Non-aqueous electrolyte and non-aqueous electrolyte battery

Abstract

Provided are: a non-aqueous electrolyte solution containing (I) a compound represented by general formula (1) described in the description, (II) a solute, (III) a non-aqueous organic solvent, and hydrogen fluoride; and a non-aqueous electrolyte solution battery comprising the non-aqueous electrolyte solution. The concentration of hydrogen fluoride relative to the total amount of the non-aqueous electrolyte solution is from 0.1 ppm by mass to 180 ppm by mass (inclusive).

Description

Technical Field

[0001] This application relates to non-aqueous electrolytes and 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 devices and communication equipment (personal computers, cameras, digital cameras, mobile phones, and smartphones), the demand for high-capacity, high-output, and high-energy-density batteries that can be integrated as auxiliary power sources for electric vehicles, hybrid vehicles, and fuel cell vehicles has expanded dramatically. Furthermore, even in large-scale, power-related energy storage systems, the demand for batteries capable of long-term operation is increasing. As a replacement for these various energy storage systems, non-aqueous electrolyte batteries, such as lithium-ion batteries, are being actively developed. Non-aqueous electrolyte batteries typically consist of a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte.

[0003] Patent document 1 proposes a scheme to improve the residual characteristics during high-temperature storage and suppress the rise in resistance by using hydrofluoric acid as an additive relative to diethylene glycol anhydride in the electrolyte.

[0004] Patent document 2 proposes a scheme to improve cycle characteristics by using anhydrides with specific ring structures and carbonates with fluorine atoms in the electrolyte.

[0005] Patent document 3 proposes a scheme to improve cycle characteristics and low-temperature characteristics by using silicon compounds in the electrolyte.

[0006] Patent document 4 proposes a scheme to improve preservation characteristics by using a non-aqueous electrolyte containing lithium difluorosulfonylimide as a solute.

[0007] Patent document 5 proposes a scheme to suppress self-discharge and improve the storage characteristics after charging by using lithium monofluorophosphate and lithium difluorophosphate in the electrolyte.

[0008] Patent document 6 proposes a scheme to maintain high input / output characteristics and impedance characteristics even after durability testing by using fluorosulfonate in a non-aqueous electrolyte.

[0009] Patent document 7 proposes a scheme to suppress the decomposition of the carbon anode that occurs during charge-discharge cycles by using cyclic sulfates in a non-aqueous electrolyte.

[0010] Patent document 8 proposes a scheme to significantly suppress the reduction and decomposition of electrolyte during high-temperature storage by using cyclic sulfonyl lactones (unsaturated sulfonyl lactones) in non-aqueous electrolytes. As a result, a battery with low self-discharge, significantly suppressed degradation of load characteristics or resistance, and low gas generation can be obtained.

[0011] Patent document 9 proposes a scheme to improve charge-discharge efficiency and cycle characteristics by using sulfonic anhydride in the electrolyte.

[0012] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2002-008717 Patent Document 2: Japanese Patent No. 5412705 Patent Document 3: Japanese Patent No. 3497812 Patent Document 4: Japanese Patent No. 4847675 Patent Document 5: Japanese Patent No. 3439085 Patent Document 6: Japanese Patent No. 5353923 Patent Document 7: Japanese Patent No. 3760540 Patent Document 8: Japanese Patent No. 4190162 Patent Document 9: Japanese Patent No. 4379567 Summary of the Invention

[0013] (a) Technical problems to be solved Patent Document 1 describes how the high-temperature storage characteristics of a secondary battery containing 0.1% by weight of hydrogen fluoride in a non-aqueous electrolyte are improved. However, according to the research of the inventors of this application, the secondary battery described in Patent Document 1 has the problem of high initial resistance.

[0014] This application was made in view of the above circumstances, and its purpose is to provide a non-aqueous electrolyte that can reduce the initial resistance of a non-aqueous electrolyte battery and a non-aqueous electrolyte battery with low initial resistance.

[0015] (II) Technical Solution The inventors of this application conducted in-depth research to solve this problem and discovered that by reducing the concentration of hydrogen fluoride in a non-aqueous electrolyte containing a specific acid anhydride compound, a non-aqueous organic solvent, and a solute to less than 1 / 5 of the concentration described in Patent Document 1, a non-aqueous electrolyte battery with low initial resistance can be provided. Specifically, the above-mentioned technical problem can be solved by the following configuration. [1] A non-aqueous electrolyte comprising (I) a compound represented by the following general formula (1), (II) a solute, (III) a non-aqueous organic solvent, and hydrogen fluoride, wherein, The concentration of hydrogen fluoride relative to the total amount of the non-aqueous electrolyte is between 0.1 ppm and 180 ppm by mass.

[0017] [Chemical Formula 1] In general formula (1), R 1 ~R 4 Each of these can be independently represented by a hydrogen atom, halogen atom, alkyl group, alkenyl group, or aryl group. X represents an oxygen atom, sulfur atom, or SО2 group. [2] According to [1], the non-aqueous electrolyte further contains (IV) at least one compound selected from the group consisting of compounds (2) to (9).

[0019] Compound (2): at least one compound selected from the group consisting of the compounds represented by the following general formula (2-1) and the compounds represented by the following general formula (2-2).

[0020] [Chemical Formula 2] In general formula (2-1), R 21 and R 22 Each of the following organic groups is independently a fluorine atom, or an organic group selected from alkoxy groups having 1 to 10 carbon atoms, alkenoxy groups having 2 to 10 carbon atoms, alkynoxy groups having 2 to 10 carbon atoms, cycloalkoxy groups having 3 to 10 carbon atoms, cycloalkenoxy groups having 3 to 10 carbon atoms, and aryloxy groups having 6 to 10 carbon atoms, wherein the organic group may optionally contain a fluorine atom, an oxygen atom, or an unsaturated bond. Furthermore, the general formula (2-1) contains at least one PF bond.

[0021] In general formula (2-2), X 21 It is a fluorine atom, or an organic group selected from alkyl with 1 to 10 carbon atoms, alkenyl with 2 to 10 carbon atoms, alkynyl with 2 to 10 carbon atoms, cycloalkyl with 3 to 10 carbon atoms, cycloalkenyl with 3 to 10 carbon atoms, aryl with 6 to 10 carbon atoms, alkoxy with 1 to 10 carbon atoms, alkenoxy with 2 to 10 carbon atoms, alkynoxy with 2 to 10 carbon atoms, cycloalkoxy with 3 to 10 carbon atoms, cycloalkenoxy with 3 to 10 carbon atoms, and aryloxy with 6 to 10 carbon atoms, wherein the organic group optionally contains at least one fluorine atom, and the organic group optionally also contains an oxygen atom and an unsaturated bond.

[0022] In general formulas (2-1) and (2-2), M1 m＋ It can be a proton, a metal cation, or an onium cation. m represents the valence of the corresponding cation.

[0023] Compound (3): at least one compound selected from the group consisting of the compound represented by the following general formula (3-1), the compound represented by the following general formula (3-2), and the compound represented by the following general formula (3-3).

[0024] [Chemical Formula 3] In general formulas (3-1) to (3-3), R 31 ~R 36 Each of the organic groups is independently composed of a fluorine atom or selected from alkoxy groups having 1 to 10 carbon atoms, alkenoxy groups having 2 to 10 carbon atoms, alkynoxy groups having 2 to 10 carbon atoms, cycloalkoxy groups having 3 to 10 carbon atoms, cycloalkenoxy groups having 3 to 10 carbon atoms, and aryloxy groups having 6 to 10 carbon atoms, wherein the organic group may also optionally contain a fluorine atom, an oxygen atom, or an unsaturated bond.

[0025] X 31 ~X 33 Each of the following is an organic group independently composed of a fluorine atom, or selected from alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, cycloalkenyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkenoxy groups having 2 to 10 carbon atoms, alkynoxy groups having 2 to 10 carbon atoms, cycloalkoxy groups having 3 to 10 carbon atoms, cycloalkenoxy groups having 3 to 10 carbon atoms, and aryloxy groups having 6 to 10 carbon atoms, wherein the organic group may optionally contain a fluorine atom, an oxygen atom, or an unsaturated bond.

[0026] Formula (3-1) contains at least one PF key. Formula (3-2) contains at least one of a PF key and an SF key. Formula (3-3) contains at least one SF key.

[0027] M1 m＋ It can be a proton, a metal cation, or an onium cation. m represents the valence of the corresponding cation.

[0028] Compound (4): at least one compound selected from the group consisting of compounds represented by the following general formula (4-1) and compounds represented by the following general formula (4-2).

[0029] [Chemical Formula 4] In general formula (4-1), W 1 Represents boron, phosphorus, or silicon atoms, where n1 is 0-3, n2 is 0-4, and p is 0 or 1. R 41 This refers to an alkylene group having 1 to 10 carbon atoms, a haloalkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a haloarylene group having 6 to 20 carbon atoms (these groups optionally contain substituents or heteroatoms in their structure). Furthermore, when n1 is 2 or more, the presence of n1 R...41 (Optional, each bonded to the other), R 42 Y represents a halogen atom. 1 and Y 2 Y represents oxygen or sulfur atoms independently, respectively. 3 Represents a carbon atom or a sulfur atom. Y 3 The carbon or sulfur atom represented has q oxo groups (=O) bonded to it. 3 When the atom is carbon, q is 1, Y 3 When q is a sulfur atom, it is 1 or 2. M a＋ This indicates an alkali metal cation, an alkaline earth metal cation, or an onium cation, where 'a' represents the valence of the corresponding cation. 'a' to 'd' are either 1 or 2 and satisfy a × b = c × d.

[0030] [Chemical Formula 5] In general formula (4-2), R 43 Y represents an alkylene group having 1 to 10 carbon atoms, a haloalkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a haloarylene group having 6 to 20 carbon atoms (these groups may optionally contain substituents or heteroatoms in their structure), where r is 0 or 1. 4 Represents a carbon atom or a sulfur atom. Y 4 The carbon or sulfur atom represented has s oxo groups (=O) bonded to it. 4 When the atom is carbon, s is 1, Y 4 When is a sulfur atom, s is 1 or 2. W 2 R represents a boron atom or a phosphorus atom. 44 This represents a halogen atom. W 2 When the atom is boron, n3 is 2, W 2 When the atom is phosphorus, n3 is 4.

[0031] Compound (5): The compound represented by the following general formula (5).

[0032] [Chemical Formula 6] In general formula (5), R 51 Each R represents a group having a carbon-carbon unsaturated bond independently. Multiple R groups exist. 52 At that time, multiple R 52 Each of the above can be independently represented as either a fluorine atom or an alkyl group having 1 to 10 carbon atoms, wherein the alkyl group optionally has at least one of a fluorine atom and an oxygen atom. v represents an integer from 2 to 4.

[0033] Compound (6): The compound represented by the following general formula (6).

[0034] [Chemical Formula 7] In general formula (6), R 61 and R 62 Each of the following can be independently represented: a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms optionally substituted with an alkyl group. R 61 and R 62 Any hydrogen atom in the alkyl, alkenyl, and aryl groups may be optionally substituted with a halogen atom. n6 is 0 or 1.

[0035] Compound (7): at least one compound selected from the group consisting of compounds represented by the following general formula (7-1) and compounds represented by the following general formula (7-2).

[0036] [Chemical Formula 8] In general formula (7-1), R 70 ~R 73 Each of these can be used independently to represent a hydrogen atom, a fluorine atom, an alkyl group with 1 to 5 carbon atoms, or a fluoroalkyl group with 1 to 4 carbon atoms. n71 represents an integer from 1 to 3.

[0037] In general formula (7-2), R 74 ~R 79 Each of these can be used independently to represent a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, or a fluoroalkyl group with 1 to 4 carbon atoms. n72 represents an integer from 0 to 2.

[0038] Compound (8): The compound represented by the following general formula (8).

[0039] [Chemical Formula 9] In general formula (8), R 81 The alkylene group has 1 to 6 carbon atoms, wherein the carbon-carbon bonds in the alkylene group optionally contain oxygen atoms, any hydrogen atom in the alkylene group is optionally substituted with an alkyl group, and any hydrogen atom in the alkylene group and the alkyl group is optionally substituted with a halogen atom.

[0040] Compound (9): The compound represented by the following general formula (9).

[0041] [Chemical Formula 10] In general formula (9), R 91 and R 92 Each can be used to independently represent an alkyl group having 1 to 6 carbon atoms. [3] According to the non-aqueous electrolyte described in [1] or [2], the concentration of hydrogen fluoride relative to the total amount of the non-aqueous electrolyte is more than 1 ppm by mass and less than 70 ppm by mass. [4] According to any one of [1] to [3], the content of (I) is 0.01% by mass or more and 10% by mass or less relative to the total amount of the non-aqueous electrolyte. [5] The non-aqueous electrolyte according to any one of [1] to [4], wherein the content of (IV) is 0.01% by mass or more and 10% by mass or less relative to the total amount of the non-aqueous electrolyte. [6] According to any one of [1] to [5], the non-aqueous electrolyte, wherein the compound represented by the general formula (1) is at least one compound selected from the group consisting of diethylene glycol anhydride, methyl diethylene glycol anhydride, dimethyl diethylene glycol anhydride, ethyl diethylene glycol anhydride, vinyl diethylene glycol anhydride, tetrafluorodiethylene glycol anhydride, allyl diethylene glycol anhydride, thioglycolic acid anhydride and sulfonyl diethylene glycol anhydride. [7] According to the non-aqueous electrolyte described in [2], wherein the compound (2) is at least one compound selected from the group consisting of lithium difluorophosphate, lithium fluorosulfonate and lithium trifluoromethanesulfonate. [8] According to the non-aqueous electrolyte described in [2], wherein the compound (3) is at least one compound selected from the group consisting of lithium bis(fluorosulfonyl)imide, lithium (fluorosulfonyl)(difluorophosphoryl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(difluorophosphoryl)imide, lithium bis(pentafluoroethanesulfonyl)imide and lithium (fluorosulfonyl)(trifluoromethanesulfonyl)imide. [9] According to the non-aqueous electrolyte described in [2], wherein the compound (4) is at least one compound selected from the group consisting of lithium tetrafluoroborate, lithium bis(oxalato)borate, lithium difluoro(oxalato)borate, lithium tri(oxalato) phosphate, lithium difluorobis(oxalato) phosphate, lithium tetrafluoro(oxalato) phosphate, lithium difluoro(malonato) borate, lithium tetrafluoro(malonato) phosphate, lithium tetrafluoro(picolinato) phosphate, and difluoro(picolinato) borate.

[10] According to the non-aqueous electrolyte of [2], wherein the compound (5) is at least one compound selected from the group consisting of trivinylmethylsilane, trivinylfluorosilane and tetravinylsilane.

[11] According to the non-aqueous electrolyte described in [2], wherein the compound (6) is at least one compound selected from the group consisting of 1,3,2-dioxothiacyclopentane-2,2-dioxide and 1,3,2-dioxothiacyclohexane-2,2-dioxide.

[12] According to the non-aqueous electrolyte of [2], wherein the compound (8) is at least one compound selected from the group consisting of 1,2-ethanedisulfonic anhydride and 1,3-propanedisulfonic anhydride.

[13] According to the non-aqueous electrolyte described in [2], wherein the compound (9) is at least one compound selected from the group consisting of methanesulfonic anhydride and ethanesulfonic anhydride.

[14] The non-aqueous electrolyte according to any one of [1] to

[13] , wherein (II) is at least one selected from the group consisting of LiPF6, LiSbF6, LiAsF6, LiClO4, LiAlO2, LiAlCl4, LiCl and LiI, or at least one selected from the group consisting of NaPF6, NaSbF6, NaAsF6, NaClO4, NaAlO2, NaAlCl4, NaCl and NaI.

[15] The non-aqueous electrolyte according to any one of [1] to

[14] , wherein (III) 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.

[16] According to the non-aqueous electrolyte of

[15] , the cyclic ester is a cyclic carbonate, and the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate and fluoroethylene carbonate.

[17] According to the non-aqueous electrolyte of

[15] , the chain ester is a chain carbonate, and the chain carbonate is at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate and methyl propyl carbonate.

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

[17] .

[19] A method for reducing the initial resistance of a non-aqueous electrolyte battery containing a non-aqueous electrolyte, wherein, The non-aqueous electrolyte is described using a non-aqueous electrolyte containing (I) a compound represented by the following general formula (1), (II) a solute, (III) a non-aqueous organic solvent, and hydrogen fluoride. The concentration of hydrogen fluoride relative to the total amount of the non-aqueous electrolyte is between 0.1 ppm and 180 ppm by mass.

[0059] [Chemical Formula 11] In general formula (1), R 1 ~R 4 Each of these can be independently represented by a hydrogen atom, halogen atom, alkyl group, alkenyl group, or aryl group. X represents an oxygen atom, sulfur atom, or SО2 group.

[0060] (III) Beneficial Effects According to this application, it is possible to provide a non-aqueous electrolyte that can reduce the initial resistance of a non-aqueous electrolyte battery and a non-aqueous electrolyte battery with low initial resistance. Detailed Implementation

[0061] In this manual, "~" is used to indicate the lower and upper limits, including the values ​​listed before and after it.

[0062] The present application will now be described in detail. The description of the constituent elements described below is an example of the implementation of the present application and is not limited to these specific contents.

[0063] 1. Regarding non-aqueous electrolytes The non-aqueous electrolyte of this application is a non-aqueous electrolyte containing (I) a compound represented by the following general formula (1), (II) a solute, (III) a non-aqueous organic solvent, and hydrogen fluoride, wherein, The concentration of hydrogen fluoride relative to the total amount of the non-aqueous electrolyte is between 0.1 ppm and 180 ppm by mass.

[0064] [Chemical Formula 12] In general formula (1), R 1 ~R 4 Each of these can be independently represented by a hydrogen atom, halogen atom, alkyl group, alkenyl group, or aryl group. X represents an oxygen atom, sulfur atom, or SО2 group.

[0065] Regarding the compounds represented by general formula (1) (I) The compounds represented by general formula (1) (also referred to as "(I)") contained in the non-aqueous electrolyte of this application are described.

[0066] In general formula (1), R 1 ~R 4 Each can be independently represented by a hydrogen atom, halogen atom, alkyl group, alkenyl group, or aryl group.

[0067] As R 1 ~R 4 The halogen atoms represented can be, for example, fluorine, chlorine, bromine, iodine, etc.

[0068] R 1 ~R 4 The alkyl group can be straight-chain or branched. Alkyl groups can have 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl. Any hydrogen atom in the alkyl group can be replaced by a halogen atom.

[0069] R 1 ~R 4 The alkenyl group can be linear or branched. Alkenyl groups can have 2 to 6 carbon atoms, such as vinyl and allyl groups. Any hydrogen atom in the alkenyl group can be substituted by at least one of a halogen atom and an alkyl group.

[0070] As R 1 ~R 4 The aryl group can be an aryl group with 6 to 20 carbon atoms, such as phenyl and naphthyl. Any hydrogen atom of the aryl group can be substituted by at least one of a halogen atom and an alkyl group.

[0071] The compound represented by general formula (1) can be a compound selected from the group consisting of diethylene glycol anhydride, methyl diethylene glycol anhydride, dimethyl diethylene glycol anhydride, ethyl diethylene glycol anhydride, vinyl diethylene glycol anhydride, tetrafluorodiethylene glycol anhydride, allyl diethylene glycol anhydride, thioglycolic acid anhydride and sulfonyl diethylene glycol anhydride.

[0072] The non-aqueous electrolyte of this application can use a single compound as (I), or two or more compounds can be mixed in any combination or ratio as (I) depending on the application.

[0073] The compound represented by general formula (1) can be prepared by various methods.

[0074] Regarding (II) solute The (II) solute (also referred to as "(II)") contained in the non-aqueous electrolyte of this application will be described.

[0075] (II) The solute is not particularly limited, for example it can be at least one of the group consisting of LiPF6, LiSbF6, LiAsF6, LiClO4, LiAlO2, LiAlCl4, LiCl and LiI, or at least one of the group consisting of NaPF6, NaSbF6, NaAsF6, NaClO4, NaAlO2, NaAlCl4, NaCl and NaI.

[0076] The non-aqueous electrolyte of this application can use a single compound as (II), or two or more compounds can be mixed in any combination or ratio as (II) depending on the application.

[0077] There are no particular restrictions on the concentration of (II) relative to the total amount of non-aqueous electrolyte. For example, the lower limit of the concentration of (II) can be 0.5 mol / L or higher, or 0.7 mol / L or higher, or 0.9 mol / L or higher. In addition, the upper limit of the concentration of (II) can be 5 mol / L or lower, or 4 mol / L or lower, or 2 mol / L or lower.

[0078] There is no particular limitation on the liquid temperature when (II) is dissolved in (III) non-aqueous organic solvent; it can be -20 to 80°C or 0 to 60°C.

[0079] Regarding (III) non-aqueous organic solvents The non-aqueous organic solvent (also referred to as "(III)") contained in the non-aqueous electrolyte of this application will be described. There is no particular limitation on the type of non-aqueous organic solvent (III), and any non-aqueous organic solvent can be used.

[0080] As specific examples of (III) non-aqueous organic solvents, the following non-aqueous organic solvents can be listed.

[0081] In addition to cyclic carbonates such as propylene carbonate (hereinafter sometimes referred to as "PC"), ethylene carbonate (hereinafter sometimes referred to as "EC"), fluoroethylene carbonate (hereinafter sometimes referred to as "FEC"), and butenyl carbonate, γ-butyrolactone and γ-valerolactone can also be listed as cyclic esters. Furthermore, for the aforementioned FEC, when its content is 10% by mass or less relative to the total amount of the non-aqueous electrolyte, it is defined as other additives as described later.

[0082] 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, methyl acetate, methyl propionate, ethyl propionate (hereinafter sometimes referred to as "EP"), etc., other chain esters include methyl acetate, methyl propionate, ethyl propionate, etc.

[0083] Examples of cyclic ethers include tetrahydrofuran, 2-methyltetrahydrofuran, and dioxane.

[0084] Examples of chain ethers include dimethoxyethane and diethyl ether.

[0085] In addition, examples include sulfone compounds such as dimethyl sulfoxide and sulfolane. Furthermore, ionic liquids can also be listed.

[0086] (III) The non-aqueous organic solvent may contain at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds and ionic liquids.

[0087] Cyclic esters are cyclic carbonates, which can be at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate.

[0088] The chain ester is a chain carbonate, which can be at least one selected from the group consisting of methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate and methyl propyl carbonate.

[0089] The non-aqueous electrolyte of this application may use a single compound as (III), or may mix two or more compounds in any combination or ratio as (III) depending on the application.

[0090] The content of cyclic carbonates is not particularly limited and can be arbitrary as long as it does not significantly impair the effect of this application. When used alone, the content can be set to 3% by volume or more in 100% by volume of a non-aqueous organic solvent, or it can be set to 5% by volume or more. By setting it within this range, it is easy to avoid the decrease in conductivity caused by the decrease in the dielectric constant of the non-aqueous electrolyte, and it is easy to keep the high-current discharge characteristics, stability relative to the negative electrode, and cycle characteristics of the non-aqueous electrolyte battery within a good range. In addition, it can be set to 90% by volume or less, preferably 85% by volume or less, and more preferably 80% by volume or less. By setting it within this range, it is easy to keep the viscosity of the non-aqueous electrolyte within a suitable range, it is easy to suppress the decrease in ionic conductivity, and thus it is easy to keep the load characteristics of the non-aqueous electrolyte battery within a good range.

[0091] Furthermore, 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. Further, the amount of propylene carbonate in the total non-aqueous organic solvent is not particularly limited, and can be arbitrary as long as it does not significantly impair the effect of this application. It can be 1% by volume or more, preferably 2% by volume or more, more preferably 3% by volume or more, and furthermore, it can be 30% by volume or less, preferably 25% by volume or less, more preferably 20% by volume or less. If propylene carbonate is included within this range, the low-temperature characteristics can be further improved while maintaining the characteristics of the combination of ethylene carbonate and dialkyl carbonate, which is therefore preferred.

[0092] Chain esters can be used alone, or two or more can be used simultaneously in any combination and ratio.

[0093] The content of the chain ester is not particularly limited, but in a 100% volume non-aqueous organic solvent, it can be 15% by volume or more, preferably 20% by volume or more, and more preferably 25% by volume or more. Furthermore, it can be 90% by volume or less, preferably 85% by volume or less, and more preferably 80% by volume or less. By keeping the content of the chain ester within the above range, it is easy to keep the viscosity of the non-aqueous electrolyte within a suitable range, to easily suppress the decrease in ionic conductivity, and thus to easily keep the input / output characteristics and charge / discharge rate characteristics of the non-aqueous electrolyte battery within a good range. Furthermore, it is easy to avoid the decrease in conductivity caused by the decrease in the dielectric constant of the non-aqueous electrolyte, and to easily keep the input / output characteristics and charge / discharge rate characteristics of the non-aqueous electrolyte battery within a good range.

[0094] Furthermore, by combining ethylene carbonate in specific amounts relative to specific chain esters, battery performance can be significantly improved.

[0095] For example, when dimethyl carbonate and ethyl methyl carbonate are selected as specific chain esters, the content of ethylene carbonate is not particularly limited. It can be arbitrary as long as it does not significantly impair the effect of this application; it can be set to 5% by volume or more, preferably 10% by volume or more, and further, it can be set to 45% by volume or less, preferably 40% by volume or less. The content of dimethyl carbonate can be set to 20% by volume or more, preferably 30% by volume or more, and further, it can be set to 50% by volume or less, preferably 45% by volume or less. The content of ethyl methyl carbonate can be set to 20% by volume or more, preferably 30% by volume or more, and further, it can be set to 50% by volume or less, preferably 45% by volume or less. By keeping the content within the above ranges, it is possible to reduce the low-temperature precipitation temperature of the electrolyte while also reducing the viscosity of the non-aqueous electrolyte and increasing the ionic conductivity, achieving high input-output even at low temperatures.

[0096] The content of the chain ether is not particularly limited, and can be arbitrary as long as it does not significantly impair the effect of this application. In 100% by volume of a non-aqueous organic solvent, it can be 1% by volume or more, preferably 2% by volume or more, more preferably 3% by volume or more. Furthermore, it can be 30% by volume or less, preferably 25% by volume or less, more preferably 20% by volume or less. If the content of the chain ether is within the above range, it is easy to ensure the improvement of lithium-ion dissociation degree of the chain ether and the improvement of ionic conductivity caused by viscosity reduction. In addition, when the negative electrode active material is a carbonaceous material, the phenomenon of co-intercalation of the chain ether and lithium ions can be suppressed, thus enabling the input / output characteristics and charge / discharge rate characteristics to be within a suitable range.

[0097] The content of sulfone compounds is not particularly limited, and can be arbitrary as long as it does not significantly impair the effects of this application. In 100% by volume of a non-aqueous organic solvent, it can be 0.3% by volume or more, preferably 0.5% by volume or more, more preferably 1% by volume or more. Furthermore, it can be 40% by volume or less, preferably 35% by volume or less, more preferably 30% by volume or less. If the content of sulfone compounds is within the above range, it is easy to obtain improved durability, such as improved cycle characteristics and storage characteristics. In addition, it allows the viscosity of the non-aqueous electrolyte to be within a suitable range, preventing a decrease in conductivity, and ensuring that the input / output characteristics and charge / discharge rate characteristics of the non-aqueous electrolyte battery are within a suitable range.

[0098] Regarding the concentration of hydrogen fluoride The concentration of hydrogen fluoride relative to the total amount of non-aqueous electrolyte is between 0.1 ppm and 180 ppm. By maintaining the concentration of hydrogen fluoride relative to the total amount of non-aqueous electrolyte within the above range, the initial resistance of the non-aqueous electrolyte battery can be reduced.

[0099] The lower limit of the concentration of hydrogen fluoride relative to the total amount of non-aqueous electrolyte can be 0.5 ppm by mass or more, or 1 ppm by mass or more. Furthermore, the upper limit of the concentration of hydrogen fluoride relative to the total amount of non-aqueous electrolyte can be 120 ppm by mass or less, 70 ppm by mass or less, or 50 ppm by mass or less.

[0100] Regarding (IV), at least one compound selected from the group consisting of compounds (2) to (9) is chosen. The non-aqueous electrolyte of this application may further contain (IV) at least one compound selected from the group consisting of compounds (2) to (9) below (also referred to as "(IV)"). By further containing (IV), the non-aqueous electrolyte of this application enables the non-aqueous electrolyte battery to have a lower initial resistance.

[0101] Compound (2): at least one compound selected from the group consisting of the compounds represented by the following general formula (2-1) and the compounds represented by the following general formula (2-2).

[0102] [Chemical Formula 13] In general formula (2-1), R 21 and R 22 Each of the following organic groups is independently a fluorine atom, or an organic group selected from alkoxy groups having 1 to 10 carbon atoms, alkenoxy groups having 2 to 10 carbon atoms, alkynoxy groups having 2 to 10 carbon atoms, cycloalkoxy groups having 3 to 10 carbon atoms, cycloalkenoxy groups having 3 to 10 carbon atoms, and aryloxy groups having 6 to 10 carbon atoms, wherein the organic group may optionally contain a fluorine atom, an oxygen atom, or an unsaturated bond. Furthermore, the general formula (2-1) contains at least one PF bond.

[0103] In general formula (2-2), X 21It is a fluorine atom, or an organic group selected from alkyl with 1 to 10 carbon atoms, alkenyl with 2 to 10 carbon atoms, alkynyl with 2 to 10 carbon atoms, cycloalkyl with 3 to 10 carbon atoms, cycloalkenyl with 3 to 10 carbon atoms, aryl with 6 to 10 carbon atoms, alkoxy with 1 to 10 carbon atoms, alkenoxy with 2 to 10 carbon atoms, alkynoxy with 2 to 10 carbon atoms, cycloalkoxy with 3 to 10 carbon atoms, cycloalkenoxy with 3 to 10 carbon atoms, and aryloxy with 6 to 10 carbon atoms, wherein the organic group optionally contains at least one fluorine atom, and the organic group optionally also contains an oxygen atom and an unsaturated bond.

[0104] In general formulas (2-1) and (2-2), M1 m＋ It can be a proton, a metal cation, or an onium cation. m represents the valence of the corresponding cation.

[0105] In general formula (2-1), R 21 and R 22 The alkoxy group can be linear or branched. Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, pentoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 1,1,1-trifluoroisopropoxy, and 1,1,1,3,3,3-hexafluoroisopropoxy, which are alkoxy groups or fluorinated alkoxy groups with 1 to 10 carbon atoms.

[0106] R 21 and R 22 The olefin group represented can be linear or branched. Examples of olefin groups include ethyleneoxy, 1-propenoxy, 2-propenoxy, isopropenoxy, 2-butenoxy, 3-butenoxy, and 1,3-butadieneoxy, which are olefin groups or fluorinated olefin groups with 2 to 10 carbon atoms.

[0107] R 21 and R 22 The alkynyloxy group can be straight-chain or branched. Examples of alkynyloxy groups include acetylyoxy, 2-propynoxy, and 1,1-dimethyl-2-propynoxy, which are alkynoxy groups with 2 to 10 carbon atoms or fluorinated alkynoxy groups.

[0108] As R 21 and R 22 The cycloalkoxy group represented may include, for example, cyclopentoxy and cyclohexyloxy, which have 3 to 10 carbon atoms or contain fluorine.

[0109] As R 21 and R 22The cycloalkenyloxy group represented may include, for example, cyclopentenyloxy and cyclohexenyloxy, which are cycloalkenyloxy groups with 3 to 10 carbon atoms or fluorinated cycloalkenyloxy groups.

[0110] As R 21 and R 22 The aryloxy group represented can be, for example, phenoxy, toluoxy, and xyleneoxy, which are aryloxy groups or fluorinated aryloxy groups with 6 to 10 carbon atoms.

[0111] If R 21 and R 22 The presence of fluorine atoms or alkoxy groups with fluorine atoms independently increases the degree of ionic dissociation due to their strong electron-withdrawing properties, thus resulting in higher ionic conductivity in the solution or composition, which is preferred. Furthermore, the presence of fluorine atoms further enhances the ionic conductivity in the solution or composition by increasing the mobility due to the smaller anion size, making it even more preferred.

[0112] In addition, R 21 and R 22 The number of carbon atoms is preferably 6 or less. If the number of carbon atoms is 6 or less, there is a tendency for the aforementioned ionic conductivity to be relatively high, which is therefore preferred.

[0113] In general formula (2-1), M1 m＋ This refers to protons, metal cations, or onium cations. There are no particular limitations on the type of substance, provided it does not impair the performance of the non-aqueous electrolyte and the non-aqueous electrolyte battery of this application; a wide variety of substances can be selected from the above.

[0114] As M1 m＋ Metal cations that can be used to represent metal cations include: alkali metal cations such as lithium ion, sodium ion, potassium ion, rubidium ion, and cesium ion; alkaline earth metal cations such as magnesium ion, calcium ion, and barium ion; and silver ion, copper ion, and iron ion.

[0115] As M1 m＋ Examples of onion cations that can be used to represent onion cations include tetraalkylammonium, tetraalkylphosphonium, and imidazolium derivatives.

[0116] m represents the valence of the corresponding cation, which can be 1 to 3, or 1 or 2.

[0117] In particular, from the perspective of playing a role in promoting ion conduction in non-aqueous electrolyte batteries, M1 m＋ Preferably, lithium ions, sodium ions, potassium ions, tetramethylammonium ions, tetraethylammonium ions, tetrabutylphosphonium ions, etc.

[0118] Furthermore, when M1 m＋When used in lithium-ion batteries, lithium-ion is preferred; when used in sodium-ion batteries, sodium-ion is preferred.

[0119] The following are specific examples of the anionic structures of compounds represented by general formula (2-1), but are not limited thereto.

[0120] [Chemical Formula 14] In general formula (2-2), X 21 The alkyl group represented can be straight-chain or branched. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, and 1,1,1,3,3,3-hexafluoroisopropyl, which are alkyl or fluorinated alkyl groups with 1 to 10 carbon atoms.

[0121] X 21 The alkenyl group represented can be linear or branched. Examples of alkenyl groups include vinyl, 1-propenyl, 2-propenyl, isopropenyl, 2-butenyl, 3-butenyl, and 1,3-butadienyl, which are alkenyl groups or fluorinated alkenyl groups with 2 to 10 carbon atoms.

[0122] X 21 The alkynyl group can be either straight-chain or branched. Examples of alkynyl groups include ethynyl, 2-propynyl, and 1,1-dimethyl-2-propynyl, which are alkynyl groups or fluorinated alkynyl groups with 2 to 10 carbon atoms.

[0123] As X 21 The cycloalkyl group referred to may include, for example, cyclopentyl and cyclohexyl groups with 3 to 10 carbon atoms, or fluorinated cycloalkyl groups.

[0124] As X 21 The cycloalkenyl groups represented include, for example, cyclopentenyl and cyclohexenyl, which are cycloalkenyl groups or fluorinated cycloalkenyl groups with 3 to 10 carbon atoms.

[0125] As X 21 The aryl group represented can be, for example, aryl or fluorinated aryl groups with 6 to 10 carbon atoms, such as phenyl, tolyl, and xylyl.

[0126] As X 21 The alkoxy, alkenoxy, alkynoxy, cycloalkoxy, cycloalkenoxy, and aryloxy groups represented can be listed as R in the aforementioned general formula (2-1). 21 and R 22 The terms "alkoxy", "alkenoxy", "acetyloxy", "cycloalkoxy", "cycloalkenoxy", and "aryloxy" are used to represent these.

[0127] In general formula (2-2), if X 21 The presence of fluorine atoms or alkyl groups containing fluorine atoms is preferred because the increased degree of ionic dissociation due to their strong electron-withdrawing properties leads to higher ionic conductivity in the solution or composition. Furthermore, the presence of fluorine atoms is even more preferred because the increased mobility due to the smaller anion size results in very high ionic conductivity in the solution or composition.

[0128] Furthermore, if X 21 If the number of carbon atoms is 6 or less, there is a tendency for the above-mentioned ionic conductivity to be relatively high. Therefore, it is preferred, more preferably, to have 1 to 4 carbon atoms, and even more preferably, to have 1 to 3 carbon atoms.

[0129] Specifically, trifluoromethyl, trifluoromethoxy, trifluoroethoxy, etc. can be listed, with trifluoromethyl being particularly preferred due to its small anionic size.

[0130] In general formula (2-2), M1 m＋ With M1 in general formula (2-1) m＋ The meanings are the same, and the specific examples and preferred examples are also the same.

[0131] The following are specific examples of the anionic structures of compounds represented by general formula (2-2), but are not limited to them.

[0132] [Chemical Formula 15] Compound (2) is preferably at least one compound selected from the group consisting of difluorophosphate, fluorosulfonate and trifluoromethanesulfonate, and more preferably at least one compound selected from the group consisting of lithium difluorophosphate, lithium fluorosulfonate and lithium trifluoromethanesulfonate.

[0133] Compound (3): at least one compound selected from the group consisting of the compound represented by the following general formula (3-1), the compound represented by the following general formula (3-2), and the compound represented by the following general formula (3-3).

[0134] [Chemical Formula 16] In general formulas (3-1) to (3-3), R 31 ~R 36 Each of the organic groups is independently composed of a fluorine atom or selected from alkoxy groups having 1 to 10 carbon atoms, alkenoxy groups having 2 to 10 carbon atoms, alkynoxy groups having 2 to 10 carbon atoms, cycloalkoxy groups having 3 to 10 carbon atoms, cycloalkenoxy groups having 3 to 10 carbon atoms, and aryloxy groups having 6 to 10 carbon atoms, wherein the organic group may also optionally contain a fluorine atom, an oxygen atom, or an unsaturated bond.

[0135] X 31 ~X 33 Each of the following is an organic group independently composed of a fluorine atom, or selected from alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, cycloalkenyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkenoxy groups having 2 to 10 carbon atoms, alkynoxy groups having 2 to 10 carbon atoms, cycloalkoxy groups having 3 to 10 carbon atoms, cycloalkenoxy groups having 3 to 10 carbon atoms, and aryloxy groups having 6 to 10 carbon atoms, wherein the organic group may optionally contain a fluorine atom, an oxygen atom, or an unsaturated bond.

[0136] Formula (3-1) contains at least one PF key. Formula (3-2) contains at least one of a PF key and an SF key. Formula (3-3) contains at least one SF key.

[0137] M1 m＋ It can be a proton, a metal cation, or an onium cation. m represents the valence of the corresponding cation.

[0138] As R 31 ~R 36 The alkoxy, alkenoxy, alkynoxy, cycloalkoxy, cycloalkenoxy, and aryloxy groups represented can be listed as R in the aforementioned general formula (2-1). 21 and R 22 The terms "alkoxy", "alkenoxy", "acetyloxy", "cycloalkoxy", "cycloalkenoxy", and "aryloxy" are used to represent these.

[0139] If R 31 ~R 36 The presence of fluorine atoms or alkoxy groups containing fluorine atoms independently increases the degree of ionic dissociation due to their strong electron-withdrawing properties, thus resulting in higher ionic conductivity in the solution or composition, which is preferred. Furthermore, the presence of fluorine atoms further enhances the ionic conductivity in the solution or composition by increasing the mobility due to the smaller anion size, making it even more preferred.

[0140] In addition, R 31 ~R 36 The number of carbon atoms is preferably 6 or less. If the number of carbon atoms is 6 or less, there is a tendency for the aforementioned ionic conductivity to be relatively high, which is therefore preferred.

[0141] As X 31 ~X 33 The alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, alkoxy, alkenyloxy, alkynoxy, cycloalkoxy, cycloalkenyloxy, and aryloxy groups represented can be listed as X in the aforementioned general formula (2-2). 21The terms alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, and aryloxy are used to represent these terms.

[0142] If X 31 ~X 33 The presence of fluorine atoms or alkyl groups containing fluorine atoms is preferred because the increased degree of ionic dissociation due to their strong electron-withdrawing properties leads to higher ionic conductivity in the solution or composition. Furthermore, the presence of fluorine atoms is even more preferred because the increased mobility due to the smaller anion size results in very high ionic conductivity in the solution or composition.

[0143] Furthermore, if X 31 ~X 33 When the number of carbon atoms is 6 or less, there is a tendency for the aforementioned ionic conductivity to be relatively high. Therefore, it is preferred, more preferably, to have 1 to 4 carbon atoms, and even more preferably, to have 1 to 3 carbon atoms. Specifically, trifluoromethyl, pentafluoroethyl, etc. can be listed, and trifluoromethyl with a small anion size is particularly preferred.

[0144] In general formulas (3-1) to (3-3), M1 m＋ With M1 in general formula (2-1) m＋ The meanings are the same, and the specific examples and preferred examples are also the same.

[0145] The following are specific examples of anionic structures of compounds represented by any of the general formulas (3-1) to (3-3), but are not limited thereto.

[0146] [Chemical Formula 17] [Chemical Formula 18] [Chemical Formula 19] Compound (3) is preferably at least one compound selected from the group consisting of bis(fluorosulfonyl)imide salt, (fluorosulfonyl)(difluorophosphoryl)imide salt, bis(trifluoromethanesulfonyl)imide salt, bis(difluorophosphoryl)imide salt, bis(pentafluoroethanesulfonyl)imide salt and (fluorosulfonyl)(trifluoromethanesulfonyl)imide salt, more preferably at least one compound selected from the group consisting of lithium bis(fluorosulfonyl)imide, lithium (fluorosulfonyl)(difluorophosphoryl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(difluorophosphoryl)imide, lithium bis(pentafluoroethanesulfonyl)imide and (fluorosulfonyl)(trifluoromethanesulfonyl)imide.

[0147] Compound (4): at least one compound selected from the group consisting of compounds represented by the following general formula (4-1) and compounds represented by the following general formula (4-2).

[0148] [Chemical Formula 20] In general formula (4-1), W 1 Represents boron, phosphorus, or silicon atoms, where n1 is 0-3, n2 is 0-4, and p is 0 or 1. R 41 This refers to an alkylene group having 1 to 10 carbon atoms, a haloalkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a haloarylene group having 6 to 20 carbon atoms (these groups optionally contain substituents or heteroatoms in their structure). Furthermore, when n1 is 2 or more, the presence of n1 R... 41 (Optional, each bonded to the other), R 42 Y represents a halogen atom. 1 and Y 2 Y represents oxygen or sulfur atoms independently, respectively. 3 Represents a carbon atom or a sulfur atom. Y 3 The carbon or sulfur atom represented has q oxo groups (=O) bonded to it. 3 When the atom is carbon, q is 1, Y 3 When q is a sulfur atom, it is 1 or 2. M a＋ This indicates an alkali metal cation, an alkaline earth metal cation, or an onium cation, where 'a' represents the valence of the corresponding cation. 'a' to 'd' are either 1 or 2 and satisfy a × b = c × d.

[0149] W 1 It represents boron atoms, phosphorus atoms, or silicon atoms, preferably boron atoms or phosphorus atoms.

[0150] R 41 The alkylene group can be linear or branched. Examples of alkylene groups with 1 to 10 carbon atoms include methylene, ethylene, n-propylene, isopropylene, n-butylene, and n-hexylene.

[0151] As R 41 The alkyl halide represented by the number of carbon atoms from 1 to 10 can be any group in which any hydrogen atom of the aforementioned alkyl halide is replaced by a halogen atom.

[0152] As R 41 The arylene groups representing 6 to 20 carbon atoms can include phenylene, naphthylene, etc.

[0153] As R 41 The halogenated aryl groups representing 6 to 20 carbon atoms can be listed as groups in which any hydrogen atom of the aforementioned aryl group is replaced by a halogen atom.

[0154] As R 41Preferably, methylene, ethylene, n-propylene, difluoromethylene, tetrafluoroethylene, hexafluoropropylene, and more preferably methylene.

[0155] As R 42 The halogen atom represented can be fluorine, chlorine, iodine, etc., with fluorine being preferred.

[0156] Y 1 and Y 2 Each can be represented independently as an oxygen atom or a sulfur atom, preferably both as oxygen atoms.

[0157] Y 3 It represents a carbon atom or a sulfur atom, preferably a carbon atom.

[0158] As M a＋ The alkali metal cations, alkaline earth metal cations, and onium cations represented can be exemplified as M1 in the aforementioned general formula (2-1). m＋ The specific examples and preferred examples of the alkali metal cations, alkaline earth metal cations, and onium cations listed are also the same.

[0159] Compounds represented by general formula (4-1) include tetrafluoroborate, bis(oxalate)borate, difluorooxalateborate, tri(oxalate) phosphate, difluorobis(oxalate) phosphate, tetrafluorooxalate phosphate, tri(oxalate) silicate, difluorobis(oxalate) silicate, difluoromalonate borate, tetrafluoromalonate phosphate, difluorosulfonylacetate borate, difluoromaleic acid borate, and difluorofumarate borate.

[0160] Compound (4) is preferably at least one compound selected from the group consisting of tetrafluoroborate, bis(oxalate)borate, difluorooxalateborate, tri(oxalate) phosphate, difluorobis(oxalate) phosphate, tetrafluorooxalate phosphate, difluoromalonate borate, and tetrafluoromalonate phosphate, and more preferably at least one compound selected from the group consisting of lithium tetrafluoroborate, lithium bis(oxalate)borate, lithium difluorooxalateborate, lithium tri(oxalate) phosphate, lithium difluorobis(oxalate) phosphate, lithium tetrafluorooxalate phosphate, lithium difluoromalonate borate, and lithium tetrafluoromalonate phosphate.

[0161] [Chemical Formula 21] In general formula (4-2), R 43 Y represents an alkylene group having 1 to 10 carbon atoms, a haloalkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a haloarylene group having 6 to 20 carbon atoms (these groups may optionally contain substituents or heteroatoms in their structure), where r is 0 or 1. 4 Represents a carbon atom or a sulfur atom. Y 4 The carbon or sulfur atom represented has s oxo groups (=O) bonded to it. 4When the atom is carbon, s is 1, Y 4 When is a sulfur atom, s is 1 or 2. W 2 R represents a boron atom or a phosphorus atom. 44 This represents a halogen atom. W 2 When the atom is boron, n3 is 2, W 2 When the atom is phosphorus, n3 is 4.

[0162] R 43 The alkylene group can be linear or branched. Examples of alkylene groups with 1 to 10 carbon atoms include methylene, ethylene, n-propylene, isopropylene, n-butylene, and n-hexylene.

[0163] As R 43 The alkyl halide represented by the number of carbon atoms from 1 to 10 can be any group in which any hydrogen atom of the aforementioned alkyl halide is replaced by a halogen atom.

[0164] As R 43 The arylene groups representing 6 to 20 carbon atoms can include phenylene, naphthylene, etc.

[0165] As R 43 The halogenated aryl groups representing 6 to 20 carbon atoms can be listed as groups in which any hydrogen atom of the aforementioned aryl group is replaced by a halogen atom.

[0166] As R 43 Preferably, methylene, ethylene, n-propylene, difluoromethylene, tetrafluoroethylene, hexafluoropropylene, and more preferably methylene.

[0167] As R 44 The halogen atom represented can be fluorine, chlorine, iodine, etc., with fluorine being preferred.

[0168] Y 4 It represents a carbon atom or a sulfur atom, preferably a carbon atom.

[0169] As compounds represented by general formula (4-2), compounds (4-2-a) to (4-2-d) can be listed below, with compound (4-2-a) being preferred.

[0170] [Chemical Formula 22] Compound (5): The compound represented by the following general formula (5).

[0171] [Chemical Formula 23] In general formula (5), R 51Each R represents a group having a carbon-carbon unsaturated bond independently. Multiple R groups exist. 52 At that time, multiple R 52 Each of the above can be independently represented as either a fluorine atom or an alkyl group having 1 to 10 carbon atoms, wherein the alkyl group optionally has at least one of a fluorine atom and an oxygen atom. v represents an integer from 2 to 4.

[0172] R 51 The group containing carbon-carbon unsaturated bonds can be linear or branched. Examples of groups containing carbon-carbon unsaturated bonds include alkenyl groups with 2 to 8 carbon atoms, such as vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, and 1,3-butadienyl; alkynyl groups with 2 to 8 carbon atoms, such as alkynyloxy, acetylenyl, 2-propynyl, and 1,1-dimethyl-2-propynyl; aryl groups with 6 to 12 carbon atoms, such as alkynyloxy, phenyl, tolyl, and xylylyl; and aryloxy groups derived from these groups. Furthermore, the above-mentioned groups may contain fluorine and oxygen atoms. Preferably, groups containing carbon-carbon unsaturated bonds with 6 or fewer carbon atoms are used. If the number of carbon atoms is 6 or fewer, there is a tendency for lower resistance when a coating is formed on the electrode. Specifically, groups selected from the group consisting of vinyl, allyl, 1-propenyl, acetylenyl, and 2-propynyl are preferred.

[0173] There are multiple R 52 At that time, multiple R 52 Each can be independently represented as either a fluorine atom or an alkyl group having 1 to 10 carbon atoms.

[0174] R 52 The alkyl group can be straight-chain or branched. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, and n-pentyl, which have 1 to 10 carbon atoms. Furthermore, the above groups may optionally have at least one of a fluorine atom and an oxygen atom.

[0175] If the group is selected from fluorine atom, methyl, ethyl, propyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl, then there is a tendency for the initial resistance to be lower when a coating is formed on the electrode, which is preferred in terms of output characteristics.

[0176] In general formula (5), v represents an integer from 2 to 4, preferably 3 or 4, and particularly preferably 4.

[0177] The following are specific examples of compounds represented by general formula (5), but are not limited thereto.

[0178] [Chemical Formula 24] Compound (5) is preferably at least one compound selected from the group consisting of trivinylmethylsilane, trivinylfluorosilane and tetravinylsilane.

[0179] Compound (6): The compound represented by the following general formula (6).

[0180] [Chemical Formula 25] In general formula (6), R 61 and R 62 Each of the following can be independently represented: a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms optionally substituted with an alkyl group. R 61 and R 62 Any hydrogen atom in the alkyl, alkenyl, and aryl groups may be optionally substituted with a halogen atom. n6 is 0 or 1.

[0181] As R 61 and R 62 When it is an alkyl group with 1 to 2 carbon atoms, examples include methyl and ethyl.

[0182] R 61 and R 62 When the alkenyl group has 2 to 5 carbon atoms, it can be either linear or branched. Examples of alkenyl groups include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, and 1,3-butadienyl.

[0183] As R 61 and R 62 It refers to an aryl group that is optionally substituted with an alkyl group and has 6 to 10 carbon atoms, such as phenyl, tolyl, xylyl, etc.

[0184] At least one of the hydrogen atoms in the aforementioned alkyl, alkenyl, and aryl groups can be replaced by a halogen atom. Examples of halogen atoms include fluorine, bromine, and iodine, with fluorine being preferred.

[0185] R 61 and R 62 The preferred representation is a hydrogen atom.

[0186] When n6 is 0, R 61 The bonded carbon atom and R 62 The carbon atoms are bonded by single bonds.

[0187] Compound (6) is preferably at least one compound selected from the group consisting of 1,3,2-dioxothiacyclopentane-2,2-dioxide and 1,3,2-dioxothiacyclohexane-2,2-dioxide.

[0188] The following are specific examples of compounds represented by general formula (6), but are not limited thereto.

[0189] [Chemical Formula 26] Compound (7): at least one compound selected from the group consisting of compounds represented by the following general formula (7-1) and compounds represented by the following general formula (7-2).

[0190] [Chemical Formula 27] In general formula (7-1), R 70 ~R 73 Each of these can be used independently to represent a hydrogen atom, a fluorine atom, an alkyl group with 1 to 5 carbon atoms, or a fluoroalkyl group with 1 to 4 carbon atoms. n71 represents an integer from 1 to 3.

[0191] In general formula (7-2), R 74 ~R 79 Each of these can be used independently to represent a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, or a fluoroalkyl group with 1 to 4 carbon atoms. n72 represents an integer from 0 to 2.

[0192] In general formula (7-1), R is... 70 ~R 73 The alkyl group represented can be either straight-chain or branched. Examples include alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and n-pentyl.

[0193] As R 70 ~R 73 The fluoroalkyl group referred to can be linear or branched. For example, fluoroalkyl groups with 1 to 4 carbon atoms can be listed, such as trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, and 1,1,1,3,3,3-hexafluoroisopropyl.

[0194] R 70 ~R 73 Preferably, it is a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and more preferably a hydrogen atom.

[0195] In general formula (7-1), n71 represents an integer from 1 to 3, which can be 1 or 2, preferably 1.

[0196] Examples of compounds represented by general formula (7-1) include 1,3-propenyl sulfonyl lactone (1-propenyl-1,3-sulfonic acid lactone), 1,4-butene sulfonyl lactone, 2,4-pentene sulfonyl lactone, 3,5-pentene sulfonyl lactone, 1-fluoro-1,3-propenyl sulfonyl lactone, 1-trifluoromethyl-1,3-propenyl sulfonyl lactone, 1,1,1-trifluoro-2,4-butene sulfonyl lactone, 1,4-butene sulfonyl lactone, and 1,5-pentene sulfonyl lactone.

[0197] In general formula (7-2), R is used as 74 ~R 79 The alkyl group represented can be either straight-chain or branched. Examples include alkyl groups with 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0198] As R 74 ~R 79 The fluoroalkyl group referred to can be linear or branched. For example, fluoroalkyl groups with 1 to 4 carbon atoms can be listed, such as trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, and 1,1,1,3,3,3-hexafluoroisopropyl.

[0199] R 74 ~R 79 Preferably, it is a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and more preferably a hydrogen atom.

[0200] In general formula (7-2), n72 represents an integer from 0 to 2, which can be 0 or 1, preferably 0.

[0201] When n72 is 0, R 76 and R 77 The bonded carbon atom and R 78 and R 79 The carbon atoms are bonded by single bonds.

[0202] Examples of compounds represented by general formula (7-2) include 1,3-propanesulfonyl lactone, α-trifluoromethyl-γ-sulfonyl lactone, β-trifluoromethyl-γ-sulfonyl lactone, γ-trifluoromethyl-γ-sulfonyl lactone, α-methyl-γ-sulfonyl lactone, α,β-di(trifluoromethyl)-γ-sulfonyl lactone, α,α-di(trifluoromethyl)-γ-sulfonyl lactone, α-heptafluoropropyl-γ-sulfonyl lactone, 1,4-butanesulfonyl lactone, and 1,5-pentanesulfonyl lactone.

[0203] Compound (7) is preferably at least one compound selected from the group consisting of 1,3-propanesulfonyl lactone and 1-propenyl-1,3-sulfonyl lactone.

[0204] Compound (8): The compound represented by the following general formula (8).

[0205] [Chemical Formula 28] In general formula (8), R 81 The alkylene group has 1 to 6 carbon atoms, wherein the carbon-carbon bonds in the alkylene group optionally contain oxygen atoms, any hydrogen atom in the alkylene group is optionally substituted with an alkyl group, and any hydrogen atom in the alkylene group and the alkyl group is optionally substituted with a halogen atom.

[0206] R 81 The alkylene groups represented by carbon atoms with 1 to 6 carbon atoms can be straight-chain or branched, and examples include methylene, ethylene, n-propylene, isopropylene, n-butylene, and n-hexylene.

[0207] Compound (8) is preferably at least one compound selected from the group consisting of 1,2-ethanedisulfonic anhydride and 1,3-propanedisulfonic anhydride.

[0208] Compound (9): The compound represented by the following general formula (9).

[0209] [Chemical Formula 29] In general formula (9), R 91 and R 92 Each can be used to independently represent an alkyl group having 1 to 6 carbon atoms.

[0210] R 91 and R 92 The alkyl groups represented by carbon atoms with 1 to 6 carbon atoms can be straight-chain or branched, and examples include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, etc.

[0211] Compound (9) is preferably at least one compound selected from the group consisting of methanesulfonic anhydride and ethanesulfonic anhydride.

[0212] The non-aqueous electrolyte of this application can use a single compound as (IV), or two or more compounds can be mixed in any combination or ratio as (IV) depending on the application.

[0213] In the non-aqueous electrolyte of this application, the content of (I) (also referred to as "concentration of (I)") relative to the total amount of the non-aqueous electrolyte can be 0.01% by mass or more and 10% by mass or less. The lower limit of the concentration of (I) can be 0.08% by mass or more, 0.3% by mass or more, or 0.8% by mass or more. The upper limit of the concentration of (I) can be 8% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, or 1.5% by mass or less.

[0214] In the non-aqueous electrolyte of this application, the content of (IV) (also referred to as "concentration of (IV)") relative to the total amount of the non-aqueous electrolyte can be 0.01% by mass or more and 10% by mass or less. The lower limit of the concentration of (IV) can be 0.08% by mass or more, 0.1% by mass or more, or 0.2% by mass or more. The upper limit of the concentration of (IV) can be 8% by mass or less, 6% by mass or less, or 5% by mass or less.

[0215] In addition, for LiN(CF3SO2)2, LiN(FSO2)2, LiN(POF2)2, LiCF3SO3, LiC4F9SO3, NaN(CF3SO2)2, NaN(FSO2)2, NaN(POF2)2, NaCF3SO3, and NaC4F9SO3, their content relative to the total amount of non-aqueous electrolyte can be between 0.01% by mass and 20% by mass.

[0216] Regarding other additives The above is a description of the basic composition of the non-aqueous electrolyte of this application. As long as it does not impair the purpose of this application, additives commonly used in the non-aqueous electrolyte of this application may be added in any ratio.

[0217] When the non-aqueous electrolyte of this application contains other additives, the content of the other additives may be more than 0.01% by mass and less than 10.0% by mass relative to the total amount of the non-aqueous electrolyte.

[0218] Specific examples of other additives include vinylene carbonate (hereinafter sometimes referred to as "VC"), oligomers of vinylene carbonate (number-average molecular weight equivalent to polystyrene of 170-5000), fluoroethylene carbonate, trans-difluoroethylene carbonate, 1,6-hexanediisocyanate, ethynyl ethylene carbonate, methanedisulfonate, methanesulfonyl fluoride, tris(trimethylsilyl)borate, (ethoxy)pentafluorocyclotriphosphazene, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-hexafluoroisopropyl)disiloxane, tert-butylbenzene, tert-amylbenzene, fluorobenzene, cyclohexylbenzene, biphenyl, difluoroanisole, 4,5-dimethyl-1,3-dioxane-2-one, and nitrates, etc.

[0219] By including the above-mentioned additives in the non-aqueous electrolyte of this application, at least one of the following effects can be improved: overcharging prevention, negative electrode coating formation, and positive electrode protection.

[0220] The non-aqueous electrolyte of this application is suitable for use in non-aqueous electrolyte batteries (preferably non-aqueous electrolyte secondary batteries).

[0221] 2. Regarding non-aqueous electrolyte batteries The non-aqueous electrolyte battery of this application includes at least the non-aqueous electrolyte, negative electrode, and positive electrode described above. Furthermore, it may include a separator or casing, etc.

[0222] The non-aqueous electrolyte battery of this application preferably includes at least a positive electrode, a negative electrode, a separator, and the non-aqueous electrolyte of this application.

[0223] The non-aqueous electrolyte battery of this application is preferably a non-aqueous electrolyte secondary battery.

[0224] As a negative electrode, there are no particular limitations; materials in which alkali metal ions, primarily lithium or sodium ions, or alkaline earth metal ions can be reversibly inserted and extracted can be used.

[0225] For example, in the case of a lithium-ion secondary battery with lithium as the primary cation, the negative electrode active material constituting the negative electrode is a material capable of lithium-ion doping / dedoping. Examples include: carbon materials with a d-value of less than 0.340 nm for the (002) crystal plane in X-ray diffraction; carbon materials with a d-value greater than 0.340 nm for the (002) crystal plane in X-ray diffraction; oxides of one or more metals selected from Si, Sn, and Al; metals selected from Si, Sn, and Al, or alloys containing these metals, or alloys of these metals or alloys with lithium; and substances containing at least one of lithium titanium oxides. These negative electrode active materials can be used individually or in combination of two or more. Furthermore, lithium metal, metal nitrides, tin compounds, conductive polymers, etc., can be used.

[0226] For example, in the case of a sodium-ion secondary battery where the cation is primarily sodium, 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, phosphorus (elemental) materials such as red phosphorus and black phosphorus, phosphorus compounds such as Co-P, Cu-P, Sn-P, Ge-P, and Mo-P, antimony (elemental), and antimony compounds such as Sb / C and Bi-Sb can be used. These negative electrode active materials can be used individually or in combination.

[0227] As a positive electrode, there are no particular limitations; materials in which alkali metal ions, primarily lithium or sodium ions, or alkaline earth metal ions can be reversibly inserted and extracted can be used.

[0228] For example, when the cation is lithium, as a positive electrode material, lithium-containing transition metal composite oxides such as LiCoO2, LiNiO2, LiMnO2, and LiMn2O4 can be used; substances formed by mixing multiple transition metals such as Co, Mn, and Ni in these lithium-containing transition metal composite oxides; substances formed by replacing some of the transition metals in these lithium-containing transition metal composite oxides with other metals besides transition metals; phosphate compounds of transition metals such as LiFePO4, LiCoPO4, and LiMnPO4, which are called olivine; oxides such as TiO2, V2O5, and MoO3; sulfides such as TiS2 and FeS; or conductive polymers such as polyacetylene, poly(p-phenylene), polyaniline, and polypyrrole; activated carbon; free radical-generating polymers; and carbon materials.

[0229] Specifically, Li[Ni] can be listed as an example. 1 / 3 Mn 1 / 3 Co 1 / 3 O2, Li[Ni 0.45 Mn 0.35 Co 0.2 O2, Li[Ni 0.5 Mn 0.3 Co 0.2 O2, Li[Ni 0.6 Mn 0.2 Co 0.2 O2, Li[Ni 0.8 Mn 0.1 Co 0.1 O2 (hereinafter, sometimes 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, LiNi 0.85 Co 0.10 Al 0.05 O2, LiNi 0.87 Co 0.10 Al 0.03 O2, LiNi 0.90 Co 0.07 Al 0.03 O2, LiNi 0.6 Co 0.3 Al 0.1 O2, LiMn 1.5 Ni 0.5 O4, etc.

[0230] 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 Sodium-containing transition metal complex oxides such as O2; substances formed by mixing multiple transition metals such as Co, Mn, and Ni into these sodium-containing transition metal complex oxides; substances formed by replacing some of the transition metals in these sodium-containing transition metal complex oxides with other metals besides the transition metals; polyanionic compounds such as NaFePO4, NaVPO4F, Na3V2(PO4)3, and Na2Fe2(SO4)3; and compounds with the formula Na... a M b [Fe(CN)6] c The terms refer to sodium salts of Prussian blue analogues (M = Cr, Mn, Fe, Co, Ni, Cu or Zn, 0≤a≤2, 0.5≤b≤1.5, 0.5≤c≤1.5), oxides such as TiO2, V2O5, and MoO3, sulfides such as TiS2 and FeS, or conductive polymers such as polyacetylene, poly(p-phenylene), polyaniline, and polypyrrole, activated carbon, free radical-generating polymers, and carbon materials.

[0231] Acetylene black, Ketjen black, carbon fiber or graphite as conductive materials, polytetrafluoroethylene, polyvinylidene fluoride or SBR resin as binders can be added to the positive or negative electrode materials, and electrode sheets can be further molded into sheet shapes.

[0232] As a diaphragm to prevent contact between the positive and negative electrodes, nonwoven fabrics or porous sheets made of polypropylene, polyethylene, paper, or glass fiber can be used.

[0233] Electrochemical devices in shapes such as coin-shaped, cylindrical, square, or aluminum laminate can be assembled from the above elements.

[0234] Example The present application will be specifically described below using examples, but the present application is not limited to these examples.

[0235] [Examples 1-1 to 1-41, Comparative Examples 1-1 to 1-37] <Preparation of Non-Aqueous Electrolytes> In a glove box with a dew point below -60°C, EC, EMC, and DMC (as part of Comparative Example 1-1) were mixed in a volume ratio of EC:EMC:DMC = 25:50:25. Then, while maintaining the internal temperature below 40°C, LiPF6 (as part of Comparative Example 1-1) was added and dissolved under stirring to make its concentration 1.0 mol / L relative to the total amount of the non-aqueous electrolyte, and compound (1-1) (as part of Comparative Example 1-1) was added and dissolved to make its concentration 1.0% by mass relative to the total amount of the non-aqueous electrolyte. Then, a specified amount of pure water was added to generate hydrogen fluoride in the non-aqueous electrolyte, and the mixture was stirred for 1 hour to prepare the non-aqueous electrolyte.

[0236] In addition, except for changing the type or concentration of (I) as shown in Tables 1-5, changing the concentration of hydrogen fluoride by adding water as described above, and changing the type or concentration of (IV), the non-aqueous electrolytes of each example and comparative example were prepared using the same steps as the non-aqueous electrolytes of Comparative Examples 1-1 described above.

[0237] Twenty-four hours after the preparation of the non-aqueous electrolyte, the concentration of hydrogen fluoride was determined by titration with a triethylamine / acetone solution. Furthermore, in all examples and comparative examples, a Karl Fischer moisture analyzer confirmed that no water remained in the non-aqueous electrolyte after 24 hours of preparation.

[0238] The following shows the compounds used in the examples and comparative examples. Only compound numbers are shown in the table.

[0239] (1-1): Diethylene glycol anhydride (1-2): Thiohydroxyacetic anhydride (1-3): Sulfonyl diacetic anhydride (2-1): Lithium difluorophosphate (2-2): Lithium fluorosulfonate (2-3): Lithium trifluoromethanesulfonate (2-4): Lithium tetrafluoroborate (3-1): Lithium bis(fluorosulfonyl)imide (3-2): (Fluorosulfonyl)(difluorophosphoryl)imine lithium (3-3): Lithium bis(trifluoromethanesulfonyl)imide (3-4): Lithium bis(difluorophosphoryl)imide (4-1): Lithium dioxalatoborate (4-2): Lithium tris(oxalato)phosphate (4-3): Lithium difluorobis(oxalato)phosphate (5-1): Trivinylmethylsilane (5-2): Trivinylfluorosilane (5-3): Tetravinylsilane (6-1): 1,3,2-Dioxothiacyclopentane-2,2-dioxide (7-1): 1,3-Propanesulfonyl lactone (7-2): 1-Propylene-1,3-sulfonyl lactone (8-1): 1,2-Isodisulfonic anhydride (9-1): Methanesulfonic anhydride (Making of NCM811 positive electrode) To 92.0% by mass of LiNi 0.8 Mn 0.1 Co 0.1 O2 powder is mixed with 3.5% by mass of polyvinylidene fluoride (hereinafter also referred to as "PVDF") as a binder and 4.5% by mass of acetylene black as a conductive material, and further additives are added relative to LiNi 0.8 Mn 0.1 Co 0.1 A positive electrode paste was prepared by mixing 45% by mass of N-methyl-2-pyrrolidone (hereinafter also referred to as "NMP"), O2 powder, binder, and conductive material. The paste was coated on both sides of aluminum foil (A1085), dried, pressurized, and then punched into 4cm×5cm pieces to obtain the experimental NCM811 positive electrode.

[0240] (Production of natural graphite anode) A negative electrode paste was prepared by mixing 97.0% by weight of natural graphite powder, 2.0% by weight of styrene-butadiene rubber (hereinafter referred to as "SBR") as a binder, 1.0% by weight of sodium carboxymethyl cellulose (hereinafter referred to as "CMC"), and water. This paste was coated onto one side of a copper foil, dried, pressurized, and then die-cut into 4.5cm × 5.5cm pieces, thus obtaining the experimental natural graphite negative electrode.

[0241] (Fabrication of silicon-containing graphite anodes) A negative electrode paste was prepared by mixing 7.0% by mass of nano-silicon, 3.0% by mass of conductive material (manufactured by Denka Company Limited, HS-100), 2.0% by mass of carbon nanofibers (manufactured by Showa Denko KK, 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 into 4.5cm × 5.5cm pieces, thus obtaining the experimental silicon-containing graphite negative electrode.

[0242] (The fabrication of non-aqueous electrolyte batteries as described in Tables 1-5) In an argon atmosphere with a dew point below -50°C, the terminals were fused to the aforementioned NCM811 positive electrode, and then sandwiched between two polyethylene separators (5cm × 6cm). Further, two natural graphite negative electrodes with pre-fused terminals were used to sandwich the outer sides, ensuring the active material surfaces of the negative and positive electrodes were aligned. These were then placed into an aluminum-laminated bag with an opening on one side, and the prepared non-aqueous electrolyte was vacuum-injected. The opening was then sealed with heat, thus producing the aluminum-laminated non-aqueous electrolyte batteries of the examples and comparative examples described in Tables 1-5 below.

[0243] (Evaluation of non-aqueous electrolyte batteries) -Initial charge and discharge- The fabricated non-aqueous electrolyte battery was placed in a 25°C constant temperature bath and connected to a charge / discharge device under these conditions. The charge / discharge rate was 0.38 mA / cm². 2 Charge to 4.2V at a current density of 0.38mA / cm². Maintain 4.2V for 1 hour, then charge at 0.38mA / cm². 2 Discharge the battery to 2.5V using the specified current density. Perform a total of three charge-discharge cycles, setting this as one cycle, to stabilize the battery. Use the discharge capacity of the third cycle as the initial charge-discharge capacity.

[0244] <Initial Resistance> After initial charge and discharge at 25℃ and 0.38 mA / cm 2 Charge to 4.2V, and then measure the resistance value using an impedance analyzer.

[0245] <High-Temperature Storage Characteristics> With a charging upper limit voltage of 4.2V and a charging current of 0.38mA / cm 2 The non-aqueous electrolyte batteries, after the initial charge-discharge cycle, were charged and then removed from the charge-discharge device maintained at 25°C and stored in a 60°C constant temperature bath for 14 days. Then, they were placed back into the charge-discharge device maintained at 25°C at a rate of 0.38 mA / cm². 2Discharge to a discharge cutoff voltage of 2.5V, and use the following formula to calculate the discharge capacity retention rate after storage at 60℃.

[0246] (Discharge capacity retention rate after storage at 60℃) Discharge capacity retention (%) = (Discharge capacity after storage at 60℃ / Initial charge / discharge capacity) × 100 (Resistance value after storage at 60℃) Next, at 25℃ and 0.38mA / cm 2 Charge to 4.2V, and then measure the resistance value using an impedance analyzer.

[0247] In Tables 1-5 below, the initial resistance values ​​represent relative values ​​when Comparative Example 1-1 is set to 100; "E1" represents the discharge capacity retention rate after storage at 60°C (relative value when Comparative Example 1-1 is set to 100); and "E2" represents the resistance value after storage at 60°C (relative value when Comparative Example 1-1 is set to 100). The concentration of hydrogen fluoride (ppm) is the mass-based concentration.

[0248] [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] As shown in Tables 1-4, when comparing under the same conditions of type and concentration of (IV), the initial resistance of the non-aqueous electrolyte battery containing the non-aqueous electrolyte of the examples is lower than that of the non-aqueous electrolyte battery containing the comparative examples. Furthermore, it is known that the E1 of the non-aqueous electrolyte battery containing the non-aqueous electrolyte of the examples is larger than that of the non-aqueous electrolyte battery containing the comparative examples, and the E2 of the non-aqueous electrolyte battery containing the non-aqueous electrolyte of the examples is smaller than that of the non-aqueous electrolyte battery containing the comparative examples.

[0249] Furthermore, as shown in Table 5, if the concentration of (I) is 0.01% by mass or more and 5.0% by mass or less, the initial resistance reduction effect is easily achieved; if it is 0.1% by mass or more and 1.5% by mass or less, the initial resistance is the lowest. It is also known that the E1 of the non-aqueous electrolyte battery containing the non-aqueous electrolyte of the embodiment is larger than that of the non-aqueous electrolyte battery containing the non-aqueous electrolyte of the comparative example, and the E2 of the non-aqueous electrolyte battery containing the non-aqueous electrolyte of the embodiment is smaller than that of the non-aqueous electrolyte battery containing the non-aqueous electrolyte of the comparative example.

[0250] [Examples 2-1 to 2-23, Comparative Examples 2-1 to 2-23] <Preparation of Non-Aqueous Electrolytes> In a glove box with a dew point below -60°C, EC, EMC, and DMC (as part of (III)) were mixed in a volume ratio of EC:EMC:DMC = 25:50:25. Then, while maintaining the internal temperature below 40°C, LiPF6 (as part of (II)) was added and dissolved under stirring to make its concentration 1.0 mol / L relative to the total amount of the non-aqueous electrolyte; compound (1-1) (as part of (I)) was added and dissolved to make its concentration 1.0% by mass relative to the total amount of the non-aqueous electrolyte; and FEC and VC (as other additives) were added and dissolved to make their concentrations 5.0% by mass and 1.0% by mass relative to the total amount of the non-aqueous electrolyte, respectively. Then, pure water was added to generate hydrogen fluoride in the non-aqueous electrolyte, and the mixture was stirred for 1 hour to prepare the non-aqueous electrolyte of Comparative Example 2-1.

[0251] In addition, except for changing the type or concentration of (I) as shown in Tables 6-8, changing the concentration of hydrogen fluoride by adding water as described above, and changing the type or concentration of (IV), the non-aqueous electrolytes of each example and comparative example were prepared using the same steps as the non-aqueous electrolyte of Comparative Example 2-1 described above.

[0252] (The fabrication of non-aqueous electrolyte batteries is described in Tables 6-8) In an argon atmosphere with a dew point below -50°C, the terminals were fused to the aforementioned NCM811 positive electrode, and then two polyethylene separators (5cm × 6cm) were used to clamp both sides of the positive electrode. Further, two silicon-containing graphite negative electrodes with pre-fused terminals were used to clamp the outer side of the positive electrode, ensuring that the active material surfaces of the negative and positive electrodes were facing each other. These were then placed into an aluminum-laminated bag with an opening on one side, and the prepared non-aqueous electrolyte was vacuum-injected. The opening was then sealed with heat, thereby producing the aluminum-laminated non-aqueous electrolyte batteries of the examples and comparative examples described in Tables 6-8 below.

[0253] (Evaluation of non-aqueous electrolyte batteries) -Initial charge and discharge- The fabricated non-aqueous electrolyte battery was placed in a 25°C constant temperature bath and connected to a charge / discharge device under these conditions. The charge / discharge rate was 0.38 mA / cm². 2 Charge to 4.2V at a current density of 0.38mA / cm². Maintain 4.2V for 1 hour, then charge at 0.38mA / cm². 2 Discharge the battery to 2.5V using a current density of 1. Perform a total of 3 charge-discharge cycles to stabilize the battery.

[0254] <Initial Resistance> After initial charge and discharge at 25℃ and 0.38 mA / cm 2 Charge to 4.2V, and then measure the resistance value using an impedance measurement device.

[0255] <Cyclic performance test at 25°C> Charge-discharge tests were conducted at an ambient temperature of 25°C to evaluate cycle characteristics. The circuit was charged to 4.2V and discharged to 2.5V at a rate of 1.9mA / cm. 2 The current density was repeatedly charged and discharged. Then, the degradation of the battery cell was evaluated using the discharge capacity retention rate after 200 cycles. The discharge capacity retention rate after 200 cycles was calculated using the following formula. In addition, the discharge capacity of the first cycle in the cycle characteristic test at an ambient temperature of 25°C was set as the initial discharge capacity.

[0256] (Discharge capacity retention after 200 cycles) Discharge capacity retention (%) = (Discharge capacity after 200 cycles / Initial discharge capacity) × 100 (Resistance value after 200 cycles) At 25℃, 0.38mA / cm 2 The non-aqueous electrolyte battery after the above cycle characteristic test was charged to 4.2V, and the resistance value was measured by impedance measurement in this state.

[0257] In Tables 6-8 below, the initial resistance values ​​represent relative values ​​when Comparative Example 2-1 is set to 100; "E3" represents the discharge capacity retention rate after the cycle characteristic test at 25°C (relative value when Comparative Example 2-1 is set to 100); and "E4" represents the resistance value after the cycle characteristic test at 25°C (relative value when Comparative Example 2-1 is set to 100). The concentration of hydrogen fluoride (ppm) is the mass-based concentration.

[0258] [Table 6] [Table 7] [Table 8] As shown in Tables 6-8, the initial resistance of the non-aqueous electrolyte battery containing the non-aqueous electrolyte of the embodiments is lower than that of the non-aqueous electrolyte battery containing the comparative examples. Furthermore, it is known that the E3 of the non-aqueous electrolyte battery containing the non-aqueous electrolyte of the embodiments is larger than that of the non-aqueous electrolyte battery containing the comparative examples, and the E4 of the non-aqueous electrolyte battery containing the non-aqueous electrolyte of the embodiments is smaller than that of the non-aqueous electrolyte battery containing the comparative examples.

[0259] Industrial applicability According to this application, it is possible to provide a non-aqueous electrolyte that can reduce the initial resistance of a non-aqueous electrolyte battery and a non-aqueous electrolyte battery with low initial resistance.

[0260] Although this application has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of this application.

[0261] This application is based on Japanese Patent Application No. 2023-123775, filed on July 28, 2023, the contents of which are incorporated herein by reference.

Claims

1. A nonaqueous electrolyte, which is a nonaqueous electrolyte containing (I) a compound represented by the following general formula (1), (II) a solute, (III) a nonaqueous organic solvent, and hydrogen fluoride, wherein the concentration of the hydrogen fluoride with respect to the total amount of the nonaqueous electrolyte is 0.1 mass ppm or more and 180 mass ppm or less, [Chemical Formula 1] ###0001### 2. The nonaqueous electrolyte according to claim 1, further containing (IV) at least one compound selected from the group consisting of the following compounds (2) to (9): Compound (2): at least one compound selected from the group consisting of a compound represented by the following general formula (2-1) and a compound represented by the following general formula (2-2), [Chemical Formula 2] ###0002### Compound (3): at least one compound selected from the group consisting of a compound represented by the following general formula (3-1), a compound represented by the following general formula (3-2), and a compound represented by the following general formula (3-3), [Chemical Formula 3] ###0003### General formula (3-1) contains at least one P-F bond, general formula (3-2) contains at least one of a P-F bond and an S-F bond, and general formula (3-3) contains at least one S-F bond, Compound (4): at least one compound selected from the group consisting of a compound represented by the following general formula (4-1) and a compound represented by the following general formula (4-2), [Chemical Formula 4] ###0004### [Chemical Formula 5] ###0005### Compound (5): a compound represented by the following general formula (5), [Chemical Formula 6] ###0006### Compound (6): a compound represented by the following general formula (6), [Chemical Formula 7] ###0007### Compound (7): at least one compound selected from the group consisting of a compound represented by the following general formula (7-1) and a compound represented by the following general formula (7-2), [Chemical Formula 8] ###0008### Compound (8): a compound represented by the following general formula (8), [Chemical Formula 9] ###0009### Compound (9): a compound represented by the following general formula (9), [Chemical Formula 10] ###0010### the concentration of the hydrogen fluoride with respect to the total amount of the nonaqueous electrolyte is 1 mass ppm or more and 70 mass ppm or less. the content of the (I) with respect to the total amount of the nonaqueous electrolyte is 0.01 mass% or more and 10 mass% or less. the content of the (IV) with respect to the total amount of the nonaqueous electrolyte is 0.01 mass% or more and 10 mass% or less. ， In General Formula (1), R 1 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group, and X represents an oxygen atom, a sulfur atom, or a SO2 group.​ the compound represented by the general formula (1) is at least one compound selected from the group consisting of diglycolic anhydride, methyl diglycolic anhydride, dimethyl diglycolic anhydride, ethyl diglycolic anhydride, vinyl diglycolic anhydride, tetrafluorodiglycolic anhydride, allyl diglycolic anhydride, thiohydroxyacetic anhydride, and sulfonyldiacetic anhydride. the compound (2) is at least one compound selected from the group consisting of lithium difluorophosphate, lithium fluorosulfonate, and lithium trifluoromethanesulfonate. the compound (3) is at least one compound selected from the group consisting of lithium bis(fluorosulfonyl)imide, lithium (fluorosulfonyl)(difluorophosphoryl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(difluorophosphoryl)imide, lithium bis(pentafluoroethanesulfonyl)imide, and lithium (fluorosulfonyl)(trifluoromethanesulfonyl)imide. ， In General Formula (2-1), R 21 and R 22 are each independently a fluorine atom, or an organic group selected from an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group optionally has a fluorine atom, an oxygen atom, and an unsaturated bond, and General Formula (2-1) includes at least one P-F bond, In General Formula (2-2), X 21 is a fluorine atom, or an organic group selected from an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, the organic group optionally containing at least one fluorine atom, and the organic group optionally having an oxygen atom and an unsaturated bond, In General Formula (2-1) and General Formula (2-2), M1 m＋ is a proton, a metal cation, or an onium cation, and m represents the valence of the corresponding cation; ​ ​ ， In General Formulae (3-1) to (3-3), R 31 36 each independently is a fluorine atom or an organic group selected from an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and a fluorine atom, an oxygen atom, and an unsaturated bond are optionally present in the organic group,​ X 31 ~X 33 each independently is a fluorine atom, or an organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and in which organic group a fluorine atom, an oxygen atom, and an unsaturated bond are optionally present, ​ M1 m＋ is a proton, a metal cation or an onium cation, m denotes the valence of the respective cation; ​ ​ ， In general formula (4-1), W 1 Represents boron, phosphorus, or silicon atoms, where n1 is 0-3, n2 is 0-4, p is 0 or 1, and R 41 This refers to alkylene groups with 1 to 10 carbon atoms, haloalkylene groups with 1 to 10 carbon atoms, arylene groups with 6 to 20 carbon atoms, or haloarylene groups with 6 to 20 carbon atoms. These groups optionally contain substituents or heteroatoms in their structure. Furthermore, when n1 is 2 or more, the n1 R groups present... 41 Choose to bond with each other separately, R 42 Y represents a halogen atom. 1 and Y 2 Y represents oxygen or sulfur atoms independently, respectively. 3 Y represents a carbon atom or a sulfur atom. 3 The carbon or sulfur atom represented has q oxo groups (=O) bonded to it, Y 3 When the atom is carbon, q is 1, Y 3 When q is a sulfur atom, it is 1 or 2, and M is... a＋ This indicates an alkali metal cation, an alkaline earth metal cation, or an onium cation, where 'a' represents the valence of the corresponding cation, and 'a' to 'd' are either 1 or 2 and satisfy a × b = c × d. ​ ， In General Formula (4-2), R 43 represents an alkylene group having 1 to 10 carbon atoms, a haloalkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a haloarylene group having 6 to 20 carbon atoms, these groups optionally having a substituent or a hetero atom in the structure thereof, r is 0 or 1, Y 4 represents a carbon atom or a sulfur atom, Y 4 represents a carbon atom or a sulfur atom, Y 4 when the carbon atom, s is 1, Y 4 when the sulfur atom, s is 1 or 2, W 2 represents a boron atom or a phosphorus atom, R 44 represents a halogen atom, W 2 when the boron atom, n3 is 2, W 2 when the phosphorus atom, n3 is 4; ​ ​ ， In General Formula (5), R 51 each independently represents a group having a carbon-carbon unsaturated bond, and a plurality of R 52 may be the same or different from each other, and each independently represents a group having a carbon-carbon unsaturated bond, and a plurality of R 52 each independently represents a fluorine atom or an alkyl group having 1 to 10 carbon atoms, the alkyl group optionally having at least any one of a fluorine atom and an oxygen atom, and v represents an integer of 2 to 4; ​ ​ ， In General Formula (6), R 61 and R 62 each independently represent a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms optionally substituted with an alkyl group, any hydrogen atom of the alkyl group, the alkenyl group, and the aryl group represented by R 61 and R 62 is optionally substituted with a halogen atom, and n6 is 0 or 1. ​ ​ ， In General Formula (7-1), R 70 73 each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms, and n71 represents an integer of 1 to 3.​ In General Formula (7-2), R 74 79 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms, and n72 represents an integer of 0 to 2.​ ​ ​ ， In General Formula (8), R 81 represents an alkylene group having 1 to 6 carbon atoms, the carbon-carbon bond in the alkylene group optionally includes an oxygen atom, any hydrogen atom of the alkylene group is optionally substituted with an alkyl group, and any hydrogen atom of the alkylene group and the alkyl group is optionally substituted with a halogen atom; ​ ​ ， In General Formula (9), R 91 and R 92 each independently represents an alkyl group having 1 to 6 carbon atoms.

3. The nonaqueous electrolyte according to claim 1, wherein ​ 4. The nonaqueous electrolyte according to claim 1, wherein ​ 5. The nonaqueous electrolyte according to claim 1, wherein ​ 6. The nonaqueous electrolyte according to claim 1, wherein ​ 7. The nonaqueous electrolyte according to claim 2, wherein ​ 8. The nonaqueous electrolyte according to claim 2, wherein ​ 9. The nonaqueous electrolyte according to claim 2, wherein The compound (4) is at least one compound selected from the group consisting of lithium tetrafluoroborate, lithium bis(oxalato)borate, lithium difluoro(oxalato)borate, lithium tris(oxalato)phosphate, lithium difluorobis(oxalato)phosphate, lithium tetrafluorophosphate, lithium difluoropropionate, lithium tetrafluorophosphate, tetrafluoro(pyridinecarboxylate)phosphate, and difluoro(pyridinecarboxylate)borate.

10. The nonaqueous electrolyte according to claim 2, wherein The compound (5) is at least one compound selected from the group consisting of trivinylmethylsilane, trivinylfluorosilane, and tetravinylsilane.

11. The nonaqueous electrolyte according to claim 2, wherein The compound (6) is at least one compound selected from the group consisting of 1,3,2-dioxathiolane-2,2-dioxide and 1,3,2-dioxathiane-2,2-dioxide.

12. The nonaqueous electrolyte according to claim 2, wherein The compound (8) is at least one compound selected from the group consisting of 1,2-ethanedisulfonic anhydride and 1,3-propanedisulfonic anhydride.

13. The nonaqueous electrolyte according to claim 2, wherein The compound (9) is at least one compound selected from the group consisting of methanesulfonic anhydride and ethanesulfonic anhydride.

14. The nonaqueous electrolyte of claim 1, wherein The (II) is at least one selected from the group consisting of LiPF6, LiSbF6, LiAsF6, LiClO4, LiAlO2, LiAlCl4, LiCl, and LiI, or at least one selected from the group consisting of NaPF6, NaSbF6, NaAsF6, NaClO4, NaAlO2, NaAlCl4, NaCl, and NaI.

15. The nonaqueous electrolyte of claim 1, wherein The (III) contains at least one selected from the group consisting of a cyclic ester, a chain ester, a cyclic ether, a chain ether, a sulfone compound, a sulfoxide compound, and an ionic liquid.

16. The nonaqueous electrolyte according to claim 15, wherein The cyclic ester is a cyclic carbonate, which is at least one selected from the group consisting of vinyl carbonate, propylene carbonate, and fluoroethylene carbonate.

17. The nonaqueous electrolyte of claim 15, wherein, The chain ester is a chain carbonate, which is at least one selected from the group consisting of methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.

18. A nonaqueous electrolyte battery at least comprising a positive electrode, a negative electrode, a separator, and the nonaqueous electrolyte according to any one of claims 1 to 17.

19. A method for reducing an initial resistance of a nonaqueous electrolyte battery containing a nonaqueous electrolyte, wherein a nonaqueous electrolyte containing (I) a compound represented by the following general formula (1), (II) a solute, (III) a nonaqueous organic solvent, and hydrogen fluoride is used as the nonaqueous electrolyte, and the concentration of the hydrogen fluoride with respect to the total amount of the nonaqueous electrolyte is 0.1 mass ppm or more and 180 mass ppm or less, [Chemical Formula 11] In General Formula (1), R 1 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group, and X represents an oxygen atom, a sulfur atom, or a SO2 group.​

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