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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/30—Only oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/30—Only oxygen atoms
  • C07D251/34—Cyanuric or isocyanuric esters
• • 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
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • 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
• • 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
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0025—Organic electrolyte
• • 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

• This disclosure relates to non-aqueous electrolytes, non-aqueous electrolyte batteries, and compounds.
• Lithium secondary batteries are mainly composed of a positive electrode, a non-aqueous electrolyte, and a negative electrode.
• metallic lithium, metal compounds capable of absorbing and releasing lithium e.g., simple metals, oxides, alloys with lithium, etc.
• carbon materials, etc. are known as negative electrodes constituting lithium secondary batteries.
• lithium secondary batteries using carbon materials capable of absorbing and releasing lithium such as coke, artificial graphite, and natural graphite, have been widely put to practical use.
• lithium secondary batteries using highly crystallized carbon materials such as natural graphite and artificial graphite as negative electrode materials, the non-aqueous organic solvent in the non-aqueous electrolyte is reduced and decomposed on the surface of the negative electrode during charging, and the decomposition products and gases generated by this inhibit the original electrochemical reaction of the battery, resulting in a decrease in cycle characteristics.
• lithium secondary batteries that use elemental metals or oxides of metals such as lithium metal or its alloys, silicon, and tin as negative electrode materials have a high initial capacity, but the negative electrode material becomes pulverized during cycling, and the nonaqueous organic solvent is more likely to be reductively decomposed than in negative electrodes made of carbon materials.
• the first cycle charge/discharge efficiency decreases due to an increase in the initial irreversible capacity of the battery, and battery performance such as battery capacity and cycle characteristics decreases significantly.
• the negative electrode and lithium cations, or the negative electrode and the electrolyte solvent react with each other to form a coating on the surface of the negative electrode, mainly composed of lithium oxide, lithium carbonate, or lithium alkyl carbonate.
• This coating on the surface of the electrode is called the Solid Electrolyte Interface (SEI), and its properties have a significant effect on battery performance, such as suppressing the reductive decomposition of the solvent and suppressing deterioration of battery performance.
• SEI Solid Electrolyte Interface
• the positive electrode for example, LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiFePO 4 and the like are known.
• the nonaqueous organic solvent in the nonaqueous electrolyte is partially oxidized and decomposed locally at the interface between the positive electrode material and the nonaqueous electrolyte, and the decomposition products and gases generated by this inhibit the inherent electrochemical reaction of the battery, resulting in a decrease in the battery performance such as cycle characteristics.
• a coating of oxidized decomposition products is formed on the surface of the positive electrode, which is also known to play an important role such as suppressing the oxidative decomposition of the solvent and suppressing the amount of gas generation.
• Patent Document 1 describes that the storage characteristics of a battery are improved by using a non-aqueous electrolyte solution containing a tricarbimide compound such as triallyl cyanurate or triallyl isocyanurate.
• Patent Document 2 describes that the use of a non-aqueous electrolyte solution containing a fluorosulfonate improves the initial charge/discharge capacity, input/output characteristics, and impedance characteristics.
• Patent Document 3 describes that the use of a nonaqueous electrolyte solution containing a compound having a cyanuric acid skeleton and at least one compound selected from the group consisting of a halogenated cyclic carbonate compound, a difluorophosphate, and a monofluorosulfonate improves battery characteristics such as cycle characteristics and high-temperature storage characteristics.
• Patent Document 4 discloses a heterocyclic sulfonyl fluoride additive having a specific structure for an electrolyte composition for a lithium battery, and describes that an electrolyte composition containing the additive has good electrochemical properties, such as a long cycle life, a high capacity retention rate, low resistance buildup during cycling, and good storage stability.
• Patent Document 1 a nonaqueous electrolyte containing a tricarbimide compound such as triallyl cyanurate or triallyl isocyanurate as in Patent Document 1 significantly reduces the initial input/output characteristics. It was also found that there is room for improvement in the initial input/output characteristics when using a nonaqueous electrolyte containing lithium fluorosulfonate as shown in Patent Document 2, a nonaqueous electrolyte containing a compound having a cyanuric acid skeleton and a compound such as monofluorosulfonate as in Patent Document 3, or a nonaqueous electrolyte containing an additive as in Patent Document 4.
• the present disclosure aims to provide a nonaqueous electrolyte that can exhibit excellent initial input/output characteristics when used in a nonaqueous electrolyte battery, a nonaqueous electrolyte battery that can exhibit excellent initial input/output characteristics, and a compound that is suitable for use in the nonaqueous electrolyte.
• a nonaqueous electrolyte battery capable of exhibiting excellent initial input/output characteristics can be obtained by using a nonaqueous electrolyte solution containing (I) at least one compound selected from the group consisting of compounds represented by general formula (1), compounds represented by general formula (2), compounds represented by general formula (3), and compounds represented by general formula (4) (hereinafter, sometimes referred to as "component (I)"), (II) a solute (hereinafter, sometimes referred to as “component (II)”), and (III) a nonaqueous organic solvent (hereinafter, sometimes referred to as "component (III)”), thereby solving the above-mentioned problem.
• component (I) at least one compound selected from the group consisting of compounds represented by general formula (1), compounds represented by general formula (2), compounds represented by general formula (3), and compounds represented by general formula (4)
• component (I) a solute
• component (III) a nonaqueous organic solvent
• R 1 to R 3 may be the same or different and each represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. However, at least one of R 1 to R 3 has a group represented by the general formula (5).]
• R 4 to R 6 may be the same or different and each represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. However, at least one of R 4 to R 6 has a group represented by the general formula (5).]
• R 7 to R 9 may be the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. However, at least one of R 7 to R 9 has a group represented by the general formula (5).]
• R 10 to R 12 may be the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent, provided that at least one of R 10 to R 12 has a group represented by the general formula (5).
• W represents a phosphorus atom or a sulfur atom
• y is 1 when W is a phosphorus atom
• y is 2 when W is a sulfur atom.
• X each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a cycloalkyl group having 5 to 20 carbon atoms which may be substituted with a halogen atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 40 carbon atoms which may be substituted with a halogen atom, a heteroaryl group having 2 to 40 carbon atoms which may be substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms which may be substituted with
• d represents 0 to 5.
• M p+ represents a proton, a metal cation, or an onium cation
• p represents the valence of the cation
• X in the general formula (5) is each independently a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a trifluoromethyl group, a trifluoroethyl group, an ethenyl group, a 2-propenyl group, a 2-propynyl group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a methoxy group
• X in the general formula (5) is each independently a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a trifluoromethyl group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a pyrrolyl group, or a pyridinyl group.
• the chain carbonate includes at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.
• a compound represented by the following general formula [1b] and a compound represented by the following general formula [1b']
• the content of (IV) in the non-aqueous electrolyte solution is 10 to 25,000 mass ppm.
• Y represents a boron atom
• R' represents a fluorine atom
• n is 0 to 4
• m' is 0 to 2
• Q + represents an alkali metal ion, a tetraalkylammonium cation, or a tetraalkylphosphonium cation.
• Q + [Z] - [1b'] (In general formula [1b'], the anion moiety represented by [Z] - is a chloride anion or the structure of the following [1b-1].
• Q+ represents an alkali metal ion, a tetraalkylammonium cation, or a tetraalkylphosphonium cation.)
• R 1 to R 3 may be the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. However, at least two of R 1 to R 3 have a group represented by the general formula (5).]
• R 4 to R 6 may be the same or different and each represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. However, at least one of R 4 to R 6 has a group represented by the general formula (5).]
• R 7 to R 9 may be the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. However, at least one of R 7 to R 9 has a group represented by the general formula (5).]
• R 10 to R 12 may be the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent, provided that at least one of R 10 to R 12 has a group represented by the general formula (5).
• W represents a phosphorus atom or a sulfur atom
• y is 1 when W is a phosphorus atom
• y is 2 when W is a sulfur atom.
• X each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a cycloalkyl group having 5 to 20 carbon atoms which may be substituted with a halogen atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 40 carbon atoms which may be substituted with a halogen atom, a heteroaryl group having 2 to 40 carbon atoms which may be substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms which may be substituted with
• the present disclosure provides a nonaqueous electrolyte that can exhibit excellent initial input/output characteristics when used in a nonaqueous electrolyte battery, a nonaqueous electrolyte battery that can exhibit excellent initial input/output characteristics, and a compound that is suitable for use in the nonaqueous electrolyte.
• the initial input/output characteristics refer to the resistance value of a non-aqueous electrolyte battery immediately after the first charge/discharge operation performed for battery stabilization. Specifically, it refers to the resistance value obtained by the first DC internal resistance measurement after four cycles of charge/discharge operation for battery stabilization.
• Nonaqueous electrolyte The nonaqueous electrolyte solution of the present disclosure is a nonaqueous electrolyte solution containing (I) at least one compound selected from the group consisting of a compound represented by general formula (1), a compound represented by general formula (2), a compound represented by general formula (3), and a compound represented by general formula (4), (II) a solute, and (III) a nonaqueous organic solvent.
• the nonaqueous electrolyte solution of the present disclosure contains, as component (I), at least one compound selected from the group consisting of a compound represented by general formula (1), a compound represented by general formula (2), a compound represented by general formula (3), and a compound represented by general formula (4).
• component (I) decomposes at least on either the positive electrode or the negative electrode, forming a coating with good cation conductivity on at least the surface of either the positive electrode or the negative electrode.
• This coating is thought to suppress direct contact between the non-aqueous organic solvent or the solute and the electrode active material, and to reduce the cation dissociation energy of the solute. As a result, the present inventors presume that this has the effect of reducing the initial resistance of the non-aqueous electrolyte battery.
• R 1 to R 3 in general formula (1) may be the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent, provided that at least one of R 1 to R 3 has a group represented by general formula (5).
• R 1 to R 3 may each be an organic group having 1 to 15 carbon atoms, or an organic group having 1 to 10 carbon atoms.
• the organic group may be linear, branched, or cyclic.
• the organic group is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, a cycloalkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, a heteroaryloxy group, etc.
• the organic group may be a group represented by general formula (5).
• the substituent that the organic group may have is not particularly limited, but examples thereof include a halogen atom, a hydroxy group, a cyano group, an isocyanate group, an acryloyloxy group, and a methacryloyloxy group.
• At least one of R 1 to R 3 has a group represented by general formula (5). That is, at least one of R 1 to R 3 is a group represented by general formula (5) or has a group represented by general formula (5) as a substituent. At least two of R 1 to R 3 may have a group represented by formula (5), or all of R 1 to R 3 may have a group represented by formula (5). When two or more of R 1 to R 3 have a group represented by general formula (5), the two or more groups represented by general formula (5) may be the same or different.
• R 4 to R 6 in general formula (2), R 7 to R 9 in general formula (3), and R 10 to R 12 in general formula (4) are the same as those of R 1 to R 3 described above.
• W represents a phosphorus atom or a sulfur atom. W may also be a sulfur atom.
• X in general formula (5) each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a cycloalkyl group having 5 to 20 carbon atoms which may be substituted with a halogen atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 40 carbon atoms which may be substituted with a halogen atom, a heteroaryl group having 2 to 40 carbon atoms which may be substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a cycloalkoxy group having 5 to 20 carbon atoms which may be substituted with a halogen atom, an alkenyloxy group having
• the halogen atom may be a fluorine atom.
• the alkyl group may be linear or branched, and may be an alkyl group having 1 to 10 carbon atoms.
• the alkyl group may contain an oxygen atom between the carbon atom-carbon atom bond. Specific examples of the alkyl group containing an oxygen atom between the carbon atom-carbon atom bond include a 2-methoxyethyl group and a 2-ethoxyethyl group.
• the cycloalkyl group may be a monocyclic or polycyclic cycloalkyl group having 5 to 15 carbon atoms.
• the alkenyl group may be linear or branched and may be an alkenyl group having 2 to 10 carbon atoms.
• the alkynyl group may be linear or branched and may be an alkynyl group having 2 to 10 carbon atoms.
• the aryl group may be a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
• the heteroaryl group may contain at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, may be a monocyclic or polycyclic heteroaryl group, and may be a heteroaryl group having 2 to 20 carbon atoms or a heteroaryl group having 2 to 15 carbon atoms.
• the alkoxy group may be linear or branched and may be an alkoxy group having 1 to 10 carbon atoms.
• the cycloalkoxy group may be a monocyclic or polycyclic cycloalkoxy group having 5 to 15 carbon atoms.
• the alkenyloxy group may be linear or branched and may be an alkenyloxy group having 2 to 10 carbon atoms.
• the alkynyloxy group may be linear or branched and may be an alkynyloxy group having 2 to 10 carbon atoms.
• the aryloxy group may be a monocyclic or polycyclic aryloxy group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 15 carbon atoms.
• the heteroaryloxy group may contain at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, may be a monocyclic or polycyclic ring, and may be a heteroaryloxy group having 2 to 20 carbon atoms or a heteroaryloxy group having 2 to 15 carbon atoms.
• each X may independently be a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a trifluoromethyl group, a trifluoroethyl group, an ethenyl group, a 2-propenyl group, a 2-propynyl group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, an n-pentyloxy group, an n-hexyloxy group, a trifluoromethoxy group, a trifluoro
• each X may independently be a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a trifluoromethyl group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a pyrrolyl group, or a pyridinyl group.
• M p+ in the general formula (5) represents a proton, a metal cation, or an onium cation, and may be a proton, a lithium cation, a sodium cation, a potassium cation, a tetraalkylammonium cation, or a tetraalkylphosphonium cation.
• p represents the valence of the cation.
• p and q may each be 1.
• the total amount of the component (I) (also referred to as the "concentration of (I)" relative to the total amount of the nonaqueous electrolyte (100 mass%) may have a lower limit of 0.01 mass% or more, 0.08 mass% or more, 0.3 mass% or more, or 0.8 mass% or more.
• the upper limit of the concentration of (I) may be 10.00 mass% or less, 5.0 mass% or less, or 2.5 mass% or less.
• the concentration of (I) By setting the concentration of (I) to 0.01% by mass or more, the effect of suppressing an increase in the initial resistance of a nonaqueous electrolyte battery using the nonaqueous electrolyte can be easily obtained, whereas by setting the concentration of (I) to 10.0% by mass or less, the increase in viscosity of the nonaqueous electrolyte can be suppressed, and the effect of suppressing an increase in the resistance of a nonaqueous electrolyte battery using the nonaqueous electrolyte can be easily obtained.
• 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 compound represented by formula (1) can be produced by various methods, and the production method is not particularly limited.
• the compound (1-1-11) can be obtained by reacting a cyanate with fluorosulfonyl isocyanate, and then reacting the resulting product with lithium chloride.
• the compound represented by formula (2) can be produced by various methods, and the production method is not particularly limited.
• compound (2-2-2) can be obtained by mixing 6-(allyloxy)-1,3,5-triazine-2,4(1H,3H)-dione with lithium hydride, and then reacting the mixture with fluorosulfonyl isocyanate.
• the compound represented by formula (3) can be produced by various methods, and the production method is not particularly limited.
• compound (3-3-3) can be obtained by mixing 4,6-(allyloxy)-1,3,5-triazin-2(1H)-one with lithium hydride, and then reacting the mixture with fluorosulfonyl isocyanate.
• the compound represented by the formula (4) can be produced by various methods, and the production method is not particularly limited.
• the compound (4-1-11) can be obtained by mixing cyanuric acid with lithium hydride and then reacting the mixture with fluorosulfonyl isocyanate.
• the present disclosure also relates to a compound represented by the above general formula (1), (2), (3) or (4).
• the above compound is suitably used as an additive in a non-aqueous electrolyte solution.
• the nonaqueous electrolyte of the present disclosure contains a solute.
• the solute is not particularly limited, but may be an ionic salt or an ionic salt containing fluorine.
• the solute may be, for example, 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 ions, and at least one anion selected from the group consisting of hexafluorophosphate anion, tetrafluoroborate anion, perchlorate anion, hexafluoroarsenate anion, hexafluoroantimonate anion, trifluoromethanesulfonate anion, bis(trifluoromethanesulfonyl)imide anion, bis(pentafluoroethanesulfonyl)imide anion, (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide anion, bis(fluorosulfonyl)imide anion, (trifluoromethan
• the solute may be at least one selected from the group consisting of LiPF6 , LiBF4 , LiSbF6 , LiAsF6 , LiClO4 , LiCF3SO3 , LiC4F9SO3, LiN( SO2F ) 2 , LiAlO2 , LiAlCl4 , LiCl , and LiI, or at least one selected from the group consisting of NaPF6 , NaBF4 , NaSbF6 , NaAsF6 , NaClO4 , NaCF3SO3, NaC4F9SO3 , NaN( SO2F ) 2, NaAlO2 , NaAlCl4 , NaCl, and NaI.
• the cation may be at least one selected from the group consisting of lithium, sodium, potassium, magnesium, and quaternary ammonium
• the anion may be at least one selected from the group consisting of a hexafluorophosphate anion, a tetrafluoroborate anion, a bis(trifluoromethanesulfonyl)imide anion, and a bis(fluorosulfonyl)imide 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 may be 0.5 mol/L or more, 0.7 mol/L or more, or 0.9 mol/L or more.
• the upper limit of the solute concentration may be 5.0 mol/L or less, 4.0 mol/L or less, or 2.0 mol/L or less.
• solute concentration By setting the solute concentration to 0.5 mol/L or more, it is easy to suppress the decrease in the cycle characteristics and output characteristics of the nonaqueous electrolyte battery caused by the decrease in ionic conductivity, and by setting it to 5.0 mol/L or less, it is easy to suppress the decrease in ionic conductivity and the decrease in the cycle characteristics and output characteristics of the nonaqueous electrolyte battery caused by the increase in viscosity of the nonaqueous electrolyte.
• the type of nonaqueous organic solvent used in the nonaqueous electrolyte solution of the present disclosure is not particularly limited, and any nonaqueous organic solvent can be used.
• the non-aqueous organic solvent may contain at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds, and ionic liquids.
• At least one nonaqueous organic solvent selected from the group consisting of cyclic esters and chain esters may be contained in the nonaqueous electrolyte solution.
• the nonaqueous electrolyte may contain at least one nonaqueous organic solvent selected from the group consisting of cyclic carbonates and chain carbonates.
• the non-aqueous organic solvent may contain a cyclic ester, and the cyclic ester may be a cyclic carbonate.
• the cyclic carbonate include EC, PC, butylene carbonate, FEC, and the like. Among them, at least one selected from the group consisting of EC, PC, and FEC may be used.
• chain ester examples include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, and ethyl 2-fluoropropionate.
• the nonaqueous electrolyte of the present disclosure further includes vinylene carbonate, bis(oxalato)borate, difluorooxalatoborate, difluorobis(oxalato)phosphate, tetrafluorooxalatophosphate, (difluorophosphoryl)(fluorosulfonyl)imide salt, difluorophosphate, fluorosulfonate, nitrate, 1,3-propene sultone, 1,3-propane sultone, 1,6-diisocyanatohexane, dimethyl dicarbonate, ethynyl ethylene carbonate, trans-difluoroethylene carbonate, 1,3,2-dioxathiolane-2,2-dioxide, 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, methylenemethane disulfonate, 1,2-ethane disulfonic acid It may contain at least one
• the content of the additive in the non-aqueous electrolyte may be 0.01% by mass or more and 5.0% by mass or less with respect to the total amount of the non-aqueous electrolyte.
• the nonaqueous electrolyte of the present disclosure may contain a compound represented by the following general formula (6) as another additive.
• R 6 to R 8 are each independently an organic group selected from a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms or a branched alkoxy group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryl group selected from a fluor
• R 6 to R 8 is a fluorine atom.
• M 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 salt having the imide anion represented by the general formula (6) may be a compound in which R 6 to R 8 are all fluorine atoms.
• At least one of R 6 to R 8 is a fluorine atom; At least one of R 6 to R 8 may be a compound selected from hydrocarbon groups having 6 or less carbon atoms which may contain a fluorine atom.
• At least one of R 6 to R 8 is a fluorine atom; At least one of R 6 to R 8 may be a compound selected from a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, a vinyl group, an allyl group, an allyloxy group, an ethynyl group, a 2-propynyl group, a 2-propynyloxy group, a phenyl group, a phenyloxy group, a 2,2-difluoroethyl group, a 2,2-difluoroethyloxy group, a 2,2,2-trifluoroethyl group, a 2,2,2-trifluoroethyloxy group, a 2,2,3,3-tetrafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 2,2,3,3-tetrafluoropropy
• the counter cation Mm + of the salt having the imide anion represented by the above general formula (6) may be selected from the group consisting of a lithium ion, a sodium ion, a potassium ion, and a tetraalkylammonium ion.
• examples of the alkyl group and alkoxy group represented by R 6 to R 8 include alkyl groups and fluorine-containing alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, a tertiary butyl group, a pentyl 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, and alkoxy groups derived from these groups.
• Alkenyl and alkenyloxy groups include alkenyl groups having 2 to 10 carbon atoms, such as vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, and 1,3-butadienyl groups, fluorine-containing alkenyl groups, and alkenyloxy groups derived from these groups.
• Alkynyl and alkynyloxy groups include alkynyl groups having 2 to 10 carbon atoms, such as ethynyl, 2-propynyl, and 1,1-dimethyl-2-propynyl groups, as well as fluorine-containing alkynyl groups, and alkynyloxy groups derived from these groups.
• Cycloalkyl groups and cycloalkoxy groups include cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopentyl and cyclohexyl groups, fluorine-containing cycloalkyl groups, and cycloalkoxy groups derived from these groups.
• Cycloalkenyl groups and cycloalkenyloxy groups include cycloalkenyl groups having 3 to 10 carbon atoms, such as cyclopentenyl and cyclohexenyl groups, fluorine-containing cycloalkenyl groups, and cycloalkenyloxy groups derived from these groups.
• Aryl and aryloxy groups include aryl groups having 6 to 10 carbon atoms, such as phenyl, tolyl, and xylyl groups, fluorine-containing aryl groups, and aryloxy groups derived from these groups.
• the content of the other additives in the non-aqueous electrolyte may be 0.01% by mass or more and 8.0% by mass or less, based on 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 the content in the nonaqueous electrolyte is less than 0.5 mol/L, which is the lower limit of the suitable concentration of the solute.
• the content in the nonaqueous electrolyte is preferably 0.01% by mass to 5.0% by mass.
• examples of the ionic salt include, when the nonaqueous electrolyte battery is a lithium ion battery, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium (trifluoromethanesulfonyl)(fluorosulfonyl)imide, etc.; when the nonaqueous electrolyte battery is a sodium ion battery, examples of the ionic salt include sodium hexafluorophosphate, sodium tetrafluoroborate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, sodium bis(fluorosulfonyl)imide, sodium (trifluoromethanesulfonyl)(fluorosulfonyl)imide, etc.
• a salt compound having a counter anion which is at least one selected from the group consisting of a tetrafluoroborate anion, a chloride anion, and a perchlorate anion and a counter cation which is at least one selected from the group consisting of a lithium cation, a sodium cation, a potassium cation, a tetraalkylammonium cation, and a tetraalkylphosphonium cation may be contained in the nonaqueous electrolyte as the above-mentioned "other additives".
• the nonaqueous electrolyte may contain a salt compound in which the counter anion is a bis(oxalato)borate anion and the counter cation is at least one selected from the group consisting of a lithium cation, a sodium cation, a potassium cation, a tetraalkylammonium cation, and a tetraalkylphosphonium cation.
• the total concentration of the salt compounds may be 50 to 5000 ppm by mass, 50 to 3000 ppm by mass, or 50 to 1000 ppm by mass, based on the total amount of the nonaqueous electrolyte.
• 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 at least one selected from vinylene carbonate, fluoroethylene carbonate, lithium bis(oxalato)borate, lithium difluorooxalatoborate, lithium difluorobis(oxalato)phosphate, lithium tetrafluorooxalatophosphate, lithium bis(fluorosulfonyl)imide, lithium (difluorophosphoryl)(fluorosulfonyl)imide, lithium difluorophosphate, lithium fluorosulfonate, 1,3-propene sultone, 1,3-propane sultone, 1,3,2-dioxathiolane-2,2-dioxide, and 4-propyl-1,3,2-dioxathiolane-2
• the nonaqueous electrolyte battery is a sodium ion battery
• at least one selected from vinylene carbonate, fluoroethylene carbonate, sodium bis(oxalato)borate, sodium difluorooxalatoborate, sodium difluorobis(oxalato)phosphate, sodium tetrafluorooxalatophosphate, sodium bis(fluorosulfonyl)imide, sodium (difluorophosphoryl)(fluorosulfonyl)imide, sodium difluorophosphate, sodium fluorosulfonate, 1,3-propene sultone, 1,3-propane sultone, 1,3,2-dioxathiolane-2,2-dioxide, and 4-propyl-1,3,2-dioxathiolane-2,2-dioxide may be contained in an amount of 0.01 to 5.0% by mass relative to the total amount of the nonaqueous electrolyte.
• the nonaqueous electrolyte solution of the present disclosure further contains (IV) at least one selected from the group consisting of a compound represented by the following general formula [1b] and a compound represented by the following general formula [1b'].
• the content of (IV) in the nonaqueous electrolyte solution is 10 to 25,000 ppm by mass, it is preferable because the initial DC internal resistance and the rate of increase in DC internal resistance after cycle testing can be improved in a balanced manner.
• the non-aqueous electrolyte "easily improves the initial DC internal resistance and the rate of increase in DC internal resistance after a cycle test in a balanced manner" means that, compared to a case where the content of (IV) in the non-aqueous electrolyte is less than 10 ppm by mass, the non-aqueous electrolyte "exhibits an initial DC internal resistance and a rate of increase in DC internal resistance after a cycle test that are equivalent to or greater than those, and is superior in at least one of the initial DC internal resistance and the rate of increase in DC internal resistance after a cycle test.”
• Y represents a boron atom
• R' represents a fluorine atom
• n is 0 to 4
• m' is 0 to 2
• Q + represents an alkali metal ion, a tetraalkylammonium cation, or a tetraalkylphosphonium cation.
• Q + [Z] - [1b'] (In general formula [1b'], the anion moiety represented by [Z] - is a chloride anion or the structure of the following [1b-1].
• Q+ represents an alkali metal ion, a tetraalkylammonium cation, or a tetraalkylphosphonium cation.)
• Compounds represented by general formula [1b] and compounds represented by general formula [1b'] (IV) may be a salt compound containing a counter anion selected from a bis(oxalato)borate anion, a tetrafluoroborate anion, a chloride anion, or a perchlorate anion, and a counter cation selected from a lithium cation, a sodium cation, a potassium cation, a tetraalkylammonium cation, or a tetraalkylphosphonium cation.
• Specific examples of the compound represented by the general formula [1b] and the compound represented by the general formula [1b'] include, but are not limited to, the following compounds.
• Lithium bis(oxalato)borate Lithium difluorooxalatoborate Lithium tetrafluoroborate Lithium perchlorate Lithium chloride Sodium bis(oxalato)borate Sodium difluorooxalatoborate Sodium tetrafluoroborate Sodium perchlorate Sodium chloride
• the cation may be selected from the group consisting of lithium bis(oxalato)borate, lithium difluorooxalatoborate, lithium tetrafluoroborate, lithium perchlorate, sodium bis(oxalato)borate, sodium difluorooxalatoborate, sodium tetrafluoroborate, and sodium perchlorate.
• the content of (IV) in the nonaqueous electrolyte may be 10 ppm by mass (parts per million), 30 ppm by mass, 50 ppm by mass, or 70 ppm by mass relative to the total amount of electrolyte.
• the upper limit may be 25000 ppm by mass, 15000 ppm by mass, 8000 ppm by mass, 7000 ppm by mass, or 5000 ppm by mass relative to the total amount of electrolyte.
• the compound represented by the general formula [1b] and the compound represented by the general formula [1b'] can be produced by various methods.
• the production method is not particularly limited.
• lithium bis(oxalato)borate, lithium tetrafluoroborate, lithium perchlorate, and lithium chloride can be commercially available products from Kishida Chemical Co., Ltd., etc.
• lithium difluorooxalatoborate commercially available products from Merck, Inc., etc. can be used.
• a commercially available product may be used for the sodium salt, or a product obtained by cation-exchanging the above lithium salt may be used.
• the content of cations other than lithium in the nonaqueous electrolyte of the present disclosure is preferably 1000 mass ppm or less in terms of initial input/output characteristics or the rate of increase in direct current internal resistance after cycle testing, more preferably 500 mass ppm or less, and particularly preferably 300 mass ppm or less.
• the non-aqueous electrolyte containing (I) and a predetermined amount (10 to 25000 ppm by mass in the non-aqueous electrolyte) of (IV) can easily improve the initial DC internal resistance and the DC internal resistance increase rate after cycle testing in a well-balanced manner. This is advantageous in controlling the content of cations other than lithium contained in the raw materials in the preparation of the non-aqueous electrolyte.
• the content of cations other than lithium in the non-aqueous electrolyte containing (I) and a predetermined amount of (IV) may be 2000 ppm by mass or less.
• the content of cations other than lithium in the nonaqueous electrolyte is preferably as small as possible, and is preferably, for example, 1000 ppm by mass or less, more preferably 500 ppm by mass or less, and particularly preferably 300 ppm by mass or less.
• the nonaqueous electrolyte battery is a lithium ion battery and the nonaqueous electrolyte contains a cation other than lithium
• the nonaqueous electrolyte may have a nonaqueous electrolyte composition in which the cation species of the solute is lithium, the cation species of (I) is lithium, and the cation species of "other salt compound (e.g., the above (IV))" is other than lithium.
• the content of cations other than lithium in the non-aqueous electrolyte of a lithium ion battery can be determined by ICP emission spectrometry.
• the content of cations other than sodium in the nonaqueous electrolyte of the present disclosure is preferably 500 mass ppm or less in terms of both the initial input/output characteristics and the rate of increase in direct current internal resistance after cycle testing, more preferably 400 mass ppm or less, and particularly preferably 200 mass ppm or less.
• the initial DC internal resistance and the DC internal resistance increase rate after cycle testing can be easily improved in a well-balanced manner in a non-aqueous electrolyte containing the (I) and a predetermined amount (10 to 25,000 ppm by mass in the non-aqueous electrolyte). This is advantageous in terms of managing the content of cations other than sodium contained in the raw material in the preparation of the non-aqueous electrolyte.
• the content of cations other than sodium in the non-aqueous electrolyte containing the (I) and a predetermined amount of the (IV) may be 700 ppm by mass or less.
• the content of cations other than sodium in the non-aqueous electrolyte is preferably as small as possible, for example, preferably 500 ppm by mass or less, more preferably 400 ppm by mass or less, and particularly preferably 200 ppm by mass or less.
• the nonaqueous electrolyte battery is a sodium ion battery and the nonaqueous electrolyte contains cations other than sodium
• the cationic species of the solute is sodium
• the cationic species of (I) is sodium
• the cationic species of "other salt compound (e.g., the above (IV)" is other than sodium.
• the content of cations other than sodium in the non-aqueous electrolyte of a sodium ion battery can be determined by ICP emission spectrometry.
• 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 component (I), 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.
• an aprotic nonaqueous organic solvent may be used from among the nonaqueous organic solvents listed above.
• 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 may further include a separator, an exterior body, and the like.
• the nonaqueous electrolyte battery of the present disclosure preferably includes at least a positive electrode, a negative electrode, a separator, and the nonaqueous electrolyte of the present disclosure.
• the nonaqueous electrolyte battery of the present disclosure is preferably a nonaqueous electrolyte secondary battery.
• 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 d value of 0.340 nm or less on the lattice plane (002) in X-ray diffraction, carbon materials having a d value of more than 0.340 nm on the lattice plane (002) 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, or alloys of these metals and lithium, and at least one selected from lithium titanium oxide.
• 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 those containing Si and/or Si metal oxide and a carbon material can be preferably mentioned.
• the above-mentioned Si is silicon metal.
• the Si metal oxide may be a compound represented by SiOx (x is a value of 0.5 to 1.5).
• the total content of Si and/or Si metal oxide contained in the negative electrode active material may be 0.1 to 50 mass%, preferably 0.1 to 30 mass%, when the total amount of the Si and/or Si metal oxide and the carbon material contained in the negative electrode active material is 100 mass%.
• graphite is preferable, and various artificial graphites, natural graphites, and hard carbons (hardly graphitizable carbons) can be used.
• Graphite has very little change in crystal structure due to the absorption and release of lithium, so that a high energy density can be obtained and excellent cycle characteristics can be obtained.
• the shape of the graphite may be any of fibrous, spherical, granular, and scaly.
• amorphous carbon and graphite with a surface coated with amorphous carbon are more preferable since they have a low reactivity between the material surface and the electrolyte.
• These negative electrode active materials may be used alone or in combination of two or more.
• 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, 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 (single element) 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.
• the positive electrode material when the cation is lithium, may be a lithium-containing transition metal composite oxide such as LiCoO2 , LiNiO2 , LiMnO2 , or LiMn2O4 , a mixture of multiple transition metals such as Co, Mn, or Ni in these lithium-containing transition metal composite oxides, or a lithium-containing transition metal composite oxide in which a portion of the transition metal is replaced with a metal other than the transition metal.
• a lithium-containing transition metal composite oxide such as LiCoO2 , LiNiO2 , LiMnO2 , or LiMn2O4
• a mixture of multiple transition metals such as Co, Mn, or Ni in these lithium-containing transition metal composite oxides
• a lithium-containing transition metal composite oxide in which a portion 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; polymers that generate radicals; and carbon materials.
• 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,
• the positive and negative electrode materials may contain conductive materials such as acetylene black, ketjen black, carbon fiber, or graphite, and binders such as polytetrafluoroethylene, polyvinylidene fluoride, or SBR resin, and may also be formed into sheet-like electrode sheets.
• conductive materials such as acetylene black, ketjen black, carbon fiber, or graphite
• binders such as polytetrafluoroethylene, polyvinylidene fluoride, or SBR resin
• a nonwoven fabric or porous sheet made of polypropylene, polyethylene, paper, glass fiber, etc. may be used.
• the above elements are used to assemble electrochemical devices in shapes such as coins, cylinders, squares, or aluminum laminate sheets.
• Compound (4-1-11) was synthesized in the same manner as compound (4-3-1), except that the raw materials were changed to match the target structure.
• Example 1-1 (Preparation of non-aqueous electrolyte 1-1) A mixed solvent of ethylene carbonate (hereinafter also referred to as “EC"), dimethyl carbonate (hereinafter also referred to as “DMC”), and EMC in a volume ratio of 3:3:4 was used as the nonaqueous organic solvent, and lithium hexafluorophosphate (hereinafter also referred to as "LiPF 6 ”) as a solute was dissolved in the solvent to a concentration of 1.0 mol/L, and the compound represented by the above formula (1-1-11) as the compound represented by general formula (1) was dissolved in a concentration of 0.05 mass% relative to the total amount of the nonaqueous electrolyte to obtain nonaqueous electrolyte 1-1.
• the above preparation was performed while maintaining the liquid temperature at 25°C.
• Non-aqueous electrolyte solutions 1-2 to 1-12 were prepared by dissolving in the same manner as in the preparation of non-aqueous electrolyte solution 1-1, except that the type and concentration of the compound represented by general formula (1) were changed as shown in Table 1.
• Non-aqueous electrolyte solutions 2-1 to 2-6 were prepared by dissolving the compound represented by the general formula (2) in place of the compound represented by the general formula (1) in the same manner as in the preparation of the non-aqueous electrolyte solution 1-1, except that the concentration of the compound represented by the general formula (2) was changed as shown in Table 1.
• Non-aqueous electrolyte solutions 3-1 to 3-6 were prepared by dissolving the compound represented by the general formula (3) in place of the compound represented by the general formula (1) in the same manner as in the preparation of the non-aqueous electrolyte solution 1-1, except that the concentration of the compound represented by the general formula (3) was changed as shown in Table 1.
• Examples 4-1 to 4-12 (Preparation of non-aqueous electrolytes 4-1 to 4-12) Instead of the compound represented by the general formula (1), the compound represented by the general formula (4) was used and its concentration was changed as shown in Table 1. The same procedure as in the preparation of the nonaqueous electrolyte 1-1 was followed to prepare nonaqueous electrolytes 4-1 to 4-12.
• Non-aqueous electrolyte solutions 5-1 to 5-9 were prepared by dissolving the compounds represented by the general formulas (1), (2), (3), or (4) in the same manner as in the preparation of non-aqueous electrolyte solution 1-1, except that the type and concentration of the compound represented by the general formula (1), (2), (3), or (4) were changed as shown in Table 2.
• Comparative nonaqueous electrolyte solution 1-1 was prepared by dissolving in the same manner as in the preparation of nonaqueous electrolyte solution 1-1, except that the compound represented by general formula (1) was not added.
• Comparative Examples 1-2 to 1-4 (Preparation of Comparative Non-Aqueous Electrolytes 1-2 to 1-4) Instead of the compound represented by the general formula (1), a compound represented by the following formula (6-1), (6-2) or (6-3) was used and its concentration was changed as shown in Table 1.
• the comparative nonaqueous electrolytes 1-2 to 1-4 were prepared by dissolving in the same procedure as in the preparation of the nonaqueous electrolyte 1-1.
• the compounds (6-1) and (6-2) were purchased from Tokyo Chemical Industry Co., Ltd. and used.
• Non-aqueous electrolyte solutions 6-1 to 6-6 and comparative non-aqueous electrolyte solutions 2-1 to 2-4 were obtained in the same manner as in the preparation of non-aqueous electrolyte solutions 1-4, 1-10, 2-4, 3-4, 4-4, and 4-10 and comparative non-aqueous electrolyte solutions 1-1 to 1-4, respectively.
• DFBOP means lithium difluorobis(oxalato)phosphate
• DFOB means lithium difluorooxalatoborate
• TFOP means lithium tetrafluorooxalatophosphate
• DTD means 1,3,2-dioxathiolane-2,2-dioxide
• DFPFSI means lithium (difluorophosphoryl)(fluorosulfonyl)imide
• FS means lithium fluorosulfonate
• TV-Si means tetravinylsilane.
• a mixed solvent of EC, fluoroethylene carbonate (hereinafter also referred to as "FEC"), DMC, and EMC in a volume ratio of 3:0.2:3:3.8 was used, and LiPF 6 and FSI were dissolved as solutes in the solvent to concentrations of 1.0 mol / L and 0.1 mol / L, respectively.
• Example 67-1> (Preparation of non-aqueous electrolyte 67-1) A mixed solvent of EC, propylene carbonate (hereinafter also referred to as "PC"), FEC, and EMC in a volume ratio of 2:1:0.2:6.8 was used as the nonaqueous organic solvent, and sodium hexafluorophosphate (hereinafter also referred to as "NaPF 6 ”) was dissolved in the solvent as a solute to a concentration of 1.0 mol/L, and the compound represented by the formula (1-1-11-Na) was dissolved as the compound represented by the general formula (1) to a concentration of 0.05 mass% relative to the total amount of the nonaqueous electrolyte to obtain nonaqueous electrolyte 67-1.
• the above preparation was performed while maintaining the liquid temperature at 25°C.
• Non-aqueous electrolyte solutions 67-2 to 67-12 were prepared by dissolving in the same manner as in the preparation of non-aqueous electrolyte solution 67-1, except that the type and concentration of the compound represented by general formula (1) were changed as shown in Table 19.
• Examples 68-1 to 68-6> (Preparation of non-aqueous electrolytes 68-1 to 68-6) Instead of the compound represented by the general formula (1), the compound represented by the general formula (2) was used and its concentration was changed as shown in Table 19.
• the nonaqueous electrolyte solutions 68-1 to 68-6 were prepared by dissolving the compound in the same manner as in the preparation of the nonaqueous electrolyte solution 67-1.
• Examples 69-1 to 69-6> (Preparation of non-aqueous electrolytes 69-1 to 69-6) Instead of the compound represented by the general formula (1), the compound represented by the general formula (3) was used and its concentration was changed as shown in Table 19.
• the nonaqueous electrolyte solutions 69-1 to 69-6 were prepared by dissolving the compound in the same manner as in the preparation of the nonaqueous electrolyte solution 67-1.
• Examples 70-1 to 70-12 (Preparation of non-aqueous electrolytes 70-1 to 70-12) Instead of the compound represented by the general formula (1), the compound represented by the general formula (4) was used and its concentration was changed as shown in Table 19.
• the nonaqueous electrolyte solutions 70-1 to 70-12 were prepared by dissolving the compound in the same manner as in the preparation of the nonaqueous electrolyte solution 67-1.
• Non-aqueous electrolyte solutions 71-1 to 71-9 were prepared by dissolving the compounds represented by the general formulas (1), (2), (3), or (4) in the same manner as in the preparation of non-aqueous electrolyte solution 67-1, except that the type and concentration of the compound represented by the general formula (1), (2), (3), or (4) were changed as shown in Table 20.
• Comparative nonaqueous electrolyte solution 59-1 was prepared by dissolving in the same manner as in the preparation of nonaqueous electrolyte solution 67-1, except that the compound represented by general formula (1) was not added.
• Comparative Non-Aqueous Electrolytes 59-2 to 59-4 were prepared by dissolving in the same manner as in the preparation of nonaqueous electrolyte solution 67-1.
• Examples 72-1 to 72-6, Comparative Examples 60-1 to 60-4> Preparation of Nonaqueous Electrolytes 72-1 to 72-6 and Comparative Nonaqueous Electrolytes 60-1 to 60-4) Furthermore, as other additive (1), sodium difluorobis(oxalato)phosphate (hereinafter also referred to as "DFBOP-Na”) was added to the concentration shown in Table 21, and dissolved therein.
• DFBOP-Na sodium difluorobis(oxalato)phosphate
• Non-aqueous electrolyte solutions 67-4, 67-10, 68-4, 69-4, 70-4, and 70-10, and comparative non-aqueous electrolyte solutions 59-1 to 59-4 were prepared in the same manner as in the preparation of non-aqueous electrolyte solutions 72-1 to 72-6, and comparative non-aqueous electrolyte solutions 60-1 to 60-4, respectively.
• Examples 73-1 to 73-6 Comparative Examples 61-1 to 61-4> to ⁇ Examples 78-1 to 78-6, Comparative Examples 66-1 to 66-4>
• Tables 21 to 22 except that the other additive (1) was changed from DFBOP-Na to the compound shown in each table, the nonaqueous electrolytes 72-1 to 72-6 and the comparative nonaqueous electrolytes 60-1 to 60-4 were dissolved in the same manner as in the preparation of the nonaqueous electrolytes 72-1 to 72-6 and the comparative nonaqueous electrolytes 60-1 to 60-4 to prepare the nonaqueous electrolytes and comparative nonaqueous electrolytes shown in each table.
• DFOB-Na means sodium difluorooxalatoborate
• TFOP-Na means sodium tetrafluorooxalatophosphate
• DFPFSI-Na means sodium (difluorophosphoryl) (fluorosulfonyl) imide
• FS-Na means sodium fluorosulfonate
• Na-BOB, K-BOB, Li-BOB, Na-BF4, K-BF4, Li-BF4, Na-ClO4, K-ClO4, and Li-ClO4 were dissolved as other additives in nonaqueous electrolyte solutions 1-4, 1-10, 2-4, 3-4, 4-4, and 4-10 to the contents shown in each table, to prepare the nonaqueous electrolyte solutions shown in each table.
• Na-BOB means sodium bisoxalatoborate
• K-BOB means potassium bisoxalatoborate
• Li-BOB means lithium bisoxalatoborate
• Na-BF4 means sodium tetrafluoroborate
• K-BF4 means potassium tetrafluoroborate
• Li-BF4 means lithium tetrafluoroborate
• Na-ClO4 means sodium perchlorate
• K-ClO4" means potassium perchlorate
• Li-ClO4" means lithium perchlorate
• Li-ClO4 means lithium perchlorate.
• the content of cations other than Li in the non-aqueous electrolyte solutions described in Tables 35 to 40 and 48 to 50 was determined by ICP emission spectroscopy.
• the content of cations other than Li in the non-aqueous electrolyte solutions described in Tables 11 to 18 was less than 1 mass ppm in each case.
• Li-BF4, K-BF4, Na-BF4, Li-ClO4, K-ClO4, and Na-ClO4 were dissolved in the nonaqueous electrolytes 67-4, 67-10, 68-4, 69-4, 70-4, and 70-10 as other additives to obtain the contents shown in each table, and the nonaqueous electrolytes described in each table were prepared.
• the content of cations other than Na in the nonaqueous electrolytes described in Tables 41 to 44 and 51 to 52 was determined by ICP emission spectroscopy.
• the content of cations other than Na in the nonaqueous electrolytes described in Tables 19 to 28 was less than 1 mass ppm in each case.
• NCM622 positive electrode 90% by mass of LiNi0.6Co0.2Mn0.2O2 powder was mixed with 5% by mass of polyvinylidene fluoride (hereinafter also referred to as "PVDF”) as a binder and 5% by mass of acetylene black as a conductive material, and N-methyl- 2 -pyrrolidone (hereinafter also referred to as "NMP”) was added to prepare a positive electrode composite paste. 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 NCM622 positive electrode.
• PVDF polyvinylidene fluoride
• NMP N-methyl- 2 -pyrrolidone
• NCM811 positive electrode (Preparation of NCM811 positive electrode) 92.0% by mass of LiNi0.8Mn0.1Co0.1O2 powder was mixed with 3.5% by mass of PVDF as a binder and 4.5% by mass of acetylene black as a conductive material, and NMP was added to prepare a positive electrode composite paste. This paste was applied to both sides of an aluminum foil (A1085), dried, pressed, and then punched out to 4 cm x 5 cm to obtain a test NCM811 positive electrode.
• Sodium ion battery positive electrode Preparation of NaNi0.5Ti0.3Mn0.2O2 positive electrode
• As the positive electrode active material 90% by mass of NaNi0.5Ti0.3Mn0.2O2 , 5% by mass of acetylene black as a conductive agent, and 5% by mass of PVDF as a binder were mixed, and NMP was further added as a solvent to prepare a positive electrode composite paste. This paste was applied to both sides of an aluminum foil (A1085), dried, pressed, and then punched out to 4 cm x 5 cm to obtain a test NaNi0.5Ti0.3Mn0.2O2 positive electrode .
• a positive electrode composite paste was prepared by mixing 90.0% by mass of LiFePO4 powder with 5% by mass of PVDF as a binder and 5% by mass of acetylene black as a conductive material, and then adding NMP. This paste was applied to both sides of an aluminum foil (A1085), dried, pressed, and then punched out to 4 cm x 5 cm to obtain a test LFP positive electrode.
• a negative electrode composite paste was prepared by mixing 92% by mass of natural graphite powder, 3% by mass of conductive material (HS-100, manufactured by Denka), 2% by mass of carbon nanofiber (VGCF, manufactured by Showa Denko), 2% by mass of styrene butadiene rubber (hereinafter also referred to as "SBR”), 1% by mass of sodium carboxymethylcellulose (hereinafter also referred to as "CMC”), and water.
• SBR styrene butadiene rubber
• CMC sodium carboxymethylcellulose
• a negative electrode composite paste was prepared by mixing 85% by mass of artificial graphite powder, 7% by mass of nanosilicon, 3% by mass of conductive material (HS-100, manufactured by Denka), 2% by mass of carbon nanofiber (VGCF, manufactured by Showa Denko), 2% by mass of SBR, 1% by mass of CMC, and water. This paste was applied onto copper foil, dried, pressed, and then punched out to 4.5 cm x 5.5 cm to obtain a silicon-containing graphite negative electrode for testing.
• a negative electrode composite paste was prepared by mixing 90% by mass of hard carbon powder (Kureha Corporation, Carbotron P) and 10% by mass of PVDF as a binder, and adding NMP as a solvent. The paste was applied onto an aluminum foil (A1085), dried, pressed, and then punched out to 4.5 cm x 5.5 cm to obtain a test hard carbon negative electrode.
• nonaqueous electrolyte batteries lithium ion batteries
• examples and comparative examples in Tables 1 to 10, 29 to 34, and 45 to 47 aluminum laminate type nonaqueous electrolyte batteries (lithium ion batteries) according to the examples and comparative examples in Tables 1 to 10, 29 to 34, and 45 to 47.
• nonaqueous electrolyte batteries lithium ion batteries
• nonaqueous electrolyte batteries sodium ion batteries
• examples and comparative examples of Tables 53 to 65 nonaqueous electrolyte batteries (lithium ion batteries - LFP positive electrode -) were similarly produced using the nonaqueous electrolytes shown in each table, an LFP positive electrode as the positive electrode, and a natural graphite negative electrode as the negative electrode.
• the prepared cell was conditioned under the following conditions at an environmental temperature of 25° C. That is, as an initial charge/discharge test, the cell was charged at a constant current and constant voltage of 5 mA at a charging upper limit voltage of 4.2 V, discharged at a constant current of 10 mA to a discharge end voltage of 2.5 V, and then charged at a constant current and constant voltage of 10 mA at a charging upper limit voltage of 4.2 V, and discharged at a constant current of 10 mA to a discharge end voltage of 2.5 V, and this charge/discharge cycle was repeated three times.
• Lithium-ion battery Lithium-ion battery> The non-aqueous electrolyte battery that had undergone the above initial charge and discharge was charged at a constant current of 10 mA for 150 minutes at an environmental temperature of 25° C., and then discharged at a constant current of 10 seconds at a predetermined current value (5 mA, 10 mA, 25 mA, 50 mA, 100 mA). The voltage at the 10th second was measured and plotted against the current value. The least squares method was applied to each plot to obtain an approximate straight line. The value of the slope of the approximate straight line was taken as the initial DC internal resistance. The smaller this value, the better the initial input/output characteristics.
• Lithium-ion battery Lithium-ion battery> The non-aqueous electrolyte battery after the cycle test (45°C) was charged and discharged in the same manner as in the initial DC internal resistance measurement, and was charged at a constant current of 10 mA for 150 minutes at an ambient temperature of 25°C. The voltage at 10 seconds was measured and plotted against the current value. The least squares method was applied to each plot to obtain an approximate straight line. The slope of the approximate straight line was taken as the DC internal resistance after the cycle test.
• nonaqueous electrolyte batteries using nonaqueous electrolytes containing components (I) to (III) of the present disclosure have low initial DC internal resistance and can exhibit excellent initial input/output characteristics.
• component (I) is (1-3-1), (2-2-2), (3-3-3), or (4-3-1)
• the increase rate of DC internal resistance after cycle testing is small and favorable.
• Tables 45 to 52 and 63 to 65 show that, when comparing under conditions where the type and concentration of component (I) is the same and the type of anion of component (IV) is the same, in the case of lithium-ion batteries, the lower the content of cations other than lithium in the non-aqueous electrolyte, the easier it is to achieve a balanced improvement in the initial DC internal resistance and the rate of increase in DC internal resistance after cycle testing. Similarly, in the case of sodium-ion batteries, the lower the content of cations other than sodium in the non-aqueous electrolyte, the easier it is to achieve a balanced improvement in the initial DC internal resistance and the rate of increase in DC internal resistance after cycle testing.
• the present disclosure provides a nonaqueous electrolyte that can exhibit excellent initial input/output characteristics when used in a nonaqueous electrolyte battery, a nonaqueous electrolyte battery that can exhibit excellent initial input/output characteristics, and a compound that is suitable for use in the nonaqueous electrolyte.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• General Chemical & Material Sciences (AREA)
• Manufacturing & Machinery (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• General Physics & Mathematics (AREA)
• Inorganic Chemistry (AREA)
• Materials Engineering (AREA)
• Secondary Cells (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=92262603

Family Applications (1)

Country Status (5)

Citations (8)

• 2024
  • 2024-02-02 JP JP2024576303A patent/JPWO2024166826A1/ja active Pending
  • 2024-02-02 KR KR1020257026320A patent/KR20250142333A/ko active Pending
  • 2024-02-02 WO PCT/JP2024/003559 patent/WO2024166826A1/ja not_active Ceased
  • 2024-02-02 CN CN202480010945.3A patent/CN120642097A/zh active Pending
  • 2024-02-02 EP EP24753269.0A patent/EP4648166A1/en active Pending

Patent Citations (8)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events