges.

[0044] Furthermore, any combination of two or more cyclic carbonates can be used. One preferred combination is a combination of ethylene carbonate and propylene carbonate. In this case, the volume ratio of ethylene carbonate to propylene carbonate is preferably 99:1 to 40:60, and particularly preferably 95:5 to 50:50. Furthermore, the amount of propylene carbonate relative to the total nonaqueous organic solvent is not particularly limited and may be any amount as long as it does not significantly impair the effects of the present disclosure. However, it may be 1% by volume or more, preferably 2% by volume or more, more preferably 3% by volume or more, or 30% by volume or less, preferably 25% by volume or less, and more preferably 20% by volume or less. When propylene carbonate is contained in this range, for example, in the case of combining ethylene carbonate with a dialkyl carbonate, this is preferred because it maintains the properties of the combination of ethylene carbonate and a dialkyl carbonate while providing even better low-temperature properties.

[0045] The chain ester may be used alone or in any combination and ratio of two or more. The content of the chain ester is not particularly limited, but may be 15% by volume or more, preferably 20% by volume or more, more preferably 25% by volume or more, and may be 90% by volume or less, preferably 85% by volume or less, more preferably 80% by volume or less, based on 100% by volume of the nonaqueous organic solvent. By setting the content of the chain ester within the above range, the viscosity of the nonaqueous electrolyte can be set to an appropriate range, a decrease in ionic conductivity can be suppressed, and the input / output characteristics and charge / discharge rate characteristics of the nonaqueous electrolyte battery can be easily set to good ranges. Furthermore, a decrease in electrical conductivity due to a decrease in the dielectric constant of the nonaqueous electrolyte can be avoided, and the input / output characteristics and charge / discharge rate characteristics of the nonaqueous electrolyte battery can be easily set to good ranges. Furthermore, by combining a specific chain ester with ethylene carbonate at a specific content, battery performance can be significantly improved.

[0046] For example, when dimethyl carbonate, ethyl methyl carbonate, or a mixture of dimethyl carbonate and ethyl methyl carbonate is selected as the specific chain ester, the content of ethylene carbonate is not particularly limited and may be any content as long as it does not significantly impair the effects of the present disclosure, but may be 5% by volume or more, preferably 10% by volume or more, or 45% by volume or less, preferably 40% by volume or less. The content of dimethyl carbonate may be 20% by volume or more, preferably 30% by volume or more, or 50% by volume or less, preferably 45% by volume or less. The content of ethyl methyl carbonate may be 20% by volume or more, preferably 30% by volume or more, or 50% by volume or less, preferably 45% by volume or less. By setting the content within the above range, the low-temperature deposition temperature of the electrolyte is lowered, while also reducing the viscosity of the nonaqueous electrolyte, improving ionic conductivity and making it easier to obtain high input / output even at low temperatures.

[0047] The content of the chain ether is not particularly limited and may be any content as long as it does not significantly impair the effects of the present disclosure. It may be 1% by volume or more, preferably 2% by volume or more, more preferably 3% by volume or more, or 30% by volume or less, preferably 25% by volume or less, more preferably 20% by volume or less, based on 100% by volume of the nonaqueous organic solvent. 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 the degree of lithium ion dissociation of the chain ether and improving ionic conductivity due to reduced viscosity. Furthermore, when the negative electrode active material is a carbonaceous material, the phenomenon of co-intercalation of the chain ether with lithium ions can be suppressed, making it easier to maintain the input / output characteristics and charge / discharge rate characteristics within appropriate ranges.

[0048] The content of the sulfone compound is not particularly limited and may be any content as long as it does not significantly impair the effects of the present disclosure, but may be 0.3 vol% or more, preferably 0.5 vol% or more, more preferably 1 vol% or more, and may be 40 vol% or less, preferably 35 vol% or less, more preferably 30 vol% or less, relative to 100 vol% of the nonaqueous organic solvent. If the content of the sulfone compound is within the above range, it is easy to obtain an effect of improving durability such as cycle characteristics and storage characteristics, and it is also possible to keep the viscosity of the nonaqueous electrolyte within an appropriate range, avoid a decrease in electrical conductivity, and make it easy to keep the input / output characteristics and charge / discharge rate characteristics of the nonaqueous electrolyte battery within appropriate ranges.

[0049] <Regarding (III) Compound Represented by General Formula (1)> The compound (III) represented by general formula (1) (also referred to as "(III)") contained in the nonaqueous electrolyte solution of the present disclosure will be described.

[0050]

[0051] In general formula (1), R is an alkenyl group or an alkynyl group, and X is an alkylene group, an alkenylene group, an alkynylene group, or an arylene group.

[0052] The alkenyl group represented by R includes linear or branched alkenyl groups having 2 to 6 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 1-methyl-2-propenyl group, a 2-methyl-2-propenyl group, a 1,1-dimethyl-2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 3-methyl-2-butenyl group, a 1,3-butadienyl group, a 4-pentenyl group, and a 5-hexenyl group.

[0053] Examples of the alkynyl group represented by R include linear or branched alkynyl groups having 2 to 6 carbon atoms, and specific examples thereof include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-methyl-2-propynyl group, a 1,1-dimethyl-2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 4-pentynyl group, and a 5-hexynyl group.

[0054] At least one arbitrary hydrogen atom of the alkenyl group and alkynyl group may be substituted with a substituent, such as a fluorine atom or an alkoxy group (a linear or branched alkoxy group having 1 to 6 carbon atoms).

[0055] R is preferably a vinyl group, an allyl group, a 2-propynyl group, a 3-butenyl group, or a 3-butynyl group, and more preferably an allyl group or a 2-propynyl group.

[0056] The alkylene group represented by X includes linear or branched alkylene groups having 1 to 6 carbon atoms, and specific examples thereof include a methylene group, an ethylene group, a 1-methylethylene group, a 2-methylethylene group, a 1,2-dimethylethylene group, an n-propylene group, an n-butylene group, and an n-hexylene group.

[0057] The alkenylene group represented by X includes linear or branched alkenylene groups having 2 to 6 carbon atoms, and specific examples thereof include a vinylene group, a 1-propenylene group, a 2-propenylene group, an isopropenylene group, a 2-butenylene group, a 3-butenylene group, a 1,3-butadienylene group, a 2-pentenylene group, and a 3-hexenylene group.

[0058] The alkynylene group represented by X includes linear or branched alkynylene groups having 2 to 6 carbon atoms, and specific examples thereof include an ethynylene group, a 1-propynylene group, a 2-butynylene group, a 2-pentynylene group, and a 3-hexynylene group.

[0059] The arylene group represented by X includes an arylene group having 6 to 8 carbon atoms, and specific examples thereof include a phenylene group, a tolylene group, and a xylylene group.

[0060] At least one of the hydrogen atoms in the alkylene group, alkenylene group, alkynylene group, and arylene group may be substituted with a substituent. Examples of the substituent include a fluorine atom and an alkoxy group (a linear or branched alkoxy group having 1 to 6 carbon atoms). In a preferred embodiment, X is an alkylene group.

[0061] X is preferably an ethylene group, a 1-methylethylene group, a 2-methylethylene group, or a phenylene group, and more preferably an ethylene group.

[0062] Specific examples of the compound represented by formula (1) are shown below, but the invention is not limited to these.

[0063]

[0064] In the nonaqueous electrolyte solution of the present disclosure, the content of the component (III) (hereinafter also referred to as the "concentration of (III)") relative to the total amount (100% by mass) of the nonaqueous electrolyte solution is preferably 0.005% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. The upper limit of the concentration of (III) is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, even more preferably 4.0% by mass or less, and particularly preferably 2.5% by mass or less. By setting the concentration of (III) to 0.01% by mass or more, it is easy to obtain the effect of suppressing gas generation during high-temperature storage tests of nonaqueous electrolyte batteries using the nonaqueous electrolyte solution. On the other hand, by setting the concentration of (III) to 10.0% by mass or less, it is possible to suppress an increase in the viscosity of the nonaqueous electrolyte solution, and it is easy to obtain the effect of suppressing an increase in the initial resistance of nonaqueous electrolyte batteries using the nonaqueous electrolyte solution. The content of the component (III) relative to the total amount of the non-aqueous electrolyte is preferably 0.005 to 10.0% by mass, more preferably 0.005 to 5.0% by mass, and even more preferably 0.05 to 5.0% by mass.

[0065] In the nonaqueous electrolyte solution of the present disclosure, as (III), one type of compound may be used alone, or two or more types of compounds may be mixed in any combination and ratio depending on the application.

[0066] The compound represented by formula (1) can be produced by a known method.

[0067] <Method for producing a compound represented by general formula (1A)> The present disclosure also relates to a method for producing a compound represented by the following general formula (1A), which includes a step of reacting a compound represented by the following general formula (2) with a compound represented by the following general formula (3).

[0068]

[0069] R １１ are each independently an alkenyl group or an alkynyl group. A is a halogen atom. Q is a single bond, an alkylene group, an alkenylene group, an alkynylene group, or an arylene group. R １２ is a hydrogen atom or a monovalent substituent.

[0070] R １１ The alkenyl group in R is the same as the alkenyl group in R in the general formula (1), and the preferred range is also the same. １１ The alkynyl group in is the same as the alkynyl group in R in the above general formula (1), and the preferred range is also the same. Examples of the halogen atom in A include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom is preferred.

[0071] The alkylene group represented by Q includes linear or branched alkylene groups having 1 to 6 carbon atoms (preferably having 1 to 4 carbon atoms), and specific examples thereof include a methylene group, an ethylene group, a 1-methylethylene group, a 2-methylethylene group, a 1,2-dimethylethylene group, an n-propylene group, an n-butylene group, and an n-hexylene group.

[0072] The alkenylene group represented by Q includes linear or branched alkenylene groups having 2 to 6 carbon atoms (preferably having 2 to 4 carbon atoms), and specific examples thereof include a vinylene group, a 1-propenylene group, a 2-propenylene group, an isopropenylene group, a 2-butenylene group, a 3-butenylene group, a 1,3-butadienylene group, a 2-pentenylene group, and a 3-hexenylene group.

[0073] The alkynylene group represented by Q includes a linear or branched alkynylene group having 2 to 6 carbon atoms (preferably having 2 to 4 carbon atoms), and specific examples thereof include an ethynylene group, a 1-propynylene group, a 2-butynylene group, a 2-pentynylene group, and a 3-hexynylene group.

[0074] The arylene group represented by Q includes an arylene group having 6 to 8 carbon atoms (preferably 6 carbon atoms), and specific examples thereof include a phenylene group, a tolylene group, and a xylylene group.

[0075] At least one of the hydrogen atoms in the alkylene group, alkenylene group, alkynylene group, and arylene group may be substituted with a substituent, such as a fluorine atom or an alkoxy group (a linear or branched alkoxy group having 1 to 6 carbon atoms).

[0076] Q is preferably a single bond or an alkylene group.

[0077] R １２ The monovalent substituent is not particularly limited, but examples thereof include an alkyl group (specifically, a linear or branched alkyl group having 1 to 6 carbon atoms), an alkoxy group (a linear or branched alkoxy group having 1 to 6 carbon atoms), and a fluorine atom.

[0078] The step (also referred to as step A) of reacting a compound represented by the general formula (2) with a compound represented by the general formula (3) will be described. The content of the compound represented by the general formula (3) is preferably 1.0 mol to 5.0 mol, more preferably 1.0 mol to 2.0 mol, relative to 1 mol of the compound represented by the general formula (2). Step A is preferably carried out in a non-aqueous organic solvent. Examples of non-aqueous organic solvents include acetonitrile, acetone, 1,2-dimethoxyethane, ethyl acetate, tetrahydrofuran, toluene, dimethyl carbonate, and ethyl methyl carbonate, with acetonitrile being preferred. The reaction temperature in step A is not particularly limited, but is preferably, for example, 25 to 120°C, more preferably 40 to 90°C. The reaction time in step A is not particularly limited, but is, for example, preferably 1 to 96 hours, more preferably 6 to 48 hours. In step A, the compound represented by the general formula (2) and the compound represented by the general formula (3) react, followed by an intramolecular cyclization reaction, to synthesize a compound represented by general formula (1A).

[0079] <Regarding Other Components That May Be Included> The nonaqueous electrolyte solution of the present disclosure is configured using the above-described components as basic constituents, but the nonaqueous electrolyte solution of the present 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 the present disclosure is not impaired. As the other components, for example, other additives commonly used in this technical field may be added in any ratio.

[0080] Examples of other components include aromatic compounds such as cyclohexylbenzene, cyclohexylfluorobenzene, biphenyl, 2-fluorobiphenyl, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, fluorobenzene, and difluoroanisole; Carbonate compounds such as vinylene carbonate (hereinafter sometimes referred to as "VC"), vinylene carbonate oligomers (having a number average molecular weight of 170 to 5000 in terms of polystyrene), vinyl ethylene carbonate, divinyl ethylene carbonate, fluoroethylene carbonate (hereinafter sometimes referred to as "FEC"), ethynyl ethylene carbonate, trans-difluoroethylene carbonate, methyl propargyl carbonate, ethyl propargyl carbonate, dipropargyl carbonate, dimethyl vinylene carbonate, dimethyl dicarbonate, bis(1,1,1,3,3,3-hexafluoro-1-propyl)carbonate, and bis(2,2,2-trifluoroethyl)carbonate; isocyanate compounds such as 1,6-diisocyanatohexane; Organic acid anhydrides such as maleic anhydride, succinic anhydride, 1,4-dioxane-2,6-dione, glutaric anhydride, and methanedisulfonic anhydride, 1,3-propane sultone, 1,3-propene sultone, 1,4-butane sultone, 2,4-butane sultone, 1,3,2-dioxathiolane-2,2-dioxide, 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, methylenemethane disulfonate, dimethylenemethane disulfonate, trimethylenemethane disulfonate, methyl methanesulfonate, methanesulfonyl fluoride, ethenesulfonyl fluoride, 1,2-ethanedisulfonic anhydride, methanesulfonic anhydride, N,Sulfonic acid ester compounds such as N'-carbonylbis(N-methylsulfamoyl fluoride), boric acid ester compounds such as difluoro(picolinato)borate, phosphate ester compounds such as phenyl difluorophosphate, tripropargyl phosphate, 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, 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 fluorosulfonate, trifluoromethanesulfonate, pentafluoroethanesulfonate, and nonafluorobutanesulfonate (among which, fluorosulfonate and trifluoromethanesulfonate are preferred), monoalkyl sulfates such as monomethyl sulfate and monoethyl sulfate, imide salts such as bis(trifluoromethanesulfonyl)imide salts, bis(pentafluoroethanesulfonyl)imide salts, (trifluoromethanesulfonyl)(nonafluorobutanesulfonyl)imide salts, (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide salts, (trifluoromethanesulfonyl)(fluorosulfonyl)imide salts, (pentafluoroethanesulfonyl)(fluorosulfonyl)imide salts, (difluorophosphoryl)(fluorosulfonyl)imide salts, (difluorophosphoryl)(trifluoromethanesulfonyl)imide salts, bis(difluorophosphoryl)imide salts (among which, preferably, bis(trifluoromethanesulfonyl)imide salts, (trifluoromethanesulfonyl)(fluorosulfonyl)imide salts, (difluorophosphoryl)(fluorosulfonyl)imide salts, (difluorophosphoryl)(trifluoromethanesulfonyl)imide salts, and bis(difluorophosphoryl)imide salts); Examples of suitable phosphates include monofluorophosphates, difluorophosphates, tetrafluoro(malonato)phosphates, tris(oxalato)phosphates, difluorobis(oxalato)phosphates, and tetrafluorooxalatophosphates; borates such as bis(oxalato)borate, difluorooxalatoborate, and difluoro(malonato)borate; 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.

[0081] The nonaqueous electrolyte solution of the present disclosure may further contain the following compounds in order to improve the cycle capacity retention rate and gas generation during cycle testing.

[0082]

[0083] The non-aqueous electrolyte solution of the present disclosure may further include cyclohexylbenzene, cyclohexylfluorobenzene, biphenyl, 2-fluorobiphenyl, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, fluorobenzene, difluoroanisole, vinylene carbonate, vinylene carbonate oligomer (having a number average molecular weight of 170 to 5000 in terms of polystyrene), vinylethylene carbonate, divinylethylene carbonate, fluoroethylene carbonate, ethynylethylene carbonate, trans-difluoroethylene carbonate, methylpropargyl carbonate, ethylpropargyl carbonate, dipropargyl carbonate, dimethylvinylene carbonate, dimethyldicarbonate, 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-dioxane-2,6-dione, glutaric anhydride, methanedisulfonic anhydride, 1,3-propane sultone, 1,3-propene sultone, 1,4-butane sultone, 2,4-butane sultone, 1,3,2-dioxathiolane-2,2-dioxide, 4-propyl -1,3,2-dioxathiolane-2,2-dioxide, methylenemethane disulfonate, dimethylenemethane disulfonate, trimethylenemethane disulfonate, methyl methanesulfonate, methanesulfonyl fluoride, ethenesulfonyl fluoride, 1,2-ethanedisulfonic anhydride, methanesulfonic anhydride, N,N'-carbonylbis(N-methylsulfamoyl fluoride), difluoro(picolinato)borate, phenyl difluorophosphate, tripropargy 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, fluorosulfonate, trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutanesulfonate, monomethyl sulfate, monoethyl sulfate, bis(trifluoromethanesulfonyl)imide salt, bis(pentafluoroethanesulfonyl)imide salt, (trifluoromethanesulfonyl)(nonafluorobutanesulfonyl)imide salt, (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide salt, (trifluoromethanesulfonyl)(fluorosulfonyl)imide salt, (pentafluoroethanesulfonyl)(fluorosulfonyl)imide salt, (difluorophosphoryl)(fluorosulfonyl)imide It is preferable that the composition contains at least one selected from the group consisting of tris(trifluoromethanesulfonyl)methide salts, (difluorophosphoryl)(trifluoromethanesulfonyl)imide salts, bis(difluorophosphoryl)imide salts, monofluorophosphates, difluorophosphates, tetrafluoro(malonato)phosphates, tris(oxalato)phosphates, difluorobis(oxalato)phosphates, tetrafluorooxalatophosphates, bis(oxalato)borate salts, difluorooxalatoborate salts, difluoro(malonato)borate salts, tris(trifluoromethanesulfonyl)methide salts, tris(fluorosulfonyl)methide salts, acrylates, methacrylates, nitrates, nitrites, hexafluoroisopropanol, and trifluoroethanol.

[0084] By adding the above-mentioned other components to the nonaqueous electrolyte solution of the present disclosure, at least one of the overcharge prevention effect, the negative electrode film formation effect, and the positive electrode protection effect may be enhanced.

[0085] In addition, the electrolyte for a non-aqueous electrolyte battery may be quasi-solidified with a gelling agent or a crosslinked polymer, as in the case of a non-aqueous electrolyte battery known as a lithium polymer battery. Examples of the polymer include a polymer having polyethylene oxide in the main chain or side chain, a homopolymer or copolymer of polyvinylidene fluoride, a methacrylic acid ester polymer, and polyacrylonitrile.

[0086] When the non-aqueous electrolyte solution of the present disclosure contains other components, the content of the other components may be 0.01% by mass or more and 10% by mass or less relative to the total amount of the non-aqueous electrolyte solution. Among the other components, the content of fluoroethylene carbonate may be 0.01% by mass or more and 55% by mass or less relative to the total amount of the non-aqueous electrolyte solution.

[0087] Furthermore, the content of bis(trifluoromethanesulfonyl)imide salt, trifluoromethanesulfonate salt, and nonafluorobutanesulfonate salt relative to the total amount of the nonaqueous electrolyte may be 0.01 mass % or more and 20 mass % or less.

[0088] 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 nonaqueous electrolyte may be 0.1 mass % or more and 70.0 mass % or less.

[0089] Furthermore, when the other component is an ionic salt, the cation is more preferably a lithium ion when used in a lithium ion battery, and more preferably a sodium ion when used in a sodium ion battery.

[0090] The nonaqueous electrolyte solution of the present disclosure may contain a total of four or more alkali metal salts by using multiple types of salt compounds of the solutes (lithium salts, sodium salts, etc.) and other components, depending on the required properties, or may contain a total of five or more alkali metal salts.

[0091] The nonaqueous electrolyte of the present disclosure is suitable for use in nonaqueous electrolyte batteries (preferably nonaqueous electrolyte secondary batteries).

[0092] 2. Regarding the Non-Aqueous Electrolyte Battery The non-aqueous electrolyte battery of the present disclosure includes at least the non-aqueous electrolyte of the present disclosure, a negative electrode, and a positive electrode. It may further include a separator, an exterior body, etc. Alternatively, a solid electrolyte may be used as a medium for impregnating the non-aqueous electrolyte instead of the separator. The non-aqueous electrolyte battery of the present disclosure preferably includes at least a positive electrode, a negative electrode, and the non-aqueous electrolyte of the present disclosure. The non-aqueous electrolyte battery of the present disclosure is preferably a non-aqueous electrolyte secondary battery.

[0093] [Negative Electrode] The negative electrode is not particularly limited, but may be made of a material that allows reversible insertion and desorption of alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions.

[0094] [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 capable of doping and dedoping lithium ions, such as carbon materials having a d value of 0.340 nm or less in the lattice plane (002) plane in X-ray diffraction such as artificial graphite or natural graphite, carbon materials having a d value of more than 0.340 nm in the lattice plane (002) plane in X-ray diffraction such as hard carbon, lithium metal, alloys of lithium metal and other metals (e.g., alloys of lithium metal and one or more metals selected from Si, Sn, Al, alloys of lithium metal and alloys containing one or more metals selected from Si, Sn, Al, etc.), intermetallic compounds of lithium metal and other metals, metal oxides (e.g., oxides of one or more metals selected from Si, Sn, Al, lithium titanium oxide, etc.), metal nitrides, tin (simple substance), tin compounds, activated carbon, conductive polymers, etc. containing at least one selected from. In addition, as the negative electrode active material, Si and / or Si metal oxide and a carbon material can be preferably mentioned. The Si is silicon metal. The Si metal oxide may be a compound represented by SiOx (where x is a value between 0.5 and 1.5). The total content of Si and / or Si metal oxide contained in the negative electrode active material may be 0.1 to 50% by mass, preferably 0.1 to 30% by mass, based on 100% by mass of the total amount of the Si and / or Si metal oxide and the carbon material contained in the negative electrode active material. 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 minimal change in its crystalline structure due to the absorption and desorption of lithium, resulting in high energy density and excellent cycle characteristics. The shape of the graphite may be fibrous, spherical, granular, or flake-like. Amorphous carbon and graphite coated with amorphous carbon are more preferred because they reduce the reactivity of the material surface with the electrolyte. These negative electrode active materials can be used alone or in combination of two or more.

[0095] For example, in the case of a sodium-ion battery in which the cation is primarily sodium, the negative electrode active material constituting the negative electrode may be sodium metal, an alloy of sodium metal with other metals such as tin, an intermetallic compound of sodium metal with other metals, various carbon materials such as hard carbon, metal oxides such as titanium oxide, metal nitrides, tin (element), tin compounds, activated carbon, conductive polymers, etc. In addition to these, phosphorus (element) such as red phosphorus or black phosphorus, phosphorus compounds such as Co—P, Cu—P, Sn—P, Ge—P, or Mo—P, antimony (element), or antimony compounds such as Sb / C or Bi—Sb, etc. may also be used. These negative electrode active materials may be used alone or in combination of two or more.

[0096] [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. For sodium ion batteries, aluminum or its alloys can also be used.

[0097] [Negative Electrode Active Material Layer] The negative electrode has, for example, a negative electrode active material layer formed on at least one surface of a negative electrode current collector. The negative electrode active material layer is composed of, for example, the above-mentioned negative electrode active material, a binder, and, if necessary, a conductive agent. Examples of the binder include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, styrene butadiene rubber (hereinafter also referred to as "SBR"), carboxymethyl cellulose, methyl cellulose, cellulose acetate phthalate, hydroxypropyl methyl cellulose, polyvinyl alcohol, and polyimide. Examples of the conductive agent that can be used include carbon materials such as acetylene black, ketjen black, furnace black, carbon fiber, graphite, and fluorinated graphite.

[0098] [Positive Electrode] The positive electrode is not particularly limited, but may be made of a material that allows reversible insertion and desorption of alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions.

[0099] [Positive Electrode Active Material] For example, when the cation is lithium, the positive electrode material (positive electrode active material) is LiCoO ２ , LiNiO ２ , LiMnO ２ , LiMn ２ O ４ Lithium-containing transition metal composite oxides such as Li[Ni], Li[Ni], Co[Ni], Mn[Ni], Ni[Ni], Co[Ni], Mn[Ni], Ni[Ni], Co[Ni], Mn[Ni], Ni[Ni], Co[Ni], Mn[Ni], Ni[Ni], Mn[Ni], Co[Ni], Mn[Ni], Ni[Ni], Mn[Ni], Co[Ni], Mn[Ni], Mn[Ni], Ni[Ni], Mn ... 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 (hereinafter, sometimes referred to as "NCM622"), Li[Ni ０．８ Mn ０．１ Co ０．１ ]O ２ (hereinafter, sometimes 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 O２ , LiNi ０．６ 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 In addition, LiFePO , which is called olivine, ４ , LiCoPO ４ , LiMnPO ４ , LiNiPO ４ transition metal phosphate compounds such as TiO ２ , V ２ O ５ , MoO ３oxides such as TiS ２ , FeS, MoS ２ Alternatively, sulfides such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole, conductive polymers such as activated carbon, radical-generating polymers, and carbon materials may be used.

[0100] For example, when the cation is sodium, the positive electrode material (positive electrode active material) is NaCrO ２ , NaFe ０．５ Co ０．５ O ２ , NaFe ０．４ Mn ０．３ Ni ０．３ O ２ , NaNi ０．５ Ti ０．３ Mn ０．２ O ２ , NaNi １／３ Ti １／３ Mn １／３ O ２ , NaNi ０．３３ Ti ０．３３ Mn ０．１６ Mg ０．１７ O ２ , Na ２／３ Ni １／３ Ti １／６ Mn １／２ O ２ , Na ２／３ Ni １／３ Mn ２／３ O ２ sodium-containing transition metal composite oxides such as those described above, in which a plurality of transition metals such as Co, Mn, and Ni are mixed, sodium-containing transition metal composite oxides in which a part of the transition metal is replaced with a metal other than the transition metal, NaFePO ４ , NaVPO ４ F, Na ３ V ２ (P.O. ４ ) ３ , Na ２ Fe ２ (SO ４ ) ３ Polyanion type compounds such as those of the formula Na α M ００１ β [Fe(CN) ６] γ The sodium salt of a Prussian blue analogue represented by ００１ = Cr, Mn, Fe, Co, Ni, Cu or Zn, and 0≦α≦2, 0.5≦β≦1.5, 0.5≦γ≦1.5), TiO ２ , V ２ O ５ , MoO ３ oxides such as TiS ２ , FeS, MoS ２ Alternatively, sulfides such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole, conductive polymers such as activated carbon, radical-generating polymers, and carbon materials may be used.

[0101] [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 an alloy thereof can be used.

[0102] [Positive Electrode Active Material Layer] The positive electrode comprises, for example, a positive electrode active material layer formed on at least one surface of a positive electrode current collector. The positive electrode active material layer is composed of, for example, the above-mentioned positive electrode active material, a binder, and, if necessary, a conductive agent. Examples of the binder include those described in [Negative Electrode Active Material Layer]. Examples of the conductive agent include carbon materials such as acetylene black, ketjen black, furnace black, carbon fiber, graphite (granular graphite or flake graphite), and fluorinated graphite. For the positive electrode, it is preferable to use acetylene black or ketjen black, which have low crystallinity.

[0103] [Method for producing electrodes (positive and negative electrodes)] The electrodes can be obtained, for example, by dispersing and kneading the active material, binder, and optionally conductive agent in predetermined amounts in a solvent such as N-methyl-2-pyrrolidone (NMP) or water, applying the resulting paste to a current collector, and drying to form an active material layer. The resulting electrode is preferably compressed by a method such as a roll press to adjust it to an electrode with an appropriate density.

[0104] [Separator] The nonaqueous electrolyte battery of the present disclosure may include a separator. Examples of separators used to prevent contact between the positive electrode and the negative electrode include nonwoven fabrics or porous sheets made of polyolefins such as polypropylene and polyethylene, cellulose, paper, or glass fiber. These films are preferably microporous so that the electrolyte can penetrate and ions can easily pass through. Examples of polyolefin separators include microporous polymer films such as porous polyolefin films, which electrically insulate the positive electrode and negative electrode and are permeable to lithium ions. Specific examples of porous polyolefin films include porous polyethylene films alone, or multilayer films formed by stacking porous polyethylene films and porous polypropylene films. Other examples include composite films of porous polyethylene and polypropylene films. The nonaqueous electrolyte of the present disclosure may be impregnated into the separator and retained therein. There are no particular limitations on the impregnation method, and any known method may be used. Specifically, the electrolyte can be finally injected into a battery equipped with a positive electrode, a separator, and a negative electrode to impregnate the battery.

[0105] [Exterior Body] As the exterior body of the nonaqueous electrolyte battery of the present disclosure, for example, a coin-shaped, cylindrical, or rectangular metal can, or even a laminate exterior body, etc. Suitable metal can materials include, for example, nickel-plated steel, stainless steel, nickel-plated stainless steel, aluminum or its alloy, nickel, titanium, etc. As the laminate exterior body, for example, an aluminum laminate film, a SUS laminate film, or a laminate film of silica-coated polypropylene, polyethylene, etc., can be used.

[0106] The configuration of the nonaqueous electrolyte battery according to this embodiment is not particularly limited, but may be configured, for example, such that an electrode element in which a positive electrode and a negative electrode are arranged opposite each other, and a nonaqueous electrolyte are enclosed in an exterior body. The shape of the nonaqueous electrolyte battery is not particularly limited, but an electrochemical device in the shape of a coin, cylinder, square, aluminum laminate sheet, or the like can be assembled from the above components.

[0107] 3. Regarding the Compound The present disclosure also relates to a compound represented by the following general formula (1):

[0108]

[0109] [In general formula (1), R represents an alkenyl group or an alkynyl group, and X represents an alkylene group, an alkenylene group, an alkynylene group, or an arylene group.]

[0110] The compound represented by the general formula (1) is the same as (III) in the nonaqueous electrolyte solution of the present disclosure, and the above description can be used as is for details of the compound and the method for producing the compound.

[0111] That is, in general formula (1), R is preferably an allyl group, a 2-propynyl group, a 3-butenyl group, or a 3-butynyl group, and more preferably an allyl group or a 2-propynyl group. Also, in general formula (1), X is preferably an ethylene group, a 1-methylethylene group, a 2-methylethylene group, or a phenylene group, and more preferably an ethylene group.

[0112] 4. Regarding the manufacturing method of the nonaqueous electrolyte battery, the manufacturing method of the nonaqueous electrolyte battery of the present disclosure includes a step of injecting the nonaqueous electrolyte of the present disclosure. The method of injecting the electrolyte is not particularly limited, and can be a conventional method. For example, vacuum injection or the like can be used.

[0113] The present disclosure will be specifically described below using examples, but the present disclosure is not limited to such examples.

[0114] The compound (III) represented by general formula (1) used in each example was synthesized as follows.

[0115] Synthesis Example 1: Synthesis of Compound (1-1)

[0116]

[0117] Acryloyl chloride (1.0 g, 11 mmol) was added to diallyl phosphite (1.6 g, 10 mmol) in 50 ml of acetonitrile, and the mixture was stirred for 24 hours at 80° C. The reaction solution was concentrated to obtain the target compound (1-1) (1.4 g, yield 90%). １ H NMR (CD ３ NC) σ2.34, 2.98, 4.63, 5.25, 5.40, 5.94ppm ３１ P NMR (CD ３ NC)σ40.0ppm

[0118] Synthesis Example 2: Synthesis of compound (1-2)

[0119]

[0120] Acryloyl chloride (1.0 g, 11 mmol) was added to dipropargyl phosphite (1.6 g, 10 mmol) in 50 ml of acetonitrile, and the mixture was stirred for 24 hours at 80° C. The reaction solution was concentrated to obtain the target compound (1-2) (1.4 g, yield 70%). １ H NMR (CD ３ NC) σ2.40, 2.91, 3.01, 4.65ppm ３１ P NMR (CD ３ NC)σ41.0ppm

[0121] The structures of comparative compounds (X) and (Z) used in the comparative examples are shown below: In the following structures, Et represents an ethyl group.

[0122]

[0123] [Examples 1-1 to 1-10, Examples 2-1 to 2-2, Examples 3-1 to 3-2, Examples 4-1 to 4-2, Examples 5-1 to 5-2, Examples 6-1 to 6-2, Examples 7-1 to 7-2, Examples 8-1 to 8-2, Comparative Examples 1-1 to 1-3, Comparative Examples 2-1 to 2-3, Comparative Examples 3-1 to 3-3, Comparative Examples 4-1 to 4-3, Comparative Examples 5-1 to 5-3, Comparative Examples 6-1 to 6-3, Comparative Examples 7-1 to 7-3, Comparative Examples 8-1 to 8-3] <Preparation of non-aqueous electrolyte> In a glove box with a dew point of -60 ° C. or less, EC, PC, EMC, and DMC were mixed in a volume ratio of EC:PC:EMC:DMC = 25:5:45:25. Then, LiPF as a solute ６ was dissolved in the electrolyte to a concentration of 1.0 mol / L relative to the total amount of the electrolyte, and at least one compound selected from the group consisting of compounds represented by general formula (1) (hereinafter, also referred to as "component (III)") or a comparative compound was dissolved in an amount relative to the total amount of the electrolyte as shown in Tables 1 to 8 below. When other components were to be contained, the compounds shown in Tables 2 to 8 below were similarly dissolved in the amounts shown. The preparation was carried out at 25°C.

[0124] In the "other components" columns of Tables 2 to 8, VC represents vinylene carbonate, BOB represents lithium bis(oxalato)borate, DFBOP represents lithium difluorobis(oxalato)phosphate, TFOP represents lithium tetrafluorooxalatophosphate, FSI represents lithium bis(fluorosulfonyl)imide, DFP represents lithium difluorophosphate, and FS represents lithium fluorosulfonate, as in the subsequent tables.

[0125] <Preparation of non-aqueous electrolyte battery> (Preparation of NCM622 positive electrode) LiNi ０．６ Co ０．２ Mn ０．２ O ２ A positive electrode composite paste was prepared by mixing 90% by weight of the powder with 5% by weight of polyvinylidene fluoride (PVDF) as a binder and 5% by weight of acetylene black as a conductive material, and then adding N-methyl-2-pyrrolidone. This paste was applied to both sides of aluminum foil (A1085), dried, pressed, and then punched out to a 4 cm x 5 cm piece to obtain a test NCM622 positive electrode.

[0126] (Preparation of Natural Graphite Negative Electrode) A slurry solution was prepared by mixing 92% by mass of natural graphite powder, 3% by mass of a conductive material (HS-100), 2% by mass of carbon nanofiber (VGCF), 2% by mass of styrene-butadiene rubber, 1% by mass of sodium carboxymethyl cellulose, and water. This slurry solution was applied to a copper foil negative electrode current collector and dried at 100°C for 12 hours to obtain a test natural graphite negative electrode having a negative electrode active material layer formed on the current collector.

[0127] (Preparation of Nonaqueous Electrolyte Batteries) In an argon atmosphere with a dew point of −50° C. or lower, a terminal was welded to the above-mentioned NCM622 positive electrode, and then the electrode was sandwiched between two polyethylene separators (5 cm × 6 cm). The outer surface of the separator was then sandwiched between two natural graphite negative electrodes with terminals previously welded, with the negative electrode active material surface facing the positive electrode active material surface. These were then placed in an aluminum laminate bag with an opening on one side. A nonaqueous electrolyte was vacuum-injected into the bag, and the opening was then heat-sealed to prepare aluminum laminate nonaqueous electrolyte batteries according to the examples and comparative examples shown in Tables 1 to 8.

[0128] [Examples 9-1 to 9-10, Examples 10-1 to 10-2, Examples 11-1 to 11-2, Examples 12-1 to 12-2, Examples 13-1 to 13-2, Examples 14-1 to 14-2, Examples 15-1 to 15-2, Examples 16-1 to 16-2, Comparative Examples 9-1 to 9-3, Comparative Examples 10-1 to 10-3, Comparative Examples 11-1 to 11-3, Comparative Examples 12-1 to 12-3, Comparative Examples 13-1 to 13-3, Comparative Examples 14-1 to 14-3, Comparative Examples 15-1 to 15-3, Comparative Examples 16-1 to 16-3] <Preparation of non-aqueous electrolyte> In a glove box with a dew point of -60 ° C. or less, EC, FEC, EMC and DMC were mixed in a volume ratio of EC: FEC: EMC: DMC = 24: 3: 48: 25. Then, LiPF as a solute ６ was dissolved in the electrolyte to a concentration of 1.0 mol / L relative to the total amount of the electrolyte, and component (III) or a comparative compound was dissolved in an amount relative to the total amount of the electrolyte as shown in Tables 9 to 16 below. When other components were to be contained, the compounds shown in Tables 10 to 16 below were similarly dissolved in the amounts shown. The above preparation was carried out at 25°C.

[0129] <Preparation of non-aqueous electrolyte battery> (Preparation of NCM811 positive electrode) LiNi ０．８ Co ０．１ Mn ０．１ O ２ A positive electrode composite paste was prepared by mixing 92.0% by mass of the 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 N-methyl-2-pyrrolidone. This paste was applied to both sides of aluminum foil (A1085), dried, pressed, and then punched out to a 4 cm x 5 cm piece to obtain a test NCM811 positive electrode.

[0130] (Preparation of silicon-containing graphite negative electrode) A slurry solution was prepared by mixing 85% by mass of artificial graphite powder, 7% by mass of nanosilicon, 3% by mass of conductive material (HS-100), 2% by mass of carbon nanofiber (VGCF), 2% by mass of styrene-butadiene rubber, 1% by mass of sodium carboxymethyl cellulose, and water. This slurry solution was applied to a copper foil negative electrode current collector and dried at 100°C for 12 hours to obtain a test silicon-containing graphite negative electrode having a negative electrode active material layer formed on the current collector.

[0131] (Fabrication of Nonaqueous Electrolyte Batteries) The aluminum laminate-type nonaqueous electrolyte batteries of the Examples and Comparative Examples in Tables 9 to 16 were fabricated in the same manner as the aluminum laminate-type nonaqueous electrolyte batteries of the Examples and Comparative Examples in Tables 1 to 8, except that the NCM622 positive electrode and natural graphite negative electrode were changed to the above-mentioned NCM811 positive electrode and silicon-containing graphite negative electrode, respectively.

[0132] [Examples 17-1 to 17-10, Examples 18-1 to 18-2, Examples 19-1 to 19-2, Examples 20-1 to 20-2, Examples 21-1 to 21-2, Examples 22-1 to 22-2, Examples 23-1 to 23-2, Examples 24-1 to 24-2, Comparative Examples 17-1 to 17-3, Comparative Examples 18-1 to 18-3, Comparative Examples 19-1 to 19-3, Comparative Examples 20-1 to 20-3, Comparative Examples 21-1 to 21-3, Comparative Examples 22-1 to 22-3, Comparative Examples 23-1 to 23-3, Comparative Examples 24-1 to 24-3] <Preparation of Non-Aqueous Electrolyte> In a glove box having a dew point of −60 ° C. or less, PC, EC, FEC, EMC, and DEC were mixed in a volume ratio of PC: EC: FEC: EMC: DEC = 20: 8: 2: 48: 22. Then, NaPF as a solute ６ was dissolved in the electrolyte to a concentration of 1.0 mol / L relative to the total amount of the electrolyte, and component (III) or a comparative compound was dissolved in an amount relative to the total amount of the electrolyte as shown in Tables 17 to 24 below. When other components were to be contained, the compounds shown in Tables 18 to 24 below were similarly dissolved in the amounts shown. The above preparation was carried out at 25°C.

[0133] In the other components columns of Tables 19 to 24, BOB-Na represents sodium bis(oxalato)borate, DFBOP-Na represents sodium difluorobis(oxalato)phosphate, TFOP-Na represents sodium tetrafluorooxalatophosphate, FSI-Na represents sodium bis(fluorosulfonyl)imide, DFP-Na represents sodium difluorophosphate, and FS-Na represents sodium fluorosulfonate.

[0134] <Fabrication of non-aqueous electrolyte battery>

[0135] (NaNi ０．５ Ti ０．３ Mn ０．２ O ２ Preparation of positive electrode) NaNi was used as the positive electrode active material. ０．５ Ti ０．３ Mn ０．２ O ２90% by mass of the positive electrode active material, 5% by mass of acetylene black as a conductive agent, and 5% by mass of PVDF as a binder were mixed, and N-methyl-2-pyrrolidone was further added as a solvent in an amount of 50% by mass relative to the total mass of the positive electrode active material, conductive agent, and binder to prepare a slurry solution. This slurry solution was applied to an aluminum foil positive electrode current collector and dried at 150°C for 12 hours to obtain a test NaNi cathode active material layer formed on the current collector. ０．５ Ti ０．３ Mn ０．２ O ２ The positive electrode was obtained.

[0136] (Preparation of Hard Carbon Negative Electrode) 90% by mass of hard carbon powder (Carbotron P, manufactured by Kureha Corporation) and 10% by mass of PVDF as a binder were mixed, and N-methylpyrrolidone as a solvent was further added in an amount of 50% by mass relative to the total mass of the negative electrode active material and binder to prepare a slurry solution. This slurry solution was applied to an aluminum foil negative electrode current collector and dried at 150°C for 12 hours to obtain a test hard carbon negative electrode having a negative electrode active material layer formed on the current collector.

[0137] (Preparation of non-aqueous electrolyte battery) The NCM622 positive electrode and the natural graphite negative electrode were prepared using the above-mentioned NaNi ０．５ Ti ０．３ Mn ０．２ O ２ Aluminum laminate-type nonaqueous electrolyte batteries of Examples and Comparative Examples in Tables 17 to 24 were fabricated in the same manner as the aluminum laminate-type nonaqueous electrolyte batteries of Examples and Comparative Examples in Tables 1 to 8, except that the positive electrode and the hard carbon negative electrode were changed, respectively.

[0138] [Evaluation] <Initial charge / discharge> The battery was placed in a thermostatic chamber at 25°C and connected to a charge / discharge device in that state. Charging was performed up to 4.2 V at a charge rate of 0.2 C (a current value that would result in a full charge in 5 hours). After maintaining 4.2 V for 1 hour, discharging was performed down to 3.0 V at a discharge rate of 0.2 C. This constituted one charge / discharge cycle, and a total of 10 charge / discharge cycles were performed to stabilize the battery.

[0139] <Measurement of Initial Battery Volume> After stabilization, the battery was completely immersed in silicone oil, and the volume of the battery was measured by Archimedes' method. This was taken as the initial battery volume.

[0140] <Measurement of Battery Capacity After 4 Weeks of Storage at 60°C> Next, the battery after the above initial charge / discharge was charged to 4.2 V at a charge rate of 0.2 C, and then the battery was removed from the charge / discharge device and placed in a thermostatic chamber at 60°C. After 4 weeks, the battery was removed from the thermostatic chamber and allowed to stand at room temperature (25°C) for 24 hours, and then discharged to 3.0 V at a discharge rate of 0.2 C. Subsequently, the battery was charged to 4.2 V at a charge rate of 0.2 C and discharged to 3.0 V at a discharge rate of 0.2 C, and the capacity obtained by this discharge was taken as the battery capacity after storage at 60°C.

[0141] <Measurement of the amount of gas generated during high-temperature storage test> The volume of the battery after discharge was measured by the Archimedes method in the same manner as in measuring the initial battery volume. The value obtained by subtracting the initial battery volume from the volume obtained here was used as the amount of gas generated during the high-temperature storage test. The results are shown in Tables 1 to 24.

[0142] The gas amounts (amounts of gas generated during high-temperature storage tests) in Tables 1 to 24 are, respectively, Comparative Example 1-1, Comparative Example 2-1, Comparative Example 3-1, Comparative Example 4-1, Comparative Example 5-1, Comparative Example 6-1, Comparative Example 7-1, Comparative Example 8-1, Comparative Example 9-1, Comparative Example 10-1, Comparative Example 11-1, Comparative Example 12-1, Comparative Example 13-1, Comparative Example 14-1, Comparative Example 15-1, Comparative Example 16-1, Comparative Example 17-1, Comparative Example 18-1, Comparative Example 19-1, Comparative Example 20-1, Comparative Example 21-1, Comparative Example 22-1, Comparative Example 23-1, and Comparative Example 24-1. These values ​​are relative to the values ​​of 100.

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167] The results in Tables 1 to 24 show that the nonaqueous electrolyte battery using the nonaqueous electrolyte of the present invention containing component (III) can significantly suppress gas generation during high-temperature storage tests.

[0168] The present disclosure provides a nonaqueous electrolyte that can significantly suppress gas generation during a high-temperature storage test when used in a nonaqueous electrolyte battery, a nonaqueous electrolyte battery, and a method for manufacturing the nonaqueous electrolyte battery. It also provides a compound that is suitably used in the nonaqueous electrolyte, and a method for manufacturing the compound.

[0169] Although the present disclosure has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present disclosure. This application is based on a Japanese patent application (Patent Application No. 2024-007525) filed on January 22, 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, and (III) a compound represented by the following general formula (1). [In general formula (1), R is an alkenyl group or an alkynyl group, and X is an alkylene group, an alkenylene group, an alkynylene group, or an arylene group.] 2. The non-aqueous electrolyte according to claim 1, wherein R in the compound represented by the general formula (1) is an allyl group or a 2-propynyl group.

3. The non-aqueous electrolyte according to claim 1 or 2, wherein X in the compound represented by the general formula (1) is an alkylene group.

4. The non-aqueous electrolyte according to claim 1 or 2, wherein the content of the compound represented by the general formula (1) relative to the total amount of the non-aqueous electrolyte is 0.005% by mass to 5.0% by mass.

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

6. Wherein (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 or 2, which is at least one selected from the group consisting of NaCl and NaI.

7. The non-aqueous electrolyte according to claim 1 or 2, wherein (II) contains at least one selected from the group consisting of a cyclic ester, a chain ester, a cyclic ether, a chain ether, a sulfone compound, a sulfoxide compound, and an ionic liquid.

8. The non-aqueous electrolyte according to claim 7, wherein the cyclic ester contains a cyclic carbonate.

9. The non-aqueous electrolyte according to claim 8, wherein the cyclic carbonate contains at least one selected from the group consisting of ethylene carbonate and propylene carbonate.

10. The non-aqueous electrolyte according to claim 7, wherein the chain ester contains a chain carbonate.

11. The non-aqueous electrolyte according to claim 10, wherein the chain carbonate contains at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.

12. The non-aqueous electrolyte according to claim 7, wherein the cyclic ether contains 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.

13. The non-aqueous electrolyte according to claim 7, wherein the chain ether contains 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.

14. Further, cyclohexylbenzene, cyclohexylfluorobenzene, biphenyl, 2-fluorobiphenyl, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, fluorobenzene, difluoroanisole, vinylene carbonate, an oligomer of vinylene carbonate (number average molecular weight in terms of polystyrene is 170 to 5000), vinyl ethylene carbonate, divinyl ethylene carbonate, fluoroethylene carbonate, ethynyl ethylene carbonate, trans-difluoroethylene carbonate, methyl propargyl carbonate, ethyl propargyl carbonate, dipropargyl carbonate, dimethyl vinylene 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-dioxane-2,6-dione, glutaric anhydride, methanedisulfonic anhydride, 1,3-propanesultone, 1,3-propenesultone, 1,4-butanesultone, 2,4-butanesultone, 1,3,2-dioxathiolane-2,2-dioxide, 4-propyl-1,3,2-dioxathiolane-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(picolinato)borate, phenyl difluorophosphate, tripropargyl phosphate, tetrafluoro(picolinato)phosphate, (ethoxy)pentafluorocyclotriphosphazene, succinonitrile, methyl difluorovinylsilane, methyl fluorodivinylsilane, dimethyl divinylsilane, trivinylmethylsilane, trivinylfluorosilane, tetravinylsilane, tris(trimethylsilyl)borate, tris(trimethylsilyl)phosphate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,The non-aqueous electrolyte according to claim 1 or 2, containing at least one selected from 3-hexafluoroisopropyl) disiloxane, fluorosulfonate, trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutanesulfonate, monomethyl sulfate, monoethyl sulfate, bis(trifluoromethanesulfonyl)imide salt, bis(pentafluoroethanesulfonyl)imide salt, (trifluoromethanesulfonyl)(nonafluorobutanesulfonyl)imide salt, (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide salt, (trifluoromethanesulfonyl)(fluorosulfonyl)imide salt, (pentafluoroethanesulfonyl)(fluorosulfonyl)imide salt, (difluorophosphoryl)(fluorosulfonyl)imide salt, (difluorophosphoryl)(trifluoromethanesulfonyl)imide salt, bis(difluorophosphoryl)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.

15. A non-aqueous electrolyte battery comprising at least a positive electrode, a negative electrode, and the non-aqueous electrolyte according to claim 1 or 2.

16. A method for manufacturing a non-aqueous electrolyte battery, which includes a step of injecting the non-aqueous electrolyte according to claim 1 or 2.

17. A compound represented by the following general formula (1). [In the general formula (1), R is an alkenyl group or an alkynyl group, and X is an alkylene group, an alkenylene group, an alkynylene group or an arylene group.] 18. The compound according to claim 17, wherein R in the compound represented by the general formula (1) is an allyl group or a 2-propynyl group.

19. The compound according to claim 17 or 18, wherein X in the compound represented by the general formula (1) is an alkylene group. A method for producing a compound represented by the following general formula (1A), comprising a step of reacting a compound represented by the following general formula (2) with a compound represented by the following general formula (3). R １１ Each R is independently an alkenyl group or an alkynyl group. A is a halogen atom. Q is a single bond, an alkylene group, an alkenylene group, an alkynylene group or an arylene group. R １２ is a hydrogen atom or a monovalent substituent.

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