Nonaqueous electrolyte and nonaqueous electrolyte battery using same

Abstract

Provided are: a non-aqueous electrolyte solution containing (I) at least one sulfonic acid anhydride represented by general formula (1) described in the description, (II) at least one compound selected from the group consisting of "2", "3", "4", "5", "6" and "7" described in the description, (III) a solute, and (IV) a non-aqueous organic solvent; the non-aqueous electrolyte battery at least comprises a positive electrode, a negative electrode, a separator and the non-aqueous electrolyte.

Description

TECHNICAL FIELD

[0001] The present application relates to a nonaqueous electrolyte and a nonaqueous electrolyte battery using the same. BACKGROUND

[0002] Hitherto, as a means for improving the durability such as cycle characteristics, high-temperature storage characteristics of a nonaqueous electrolyte battery, optimization of various battery constituent elements typified by active materials of a positive electrode or a negative electrode has been studied. Nonaqueous electrolyte-related technologies are no exception, and various additives have been proposed to suppress deterioration of the active positive electrode or negative electrode surface due to electrolyte decomposition.

[0003] For example, Patent Literature 1 proposes use of a sulfonic acid anhydride for an electrolyte to improve cycle characteristics.

[0004] Patent Literature 2 proposes improvement of cycle characteristics and low-temperature characteristics by use of a silicon compound for an electrolyte.

[0005] Patent Literature 3 proposes use of a nonaqueous electrolyte containing lithium bisfluorosulfonylimide as a solute to improve storage characteristics.

[0006] Patent Literature 4 proposes improvement of storage characteristics after charging by use of lithium monofluorophosphate, lithium difluorophosphate for an electrolyte.

[0007] Patent Literature 5 proposes maintenance of high input-output characteristics and impedance characteristics after durability tests by use of a nonaqueous electrolyte characterized by containing a fluorosulfonate.

[0008] Patent Literature 6 proposes suppression of decomposition on a carbon negative electrode accompanying progress of charge-discharge cycles by use of a nonaqueous electrolyte characterized by containing a cyclic sulfate.

[0009] Patent Literature 7 proposes a battery in which deterioration of load characteristics or resistance is greatly suppressed and the amount of gas generation in the battery is small, by use of a nonaqueous electrolyte characterized by containing a cyclic sulfone lactone (unsaturated sulfone lactone).

[0010] Patent Literature 8 discloses an electrolyte having high heat resistance and hydrolysis resistance, which contains various oxalate salts or malonate salts.

[0011] Further, Patent Literature 9 discloses a nonaqueous electrolyte battery having high-temperature durability, which is obtained by causing a nonaqueous electrolyte to contain a picolinic acid derivative represented by general formula (3) in the literature.

[0012] PRIOR ART DOCUMENTS PATENT LITERATURE Patent Literature 1: Japanese Patent No. 3760539 Patent Literature 2: Japanese Patent No. 3497812 Patent Literature 3: Japanese Patent No. 4847675 Patent Literature 4: Japanese Patent No. 3439085 Patent Literature 5: Japanese Patent No. 5353923 Patent Literature 6: Japanese Patent No. 3760540 Patent Literature 7: Japanese Patent No. 4190162 Patent Literature 8: Japanese Patent No. 3722685 Patent Literature 9: WO2016 / 002774A1 SUMMARY

[0013] (1) Technical problem to be solved However, the present inventors have conducted studies, and as a result, it has become clear that in the batteries disclosed in the prior art documents, although the battery characteristics have indeed been improved, there is still room for improvement with respect to the initial resistance.

[0014] The present application was completed in view of the above-described circumstances, and the technical problem thereof is to provide a nonaqueous electrolyte capable of reducing the initial resistance value of a battery, and a nonaqueous electrolyte battery.

[0015] (2) Technical solution The present inventors have conducted intensive studies in order to solve the problem, and as a result, it has been found that by causing a nonaqueous electrolyte for a nonaqueous electrolyte battery, which contains a nonaqueous solvent and a solute, to contain a specific sulfonic acid anhydride and at least one selected from the group consisting of a specific phosphate, a sulfonate, an imide salt, a borate, a picolinic acid derivative, a silicon compound, a cyclic sulfate, and a cyclic sultone, when the electrolyte is used in a nonaqueous electrolyte battery, the initial resistance value of the battery can be reduced, and the present application has thus been completed.

[0016] That is, the present application is as shown below. [1] A nonaqueous electrolyte containing: (I) at least one sulfonic acid anhydride "1" represented by the following general formula (1), (II) at least one compound selected from the group consisting of "2", "3", "4", "5", "6", and "7" represented by the following "2", "3", "4", "5", "6", and "7", (III) a solute, and (IV) a nonaqueous organic solvent.

[0018] [Chemical Formula 1] In general formula (1), R 1 and R 2each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms optionally substituted with an alkyl group. R 1 and R 2 Any of the hydrogen atoms of the alkyl group, alkenyl group, and aryl group represented by R

[0019] The "2" is at least one compound selected from the group consisting of compounds represented by General Formula (2-1) to General Formula (2-2), [Chemical Formula 2] In General Formula (2-1), R 3 and R 4 each independently is a fluorine atom, or an organic group selected from linear or branched alkoxy groups having 1 to 10 carbon atoms, alkenyloxy groups having 2 to 10 carbon atoms, alkynyloxy groups having 2 to 10 carbon atoms, cycloalkoxy groups having 3 to 10 carbon atoms, cycloalkenyloxy groups having 3 to 10 carbon atoms, and aryloxy groups having 6 to 10 carbon atoms, and the organic group can also contain a fluorine atom, an oxygen atom, and an unsaturated bond. Further, General Formula (2-1) contains at least one P-F bond.

[0020] In General Formula (2-2), X 1 is a fluorine atom, or an organic group selected from linear or branched 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, linear or branched alkoxy groups having 1 to 10 carbon atoms, alkenyloxy groups having 2 to 10 carbon atoms, alkynyloxy groups having 2 to 10 carbon atoms, cycloalkoxy groups having 3 to 10 carbon atoms, cycloalkenyloxy groups having 3 to 10 carbon atoms, and aryloxy groups having 6 to 10 carbon atoms, and the organic group can contain at least one fluorine atom, and the organic group can also contain an oxygen atom and an unsaturated bond.

[0021] In General Formula (2-1) and General Formula (2-2), M1 m＋ is a proton, a metal cation, or an onium cation. m represents the valence of the corresponding cation.

[0022] The "3" is at least one compound selected from the group consisting of compounds represented by General Formula (3-1) to General Formula (3-3), [Chemical Formula 3] In General Formula (3-1) to General Formula (3-3), R 5 to R10 each independently is a fluorine atom, or an organic group selected from a linear or branched 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, and an aryl group having 6 to 10 carbon atoms, and a fluorine atom, an oxygen atom, and an unsaturated bond can be present in the organic group.

[0023] X 2 ~X 4 each independently is a fluorine atom, or an organic group selected from a linear or branched 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, and an aryl group having 6 to 10 carbon atoms, and a fluorine atom, an oxygen atom, and an unsaturated bond can be present in the organic group.

[0024] Further, at least one P-F bond and / or S-F bond is included in General Formulae (3-1) to (3-3).

[0025] M1 m＋ is a proton, a metal cation, or an onium cation. m represents the valence number of the corresponding cation.

[0026] The "4" is 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] In General Formula (4-1), W represents a boron atom, a phosphorus atom, or a silicon atom, n1 is 0 to 3, n2 is 0 to 4, and p is 0 or 1. R 41 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 have a substituent or optionally have a hetero atom in the structure thereof. Further, when n1 is 2 or more, the n1 R 41 optionally bonded to each other), R 42 represents a halogen atom, Y 1 , Y 2 each independently represents an oxygen atom or a sulfur atom, Y 3 represents a carbon atom or a sulfur atom. Y 3 when Y is a carbon atom, q is 1, and3 q is 1 or 2 when Y represents a sulfur atom. M a＋ represents an alkali metal cation, an alkaline earth metal cation or an onium cation, and a represents the valence of the corresponding cation. a ~ d are 1 or 2, and satisfy a x b = c x d.

[0027] [Chemical Formula 5] 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 have a substituent in the structure thereof or optionally have a hetero atom), and r is 0 or 1. Y 4 represents a carbon atom or a sulfur atom. Y 4 s is 1 when Y represents a carbon atom, and Y 4 s is 1 or 2 when Y represents a sulfur atom. W 2 represents a boron atom or a phosphorus atom, and R 44 represents a halogen atom. W 2 n3 is 2 when W represents a boron atom, and W 2 n3 is 4 when W represents a phosphorus atom.

[0028] The "5" is at least one compound represented by the following General Formula (5), [Chemical Formula 6] In General Formula (5), R 51 each independently represents a group having a carbon-carbon unsaturated bond. When a plurality of R 52 are present, the plurality of R 52 each independently represents a fluorine atom or a linear or branched 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. v represents an integer of 2 to 4.

[0029] The "6" is at least one compound represented by the following General Formula (6), [Chemical Formula 7] In General Formula (6), R 61 and R 62 each independently represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, a linear or branched 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 of the alkyl group, the alkenyl group and the aryl group represented by R 70 n6 is 0 or 1.

[0030] The "7" is at least one compound selected from the group consisting of compounds represented by General Formula (7-1) to General Formula (7-2).

[0031] [Chemical Formula 8] In General Formula (7-1), R 70 R 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. n71 represents an integer of 1 to 3.

[0032] In General Formula (7-2), R 74 R 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. n72 represents an integer of 0 to 2. [2] The nonaqueous electrolyte solution according to [1], wherein the content of the (I) is 0.01 to 10 mass% with respect to the total amount of the nonaqueous electrolyte solution. [3] The nonaqueous electrolyte solution according to [1] or [2], wherein the content of the (II) is 0.01 to 10 mass% with respect to the total amount of the nonaqueous electrolyte solution. [4] The nonaqueous electrolyte solution according to any one of [1] to [3], wherein the (I) is at least one selected from the group consisting of methanesulfonic anhydride and ethanesulfonic anhydride. [5] The nonaqueous electrolyte solution according to any one of [1] to [4], wherein the "2" is at least one compound selected from the group consisting of lithium difluorophosphate, lithium fluorosulfonate, and lithium trifluoromethanesulfonate. [6] The nonaqueous electrolyte solution according to any one of [1] to [5], wherein the "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. [7] The nonaqueous electrolyte solution according to any one of [1] to [6], wherein the "4" is at least one compound selected from the group consisting of lithium tetrafluoroborate, lithium bis(oxalato)borate, lithium difluoro(oxalato)borate, lithium bis(oxalato)phosphate, lithium difluoro-bis(oxalato)phosphate, lithium tetrafluoro(oxalato)phosphate, lithium difluoro(malonato)borate, lithium tetrafluoro(malonato)phosphate, lithium tetrafluoro(pyridinecarboxylato)phosphate, and lithium difluoro(pyridinecarboxylato)borate. [8] The nonaqueous electrolyte according to any one of [1] to [7], wherein the "5" is at least one compound selected from the group consisting of trivinylmethylsilane, trivinylfluorosilane, and tetravinylsilane. [9] The nonaqueous electrolyte according to any one of [1] to [8], wherein the "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.

[10] The nonaqueous electrolyte according to any one of [1] to [9], wherein the (III) is at least one selected from the group consisting of LiPF6, LiSbF6, LiAsF6, LiClO4, LiAlO2, LiAlCl4, LiCl, and LiI, or is at least one selected from the group consisting of NaPF6, NaSbF6, NaAsF6, NaClO4, NaAlO2, NaAlCl4, NaCl, and NaI.

[11] The nonaqueous electrolyte according to any one of [1] to

[10] , wherein the (IV) is 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.

[12] The nonaqueous electrolyte according to

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

[13] The nonaqueous electrolyte according to

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

[14] A nonaqueous electrolyte battery including at least a positive electrode, a negative electrode, a separator, and the nonaqueous electrolyte according to any one of [1] to

[13] .

[0046] (III) Advantageous Effects According to the present application, it is possible to provide a nonaqueous electrolyte and a nonaqueous electrolyte battery that can reduce the initial resistance value of a battery. DETAILED DESCRIPTION

[0047] The structures and combinations thereof in the following embodiments are examples. Additional structures, substitutions, and other modifications may be made without departing from the spirit of the invention. Furthermore, the invention is not limited to the embodiments, but only to the claims.

[0048] In this specification, "~" is used to indicate that the values ​​recorded before and after it are the lower limit and upper limit values.

[0049] [1. Non-aqueous electrolyte] The non-aqueous electrolyte of the present invention contains: (I) At least one sulfonic anhydride "1" represented by the above general formula (1), (II) At least one compound selected from groups “2”, “3”, “4”, “5”, “6” and “7” above; (III) Solute, and (IV) Non-aqueous organic solvents.

[0050] If a non-aqueous electrolyte containing either component (I) or component (II) is used in a non-aqueous electrolyte battery (e.g., a lithium-ion secondary battery or a sodium-ion secondary battery), components (I) and (II) decompose at least on either the positive or negative electrode, forming a coating with good cation conductivity on the surface of at least either the positive or negative electrode. This coating is believed to inhibit direct contact between the non-aqueous organic solvent or solute and the electrode active material, and to reduce the cation dissociation energy of the solute. As a result, the inventors of this application hypothesize that this can achieve a reduction in the initial resistance value of the non-aqueous electrolyte battery.

[0051] [About the ingredients (I)] The non-aqueous electrolyte of the present invention comprises at least one sulfonic anhydride "1" represented by general formula (1) as component (I).

[0052] [Chemical Formula 9] In general formula (1), R 1 and R 2 Each of the following can independently represent a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a straight-chain or branched alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms optionally substituted with an alkyl group. R 1 and R 2 Any hydrogen atom of the alkyl, alkenyl, and aryl groups may optionally be replaced by a halogen atom.

[0053] As when R 1 and R 2Alkyl groups that are straight-chain or branched alkyl groups with 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, and n-hexyl.

[0054] As when R 1 and R 2 Alkenes that are straight-chain or branched with 2 to 10 carbon atoms include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, and 1,3-butadienyl.

[0055] As when R 1 and R 2 Aryl groups that are optionally substituted with alkyl groups and have 6 to 10 carbon atoms can be exemplified by phenyl, tolyl, xylyl, etc.

[0056] In addition, the number of carbon atoms 6 to 10 indicates the total number of carbon atoms in the aryl group and the total number of carbon atoms in the alkyl group when the aryl group is replaced by an alkyl group.

[0057] At least one of the hydrogen atoms in any of the 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.

[0058] R 1 and R 2 Each of the alkyl groups is preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms, more preferably methyl, ethyl or isopropyl, and even more preferably methyl or ethyl.

[0059] R is the preferred choice 1 and R 2 Both indicate methyl, or both indicate ethyl.

[0060] That is, component (I) is preferably selected from at least one of the groups consisting of methanesulfonic anhydride and ethanesulfonic anhydride.

[0061] The following shows specific examples of sulfonic anhydrides represented by general formula (1), but are not limited thereto.

[0062] [Chemical Formula 10] In the non-aqueous electrolyte of the present invention, the lower limit of the content (hereinafter also referred to as "concentration of (I)") of the above-mentioned component (I) relative to the total amount (100% by mass) of the non-aqueous electrolyte can be 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more. The upper limit of the concentration of (I) can be 10% by mass or less, 5% by mass or less, 4% by mass or less, or 2.5% by mass or less.

[0063] By making the concentration of (I) 0.01 mass% or more, it is easy to obtain the initial resistance rise suppression effect and the improvement effect on the cycle characteristics of the nonaqueous electrolyte battery using the nonaqueous electrolyte. On the other hand, by making the concentration of (I) 10 mass% or less, it is possible to suppress the viscosity rise of the nonaqueous electrolyte, and it is easy to obtain the initial resistance rise suppression effect of the nonaqueous electrolyte battery using the nonaqueous electrolyte.

[0064] The content of the above component (I) with respect to the total amount of the nonaqueous electrolyte is preferably 0.01 to 10 mass%, and more preferably 0.01 to 5 mass%.

[0065] The nonaqueous electrolyte of the present application can use one compound alone as the component (I), or can mix two or more compounds in any combination and ratio as the component (I) according to the use.

[0066] The sulfonic acid anhydride represented by General Formula (1) can be produced by a publicly known method.

[0067] [For Component (II)] The nonaqueous electrolyte of the present application contains, as the component (II), at least one compound selected from the group consisting of "2", "3", "4", "5", "6", and "7" shown below.

[0068] <2> "2" is at least one compound selected from the group consisting of the compounds represented by General Formula (2-1) to General Formula (2-2) below.

[0069] [Chemical Formula 11] In General Formula (2-1), R 3 and R 4 each independently is a fluorine atom, or an organic group selected from a linear or branched 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. Further, General Formula (2-1) contains at least one P-F bond.

[0070] In General Formula (2-2), X 1a fluorine atom, or an organic group selected from a linear or branched 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, a linear or branched 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 further containing an oxygen atom or an unsaturated bond.

[0071] In General Formula (2-1) and General Formula (2-2), M1 m＋ is a proton, a metal cation, or an onium cation. m represents the valence of the corresponding cation.

[0072] In General Formula (2-1), as the alkyl group represented by R 3 and R 4 , for example, there can be mentioned a linear or branched alkyl group having 1 to 10 carbon atoms, such as a methyi group, an ethyi group, a propyi group, an isopropyi group, a butyi group, a sec-butyl group, a tert-butyl group, a pentyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,1-trifluoroisopropyl group, and a 1,1,1,3,3,3-hexafluoroisopropyl group.

[0073] As the alkenyi group represented by R 3 and R 4 , for example, there can be mentioned an alkenyi group having 2 to 10 carbon atoms, such as an ethenyi group, a 1-propenyi group, a 2-propenyi group, an isopropenyi group, a 2-butenyi group, a 3-butenyi group, and a 1,3-butadienyl group.

[0074] As the alkynyi group represented by R 3 and R 4 , for example, there can be mentioned an alkynyi group having 2 to 10 carbon atoms, such as an ethynyi group, a 2-propynyi group, and a 1,1-dimethyl-2-propynyi group.

[0075] As the cycloalkyi group represented by R 3 and R 4 , for example, there can be mentioned a cycloalkyi group having 3 to 10 carbon atoms, such as a cyclopentanoi group and a cyclohexanoi group.

[0076] As the cycloalkenyi group represented by R 3 and R 4 , for example, there can be mentioned a cycloalkenyi group having 3 to 10 carbon atoms, such as a cyclopentenoyi group and a cyclohexenoyi group.

[0077] as R 3 and R 4 representing an aryloxy group, for example, a carbon number of 6 to 10 aryloxy group such as phenyloxy, tolyloxy and xylyloxy, or a fluorine-containing aryloxy group can be exemplified.

[0078] If R 3 and R 4 each independently is a fluorine atom or an alkoxy group having a fluorine atom, the ion dissociation degree is increased by the strong electron-withdrawing property thereof, and the ion conductivity in the solution or the composition becomes high, and thus is preferred. Further, if it is a fluorine atom, the ion conductivity in the solution or the composition becomes very high by the effect of the increase in the mobility due to the decrease in the size of the anion, and thus is preferred.

[0079] Further, R 3 and R 4 are preferably a carbon number of 6 or less. If the carbon number is 6 or less, the ion conductivity is relatively high, and thus is preferred.

[0080] In General Formula (2-1), M1 m＋ represents a proton, a metal cation or an onium cation. As long as the performance of the nonaqueous electrolyte and the nonaqueous electrolyte battery of the present application is not impaired, the kind thereof is not particularly limited, and various kinds of substances can be selected from the above.

[0081] As the metal cation when M1 m＋ represents a metal cation, 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 can be exemplified.

[0082] As the onium cation when M1 m＋ represents an onium cation, onium cations such as tetraalkylammonium, tetraalkylphosphonium and imidazolium derivatives can be exemplified.

[0083] In particular, from the viewpoint of exerting an effect of contributing to the ion conduction in the nonaqueous electrolyte battery, M1 m＋ is preferably lithium ion, sodium ion, potassium ion, tetramethylammonium ion, tetraethylammonium ion, tetrabutylphosphonium ion or the like.

[0084] Further, when used for lithium ion battery applications, M1 m＋ is more preferably lithium ion, and when used for sodium ion battery applications, M1 m＋ is preferably sodium ion.

[0085] The following shows specific examples of the anion structure of the compound represented by General Formula (2-1), but is not limited thereto.

[0086] [Chemical Formula 12] In general formula (2-2), X is... 1 The alkyl group represented may include, for example, methyl, ethyl, propyl, isopropyl, 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.

[0087] As X 1 The alkenyl groups represented include, for example, vinyl, 1-propenyl, 2-propenyl, isopropenyl, 2-butenyl, 3-butenyl, and 1,3-butadienyl alkenyl groups with 2 to 10 carbon atoms, or fluorinated alkenyl groups.

[0088] As X 1 The alkynyl group represented may include, for example, ethynyl, 2-propynyl and 1,1-dimethyl-2-propynyl, which are alkynyl groups or fluorinated alkynyl groups with 2 to 10 carbon atoms.

[0089] As X 1 The cycloalkyl group referred to may include, for example, cyclopentyl and cyclohexyl groups with 3 to 10 carbon atoms, or fluorinated cycloalkyl groups.

[0090] As X 1 The cycloalkenyl groups represented include, for example, cyclopentenyl and cyclohexenyl, which are cycloalkenyl groups or fluorinated cycloalkenyl groups with 3 to 10 carbon atoms. As X 1 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.

[0091] As X 1 The alkoxy, alkenoxy, alkynoxy, cycloalkoxy, cycloalkenoxy, and aryloxy groups represented can be listed as R in the general formula (2-1) above. 3 and R 4 The terms "alkoxy", "alkenoxy", "acetyloxy", "cycloalkoxy", "cycloalkenoxy", and "aryloxy" are used to represent these.

[0092] In general formula (2-2), if X 1 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 also preferred because the increased mobility due to the smaller anion size results in very high ionic conductivity in the solution or composition.

[0093] Furthermore, if X 1When the number of carbon atoms of the above-mentioned substituent is 6 or less, the ion conductivity tends to be high, and therefore the number of carbon atoms is preferably 1 to 4, and more preferably 1 to 3.

[0094] Specific examples include a trifluoromethyl group, a trifluoromethoxy group, a trifluoroethoxy group, and the like, and a trifluoromethyl group, which is small in size, is particularly preferred.

[0095] In General Formula (2-2), M1 m＋ is the same as M1 m＋ is the same as M1

[0096] The following shows specific examples of the anion structure of the compound represented by General Formula (2-2), but is not limited thereto.

[0097] [Chemical Formula 13] "2" is preferably at least one compound selected from the group consisting of a difluorophosphate salt, a fluorosulfonate salt, and a triflate salt, and more preferably at least one compound selected from the group consisting of lithium difluorophosphate, lithium fluorosulfonate, and lithium triflate.

[0098] <3> "3" is at least one compound selected from the group consisting of the compounds represented by General Formula (3-1) to General Formula (3-3).

[0099] [Chemical Formula 14] In General Formula (3-1) to General Formula (3-3), R 5 ~R 10 each independently is a fluorine atom, or an organic group selected from a linear or branched 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.

[0100] X 2 ~X 4each independently is a fluorine atom or an organic group selected from a linear or branched 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, a linear or branched 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 optionally further has a fluorine atom, an oxygen atom, or an unsaturated bond in the organic group.

[0101] Further, at least one P-F bond and / or S-F bond is contained in General Formulae (3-1) to (3-3).

[0102] M1 m＋ is a proton, a metal cation, or an onium cation. m represents the valence of the corresponding cation.

[0103] as R 5 to R 10 representing an alkoxy group, an alkenyloxy group, an alkynyloxy group, a cycloalkoxy group, a cycloalkenyloxy group, and an aryloxy group in General Formula (2-1) above can be exemplified. 3 and R 4 representing an alkoxy group, an alkenyloxy group, an alkynyloxy group, a cycloalkoxy group, a cycloalkenyloxy group, and an aryloxy group.

[0104] If R 5 to R 10 each independently is a fluorine atom or an alkoxy group having a fluorine atom, the ion dissociation degree is increased by the strong electron-withdrawing property thereof, and thus the ionic conductivity in a solution or a composition becomes high, and thus is preferred. Further, if it is a fluorine atom, the mobility is increased by the effect of the decrease in the size of the anion, and thus the ionic conductivity in a solution or a composition becomes very high, and thus is preferred.

[0105] Further, R 5 to R 10 is preferably 6 or less. If the number of carbon atoms is 6 or less, the ionic conductivity is relatively high, and thus is preferred.

[0106] as X 2 to X 4 representing an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a cycloalkoxy group, a cycloalkenyloxy group, and an aryloxy group in General Formula (2-1) above can be exemplified. 1 representing an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a cycloalkoxy group, a cycloalkenyloxy group, and an aryloxy group.

[0107] If X 2 ~X 4 is a fluorine atom or an alkyl group containing a fluorine atom, the ion dissociation degree is increased by the strong electron-withdrawing property thereof, and the ionic conductivity in the solution or the composition becomes high, and thus is preferred. Further, if it is a fluorine atom, the mobility is increased by the effect of the small size of the anion, and the ionic conductivity in the solution or the composition becomes very high, and thus is preferred.

[0108] Further, if the number of carbon atoms of X 2 ~X 4 is 6 or less, there is a tendency that the ionic conductivity is relatively high, and thus is preferred, and more preferably the number of carbon atoms is 1 to 4, and further preferably the number of carbon atoms is 1 to 3. Specifically, mention can be made of a trifluoromethyl group, a pentafluoroethyl group, and the like, and a trifluoromethyl group, which is small in the size of the anion, is particularly preferred.

[0109] In General Formulae (3-1) to (3-3), M1 m＋ is the same as M1 m＋ in General Formula (2-1), and the preferred examples are also the same.

[0110] The following shows specific examples of the anion structure of the compounds represented by General Formulae (3-1) to (3-3), but is not limited thereto.

[0111] [Chemical Formula 15] [Chemical Formula 16] [Chemical Formula 17] "3" is preferably at least one compound selected from the group consisting of a bis(fluorosulfonyl)imide salt, a (fluorosulfonyl)(difluorophosphoryl)imide salt, a bis(trifluoromethanesulfonyl)imide salt, a bis(difluorophosphoryl)imide salt, a bis(pentafluoroethanesulfonyl)imide salt, and a (fluorosulfonyl)(trifluoromethanesulfonyl)imide salt, and 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 lithium (fluorosulfonyl)(trifluoromethanesulfonyl)imide.

[0112] <4> "4" is 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).

[0113] [Chemical Formula 18] In General Formula (4-1), W represents a boron atom, a phosphorus atom, or a silicon atom, n1 is 0 to 3, n2 is 0 to 4, and p is 0 or 1. R 41 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 have a substituent in the structure thereof or optionally have a hetero atom. In addition, when n1 is 2 or more, the n1 R 41 groups optionally bind to each other), R 42 represents a halogen atom, Y 1 represents a halogen atom, Y 2 each independently represents an oxygen atom or a sulfur atom, Y 3 represents a carbon atom or a sulfur atom. Y 3 when Y represents a carbon atom, q is 1, Y 3 when Y represents a sulfur atom, q is 1 or 2. M a＋ represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and a represents the valence of the corresponding cation. a to d are 1 or 2, and satisfy a x b = c x d.

[0114] [Chemical Formula 19] 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 have a substituent in the structure thereof or optionally have a hetero atom), and r is 0 or 1. Y 4 represents a carbon atom or a sulfur atom. Y 4 when Y represents a carbon atom, s is 1, Y 4 when Y represents a 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 W represents a boron atom, n3 is 2, W 2 when W represents a phosphorus atom, n3 is 4.

[0115] W represents a boron atom, a phosphorus atom, or a silicon atom, and is preferably a boron atom or a phosphorus atom.

[0116] As the alkylene group having 1 to 10 carbon atoms represented by R 41 , methylene, ethylene, n-propylene, i-propylene, n-butylene, n-hexylene, and the like can be mentioned.

[0117] As the haloalkylene group having 1 to 10 carbon atoms represented by R 41 , a group in which any hydrogen atom of the above alkylene group is replaced with a halogen atom can be mentioned.

[0118] as R 41 as R

[0119] as R 41 as R

[0120] R 41 as R

[0121] as R 42 as R

[0122] Y 1 , Y 2 each independently represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.

[0123] Y 3 represents a carbon atom or a sulfur atom, and is preferably a carbon atom.

[0124] as M a＋ as M m＋ as M

[0125] as represented by general formula (4-1), can be exemplified by tetrafluoroborate, bisoxalate borate, difluorooxalate borate, trioxalate phosphate, difluorobisoxalate phosphate, tetrafluorooxalate phosphate, trioxalate silicate, difluorobisoxalate silicate, difluoromalonate borate, tetrafluoromalonate phosphate, difluoro(sulfoacetic acid) borate, difluoro(maleic acid) borate, and difluoro(fumaric acid) borate.

[0126] as R 43 as R

[0127] as R 43 as R

[0128] as R 43 as R

[0129] as R 43 The halogen atom represented by R

[0130] as R 43 , preferably methylene, ethylene, n-propylene, difluoromethylene, tetrafluoroethylene, hexafluoropropylene, and more preferably methylene.

[0131] as R 44 The halogen atom represented by R

[0132] Y 4 represents a carbon atom or a sulfur atom, and is preferably a carbon atom.

[0133] The compound represented by General Formula (4-2) can be exemplified by the following compounds.

[0134] [Chemical Formula 20] Among them, the following compounds are preferable.

[0135] [Chemical Formula 21] "4" is preferably at least one compound selected from the group consisting of tetrafluoroborate, bisoxalate borate, difluorooxalate borate, trisoxalate phosphate, difluorobisoxalate phosphate, tetrafluorooxalate phosphate, difluoromalonate borate, tetrafluoromalonate phosphate, tetrafluoro(pyridinecarboxylate) phosphate, and difluoro(pyridinecarboxylate) borate, and more preferably at least one compound selected from the group consisting of lithium tetrafluoroborate, lithium bisoxalate borate, lithium difluorooxalate borate, lithium trisoxalate phosphate, lithium difluorobisoxalate phosphate, lithium tetrafluorooxalate phosphate, lithium difluoromalonate borate, lithium tetrafluoromalonate phosphate, tetrafluoro(pyridinecarboxylate) phosphate, and difluoro(pyridinecarboxylate) borate.

[0136] <5> "5" is at least one compound represented by General Formula (5) below.

[0137] [Chemical Formula 22] In General Formula (5), R 51 each independently represents a group having a carbon-carbon unsaturated bond. When a plurality of R 52 each independently represents a group having a carbon-carbon unsaturated bond. When a plurality of R 52 each independently represents a fluorine atom, or a linear or branched 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. v represents an integer of 2 to 4.

[0138] As R 51 The groups containing carbon-carbon unsaturated bonds mentioned include alkenyl groups with 2 to 8 carbon atoms, such as vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, and 1,3-butadienyl; or alkynyl groups with 2 to 8 carbon atoms, such as alkynyloxy, acetylenyl, 2-propynyl, and 1,1-dimethyl-2-propynyl; or aryl groups with 6 to 12 carbon atoms, such as alkynyloxy, phenyl, tolyl, and xylylyl; or aryloxy groups derived from these groups. Furthermore, the aforementioned groups may contain fluorine and oxygen atoms. Preferably, groups containing carbon-carbon unsaturated bonds with 6 or fewer carbon atoms are preferred. If the number of carbon atoms is 6 or fewer, there is a tendency for lower resistance when forming a coating on the electrode. Specifically, groups selected from the group consisting of vinyl, allyl, 1-propenyl, acetylenyl, and 2-propynyl are preferred.

[0139] There are multiple R 52 At that time, multiple R 52 Each can independently represent a straight-chain or branched alkyl group having 1 to 10 carbon atoms.

[0140] As R 52 The alkyl group represented is a straight-chain or branched alkyl group with 1 to 10 carbon atoms, and examples include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, and n-pentyl. Furthermore, the above groups may have at least one of fluorine atoms and oxygen atoms.

[0141] 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 it tends to have a smaller initial resistance when forming a coating on the electrode, which is preferred from the perspective of output characteristics.

[0142] In general formula (5), v represents an integer from 2 to 4, preferably 3 or 4, and particularly preferably 4.

[0143] The following shows specific examples of compounds represented by general formula (5), but are not limited thereto.

[0144] [Chemical Formula 23] [Chemical Formula 24] "5" is preferably at least one compound selected from the group consisting of trivinylmethylsilane, trivinylfluorosilane and tetravinylsilane.

[0145] <6> "6" is at least one compound represented by the following general formula (6).

[0146] [Chemical Formula 25] In general formula (6), R 61 and R 62 each independently represent a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, a linear or branched 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 of the alkyl group, alkenyl group, and aryl group represented by R 61 and R 62 may be optionally substituted with a halogen atom. n6 is 0 or 1.

[0147] As the alkyl group when R 61 and R 62 are an alkyl group having 1 to 2 carbon atoms, a methyl group and an ethyl group can be mentioned.

[0148] As the alkenyl group when R 61 and R 62 are a linear or branched alkenyl group having 2 to 5 carbon atoms, an ethenyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, a 1,3-butadienyl group, and the like can be mentioned.

[0149] As the aryl group when R 61 and R 62 are an aryl group having 6 to 10 carbon atoms optionally substituted with an alkyl group, a phenyl group, a tolyl group, a xylyl group, and the like can be mentioned.

[0150] Further, the total number of carbon atoms as the aryl group and the number of carbon atoms of the alkyl group when the aryl group is substituted with an alkyl group is 6 to 10.

[0151] At least one of any hydrogen atom of the alkyl group, alkenyl group, and aryl group can be substituted with a halogen atom. As the halogen atom, a fluorine atom, a bromine atom, an iodine atom, and the like can be mentioned, and a fluorine atom is preferred.

[0152] R 61 and R 62 preferably represent a hydrogen atom. When n6 is 0, the carbon atom to which R 61 is bonded and the carbon atom to which R 62 is bonded are bonded with a single bond.

[0153] That is, "6" is preferably at least one compound selected from the group consisting of 1,3,2-dioxazolothiophene-2,2-dioxide and 1,3,2-dioxathiane-2,2-dioxide.

[0154] The following shows specific examples of compounds represented by General Formula (6), but is not limited thereto.

[0155] [Chemical Formula 26] [Chemical Formula 27] <7> The "7" is at least one compound selected from the group consisting of compounds represented by General Formula (7-1) to General Formula (7-2).

[0156] [Chemical Formula 28] In General Formula (7-1), R 70 ~R 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. n71 represents an integer of 1 to 3.

[0157] In General Formula (7-2), R 74 ~R 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. n 72 represents an integer of 0 to 2.

[0158] In General Formula (7-1), as the alkyl group represented by R 70 ~R 73 for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, and the like can be exemplified as the alkyl group having 1 to 5 carbon atoms.

[0159] As the fluoroalkyl group represented by R 70 ~R 73 for example, a trifluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,1,3,3,3-hexafluoroisopropyl group, and the like can be exemplified as the fluoroalkyl group having 1 to 4 carbon atoms.

[0160] R 70 ~R 73 is preferably a hydrogen atom, a fluorine atom, a trifluoromethyl group, and more preferably a hydrogen atom.

[0161] In General Formula (7-1), n 71 represents an integer of 1 to 3, and can be 1 or 2, and is preferably 1.

[0162] As the compound represented by General Formula (7-1), 1,3-propene sultone (1-propenyl-1,3-sultone), 1,4-butene sultone, 2,4-pentene sultone, 3,5-pentene sultone, 1-fluoro-1,3-propene sultone, 1-trifluoromethyl-1,3-propene sultone, 1,1,1-trifluoro-2,4-butene sultone, 1,4-butene sultone, 1,5-pentene sultone, and the like can be exemplified.

[0163] In General Formula (7-2), as R 74 ~R 79 As the alkyl group represented by R

[0164] As the fluoroalkyl group represented by R 74 ~R 79 As the fluoroalkyl group represented by R

[0165] R 74 ~R 79 Preferably, it is a hydrogen atom, a fluorine atom, a trifluoromethyl group, and more preferably, it is a hydrogen atom.

[0166] In General Formula (7-2), n72 represents an integer of 0 to 2, and can be 0 or 1, and preferably, it is 0. When n72 is 0, R 76 and the carbon atom to which R 77 and the carbon atom to which R 78 and the carbon atom to which R 79 are bonded are bonded with a single bond.

[0167] As the compound represented by General Formula (7-2), 1,3-propane sultone, α-trifluoromethyl-γ-sultone, β-trifluoromethyl-γ-sultone, γ-trifluoromethyl-γ-sultone, α-methyl-γ-sultone, α,β-di(trifluoromethyl)-γ-sultone, α,α-di(trifluoromethyl)-γ-sultone, α-heptafluoropropyl-γ-sultone, 1,4-butan sultone, 1,5-pentane sultone, and the like can be exemplified.

[0168] Preferably, "7" is at least one compound selected from the group consisting of 1,3-propane sultone and 1-propene-1,3-sultone.

[0169] The lower limit of the content of the above component (II) (hereinafter, also referred to as "the concentration of (II)") with respect to the total amount of the nonaqueous electrolyte solution (100 mass%) can be 0.01 mass% or more, 0.05 mass% or more, or 0.1 mass% or more. The upper limit of the concentration of (II) can be 10 mass% or less, 5 mass% or less, 4 mass% or less, or 2.5 mass% or less.

[0170] By setting the concentration of (II) to 0.01 mass% or more, it is easy to obtain the initial resistance increase suppression effect and the improvement effect of the cycle characteristics of the nonaqueous electrolyte battery using the nonaqueous electrolyte solution. On the other hand, by setting the concentration of (II) to 10 mass% or less, it is possible to suppress the increase in the viscosity of the nonaqueous electrolyte solution, and it is easy to obtain the initial resistance increase suppression effect of the nonaqueous electrolyte battery using the nonaqueous electrolyte solution.

[0171] The content of the above component (II) with respect to the total amount of the nonaqueous electrolyte solution can be 0.01 mass% to 10 mass%, or 0.01 to 5 mass%.

[0172] In addition, with respect to LiN(CF3SO2)2, LiN(FSO2)2, LiN(POF2)2, LiCF3SO3, LiC4F9SO3, NaN(CF3SO2)2, NaN(FSO2)2, NaN(POF2)2, NaCF3SO3, and NaC4F9SO3, the content with respect to the total amount of the nonaqueous electrolyte solution can be 0.01 mass% or more and 20 mass% or less.

[0173] The nonaqueous electrolyte solution of the present application can use one compound alone as component (II), or can mix two or more compounds in any combination and ratio as component (II) according to the use.

[0174] The above compound represented by the above "2" to "7" can be produced by a publicly known method.

[0175] <Concerning (III) Solute> The nonaqueous electrolyte solution of the present application contains a solute.

[0176] The solute is not particularly limited, and is preferably an ionic salt, and more preferably an ionic salt containing fluorine.

[0177] As the solute, for example, an ionic salt formed from an ion pair of at least one cation selected from the group consisting of alkali metal ions represented by lithium ions or sodium ions, alkaline earth metal ions, and quaternary ammonium, and at least one anion selected from the group consisting of hexafluorophosphate anions, perchlorate anions, hexafluoroarsenate anions, hexafluoroantimonate anions, and tris(trifluoromethane sulfonyl)methyl methide anions can be exemplified.

[0178] The solute is preferably 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.

[0179] These solutes can be used singly or in a mixture of two or more in any combination and ratio according to the use.

[0180] Among them, from the viewpoint of the energy density, output characteristics, life, and the like of the nonaqueous electrolyte battery, the cation is preferably at least one selected from the group consisting of lithium, sodium, potassium, magnesium, and quaternary ammonium, and the anion is preferably at least one selected from the group consisting of hexafluorophosphate anions and tetrafluoroborate anions.

[0181] The total amount of the solute in the nonaqueous electrolyte of the present application (hereinafter, also referred to as "solute concentration") is not particularly limited, and the lower limit is preferably 0.5 mol / L or more, more preferably 0.7 mol / L or more, and further preferably 0.9 mol / L or more. In addition, the upper limit of the solute concentration is preferably 5 mol / L or less, more preferably 4 mol / L or less, and further preferably 2 mol / L or less. By setting the solute concentration to 0.5 mol / L or more, it is possible to suppress the decrease in the cycle characteristics and output characteristics of the nonaqueous electrolyte battery due to the decrease in the ionic conductivity, and by setting it to 5 mol / L or less, it is possible to suppress the decrease in the ionic conductivity and the decrease in the cycle characteristics and output characteristics of the nonaqueous electrolyte battery due to the increase in the viscosity of the nonaqueous electrolyte.

[0182] <Concerning (IV) nonaqueous organic solvent> The (IV) nonaqueous organic solvent (also referred to as "(IV)") contained in the nonaqueous electrolyte of the present application will be described. The kind of the (IV) nonaqueous organic solvent is not particularly limited, and any nonaqueous organic solvent can be used.

[0183] As specific examples of the (IV) nonaqueous organic solvent, the following nonaqueous organic solvents can be exemplified.

[0184] As the cyclic ester, in addition to propylene carbonate (hereinafter, sometimes referred to as "PC"), ethylene carbonate (hereinafter, sometimes referred to as "EC"), fluoroethylene carbonate (hereinafter, sometimes referred to as "FEC"), butylene carbonate and the like, γ-butyrolactone, γ-valerolactone and the like can be exemplified. In addition, with respect to the FEC, when the content with respect to the total amount of the nonaqueous electrolyte solution is 10% by mass or less, it is defined as the other additive described later.

[0185] As the chain ester, in addition to diethyl carbonate (hereinafter, sometimes referred to as "DEC"), dimethyl carbonate (hereinafter, sometimes referred to as "DMC"), ethyl methyl carbonate (hereinafter, sometimes referred to as "EMC"), methyl propyl carbonate and the like, methyl acetate, methyl propionate, ethyl propionate (hereinafter, sometimes referred to as "EP") and the like can be exemplified.

[0186] As the cyclic ether, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane and the like can be exemplified.

[0187] As the chain ether, dimethoxyethane, diethyl ether and the like can be exemplified.

[0188] In addition thereto, a sulfone compound or a sulfoxide compound such as dimethyl sulfoxide, sulfolane and the like can be exemplified. Further, an ionic liquid and the like can be exemplified.

[0189] The nonaqueous organic solvent can contain 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.

[0190] The cyclic ester is a cyclic carbonate, and the cyclic carbonate can be at least one selected from the group consisting of ethylene carbonate, propylene carbonate and fluoroethylene carbonate.

[0191] The chain ester is a chain carbonate, and the chain carbonate can be at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate and methyl propyl carbonate.

[0192] The nonaqueous electrolyte solution of the present application can use one compound alone as (IV), or two or more compounds can be mixed in an arbitrary combination and ratio according to the use as (IV).

[0193] The content of the cyclic carbonate is not particularly limited and can be any content as long as the effect of the present application is not significantly impaired, and when one type is used alone, the content can be 3% by volume or more, more preferably 5% by volume or more, in 100% by volume of the nonaqueous organic solvent. By setting to this range, it is easy to avoid a decrease in the conductivity resulting from a decrease in the dielectric constant of the nonaqueous electrolyte solution, and it is easy to make the large-current discharge characteristics, stability with respect to the negative electrode, and cycle characteristics of the nonaqueous electrolyte battery be in a good range. In addition, it is usually 90% by volume or less, preferably 85% by volume or less, and more preferably 80% by volume or less. By setting to this range, it is easy to make the viscosity of the nonaqueous electrolyte solution be in an appropriate range, it is easy to suppress a decrease in the ionic conductivity, and it is easy to make the load characteristics of the nonaqueous electrolyte battery be in a good range.

[0194] In addition, the cyclic carbonate can also be used in an arbitrary combination of two or more types. One of the preferred combinations is a combination of ethylene carbonate and propylene carbonate. The volume ratio of ethylene carbonate to propylene carbonate at this time is preferably 99: 1 to 40: 60, and particularly preferably 95: 5 to 50: 50. In addition, the amount of propylene carbonate in the entire nonaqueous organic solvent is not particularly limited and can be any amount as long as the effect of the present application is not significantly impaired, and is usually 1% by volume or more, preferably 2% by volume or more, and more preferably 3% by volume or more, and in addition, is usually 30% by volume or less, preferably 25% by volume or less, and more preferably 20% by volume or less. If propylene carbonate is contained within this range, it is possible to further make the low-temperature characteristics excellent while maintaining the characteristic state of the combination of ethylene carbonate and the dialkyl carbonate, and thus is preferred.

[0195] The chain ester can be used alone or two or more types can be used simultaneously in an arbitrary combination and ratio.

[0196] The content of the chain ester is not particularly limited and is usually 15% by volume or more, preferably 20% by volume or more, and more preferably 25% by volume or more, in 100% by volume of the nonaqueous organic solvent. In addition, it is usually 90% by volume or less, preferably 85% by volume or less, and more preferably 80% by volume or less. By making the content of the chain ester be in the above range, it is easy to make the viscosity of the nonaqueous electrolyte solution be in an appropriate range, it is easy to suppress a decrease in the ionic conductivity, and it is easy to make the input-output characteristics or charge-discharge rate characteristics of the nonaqueous electrolyte battery be in a good range. In addition, it is easy to avoid a decrease in the conductivity resulting from a decrease in the dielectric constant of the nonaqueous electrolyte solution, and it is easy to make the input-output characteristics or charge-discharge rate characteristics of the nonaqueous electrolyte battery be in a good range.

[0197] In addition, by combining ethylene carbonate with a specific chain ester in a specific content, it is possible to significantly improve the battery performance.

[0198] For example, when dimethyl carbonate and methyl ethyl carbonate are selected as the specific chain ester, the content of ethylene carbonate is not particularly limited, and can be any content as long as the effect of the present application is not significantly impaired, and is usually 5% by volume or more, preferably 10% by volume or more, and in addition, is usually 45% by volume or less, preferably 40% by volume or less, the content of dimethyl carbonate is usually 20% by volume or more, preferably 30% by volume or more, and in addition, is usually 50% by volume or less, preferably 45% by volume or less, and the content of methyl ethyl carbonate is usually 20% by volume or more, preferably 30% by volume or more, and in addition, is usually 50% by volume or less, preferably 45% by volume or less. By setting the content within the above range, the low-temperature precipitation temperature of the electrolyte can be reduced while also reducing the viscosity of the nonaqueous electrolyte, thereby increasing the ionic conductivity, and a high input and output can be obtained even at low temperatures.

[0199] The content of the chain ether is not particularly limited, and can be any content as long as the effect of the present application is not significantly impaired, and is usually 1% by volume or more, preferably 2% by volume or more, more preferably 3% by volume or more, and in addition, is usually 30% by volume or less, preferably 25% by volume or less, more preferably 20% by volume or less, in 100% by volume of the nonaqueous organic solvent. If the content of the chain ether is within the above range, the effects of increasing the lithium ion dissociation degree of the chain ether and increasing the ionic conductivity due to a decrease in viscosity can be easily ensured. In addition, when the negative electrode active material is a carbonaceous material, the phenomenon of the chain ether being intercalated together with lithium ions can be suppressed, and thus the input and output characteristics and the charge and discharge rate characteristics can be made within an appropriate range.

[0200] The content of the sulfone compound is not particularly limited, and can be any content as long as the effect of the present application is not significantly impaired, and is usually 0.3% by volume or more, preferably 0.5% by volume or more, more preferably 1% by volume or more, and in addition, is usually 40% by volume or less, preferably 35% by volume or less, more preferably 30% by volume or less, in 100% by volume of the nonaqueous organic solvent. If the content of the sulfone compound is within the above range, the effects of increasing the durability of the cycle characteristics and storage characteristics, and in addition, the viscosity of the nonaqueous electrolyte can be made within an appropriate range, the decrease in conductivity can be avoided, and the input and output characteristics and the charge and discharge rate characteristics of the nonaqueous electrolyte battery can be made within an appropriate range.

[0201] <Concerning Other Additives> As long as the gist of the present application is not impaired, a generally used additive component can be further added to the nonaqueous electrolyte of the present application at an arbitrary ratio.

[0202] As specific examples of the other additive, cyclohexylbenzene, cyclohexylfluorobenzene, fluorobenzene, biphenyl, difluorobenzene anisole, t-butylbenzene, t-amylbenzene, 2-fluorotoluene, 2-fluorobiphenyl, vinylene carbonate, an oligomer of vinylene carbonate (number average molecular weight in terms of polystyrene: 170 to 5,000), dimethylvinylene carbonate, vinyl ethylene carbonate, fluorovinyl ethylene carbonate, trans-difluorovinylene carbonate, methyl propargyl carbonate, ethyl propargyl carbonate, dipropargyl carbonate, ethynyl vinyl carbonate, maleic anhydride, succinic anhydride, 1,2-ethane disulfonic anhydride, methylenemethane disulfonate, dimethylenemethane disulfonate, trimethylenemethane disulfonate, methyl methanesulfonate, 1,6-diisocyanatohexane, tris(trimethylsilyl) borate, butanedinitrile, (ethoxy) pentafluorocyclotriphosphazene, lithium monofluorophosphate, sodium monofluorophosphate, potassium monofluorophosphate, methylsulfonyl fluoride, ethylenesulfonyl fluoride, phenyl difluorophosphate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-hexafluoroisopropyl) disiloxane, nitrate, and the like can be contained in the nonaqueous electrolyte of the present application. The content of the above additive in the nonaqueous electrolyte can be 0.01 mass% or more and 5 mass% or less with respect to the total amount of the nonaqueous electrolyte.

[0203] By containing the above additive in the nonaqueous electrolyte of the present application, at least one of the overcharge prevention effect, the negative electrode coating film formation effect, and the positive electrode protection effect can be improved.

[0204] The nonaqueous electrolyte of the present application can contain a compound represented by General Formula (3-4) as the other additive. Among them, the compound belonging to General Formula (3-2) is excluded.

[0205] [Chemical Formula 29] In General Formula (3-4), R 31 ~R 33 are the same as X 2 in General Formula (3-2). Among them, at least one of R 31 ~R 33 is a fluorine atom.

[0206] M2 m＋ is an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m represents an integer equal to the valence number of the corresponding cation. As the alkali metal cation, the alkaline earth metal cation, and the onium cation represented by M2 m＋ , the alkali metal cation, the alkaline earth metal cation, and the onium cation listed as M1 m＋ in General Formula (3-2) can be listed.

[0207] The content of the other additive in the nonaqueous electrolyte can be 0.01 mass% or more and 8 mass% or less relative to the total amount of the nonaqueous electrolyte.

[0208] Further, the ionic salt exemplified as the solute can exert the negative electrode coating film formation effect or the positive electrode protection effect as the "other additive" when the content in the nonaqueous electrolyte is less than the lower limit of the appropriate concentration of the solute, 0.5 mol / L. In this case, the content in the nonaqueous electrolyte can be 0.01 mass% to 5 mass%.

[0209] Further, an alkali metal salt other than the above solute can be used as the additive.

[0210] Specifically, lithium acrylate, sodium acrylate, lithium methacrylate, sodium methacrylate, carboxylic acid salts, lithium methyl sulfate, sodium methyl sulfate, lithium ethyl sulfate, sodium ethyl sulfate, and the like can be exemplified.

[0211] With respect to the nonaqueous electrolyte of the present application, from the viewpoint of improving the durability (life) of the battery, when the nonaqueous electrolyte battery is a lithium ion battery, at least one selected from the group consisting of vinylene carbonate and fluoroethylene carbonate can be contained in the above other additive at 0.01 to 5 mass% relative to the total amount of the nonaqueous electrolyte.

[0212] When the nonaqueous electrolyte battery is a sodium ion battery, at least one selected from the group consisting of vinylene carbonate and fluoroethylene carbonate can be contained at 0.01 to 5 mass% relative to the total amount of the nonaqueous electrolyte.

[0213] Further, the nonaqueous electrolyte of the present application can also include a polymer, and can also be used after being quasi-solidified using a gelling agent or a crosslinked polymer, as when used in a nonaqueous electrolyte battery called a polymer battery. A substance containing a nonaqueous organic solvent can also be included as a plasticizer in the polymer solid electrolyte.

[0214] The above polymer is not particularly limited as long as it is aprotic and can dissolve the sulfonic acid anhydride "1" represented by the above general formula (1), at least one compound selected from the group represented by the above "2" to "7", the above solute, and the above other additive. For example, polymers having a polyethylene oxide in the main chain or side chain, homopolymers or copolymers of polyvinylidene fluoride, methacrylate polymers, polyacrylonitrile, and the like can be exemplified. When a plasticizer is added to these polymers, a nonprotic nonaqueous organic solvent is preferable among the above nonaqueous organic solvents.

[0215] [2. Nonaqueous electrolyte battery] The nonaqueous electrolyte battery of the present application includes at least the above nonaqueous electrolyte of the present application, a negative electrode, and a positive electrode. It is preferable to further include a separator, an exterior body, and the like.

[0216] The present application relates to a nonaqueous electrolyte battery comprising at least a positive electrode, a negative electrode, a separator, and the nonaqueous electrolyte of the present application.

[0217] As the negative electrode, there is no particular limitation, and a material capable of reversibly intercalating and deintercalating alkali metal ions or alkaline earth metal ions represented by lithium ions or sodium ions can be used.

[0218] In the case of a lithium ion secondary battery in which lithium ions are the main cations, for example, as the negative electrode active material constituting the negative electrode, a substance capable of doping and undoping lithium ions can be used, such as a carbon material having a d value of 0.340 nm or less for the lattice plane (002 plane) in X-ray diffraction; a carbon material having a d value of more than 0.340 nm for the lattice plane (002 plane) in X-ray diffraction; an oxide of one or more metals selected from Si, Sn, and Al; an alloy of one or more metals selected from Si, Sn, and Al or containing these metals, or an alloy of these metals or alloy and lithium; and a substance containing at least one selected from lithium titanium oxides. These negative electrode active materials can be used alone or in combination with two or more. In addition, lithium metal, metal nitrides, tin compounds, conductive polymers, and the like can be used.

[0219] In the case of a sodium ion secondary battery in which sodium ions are the main cations, for example, as the negative electrode active material constituting the negative electrode, sodium metal, an alloy of sodium metal and another metal such as tin, an intermetallic compound of sodium metal and another metal, various carbon materials including hard carbon, metal oxides such as titanium oxide, metal nitrides, tin (single body), tin compounds, activated carbon, conductive polymers, and the like can be used. In addition to these, red phosphorus, black phosphorus, and the like (single body), phosphorus compounds such as Co-P, Cu-P, Sn-P, Ge-P, Mo-P, antimony (single body), Sb / C, Bi-Sb, and the like can be used. These negative electrode active materials can be used alone or in combination with two or more.

[0220] As the positive electrode, there is no particular limitation, and a material capable of reversibly intercalating and deintercalating alkali metal ions or alkaline earth metal ions represented by lithium ions or sodium ions can be used.

[0221] For example, when the cation is lithium, as the positive electrode material, LiCoO2, LiNiO2, LiMnO2, LiMn2O4, and the like lithium-containing transition metal complex oxides, a mixture of these lithium-containing transition metal complex oxides with various transition metals such as Co, Mn, and Ni, a substance in which part of the transition metal of these lithium-containing transition metal complex oxides is substituted with a metal other than a transition metal, a transition metal phosphorus oxide such as LiFePO4, LiCoPO4, and LiMnPO4, which is called an olivine, an oxide such as TiO2, V2O5, and MoO3, a sulfide such as TiS2and FeS, or a conductive polymer such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole, activated carbon, a radical-generating polymer, a carbon material, and the like can be used.

[0222] Specifically, Li[Ni 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 expressed 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 O 2、 LiMn 1.5 Ni 0.5 O4, and the like can be cited.

[0223] For example, when the cation is sodium, as the positive electrode material (positive electrode active material), NaCrO2, NaFe 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 / 3Ni 1 / 3 Ti 1 / 6 Mn 1 / 2 O2, Na 2 / 3 Ni 1 / 3 Mn 2 / 3 O2, and the like, a mixture of these sodium-containing transition metal complex oxides with various transition metals such as Co, Mn, and Ni, a substance in which a part of the transition metals of these sodium-containing transition metal complex oxides is substituted with a metal other than a transition metal, NaFePO4, NaVPO4F, Na3V2(PO4)3, Na2Fe2(SO4)3, and the like, polyanion-type compounds, a substance having a composition formula of Na a M b [Fe(CN)6] c a sodium salt of a Prussian blue analog represented by the formula of M = Cr, Mn, Fe, Co, Ni, Cu, or Zn, 0 ≤ a ≤ 2, 0.5 ≤ b ≤ 1.5, 0.5 ≤ c ≤ 1.5, TiO2, V2O5, MoO3, and the like, an oxide, TiS2, FeS, and the like, a sulfide, or a conductive polymer such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole, activated carbon, a radical-generating polymer, a carbon material, and the like.

[0224] In the positive electrode or negative electrode material, as the conductive material, acetylene black, Ketjen black, carbon fiber, or graphite can be added, as the binder, polytetrafluoroethylene, polyvinylidene fluoride, or SBR resin, and the like, and an electrode sheet formed into a sheet shape can also be used.

[0225] As a separator for preventing the positive electrode from contacting the negative electrode, a non-woven fabric or a porous sheet made of polypropylene, polyethylene, paper, or glass fiber, and the like can be used.

[0226] An electrochemical device in a coin shape, a cylindrical shape, a square shape, or an aluminum laminate sheet type, and the like can be assembled from the above elements.

[0227] Examples Hereinafter, the present application will be specifically described using examples, but the present application is not limited by these examples.

[0228] Hereinafter, each compound of component (I) and component (II) used in each of the examples and comparative examples is shown.

[0229] Compound (1-1): Methanesulfonic anhydride Compound (1-2): Ethanesulfonic anhydride Compound (2-1): Lithium difluorophosphate Compound (2-2): Lithium fluorosulfonate Compound (3-1): Lithium bis(fluorosulfonyl)imide Compound (4-1): Lithium bis(oxalato)borate Compound (4-2): Lithium difluorobis(oxalato)borate Compound (4-3): Lithium tris(oxalato)phosphate Compound (4-4): Lithium difluorobis(oxalato)phosphate Compound (4-5): Lithium tetrafluorobis(oxalato)phosphate Compound (4-6): Lithium tetrafluoroborate Compound (5-1): Trivinylmethylsilane Compound (5-2): Trivinylfluorosilane Compound (5-3): Tetravinylsilane Compound (6-1): 1,3,2-Dioxazolothiophene-2,2-dioxide Compound (7-1): 1,3-Propanesultone Compound (7-2): 1-Propene-1,3-sultone The structures of comparative compound (3-X) and comparative compound (5-X) are shown below.

[0230] [Chemical Formula 30] [Preparation of nonaqueous electrolyte] [Example 1-1] In a glove box in which the dew point was -60°C or lower, EC, EMC, and DMC were mixed at a volume ratio of 25:55:20. Then, while the internal temperature was maintained at 40°C or lower, LiPF6 (component (III)) was added in an amount so as to be 1.0 mol / L in concentration, the compound (1-1) (component (I)) was added so as to be 1.0 mass% in concentration with respect to the total amount of the nonaqueous electrolyte, and the compound (2-1) (component (II)) was further added so as to be 1.0 mass% in concentration with respect to the total amount of the nonaqueous electrolyte, and it was stirred for 1 hour to dissolve, whereby the nonaqueous electrolyte of Example 1-1 was prepared.

[0231] Further, the kind or concentration of component (I), component (II), and other additives was changed as shown in Tables 1 to 12 below, and the nonaqueous electrolytes of Examples 1-2 to 1-87, Comparative Examples 1-1 to 1-43, Examples 2-1 to 2-87, and Comparative Examples 2-1 to 2-43 were prepared by the same procedure as the preparation of the electrolyte 1-1, except for this.

[0232] VC in the column of other additives in Tables 7 to 12 indicates vinylene carbonate, and FEC indicates fluoroethylene carbonate.

[0233] The concentrations of component (I), component (II), and other additives in Tables 1 to 12 each indicate the concentration with respect to the total amount of the nonaqueous electrolyte.

[0234] [Production of nonaqueous electrolyte battery] (Production of lithium ion battery: NCM811 positive electrode) A polyvinylidene fluoride (hereinafter, also written as PVDF) of 3.5 mass% as a binder, acetylene black of 4.5 mass% as a conductive material, and LiNi 0.8 Co 0.1 Mn 0.1 O2 powder, and then N-methyl-2-pyrrolidone was added, to produce a positive electrode composite paste. This paste was coated on both sides of an aluminum foil (A1085), dried, pressed, and then punched into 4 cm x 5 cm, to thereby obtain a test NCM811 positive electrode.

[0235] (Production of natural graphite negative electrode) A natural graphite powder of 97.0 mass%, a styrene butadiene rubber of 2.0 mass% as a binder, sodium carboxymethyl cellulose of 1.0 mass%, and water were mixed, to produce a negative electrode composite paste. This paste was coated on one side of a copper foil, dried, pressed, and then punched into 4.5 cm x 5.5 cm, to thereby obtain a test natural graphite negative electrode.

[0236] (Production of silicon-containing graphite negative electrode) A negative electrode composite paste was prepared by mixing 20.0 mass% SiO x A negative electrode composite paste was prepared by mixing 20.0 mass% SiO

[0237] (Production of non-aqueous electrolyte battery) The above NCM811 positive electrode and a terminal were fusion-welded in an argon atmosphere at a dew point of -50°C or lower, and then two pieces of a polyethylene separator (5 cm x 6 cm) were used to sandwich both sides thereof, and further two pieces of a natural graphite negative electrode or a silicon-containing graphite negative electrode, which had a terminal fusion-welded in advance, were used to sandwich the outer sides thereof in such a manner that the negative electrode active material surface and the positive electrode active material surface faced each other. Then, they were put into an aluminum laminated bag with an opening on one side, and a non-aqueous electrolyte was vacuum-injected, and then the opening was sealed by heat, thereby producing an aluminum laminated non-aqueous electrolyte battery of the examples and comparative examples. In addition, as the non-aqueous electrolyte, the substances described in Tables 1 to 12 were used. In addition, a natural graphite negative electrode was used in the examples and comparative examples of Tables 1 to 6, and a silicon-containing graphite negative electrode was used in the examples and comparative examples of Tables 7 to 12.

[0238] Using the battery produced by the above-described method, the initial resistance, the cycle characteristics, and the high-temperature storage characteristics were evaluated by the methods described below.

[0239] [Evaluation of non-aqueous electrolyte battery] (Evaluation of non-aqueous electrolyte battery described in Tables 1 to 6) -Initial charge and discharge- The produced non-aqueous electrolyte battery was put into a 25°C constant-temperature tank, and connected to a charge and discharge device in this state. Charge was performed to 4.2 V at a current density of 0.38 mA / cm 2 Charge was performed to 4.2 V at a current density of 0.38 mA / cm 2 Discharge was performed to 2.5 V. This operation was set as one charge and discharge cycle, and charge and discharge were performed for a total of 3 cycles to stabilize the battery. The discharge capacity of the 3rd cycle was taken as the initial charge and discharge capacity.

[0240] <Initial resistance> After the initial charge and discharge, the resistance value was measured by impedance measurement at 25°C, 0.38 mA / cm 2 Charge was performed to 4.2 V at a current density of 0.38 mA / cm

[0241] In addition, the values of the initial resistance of Examples 1-1 to 1-87 and Comparative Examples 1-1 to 1-43 described in Tables 1 to 6 are relative values when the value of the initial resistance of Comparative Example 1-1 is taken as 100.

[0242] <High-temperature storage characteristics> The nonaqueous electrolyte batteries of Examples 1-1 to 1-87 and Comparative Examples 1-1 to 1-43 described in Tables 1 to 6 after the initial charge and discharge described above were charged to a charge upper limit voltage of 4.2 V and discharged to a discharge termination voltage of 2.5 V at a current density of 0.38 mA / cm 2 Charging was performed, and then the batteries were taken out of the charge and discharge device maintained at 25°C and put into a constant-temperature bath at 60°C for storage for 14 days. Then, the batteries were put into a charge and discharge device maintained at 25°C, and 0.38 mA / cm 2 Discharge was performed to a discharge termination voltage of 2.5 V, and the capacity retention after storage was evaluated. The capacity retention after storage at 60°C was calculated using the following equation.

[0243] (Capacity retention after storage at 60°C) Capacity retention (%) = (capacity after storage at 60°C / initial charge and discharge capacity) x 100 In addition, the values of the capacity retention after storage at 60°C of Examples 1-1 to 1-87 and Comparative Examples 1-1 to 1-43 described in Tables 1 to 6 are relative values when the capacity retention after storage at 60°C of Comparative Example 1-1 is taken as 100.

[0244] The capacity retention after storage at 60°C of Examples 1-1 to 1-87 and Comparative Examples 1-1 to 1-43 is described in Tables 1 to 6 as "capacity after storage at 60°C".

[0245] (Resistance value after storage at 60°C) Next, the batteries were charged to 4.2 V at 25°C and 0.38 mA / cm 2 The resistance value was measured directly by impedance measurement.

[0246] In addition, the values of the resistance after storage at 60°C of Examples 1-1 to 1-87 and Comparative Examples 1-1 to 1-43 described in Tables 1 to 6 are relative values when the resistance after storage at 60°C of Comparative Example 1-1 is taken as 100.

[0247] The resistance after storage at 60°C of Examples 1-1 to 1-87 and Comparative Examples 1-1 to 1-43 is described in Tables 1 to 6 as "resistance after storage at 60°C".

[0248] (Evaluation of nonaqueous electrolyte batteries described in Tables 7 to 12) -Initial charge and discharge- The prepared nonaqueous electrolyte battery was placed in a 25°C thermostat, and connected to a charge-discharge device in this state. Charging was performed to 4.2 V at a current density of 0.38 mA / cm 2 Charging was performed to 4.2 V. After maintaining at 4.2 V for 1 hour, discharging was performed to 2.5 V at a current density of 0.38 mA / cm 2 Discharging was performed to 2.5 V. This operation was set to 1 charge-discharge cycle, and charging and discharging were performed for a total of 3 cycles to stabilize the battery.

[0249] <Initial resistance> The initial charge-discharge was performed at 25°C, 0.38 mA / cm 2 Charging was performed to 4.2 V, and the resistance value was measured directly by impedance measurement.

[0250] In addition, the values of the initial resistance described in Examples 2-1 to 2-87 and Comparative Examples 2-1 to 2-43 in Tables 7 to 12 are relative values when the value of the initial resistance of Comparative Example 2-1 is set to 100.

[0251] <Cycle characteristics test> The nonaqueous electrolyte batteries of Examples 2-1 to 2-87 and Comparative Examples 2-1 to 2-43 described in Tables 7 to 12 were subjected to a charge-discharge test at an ambient temperature of 25°C, and the cycle characteristics were evaluated. Charging was performed to 4.2 V, and discharging was performed to 2.5 V at a current density of 1.9 mA / cm 2 The charge-discharge cycle was repeated. Then, the deterioration of the battery cell was evaluated in terms of the discharge capacity retention rate after 200 cycles. The discharge capacity retention rate after 200 cycles was calculated using the following equation.

[0252] (Discharge capacity retention rate after 200 cycles) Discharge capacity retention rate (%) = (discharge capacity after 200 cycles / initial capacity) x 100 In addition, the values of the discharge capacity retention rate after 200 cycles described in Examples 2-1 to 2-87 and Comparative Examples 2-1 to 2-43 in Tables 7 to 12 are relative values when the discharge capacity retention rate after 200 cycles of Comparative Example 2-1 is set to 100. Furthermore, the discharge capacity of the first cycle in the cycle characteristics test at an ambient temperature of 25°C was set to the initial discharge capacity.

[0253] The discharge capacity retention rate after 200 cycles of Examples 2-1 to 2-87 and Comparative Examples 2-1 to 2-43 is described as "capacity after 200 cycles" in Tables 7 to 12.

[0254] (Resistance value after 200 cycles) The nonaqueous electrolyte battery after the above cycle characteristics test was subjected to impedance measurement at 25°C, 0.38 mA / cm 2Charged to 4.2 V, the resistance value was determined directly by impedance measurement.

[0255] In addition, the resistance value after 200 cycles of Examples 2-1 to 2-87 and Comparative Examples 2-1 to 2-43 described in Tables 7 to 12 is a relative value when the resistance value after 200 cycles of Comparative Example 2-1 is set to 100.

[0256] The resistance value after 200 cycles of Examples 2-1 to 2-87 and Comparative Examples 2-1 to 2-43 is described in Tables 7 to 12 as "resistance after 200 cycles".

[0257] [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8] [Table 9] [Table 10] [Table 11] [Table 12] Industrial applicability According to the present application, a nonaqueous electrolyte and a nonaqueous electrolyte battery capable of reducing the initial resistance value of a battery can be provided.

[0258] While the application has been described in detail with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the application.

[0259] In addition, the present application is based on Japanese Patent Application (Japanese Patent Application No. 2023-123779) filed on July 28, 2023, and the contents thereof are incorporated into the present specification by reference.

Claims

1. A non-aqueous electrolyte, comprising: (I) At least one sulfonic anhydride "1" represented by the following general formula (1), (II) At least one compound selected from the groups "2", "3", "4", "5", "6" and "7" below; (III) Solute, and (IV) Non-aqueous organic solvents [Chemical Formula 1] ， In general formula (1), R 1 and R 2 Each of the following can independently represent a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a straight-chain or branched alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms optionally substituted with an alkyl group; R 1 and R 2 Any hydrogen atom in the alkyl, alkenyl, and aryl groups may optionally be replaced by a halogen atom. The "2" refers to at least one compound selected from the group consisting of compounds represented by general formulas (2-1) to (2-2). [Chemical Formula 2] ， In general formula (2-1), R 3 and R 4 Each of the following organic groups is independently a fluorine atom, or an organic group selected from straight-chain or branched 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. In general formula (2-2), X 1 The organic group is a fluorine atom, or an organic group selected from the following: a straight-chain or branched 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; a straight-chain or branched 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 contains at least one fluorine atom and optionally also contains an oxygen atom and an unsaturated bond. 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. The "3" refers to at least one compound selected from the group consisting of compounds represented by general formulas (3-1) to (3-3). [Chemical Formula 3] ， In general formulas (3-1) to (3-3), R 5 ~R 10 Each of the organic groups is independently composed of a fluorine atom, or an organic group selected from straight-chain or branched 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. X 2 ~X 4 Each of the organic groups is independently composed of a fluorine atom, or is selected from a straight-chain or branched 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, a straight-chain or branched 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, wherein the organic group may optionally contain a fluorine atom, an oxygen atom, or an unsaturated bond. Furthermore, general formulas (3-1) to (3-3) contain at least one PF bond and / or SF bond. M1 m＋ It can be a proton, a metal cation, or an onium cation; m represents the valence of the corresponding cation. The "4" refers to 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). [Chemical Formula 4] ， In general formula (4-1), W represents boron, phosphorus, or silicon atoms, n1 is 0~3, n2 is 0~4, and p is 0 or 1; R 41 This refers to alkylene groups having 1 to 10 carbon atoms, haloalkylene groups having 1 to 10 carbon atoms, arylene groups having 6 to 20 carbon atoms, or haloarylene groups having 6 to 20 carbon atoms, wherein... These groups may optionally contain substituents or heteroatoms in their structure; furthermore, when n1 is 2 or more, there are n1 R groups. 41 Optional mutual bonding, R 42 Y represents a halogen atom. 1 Y 2 Each can independently represent an oxygen atom or a sulfur atom, Y 3 Y represents a carbon atom or a sulfur atom. 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. [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 aryl group having 6 to 20 carbon atoms, or a haloaryl group having 6 to 20 carbon atoms, wherein these groups may optionally contain substituents or heteroatoms in their structure, and r is 0 or 1; 4 Y represents a carbon atom or a sulfur atom. 4 When the atom is carbon, s is 1, Y 4 When s is a sulfur atom, s is 1 or 2; W 2 R represents a boron atom or a phosphorus atom. 44 Represents a halogen atom; W 2 When the atom is boron, n3 is 2, W 2 When the atom is phosphorus, n3 is 4. The "5" refers to at least one compound represented by the following general formula (5). [Chemical Formula 6] ， In general formula (5), R 51 Each independently represents a group having a carbon-carbon unsaturated bond; multiple R groups exist. 52 At that time, multiple R 52 Each of these terms independently represents a fluorine atom or a straight-chain or branched 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. The "6" refers to at least one compound represented by the following general formula (6). [Chemical Formula 7] ， In general formula (6), R 61 and R 62 Each of the following can independently represent a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, a straight-chain or branched 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 represented may be optionally replaced by a halogen atom; n6 is 0 or 1. The "7" refers to at least one compound selected from the group consisting of compounds represented by the following general formulas (7-1) to (7-2). [Chemical Formula 8] ， In general formula (7-1), R 70 ~R 73 Each can independently 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. In general formula (7-2), R 74 ~R 79 Each can independently 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.

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

3. The non-aqueous electrolyte according to claim 1 or 2, wherein, The content of (II) is 0.01% to 10% by mass relative to the total amount of the non-aqueous electrolyte.

4. The non-aqueous electrolyte according to claim 1 or 2, wherein, The (I) is selected from at least one of the groups consisting of methanesulfonic anhydride and ethanesulfonic anhydride.

5. The non-aqueous electrolyte according to claim 1 or 2, wherein, The "2" is at least one compound selected from the group consisting of lithium difluorophosphate, lithium fluorosulfonate and lithium trifluoromethanesulfonate.

6. The non-aqueous electrolyte according to claim 1 or 2, wherein, The "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.

7. The non-aqueous electrolyte according to claim 1 or 2, wherein, The "4" is 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, lithium tetrafluoromalonate phosphate, tetrafluoro(pyridinecarboxylate) phosphate, and difluoro(pyridinecarboxylate) borate.

8. The non-aqueous electrolyte according to claim 1 or 2, wherein, The "5" refers to at least one compound selected from the group consisting of trivinylmethylsilane, trivinylfluorosilane, and tetravinylsilane.

9. The non-aqueous electrolyte according to claim 1 or 2, wherein, The "6" is at least one compound selected from the group consisting of 1,3,2-dioxazothiophene-2,2-dioxide and 1,3,2-dioxothiacyclohexane-2,2-dioxide.

10. The non-aqueous electrolyte according to claim 1 or 2, wherein, The (III) is selected from at least one of the following groups: LiPF6, LiSbF6, LiAsF6, LiClO4, LiAlO2, LiAlCl4, LiCl and LiI, or from at least one of the following groups: NaPF6, NaSbF6, NaAsF6, NaClO4, NaAlO2, NaAlCl4, NaCl and NaI.

11. The non-aqueous electrolyte according to claim 1 or 2, wherein, The (IV) is selected from at least one of the following groups: cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds and ionic liquids.

12. The non-aqueous electrolyte according to claim 11, wherein, The cyclic ester is a cyclic carbonate, and the cyclic carbonate is selected from at least one of the groups consisting of ethylene carbonate, propylene carbonate and fluoroethylene carbonate.

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

14. A non-aqueous electrolyte battery, comprising at least a positive electrode, a negative electrode, a separator, and the non-aqueous electrolyte as described in claim 1 or 2.

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