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

Abstract

The present disclosure provides: a nonaqueous electrolytic solution containing a specific compound represented by general formula (1), a solute, and a nonaqueous organic solvent; a nonaqueous electrolytic solution battery comprising a positive electrode, a negative electrode and the nonaqueous electrolytic solution; and a method for producing a nonaqueous electrolytic solution battery having a step for preparing the nonaqueous electrolytic solution and a step for filling an empty cell provided with at least a positive electrode and a negative electrode, with the nonaqueous electrolytic solution.

Description

Technical Field

[0001] The present disclosure relates to a non-aqueous electrolyte, a non-aqueous electrolyte battery, and a method for manufacturing a non-aqueous electrolyte battery.

Background Art

[0002] Hitherto, as means for improving the durability such as cycle characteristics and high-temperature storage properties of non-aqueous electrolyte batteries, optimization of various battery components including active materials of the positive and negative electrodes has been studied. The non-aqueous electrolyte-related technology is no exception, and it has been proposed to suppress deterioration due to decomposition of the electrolyte on the surfaces of the active positive and negative electrodes using various additives. For example, Patent Document 1 proposes improving each battery characteristic such as high-temperature storage characteristics by adding vinylene carbonate to the electrolyte. This method prevents decomposition on the surface of the electrolyte by coating the electrode with a polymer film formed by polymerization of vinylene carbonate, but since lithium ions also have difficulty passing through this film, there are problems such as an increase in internal resistance and a large amount of gas generation during high-temperature storage. To solve this problem, the addition of lithium difluorophosphate disclosed in Patent Document 2 is effective, and it is known that a battery with suppressed increase in internal resistance and gas generation while maintaining high high-temperature storage characteristics can be obtained by using vinylene carbonate and lithium difluorophosphate together.

[0003] Also, as a single additive rather than a combination of multiple additives, Patent Document 3 discloses that adding a cyclic sulfur compound such as 1,3-propene sultone (PRS) can also suppress the amount of gas generation and increase in resistance.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

[0005] However, our inventors' investigation revealed that even with the addition of PRS, there is still room for improvement in suppressing the rise in initial resistance.

[0006] This disclosure is made in view of the above circumstances and aims to provide a non-aqueous electrolyte, a non-aqueous electrolyte battery, and a method for manufacturing a non-aqueous electrolyte battery that are excellent in suppressing the rise in initial resistance. [Means for solving the problem]

[0007] In view of the above problems, the present inventors conducted extensive research and discovered that a non-aqueous electrolyte battery with excellent effect in suppressing the rise in initial resistance can be obtained by using a non-aqueous electrolyte containing a compound represented by the following general formula (1), a solute, and a non-aqueous organic solvent, thus completing the present invention.

[0008] In other words, the inventors have found that the above problem can be solved by the following configuration. <1> A non-aqueous electrolyte containing a compound represented by the following general formula (1), a solute, and a non-aqueous organic solvent, The content of the compound represented by general formula (1) relative to the total amount of the compound represented by general formula (1), the solute, and the nonaqueous organic solvent is 0.03% by mass to 1.3% by mass. A non-aqueous electrolyte in which the solute is an ionic salt containing lithium ions. [ka] [In general formula (1), m and n are 2. A is -CH 2 -It is a base. D is -C 2 H 4 -Base or -C 3 H 6 -It is the basis. <2> A non-aqueous electrolyte containing a compound represented by the following general formula (1), a solute, and a non-aqueous organic solvent, The compound represented by the general formula (1) is at least one compound selected from the group consisting of compounds represented by (1a) to (1c), (1e) to (1f), (1h), (1k), and (1m) to (1r) below. The content of the compound represented by general formula (1) relative to the total amount of the compound represented by general formula (1), the solute, and the nonaqueous organic solvent is 0.03% by mass to 1.3% by mass. A non-aqueous electrolyte in which the solute is an ionic salt containing lithium ions.

change

[11] below) are also described below.

[0009] [1] A non-aqueous electrolyte containing a compound represented by the following general formula (1), a solute, and a non-aqueous organic solvent.

[0010] [ka]

[0011] [In general formula (1), m and n are independently 1 or 2. A is a single-bonded, linear hydrocarbon group having 1 to 5 carbon atoms, or a branched hydrocarbon group having 2 to 5 carbon atoms, where any hydrogen atom of the hydrocarbon group may be substituted with a fluorine atom, and oxygen atoms may be present between the carbon-carbon bonds in the hydrocarbon group. D is a linear hydrocarbon group having 1 to 5 carbon atoms, or a branched hydrocarbon group having 2 to 5 carbon atoms, where any hydrogen atom of the hydrocarbon group may be substituted with a fluorine atom, and oxygen atoms may be present between the carbon-carbon bonds in the hydrocarbon group. The total number of carbon atoms in A and D is 3 or more.]

[0012] [2] The non-aqueous electrolyte according to [1], wherein A is a -CH2- group, D is a -C2H4- group or a -C3H6- group, and both m and n are 2.

[0013] [3] The non-aqueous electrolyte according to [1], wherein the compound represented by the general formula (1) is at least one compound selected from the group consisting of compounds represented by (1a) to (1r) below. (1a) A=-CH2- group, D=-C2H4- group, m=1, n=1 (1b) A=-CH(CH3)- group, D=-C2H4- group, m=1, n=1 (1c)A=-C(CH3)2- group, D=-C2H4- group, m=1, n=1 (1d) A = single bond, D = -C3H6- group, m = 1, n = 1 (1e) A=-CH2- group, D=-C2H4- group, m=2, n=2 (1f) A=-CH(CH3)- group, D=-C2H4- group, m=2, n=2 (1g)A=-C(CH3)2- group, D=-C2H4- group, m=2, n=2 (1h)A=single bond, D=-C3H6- group, m=2, n=2 (1i) A=-CH2- group, D=-C3H6- group, m=1, n=1 (1j)A=-CH(CH3)- group, D=-C3H6- group, m=1, n=1 (1k)A=-C(CH3)2- group, D=-C3H6- group, m=1, n=1 (1l)A=single bond, D=-C4H8- group, m=1, n=1 (1m)A=-C2H4- group, D=-C2H4- group, m=1, n=1 (1n)A=-CH2- group, D=-C3H6- group, m=2, n=2 (1o)A=-CH(CH3)- group, D=-C3H6- group, m=2, n=2 (1p)A=-C(CH3)2- group, D=-C3H6- group, m=2, n=2 (1q) A = single bond, D = -C4H8- group, m = 2, n = 2 (1r)A=-C2H4- group, D=-C2H4- group, m=2, n=2

[0014] [4] The non-aqueous electrolyte according to [3], wherein the compound represented by the general formula (1) is at least one compound selected from the group consisting of the compounds represented by (1a), (1b), (1c), (1d), (1e), (1f), (1h), (1i), (1j), (1l), (1m), (1n), (1o), (1q), and (1r).

[0015] [5] The non-aqueous electrolyte according to [3] or [4], wherein the compound represented by the general formula (1) is the compound represented by (1e) or (1n).

[0016] [6] The nonaqueous electrolyte according to any one of [1] to [5], wherein the nonaqueous organic solvent contains at least one selected from the group consisting of cyclic carbonates and linear carbonates.

[0017] [7] The non-aqueous electrolyte according to [6], wherein the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene 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.

[0018] [8] A non-aqueous electrolyte according to any one of [1] to [7], wherein the content of the compound represented by general formula (1) relative to the total amount of the compound represented by general formula (1), the solute, and the non-aqueous organic solvent is 0.01% to 10.0% by mass. [9] Furthermore, the non-aqueous electrolyte according to any one of [1] to [8] contains at least one selected from vinylene carbonate, fluoroethylene carbonate, ethylene sulfate, lithium bis(oxalato)borate, lithium difluorooxalatoborate, lithium difluorobis(oxalato)phosphate, lithium tetrafluorooxalatophosphate, lithium bis(fluorosulfonyl)imide, lithium bis(difluorophosphonyl)imide, lithium (difluorophosphonyl)(fluorosulfonyl)imide, lithium difluorophosphate, lithium fluorosulfonate, and methanesulfonyl fluoride.

[10] A non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte as described in any one of items [1] to [9].

[11] The process of preparing a non-aqueous electrolyte as described in any one of items [1] to [9], and A step of filling an empty cell, which is equipped with at least a positive electrode and a negative electrode, with the non-aqueous electrolyte. A method for manufacturing a non-aqueous electrolyte battery. [Effects of the Invention]

[0019] According to this disclosure, it is possible to provide a non-aqueous electrolyte, a non-aqueous electrolyte battery, and a method for manufacturing a non-aqueous electrolyte battery that are excellent in suppressing the rise in initial resistance. [Modes for carrying out the invention]

[0020] The configurations and combinations thereof in the following embodiments are merely illustrative, and various modifications are possible without departing from the spirit of this disclosure. Furthermore, this disclosure is not limited by the embodiments, but is limited only by the claims.

[0021] In this specification, "~" is used to mean that the numbers written before and after it include the lower and upper limits, respectively.

[0022] In this specification, the initial resistance value refers to the resistance value of a non-aqueous electrolyte battery after the initial charge-discharge cycle to form the electrode film and the subsequent two charge-discharge cycles for battery stabilization. Specifically, it refers to the value obtained by charging the battery to 4.2V at 25°C and 20mA after the initial charge-discharge cycle to form the electrode film and the subsequent two charge-discharge cycles for battery stabilization, and then measuring the AC impedance at 25°C.

[0023] Furthermore, in this specification, the capacity value after the storage test refers to the capacity obtained when the battery, after the AC impedance measurement described above has been completed, is stored at 60°C for two weeks, discharged to 2.5V at 20mA at 25°C, charged to 4.2V at 20mA, and then discharged again to 2.5V, and the capacity obtained during this final discharge. Furthermore, in this specification, the resistance value after the storage test refers to the value obtained by measuring the AC impedance at 25°C after measuring the capacitance value after the above-mentioned storage test, and then charging it again to 4.2V at 20mA. Note that the capacitance and resistance after storage testing are sometimes simply referred to as "storage characteristics."

[0024] [1. Non-aqueous electrolyte] The non-aqueous electrolyte of this disclosure is a non-aqueous electrolyte containing a compound represented by the above general formula (1), a solute, and a non-aqueous organic solvent.

[0025] <(I) Regarding compounds represented by general formula (1)> The non-aqueous electrolyte of this disclosure contains a compound represented by general formula (1). Hereafter, the compound represented by general formula (1) may be referred to as "component (I)". When a non-aqueous electrolyte containing the compound represented by general formula (1) is used in a non-aqueous electrolyte battery (e.g., a lithium-ion secondary battery or a sodium-ion secondary battery), the compound represented by general formula (1) decomposes at least on either the positive electrode or the negative electrode, forming a film with good ion conductivity on at least one of the positive or negative electrode surfaces. This film is thought to suppress direct contact between the non-aqueous organic solvent or solute and the electrode active material, thereby lowering the Li or Na ion dissociation energy of the solute. As a result, the inventors estimate that this has the effect of suppressing the increase in the initial resistance of the non-aqueous electrolyte battery.

[0026] The following describes compounds represented by general formula (1).

[0027] [ka]

[0028] In general formula (1), m and n are independently either 1 or 2. A is a single-bonded, linear hydrocarbon group having 1 to 5 carbon atoms, or a branched hydrocarbon group having 2 to 5 carbon atoms, wherein any hydrogen atom of the hydrocarbon group may be substituted with a fluorine atom, and oxygen atoms may be present between the carbon-carbon bonds in the hydrocarbon group. D is a linear hydrocarbon group having 1 to 5 carbon atoms, or a branched hydrocarbon group having 2 to 5 carbon atoms, wherein any hydrogen atom in the hydrocarbon group may be substituted with a fluorine atom, and oxygen atoms may be present between carbon atoms in the hydrocarbon group. The total number of carbon atoms in A and D is 3 or more.

[0029] When A represents a linear hydrocarbon group having 1 to 5 carbon atoms, the linear hydrocarbon group having 1 to 5 carbon atoms is not particularly limited, but a linear alkyl group having 1 to 5 carbon atoms is preferred. Examples of linear alkyl groups having 1 to 5 carbon atoms include -CH2- groups, -C2H4- groups, -C3H6- groups, -C4H8- groups, etc. When A represents a branched hydrocarbon group having 2 to 5 carbon atoms, the branched hydrocarbon group having 2 to 5 carbon atoms is not particularly limited, but a branched alkyl group having 2 to 5 carbon atoms is preferred. Examples of branched alkyl groups having 2 to 5 carbon atoms include -CH(CH3)- groups, -C(CH3)2- groups, and -CH2CH(CH3)- groups. When D represents a linear hydrocarbon group having 1 to 5 carbon atoms, the linear hydrocarbon group having 1 to 5 carbon atoms can be the same as the linear hydrocarbon group having 1 to 5 carbon atoms when A represents a linear hydrocarbon group having 1 to 5 carbon atoms, and the preferred range is also the same. When D represents a branched hydrocarbon group having 2 to 5 carbon atoms, the branched hydrocarbon group having 2 to 5 carbon atoms can be the same as the branched hydrocarbon group having 2 to 5 carbon atoms when A represents a branched hydrocarbon group having 2 to 5 carbon atoms, and the preferred range is also the same. The sum of the number of carbon atoms in A and D is 3 or more. There is no particular upper limit to the sum of the number of carbon atoms in A and D, but for example, it is 10.

[0030] In the compound represented by general formula (1), when A represents a hydrocarbon group, the hydrocarbon group represented by D is preferable as the number of carbon atoms in the hydrocarbon group decreases within the range in which a stable cyclic structure can be formed, as this tends to reduce the resistance when a coating is formed. In particular, it is preferable that A is a -CH2- group and D is a -C2H4- group or a -C3H6- group. At least one of m and n is preferably 2 from the viewpoint of ease of synthesis, and it is more preferable that both m and n are 2 from the viewpoint of ease of synthesis. Therefore, compounds having a structure in which A is a -CH2- group, D is a -C2H4- group or a -C3H6- group, and both m and n are 2 are particularly preferred.

[0031] The compound represented by general formula (1) is preferably at least one selected from the group consisting of the compounds represented by (1a) to (1r) below. Furthermore, the compound represented by the general formula (1) may be at least one compound selected from the group consisting of the following compounds, which have a small total number of carbon atoms in A and D, from the viewpoint of suppressing the increase in initial resistance: (1a), (1b), (1c), (1d), (1e), (1f), (1h), (1i), (1j), (1l), (1m), (1n), (1o), (1q), and (1r). From the viewpoint of ease of synthesis, the compound represented by general formula (1) is more preferably the compound represented by (1e) or (1n).

[0032] (1a) A=-CH2- group, D=-C2H4- group, m=1, n=1 (1b) A=-CH(CH3)- group, D=-C2H4- group, m=1, n=1 (1c)A=-C(CH3)2- group, D=-C2H4- group, m=1, n=1 (1d) A = single bond, D = -C3H6- group, m = 1, n = 1 (1e) A=-CH2- group, D=-C2H4- group, m=2, n=2 (1f) A=-CH(CH3)- group, D=-C2H4- group, m=2, n=2 (1g)A=-C(CH3)2- group, D=-C2H4- group, m=2, n=2 (1h)A=single bond, D=-C3H6- group, m=2, n=2 (1i) A=-CH2- group, D=-C3H6- group, m=1, n=1 (1j)A=-CH(CH3)- group, D=-C3H6- group, m=1, n=1 (1k)A=-C(CH3)2- group, D=-C3H6- group, m=1, n=1 (1l)A=single bond, D=-C4H8- group, m=1, n=1 (1m)A=-C2H4- group, D=-C2H4- group, m=1, n=1 (1n)A=-CH2- group, D=-C3H6- group, m=2, n=2 (1o)A=-CH(CH3)- group, D=-C3H6- group, m=2, n=2 (1p)A=-C(CH3)2- group, D=-C3H6- group, m=2, n=2 (1q) A = single bond, D = -C4H8- group, m = 2, n = 2 (1r)A=-C2H4- group, D=-C2H4- group, m=2, n=2

[0033] In the non-aqueous electrolyte of this disclosure, the content of the compound represented by general formula (1) (hereinafter also referred to as "concentration of the compound represented by general formula (1)") relative to the total amount (100% by mass) of the compound represented by general formula (1), solute, and non-aqueous organic solvent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.2% by mass or more. The upper limit of the concentration of the compound represented by general formula (1) is preferably 10.0% by mass or less, more preferably 2.0% by mass or less, even more preferably 1.2% by mass or less, and particularly preferably 0.6% by mass or less. By setting the concentration of the compound represented by general formula (1) to 0.01% by mass or higher, it is easier to suppress the initial resistance increase of a non-aqueous electrolyte battery using the non-aqueous electrolyte. On the other hand, by setting the concentration of the compound represented by general formula (1) to 10.0% by mass or lower, it is possible to suppress excess residue in the electrolyte. If a saturation concentration of the compound represented by general formula (1) exists within the above preferred concentration range, it is preferable that the upper limit of the concentration range be the saturation concentration of the compound represented by general formula (1) from the viewpoint of suppressing the generation of excess insoluble components in the electrolyte. The above saturation concentration is at 25°C and 1 atm (=0.10132 MPa).

[0034] In one embodiment of the non-aqueous electrolyte of this disclosure, the compound represented by general formula (1) may be used as a single compound, or two or more compounds may be mixed in any combination and ratio according to the application.

[0035] The synthesis method for the compounds represented by the above general formula (1) is not particularly limited, but for example, compounds (1a), (1d), (1e), (1h), (1i), (1l), (1m), (1n), (1q), and (1r) can be obtained by oxidizing 1,3-dithiolane, 1,2-dithiolane, 1,3-dithiane, and 1,4-dithiane, which can be purchased from Tokyo Chemical Industry Co., Ltd. and others, in an aqueous hydrogen peroxide solution. Similarly, compounds (1b) and (1f) can be obtained by oxidizing 2-methyl-1,3-dithiolane, which is obtained by reacting ethanedithiol and acetaldehyde in water, in an aqueous hydrogen peroxide solution. Similarly, compounds (1j) and (1o) can be obtained by oxidizing 2-methyl-1,3-dithiane, which is obtained by reacting propanedithiol and acetaldehyde in water, in an aqueous hydrogen peroxide solution. Furthermore, compounds (1c) and (1g) can be obtained by similarly oxidizing 2,2-dimethyl-1,3-dithiolane, which is obtained by reacting ethanedithiol and acetone in water, in an aqueous hydrogen peroxide solution. Compounds (1k) and (1p) can be obtained by similarly oxidizing 2,2-dimethyl-1,3-dithiane, which is obtained by reacting propanedithiol and acetone in water, in an aqueous hydrogen peroxide solution.

[0036] (II) Regarding solutes The non-aqueous electrolyte of this disclosure contains a solute. The solute is not particularly limited, but it is preferably an ionic salt, and more preferably an ionic salt containing fluorine.

[0037] As solutes, for example, at least one cation selected from the group consisting of alkali metal ions such as lithium ions and sodium ions, alkaline earth metal ions such as magnesium ions, and quaternary ammonium, and hexafluorophosphate anion, tetrafluoroborate anion, perchlorate anion, hexafluoroarsenate anion, hexafluoroantimonate anion, trifluoromethanesulfonate anion, bis(trifluoromethanesulfonyl)imide anion, bis(pentafluoroethanesulfonyl)imide anion, (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl) It is preferable that the salt is an ionic salt consisting of a pair of at least one anion selected from the group consisting of nyl)imide anion, bis(fluorosulfonyl)imide anion, (trifluoromethanesulfonyl)(fluorosulfonyl)imide anion, (pentafluoroethanesulfonyl)(fluorosulfonyl)imide anion, tris(trifluoromethanesulfonyl)methide anion, bis(difluorophosphonyl)imide anion, (difluorophosphonyl)(trifluoromethanesulfonyl)imide anion, (difluorophosphonyl)(fluorosulfonyl)imide anion, and difluorophosphate anion.

[0038] These solutes may be used individually, or two or more may be mixed in any combination and ratio according to the application. In particular, considering the energy density, output characteristics, and lifespan of the non-aqueous electrolyte battery, it is preferable that the cation be at least one selected from the group consisting of lithium ions, sodium ions, magnesium ions, and quaternary ammonium compounds, and that the anion be at least one selected from the group consisting of hexafluorophosphate anion, tetrafluoroborate anion, bis(trifluoromethanesulfonyl)imide anion, bis(fluorosulfonyl)imide anion, bis(difluorophosphonyl)imide anion, (difluorophosphonyl)(fluorosulfonyl)imide anion, and difluorophosphate anion.

[0039] The total amount of solute in the non-aqueous electrolyte of this disclosure (hereinafter also referred to as "solute concentration") is not particularly limited, but the lower limit is preferably 0.5 mol / L or more, more preferably 0.7 mol / L or more, and even more preferably 0.9 mol / L or more. The upper limit of the solute concentration is preferably 5.0 mol / L or less, more preferably 4.0 mol / L or less, and even more preferably 2.0 mol / L or less. Setting the solute concentration to 0.5 mol / L or more can suppress the decrease in cycle characteristics and output characteristics of the non-aqueous electrolyte battery due to a decrease in ionic conductivity, and setting it to 5.0 mol / L or less can suppress the decrease in ionic conductivity and the decrease in cycle characteristics and output characteristics of the non-aqueous electrolyte battery due to an increase in the viscosity of the non-aqueous electrolyte.

[0040] <(III) Regarding non-aqueous organic solvents> The type of non-aqueous organic solvent used in the non-aqueous electrolyte of this disclosure is not particularly limited as long as it can dissolve the compound represented by the above general formula (1) and the solute. For example, any non-aqueous organic solvent such as carbonates, esters, ethers, lactones, nitriles, imides, and sulfones can be used. Specifically, ethyl methyl carbonate (hereinafter also referred to as "EMC"), dimethyl carbonate (hereinafter also referred to as "DMC"), diethyl carbonate (hereinafter also referred to as "DEC"), methyl propyl carbonate, ethyl propyl carbonate, methyl butyl carbonate, 2,2,2-trifluoroethyl methyl carbonate, 2,2,2-trifluoroethyl ethyl carbonate, 2,2,2-trifluoroethyl propyl carbonate, bis(2,2,2-trifluoroethyl) carbonate, 1,1,1,3,3,3-hexafluoro-1-propylmethyl carbonate, 1,1,1,3,3,3-hexafluoro-1-propylethyl carbonate, 1,1,1,3,3,3-hexafluoro-1-propylpropyl carbonate, bis(1,1,1,3,3,3-hexafluoro-1-propyl) carbonate, ethylene carbonate ( Preferably, it is at least one selected from the group consisting of EC (hereinafter also referred to as PC), propylene carbonate (hereinafter also referred to as PC), butylene carbonate, fluoroethylene carbonate (hereinafter also referred to as FEC), vinylene carbonate (hereinafter also referred to as VC), difluoroethylene carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, ethyl 2-fluoropropionate, diethyl ether, dibutyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, furan, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, N,N-dimethylformamide, acetonitrile, propionitrile, dimethyl sulfoxide, sulfolane, γ-butyrolactone, and γ-valerolactone. Furthermore, in this disclosure, an ionic liquid that adopts a salt structure may be used as the non-aqueous organic solvent.

[0041] Furthermore, the non-aqueous organic solvent is preferable if it contains at least one selected from the group consisting of cyclic carbonates and linear carbonates, as this provides excellent cycling characteristics at high temperatures. Furthermore, the non-aqueous organic solvent is preferable if it contains at least one selected from the group consisting of esters, as this provides excellent input / output characteristics at low temperatures. When the above non-aqueous organic solvent contains at least one selected from the group consisting of cyclic carbonates and linear carbonates, the content of at least one selected from the group consisting of cyclic carbonates and linear carbonates (or the total amount if there are multiple) is preferably 60 to 100% by mass of the total amount of the non-aqueous organic solvent. If the above non-aqueous organic solvent contains at least one selected from the group consisting of esters, the content of at least one selected from the group consisting of esters (or the total amount if there are multiple) is preferably 1 to 20% by mass relative to the total amount of the non-aqueous organic solvent.

[0042] Specific examples of the above-mentioned cyclic carbonates include EC, PC, butylene carbonate, and FEC, with at least one selected from the group consisting of EC, PC, and FEC being preferred.

[0043] Specific examples of the above-mentioned linear carbonates include EMC, DMC, DEC, methylpropyl carbonate, ethylpropyl carbonate, 2,2,2-trifluoroethylmethyl carbonate, 2,2,2-trifluoroethylethyl carbonate, 1,1,1,3,3,3-hexafluoro-1-propylmethyl carbonate, and 1,1,1,3,3,3-hexafluoro-1-propylethyl carbonate, among which at least one selected from the group consisting of EMC, DMC, DEC, and methylpropyl carbonate is preferred.

[0044] Furthermore, specific examples of the above esters include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, and ethyl 2-fluoropropionate. These non-aqueous organic solvents may be used individually, or two or more may be mixed in any combination and ratio depending on the application.

[0045] <About other additives> Insofar as it does not impair the essence of this disclosure, additives commonly used in the non-aqueous electrolytes of this disclosure may be added in any proportion. Other specific examples of additives include cyclohexylbenzene, cyclohexylfluorobenzene, fluorobenzene, biphenyl, difluoroanisole, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, 2-fluorobiphenyl, vinylene carbonate, dimethylvinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate, trans-difluoroethylene carbonate, methylpropargyl carbonate, ethylpropargyl carbonate, dipropargyl carbonate, and male anhydride. Ionic acid, succinic anhydride, propanesultone, 1,3-propanesultone, 1,3-propensultone (hereinafter also referred to as "PRS"), butanesultone, ethylene sulfate (hereinafter also referred to as "ESA"), methylene methanedisulfate, dimethylene methanedisulfate, trimethylene methanedisulfate, methyl methanesulfonate, 1,6-diisocyanatohexane, tris(trimethylsilyl)borate, succinonitrile, adiponitrile, (ethoxy)pentafluorocyclotriphosphazene, difluorobis(oxalate) ) Lithium phosphate (hereinafter also referred to as "DFBOP"), sodium difluorobis(oxalato)phosphate, potassium difluorobis(oxalato)phosphate, lithium difluorooxalatoborate (hereinafter also referred to as "DFOB"), sodium difluorooxalatoborate, potassium difluorooxalatoborate, lithium bis(oxalato)borate (hereinafter also referred to as "BOB"), sodium bis(oxalato)borate, potassium bis(oxalato)borate, lithium tetrafluorooxalatophosphate (hereinafter also referred to as "TFOP") Examples of compounds that have overcharge prevention effects, negative electrode film formation effects, and positive electrode protection effects include sodium tetrafluorooxalatophosphate, potassium tetrafluorooxalatophosphate, lithium tris(oxalato)phosphate, lithium ethylfluorophosphate, lithium difluorophosphate, lithium fluorophosphate, ethenesulfonyl fluoride, lithium fluorosulfonate (hereinafter also referred to as "FS"), trifluoromethanesulfonyl fluoride, methanesulfonyl fluoride (hereinafter also referred to as "MSF"), and phenyl difluorophosphate.

[0046] The content of the other additives in the non-aqueous electrolyte is preferably 0.01% by mass or more and 8.0% by mass or less, relative to the total amount of the non-aqueous electrolyte.

[0047] Furthermore, the ionic salt listed as a solute can exhibit negative electrode film formation and positive electrode protection effects as an "other additive" when its content in the non-aqueous electrolyte is less than the lower limit of the solute's preferred concentration, which is 0.5 mol / L. In this case, it is preferable that the content in the non-aqueous electrolyte is 0.01% to 5.0% by mass relative to the total amount of the non-aqueous electrolyte. Examples of ionic salts in this case include lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, bis(trifluoromethanesulfonyl)imide lithium, bis(trifluoromethanesulfonyl)imide sodium, bis(trifluoromethanesulfonyl)imide potassium, bis(trifluoromethanesulfonyl)imide magnesium, bis(fluorosulfonyl)imide lithium (hereinafter also referred to as "FSI"), bis(fluorosulfonyl)imide sodium, bis(fluorosulfonyl)imide potassium, bis(fluorosulfonyl)imide magnesium, (trifluoromethanesulfonyl)(fluorosulfonyl)imide lithium, (trifluoromethanesulfonyl)(fluorosulfonyl)imide sodium, (trifluoromethanesulfonyl)(fluorosulfonyl)imide potassium, (trifluoromethanesulfonyl)(full Examples include magnesium difluorophosphate (difluorophosphonyl), lithium bis(difluorophosphonyl)imide, sodium bis(difluorophosphonyl)imide, potassium bis(difluorophosphonyl)imide, magnesium bis(difluorophosphonyl)imide, lithium (difluorophosphonyl)(fluorosulfonyl)imide, sodium (difluorophosphonyl)(fluorosulfonyl)imide, potassium (difluorophosphonyl)(fluorosulfonyl)imide, magnesium (difluorophosphonyl)(fluorosulfonyl)imide, lithium (difluorophosphonyl)(trifluoromethanesulfonyl)imide, sodium (difluorophosphonyl)(trifluoromethanesulfonyl)imide, potassium (difluorophosphonyl)(trifluoromethanesulfonyl)imide, magnesium (difluorophosphonyl)(trifluoromethanesulfonyl)imide, lithium difluorophosphate (hereinafter also referred to as "DFP"), sodium difluorophosphate, etc.

[0048] Furthermore, alkali metal salts other than the above-mentioned solutes (lithium salts, sodium salts, potassium salts, magnesium salts) may be used as additives. Specifically, examples include carboxylates such as lithium acrylate, sodium acrylate, lithium methacrylate, and sodium methacrylate, as well as sulfate esters such as lithium methyl sulfate, sodium methyl sulfate, lithium ethyl sulfate, and sodium ethyl sulfate.

[0049] Furthermore, the compounds listed as solvents can also exert negative electrode film formation and positive electrode protection effects as "other additives" when their content in the non-aqueous electrolyte is small, between 0.1% and 2.0% by mass relative to the total amount of the non-aqueous electrolyte. Specific examples of such compounds include FEC and VC.

[0050] The non-aqueous electrolyte of this disclosure is preferable, from the viewpoint of at least one of the following: an effect of suppressing the increase in initial resistance, an effect of improving the capacity after storage testing, and an effect of improving the resistance after storage testing. The content of the above-mentioned other additives is preferably 0.01% to 5.0% by mass relative to the total amount of the non-aqueous electrolyte. In particular, from the viewpoint of suppressing the initial increase in resistance, at least one selected from ethylene sulfate, lithium difluorooxalatoborate, lithium bis(fluorosulfonyl)imide, lithium difluorophosphate, lithium fluorosulfonate, and methanesulfonyl fluoride is even more preferred.

[0051] Furthermore, the non-aqueous electrolyte of this disclosure may also contain polymers, and it is possible to use the non-aqueous electrolyte in a pseudo-solid state with a gelling agent or crosslinked polymer, as is the case when used in non-aqueous electrolyte batteries called polymer batteries. Polymer solid electrolytes may also include those containing a non-aqueous organic solvent as a plasticizer.

[0052] The polymer described above is not particularly limited as long as it is an aprotic polymer capable of dissolving the compound represented by the general formula (1), the solute, and the other additives described above. Examples include polymers having polyethylene oxide as the main chain or side chain, homopolymers or copolymers of polyvinylidene fluoride, methacrylate polymers, and polyacrylonitrile. When a plasticizer is added to these polymers, an aprotic nonaqueous organic solvent is preferred among the nonaqueous organic solvents described above.

[0053] [2. Nonaqueous electrolyte battery] The non-aqueous electrolyte battery of this disclosure comprises at least the non-aqueous electrolyte of this disclosure, a negative electrode, and a positive electrode. Furthermore, it is preferable to include a separator, an outer casing, etc.

[0054] While not particularly limited, it is preferable to use a material that allows for the reversible insertion and removal of alkali metal ions, such as lithium ions and sodium ions, or alkaline earth metal ions.

[0055] While not particularly limited, it is preferable to use a material that allows for the reversible insertion and removal of alkali metal ions, such as lithium ions and sodium ions, or alkaline earth metal ions, as the positive electrode.

[0056] For example, when the cation is a lithium ion, lithium metal, alloys and intermetallic compounds of lithium with other metals, various carbon materials capable of intercalating and releasing lithium, metal oxides, metal nitrides, activated carbon, conductive polymers, etc., are used as the negative electrode material. Examples of the above carbon materials include easily graphitizable carbon, poorly graphitizable carbon (also called hard carbon) with a (002) plane interplanar spacing of 0.37 nm or more, and graphite with a (002) plane interplanar spacing of 0.37 nm or less. For the latter, artificial graphite and natural graphite are used.

[0057] For example, when the cation is a lithium ion, lithium-containing transition metal composite oxides such as LiCoO2, LiNiO2, LiMnO2, and LiMn2O4 are used as positive electrode materials; these lithium-containing transition metal composite oxides contain a mixture of multiple transition metals such as Co, Mn, and Ni; these lithium-containing transition metal composite oxides have some of their transition metals replaced by other metals; phosphate compounds of transition metals called olivine, such as LiFePO4, LiCoPO4, and LiMnPO4; 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; polymers that generate radicals; and carbon materials.

[0058] For the positive and negative electrode materials, conductive materials such as acetylene black, Ketjen black, carbon fiber, or graphite, and binders such as polytetrafluoroethylene, polyvinylidene fluoride, or SBR resin can be added, and electrode sheets molded into a sheet shape can be used.

[0059] Nonwoven fabrics or porous sheets made of polypropylene, polyethylene, paper, or glass fiber are used as separators to prevent contact between the positive and negative electrodes.

[0060] From these elements, electrochemical devices in shapes such as coin-shaped, cylindrical, rectangular, or aluminum laminate sheet can be assembled.

[0061] [3. Manufacturing method of non-aqueous electrolyte battery] Furthermore, this disclosure also relates to a method for manufacturing a non-aqueous electrolyte battery. The aforementioned manufacturing method is A step for preparing a non-aqueous electrolyte, and A step of filling an empty cell, which is equipped with at least a positive electrode and a negative electrode, with the non-aqueous electrolyte. This is a method for manufacturing a non-aqueous electrolyte battery having [the specified characteristics]. [Examples]

[0062] The present disclosure will be further described in detail below with reference to examples, but the scope of the present disclosure is not limited in any way by the description of these examples.

[0063] [Preparation of non-aqueous electrolytes in the examples and comparative examples] <Comparative Example 1-1> (Preparation of comparative non-aqueous electrolyte 1-1) In a glove box with a dew point of -60°C or lower, EC and EMC were mixed in a volume ratio of 30:70. Then, while maintaining the internal temperature below 40°C, an amount of LiPF6 was added to a concentration of 1.0 mol / L relative to the total amount of the non-aqueous electrolyte. PRS was added as a comparative compound to a concentration of 0.03% by mass relative to the total amount of the non-aqueous organic solvent, LiPF6, and PRS, and the mixture was stirred for 1 hour to dissolve it, thereby preparing comparative non-aqueous electrolyte 1-1 according to comparative example 1-1.

[0064] <Comparative Examples 1-2 to 1-6> (Preparation of comparative non-aqueous electrolytes 1-2 to 1-6) Comparative non-aqueous electrolytes 1-2 to 1-6 were prepared in the same manner as comparative non-aqueous electrolyte 1-1, except that the PRS content was changed as shown in Tables 1 and 2.

[0065] <Example 1-1> (Preparation of non-aqueous electrolyte 1-1) In a glove box with a dew point of -60°C or lower, EC and EMC were mixed in a volume ratio of 30:70. Then, while maintaining the internal temperature at 40°C or lower, an amount of LiPF6 was added to a concentration of 1.0 mol / L relative to the total amount of the non-aqueous electrolyte. Compound (1e) was added as component (I) to a concentration of 0.03% by mass relative to the total amount of the non-aqueous organic solvent, LiPF6, and compound (1e), and the mixture was stirred for 1 hour to dissolve it, thereby preparing non-aqueous electrolyte 1-1 according to Example 1-1.

[0066] <Examples 1-2 to 1-10> (Preparation of non-aqueous electrolytes 1-2 to 1-10) Except for changing the type and content of component (I) as shown in Tables 1 and 2, non-aqueous electrolytes 1-2 to 1-10 were prepared in the same manner as non-aqueous electrolyte 1-1.

[0067] <Examples 2-1 to 2-7> (Preparation of non-aqueous electrolytes 2-1 to 2-7) Non-aqueous electrolytes 2-1 to 2-7 according to Examples 2-1 to 2-7 were prepared in the same manner as in Examples 1-3, except that the compounds listed in Table 4 were dissolved as additional additives in the amounts listed in Table 4.

[0068] <Examples 3-1 to 3-7> (Preparation of non-aqueous electrolytes 3-1 to 3-7) Non-aqueous electrolytes 3-1 to 3-7 according to Examples 3-1 to 3-7 were prepared in the same manner as in Examples 1-9, except that the compounds listed in Table 5 were dissolved as additional additives in the amounts listed in Table 5.

[0069] <Examples 4-1 to 4-4> (Preparation of non-aqueous electrolytes 4-1 to 4-2) Non-aqueous electrolytes 4-1 and 4-2 according to Examples 4-3 and 4-4 were prepared in the same manner as in Examples 1-3 and 1-9, except that the compounds listed in Table 7 were dissolved as additional additives in the amounts listed in Table 7. In Examples 4-1 and 4-2, non-aqueous electrolytes 1-3 and 1-9 were used, respectively.

[0070] <Example 1-3a> (Preparation of non-aqueous electrolyte 1-3a) As shown in Table 6, non-aqueous electrolyte 1-3a was prepared in the same manner as in Example 1-3, except that the content of component (I) was 0.3% by mass and PRS was dissolved as an additional additive at a content of 0.1% by mass. In this non-aqueous electrolyte 1-3a, PRS is not a comparative compound, but is included as an additional additive used in combination with component (I).

[0071] In Tables 1-7 below, the content of other additives is expressed as the concentration (mass%) relative to the total amount of component (I), other additives, non-aqueous organic solvent, and solute. In Tables 1 to 7 below, the content of component (I) represents the concentration (mass%) relative to the total amount of component (I), solute, and non-aqueous organic solvent.

[0072] [Construction of a non-aqueous electrolyte battery] (Fabrication of NCM811 positive electrode) LiRing 0.8 Co 0.1 Mn 0.1 A cathode composite paste was prepared by mixing 91.0% by mass of O2 powder with 4.5% by mass of polyvinylidene fluoride (PVDF) as a binder and 4.5% by mass of acetylene black as a conductive material, and then adding N-methyl-2-pyrrolidone. This paste was applied to both sides of aluminum foil (A1085), dried, and pressurized, and then punched out to a 4cm x 5cm rectangle to obtain a test NCM811 cathode. (Fabrication of natural graphite anodes) A negative electrode mixture paste was prepared by mixing 96.5% by mass of natural graphite powder with 0.5% by mass of carbon nanotubes, 2.0% by mass of styrene-butadiene rubber, 1.0% by mass of carboxymethylcellulose sodium, and water. This paste was applied to one side of a copper foil, dried, and then punched out to a 4cm x 5cm shape to obtain a test natural graphite negative electrode. (Fabrication of silicon-containing graphite anode) A negative electrode composite paste was prepared by mixing 85.0% by mass of artificial graphite powder with 7.0% by mass of nanosilicon, 3.0% by mass of conductive material (HS-100), 2.0% by mass of carbon nanotubes (VGCF), 2.0% by mass of styrene-butadiene rubber, 1.0% by mass of carboxymethylcellulose sodium, and water. This paste was applied to both sides of a copper foil, dried, and then punched out to a 4cm x 5cm shape to obtain a silicon-containing graphite negative electrode for testing.

[0073] (Construction of non-aqueous electrolyte batteries) In an argon atmosphere with a dew point of -50°C or lower, terminals were welded to the NCM811 positive electrode as described above. Then, two polyethylene separators (5cm x 6cm) were placed on both sides of the positive electrode, and two natural graphite negative electrodes (or silicon-containing graphite negative electrodes) with pre-welded terminals were placed on the outside, so that the negative electrode active material surface faced the positive electrode active material surface. These were then placed in an aluminum laminate bag with an opening on one side, and after vacuum injection of the non-aqueous electrolyte, the opening was heat-sealed to produce the aluminum laminate type non-aqueous electrolyte batteries of the example and comparative example. The non-aqueous electrolytes used were those listed in Tables 1 to 67. The capacity of the battery, standardized by the weight of the positive electrode active material, was 100mAh. 1mAh = 3.6C. Furthermore, the non-aqueous electrolyte batteries described in Tables 1-6 below used natural graphite negative electrodes, while the non-aqueous electrolyte batteries described in Table 7 below used silicon-containing graphite negative electrodes.

[0074] 〔evaluation〕 -Initial charge / discharge- A non-aqueous electrolyte battery was placed in a 25°C constant temperature bath and connected to a charge / discharge device. It was charged to 4.2V at 20mA (0.2C rate). After maintaining 4.2V for 1 hour, it was discharged to 2.5V at 20mA. This constituted one charge / discharge cycle, and a total of three charge / discharge cycles were performed to stabilize the battery. -Initial resistance measurement- After initial charging and discharging, the battery was charged to 4.2V at 25°C and 20mA. The battery was then removed from the charge / discharge device, and the AC impedance was measured at 25°C. This AC impedance value was defined as the initial resistance value. -Capacitance and resistance measurement after storage test- After measuring the AC impedance, the batteries were placed in a 60°C constant temperature bath. After two weeks, the batteries were removed, placed in a 25°C constant temperature bath, and connected to a charge / discharge device, where they were discharged at 20mA to 2.5V. Subsequently, they were charged at 20mA to 4.2V and then discharged to 2.5V. The capacity obtained during this discharge was defined as the capacity after the 60°C storage test. Then, after charging again at 20mA to 4.2V, the batteries were removed from the charge / discharge device, and the AC impedance was measured at 25°C. The AC impedance value at this time was defined as the resistance value after the storage test.

[0075] The evaluation results for Example 1-1 are shown in Table 1 as relative values, with the initial resistance, and the resistance and capacitance after storage testing of Comparative Example 1-1 set to 100. Similarly, in Tables 1 and 2, the evaluation results for the corresponding examples and comparative examples, where the content of component (I) and the content of the comparative compound are the same, are also shown as relative values. Table 3 also shows the evaluation results for Examples 1-1 to 1-10 and Comparative Examples 1-1, 1-2, 1-4 to 1-6 as relative values, with the initial resistance and the resistance and capacitance after storage testing of Comparative Example 1-3 set to 100. The evaluation results for Examples 2-4 and 3-4, described later, are also shown as relative values ​​with the evaluation result of Comparative Example 1-3 set to 100. Furthermore, the evaluation results for Examples 2-1 to 2-7 in Table 4 and Examples 3-1 to 3-7 in Table 5 are also shown as relative values. In Table 4, the evaluation results for Example 1-3 are shown as relative values ​​when the evaluation results for Example 1-9 are set to 100. Table 6 shows the relative values ​​of the evaluation results in each example, with the evaluation results of Comparative Example 1-3 set to 100. Table 7 also shows the relative values ​​of the evaluation results in each example, with the evaluation results of Example 4-1 set to 100.

[0076] [Table 1]

[0077] [Table 2]

[0078] [Table 3]

[0079] [Table 4]

[0080] [Table 5]

[0081] [Table 6]

[0082] [Table 7]

[0083] As shown in Table 1, in all of Examples 1-1 to 1-6, in which the content of component (I) was varied, each example was able to suppress the increase in initial resistance compared to the respective comparative examples in Comparative Examples 1-1 to 1-6, where the content of the comparative compound corresponds to the content of component (I). Furthermore, as shown in the results in Table 2, in Examples 1-7 to 1-10 and Comparative Examples 1-1 to 1-4, in which the type of component (I) was changed, each example was able to suppress the increase in initial resistance compared to the corresponding comparative examples. Furthermore, the results in Table 3 show that when the content of component (I) is 0.05% by mass or more, the effect of suppressing the rise in initial resistance is greater, as is the effect of suppressing resistance after the storage test, which is more preferable. Furthermore, when the content of component (I) is 0.2% by mass or more, the effect of suppressing the rise in initial resistance and the effect of improving capacity and resistance after the storage test are even greater, which is more preferable. Furthermore, when the content of component (I) is 1.2% by mass or less, the effect of suppressing the rise in initial resistance is greater, as is the effect of improving capacity after the storage test, which is more preferable. Furthermore, when the content of component (I) is 0.6% by mass or less, the effect of suppressing the rise in initial resistance is even greater, which is more preferable.

[0084] Furthermore, as can be seen from the results in Tables 4 and 5, using component (I) simultaneously with other additives (ESA, DFOB, FSI, DFP, FS, MSF, VC, TFOP, DFBOP, BOB) resulted in further improvement of capacity and resistance after storage testing while maintaining the effect of suppressing the rise in initial resistance. While the inclusion of VC as another additive resulted in slightly higher initial resistance compared to the case without VC (comparison of Examples 2-4 and 1-3 in Table 4, and comparison of Examples 3-4 and 1-9 in Table 5), as shown in Table 3, it can be seen that the effect of suppressing the rise in initial resistance can be maintained even when VC is included as another additive. Similarly, in Examples 2-7 and 3-6, although the initial resistance was slightly higher compared to the case without other additives, considering the results of Examples 2-4 and 3-4 shown in Table 3 (relative values ​​of 73 and 75, respectively, when the initial resistance value in Comparative Example 1-3 is set to 100), it can be seen that the effect of suppressing the rise in initial resistance can be maintained.

[0085] The non-aqueous electrolyte 1-3a in Example 1-3a of Table 6 has a composition in which a portion of the PRS in comparative non-aqueous electrolyte 1-3 is replaced with compound (1e), which is component (I). As can be seen from the results in Table 6, it was confirmed that the initial resistance increase suppression effect can be maintained even when PRS is used as another additive, as long as component (I) is included. Furthermore, as shown in Table 7, even when the negative electrode was changed to a silicon-containing graphite negative electrode and FEC was used as another additive, the initial resistance increase suppression effect was maintained, and the capacity and resistance after the storage test were further improved. [Industrial applicability]

[0086] According to this disclosure, it is possible to provide a non-aqueous electrolyte, a non-aqueous electrolyte battery, and a method for manufacturing a non-aqueous electrolyte battery that are excellent in suppressing the rise in initial resistance.

[0087] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2021-58532 filed on March 30, 2021, the contents of which are incorporated herein by reference.

Claims

1. A non-aqueous electrolyte containing a compound represented by the following general formula (1), a solute, and a non-aqueous organic solvent, The content of the compound represented by general formula (1) relative to the total amount of the compound represented by general formula (1), the solute, and the nonaqueous organic solvent is 0.03% by mass to 1.3% by mass. A non-aqueous electrolyte in which the solute is an ionic salt containing lithium ions. 【Chemistry 1】 [In general formula (1), m and n are 2. A is a -CH2- group. D is a -C2H4- group or a -C3H6- group.]

2. A non-aqueous electrolyte containing a compound represented by the following general formula (1), a solute, and a non-aqueous organic solvent, The compound represented by the general formula (1) is at least one compound selected from the group consisting of compounds represented by (1a) to (1c), (1e) to (1f), (1h), (1k), (1m) to (1r) below. The content of the compound represented by general formula (1) relative to the total amount of the compound represented by general formula (1), the solute, and the nonaqueous organic solvent is 0.03% by mass to 1.3% by mass. A non-aqueous electrolyte in which the solute is an ionic salt containing lithium ions. 【Chemistry 2】 (1a) A=-CH 2 - group, D=-C 2 H 4 - group, m=1, n=1 (1b) A=-CH(CH 3 )- group, D=-C 2 H 4 - group, m=1, n=1 (1c) A=-C(CH 3 ) 2 - group, D=-C 2 H 4 - group, m=1, n=1 (1e) A=-CH 2 - group, D=-C 2 H 4 - group, m=2, n=2 (1f) A=-CH(CH 3 )- group, D=-C 2 H 4 - group, m=2, n=2 (1h) A = single bond, D = -C 3 H 6 - group, m = 2, n = 2 (1k) A=-C(CH 3 ) 2 - group, D=-C 3 H 6 - group, m=1, n=1 (1m) A=-C 2 H 4 - group, D=-C 2 H 4 - group, m=1, n=1 (1n) A=-CH 2 - group, D=-C 3 H 6 - group, m=2, n=2 (1o) A=-CH(CH 3 )- group, D=-C 3 H 6 - group, m=2, n=2 (1r) A=-C 2 H 4 - group, D=-C 2 H 4 - group, m=2, n=2

3. The non-aqueous electrolyte according to claim 2, wherein the compound represented by the general formula (1) is the compound represented by (1e) or (1n).

4. The non-aqueous electrolyte according to any one of claims 1 to 3, wherein the non-aqueous organic solvent contains at least one selected from the group consisting of cyclic carbonates and linear carbonates.

5. The non-aqueous electrolyte according to claim 4, wherein the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene 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.

6. Furthermore, it contains at least one selected from vinylene carbonate, fluoroethylene carbonate, ethylene sulfate, lithium bis(oxalato)borate, lithium difluorooxalatoborate, lithium difluorobis(oxalato)phosphate, lithium tetrafluorooxalatophosphate, lithium bis(fluorosulfonyl)imide, lithium bis(difluorophosphonyl)imide, lithium (difluorophosphonyl)(fluorosulfonyl)imide, lithium difluorophosphate, lithium fluorosulfonate, and methanesulfonyl fluoride as an additive component. The content of vinylene carbonate and fluoroethylene carbonate as additive components is 0.1% to 2.0% by mass relative to the total amount of the non-aqueous electrolyte. A non-aqueous electrolyte according to any one of claims 1 to 5.

7. A non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte according to any one of claims 1 to 6.

8. A step of preparing a non-aqueous electrolyte according to any one of claims 1 to 6, and A step of filling an empty cell, which is equipped with at least a positive electrode and a negative electrode, with the non-aqueous electrolyte. A method for manufacturing a non-aqueous electrolyte battery.

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