Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0567—Liquid materials characterised by the additives
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0568—Liquid materials characterised by the solutes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0569—Liquid materials characterised by the solvents
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a nonaqueous electrolyte and a nonaqueous electrolyte battery using the same.
• Non-aqueous electrolyte-related technologies are no exception, and it has been proposed to use various additives to suppress deterioration caused by the decomposition of non-aqueous electrolyte on the surface of active positive and negative electrodes.
• Patent Document 1 proposes using a sulfonic acid anhydride in an electrolyte solution to improve cycle characteristics.
• Patent Document 2 proposes using a silicon compound in an electrolyte to improve cycle characteristics and low-temperature characteristics.
• Patent Document 3 proposes using a non-aqueous electrolyte solution containing lithium bisfluorosulfonylimide as a solute to improve storage characteristics.
• Patent Document 4 proposes using lithium monofluorophosphate or lithium difluorophosphate as an electrolyte to improve storage characteristics after charging.
• Patent Document 5 proposes that high input/output characteristics and impedance characteristics are maintained even after a durability test by using a non-aqueous electrolyte solution containing a fluorosulfonate.
• Patent Document 6 proposes that the use of a non-aqueous electrolyte solution containing a cyclic sulfate ester can suppress decomposition on a carbon negative electrode that occurs with the progress of charge-discharge cycles.
• Patent Document 7 proposes that by using a nonaqueous electrolyte solution containing cyclic sultone (unsaturated sultone), it is possible to obtain a battery in which deterioration of load characteristics and resistance is significantly suppressed and a small amount of gas is generated within the battery.
• Patent Document 8 discloses electrolytes containing various oxalate salts and malonate salts, which have high heat resistance and hydrolysis resistance.
• Patent Document 9 discloses that a nonaqueous electrolyte battery having high temperature durability can be obtained by incorporating a picolinic acid derivative represented by general formula (3) in the document into a nonaqueous electrolyte.
• the present disclosure has been made in consideration of the above circumstances, and aims to provide a nonaqueous electrolyte and a nonaqueous electrolyte battery that can reduce the initial resistance value of a battery.
• the inventors conducted extensive research to solve this problem, and discovered that by incorporating a specific sulfonic acid anhydride and at least one selected from the group consisting of phosphates, sulfonates, imide salts, borates, picolinic acid derivatives, silicon compounds, cyclic sulfates, and cyclic sultones with specific structures in a nonaqueous electrolyte for nonaqueous electrolyte batteries, the initial resistance of the battery can be reduced when the electrolyte is used in the nonaqueous electrolyte battery, leading to the present invention.
• the present invention is as follows. [1] (I) at least one sulfonic acid anhydride "1" represented by the following general formula (1), (II) at least one compound selected from the group represented by the following "2", “3”, “4", “5", “6”, and “7”, (III) a solute; and (IV) a nonaqueous organic solvent.
• R1 and R2 each independently represent 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 which may be substituted with an alkyl group having 6 to 10 carbon atoms. Any hydrogen atom in the alkyl group, alkenyl group, and aryl group represented by R1 and R2 may be substituted with a halogen atom.
• the above “2" is at least one compound selected from the group consisting of compounds represented by the following general formulas (2-1) to (2-2):
• R 3 and R 4 are each independently 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 may contain a fluorine atom, an oxygen atom, or an unsaturated bond.
• general formula (2-1) contains at least one P-F bond.
• X 1 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 the organic group may contain at least one fluorine atom, and the organic group may also
• M 1 m+ represents a proton, a metal cation or an onium cation, and m represents the valence of the corresponding cation.
• the above “3” is at least one compound selected from the group consisting of compounds represented by the following general formulas (3-1) to (3-3):
• R 5 to R 10 each independently represent 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 may contain a fluorine atom, an oxygen atom, or an unsaturated bond.
• X 2 to X 4 are each independently 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 the organic group may contain a fluorine atom, an oxygen atom, or an
• each of the general formulae (3-1) to (3-3) contains at least one P—F bond and/or S—F bond.
• M 1 m+ is a proton, a metal cation or an onium cation, and m represents the valence of the corresponding cation.
• the above "4" is 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):
• W represents a boron atom, a phosphorus atom, or a silicon atom
• n1 represents 0 to 3
• n2 represents 0 to 4
• p represents 0 or 1.
• R 41 represents an alkylene group having 1 to 10 carbon atoms, a halogenated alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms (these groups may contain a substituent or a heteroatom in the structure.
• R 42 represents a halogen atom
• Y 1 and Y 2 each independently represent an oxygen atom or a sulfur atom
• Y 3 represents a carbon atom or a sulfur atom.
• q is 1 when Y 3 is a carbon atom, and is 1 or 2 when Y 3 is a sulfur atom.
• M a+ represents an alkali metal cation, an alkaline earth metal cation, or an onium cation
• a represents the valence of the corresponding cation
• R 43 represents an alkylene group having 1 to 10 carbon atoms, a halogenated alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms (these groups may contain a substituent or a heteroatom in the structure), and r is 0 or 1.
• Y 4 represents a carbon atom or a sulfur atom. s is 1 when Y 4 is a carbon atom, and 1 or 2 when Y 4 is a sulfur atom.
• W 2 represents a boron atom or a phosphorus atom, and R 44 represents a halogen atom.
• n3 is 2 when W 2 is a boron atom, and 4 when W 2 is a phosphorus atom.
• the "5" is at least one compound represented by the following general formula (5):
• R 51 each independently represents a group having a carbon-carbon unsaturated bond.
• R 52 each independently represents a fluorine atom or a linear or branched alkyl group having 1 to 10 carbon atoms, and the alkyl group may have at least one of a fluorine atom and an oxygen atom.
• v represents an integer of 2 to 4.
• the "6" is at least one compound represented by the following 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 which may be substituted with an alkyl group having 6 to 10 carbon atoms. Any hydrogen atom of the alkyl group, alkenyl group, and aryl group represented by R 61 and R 62 may be substituted with a halogen atom.
• n6 is 0 or 1.
• the above "7" is at least one compound selected from the group consisting of compounds represented by the following general formulas (7-1) to (7-2).
• R 70 to R 73 each independently represent 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.
• R 74 to R 79 each independently represent 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.
• the cyclic ester is a cyclic carbonate
• the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate.
• a nonaqueous electrolyte battery comprising at least a positive electrode, a negative electrode, a separator, and the non-aqueous electrolyte according to any one of [1] to [13].
• This disclosure makes it possible to provide a nonaqueous electrolyte and a nonaqueous electrolyte battery that can reduce the initial resistance value of a battery.
• Nonaqueous electrolyte The nonaqueous electrolyte of the present disclosure is (I) at least one sulfonic acid anhydride "1" represented by the above general formula (1), (II) at least one compound selected from the group represented by "2", “3", “4", "5", “6", and “7”above; (III) a solute; and (IV) a nonaqueous organic solvent.
• a nonaqueous electrolyte containing both components (I) and (II) is used in a nonaqueous electrolyte battery (e.g., a lithium ion secondary battery or a sodium ion secondary battery)
• a nonaqueous 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 electrode or the negative electrode, forming a film with good cation conductivity on at least the surface of either the positive electrode or the negative electrode.
• This film is thought to suppress direct contact between the nonaqueous organic solvent or the solute and the electrode active material, and to reduce the cation dissociation energy of the solute.
• the inventors presume that this results in a reduction in the initial resistance value of the nonaqueous electrolyte battery.
• the non-aqueous electrolyte of the present disclosure contains at least one sulfonic acid anhydride "1" represented by general formula (1), which is component (I).
• R1 and R2 each independently represent 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 which may be substituted with an alkyl group having 6 to 10 carbon atoms. Any hydrogen atom in the alkyl group, alkenyl group, and aryl group represented by R1 and R2 may be substituted with a halogen atom.
• R 1 and R 2 are linear or branched alkyl groups having 1 to 6 carbon atoms
• examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.
• R 1 and R 2 are linear or branched alkenyl groups having 2 to 10 carbon atoms
• examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, and a 1,3-butadienyl group.
• examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group.
• the number of carbon atoms of 6 to 10 refers to the total number of carbon atoms in the aryl group and, when the aryl group is substituted with an alkyl group, the total number of carbon atoms in the alkyl group.
• At least one of the hydrogen atoms in the alkyl group, alkenyl group, and aryl group may be substituted with a halogen atom.
• halogen atoms include fluorine atoms, bromine atoms, and iodine atoms, and fluorine atoms are preferred.
• R 1 and R 2 are each preferably independently a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, or an isopropyl group, and further preferably a methyl group or an ethyl group.
• R 1 and R 2 both represent a methyl group, or that R 1 and R 2 both represent an ethyl group. That is, it is preferable that the component (I) is at least one selected from the group consisting of methanesulfonic anhydride and ethanesulfonic anhydride.
• the content of the component (I) (hereinafter also referred to as the "concentration of (I)") relative to the total amount (100 mass%) of the nonaqueous electrolyte may have a lower limit of 0.01 mass% or more, 0.05 mass% or more, or 0.1 mass% or more.
• the upper limit of the concentration of (I) may be 10 mass% or less, 5 mass% or less, 4 mass% or less, or 2.5 mass% or less.
• the content of the component (I) relative to the total amount of the nonaqueous electrolyte is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass.
• the nonaqueous electrolyte of the present disclosure may use one type of compound alone as component (I), or may use two or more types of compounds mixed in any combination and ratio according to the application.
• the sulfonic acid anhydride represented by general formula (1) can be produced by known methods.
• the nonaqueous electrolyte solution of the present disclosure contains, as component (II), at least one compound selected from the group represented by "2", “3", “4", "5", “6", and “7” below.
• ⁇ 2 ⁇ > "2" is at least one compound selected from the group consisting of compounds represented by the following general formulas (2-1) to (2-2).
• R 3 and R 4 are each independently 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 may contain a fluorine atom, an oxygen atom, or an unsaturated bond.
• general formula (2-1) contains at least one P-F bond.
• X 1 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 the organic group may contain at least one fluorine atom, and the organic group may also
• examples of the alkoxy group represented by R 3 and R 4 include alkoxy groups having 1 to 10 carbon atoms and fluorine-containing alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 1,1,1-trifluoroisopropoxy group, and a 1,1,1,3,3,3-hexafluoroisopropoxy group.
• fluorine-containing alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group
• alkenyloxy group represented by R3 and R4 examples include alkenyloxy groups having 2 to 10 carbon atoms and fluorine-containing alkenyloxy groups, such as a vinyloxy group, a 1-propenyloxy group, a 2-propenyloxy group, an isopropenyloxy group, a 2-butenyloxy group, a 3-butenyloxy group, and a 1,3-butadienyloxy group.
• alkynyloxy group represented by R3 and R4 examples include alkynyloxy groups having 2 to 10 carbon atoms and fluorine-containing alkynyloxy groups, such as an ethynyloxy group, a 2-propynyloxy group, and a 1,1-dimethyl-2-propynyloxy group.
• cycloalkoxy group represented by R3 and R4 examples include cycloalkoxy groups having 3 to 10 carbon atoms, such as a cyclopentyloxy group and a cyclohexyloxy group, and fluorine-containing cycloalkoxy groups.
• Examples of the cycloalkenyloxy group represented by R3 and R4 include cycloalkenyloxy groups having 3 to 10 carbon atoms, such as a cyclopentenyloxy group and a cyclohexenyloxy group, and fluorine-containing cycloalkenyloxy groups.
• Examples of the aryloxy group represented by R3 and R4 include aryloxy groups having 6 to 10 carbon atoms, such as a phenyloxy group, a tolyloxy group, and a xylyloxy group, and fluorine-containing aryloxy groups.
• R3 and R4 are each preferably a fluorine atom or an alkoxy group having a fluorine atom, since the degree of ionic dissociation is improved due to its strong electron-withdrawing property, thereby increasing the ionic conductivity in a solution or composition.Furthermore, a fluorine atom is more preferable, since the anion size is reduced, leading to an effect of improving mobility, thereby extremely increasing the ionic conductivity in a solution or composition.
• R3 and R4 preferably have a carbon number of 6 or less. When the carbon number is 6 or less, the ionic conductivity tends to be relatively high, which is preferable.
• M 1 m+ represents a proton, a metal cation, or an onium cation.
• the type of the cation and various cations can be selected from the above, as long as they do not impair the performance of the nonaqueous electrolyte and the nonaqueous electrolyte battery of the present invention.
• examples of the metal cation include alkali metal cations such as lithium ion, sodium ion, potassium ion, rubidium ion, and cesium ion, alkaline earth metal cations such as magnesium ion, calcium ion, and barium ion, silver ion, copper ion, and iron ion.
• examples of the onium cation include onium cations such as tetraalkylammonium, tetraalkylphosphonium, and imidazolium derivatives.
• M 1 m+ is preferably a lithium ion, a sodium ion, a potassium ion, a tetramethylammonium ion, a tetraethylammonium ion, a tetrabutylphosphonium ion, or the like. Furthermore, M 1 m+ is more preferably a lithium ion when used in a lithium ion battery, and is more preferably a sodium ion when used in a sodium ion battery.
• examples of the alkyl group represented by X1 include alkyl groups having 1 to 10 carbon atoms and fluorine-containing alkyl groups, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl 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, and a 1,1,1,3,3,3-hexafluoroisopropyl group.
• fluorine-containing alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pent
• alkenyl group represented by X1 examples include alkenyl groups having 2 to 10 carbon atoms, such as vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 2-butenyl group, 3-butenyl group, and 1,3-butadienyl group, and fluorine-containing alkenyl groups.
• alkynyl group represented by X1 examples include alkynyl groups having 2 to 10 carbon atoms and fluorine-containing alkynyl groups, such as an ethynyl group, a 2-propynyl group, and a 1,1-dimethyl-2-propynyl group.
• Examples of the cycloalkyl group represented by X1 include cycloalkyl groups having 3 to 10 carbon atoms, such as a cyclopentyl group and a cyclohexyl group, and fluorine-containing cycloalkyl groups.
• Examples of the cycloalkenyl group represented by X1 include cycloalkenyl groups having 3 to 10 carbon atoms, such as a cyclopentenyl group and a cyclohexenyl group, and fluorine-containing cycloalkenyl groups.
• Examples of the aryl group represented by X1 include aryl groups having 6 to 10 carbon atoms, such as a phenyl group, a tolyl group, and a xylyl group, and fluorine-containing aryl groups.
• Examples of the alkoxy group, alkenyloxy group, alkynyloxy group, cycloalkoxy group, cycloalkenyloxy group, and aryloxy group represented by X1 include the alkoxy group, alkenyloxy group, alkynyloxy group, cycloalkoxy group, cycloalkenyloxy group, and aryloxy group represented by R3 and R4 in the above general formula (2-1).
• X1 is preferably a fluorine atom or an alkyl group containing a fluorine atom, since the degree of ionic dissociation is improved due to its strong electron-withdrawing property, thereby increasing the ionic conductivity in a solution or a composition. Furthermore, a fluorine atom is more preferable, since the anion size is reduced, thereby improving the mobility, thereby extremely increasing the ionic conductivity in a solution or a composition. Furthermore, X1 preferably has 6 or less carbon atoms since the ionic conductivity tends to be relatively high, more preferably has 1 to 4 carbon atoms, and further preferably has 1 to 3 carbon atoms. Specific examples include a trifluoromethyl group, a trifluoromethoxy group, and a trifluoroethoxy group, with a trifluoromethyl group being particularly preferred because of its small anion size.
• M 1 m+ has the same meaning as M 1 m+ in the general formula (2-1), and preferred examples thereof are also the same.
• “2" is preferably at least one compound selected from the group consisting of difluorophosphates, fluorosulfonates, and trifluoromethanesulfonates, and more preferably at least one compound selected from the group consisting of lithium difluorophosphate, lithium fluorosulfonate, and lithium trifluoromethanesulfonate.
• ⁇ “3”> "3" is at least one compound selected from the group consisting of compounds represented by the following general formulas (3-1) to (3-3).
• R 5 to R 10 each independently represent 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 may contain a fluorine atom, an oxygen atom, or an unsaturated bond.
• X 2 to X 4 are each independently 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 the organic group may contain a fluorine atom, an oxygen atom, or an
• each of the general formulae (3-1) to (3-3) contains at least one P—F bond and/or S—F bond.
• M 1 m+ is a proton, a metal cation or an onium cation, and m represents the valence of the corresponding cation.
• Examples of the alkoxy group, alkenyloxy group, alkynyloxy group, cycloalkoxy group, cycloalkenyloxy group, and aryloxy group represented by R5 to R10 include the alkoxy group, alkenyloxy group, alkynyloxy group, cycloalkoxy group, cycloalkenyloxy group, and aryloxy group represented by R3 and R4 in the above general formula (2-1).
• R 5 to R 10 are each independently a fluorine atom or an alkoxy group having a fluorine atom, since the degree of ionic dissociation is improved due to the strong electron-withdrawing property, thereby increasing the ionic conductivity in a solution or composition.
• R 5 to R 10 are a fluorine atom, since the anion size is reduced, thereby improving the mobility, thereby extremely increasing the ionic conductivity in a solution or composition.
• R 5 to R 10 each have a carbon number of 6 or less. When the carbon number is 6 or less, the ionic conductivity tends to be relatively high, which is preferable.
• alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, cycloalkoxy group, cycloalkenyloxy group, and aryloxy group represented by X 2 to X 4 include the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, cycloalkoxy group, cycloalkenyloxy group, and aryloxy group represented by X 1 in the above general formula (2-1).
• X 2 to X 4 are fluorine atoms or alkyl groups containing fluorine atoms, since the degree of ionic dissociation is improved due to their strong electron-withdrawing property, thereby increasing the ionic conductivity in a solution or composition.Furthermore, it is more preferable that X 2 to X 4 are fluorine atoms, since the anion size is reduced, thereby improving the mobility, thereby extremely increasing the ionic conductivity in a solution or composition. Furthermore, X2 to X4 each preferably have 6 or less carbon atoms since the ionic conductivity tends to be relatively high, more preferably have 1 to 4 carbon atoms, and even more preferably have 1 to 3 carbon atoms. Specific examples include a trifluoromethyl group and a pentafluoroethyl group, and the trifluoromethyl group, which has a small anion size, is particularly preferred.
• M 1 m+ has the same meaning as M 1 m+ in the general formula (2-1), and preferred examples thereof are also the same.
• "3" is preferably at least one compound selected from the group consisting of bis(fluorosulfonyl)imide salts, (fluorosulfonyl)(difluorophosphoryl)imide salts, bis(trifluoromethanesulfonyl)imide salts, bis(difluorophosphoryl)imide salts, bis(pentafluoroethanesulfonyl)imide salts, and (fluorosulfonyl)(trifluoromethanesulfonyl)imide salts, and more preferably at least one compound selected from the group consisting of bis(fluorosulfonyl)imide lithium, (fluorosulfonyl)(difluorophosphoryl)imide lithium, bis(trifluoromethanesulfonyl)imide lithium, bis(difluorophosphoryl)imide lithium, bis(pentafluoroethanesulfonyl)imide lithium, and
• ⁇ 4 ⁇ > is 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).
• W represents a boron atom, a phosphorus atom, or a silicon atom
• n1 represents 0 to 3
• n2 represents 0 to 4
• p represents 0 or 1.
• R 41 represents an alkylene group having 1 to 10 carbon atoms, a halogenated alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms (these groups may contain a substituent or a heteroatom in the structure.
• R 42 represents a halogen atom
• Y 1 and Y 2 each independently represent an oxygen atom or a sulfur atom
• Y 3 represents a carbon atom or a sulfur atom.
• q is 1 when Y 3 is a carbon atom, and is 1 or 2 when Y 3 is a sulfur atom.
• M a+ represents an alkali metal cation, an alkaline earth metal cation, or an onium cation
• a represents the valence of the corresponding cation
• R 43 represents an alkylene group having 1 to 10 carbon atoms, a halogenated alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms (these groups may contain a substituent or a heteroatom in the structure), and r is 0 or 1.
• Y 4 represents a carbon atom or a sulfur atom. s is 1 when Y 4 is a carbon atom, and 1 or 2 when Y 4 is a sulfur atom.
• W 2 represents a boron atom or a phosphorus atom, and R 44 represents a halogen atom.
• n3 is 2 when W 2 is a boron atom, and 4 when W 2 is a phosphorus atom.
• W represents a boron atom, a phosphorus atom, or a silicon atom, and is preferably a boron atom or a phosphorus atom.
• Examples of the alkylene group having 1 to 10 carbon atoms represented by R 41 include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, and an n-hexylene group.
• Examples of the halogenated alkylene group having 1 to 10 carbon atoms represented by R 41 include the above alkylene groups in which any hydrogen atom has been substituted with a halogen atom.
• Examples of the arylene group having 6 to 20 carbon atoms represented by R 41 include a phenylene group and a naphthylene group.
• Examples of the halogenated arylene group having 6 to 20 carbon atoms represented by R 41 include the above arylene groups in which any hydrogen atom has been substituted with a halogen atom.
• R 41 is preferably a methylene group, an ethylene group, an n-propylene group, a difluoromethylene group, a tetrafluoroethylene group or a hexafluoropropylene group, and more preferably a methylene group.
• Examples of the halogen atom represented by R 42 include a fluorine atom, a chlorine atom, an iodine atom, etc., and a fluorine atom is preferable.
• Y 1 and Y 2 each independently represent an oxygen atom or a sulfur atom, and it is preferable that both are oxygen atoms.
• Y3 represents a carbon atom or a sulfur atom, and is preferably a carbon atom.
• Examples of the alkali metal cation, alkaline earth metal cation, and onium cation represented by M a+ include the alkali metal cations, alkaline earth metal cations, and onium cations exemplified as M 1 m+ in the above general formula (2-1), and preferred examples are also the same.
• Examples of compounds represented by general formula (4-1) include tetrafluoroborate, bis(oxalato)borate, difluoro(oxalato)borate, tris(oxalato)phosphate, difluorobis(oxalato)phosphate, tetrafluoro(oxalato)phosphate, tris(oxalato)silicate, difluorobis(oxalato)silicate, difluoro(malonato)borate, tetrafluoro(malonato)phosphate, difluoro(sulfoacetato)borate, difluoro(maleato)borate, and difluoro(fumarato)borate.
• Examples of the alkylene group having 1 to 10 carbon atoms represented by R 43 include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, and an n-hexylene group.
• Examples of the halogenated alkylene group having 1 to 10 carbon atoms represented by R 43 include the above alkylene groups in which any hydrogen atom has been substituted with a halogen atom.
• Examples of the arylene group having 6 to 20 carbon atoms represented by R 43 include a phenylene group and a naphthylene group.
• Examples of the halogenated arylene group having 6 to 20 carbon atoms represented by R 43 include the above arylene groups in which any hydrogen atom has been substituted with a halogen atom.
• R 43 is preferably a methylene group, an ethylene group, an n-propylene group, a difluoromethylene group, a tetrafluoroethylene group or a hexafluoropropylene group, and more preferably a methylene group.
• Examples of the halogen atom represented by R 44 include a fluorine atom, a chlorine atom, an iodine atom, etc., and a fluorine atom is preferable.
• Y4 represents a carbon atom or a sulfur atom, and is preferably a carbon atom.
• the compounds represented by general formula (4-2) include the following compounds:
• "4" is preferably at least one compound selected from the group consisting of tetrafluoroborate, bis(oxalato)borate, difluoro(oxalato)borate, tris(oxalato)phosphate, difluorobis(oxalato)phosphate, tetrafluoro(oxalato)phosphate, difluoro(malonato)borate, tetrafluoro(malonato)phosphate, tetrafluoro(picolinato)phosphate, and difluoro(picolinato)borate, and more preferably at least one compound selected from the group consisting of lithium tetrafluoroborate, lithium bis(oxalato)borate, lithium difluoro(oxalato)borate, lithium tris(oxalato)phosphate, lithium difluorobis(oxalato)phosphate, lithium tetrafluoro(oxalato)phosphate, lithium di
• ⁇ 5 ⁇ > "5" is at least one compound represented by the following general formula (5).
• R 51 each independently represents a group having a carbon-carbon unsaturated bond.
• R 52 each independently represents a fluorine atom or a linear or branched alkyl group having 1 to 10 carbon atoms, and the alkyl group may have at least one of a fluorine atom and an oxygen atom.
• v represents an integer of 2 to 4.
• Examples of the group having a carbon-carbon unsaturated bond represented by R 51 include alkenyl groups having 2 to 8 carbon atoms, such as vinyl groups, allyl groups, 1-propenyl groups, isopropenyl groups, 2-butenyl groups, and 1,3-butadienyl groups, or alkenyloxy groups derived from these groups; alkynyl groups having 2 to 8 carbon atoms, such as ethynyl groups, 2-propynyl groups, and 1,1 dimethyl-2-propynyl groups, or alkynyloxy groups derived from these groups; aryl groups having 6 to 12 carbon atoms, such as phenyl groups, tolyl groups, and xylyl groups, or aryloxy groups derived from these groups.
• alkenyl groups having 2 to 8 carbon atoms such as vinyl groups, allyl groups, 1-propenyl groups, isopropenyl groups, 2-butenyl groups, and 1,3-butadieny
• the above groups may also have fluorine atoms and oxygen atoms.
• groups containing a carbon-carbon unsaturated bond having 6 or less carbon atoms are preferred. If the carbon number is 6 or less, the resistance when a film is formed on an electrode tends to be relatively small.
• groups selected from the group consisting of vinyl groups, allyl groups, 1-propenyl groups, ethynyl groups, and 2-propynyl groups are preferred.
• the linear or branched alkyl group having 1 to 10 carbon atoms represented by R52 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, etc.
• the above groups may have at least one of a fluorine atom and an oxygen atom.
• groups selected from a fluorine atom, a methyl group, an ethyl group, a propyl 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 tend to have a smaller initial resistance when a film is formed on an electrode, and as a result are preferred from the standpoint of output characteristics.
• v represents an integer of 2 to 4, preferably 3 or 4, and particularly preferably 4.
• "5" is preferably at least one compound selected from the group consisting of trivinylmethylsilane, trivinylfluorosilane, and tetravinylsilane.
• ⁇ 6 ⁇ > "6" is at least one compound represented by the following 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 which may be substituted with an alkyl group having 6 to 10 carbon atoms. Any hydrogen atom of the alkyl group, alkenyl group, and aryl group represented by R 61 and R 62 may be substituted with a halogen atom.
• n6 is 0 or 1.
• R 61 and R 62 are an alkyl group having 1 to 2 carbon atoms
• examples of the alkyl group include a methyl group and an ethyl group.
• examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, and a 1,3-butadienyl group.
• R 61 and R 62 are an aryl group which may be substituted with an alkyl group having 6 to 10 carbon atoms
• examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group.
• the number of carbon atoms of 6 to 10 refers to the total number of carbon atoms in the aryl group and, when the aryl group is substituted with an alkyl group, the total number of carbon atoms in the alkyl group.
• At least one of the hydrogen atoms in the alkyl group, alkenyl group, and aryl group may be substituted with a halogen atom.
• halogen atoms include fluorine atoms, bromine atoms, and iodine atoms, and fluorine atoms are preferred.
• R 61 and R 62 preferably represent a hydrogen atom.
• n6 is 0, the carbon atom to which R 61 is bonded and the carbon atom to which R 62 is bonded are bonded via a single bond. That is, "6" is preferably 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.
• the above "7” is at least one compound selected from the group consisting of compounds represented by the following general formulas (7-1) to (7-2).
• R 70 to R 73 each independently represent 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.
• R 74 to R 79 each independently represent 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.
• examples of the alkyl group represented by R 70 to R 73 include alkyl groups having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group.
• fluoroalkyl group represented by R 70 to R 73 examples include fluoroalkyl groups having 1 to 4 carbon atoms, such as a trifluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3-tetrafluoropropyl group, and a 1,1,1,3,3,3-hexafluoroisopropyl group.
• R 70 to R 73 are preferably a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and more preferably a hydrogen atom.
• n71 represents an integer from 1 to 3, may be 1 or 2, and is preferably 1.
• Examples of the compound represented by general formula (7-1) include 1,3-propene sultone (1-propene-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, and 1,5-pentene sultone.
• examples of the alkyl group represented by R 74 to R 79 include alkyl groups having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.
• fluoroalkyl group represented by R 74 to R 79 examples include fluoroalkyl groups having 1 to 4 carbon atoms, such as a trifluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3-tetrafluoropropyl group, and a 1,1,1,3,3,3-hexafluoroisopropyl group.
• R 74 to R 79 are preferably a hydrogen atom, a fluorine atom or a trifluoromethyl group, and more preferably a hydrogen atom.
• n72 represents an integer of 0 to 2 and may be 0 or 1, and is preferably 0.
• n72 is 0, the carbon atom to which R 76 and R 77 are bonded and the carbon atom to which R 78 and R 79 are bonded are bonded via a single bond.
• Examples of compounds represented by general formula (7-2) include 1,3-propane sultone, ⁇ -trifluoromethyl- ⁇ -sultone, ⁇ -trifluoromethyl- ⁇ -sultone, ⁇ -trifluoromethyl- ⁇ -sultone, ⁇ -methyl- ⁇ -sultone, ⁇ , ⁇ -di(trifluoromethyl)- ⁇ -sultone, ⁇ , ⁇ -di(trifluoromethyl)- ⁇ -sultone, ⁇ -heptafluoropropyl- ⁇ -sultone, 1,4-butane sultone, and 1,5-pentane sultone.
• “7” is preferably at least one compound selected from the group consisting of 1,3-propane sultone and 1-propene-1,3-sultone.
• the content of the component (II) (hereinafter also referred to as the "concentration of (II)" relative to the total amount (100 mass%) of the nonaqueous electrolyte may have a lower limit of 0.01 mass% or more, 0.05 mass% or more, or 0.1 mass% or more.
• the upper limit of the concentration of (II) may be 10 mass% or less, 5 mass% or less, 4 mass% or less, or 2.5 mass% or less.
• the content of the component (II) relative to the total amount of the nonaqueous electrolyte may be 0.01 to 10% by mass, or may be 0.01 to 5% by mass.
• the content relative to the total amount of the non-aqueous electrolyte may be 0.01 mass% or more and 20 mass % or less.
• the nonaqueous electrolyte of the present disclosure may use one type of compound alone as component (II), or may use two or more types of compounds mixed in any combination and ratio according to the application.
• the nonaqueous electrolyte of the present disclosure contains a solute.
• the solute is not particularly limited, but is preferably an ionic salt, and more preferably an ionic salt containing fluorine.
• the solute is preferably an ionic salt consisting of a pair of at least one cation selected from the group consisting of alkali metal ions, such as lithium ions and sodium ions, alkaline earth metal ions, and quaternary ammonium, and at least one anion selected from the group consisting of hexafluorophosphate anion, perchlorate anion, hexafluoroarsenate anion, hexafluoroantimonate anion, and tris(trifluoromethanesulfonyl)methide anion.
• alkali metal ions such as lithium ions and sodium ions, alkaline earth metal ions, and quaternary ammonium
• anion selected from the group consisting of hexafluorophosphate anion, perchlorate anion, hexafluoroarsenate anion, hexafluoroantimonate anion, and tris(trifluoromethanesulfonyl)me
• the solute is at least one selected from the group consisting of LiPF6 , LiSbF6 , LiAsF6 , LiClO4 , LiAlO2 , LiAlCl4 , LiCl, and LiI, or at least one selected from the group consisting of NaPF6 , NaSbF6 , NaAsF6 , NaClO4 , NaAlO2 , NaAlCl4 , NaCl, and NaI.
• solutes may be used alone or in any combination and ratio of two or more kinds depending on the application.
• the cation is at least one selected from the group consisting of lithium, sodium, potassium, magnesium, and quaternary ammonium
• the anion is at least one selected from the group consisting of hexafluorophosphate anion and tetrafluoroborate anion.
• the total amount of solutes in the nonaqueous electrolyte of the present disclosure (hereinafter also referred to as "solute concentration") is not particularly limited, but the lower limit is preferably 0.5 mol/L or more, more preferably 0.7 mol/L or more, and even more preferably 0.9 mol/L or more.
• the upper limit of the solute concentration is preferably 5 mol/L or less, more preferably 4 mol/L or less, and even more preferably 2 mol/L or less.
• solute concentration By setting the solute concentration to 0.5 mol/L or more, it is possible to suppress the deterioration of the cycle characteristics and output characteristics of the nonaqueous electrolyte battery caused by a decrease in ionic conductivity, and by setting it to 5 mol/L or less, it is possible to suppress the deterioration of the cycle characteristics and output characteristics of the nonaqueous electrolyte battery caused by an increase in the viscosity of the nonaqueous electrolyte.
• the nonaqueous organic solvent (IV) contained in the nonaqueous electrolyte solution of the present disclosure (also referred to as "IV") will be described.
• the type of the nonaqueous organic solvent (IV) is not particularly limited, and any nonaqueous organic solvent can be used.
• Specific examples of the nonaqueous organic solvent (IV) include the following nonaqueous organic solvents.
• cyclic ester examples include cyclic carbonates such as propylene carbonate (hereinafter sometimes referred to as "PC"), ethylene carbonate (hereinafter sometimes referred to as “EC”), fluoroethylene carbonate (hereinafter sometimes referred to as “FEC”), butylene carbonate, etc., as well as ⁇ -butyrolactone, ⁇ -valerolactone, etc. Note that when the content of the FEC relative to the total amount of the non-aqueous electrolyte is 10 mass% or less, it is defined as an other additive described below.
• PC propylene carbonate
• EC ethylene carbonate
• FEC fluoroethylene carbonate
• butylene carbonate etc.
• ⁇ -butyrolactone ⁇ -valerolactone
• chain esters examples include chain carbonates such as 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”), and methyl propyl carbonate, as well as methyl acetate, methyl propionate, and ethyl propionate (hereinafter sometimes referred to as "EP”).
• chain carbonates such as 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”), and methyl propyl carbonate, as well as methyl acetate, methyl propionate, and ethyl propionate (hereinafter sometimes referred to as "EP”).
• Examples of cyclic ethers include tetrahydrofuran, 2-methylt
• the nonaqueous organic solvent may contain at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds, and ionic liquids.
• the cyclic ester may be a cyclic carbonate, and the cyclic carbonate may be at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate.
• the chain ester may be a chain carbonate, and the chain carbonate may be at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.
• the nonaqueous electrolyte of the present disclosure may use one type of compound alone as (IV), or may use two or more types of compounds mixed in any combination and ratio according to the application.
• the content of the cyclic carbonate is not particularly limited and may be any content as long as it does not significantly impair the effects of the present disclosure, but when one type is used alone, the content is 3 vol% or more, more preferably 5 vol% or more, in 100 vol% of the nonaqueous organic solvent.
• the content is usually 90 vol% or less, preferably 85 vol% or less, and more preferably 80 vol% or less.
• the viscosity of the nonaqueous electrolyte can be set in an appropriate range, a decrease in ion conductivity can be suppressed, and the load characteristics of the nonaqueous electrolyte battery can be easily set in a good range.
• two or more types of cyclic carbonates can be used in any combination.
• One of the preferred combinations is a combination of ethylene carbonate and propylene carbonate.
• the volume ratio of ethylene carbonate to propylene carbonate is preferably 99:1 to 40:60, and particularly preferably 95:5 to 50:50.
• the amount of propylene carbonate in the entire nonaqueous organic solvent is not particularly limited and can be any amount as long as it does not significantly impair the effects of the present disclosure, but is usually 1 vol.% or more, preferably 2 vol.% or more, more preferably 3 vol.% or more, and usually 30 vol.% or less, preferably 25 vol.% or less, more preferably 20 vol.% or less.
• propylene carbonate is contained within this range, it is preferable because the low-temperature properties are further improved while maintaining the properties of the combination of ethylene carbonate and dialkyl carbonates.
• the chain ester may be used alone or in any combination of two or more kinds in any ratio.
• the content of the chain ester is not particularly limited, but is usually 15% by volume or more, preferably 20% by volume or more, more preferably 25% by volume or more, in 100% by volume of the nonaqueous organic solvent. Also, it is usually 90% by volume or less, preferably 85% by volume or less, more preferably 80% by volume or less.
• the decrease in electrical conductivity due to the decrease in the dielectric constant of the nonaqueous electrolyte is avoided, and the input/output characteristics and charge/discharge rate characteristics of the nonaqueous electrolyte battery are easily set to a good range. Furthermore, by combining a specific chain ester with a specific amount of ethylene carbonate, the battery performance can be significantly improved.
• the content of ethylene carbonate is not particularly limited and can be any content as long as it does not significantly impair the effects of the present disclosure, but is usually 5 vol% or more, preferably 10 vol% or more, and usually 45 vol% or less, preferably 40 vol% or less
• the content of dimethyl carbonate is usually 20 vol% or more, preferably 30 vol% or more, and usually 50 vol% or less, preferably 45 vol% or less
• the content of ethyl methyl carbonate is usually 20 vol% or more, preferably 30 vol% or more, and usually 50 vol% or less, preferably 45 vol% or less.
• the low-temperature deposition temperature of the electrolyte can be lowered while also lowering the viscosity of the nonaqueous electrolyte, improving ionic conductivity, and obtaining high input and output even at low temperatures.
• the amount of the chain ether is not particularly limited and may be any amount as long as it does not significantly impair the effects of the present disclosure, but is usually 1 vol.% or more, preferably 2 vol.% or more, more preferably 3 vol.% or more, and usually 30 vol.% or less, preferably 25 vol.% or less, more preferably 20 vol.% or less, based on 100 vol.% of the nonaqueous organic solvent. If the amount of the chain ether is within the above range, it is easy to ensure the effect of improving the degree of lithium ion dissociation of the chain ether and improving the ion conductivity due to the reduced viscosity.
• the negative electrode active material is a carbonaceous material
• the phenomenon in which the chain ether is co-inserted with the lithium ion can be suppressed, and therefore the input/output characteristics and the charge/discharge rate characteristics can be set within appropriate ranges.
• the content of the sulfone compound is not particularly limited and may be any amount as long as it does not significantly impair the effects of the present disclosure, but is usually 0.3 vol.% or more, preferably 0.5 vol.% or more, more preferably 1 vol.% or more, and usually 40 vol.% or less, preferably 35 vol.% or less, more preferably 30 vol.% or less, based on 100 vol.% of the nonaqueous organic solvent.
• the content of the sulfone compound is within the above range, it is easy to obtain an effect of improving durability such as cycle characteristics and storage characteristics, and it is possible to keep the viscosity of the nonaqueous electrolyte in an appropriate range, avoid a decrease in electrical conductivity, and keep the input/output characteristics and charge/discharge rate characteristics of the nonaqueous electrolyte battery in appropriate ranges.
• additive components that are generally used in the nonaqueous electrolyte solution of the present disclosure may be further added in any ratio.
• specific examples of other additives include cyclohexylbenzene, cyclohexylfluorobenzene, fluorobenzene, biphenyl, difluoroanisole, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, 2-fluorobiphenyl, vinylene carbonate, vinylene carbonate oligomer (having a number average molecular weight of 170 to 5000 in terms of polystyrene), dimethylvinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate, trans-difluoroethylene carbonate, methylpropargyl carbonate, ethylpropargyl carbonate, dipropargyl carbonate, ethynylethylene carbonate
• the nonaqueous electrolyte of the present disclosure may contain at least one of the additives.
• the content of the additive in the nonaqueous electrolyte may be 0.01% by mass or more and 5% by mass or less with respect to the total amount of the nonaqueous electrolyte.
• the nonaqueous electrolyte of the present disclosure may contain a compound represented by the following general formula (3-4) as another additive. However, this excludes compounds that fall under the above general formula (3-2).
• R 31 to R 33 have the same meaning as X 2 in the above general formula (3-2), provided that at least one of R 31 to R 33 is a fluorine atom.
• M 2 m+ is an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m is an integer equal to the valence of the corresponding cation.
• the alkali metal cation, alkaline earth metal cation, and onium cation represented by M 2 m+ include the alkali metal cations, alkaline earth metal cations, and onium cations exemplified as M 1 m+ in the above general formula (3-2).
• the content of the other additives in the non-aqueous electrolyte may be 0.01% by mass or more and 8% by mass or less relative to the total amount of the non-aqueous electrolyte.
• the ionic salts listed as solutes can exert a negative electrode film forming effect and a positive electrode protecting effect as "other additives" when their content in the non-aqueous electrolyte is less than 0.5 mol/L, which is the lower limit of the suitable concentration of the solute.
• their content in the non-aqueous electrolyte may be 0.01% by mass to 5% by mass.
• alkali metal salts other than the above solutes may be used as additives.
• Specific examples include carboxylates such as lithium acrylate, sodium acrylate, lithium methacrylate, and sodium methacrylate; and sulfates such as lithium methyl sulfate, sodium methyl sulfate, lithium ethyl sulfate, and sodium ethyl sulfate.
• the nonaqueous electrolyte solution of the present disclosure may contain, among the above-mentioned other additives, in the case where the nonaqueous electrolyte battery is a lithium ion battery, at least one selected from vinylene carbonate and fluoroethylene carbonate in an amount of 0.01 to 5 mass % relative to the total amount of the nonaqueous electrolyte solution.
• the non-aqueous electrolyte battery is a sodium ion battery
• the non-aqueous electrolyte may contain 0.01 to 5 mass % of at least one selected from vinylene carbonate and fluoroethylene carbonate based on the total amount of the non-aqueous electrolyte.
• the nonaqueous electrolyte of the present disclosure may also contain a polymer, and may be used after being quasi-solidified with a gelling agent or crosslinked polymer, as in the case of nonaqueous electrolyte batteries known as polymer batteries.
• Polymer solid electrolytes also include those that contain a nonaqueous organic solvent as a plasticizer.
• the polymer is not particularly limited as long as it is an aprotic polymer capable of dissolving the sulfonic acid anhydride "1" represented by the above general formula (1), at least one compound selected from the group represented by "2" to "7” above, the solute, and the other additives.
• aprotic polymer capable of dissolving the sulfonic acid anhydride "1" represented by the above general formula (1), at least one compound selected from the group represented by "2" to "7” above, the solute, and the other additives.
• examples include polymers having polyethylene oxide in the main chain or side chain, homopolymers or copolymers of polyvinylidene fluoride, methacrylic acid ester polymers, polyacrylonitrile, and the like.
• a plasticizer is added to these polymers, aprotic nonaqueous organic solvents are preferred among the above nonaqueous organic solvents.
• the nonaqueous electrolyte battery of the present disclosure includes at least the nonaqueous electrolyte of the present disclosure, a negative electrode, and a positive electrode, and preferably further includes a separator, an exterior body, and the like.
• the present invention also relates to a nonaqueous electrolyte battery including at least a positive electrode, a negative electrode, a separator, and the nonaqueous electrolyte of the present disclosure described above.
• the negative electrode is not particularly limited, but may be a material that allows reversible insertion and removal of alkali metal ions, such as lithium ions or sodium ions, or alkaline earth metal ions.
• the negative electrode active material constituting the negative electrode is capable of doping and dedoping lithium ions, and examples thereof include carbon materials having a lattice plane (002 plane) d value of 0.340 nm or less in X-ray diffraction, carbon materials having a lattice plane (002 plane) d value of more than 0.340 nm in X-ray diffraction, oxides of one or more metals selected from Si, Sn, and Al, alloys containing one or more metals selected from Si, Sn, and Al, alloys containing these metals, alloys of these metals or alloys with lithium, and lithium titanium oxide.
• These negative electrode active materials can be used alone or in combination of two or more. Lithium metal, metal nitrides, tin compounds, conductive polymers, etc. may also be used.
• the negative electrode active material constituting the negative electrode may be sodium metal, an alloy of sodium metal with other metals such as tin, an intermetallic compound of sodium metal with other metals, various carbon materials such as hard carbon, metal oxides such as titanium oxide, metal nitrides, tin (single element), tin compounds, activated carbon, conductive polymers, etc.
• phosphorus such as red phosphorus and black phosphorus
• phosphorus compounds such as Co-P, Cu-P, Sn-P, Ge-P, Mo-P, antimony (single element), antimony compounds such as Sb/C and Bi-Sb, etc.
• These negative electrode active materials may be used alone or in combination of two or more types.
• the positive electrode is not particularly limited, but may be a material that allows reversible insertion and removal of alkali metal ions, such as lithium ions or sodium ions, or alkaline earth metal ions.
• examples of the positive electrode material that can be used include lithium-containing transition metal composite oxides such as LiCoO2 , LiNiO2 , LiMnO2 , and LiMn2O4 , mixtures of multiple transition metals such as Co, Mn, and Ni in these lithium-containing transition metal composite oxides, lithium-containing transition metal composite oxides in which a part of the transition metal is replaced with a metal other than the transition metal, transition metal phosphate compounds called olivine such as LiFePO4 , LiCoPO4 , and LiMnPO4 , oxides such as TiO2 , V2O5 , and MoO3 , sulfides such as TiS2 and FeS, conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole, activated carbon, radical-generating polymers, and carbon materials.
• lithium-containing transition metal composite oxides such as LiCoO2 , LiNiO2 , LiMnO2 , and LiMn2O
• examples of the positive electrode material include NaCrO2 , NaFe0.5Co0.5O2 , NaFe0.4Mn0.3Ni0.3O2 , NaNi0.5Ti0.3Mn0.2O2 , NaNi1 / 3Ti1 /3Mn1/3O2, NaNi0.33Ti0.33Mn0.16Mg0.17O2 , Na2/3Ni1 / 3Ti1 / 6Mn1 / 2O2 , and Na2 / 3Ni1 / 3Mn2 / 3O .
• sodium-containing transition metal composite oxides in which a plurality of transition metals such as Co, Mn, Ni are mixed, sodium-containing transition metal composite oxides in which a part of the transition metal is replaced with a metal other than the transition metal, polyanion type compounds such as NaFePO4 , NaVPO4F , Na3V2 ( PO4 ) 3 , Na2Fe2 ( SO4 ) 3 , sodium salts of Prussian blue analogues represented by the composition formula NaaMb [Fe(CN) 6 ] c (M Cr , Mn, Fe, Co, Ni, Cu or Zn, 0 ⁇ a ⁇ 2, 0.5 ⁇ b ⁇ 1.5, 0.5 ⁇ c ⁇ 1.5), oxides such as TiO2 , V2O5 , MoO3 , TiS2 Alternatively, a sulfide such as FeS, a conductive polymer such as polyacetylene, polyparaphenylene, polyaniline, or polypyrrole, activated carbon, a polymer
• the positive and negative electrode materials may contain conductive materials such as acetylene black, ketjen black, carbon fiber, or graphite, and a binder such as polytetrafluoroethylene, polyvinylidene fluoride, or SBR resin, and may be molded into an electrode sheet.
• conductive materials such as acetylene black, ketjen black, carbon fiber, or graphite
• binder such as polytetrafluoroethylene, polyvinylidene fluoride, or SBR resin
• a nonwoven fabric or porous sheet made of polypropylene, polyethylene, paper, or glass fiber may be used.
• the above elements are used to assemble electrochemical devices in shapes such as coins, cylinders, squares, or aluminum laminate sheets.
• LiPF 6 component (III)
• compound (1-1) component (I)
• compound (1-1) component (I)
• compound (2-1) component (component (II)
• component (II) component (II)
• component (I), component (II), and other additives were changed as shown in Tables 1 to 12 below, but otherwise 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 using the same procedure as for preparing electrolyte solution 1-1.
• LiNi0.8Co0.1Mn0.1O2 powder LiNi0.8Co0.1Mn0.1O2 powder with 3.5% by mass of polyvinylidene fluoride (hereinafter also referred to as PVDF) as a binder and 4.5% by mass of acetylene black as a conductive material, and further adding N-methyl-2-pyrrolidone.
• PVDF polyvinylidene fluoride
• This paste was applied to both sides of aluminum foil (A1085), dried, pressed, and then punched out to 4 cm x 5 cm to obtain a test NCM811 positive electrode.
• a negative electrode composite paste was prepared by mixing 97.0% by mass of natural graphite powder, 2.0% by mass of styrene butadiene rubber as a binder, 1.0% by mass of sodium carboxymethylcellulose, and water. The paste was applied to one side of a copper foil, dried, pressed, and then punched out to a size of 4.5 cm x 5.5 cm to obtain a natural graphite negative electrode for testing.
• the nonaqueous electrolytes listed in Tables 1 to 12 were used.
• a natural graphite negative electrode was used, and in the examples and comparative examples of Tables 7 to 12, a silicon-containing graphite negative electrode was used.
• the cells prepared in the above manner were used to evaluate the initial resistance, cycle characteristics, and high-temperature storage characteristics by the methods described below.
• Discharge capacity retention rate (%) (discharge capacity after storage at 60°C/initial charge/discharge capacity) x 100
• Tables 1 to 6 The values of the discharge capacity retention rates after storage at 60° C. of Examples 1-1 to 1-87 and Comparative Examples 1-1 to 1-43 shown in Tables 1 to 6 are relative values when the discharge capacity retention rate after storage at 60° C. of Comparative Example 1-1 is set to 100.
• the discharge capacity retention rates after storage at 60° C. in Examples 1-1 to 1-87 and Comparative Examples 1-1 to 1-43 are described as "Capacity after storage at 60° C.” in Tables 1 to 6.
• ⁇ Cycle characteristic test> A charge/discharge test was carried out at an environmental temperature of 25°C using the nonaqueous electrolyte batteries of Examples 2-1 to 2-87 and Comparative Examples 2-1 to 2-43 shown in Tables 7 to 12, and cycle characteristics were evaluated. Charge was performed up to 4.2 V, and discharge was performed up to 2.5 V, and charge/discharge cycles were repeated at a current density of 1.9 mA/ cm2 . Then, the deterioration of the cell was evaluated based on the discharge capacity retention rate after 200 cycles. The discharge capacity retention rate after 200 cycles was calculated using the following formula.
• Discharge capacity retention rate (%) (discharge capacity after 200 cycles/initial discharge capacity) x 100
• the values of the discharge capacity retention ratios after 200 cycles 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 ratio after 200 cycles in Comparative Example 2-1 is set to 100.
• the discharge capacity in the first cycle in the cycle characteristic test at an environmental temperature of 25° C. was defined as the initial discharge capacity.
• the discharge capacity retention rates after 200 cycles for Examples 2-1 to 2-87 and Comparative Examples 2-1 to 2-43 are shown in Tables 7 to 12 as "Capacity after 200 cycles.”
• This disclosure makes it possible to provide a nonaqueous electrolyte and a nonaqueous electrolyte battery that can reduce the initial resistance value of a battery.

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