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

Abstract

A non-aqueous electrolyte comprising: (I) a solute, (II) a non-aqueous organic solvent, and (III) at least one compound selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (2), a non-aqueous electrolyte battery comprising the above-mentioned non-aqueous electrolyte, and a method for manufacturing the above-mentioned non-aqueous electrolyte battery.

Description

Technical Field

[0001] This disclosure relates to non-aqueous electrolytes, non-aqueous electrolyte batteries, and methods for manufacturing non-aqueous electrolyte batteries. Background Technology

[0002] In recent years, in addition to energy storage systems for small, high-energy-density applications such as information-related equipment and communication devices (personal computers, camcorders, digital cameras, mobile phones, and smartphones), the demand for high-capacity, high-output, and high-energy-density batteries that can be used as auxiliary power sources for electric vehicles, hybrid vehicles, and fuel cell vehicles has also expanded dramatically. Furthermore, the demand for batteries capable of long-term use is increasing even for large-scale, power storage systems. As alternatives to these various energy storage systems, non-aqueous electrolyte batteries, such as lithium-ion batteries, are becoming increasingly popular. Non-aqueous electrolyte batteries typically consist of a positive electrode, a negative electrode, and a non-aqueous electrolyte.

[0003] To date, as a means to improve the durability of non-aqueous electrolyte batteries, research is being conducted on optimizing various battery components, primarily the active materials of the positive and negative electrodes. Non-aqueous electrolyte-related technologies are no exception, with proposals to suppress degradation caused by the decomposition of non-aqueous electrolytes on the surfaces of the active positive and negative electrodes using various additives.

[0004] Patent Document 1 describes a method that, by using a non-aqueous electrolyte containing at least one of a dinitramide salt and a nitramide salt as a main electrolyte, auxiliary electrolyte, or additive, achieves cycle characteristics equivalent to those of lithium hexafluorophosphate, which is typically used as a main electrolyte. Furthermore, it describes improvements in charge / discharge efficiency and self-discharge characteristics when applied to lithium-sulfur batteries.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: U.S. Patent Application Publication No. 2006 / 0154144 Summary of the Invention

[0008] The problem the invention aims to solve

[0009] However, as a result of the inventors' research, it was determined that the non-aqueous electrolyte containing lithium dinitramide used in the embodiments of Patent Document 1 has room for improvement in terms of high-temperature storage characteristics when used in non-aqueous electrolyte batteries.

[0010] The purpose of this disclosure is to provide a non-aqueous electrolyte that exhibits excellent high-temperature storage properties when used in non-aqueous electrolyte batteries, and a method for manufacturing the aforementioned non-aqueous electrolyte battery. Furthermore, the purpose of this disclosure is to provide a non-aqueous electrolyte battery with excellent high-temperature storage properties.

[0011] Solution for solving the problem [1]

[0013] A non-aqueous electrolyte containing:

[0014] (I) Solute,

[0015] (II) Non-aqueous organic solvents, and

[0016] (III) Select at least one compound from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2).

[0017]

[0018] [A in general formula (1)] 1 Indicates -N(H)- or -N - (M1 + )-. M1 + Represents a metal cation or an onium cation. R 1 The following groups represent halogen atoms, alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkenyloxy groups with 2 to 10 carbon atoms, alkynyloxy groups with 2 to 10 carbon atoms, aryloxy groups with 6 to 15 carbon atoms, OH groups, and O groups. - Mx + Or N(Rx)2. Mx + Representing a metal cation or an onium cation. Each Rx independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or a fluorosulfonyl group. Multiple Rx groups may be identical or different. Multiple Rx groups may optionally be bonded to each other.

[0019]

[0020] [A in general formula (2)] 2 Indicates -N(H)- or -N - (M2 + M2 + Represents a metal cation or an onium cation. R 2 and R 3 Each of these groups independently represents a halogen atom, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkenyloxy group with 2 to 10 carbon atoms, an alkynyloxy group with 2 to 10 carbon atoms, an aryloxy group with 6 to 15 carbon atoms, an OH group, or an O group. - My + Or N(Ry)2. My +Represents a metal cation or an onium cation. Each Ry group independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkynyl group with 2 to 10 carbon atoms, or a fluorosulfonyl group. Multiple Ry groups may be identical or different. Multiple Ry groups may optionally be bonded to each other. [2]

[0022] According to the non-aqueous electrolyte described in [1], wherein R in the general formula (1) 1 For fluorine atoms, methyl, ethyl, vinyl, methoxy, O - Mx + Or N(Rx)2. [3]

[0024] According to the non-aqueous electrolyte described in [1], wherein R in the general formula (2) 2 and R 3 At least one of them is a fluorine atom, methyl, ethyl, vinyl, methoxy, or O atom. - My + Or N(Ry)2. [4]

[0026] According to the non-aqueous electrolyte described in [1] or [2], wherein A in the general formula (1) 1 Indicates -N(H)- or -N - (M1 + )-, and M1 + It consists of lithium ions or sodium ions. [5]

[0028] According to the non-aqueous electrolyte described in [1] or [3], wherein A in the general formula (2) 2 Indicates -N(H)- or -N - (M2 + )-, and M2 + It consists of lithium ions or sodium ions. [6]

[0030] According to any one of [1] to [5], the concentration of (III) is 0.01 to 10 by mass relative to the total amount of the non-aqueous electrolyte. [7]

[0032] The non-aqueous electrolyte according to any one of [1] to [6], wherein (I) is at least one selected from the group consisting of LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiN(SO2F)2, LiAlO2, LiAlCl4, LiCl and LiI. [8]

[0034] The non-aqueous electrolyte according to any one of [1] to [6], wherein (I) is at least one selected from the group consisting of NaPF6, NaBF4, NaSbF6, NaAsF6, NaClO4, NaN(SO2F)2, NaAlO2, NaAlCl4, NaCl and NaI. [9]

[0036] The non-aqueous electrolyte according to any one of [1] to [8], wherein (II) comprises at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds and ionic liquids.

[10]

[0038] According to the non-aqueous electrolyte described in [9], the cyclic ester comprises a cyclic carbonate.

[11]

[0040] According to the non-aqueous electrolyte of

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

[12]

[0042] According to the non-aqueous electrolyte described in [9], the chain ester comprises a chain carbonate.

[13]

[0044] According to the non-aqueous electrolyte of

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

[14]

[0046] According to the non-aqueous electrolyte of [9], 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.

[15]

[0048] According to the non-aqueous electrolyte of [9], 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.

[16]

[0050] According to any one of [1] to

[15] , the non-aqueous electrolyte further contains oligomers selected from cyclohexylbenzene, cyclohexylfluorobenzene, biphenyl, 2-fluorobiphenyl, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, fluorobenzene, difluoroanisole, vinylene carbonate, vinylene carbonate (with a number average molecular weight of 170 to 5000 converted from polystyrene), vinylene carbonate, divinylene carbonate, fluoroethylene carbonate, ethynylene carbonate, trans-difluoroethylene carbonate, methylpropynyl carbonate, ethylene Propylene carbonate, dipropyne 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-diisocyanate hexane, maleic anhydride, succinic anhydride, 1,4-dioxane-2,6-dione, glutaric anhydride, methanedisulfonic anhydride, 1,3-propanesulfonyl lactone, 1,3-propenesulfonyl lactone, 1,4-butanesulfonyl lactone, 2,4-butanesulfonyl lactone, 1,3,2-dioxane-thiacyclopentane -2,2-dioxide, 4-propyl-1,3,2-dioxane-2,2-dioxide, methylene methane disulfonate, dimethylene methane disulfonate, trimethylene methane disulfonate, methyl methanesulfonate, methanesulfonyl fluoride, ethylene sulfonyl fluoride, 1,2-ethane disulfonic anhydride, methanesulfonic anhydride, N,N'-carbonylbis(N-methylaminosulfonyl fluoride), difluoro(picolinato)borate, phenyl difluorophosphate, triargyl phosphate Tetrafluoro(picolinato) phosphate, (ethoxy)pentafluorocyclotriphosphonon, succinic anion, methyldifluorovinylsilane, methylfluorodivinylsilane, dimethyldivinylsilane, trivinylmethylsilane, trivinylfluorosilane, tetravinylsilane, tri(trimethylsilyl)boronic acid ester, tri(trimethylsilyl) phosphate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-Hexafluoroisopropyl)disiloxane, fluorosulfonates, trifluoromethanesulfonates, pentafluoroethanesulfonates, nonafluorobutanesulfonates, monomethyl sulfates, monoethyl sulfates, 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 At least one of the following groups: amine salts, (difluorophosphoryl)(trifluoromethanesulfonyl)imide salts, bis(difluorophosphoryl)imide salts, monofluorophosphates, difluorophosphates, tetrafluoro(malonic acid) phosphates, tri(oxalate) phosphates, difluorobis(oxalate) phosphates, tetrafluorooxalate phosphates, bis(oxalate) borates, difluorooxalate borates, difluoro(malonic acid) borates, tri(trifluoromethanesulfonyl) methyl salts, tri(fluorosulfonyl) methyl salts, acrylates, methacrylates, nitrates, nitrites, hexafluoroisopropanol, and trifluoroethanol.

[17]

[0052] A non-aqueous electrolyte battery, comprising at least a positive electrode, a negative electrode, and a non-aqueous electrolyte as described in any one of [1] to

[16] .

[18]

[0054] According to the non-aqueous electrolyte battery of

[17] , the negative electrode comprises at least one of an alkali metal, an alkali metal alloy, and a material for embedding the alkali metal.

[19]

[0056] A method for manufacturing a non-aqueous electrolyte battery, comprising a step of injecting a non-aqueous electrolyte as described in any one of [1] to

[16] .

[0057] The effects of the invention

[0058] According to this disclosure, a non-aqueous electrolyte exhibiting excellent high-temperature storage properties when used in a non-aqueous electrolyte battery, and a method for manufacturing the aforementioned non-aqueous electrolyte battery, can be provided. Furthermore, according to this disclosure, a non-aqueous electrolyte battery with excellent high-temperature storage properties can be provided. Detailed Implementation

[0059] In this specification, "~" is used to indicate the lower and upper limits of the values ​​listed before and after it.

[0060] The present disclosure will now be described in detail, but the description of the constituent elements described below is only an example of an embodiment of the present disclosure and is not limited to these specific contents.

[0061] 1. Regarding non-aqueous electrolytes

[0062] The non-aqueous electrolyte of this disclosure contains: (I) a solute, (II) a non-aqueous organic solvent, and (III) at least one compound selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (2).

[0063]

[0064] [A in general formula (1)] 1 Indicates -N(H)- or -N - (M1 + )-. M1 + Represents a metal cation or an onium cation. R 1 The following groups represent halogen atoms, alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkenyloxy groups with 2 to 10 carbon atoms, alkynyloxy groups with 2 to 10 carbon atoms, aryloxy groups with 6 to 15 carbon atoms, OH groups, and O groups. - Mx + Or N(Rx)2. Mx + Representing a metal cation or an onium cation. Each Rx independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or a fluorosulfonyl group. Multiple Rx groups may be identical or different. Multiple Rx groups may optionally be bonded to each other.

[0065]

[0066] [A in general formula (2)] 2 Indicates -N(H)- or -N - (M2 + M2 + Represents a metal cation or an onium cation. R 2 and R 3 Each of these groups independently represents a halogen atom, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkenyloxy group with 2 to 10 carbon atoms, an alkynyloxy group with 2 to 10 carbon atoms, an aryloxy group with 6 to 15 carbon atoms, an OH group, or an O group. - My + Or N(Ry)2. My + Represents a metal cation or an onium cation. Each Ry group independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkynyl group with 2 to 10 carbon atoms, or a fluorosulfonyl group. Multiple Ry groups may be identical or different. Multiple Ry groups may optionally be bonded to each other.

[0067] <Regarding (I) Solute>

[0068] The (I) solute (also referred to as "(I)") contained in the non-aqueous electrolyte of this disclosure will be described.

[0069] (I) The solute can be any of the solutes that have been used in the field of such non-aqueous electrolytes in the past without particular limitation. As such a solute, an ionic salt consisting of any pair of cations and anions is preferred. There are no particular limitations as long as the solute exists in the non-aqueous organic solvent in the ionic state as a cation and anion, and various solutes can be used.

[0070] Such a solute is preferably, for example, an ionic salt formed by pairing with at least one cation selected from the group consisting of alkali metal ions represented by lithium ions or sodium ions, alkaline earth metal ions, and quaternary ammonium ions; 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 ions, and iodide ions.

[0071] Specifically, it is preferable to select at least one from the group consisting of LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiN(SO2F)2, LiAlO2, LiAlCl4, LiCl and LiI, or select at least one from the group consisting of NaPF6, NaBF4, NaSbF6, NaAsF6, NaClO4, NaN(SO2F)2, NaAlO2, NaAlCl4, NaCl and NaI.

[0072] Among them, considering the energy density, output characteristics, and lifespan of the non-aqueous electrolyte battery, the cation is preferably selected from at least one of the group consisting of lithium ion, sodium ion, potassium ion, magnesium ion and quaternary ammonium cation, and the anion is preferably selected from at least one of the group consisting of hexafluorophosphate anion, tetrafluoroborate anion and bis(fluorosulfonyl)imide anion.

[0073] In the non-aqueous electrolyte of this disclosure, as (I), a single compound can be used alone, or two or more compounds can be mixed in any combination or ratio depending on the application.

[0074] The concentration of (I) is not particularly limited relative to the total amount of non-aqueous electrolyte. For example, the lower limit of the concentration of (I) can be 0.5 mol / L or more, 0.7 mol / L or more, or 0.9 mol / L or more. Furthermore, the upper limit of the concentration of (I) can be 5 mol / L or less, 4 mol / L or less, or 2 mol / L or less. If it is 0.5 mol / L or more, the ionic conductivity is difficult to decrease, and the cycle characteristics and output characteristics of the non-aqueous electrolyte battery are difficult to decrease, therefore it is preferred. On the other hand, if it is 5 mol / L or less, the viscosity of the non-aqueous electrolyte is difficult to increase, and the ionic conductivity is difficult to decrease, therefore it is preferred. It should be noted that when two or more types of (I) are used, the total concentration of these solutes is preferably within the above-mentioned range.

[0075] There is no particular limitation on the liquid temperature when (I) is dissolved in (II) non-aqueous organic solvent; it can be -20 to 80°C or 0 to 60°C.

[0076] Furthermore, the cation of the solute is more preferably lithium ion when used in lithium-ion batteries, and more preferably sodium ion when used in sodium-ion batteries.

[0077] <Regarding (II) Non-aqueous organic solvents>

[0078] The non-aqueous organic solvent (also referred to as "(II)") contained in the non-aqueous electrolyte of this 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. Preferably, such a non-aqueous organic solvent comprises 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; more preferably, it comprises at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds, and ionic liquids. It should be noted that cyclic carbonate is a subcategory of cyclic ester, and chain carbonate is a subcategory of chain ester.

[0079] As specific examples of (II) non-aqueous organic solvents, the following non-aqueous organic solvents can be cited.

[0080] In addition to cyclic carbonates such as propylene carbonate (hereinafter sometimes referred to as "PC"), ethylene carbonate (hereinafter sometimes referred to as "EC"), and butyl carbonate, γ-butyrolactone and γ-valerolactone can also be listed as cyclic esters.

[0081] In addition to diethyl carbonate (hereinafter sometimes referred to as "DEC"), dimethyl carbonate (hereinafter sometimes referred to as "DMC"), methyl ethyl carbonate (hereinafter sometimes referred to as "EMC"), methyl propyl carbonate, ethyl propyl carbonate, methyl butyl carbonate, methyl ethyl 2,2,2-trifluorocarbonate, ethyl ethyl 2,2,2-trifluorocarbonate, ethyl propyl 2,2,2-trifluorocarbonate, methyl 1,1,1,3,3,3-hexafluoro-1-carbonate, ethyl 1,1,1,3,3,3-hexafluoro-1-carbonate, and propyl propyl 1,1,1,3,3,3-hexafluoro-1-carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate (hereinafter sometimes referred to as "EP"), methyl 2-fluoropropionate, and ethyl 2-fluoropropionate are also listed as chain esters.

[0082] Examples of cyclic ethers include tetrahydrofuran, 2-methyltetrahydrofuran, furan, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, 1,3-dioxolane, and trioxane.

[0083] 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.

[0084] In addition, examples include sulfone compounds such as dimethyl sulfoxide and sulfolane, sulfoxide compounds, N,N-dimethylformamide, acetonitrile, and propionitrile. Ionic liquids can also be cited.

[0085] (II) The non-aqueous organic solvent may include at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, chain ethers, sulfones, sulfoxides and ionic liquids.

[0086] Cyclic esters may include cyclic carbonates, which may include at least one selected from the group consisting of ethylene carbonate and propylene carbonate.

[0087] The chain ester may include the chain carbonate, which may include at least one selected from the group consisting of methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate and methyl propyl carbonate.

[0088] The cyclic ether may contain 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.

[0089] 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.

[0090] In the non-aqueous electrolyte of this disclosure, as (II), a single compound may be used alone, or two or more compounds may be used in any combination or ratio depending on the application. Among them, from the viewpoint of its electrochemical stability against redox reactions and its chemical stability related to heat and the reactions of the aforementioned solutes, it is particularly preferred to include at least one compound selected from the group consisting of PC, EC, DEC, DMC and EMC.

[0091] Furthermore, as a non-aqueous organic solvent, for example, if it contains one or more cyclic carbonates with high dielectric constants and one or more chain carbonates or chain esters with low liquid viscosity, the ionic conductivity of the electrolyte is improved, and therefore preferred. Specifically, a combination of the following is more preferred.

[0092] (1) Combining EC and EMC,

[0093] (2) Combination of EC and DEC

[0094] (3) Combination of EC, DMC and EMC

[0095] (4) Combinations of EC, DEC, and EMC

[0096] (5) Combinations of EC, EMC, and EP

[0097] (6) Combination of PC and DEC

[0098] (7) Combination of PC and EMC

[0099] (8) Combination of PC and EP

[0100] (9) Combination of PC, DMC, and EMC

[0101] (10) Combination of PC, DEC, and EMC

[0102] (11) Combinations of PC, DEC, and EP

[0103] (12) Combination of PC, EC and EMC

[0104] (13) Combinations of PC with EC with DMC with EMC

[0105] (14) Combinations of PC with EC with DEC with EMC

[0106] (15) Combination of PC with EC with EMC with EP

[0107] 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. Relative to the total amount (100% by mass) of the non-aqueous electrolyte, it can be set to, for example, 40-99% by mass, preferably 50-95% by mass, and particularly preferably 70-93% by mass.

[0108] The content of cyclic carbonate is not particularly limited and can be arbitrary as long as it does not significantly impair the effects of this disclosure. When using a single type, the content can be set to 3% by volume or more, more preferably 5% by volume or more, in 100% by volume of the non-aqueous organic solvent. By setting it within this range, the decrease in conductivity caused by the decrease in the dielectric constant of the non-aqueous electrolyte can be avoided, and the high-current discharge characteristics, stability to the negative electrode, and cycle characteristics of the non-aqueous electrolyte battery can be easily achieved within a favorable range. In addition, it can be 90% by volume or less, preferably 85% by volume or less, more preferably 80% by volume or less. By setting it within this range, the viscosity of the non-aqueous electrolyte is within an appropriate range, the decrease in ionic conductivity is suppressed, and the load characteristics of the non-aqueous electrolyte battery can be easily achieved within a favorable range.

[0109] Alternatively, cyclic carbonates can be used in any combination of two or more. 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, particularly preferably 95:5 to 50:50. Furthermore, the amount of propylene carbonate in the total non-aqueous organic solvent is not particularly limited, and can be set at any amount as long as it does not significantly impair the effects of this disclosure. It can be 1% by volume or more, preferably 2% by volume or more, more preferably 3% by volume or more, and can be 30% by volume or less, preferably 25% by volume or less, more preferably 20% by volume or less. If propylene carbonate is contained within this range, for example, when ethylene carbonate is combined with dialkyl carbonates, the low-temperature properties are superior while maintaining the characteristics of the combination of ethylene carbonate and dialkyl carbonates, which is therefore preferred.

[0110] Chain esters can be used alone or in any combination and ratio of two or more.

[0111] The content of the chain ester is not particularly limited. In 100% by volume of a non-aqueous organic solvent, it can be set to 15% by volume or more, preferably 20% by volume or more, more preferably 25% by volume or more. Alternatively, it can be set to 90% by volume or less, preferably 85% by volume or less, more preferably 80% by volume or less. By setting the content of the chain ester within the above range, the viscosity of the non-aqueous electrolyte is within an appropriate range, suppressing the decrease in ionic conductivity, and thus easily achieving favorable input / output characteristics and charge / discharge rate characteristics of the non-aqueous electrolyte battery. Furthermore, it avoids the decrease in conductivity caused by the decrease in the dielectric constant of the non-aqueous electrolyte, making it easier to achieve favorable input / output characteristics and charge / discharge rate characteristics of the non-aqueous electrolyte battery.

[0112] Furthermore, by combining specific chain esters with ethylene carbonate in specific amounts, battery performance can be significantly improved.

[0113] For example, when choosing dimethyl carbonate, ethyl methyl carbonate, or a mixture of dimethyl carbonate and ethyl methyl carbonate as specific chain esters, the content of ethylene carbonate is not particularly limited, and can be arbitrary as long as it does not significantly impair the effects of this disclosure. It can be 5% by volume or more, preferably 10% by volume or more, and also 45% by volume or less, preferably 40% by volume or less. The content of dimethyl carbonate can be 20% by volume or more, preferably 30% by volume or more, and also 50% by volume or less, preferably 45% by volume or less. The content of ethyl methyl carbonate can be 20% by volume or more, preferably 30% by volume or more, and also 50% by volume or less, preferably 45% by volume or less. By setting the content within the above ranges, it is possible to lower the low-temperature precipitation temperature of the electrolyte while simultaneously reducing the viscosity of the non-aqueous electrolyte, thereby increasing ionic conductivity and easily obtaining high input-output even at low temperatures.

[0114] The content of the chain ether is not particularly limited, and can be arbitrary as long as it does not significantly impair the effects of this disclosure. In 100% by volume of a non-aqueous organic solvent, it can be 1% by volume or more, preferably 2% by volume or more, preferably 3% by volume or more, and can be 30% by volume or less, preferably 25% by volume or less, and more preferably 20% by volume or less. If the content of the chain ether is within the above range, for example in the case of a lithium-ion battery where the cation is the lithium host, it is easy to ensure the improved lithium-ion dissociation degree of the chain ether and the improved ionic conductivity caused by the 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, thus making it easy to set the input / output characteristics and charge / discharge rate characteristics to an appropriate range.

[0115] The content of the sulfone compound is not particularly limited, and can be arbitrary as long as it does not significantly impair the effects of this disclosure. In 100% by volume of a non-aqueous organic solvent, it can be 0.3% by volume or more, 0.5% by volume or more, more preferably 1% by volume or more, and can be 40% by volume or less, preferably 35% by volume or less, more preferably 30% by volume or less. When the content of the sulfone compound is within the above range, it is easy to obtain improved durability effects such as cycling characteristics and storage characteristics. Furthermore, setting the viscosity of the non-aqueous electrolyte within an appropriate range can prevent a decrease in conductivity, making it easier to achieve appropriate input / output characteristics and charge / discharge rate characteristics of the non-aqueous electrolyte battery.

[0116] <About (III)>

[0117] The non-aqueous electrolyte of this disclosure contains at least one compound selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (2) (also referred to as "(III)").

[0118]

[0119] [A in general formula (1)] 1 Indicates -N(H)- or -N - (M1 + )-. M1 + Represents a metal cation or an onium cation. R 1 The following groups represent halogen atoms, alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkenyloxy groups with 2 to 10 carbon atoms, alkynyloxy groups with 2 to 10 carbon atoms, aryloxy groups with 6 to 15 carbon atoms, OH groups, and O groups. - Mx + Or N(Rx)2. Mx + Representing a metal cation or an onium cation. Each Rx independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or a fluorosulfonyl group. Multiple Rx groups may be identical or different. Multiple Rx groups may optionally be bonded to each other.

[0120]

[0121] [A in general formula (2)] 2 Indicates -N(H)- or -N - (M2 + M2 + Represents a metal cation or an onium cation. R 2 and R 3Each of these groups independently represents a halogen atom, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkenyloxy group with 2 to 10 carbon atoms, an alkynyloxy group with 2 to 10 carbon atoms, an aryloxy group with 6 to 15 carbon atoms, an OH group, or an O group. - My + Or N(Ry)2. My + Represents a metal cation or an onium cation. Each Ry group independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkynyl group with 2 to 10 carbon atoms, or a fluorosulfonyl group. Multiple Ry groups may be identical or different. Multiple Ry groups may optionally be bonded to each other.

[0122] The compounds represented by general formula (1) will be described.

[0123] In general formula (1) A 1 Indicates -N(H)- or -N - (M1 + )-.

[0124] M1 + This refers to either a metal cation or an onium cation. Examples of metal cations include alkali metal ions and alkaline earth metal ions; specifically, examples include lithium ions, sodium ions, potassium ions, and magnesium ions. Examples of onium cations include quaternary ammonium cations.

[0125] In general formula (1) A 1 Indicates -N(H)- or -N - (M1 + )-, and M1 + Lithium ions or sodium ions are preferred.

[0126] R in general formula (1) 1 The following groups represent halogen atoms, alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkenyloxy groups with 2 to 10 carbon atoms, alkynyloxy groups with 2 to 10 carbon atoms, aryloxy groups with 6 to 15 carbon atoms, OH groups, and O groups. - Mx + Or N(Rx)2.

[0127] R 1 The alkyl group having 1 to 10 carbon atoms can be straight-chain or branched, and preferably has 1 to 5 carbon atoms. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, and n-decyl. The alkyl group having 1 to 10 carbon atoms preferably does not have substituents (i.e., preferably unsubstituted alkyl groups having 1 to 10 carbon atoms).

[0128] R 1The alkoxy group having 1 to 10 carbon atoms can be straight-chain or branched, preferably having 1 to 5 carbon atoms. Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, n-hexoxy, n-octoxy, and n-decoxy. The alkoxy group having 1 to 10 carbon atoms may have substituents.

[0129] As R 1 The alkenyl group representing 2 to 10 carbon atoms can be either straight-chain or branched, but is preferably an alkenyl group with 2 to 5 carbon atoms. Furthermore, the alkenyl group may have two or more unsaturated bonds. Examples of such alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methylpropenyl, 1-pentenyl, and 1,3-butadienyl. The alkenyl group with 2 to 10 carbon atoms may have substituents.

[0130] As R 1 The olefinic group representing 2 to 10 carbon atoms can be either straight-chain or branched, but is preferably olefinic groups with 2 to 5 carbon atoms. Furthermore, the olefinic group may have two or more unsaturated bonds. Examples of such olefinic groups include vinyloxy, 1-propenoxy, 2-propenoxy, 1-methylvinyloxy, 1-butenoxy, 2-butenoxy, 3-butenoxy, 1-methylpropenoxy, 1-pentenoxy, and 1,3-butadieneoxy. The olefinic group with 2 to 10 carbon atoms may have substituents.

[0131] As R 1 The alkynoxy group representing 2 to 10 carbon atoms can be either straight-chain or branched, but is preferably alkynoxy group representing 2 to 5 carbon atoms. Furthermore, the alkynoxy group can have two or more unsaturated bonds. Examples of such alkynoxy groups include acetylenoxy, 1-propynoxy, 2-propynoxy, 1-methylacetylenoxy, 1-butynoxy, 2-butynoxy, 3-butynoxy, 1-methylpropynoxy, and 1-pentynoxy. The alkynoxy group representing 2 to 10 carbon atoms can have substituents.

[0132] As R 1 The aryloxy group representing 6 to 15 carbon atoms is preferably phenoxy or naphthoxy. Additionally, aryloxy groups may include those with a linking group such as a methylene group, such as benzyloxy. The aryloxy group with 6 to 15 carbon atoms may have substituents.

[0133] R 1 Preferably, the atom is fluorine, methyl, ethyl, vinyl, methoxy, or O. - Mx + Or N(Rx)2.

[0134] Mx +This refers to either a metal cation or an onium cation. Examples of metal cations include alkali metal ions and alkaline earth metal ions; specifically, examples include lithium ions, sodium ions, potassium ions, and magnesium ions. Examples of onium cations include quaternary ammonium cations.

[0135] Rx can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkynyl group with 2 to 10 carbon atoms, or a fluorosulfonyl group.

[0136] The alkyl group represented by Rx, having 1 to 10 carbon atoms, can be straight-chain or branched, and preferably has 1 to 5 carbon atoms. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, and n-decyl. The alkyl group having 1 to 10 carbon atoms may have substituents.

[0137] Examples of alkenyl groups with 2 to 10 carbon atoms, represented by Rx, include straight-chain or branched alkenyl groups, with alkenyl groups having 2 to 5 carbon atoms being preferred. Furthermore, the alkenyl group may have two or more unsaturated bonds. Examples of such alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methylpropenyl, 1-pentenyl, and 1,3-butadienyl. Alkenyl groups with 2 to 10 carbon atoms may have substituents.

[0138] The alkynyl group represented by Rx, having 2 to 10 carbon atoms, can be either straight-chain or branched, but is preferably alkynyl groups with 2 to 5 carbon atoms. Furthermore, the alkynyl group may have two or more unsaturated bonds. Examples of such alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, 1-methylethynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpropynyl, and 1-pentynyl. The alkynyl group with 2 to 10 carbon atoms may have substituents.

[0139] Multiple Rx atoms can be the same or different. Multiple Rx atoms can bond together. When multiple Rx atoms are bonded together, 3- to 10-membered rings containing nitrogen atoms, or 5- to 8-membered rings, can be formed. These rings can have substituents.

[0140] The following are specific examples of compounds represented by general formula (1), but are not limited to these. It should be noted that the "-NM1-" in each compound is different from the "-N" in the general formula (1) above. - (M1 + )-” is synonymous.

[0141]

[0142] The compounds represented by general formula (2) will be described.

[0143] A in general formula (2) 2Indicates -N(H)- or -N - (M2 + )-.

[0144] M2 + This refers to either a metal cation or an onium cation. Examples of metal cations include alkali metal ions and alkaline earth metal ions; specifically, examples include lithium ions, sodium ions, potassium ions, and magnesium ions. Examples of onium cations include quaternary ammonium cations.

[0145] A in general formula (2) 2 Indicates -N(H)- or -N - (M2 + )-, and M2 + Lithium ions or sodium ions are preferred.

[0146] R in general formula (2) 2 and R 3 Each of these groups independently represents a halogen atom, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkenyloxy group with 2 to 10 carbon atoms, an alkynyloxy group with 2 to 10 carbon atoms, an aryloxy group with 6 to 15 carbon atoms, an OH group, or an O group. - My + Or N(Ry)2. R 2 and R 3 They can be the same or different.

[0147] R 2 and R 3 The alkyl group having 1 to 10 carbon atoms can be straight-chain or branched, preferably having 1 to 5 carbon atoms. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, and n-decyl. The alkyl group having 1 to 10 carbon atoms may have substituents.

[0148] R 2 and R 3 The alkoxy group having 1 to 10 carbon atoms can be straight-chain or branched, preferably having 1 to 5 carbon atoms. Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, n-hexoxy, n-octoxy, and n-decoxy. The alkoxy group having 1 to 10 carbon atoms may have substituents.

[0149] As R 2 and R 3The alkenyl group representing 2 to 10 carbon atoms can be either straight-chain or branched, but is preferably an alkenyl group with 2 to 5 carbon atoms. Furthermore, the alkenyl group may have two or more unsaturated bonds. Examples of such alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methylpropenyl, 1-pentenyl, and 1,3-butadienyl. The alkenyl group with 2 to 10 carbon atoms may have substituents.

[0150] As R 2 and R 3 The olefinic group representing 2 to 10 carbon atoms can be either straight-chain or branched, but is preferably olefinic groups with 2 to 5 carbon atoms. Furthermore, the olefinic group may have two or more unsaturated bonds. Examples of such olefinic groups include vinyloxy, 1-propenoxy, 2-propenoxy, 1-methylvinyloxy, 1-butenoxy, 2-butenoxy, 3-butenoxy, 1-methylpropenoxy, 1-pentenoxy, and 1,3-butadieneoxy. The olefinic group with 2 to 10 carbon atoms may have substituents.

[0151] As R 2 and R 3 The alkynoxy group representing 2 to 10 carbon atoms can be either straight-chain or branched, but is preferably alkynoxy group representing 2 to 5 carbon atoms. Furthermore, the alkynoxy group can have two or more unsaturated bonds. Examples of such alkynoxy groups include acetylenoxy, 1-propynoxy, 2-propynoxy, 1-methylacetylenoxy, 1-butynoxy, 2-butynoxy, 3-butynoxy, 1-methylpropynoxy, and 1-pentynoxy. The alkynoxy group representing 2 to 10 carbon atoms can have substituents.

[0152] As R 2 and R 3 The aryloxy group representing 6 to 15 carbon atoms is preferably phenoxy or naphthoxy. Additionally, aryloxy groups may include those with a linking group such as a methylene group, such as benzyloxy. The aryloxy group with 6 to 15 carbon atoms may have substituents.

[0153] R 2 and R 3 At least one of them is preferably a fluorine atom, methyl, ethyl, vinyl, methoxy, or O atom. - My + Or N(Ry)2.

[0154] My + This refers to either a metal cation or an onium cation. Examples of metal cations include alkali metal ions and alkaline earth metal ions; specifically, examples include lithium ions, sodium ions, potassium ions, and magnesium ions. Examples of onium cations include quaternary ammonium cations.

[0155] Ry can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkynyl group with 2 to 10 carbon atoms, or a fluorosulfonyl group.

[0156] The alkyl group represented by Ry, having 1 to 10 carbon atoms, can be straight-chain or branched, and preferably has 1 to 5 carbon atoms. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, and n-decyl. The alkyl group having 1 to 10 carbon atoms may have substituents.

[0157] Examples of alkenyl groups with 2 to 10 carbon atoms, represented by Ry, include straight-chain or branched alkenyl groups, with alkenyl groups having 2 to 5 carbon atoms being preferred. Furthermore, the alkenyl group may have two or more unsaturated bonds. Examples of such alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methylpropenyl, 1-pentenyl, and 1,3-butadienyl. Alkenyl groups with 2 to 10 carbon atoms may have substituents.

[0158] Ry, representing an alkynyl group with 2 to 10 carbon atoms, can be either straight-chain or branched, but is preferably an alkynyl group with 2 to 5 carbon atoms. Furthermore, the alkynyl group may have two or more unsaturated bonds. Examples of such alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, 1-methylethynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpropynyl, and 1-pentynyl. The alkynyl group with 2 to 10 carbon atoms may have substituents.

[0159] Multiple Ry atoms can be the same or different. Multiple Ry atoms can bond together. When multiple Ry atoms are bonded together, they can form 3- to 10-membered rings containing nitrogen atoms, or 5- to 8-membered rings. These rings can have substituents.

[0160] The following are specific examples of compounds represented by general formula (2), but are not limited to these. It should be noted that the "-NM2-" in each compound is different from the "-N" in the general formula (2) above. - (M2 + )-” is synonymous.

[0161]

[0162] The content of (III) in the non-aqueous electrolyte of this disclosure relative to the total amount of the non-aqueous electrolyte can be more than 0.01% by mass and less than 10% by mass, more than 0.07% by mass and less than 5.5% by mass, or more than 0.08% by mass and less than 5% by mass.

[0163] <Regarding other optional ingredients>

[0164] The non-aqueous electrolyte of this disclosure is composed of the above-described components as its basic constituents. However, without prejudice to the spirit of this disclosure, the non-aqueous electrolyte of this disclosure may contain the components described below in any combination / ratio (hereinafter also referred to as "other optional components" or "other components"). As other components, for example, other commonly used additives may be added in any ratio in this art.

[0165] 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 (sometimes referred to as "VC"); oligomers of vinylene carbonate (with a number average molecular weight of 170-5000 converted from polystyrene); vinyl ethylene carbonate; divinyl ethylene carbonate; fluoroethylene carbonate (sometimes referred to as "FEC"); ethynyl ethylene carbonate; and trans-difluoroethylene carbonate. methylpropynyl carbonate, ethylpropynyl carbonate, dipropynyl carbonate, dimethyl vinylene carbonate, dimethyl dicarbonate, bis(1,1,1,3,3,3-hexafluoro-1-propyl) carbonate, bis(2,2,2-trifluoroethyl) carbonate and other carbonate compounds; isocyanate compounds such as 1,6-diisocyanate hexane; maleic anhydride, succinic anhydride, 1,4-dioxane-2,6-dione, glutaric anhydride, methanedisulfonic anhydride and other organic acid anhydrides; 1,3-propanesulfonyl lactone, 1,3-propenesulfonyl lactone, 1,4 Butane sulfanolactone, 2,4-butane sulfanolactone, 1,3,2-dioxothiacyclopentane-2,2-dioxide, 4-propyl-1,3,2-dioxothiacyclopentane-2,2-dioxide, methylene methane disulfonate, dimethylene methane disulfonate, trimethylene methane disulfonate, methyl methanesulfonate, methanesulfonyl fluoride, ethylene sulfonyl fluoride, 1,2-ethane disulfonic anhydride, methanesulfonic anhydride, N,N'-carbonylbis(N-methylaminosulfonyl fluoride) and other sulfonate compounds, difluoro(pyridinecarboxylic acid) borate and other borate compounds, di... Phosphate compounds such as phenyl fluorophosphate, triargyl phosphate, tetrafluoro(pyridinecarboxylic acid) phosphate, phosphazene compounds such as (ethoxy)pentafluorocyclotriphosphazene, nitrile compounds such as succinic anhydride, methyl difluorovinylsilane, methyl fluorodivinylsilane, dimethyl divinylsilane, trivinylmethylsilane, trivinylfluorosilane, tetravinylsilane, tris(trimethylsilyl)borate, tris(trimethylsilyl)phosphate, and silane compounds such as 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,Siloxane compounds such as 3-hexafluoroisopropyl)disiloxane, fluorosulfonates, trifluoromethanesulfonates, pentafluoroethanesulfonates, nonafluorobutanesulfonates (preferably fluorosulfonates and trifluoromethanesulfonates), monoalkyl sulfates such as monomethyl sulfates and monoethyl sulfates, 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 (preferably fluorosulfonates and trifluoromethanesulfonyl)imide salts, etc. Preferably, it contains imide salts such as bis(trifluoromethanesulfonyl)imide, (trifluoromethanesulfonyl)(fluorosulfonyl)imide, (difluorophosphoryl)(fluorosulfonyl)imide, (difluorophosphoryl)(trifluoromethanesulfonyl)imide, and bis(difluorophosphoryl)imide; monofluorophosphates, difluorophosphates, tetrafluoro(malonic acid) phosphates, tri(oxalic acid) phosphates, difluorobis(oxalic acid) phosphates, tetrafluorooxalate phosphates, bis(oxalate) borates, difluorooxalate borates, difluoro(malonic acid) borates, tri(trifluoromethanesulfonyl) methylates, tri(fluorosulfonyl) methylates, acrylates, methacrylates, and other carboxylates; nitrates, nitrites, and other inorganic salts; and fluorinated alcohols such as hexafluoroisopropanol and trifluoroethanol.

[0166] In addition, to improve the cycle capacity retention rate and gas generation during cycle testing, the non-aqueous electrolyte of this disclosure may also contain the following compounds.

[0167]

[0168] By including the other components mentioned above in the non-aqueous electrolyte of this disclosure, at least one of the following can be improved: overcharge prevention effect, negative electrode coating formation effect, and positive electrode protection effect.

[0169] Alternatively, as in the case of non-aqueous electrolyte batteries known as lithium polymer batteries, the non-aqueous electrolyte battery can be used by quasi-solidifying the electrolyte with a gelling agent and a crosslinking polymer. Examples of such polymers include polymers with polyethylene oxide in the main chain or side chain, homopolymers or copolymers of polyvinylidene fluoride, methacrylate polymers, and polyacrylonitrile.

[0170] In cases where the non-aqueous electrolyte of this disclosure contains other components, the content of the other components relative to the total amount of the non-aqueous electrolyte may be more than 0.01% by mass and less than 10% by mass.

[0171] It should be noted that, among the other components mentioned above, the content of fluoroethylene carbonate relative to the total amount of the non-aqueous electrolyte can be more than 0.01% by mass and less than 55% by mass.

[0172] In addition, the content of bis(trifluoromethanesulfonyl)imide salt, trifluoromethanesulfonate, and nonafluorobutanesulfonate relative to the total amount of nonaqueous electrolyte can be more than 0.01% by mass and less than 20% by mass.

[0173] In addition, 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 non-aqueous electrolyte can be more than 0.1% by mass and less than 70% by mass.

[0174] Furthermore, when the other components mentioned above are ionic salts, the cation is more preferably lithium ion when used in lithium-ion batteries, and more preferably sodium ion when used in sodium-ion batteries.

[0175] The non-aqueous electrolyte of this disclosure can use various salt compounds of the aforementioned solutes (lithium salts, sodium salts, etc.) and other components, depending on the required characteristics, thereby increasing the total number of alkali metal salts to four or more. Alternatively, the total number of the aforementioned alkali metal salts can be five or more.

[0176] The non-aqueous electrolyte disclosed herein is suitable for use in non-aqueous electrolyte batteries (preferably non-aqueous electrolyte secondary batteries).

[0177] 2. Regarding non-aqueous electrolyte batteries

[0178] The non-aqueous electrolyte battery of this disclosure includes at least the non-aqueous electrolyte, negative electrode, and positive electrode described above. Furthermore, it may also include a separator, an outer casing, etc. Alternatively, a solid electrolyte may be used as the medium for impregnating the non-aqueous electrolyte, instead of a separator.

[0179] The non-aqueous electrolyte battery of this disclosure preferably includes at least a positive electrode, a negative electrode, a separator, and the non-aqueous electrolyte of this disclosure.

[0180] The non-aqueous electrolyte battery disclosed herein is preferably a non-aqueous electrolyte secondary battery.

[0181] [negative electrode]

[0182] As a negative electrode, there are no particular limitations; the negative electrode may contain at least one of alkali metals, alkali metal alloys, and materials in which alkali metals are embedded.

[0183] As a negative electrode, materials in which alkali metal ions, such as lithium ions and sodium ions, or alkaline earth metal ions can be reversibly inserted and extracted can be used.

[0184] [Negative Electrode Active Material]

[0185] For example, in the case of lithium-ion batteries where the cation is the main lithium component, the negative electrode active material constituting the negative electrode can be doped / dedoped with lithium ions. Examples include carbon materials such as artificial graphite and natural graphite with a d-value of less than 0.340 nm in the (002) plane of X-ray diffraction; carbon materials such as hard carbon with a d-value of more than 0.340 nm in the (002) plane of X-ray diffraction; lithium metal; alloys of lithium metal with other metals (e.g., alloys of lithium metal with one or more metals selected from Si, Sn, and Al, alloys of lithium metal containing one or more metals selected from Si, Sn, and Al, etc.); intermetallic compounds of lithium metal with other metals; metal oxides (e.g., oxides of one or more metals selected from Si, Sn, and Al, lithium titanium oxide, etc.); metal nitrides; elemental tin; tin compounds; activated carbon; and at least one of conductive polymers.

[0186] Furthermore, as the negative electrode active material, materials containing Si and / or Si metal oxides and carbon materials are preferably included. The Si mentioned above refers to silicon metal. Additionally, the Si metal oxide can also be a compound represented as SiOx (x is a value of 0.5 to 1.5). In this case, when the total amount of Si and / or Si metal oxides and carbon materials contained in the negative electrode active material is set to 100% by mass, the total content of the Si and / or Si metal oxides contained in the negative electrode active material can be 0.1 to 50% by mass, preferably 0.1 to 30% by mass. As the aforementioned carbon material, graphite is preferred, and various types of artificial graphite, natural graphite, and hard carbon (difficult-to-graphitize carbon) can be used. Graphite exhibits very little change in its crystal structure with lithium insertion and extraction, thus achieving high energy density and excellent cycle characteristics. The shape of the graphite can be any of fibrous, spherical, granular, or flake-like. Furthermore, amorphous carbon and graphite materials with amorphous carbon coating are more preferred because their surface reactivity with the electrolyte is lower.

[0187] These negative electrode active materials can be used alone or in combination of two or more.

[0188] For example, in sodium-ion batteries where sodium is the primary cation, the negative electrode active material can be sodium metal, alloys of sodium metal with other metals such as tin, intermetallic compounds of sodium metal with other metals, various carbon materials, primarily hard carbon, metal oxides such as titanium oxide, metal nitrides, elemental tin, tin compounds, activated carbon, conductive polymers, etc. In addition, 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., can also be used. One of these negative electrode active materials can be used alone, or two or more can be used in combination.

[0189] [Negative current collector]

[0190] The negative electrode has a negative current collector. For example, copper, stainless steel, nickel, titanium, or alloys thereof can be used as the negative current collector. Additionally, aluminum or its alloys can also be used in sodium-ion batteries.

[0191] [Negative electrode active material layer]

[0192] For example, a negative electrode active material layer is formed on at least one side of the negative electrode current collector. The negative electrode active material layer is composed, for example, the aforementioned negative electrode active material, a binder, and a conductive agent as needed.

[0193] Examples of adhesives 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.

[0194] As a conductive agent, carbon materials such as acetylene black, Ketjen black, furnace black, carbon fiber, graphite, and fluorinated graphite can be used.

[0195] [positive electrode]

[0196] As a positive electrode, there are no particular limitations; materials in which alkali metal ions, such as lithium ions and sodium ions, or alkaline earth metal ions can be reversibly inserted and extracted can be used.

[0197] [Positive electrode active material]

[0198] For example, when the cation is lithium, as a positive electrode material (positive electrode active material), lithium-containing transition metal composite oxides such as LiCoO2, LiNiO2, LiMnO2, and LiMn2O4, substances composed of various transition metals such as Co, Mn, and Ni in these lithium-containing transition metal composite oxides, and substances formed by replacing a portion of the transition metals in these lithium-containing transition metal composite oxides with metals other than other transition metals can be used. Specifically, Li[Ni1 / 3 Mn 1 / 3 Co 1 / 3 ]O2, Li[Ni 0.45 Mn 0.35 Co 0.2 ]O2, Li[Ni 0.5 Mn 0.3 Co 0.2 ]O2, Li[Ni 0.6 Mn 0.2 Co 0.2 ]O2, Li[Ni 0.8 Mn 0.1 Co 0.1 ]O2 (hereinafter referred to as “NCM811”), Li[Ni 0.49 Mn 0.3 Co 0.2 Zr 0.01 ]O2, Li[Ni 0.49 Mn 0.3 Co 0.2 Mg 0.01 ]O2, LiNi 0.8 Co 0.2 O2, LiLiLi 0.85 Co 0.10 Al 0.05 O2, LiLiLi 0.87 Co 0.10 Al 0.03 O2, LiLiLi 0.90 Co 0.07 Al 0.03 O2, LiLiLi 0.6 Co 0.3 Al 0.1 O 2、 LiRing 0.5 Mn 1.5 O 4、 LiRing 0.5 Mn 0.5 O 2、 LiRing 0.1 Mn 1.9 O 4、 Lisco 0.5 Mn 0.5 O2, 0.5[LiNi 0.5 Mn 0.5 O2]·0.5[Li2MnO3], 0.5[LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2]·0.5[Li2MnO3], 0.5[LiNi 0.375 Co 0.25 Mn 0.375O2]·0.5[Li2MnO3]、0.5[LiNi 0.375 Co 0.125 Fe 0.125 Mn 0.375 O2]·0.5[Li2MnO3]、0.45[LiNi 0.375 Co 0.25 Mn 0.375 O2]·0.10[Li2TiO3]·0.45[Li2MnO3] etc.

[0199] Alternatively, phosphoric acid compounds of transition metals such as LiFePO4, LiCoPO4, LiMnPO4, and LiNiPO4 (also known as olivine); oxides such as TiO2, V2O5, and MoO3; sulfides such as TiS2, FeS, and MoS2; or conductive polymers such as polyacetylene, poly(p-phenylene), polyaniline, and polypyrrole, activated carbon, free radical-generating polymers, and carbon materials can be used.

[0200] For example, when the cation is sodium, NaCrO2 or NaFe can be used as the positive electrode material (positive electrode active material). 0.5 Co 0.5 O2, NaFe 0.4 Mn 0.3 Ni 0.3 O2, NaNi 0.5 Ti 0.3 Mn 0.2 O2, NaNi 1 / 3 Ti 1 / 3 Mn 1 / 3 O2, NaNi 0.33 Ti 0.33 Mn 0.16 Mg 0.17 O2, Na 2 / 3 Ni 1 / 3 Ti 1 / 6 Mn 1 / 2 O2, Na 2 / 3 Ni 1 / 3 Mn 2 / 3 O2 and other sodium-containing transition metal composite oxides; substances formed by mixing multiple transition metals such as Co, Mn, and Ni in these sodium-containing transition metal composite oxides; substances formed by replacing a portion of the transition metals in these sodium-containing transition metal composite oxides with metals other than other transition metals; polyanionic compounds such as NaFePO4, NaVPO4F, Na3V2(PO4)3, and Na2Fe2(SO4)3; with the formula Na α M 001 β [Fe(CN)6] γThe sodium salt of the Prussian blue analogue (M) 001 =Cr, Mn, Fe, Co, Ni, Cu or Zn, 0≤α≤2, 0.5≤β≤1.5, 0.5≤γ≤1.5); oxides such as TiO2, V2O5, MoO3; sulfides such as TiS2, FeS, MoS2; or conductive polymers such as polyacetylene, poly(p-phenylene), polyaniline and polypyrrole; activated carbon; polymers that generate free radicals; carbon materials, etc.

[0201] [Positive current collector]

[0202] The positive electrode has a positive current collector. For example, aluminum, stainless steel, nickel, titanium, or alloys thereof can be used as the positive current collector.

[0203] [Positive electrode active material layer]

[0204] For example, a positive electrode active material layer is formed on at least one side of the positive electrode current collector. The positive electrode active material layer is composed, for example, the aforementioned positive electrode active material, a binder, and a conductive agent as needed.

[0205] As a binder, the binders described in [Negative Electrode Active Material Layer] can also be cited.

[0206] As conductive agents, carbon materials such as acetylene black, Ketjen black, furnace black, carbon fiber, graphite (granular graphite, flake graphite), and fluorinated graphite can be used. In the positive electrode, acetylene black and Ketjen black with low crystallinity are preferred.

[0207] [Manufacturing method of electrodes (positive and negative electrodes)]

[0208] Electrodes can be obtained, for example, by dispersing and mixing active materials, binders, and conductive agents as needed in a prescribed amount in a solvent such as N-methyl-2-pyrrolidone (NMP) and water, coating the resulting paste onto a current collector, and drying it to form an active material layer. The resulting electrode is preferably compressed to an appropriate density using methods such as rolling.

[0209] [Separator]

[0210] The non-aqueous electrolyte battery disclosed herein can include a separator. As a separator to prevent contact between the positive and negative electrodes, materials such as polyolefins (polypropylene, polyethylene, etc.), nonwoven fabrics (cellulose, paper, glass fiber, etc.), and porous sheets are used. These films are preferably microporous to allow electrolyte penetration while ion permeation is easy.

[0211] As a polyolefin separator, examples include microporous polymer films such as porous polyolefin films, which are electrically insulated from the positive and negative electrodes and allow lithium ions to permeate. Specific examples of porous polyolefin films include porous polyethylene films used alone, or porous polyethylene films and porous polypropylene films stacked together to form a multilayer film. Additionally, films formed by combining porous polyethylene films and polypropylene films can be cited.

[0212] The non-aqueous electrolyte of this disclosure can be retained by impregnating the aforementioned separator. There are no particular limitations on the impregnation method; it can be carried out using any known method. Specifically, impregnation can be performed by finally injecting the electrolyte into a battery having a positive electrode, a separator, and a negative electrode.

[0213] [Exterior body]

[0214] As the outer casing of the non-aqueous electrolyte battery disclosed herein, coin-shaped, cylindrical, or square metal cans, as well as laminated casings, are preferred. For the metal can material, examples include nickel-plated steel, stainless steel, nickel-plated stainless steel, aluminum or its alloys, nickel, and titanium. For the laminated casing, aluminum laminated films, SUS laminated films, polypropylene coated with silica, polyethylene, and other laminated films can be used.

[0215] The configuration of the non-aqueous electrolyte battery in this embodiment is not particularly limited. For example, it can be composed of electrode elements with positive and negative electrodes arranged opposite each other and a non-aqueous electrolyte encapsulated in an outer casing. The shape of the non-aqueous electrolyte battery is not particularly limited, and an electrochemical device in the shape of a coin, cylinder, square, or aluminum laminate can be assembled from the above elements.

[0216] 3. Manufacturing methods for non-aqueous electrolyte batteries

[0217] The method for manufacturing a non-aqueous electrolyte battery disclosed herein includes a step of injecting the non-aqueous electrolyte described above. There are no particular limitations on the injection method; conventional methods can be used. Examples include vacuum injection.

[0218] Example

[0219] The present disclosure is described in detail below through embodiments, but the present disclosure is not limited to these embodiments.

[0220] <Synthesis example 1-1>

[0221] Synthesis of compound (1-1-Li)

[0222]

[0223] In a 50 ml round-bottom flask, 30 g of acetonitrile (hereinafter referred to as "MeCN") and 0.45 g (6.5 mmol) of lithium nitrate were added. After stirring at 20–30 °C, 0.98 g (7.8 mmol) of fluorosulfonyl isocyanate was slowly added. After stirring at below 30 °C for 1 hour, the mixture was concentrated to give 0.69 g of compound (1–1-Li) (70% recovery).

[0224] <Synthesis example 1-2>

[0225] Synthesis of compound (1-5-Li)

[0226]

[0227] In a 50 ml round-bottom flask, 30 g of MeCN and 0.30 g (4.4 mmol) of lithium nitrate were added. After stirring at 20–30 °C, 0.66 g (4.8 mmol) of methoxysulfonyl isocyanate was slowly added. After stirring at below 30 °C for 1 hour, the mixture was concentrated to give 0.51 g of compound (1–5–Li) (72% recovery).

[0228] <Synthesis example 1-3>

[0229] Synthesis of compound (1-11-Li)

[0230]

[0231] In a 50 ml round-bottom flask, 30 g of MeCN and 0.25 g (3.6 mmol) of lithium nitrate were added. After stirring at 20–30 °C, 0.67 g (3.8 mmol) of pyrrolidine-1-sulfonyl isocyanate was slowly added. After stirring at below 30 °C for 1 hour, the mixture was concentrated to give 0.53 g of compound (1-11-Li) (73% recovery).

[0232] <Synthesis example 2-1>

[0233] Synthesis of compound (2-1-Li)

[0234]

[0235] In a 50 ml round-bottom flask, 30 g of MeCN and 0.35 g (5.1 mmol) of lithium nitrate were added. After stirring at 20–30 °C, 0.84 g (6.6 mmol) of difluorophosphoryl isocyanate was slowly added. After stirring at below 30 °C for 1 hour, the mixture was concentrated to give 0.51 g of compound (2–1-Li) (66% recovery).

[0236] <Synthesis example 2-2>

[0237] Synthesis of compound (2-6-Li)

[0238]

[0239] In a 50 ml round-bottom flask, 30 g of tetrahydrofuran and 0.25 g (1.6 mmol) of compound (2-1-Li) were added. After stirring at 20–30 °C, 0.13 g (1.6 mmol) of 2-mercaptoethanol was slowly added until the temperature dropped below -10 °C. After stirring for 10 hours, 0.12 g (3.3 mmol) of lithium hydride was slowly added. The lower layer was removed by decantation, and 30 g of ethyl acetate was added to the solid obtained by pressure filtration. The mixture was centrifuged at 2000 rpm for 1 hour. The supernatant was then pressure filtered, and the filtrate was concentrated and dried to give 0.13 g of compound (2-6-Li) (62% recovery).

[0240] In addition, the above compounds were subjected to cation exchange reactions to obtain the following compounds: (1-1-Na), (1-5-Na), (1-11-Na), (2-1-Na) and (2-6-Na).

[0241]

[0242] [Preparation of non-aqueous electrolytes]

[0243] (Preparation of non-aqueous electrolyte 1-1)

[0244] Using a mixed solvent of EC, DMC, and EMC in a volume ratio of 3:3:4 as the non-aqueous organic solvent, the compound represented by the above formula (1-1-Li) of (III) was dissolved in this solvent at a concentration of 1.0 mol / L, with LiPF6 as the solute, at a concentration of 0.05% by mass relative to the total amount of the non-aqueous electrolyte, to prepare non-aqueous electrolyte 1-1. It should be noted that the above preparation was carried out while maintaining the liquid temperature at 25°C.

[0245] <Examples 1-2~1-10>

[0246] (Preparation of non-aqueous electrolytes 1-2 to 1-10)

[0247] Except for changing the type and concentration of (III) as shown in Table 1, dissolve the electrolytes using the same steps as the preparation of non-aqueous electrolyte 1-1 above to prepare non-aqueous electrolytes 1-2 to 1-10.

[0248] <Comparative Example 1-1>

[0249] (Comparison of the preparation of non-aqueous electrolyte 1-1)

[0250] Without adding (III), the non-aqueous electrolyte 1-1 was prepared by dissolving it in the same manner as the non-aqueous electrolyte 1-1.

[0251] <Comparative Examples 1-2~1-4>

[0252] (Comparison of the preparation of non-aqueous electrolytes 1-2 to 1-4)

[0253] Comparative nonaqueous electrolytes 1-2 to 1-4 were prepared by dissolving lithium dinitramide (hereinafter also referred to as "DN"), which was used as a comparative compound, in place of (III) and by changing its concentration as shown in Table 1. The preparation of nonaqueous electrolytes 1-2 to 1-4 was carried out using the same steps as those for nonaqueous electrolyte 1-1. It should be noted that DN was obtained using reference to Patent Document 1 as follows.

[0254] Synthesis of DN

[0255] In a 50 ml round-bottom flask, add 5.5 ml of fuming nitric acid and 2 ml of fuming sulfuric acid. Slowly add 2.0 g of lithium aminosulfonate at -40 °C. After stirring at -40 °C for 30 minutes, add 40 ml of ice water and neutralize with LiOH aqueous solution to pH 7.0. Evaporate the neutralized solution to dryness and extract with 2 ml of acetone. Add 20 ml of 2-propanol to the acetone solution and dry the mixture under reduced pressure to obtain the final product.

[0256] In addition, DN-Na was obtained by subjecting the above compounds to a cation exchange reaction.

[0257]

[0258] <Examples 2-1~2-5, Comparative Examples 2-1~2-2>

[0259] (Preparation of non-aqueous electrolytes 2-1 to 2-5 and comparative non-aqueous electrolytes 2-1 to 2-2)

[0260] Furthermore, VC as other additive (1) and lithium bis(oxalate)borate (hereinafter also referred to as "BOB") as other additive (2) were added to achieve the concentrations recorded in Table 2, and dissolved. Otherwise, non-aqueous electrolytes 2-1 to 2-5 and comparative non-aqueous electrolytes 2-1 to 2-2 were obtained in the same manner as the preparation of non-aqueous electrolytes 1-4, 1-6 to 1-9 and comparative non-aqueous electrolytes 1-1 and 1-3. It should be noted that other additives (1) and other additives (2) are equivalent to the other optional components mentioned above.

[0261] <Examples 3-1~3-5, Comparative Examples 3-1~3-2>~<Examples 9-1~9-5, Comparative Examples 9-1~9-2>

[0262] As described in Tables 2-3, other additives (2) were changed from BOB to the compounds listed in their respective tables. Otherwise, the non-aqueous electrolytes and comparative non-aqueous electrolytes listed in the tables were prepared by dissolving them in the same manner as the preparation of non-aqueous electrolytes 2-1-2-5 and comparative non-aqueous electrolytes 2-1-2-2. It should be noted that "DFBOP" refers to lithium difluorobis(oxalate)phosphate, "DFOB" refers to lithium difluorooxalate borate, "TFOP" refers to lithium tetrafluorooxalate phosphate, "DTD" refers to 1,3,2-dioxothiacyclopentane-2,2-dioxide, "DFPFSI" refers to lithium (difluorophosphoryl)(fluorosulfonyl)imide, "FS" refers to lithium fluorosulfonate, and "TV-Si" refers to tetravinylsilane.

[0263] <Examples 10-1~10-5, Comparative Examples 10-1~10-2>~<Examples 33-1~33-5, Comparative Examples 33-1~33-2>

[0264] As described in Tables 4-9, the compounds listed in the "Additional Solutes" section of each table were added as solutes in the amounts described. Other additives (2) were replaced with compounds listed in their respective tables. Otherwise, the non-aqueous electrolytes and comparative non-aqueous electrolytes were prepared in the same manner as those prepared for non-aqueous electrolytes 2-1-2-5 and comparative non-aqueous electrolytes 2-1-2-2. It should be noted that "DFP" refers to lithium difluorophosphate, "FSI" refers to lithium bis(fluorosulfonyl)imide, and "BF4" refers to lithium tetrafluoroborate.

[0265] <Examples 34-1 to 34-10, Comparative Examples 34-1 to 34-4> to <Examples 59-1 to 59-5, Comparative Examples 59-1 to 59-2>

[0266] As a mixed solution of non-aqueous organic solvent and other components, a mixed solution of EC, FEC, DMC and EMC with a volume ratio of 3:0.2:3:3.8 was obtained. In this mixed solution, LiPF6 and FSI, as solutes, were dissolved at concentrations of 1.0 mol / L and 0.1 mol / L, respectively, as described in Tables 10 to 16. Other additives (2) were replaced with compounds described in their respective tables. Furthermore, compounds described in the "Additional Solutes" section of each table were added as solutes in the amounts described. Otherwise, the electrolytes were dissolved in the same manner as those described in Tables 1 to 9 to prepare non-aqueous electrolytes and comparative non-aqueous electrolytes as described in each table.

[0267] <Example 60-1>

[0268] (Preparation of non-aqueous electrolyte 60-1)

[0269] A mixed solution of EC, PC, FEC, and EMC in a volume ratio of 2:1:0.2:6.8 was obtained as a non-aqueous organic solvent and other components. Sodium hexafluorophosphate (hereinafter also referred to as "NaPF6") was dissolved in this mixed solution at a concentration of 1.0 mol / L, and the compound represented by the above formula (1-1-Na) in (III) was dissolved at a concentration of 0.05% by mass relative to the total amount of the non-aqueous electrolyte to prepare non-aqueous electrolyte 60-1. It should be noted that the above preparation was carried out while maintaining the liquid temperature at 25°C.

[0270] <Examples 60-2~60-10>

[0271] (Preparation of non-aqueous electrolytes 60-2 to 60-10)

[0272] Except for changing the type and concentration of (III) as shown in Table 17, dissolve the electrolytes using the same steps as the preparation of the non-aqueous electrolyte 60-1 above to prepare non-aqueous electrolytes 60-2 to 60-10.

[0273] <Comparative Example 60-1>

[0274] (Comparison of the preparation of non-aqueous electrolyte 60-1)

[0275] Without adding (III), the non-aqueous electrolyte 60-1 was prepared by dissolving it in the same manner as the non-aqueous electrolyte 60-1.

[0276] <Comparative Examples 60-2~60-4>

[0277] (Comparison of the preparation of non-aqueous electrolytes 60-2 to 60-4)

[0278] Comparative nonaqueous electrolytes 60-2 to 60-4 were prepared by dissolving DN-Na, a comparative compound, in place of (III), as shown in Table 17, otherwise following the same steps as the preparation of nonaqueous electrolyte 60-1.

[0279] <Examples 61-1 to 61-5, Comparative Examples 61-1 to 61-2>

[0280] (Preparation of non-aqueous electrolytes 61-1~61-5 and comparative non-aqueous electrolytes 61-1~61-2)

[0281] Furthermore, sodium difluorobis(oxalate) phosphate (hereinafter also referred to as "DFBOP-Na") as another additive (1) was added and dissolved in such a way as the concentration described in Table 18. Otherwise, non-aqueous electrolytes 61-1 to 61-5 and comparative non-aqueous electrolytes 61-1 to 61-2 were obtained in the same manner as the preparation of non-aqueous electrolytes 60-4, 60-6 to 60-9 and comparative non-aqueous electrolytes 60-1 and 60-3.

[0282] Examples 62-1 to 62-5, Comparative Examples 62-1 to 62-4> to Examples 67-1 to 67-5, Comparative Examples 67-1 to 67-2>

[0283] As described in Tables 18-19, other additives (1) were changed from DFBOP-Na to the compounds listed in their respective tables. Otherwise, the non-aqueous electrolytes and comparative non-aqueous electrolytes listed in each table were prepared by dissolving them in the same manner as the preparation of non-aqueous electrolytes 61-1 to 61-5 and comparative non-aqueous electrolytes 61-1 to 61-2. It should be noted that "DFOB-Na" refers to sodium difluorooxalatoborate, "TFOP-Na" refers to sodium tetrafluorooxalatophosphate, "DFPFSI-Na" refers to sodium (difluorophosphoryl)(fluorosulfonyl)imide, and "FS-Na" refers to sodium fluorosulfonate.

[0284] Examples 68-1 to 68-5, Comparative Examples 68-1 to 68-2> to Examples 88-1 to 88-5, Comparative Examples 88-1 to 88-2>

[0285] As described in Tables 20-25, the compounds listed in the "Additional Solutes" section of each table were added as solutes in the amounts described, and other additives (1) were replaced with the compounds listed in their respective tables. Otherwise, the non-aqueous electrolytes and comparative non-aqueous electrolytes listed in each table were prepared by dissolving them in the same manner as the preparation of non-aqueous electrolytes 61-1 to 61-5 and comparative non-aqueous electrolytes 61-1 to 61-2. It should be noted that "DFP-Na" refers to sodium difluorophosphate, "FSI-Na" refers to sodium bis(fluorosulfonyl)imide, and "BF4-Na" refers to sodium tetrafluoroborate.

[0286] <Example 89-1>

[0287] (Preparation of non-aqueous electrolyte 89-1)

[0288] A non-aqueous electrolyte 89-1 was prepared by dissolving a compound of (III) in a volume ratio of 1:2 (1,3-dioxolane (hereinafter referred to as "DOL") and dimethoxymethane (hereinafter referred to as "DME") as a non-aqueous organic solvent, with the concentration of FSI as the solute in the solvent being 0.8 mol / L and the concentration of the compound represented by the above formula (1-1-Li) being 1.0% by mass relative to the total amount of the non-aqueous electrolyte. It should be noted that the above preparation was carried out while maintaining the liquid temperature at 25°C.

[0289] <Examples 89-2~89-9>

[0290] (Preparation of non-aqueous electrolytes 89-2~89-9)

[0291] Except for changing the type and concentration of (III) as shown in Table 26, dissolve the non-aqueous electrolytes 89-2 to 89-9 using the same steps as the preparation of the non-aqueous electrolyte 89-1 described above.

[0292] <Comparative Example 89-1>

[0293] (Comparison of the preparation of non-aqueous electrolyte 89-1)

[0294] Without adding (III), the non-aqueous electrolyte 89-1 was prepared by dissolving it in the same manner as the non-aqueous electrolyte 89-1.

[0295] <Comparative Examples 89-2~89-4>

[0296] (Comparison of the preparation of non-aqueous electrolytes 89-2~89-4)

[0297] Comparative nonaqueous electrolytes 89-2 to 89-4 were prepared by dissolving DN (III) as a comparative compound, as shown in Table 26, and otherwise by dissolving it in the same manner as the preparation of nonaqueous electrolyte 89-1.

[0298] [Fabrication of non-aqueous electrolyte batteries]

[0299] (Making of NCM622 positive electrode)

[0300] In LiNi 0.6 Co 0.2 Mn 0.2In a mixture of 90.0% by mass of O2 powder, 5.0% by mass of polyvinylidene fluoride (hereinafter referred to as "PVDF") as a binder and 5.0% by mass of acetylene black as a conductive material were mixed, and then N-methyl-2-pyrrolidone (hereinafter referred to as "NMP") was added to prepare a positive electrode paste. This paste was coated on both sides of an aluminum foil (A1085), dried, pressed, and then punched into 4cm × 5cm pieces, thus obtaining the experimental NCM622 positive electrode.

[0301] (Making of NCM811 positive electrode)

[0302] In LiNi 0.8 Mn 0.1 Co 0.1 In a mixture of 92.0% by mass of O2 powder, 3.5% by mass of PVDF as a binder and 4.5% by mass of acetylene black as a conductive material were mixed, and NMP was further added to prepare a positive electrode paste. This paste was coated on both sides of an aluminum foil (A1085), dried, pressed, and then punched into 4cm × 5cm pieces, thus obtaining the experimental NCM811 positive electrode.

[0303] (Sodium-ion battery cathode: NaNi) 0.5 Ti 0.3 Mn 0.2 (Production of O2 positive electrode)

[0304] 90.0% by mass of NaNi was used as the positive electrode active material. 0.5 Ti 0.3 Mn 0.2 O2, 5.0% by mass of acetylene black as a conductive agent, and 5.0% by mass of PVDF as a binder were mixed, and NMP was further added as a solvent to prepare a positive electrode paste. This paste was coated on both sides of an aluminum foil (A1085), dried, pressed, and then punched into 4cm × 5cm pieces, thus obtaining the experimental NaNi. 0.5 Ti 0.3 Mn 0.2 O2 positive electrode.

[0305] (Preparation of a sulfur cathode)

[0306] A positive electrode paste was prepared by mixing 80.0% by mass of a sulfur-CNT complex (sulfur:carbon = 70:30 by weight), 10.0% by mass of a conductive material (Denka, HS-100), 6.5% by mass of styrene-butadiene rubber (hereinafter also referred to as "SBR"), and 3.5% by mass of sodium carboxymethyl cellulose (hereinafter also referred to as "CMC") with water. This paste was coated onto one side of an aluminum foil (A1085), dried, pressurized, and then punched into a circular electrode with a diameter of 10 mm, thus obtaining the experimental sulfur positive electrode.

[0307] (Production of natural graphite anode)

[0308] A negative electrode 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 SBR, 1.0% by mass of CMC, and water. This paste was coated onto one side of a copper foil, dried, pressurized, and then punched to a size of 4.5cm × 5.5cm, thus obtaining the experimental natural graphite negative electrode.

[0309] (Fabrication of silicon-containing graphite anodes)

[0310] A negative electrode paste was prepared by mixing 7.0% by mass of nano-silicon, 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 into 85.0% by mass of artificial graphite powder. This paste was coated onto one side of a copper foil, dried, pressurized, and then punched to a size of 4.5cm × 5.5cm, thus obtaining the experimental silicon-containing graphite negative electrode.

[0311] (Fabrication of hard carbon anode)

[0312] A negative electrode paste was prepared by mixing 90.0% by mass of hard carbon powder (Carbotron P manufactured by Kureha) and 10% by mass of PVDF as a binder, with NMP added as a solvent. This paste was coated onto one side of an aluminum foil (A1085), dried, pressurized, and then punched to a size of 4.5 cm × 5.5 cm, thus obtaining the experimental hard carbon negative electrode.

[0313] (Fabrication of lithium metal anode)

[0314] The sheet-like lithium metal was punched into a circular electrode with a diameter of 12 mm, thus obtaining the lithium metal negative electrode for the experiment.

[0315] (Fabrication of non-aqueous electrolyte batteries)

[0316] Under an argon atmosphere with a dew point below -50°C, the terminals were soldered to the aforementioned NCM622 positive electrode, and then the two sides were clamped together using two polyethylene separators (5cm × 6cm). Two natural graphite negative electrodes, with terminals pre-soldered to their outer sides, were then clamped together with the negative electrode active material side facing the positive electrode active material side. These were then placed in an aluminum-laminated bag with one side remaining open, and a non-aqueous electrolyte was vacuum-filled. The opening was then heat-sealed, thus fabricating the aluminum-laminated non-aqueous electrolyte batteries (lithium-ion batteries) of the examples and comparative examples listed in Tables 1 to 9.

[0317] In addition, in the examples and comparative examples in Tables 10-16, NCM811 was used as the positive electrode and silicon-containing graphite was used as the negative electrode to similarly fabricate non-aqueous electrolyte batteries (lithium-ion batteries).

[0318] In addition, in the examples and comparative examples in Tables 17-25, NaNi was used. 0.5 Ti 0.3 Mn 0.2 Using O2 as the positive electrode and hard carbon as the negative electrode, a non-aqueous electrolyte battery (sodium-ion battery) is similarly constructed.

[0319] In addition, regarding the embodiments and comparative examples in Table 26, in an argon atmosphere with a dew point below -50°C, a sulfur positive electrode was used as the positive electrode and a lithium metal negative electrode was used as the negative electrode. They were positioned face to face, with a polyethylene separator (15 mm in diameter) sandwiched between them. The electrolyte manufactured above was then injected, thereby producing a coin-shaped non-aqueous electrolyte battery (lithium-sulfur battery).

[0320] [evaluate]

[0321] Initial Charge / Discharge Test: Lithium-ion Battery

[0322] First, using the manufactured battery, adjustments were performed at an ambient temperature of 25°C under the following conditions: As an initial charge-discharge test, the following charge-discharge cycle was repeated three times: constant current and constant voltage charging at 5mA with a charging upper limit voltage of 4.2V, constant current discharging at 10mA until the discharge termination voltage of 2.5V; subsequently, constant current and constant voltage charging at 10mA with a charging upper limit voltage of 4.2V, constant current and constant voltage discharging at 10mA until the discharge termination voltage of 2.5V. The discharge capacity of the third cycle was taken as the initial discharge capacity.

[0323] Initial Charge / Discharge Test: Sodium-ion Battery

[0324] First, using the manufactured battery, adjustments were performed at an ambient temperature of 25°C under the following conditions: As an initial charge-discharge test, the following charge-discharge cycle was repeated three times: constant current and constant voltage charging at 5mA with a charging upper limit voltage of 4.1V, constant current discharging at 10mA until the discharge termination voltage of 1.5V; subsequently, constant current and constant voltage charging at 10mA with a charging upper limit voltage of 4.1V, constant current and constant voltage discharging at 10mA until the discharge termination voltage of 1.5V. The discharge capacity of the third cycle was taken as the initial discharge capacity.

[0325] Initial Charge-Discharge Test: Lithium-Sulfur Battery

[0326] First, using the manufactured battery, adjustments were performed at an ambient temperature of 25°C under the following conditions: As an initial charge-discharge test, a constant current of 0.24mA was used for discharge until the discharge termination voltage of 1.8V was reached. Subsequently, two more tests were conducted: charging at the upper charging limit voltage of 2.5V and 0.24mA with constant current and constant voltage, followed by discharge at 0.24mA with constant current until the discharge termination voltage of 1.8V. The discharge capacity of the second test was taken as the initial discharge capacity.

[0327] <Cyclic Test (25°C): Lithium-ion Batteries>

[0328] The non-aqueous electrolyte battery that had completed the initial charge-discharge test was charged at a constant current and constant voltage of 100mA with a charging upper limit voltage of 4.2V, and then discharged at a constant current of 100mA until the discharge termination voltage of 2.5V. This charge-discharge cycle at 100mA under 25°C was repeated 500 times. Subsequently, it was charged at a constant current and constant voltage of 10mA with a charging upper limit voltage of 4.2V, and then discharged at a constant current of 10mA until the discharge termination voltage of 2.5V. The discharge capacity was taken as the discharge capacity after the cycle test.

[0329] <Cyclic Test (25℃): Sodium-ion Battery>

[0330] The upper limit of charging voltage was changed to 4.1V and the discharge termination voltage was changed to 1.5V. Otherwise, it was evaluated in the same way as lithium-ion batteries.

[0331] <Cyclic Test (25℃): Lithium-Sulfur Battery>

[0332] The non-aqueous electrolyte battery that had completed the initial charge-discharge test was charged with a constant current and constant voltage of 1.2mA at the upper limit of the charging voltage (2.5V), and then discharged with a constant current of 1.2mA until the discharge termination voltage of 1.8V. This charge-discharge cycle at 1.2mA under 25°C was repeated 50 times. Subsequently, it was charged with a constant current and constant voltage of 0.24mA at the upper limit of the charging voltage (2.5V), and then discharged with a constant current of 0.24mA until the discharge termination voltage of 1.8V. The discharge capacity was taken as the discharge capacity after the cycle test.

[0333] <Capacity retention after cycling tests: Lithium-ion batteries>

[0334] The capacity retention rate after cycling is calculated using the following formula. A larger value indicates better cycling performance.

[0335] Capacity retention after cyclic testing (%) = (Discharge capacity after cyclic testing / Initial discharge capacity) × 100

[0336] <Capacity retention after cycling tests: Sodium-ion batteries>

[0337] It is evaluated in the same way as lithium-ion batteries. The higher the value, the better the cycle performance.

[0338] <Capacity retention after cycling tests: Lithium-sulfur batteries>

[0339] It is evaluated in the same way as lithium-ion batteries. The higher the value, the better the cycle performance.

[0340] High-Temperature Storage Test (70℃): Lithium-ion Batteries

[0341] The non-aqueous electrolyte batteries that had completed the initial charge-discharge test were charged at a constant current and constant voltage of 10mA with a charging upper limit voltage of 4.2V and stored at 70°C for 60 days. Then, they were left to stand at 25°C for 4 hours and discharged at a constant current of 10mA until the discharge termination voltage of 2.5V was reached. Subsequently, they were charged at a constant current and constant voltage of 10mA with a charging upper limit voltage of 4.2V and discharged at a constant current of 10mA until the discharge termination voltage of 2.5V was reached. The discharge capacity of these batteries was taken as the discharge capacity after the high-temperature storage test.

[0342] High-Temperature Storage Test (70℃): Sodium-ion Batteries

[0343] The upper limit of charging voltage was changed to 4.1V and the discharge termination voltage was changed to 1.5V. Otherwise, it was evaluated in the same way as lithium-ion batteries.

[0344] High-Temperature Storage Test (45℃): Lithium-Sulfur Batteries

[0345] The non-aqueous electrolyte batteries that had completed the initial charge-discharge test were charged at a constant current and constant voltage of 0.24mA with a maximum charging voltage of 2.5V, and then placed at 45°C for 24 hours. Next, they were left to stand at 25°C for 2 hours, and then discharged at a constant current of 0.24mA until the discharge termination voltage of 1.8V was reached. Subsequently, they were charged at a constant current and constant voltage of 2.5V and 0.24mA, and then discharged at a constant current of 0.24mA until the discharge termination voltage of 1.8V was reached. The discharge capacity of these discharged batteries was taken as the discharge capacity after the high-temperature storage test.

[0346] Capacity retention after high-temperature storage test: Lithium-ion batteries

[0347] The capacity retention rate after the high-temperature storage test is calculated using the following formula. The larger the value, the better the high-temperature storage characteristics.

[0348] Capacity retention rate (%) after high-temperature storage test = (Discharge capacity after high-temperature storage test / Initial discharge capacity) × 100

[0349] <Capacity retention after high-temperature storage test: Sodium-ion batteries>

[0350] The evaluation is conducted in the same manner as for lithium-ion batteries. A higher value indicates better high-temperature storage characteristics.

[0351] <Capacity retention after high-temperature storage test: Lithium-sulfur batteries>

[0352] The evaluation is conducted in the same manner as for lithium-ion batteries. A higher value indicates better high-temperature storage characteristics.

[0353] [Table 1]

[0354]

[0355] [Table 2]

[0356]

[0357] [Table 3]

[0358]

[0359] [Table 4]

[0360]

[0361] [Table 5]

[0362]

[0363] [Table 6]

[0364]

[0365] [Table 7]

[0366]

[0367] [Table 8]

[0368]

[0369] [Table 9]

[0370]

[0371] [Table 10]

[0372]

[0373] [Table 11]

[0374]

[0375] [Table 12]

[0376]

[0377] [Table 13]

[0378]

[0379] [Table 14]

[0380]

[0381] [Table 15]

[0382]

[0383] [Table 16]

[0384]

[0385] [Table 17]

[0386]

[0387] [Table 18]

[0388]

[0389] [Table 19]

[0390]

[0391] [Table 20]

[0392]

[0393] [Table 21]

[0394]

[0395] [Table 22]

[0396]

[0397] [Table 23]

[0398]

[0399] [Table 24]

[0400]

[0401] [Table 25]

[0402]

[0403] [Table 26]

[0404]

[0405] The results above show that, compared with the non-aqueous electrolyte battery containing the non-aqueous electrolyte of the comparative example, the non-aqueous electrolyte battery containing the non-aqueous electrolyte of the embodiment exhibits superior high-temperature storage characteristics. Furthermore, when comparing the embodiment with the comparative example where the content of (III) in the non-aqueous electrolyte is the same as the content of the comparative compound, it is evident that the cycle characteristics of the embodiment are superior.

[0406] Industrial availability

[0407] According to this disclosure, a non-aqueous electrolyte exhibiting excellent high-temperature storage properties when used in a non-aqueous electrolyte battery, and a method for manufacturing the aforementioned non-aqueous electrolyte battery, can be provided. Furthermore, according to this disclosure, a non-aqueous electrolyte battery with excellent high-temperature storage properties can be provided.

[0408] Although this disclosure has been described in detail with reference to specific embodiments, those skilled in the art will recognize that various changes and modifications can be made without departing from the spirit and scope of this disclosure.

[0409] This application is based on Japanese Patent Application No. 2024-003378, filed on January 12, 2024, the contents of which are incorporated herein by reference.

Claims

1. A non-aqueous electrolyte, comprising: (I) Solute, (II) Non-aqueous organic solvents, and (III) Select at least one compound from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2); A in General Formula (1) 1 represents -N(H)- or -N - (M1 + ); M1 + represents a metal cation or a onium cation; R 1 represents a halogen atom, an alkyl group having a carbon number of 1 to 10, an alkoxy group having a carbon number of 1 to 10, an alkenyl group having a carbon number of 2 to 10, an alkenyloxy group having a carbon number of 2 to 10, an alkynyloxy group having a carbon number of 2 to 10, an aryloxy group having a carbon number of 6 to 15, an OH group, an O - Mx + , or N(Rx)2; Mx + represents a metal cation or a onium cation; each Rxindependently represents a hydrogen atom, an alkyl group having a carbon number of 1 to 10, an alkenyl group having a carbon number of 2 to 10, an alkynyl group having a carbon number of 2 to 10, or a fluorosulfonyl group; the plurality of Rxare optionally the same or different; and the plurality of Rxare optionally bonded to each other. A in General Formula (2) 2 represents -N(H)- or -N - (M2 + ); M2 + represents a metal cation or a onium cation; R 2 and R 3 each independently represents a halogen atom, an alkyl group having a carbon number of 1 to 10, an alkoxy group having a carbon number of 1 to 10, an alkenyl group having a carbon number of 2 to 10, an alkenyloxy group having a carbon number of 2 to 10, an alkynyloxy group having a carbon number of 2 to 10, an aryloxy group having a carbon number of 6 to 15, an OH group, an O - My + or N(Ry)2; My + represents a metal cation or a onium cation; each Ry independently represents a hydrogen atom, an alkyl group having a carbon number of 1 to 10, an alkenyl group having a carbon number of 2 to 10, an alkynyl group having a carbon number of 2 to 10, or a fluorosulfonyl group; a plurality of Ry are optionally the same or different; a plurality of Ry are optionally bonded to each other.

2. The non-aqueous electrolyte according to claim 1, wherein, R in the general formula (1) 1 is a fluorine atom, a methyl group, an ethyl group, a vinyl group, a methoxy group, O - Mx + or N(Rx)2.

3. The non-aqueous electrolyte according to claim 1, wherein, In the general formula (2), R 2 and R 3 At least one of them is a fluorine atom, methyl, ethyl, vinyl, methoxy, or O atom. - My + Or N(Ry)2.

4. The non-aqueous electrolyte according to claim 1, wherein, In the general formula (1), A 1 Indicates -N(H)- or -N - (M1 + )-, and M1 + It consists of lithium ions or sodium ions.

5. The non-aqueous electrolyte according to claim 1, wherein, In the general formula (2), A 2 Indicates -N(H)- or -N - (M2 + )-, and M2 + It consists of lithium ions or sodium ions.

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

7. The non-aqueous electrolyte according to claim 1, wherein, The (I) is selected from at least one of the following groups: LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiN(SO2F)2, LiAlO2, LiAlCl4, LiCl and LiI.

8. The non-aqueous electrolyte according to claim 1, wherein, The (I) is selected from at least one of the following groups: NaPF6, NaBF4, NaSbF6, NaAsF6, NaClO4, NaN(SO2F)2, NaAlO2, NaAlCl4, NaCl, and NaI.

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

10. The non-aqueous electrolyte according to claim 9, wherein, The cyclic ester comprises cyclic carbonates.

11. The non-aqueous electrolyte according to claim 10, wherein, The cyclic carbonate comprises at least one selected from the group consisting of ethylene carbonate and propylene carbonate.

12. The non-aqueous electrolyte according to claim 9, wherein, The chain ester comprises chain carbonates.

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

14. The non-aqueous electrolyte according to claim 9, 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.

15. The non-aqueous electrolyte according to claim 9, 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.

16. The non-aqueous electrolyte according to claim 1, further comprising, selected from cyclohexylbenzene, cyclohexylfluorobenzene, biphenyl, 2-fluorobiphenyl, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, fluorobenzene, difluoroanisole, vinylene carbonate, oligomers of vinylene carbonate, vinylene carbonate, divinylene carbonate, fluoroethylene carbonate, ethynylene carbonate, trans-difluoroethylene carbonate, methylpropynyl carbonate, and ethylpropynyl carbonate. Dipropyne 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-diisocyanate hexane, maleic anhydride, succinic anhydride, 1,4-dioxane-2,6-dione, glutaric anhydride, methanedisulfonic anhydride, 1,3-propanesulfonyl lactone, 1,3-propenesulfonyl lactone, 1,4-butanesulfonyl lactone, 2,4-butane Sulfolactone, 1,3,2-dioxothiacyclopentane-2,2-dioxide, 4-propyl-1,3,2-dioxothiacyclopentane-2,2-dioxide, methylene methane disulfonate, dimethylene methane disulfonate, trimethylene methane disulfonate, methyl methanesulfonate, methanesulfonyl fluoride, ethylene sulfonyl fluoride, 1,2-ethane disulfonic anhydride, methane sulfonic anhydride, N,N'-carbonylbis(N-methylaminosulfonyl fluoride), difluoro(pyridinecarboxylic acid)borate, difluoro Phenyl phosphate, triargyl phosphate, tetrafluoro(pyridinecarboxylic acid) phosphate, (ethoxy)pentafluorocyclotriphosphonon, succinic acid, methyldifluorovinylsilane, methylfluorodivinylsilane, dimethyldivinylsilane, trivinylmethylsilane, trivinylfluorosilane, tetravinylsilane, tri(trimethylsilyl)borate, tri(trimethylsilyl)phosphate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-Hexafluoroisopropyl)disiloxane, fluorosulfonates, trifluoromethanesulfonates, pentafluoroethanesulfonates, nonafluorobutanesulfonates, monomethyl sulfates, monoethyl sulfates, 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 The polystyrene oligomer of the vinylene carbonate comprises at least one of the following groups: di(difluorophosphoryl)imide salt, bis(difluorophosphoryl)imide salt, monofluorophosphate, difluorophosphate, tetrafluoro(malonic acid) phosphate, tri(oxalate) phosphate, difluorobis(oxalate) phosphate, tetrafluorooxalate phosphate, bis(oxalate) borate, difluorooxalate borate, difluoro(malonic acid) borate, tri(trifluoromethanesulfonyl) methyl salt, tri(fluorosulfonyl) methyl salt, acrylate, methacrylate, nitrate, nitrite, hexafluoroisopropanol, and trifluoroethanol, wherein the number-average molecular weight of the polystyrene-based oligomer of the vinylene carbonate is 170 to 5000.

17. A non-aqueous electrolyte battery, comprising at least a positive electrode, a negative electrode, and a non-aqueous electrolyte according to any one of claims 1 to 16.

18. The non-aqueous electrolyte battery according to claim 17, wherein, The negative electrode comprises at least one of an alkali metal, an alkali metal alloy, and a material in which the alkali metal is embedded.

19. A method for manufacturing a non-aqueous electrolyte battery, comprising the step of injecting the non-aqueous electrolyte according to any one of claims 1 to 16.

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