WO2022138893A1 - Solution électrolytique non aqueuse et batterie à solution électrolytique non aqueuse - Google Patents

Solution électrolytique non aqueuse et batterie à solution électrolytique non aqueuse Download PDF

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WO2022138893A1
WO2022138893A1 PCT/JP2021/048103 JP2021048103W WO2022138893A1 WO 2022138893 A1 WO2022138893 A1 WO 2022138893A1 JP 2021048103 W JP2021048103 W JP 2021048103W WO 2022138893 A1 WO2022138893 A1 WO 2022138893A1
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group
carbon atoms
compound
mass
aqueous electrolyte
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PCT/JP2021/048103
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Japanese (ja)
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英司 中澤
泰樹 阿部
花穂 玉井
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Ｍｕアイオニックソリューションズ株式会社
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Publication of WO2022138893A1 publication Critical patent/WO2022138893A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • 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
    • H01M10/056—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy

Definitions

  • the present invention relates to a non-aqueous electrolyte solution and a non-aqueous electrolyte battery, and more particularly to a non-aqueous electrolyte solution containing a specific compound and a non-aqueous electrolyte battery using this non-aqueous electrolyte solution.
  • Non-aqueous electrolyte batteries such as lithium secondary batteries are practically used in a wide range of applications such as power supplies for so-called consumer small devices such as mobile phones such as smartphones and laptop computers, and in-vehicle power supplies for driving such as electric vehicles. It has been converted.
  • Patent Document 1 discloses a study of improving the cycle capacity retention rate and suppressing an increase in the internal resistance of a battery by adding a specific unsaturated silane compound or unsaturated siloxane compound to a non-aqueous electrolytic solution.
  • Patent Document 2 discloses a study of improving the cycle capacity retention rate of a non-aqueous secondary battery having a rated charging voltage of more than 4.2 V by adding a silicon compound having a specific structure to the non-aqueous electrolyte solution. ing.
  • R 1 to R 3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and at least one of R 1 to R 3 has 1 to 12 carbon atoms.
  • R 4 to R 5 independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
  • R 6 is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or carbon. Indicates an alkoxy group of numbers 1 to 12.
  • R 7 to R 12 each independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or a substituent. It indicates an alkoxy group having 1 to 12 carbon atoms which may be used.
  • N indicates an integer of 1 to 5).
  • R 13 to R 14 each independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or a substituent. It indicates an alkoxy group having 1 to 12 carbon atoms which may be used, and k indicates an integer of 3 to 6).
  • R15 to R17 each independently represent a hydrocarbon group having 1 to 12 carbon atoms or a trialkylsilyl group which may have a heteroatom, and R15 to R15.
  • R 17 may be bonded to each other to form a ring.
  • R 21 and R 22 each independently represent an alkylene group having 1 to 10 carbon atoms which may have a substituent.
  • M represents an integer of 0 or 1. When 0, the sulfur atom and the oxygen atom form a direct bond.
  • a non-aqueous electrolyte battery including a positive electrode, a negative electrode, and a non-aqueous electrolytic solution, wherein the non-aqueous electrolytic solution is the non-aqueous electrolytic solution according to any one of ⁇ 1> to ⁇ 4>.
  • Non-aqueous electrolyte battery including a positive electrode, a negative electrode, and a non-aqueous electrolytic solution, wherein the non-aqueous electrolytic solution is the non-aqueous electrolytic solution according to any one of ⁇ 1> to ⁇ 4>.
  • M represents at least one element selected from the group consisting of Mn, Co, Al, Mg, Zr, Fe, Ti and Er.
  • the positive electrode has a positive electrode active material
  • the positive electrode active material is a transition metal oxide represented by the following composition formula (2).
  • Li a2 Ni b2 Co c2 M d2 O 2 (2) (In the above formula (2), a2, b2, c2 and d2 are 0.90 ⁇ a2 ⁇ 1.10, 0.01 ⁇ b2 ⁇ 0.98, 0.01 ⁇ c2 ⁇ 0.50, 0.01.
  • M represents at least one element selected from the group consisting of Mn, Al, Mg, Zr, Fe, Ti and Er.
  • the negative electrode has a negative electrode active material and contains a material containing a metal element that can be alloyed with Li and / or a material containing a semi-metal element that can be alloyed with Li.
  • ⁇ 12> The non-aqueous electrolysis according to any one of ⁇ 1> to ⁇ 4>, further containing at least one compound (III) selected from the group consisting of unsaturated cyclic carbonate and cyclic carbonate having a fluorine atom. liquid.
  • ⁇ 13> The non-aqueous electrolyte solution according to ⁇ 12>, which contains an unsaturated cyclic carbonate and a cyclic carbonate having a fluorine atom.
  • ⁇ 14> The non-aqueous electrolyte solution according to ⁇ 12> or ⁇ 13>, wherein the unsaturated cyclic carbonate is vinylene carbonate.
  • the compound (I) contains at least one compound selected from the group consisting of a fluorosulfonic acid anion-containing compound, a sulfonylimide anion-containing compound, an alkyl sulfate anion-containing compound, and an oxalate complex anion-containing compound.
  • the compound (II) is selected from at least a group consisting of a compound represented by the general formula (B), a compound represented by the general formula (C), and a compound represented by the general formula (D).
  • the non-aqueous electrolyte solution according to ⁇ 4> which contains one compound.
  • the compound (II) contains at least one compound selected from the group consisting of the compound represented by the general formula (B) and the compound represented by the general formula (C), ⁇ 4>.
  • ⁇ 21> The non-aqueous electrolytic solution according to ⁇ 3>, wherein the content of the compound (I) is 0.001 to 8% by mass with respect to the total amount of the non-aqueous electrolytic solution.
  • ⁇ 22> The non-aqueous electrolytic solution according to ⁇ 3>, wherein the content of the compound (I) is 0.001 to 5% by mass with respect to the total amount of the non-aqueous electrolytic solution.
  • ⁇ 23> The non-aqueous electrolytic solution according to ⁇ 4>, wherein the content of the compound (II) is 0.001 to 10% by mass with respect to the total amount of the non-aqueous electrolytic solution.
  • ⁇ 24> The non-aqueous electrolytic solution according to ⁇ 12>, wherein the content of the compound (III) is 0.001 to 10% by mass with respect to the total amount of the non-aqueous electrolytic solution.
  • the present invention it is possible to obtain a non-aqueous electrolyte solution excellent in suppressing gas generation during initial conditioning of the non-aqueous electrolyte battery and a non-aqueous electrolyte battery in which gas generation is suppressed during initial conditioning.
  • Non-aqueous electrolytic solution according to the present invention contains a compound represented by the general formula (A) described below.
  • the mechanism for suppressing gas generation during initial conditioning by using a non-aqueous electrolytic solution containing a specific silicon compound represented by the general formula (A) is not clear, but is presumed as follows.
  • the compound represented by the general formula (A) has a silyl group (-SiR 1 R 2 R 3 ) having at least one hydrocarbon group having 1 to 12 carbon atoms in the molecule.
  • a silicon atom has a large electron cloud spread and has no steric obstacle when forming a bond, so that it easily forms a bond with a ⁇ electron or an unpaired electron via an empty d-orbital.
  • a silyl group having at least one hydrocarbon group having 1 to 12 carbon atoms is bonded to a carbon-carbon double bond via an oxygen atom. As the electron density of the carbon-carbon double bond increases, the reaction activity with a demanding compound such as Lewis acid increases.
  • the compound represented by the general formula (A) interacts with the unpaired electron of the oxygen atom of the positive electrode active material and the Lewis acid point such as the transition metal at the time of initial charging, and reacts with the insulating property. Form a high film of. It is presumed that this coating suppresses side reactions of the electrolytic solution during initial conditioning and reduces the amount of gas generated.
  • the non-aqueous electrolytic solution according to the embodiment of the present invention is characterized by containing a silicon compound represented by the following general formula (A).
  • identification and measurement of the content of a compound such as a silicon compound represented by the general formula (A) contained in a non-aqueous electrolyte solution are performed by nuclear magnetic resonance (NMR) spectroscopy.
  • R 1 to R 3 independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and at least one of R 1 to R 3 is a hydrocarbon having 1 to 12 carbon atoms. It is a hydrogen group.
  • R 4 to R 5 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
  • R 6 represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. Either one of R 4 or R 5 and R 6 may be coupled to each other to form a ring.
  • the hydrocarbon group having 1 to 12 carbon atoms is preferably a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 4 carbon atoms.
  • the hydrocarbon group may be linear or branched and may contain a cyclic structure and / or an unsaturated bond.
  • hydrocarbon group examples include an alkyl group, an alkenyl group, an alkynyl group, an aryl group and an aralkyl group.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, n-pentyl group, hexyl group, heptyl group, octyl group and nonyl group. , Decyl group and the like.
  • a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tert-butyl group, an n-pentyl group and a hexyl group are preferable, and a methyl group, an ethyl group, an n-propyl group and an n-butyl group are more preferable.
  • examples thereof include a group, a tert-butyl group and an n-pentyl group, and particularly preferably a methyl group, an ethyl group, an n-butyl group and a tert-butyl group.
  • the above-mentioned alkyl group is preferable because the compound according to the general formula (A) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material.
  • alkenyl group examples include a vinyl group, an allyl group, a metallicyl group, a 2-butenyl group, a 3-methyl2-butenyl group, a 3-butenyl group, a 4-pentenyl group and the like.
  • a vinyl group, an allyl group, a methallyl group and a 2-butenyl group are preferable, and a vinyl group, an allyl group and a methallyl group are more preferable, and a vinyl group or an allyl group is particularly preferable.
  • the above-mentioned alkenyl group is preferable because the compound according to the general formula (A) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material.
  • alkynyl group examples include an ethynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 4-pentynyl group, a 5-hexynyl group and the like.
  • ethynyl group, 2-propynyl group, 2-butynyl group and 3-butynyl group are more preferable
  • 2-propynyl group and 3-butynyl group are more preferable
  • 2-propynyl group is particularly preferable.
  • the above-mentioned alkynyl group is preferable because the compound according to the general formula (A) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material.
  • the aryl group include a phenyl group and a tolyl group. Of these, a phenyl group is preferable from the viewpoint that the compound according to the general formula (A) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material.
  • the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, a phenylisopropyl group and the like.
  • a benzyl group and a phenethyl group are more preferable, and a benzyl group is particularly preferable, from the viewpoint that the compound represented by the general formula (A) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material. preferable.
  • the alkoxy group having 1 to 12 carbon atoms is preferably an alkoxy group having 1 to 6 carbon atoms, and particularly preferably an alkoxy group having 1 to 4 carbon atoms.
  • Specific examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group and the like.
  • the methoxy group and the ethoxy group are preferably concentrated on the surface of the active material with less steric hindrance of the compound represented by the general formula (A).
  • hydrocarbon groups having at least two carbon atoms having 1 to 12 carbon atoms are preferable from the viewpoint of less steric damage and suitable action on the electrode surface, and they can preferably interact with the reaction point of the positive electrode active material.
  • all of R 1 to R 3 are more preferably hydrocarbon groups having 1 to 12 carbon atoms, and all of R 1 to R 3 are more preferably alkyl groups having 1 to 6 carbon atoms, and all of R 1 to R 3 are more preferably alkyl groups having 1 to 6 carbon atoms.
  • Alkyl groups, all of which have 1 to 4 carbon atoms, are particularly preferred.
  • R 4 or R 5 and R 6 may be coupled to each other to form a ring.
  • R5 and R6 are bonded to each other to form a ring.
  • R 4 , R 5 and R 6 are one carbon-in a ring formed by bonding R 4 and R 6 to each other or a ring formed by bonding R 5 and R 6 to each other. It also includes a group formed when a carbon bond is broken.
  • the alicyclic carbon ring composed of the carbon-carbon double bond between the carbon to which R 5 , R 6 and R 4 and R 5 are bonded and the carbon to which the Si—O bond and R 6 are bonded includes cyclobutene and cyclohexene. , 1,3-Cyclohexadiene and the like.
  • the divalent hydrocarbon group formed from R 5 and R 6 is represented by-(CH 2 ) n- (n represents an integer of 3 to 6). It is preferable that it is a polymethylene group, that is, R 5 and R 6 are alkyl groups and are bonded to each other to form a ring.
  • the divalent hydrocarbon group formed from R 5 and R 6 contains an unsaturated bond, that is, R 5 and R 6 are an alkyl group or an alkenyl group and are bonded to each other to form a ring. Is particularly preferable.
  • R 1 to R 6 R 1 to R 3 are independent alkyl groups having 1 to 12 carbon atoms;
  • R 4 to R 5 are independent hydrogen atoms or alkyl groups having 1 to 12 carbon atoms, respectively;
  • R 6 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms (R 4 to R 5 and R 6 form a ring).
  • R 1 to R 3 are independent alkyl groups having 1 to 6 carbon atoms; R 4 to R 5 are independent hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, respectively; R 6 is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms (even if R 4 to R 5 and R 6 form a ring). The better) aspect is more preferred. From the viewpoint of availability of the compound, R 1 to R 3 are independently alkyl groups having 1 to 6 carbon atoms; R 4 to R 5 are independently alkyl groups having 1 to 6 carbon atoms; R 6 is.
  • R 1 to R 3 are independently alkyl groups having 1 to 6 carbon atoms; and R 4 to R 5 are independently alkyl groups having 1 to 6 carbon atoms.
  • Group; R6 is preferably an alkenyl group having 2 to 6 carbon atoms.
  • Alkyl group; R 6 is an alkyl group having 1 to 6 carbon atoms (R 4 to R 5 and R 6 may form a ring), and R 1 to R 3 are independent of each other.
  • R 1 to R 6 is not particularly limited, but R 1 to R 3 are alkyl groups, R 4 is a hydrogen atom, R 5 is a hydrogen atom, and R 6 is a hydrogen atom; R 1 to R 3 are alkyl groups, R 4 is a hydrogen atom, R 5 is a hydrogen atom, and R 6 is an alkyl group; R 1 to R 3 are alkyl groups, R 4 is a hydrogen atom, R 5 is a hydrogen atom, and R 6 is an alkenyl group; R1 to R3 are alkyl groups, R4 is a hydrogen atom, R5 is a hydrogen atom, and R6 is an alkynyl group; R 1 to R 3 are alkyl groups, R 4 is a hydrogen atom, R 5 is a hydrogen atom, and R 6 is an alkoxy group; R 1 to R 3 are alkyl groups, R 4 is a hydrogen atom, R 5 is an alkyl group, and R 6 is a hydrogen atom; R 1 to R 3 are
  • R 1 to R 3 are alkyl groups, R 4 is a hydrogen atom, R 5 is a hydrogen atom, and R 6 is a hydrogen atom;
  • R 1 to R 3 are alkyl groups, R 4 is a hydrogen atom, R 5 is a hydrogen atom, and R 6 is an alkyl group;
  • R 1 to R 3 are alkyl groups, R 4 is a hydrogen atom, R 5 is a hydrogen atom, and R 6 is an alkenyl group;
  • R1 to R3 are alkyl groups, R4 is a hydrogen atom, R5 is a hydrogen atom, and R6 is an alkynyl group;
  • R 1 to R 3 are alkyl groups, R 4 is a hydrogen atom, R 5 is an alkyl group, and R 6 is a hydrogen atom;
  • R 1 to R 3 are alkyl groups, R 4 is a hydrogen atom, R 5 is an alkyl group, and R 6 is an alkyl group;
  • R 1 to R 3
  • R 1 to R 3 are alkyl groups, R 4 is a hydrogen atom, R 5 is a hydrogen atom, and R 6 is an alkyl group;
  • R 1 to R 3 are alkyl groups, R 4 is a hydrogen atom, R 5 is a hydrogen atom, and R 6 is an alkenyl group;
  • R1 to R3 are alkyl groups, R4 is a hydrogen atom, R5 is a hydrogen atom, and R6 is an alkynyl group;
  • R 1 to R 3 are alkyl groups, R 4 is a hydrogen atom, R 5 is an alkyl group, and R 6 is an alkyl group;
  • R 1 to R 3 are alkyl groups, R 4 is a hydrogen atom, R 5 is an alkyl group, and R 6 is an alkenyl group;
  • R 1 to R 3 are alkyl groups, R 4 is a hydrogen atom, R 5 is an alkyl group, and R 6 is an alkynyl group;
  • Specific examples of the compound represented by the general formula (A) include compounds having the following structures.
  • the compound represented by the general formula (A) may be used alone or in combination of two or more.
  • the content of the compound represented by the general formula (A) with respect to the total amount of the non-aqueous electrolyte solution according to the embodiment of the present invention is not particularly limited, but is usually 0.001 to 10% by mass, preferably 0.001 to 10% by mass. 0.01% by mass or more, more preferably 0.1% by mass or more, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, still more preferably 1.0% by mass or less. Particularly preferably, it is 0.5% by mass or less.
  • the non-aqueous electrolyte solution contains two or more compounds represented by the general formula (A)
  • the total amount thereof is taken as the content of the compound (A).
  • the concentration of the compound in the active material proceeds favorably, and the battery with less gas generation during the initial conditioning is generated.
  • a commercially available product may be used, or a synthetic product may be used.
  • the non-aqueous electrolyte solution of the present embodiment usually contains an electrolyte as a component thereof, like a general non-aqueous electrolyte solution.
  • the electrolyte used in the non-aqueous electrolyte solution of the present embodiment is not particularly limited as long as it is an alkali metal salt, and LiBF 4 , LiPF 6 , LiN (FSO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , and lithium difluorooxa. It is preferable to use a lithium salt such as latborate, it is more preferable to use LiBF 4 , LiPF 6 , LiN (CF 3 SO 2 ) 2 , and LiPF 6 is more preferable. In addition, these lithium salts can be used alone or in combination of two or more.
  • the total concentration of the alkali metal salt in the non-aqueous electrolyte solution is not particularly limited, but is usually 8% by mass or more, preferably 8.5% by mass or more, more preferably 8.5% by mass or more, based on the total amount of the non-aqueous electrolyte solution. It is 9% by mass or more. Further, it is usually 18% by mass or less, preferably 17% by mass or less, and more preferably 16% by mass or less. It is preferably 8.5% by mass to 17% by mass, and more preferably 9% by mass to 16% by mass.
  • the total concentration of the alkali metal salt as an electrolyte is within the above range, the electric conductivity becomes appropriate for battery operation, so that sufficient output characteristics tend to be obtained.
  • the electrolyte compound corresponding to the auxiliary agent> When the electrolyte compound corresponding to the auxiliary agent> is contained in the non-aqueous electrolyte solution, the electrolyte other than the lithium salt corresponding to the auxiliary agent must be contained. Further, when the content of the electrolyte compound is 5.0% by mass or less, it is classified as an "auxiliary agent" in the present specification. Therefore, even if the "compound corresponding to the auxiliary agent" corresponds to the "electrolyte” as a constituent component of the non-aqueous electrolyte solution of the present embodiment, the amount of the "electrolyte” corresponds to the "auxiliary agent". The amount of "compounds" is not included.
  • the non-aqueous electrolyte solution of the present embodiment usually contains a non-aqueous solvent that dissolves the above-mentioned electrolyte as its main component.
  • the non-aqueous solvent is not particularly limited, and a known organic solvent can be used.
  • the organic solvent include saturated cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate, and ethylmethyl carbonate; and methyl acetate, ethyl acetate, propyl acetate, and butyl acetate.
  • Carboxylic acid esters ethereal compounds such as dimethoxymethane, diethoxymethane, ethoxymethoxymethane, tetrahydrofuran, 1,3-dioxane, and 1,4-dioxane; 2-methylsulfone, 3-methylsulfolane, 2-fluorosulfolane, Sulfone-based compounds such as 3-fluorosulfolane, dimethylsulfone, ethylmethylsulfone, and monofluoromethylmethylsulfone; and the like.
  • Saturated cyclic carbonate, chain carbonate or carboxylic acid ester is preferable, and saturated cyclic carbonate or chain carbonate is more preferable.
  • These non-aqueous solvents may be used alone or in combination of two or more.
  • the non-aqueous electrolytic solution of the present embodiment may contain an auxiliary agent as long as the effect of the present invention is exhibited.
  • an auxiliary agent As an aid, Difluorophosphate anion-containing compound; Fluorosulfuric acid anion-containing compound; Sulfonylimide anion-containing compound; Alkyl sulfate anion-containing compound; Oxalate anion-containing compound; Unsaturated cyclic carbonates such as vinylene carbonate, vinylethylene carbonate and ethynylethylene carbonate; Fluorinated cyclic carbonates such as monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate and 4,5-difluoro-4,5-dimethylethylene carbonate; Carbonate compounds such as methoxyethyl-methyl carbonate; Spiro compounds such as methyl-2-propynyl oxalate; Diisocyanate having a cycloalkylene group such
  • Isocyanate compounds such as aliphatic polyisocyanates with added alcohol; Nitrogen-containing compounds such as 1-methyl-2-pyrrolidinone; Hydrocarbon compounds such as cycloheptane; Fluoro-containing aromatic compounds such as fluorobenzene; Ester compounds such as 2- (methanesulfonyloxy) propionic acid 2-propynyl; Lithium salts such as lithium ethylmethyloxycarbonylphosphonate;
  • R 7 to R 12 each independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or a substituent.
  • R 13 to R 14 each independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or a substituent. It indicates an alkoxy group having 1 to 12 carbon atoms which may be used, and k indicates an integer of 3 to 6).
  • R 17 may be bonded to each other to form a ring.
  • R 21 and R 22 each independently represent an alkylene group having 1 to 10 carbon atoms which may have a substituent.
  • M represents an integer of 0 or 1. When 0, the sulfur atom and the oxygen atom form a direct bond.) And so on. These may be used alone or in combination of two or more. By adding these auxiliaries, it is possible to suppress gas generation during initial conditioning and improve capacity retention characteristics and cycle characteristics after high temperature storage.
  • the non-aqueous electrolyte solution according to the embodiment of the present invention contains a difluorophosphate anion-containing compound and a fluorosulfonic acid anion in that gas generation during initial conditioning is further suppressed and a battery that does not easily swell can be obtained. It has one or more unsaturated cyclic carbonates and a fluorine atom selected from a compound, an oxalate complex anion-containing compound, and a sulfonylimide anion-containing compound (hereinafter, also referred to as “specific anion-containing compound (compound (I))”).
  • the specific anion-containing compound is preferably at least one compound selected from the group from a fluorosulfonic acid anion-containing compound, a sulfonylimide anion-containing compound, an alkyl sulfate anion-containing compound, and an oxalate complex anion-containing compound.
  • At least one compound selected from the group consisting of a fluorosulfonic acid anion-containing compound, an alkyl sulfate anion-containing compound, and an oxalate complex anion-containing compound is more preferable, and a group consisting of a fluorosulfonic acid anion-containing compound and an alkyl sulfate anion-containing compound.
  • the specific compound (Compound II) is at least one selected from the group consisting of a compound represented by the general formula (B), a compound represented by the general formula (C), and a compound represented by the general formula (D). Species of compounds are preferred, and at least one compound selected from the group consisting of compounds of the general formula (B) and compounds of the general formula (C) is more preferred.
  • a specific anion-containing compound and a specific carbonate compound, or a specific compound and a specific carbonate compound may be used in combination. preferable.
  • the content of the auxiliary agent is usually 0.001 to 10% by mass, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0 in 100% by mass of the non-aqueous electrolyte solution. It is .2% by mass or more, and usually 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less. It is preferably 0.001 to 8% by mass, more preferably 0.001 to 5% by mass, and further preferably 3% by mass or less. When two or more auxiliaries are used in combination, it is preferable that the total amount satisfies the above range.
  • the particular anion-containing compound is usually an acid or salt, preferably a salt.
  • the counter cation of the salt of the specific anion-containing compound is not particularly limited, but lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, and NR 23 R 24 R 25 R 26 (in the formula, R 23 ).
  • ⁇ R 26 each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms), and examples thereof include ammonium. Of these, lithium is preferable.
  • the organic group having 1 to 12 carbon atoms represented by R 23 to R 26 of the ammonium is not particularly limited, and is, for example, substituted with an alkyl group which may be substituted with a halogen atom, a halogen atom or an alkyl group.
  • Examples thereof include a cycloalkyl group which may be present, an aryl group which may be substituted with a halogen atom or an alkyl group, a nitrogen atom-containing heterocyclic group which may have a substituent, and the like.
  • R 23 to R 26 are independently hydrogen atom, alkyl group, cycloalkyl group, or nitrogen atom-containing heterocyclic group.
  • difluorophosphate anion As the difluorophosphate anion, one type may be used alone, or two or more types may be used in combination in any combination and ratio.
  • the content of difluorophosphate (total content in the case of two or more types) with respect to the total amount of the non-aqueous electrolyte solution is not particularly limited and is arbitrary as long as the effect of the present invention is not significantly impaired. It is 001 to 8% by mass, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 5.0% by mass or less, more preferably 3.0% by mass or less. It is more preferably 2.0% by mass or less, and most preferably 1.5% by mass or less.
  • the initial gas generation can be suitably suppressed.
  • fluorosulfuric acid anion As the fluorosulfonic acid anion, one type may be used alone, or two or more types may be used in combination in any combination and ratio.
  • the content of the fluorosulfonate (total content in the case of two or more types) with respect to the total amount of the non-aqueous electrolyte solution is not particularly limited and is arbitrary as long as the effect of the present invention is not significantly impaired. It is 001 to 8% by mass, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and further. It is preferably 2.0% by mass or less, and most preferably 1.5% by mass or less.
  • sulfonylimide anion Specific examples of the sulfonylimide anion include N- ( FSO 2 ) 2 , N- ( FSO 2 ) (CF 3 SO 2 ), N- ( CF 3 SO 2 ) 2 , N- ( C 2 F 5 SO 2 ). 2.
  • the sulfonylimide anion one type may be used alone, or two or more types may be used in combination in any combination and ratio.
  • the content of the sulfonylimide anion with respect to the total amount of the non-aqueous electrolyte solution is not particularly limited and is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.001. -8% by mass, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and further. It is preferably 2.0% by mass or less, and most preferably 1.5% by mass or less.
  • alkyl sulfate anion Specific examples of the alkyl sulfate anion include compounds represented by C n H 2n + 1 OSO 3- ( 1 ⁇ n ⁇ 10), and a methyl sulfate anion or an ethyl sulfate anion is preferable.
  • the content of the alkyl sulfate anion is not particularly limited and is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.001 to 8% by mass, preferably 0.01% by mass or more, more preferably. 0.1% by mass or more, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, still more preferably 2.0% by mass or less, and most preferably 1.5% by mass or less.
  • the initial gas generation can be suitably suppressed.
  • oxalate complex anion Specific examples of the oxalate complex anion include (oxalate) borate anion, bis (oxalate) borate anion, tetrafluorooxalate phosphate anion, difluorobis (oxalate) phosphate anion, and tris (oxalate) phosphate anion.
  • Bis (oxalate) borate and difluorobis (oxalate) phosphate anion are preferable, and bis (oxalate) borate anion is particularly preferable.
  • the oxalate complex anion one kind may be used alone, or two or more kinds may be used in any combination and ratio.
  • the content of the oxalate complex anion (total content in the case of two or more kinds) is not particularly limited and is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.001 to 8% by mass, preferably 0.001 to 8% by mass. Is 0.01% by mass or more, more preferably 0.1% by mass or more, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, still more preferably 2.0% by mass or less. Most preferably, it is 1.5% by mass or less.
  • the content of the oxalate complex anion is within this range, the initial gas generation can be suppressed.
  • the non-aqueous electrolyte solution preferably contains at least one carbonate compound selected from the group consisting of unsaturated cyclic carbonates having carbon-carbon unsaturated bonds and cyclic carbonates having fluorine atoms.
  • unsaturated cyclic carbonate and more preferably to contain a vinylene carbonate can be used alone or in combination of two or more at any ratio, preferably containing unsaturated cyclic carbonate and fluorinated cyclic carbonate, and containing vinylene carbonate and fluorinated cyclic carbonate.
  • the unsaturated cyclic carbonate is not particularly limited as long as it is a cyclic carbonate having a carbon-carbon double bond or a carbon-carbon triple bond. Cyclic carbonates having an aromatic ring are also included in unsaturated cyclic carbonates.
  • unsaturated cyclic carbonates include vinylene carbonates, aromatic rings, ethylene carbonates substituted with substituents having carbon-carbon double bonds or carbon-carbon triple bonds, phenyl carbonates, vinyl carbonates, allyl carbonates, and the like.
  • examples thereof include catechol carbonates.
  • vinylene carbonates, aromatic rings or ethylene carbonates substituted with a substituent having a carbon-carbon double bond or a carbon-carbon triple bond are preferable.
  • vinylene carbonates examples include vinylene carbonate, methylvinylene carbonate, 4,5-dimethylvinylene carbonate, phenylvinylene carbonate, 4,5-diphenylvinylene carbonate, vinylvinylene carbonate, 4,5-vinylvinylene carbonate, allylvinylene carbonate, 4 , 5-Diallyl vinylene carbonate and the like.
  • ethylene carbonates substituted with an aromatic ring or a substituent having a carbon-carbon double bond or a carbon-carbon triple bond include vinyl ethylene carbonate, 4,5-divinylethylene carbonate, and 4-methyl-5-vinylethylene carbonate.
  • vinylene carbonate, vinylethylene carbonate, and ethynylethylene carbonate are preferable because they form a more stable composite film on the electrode, and one or more selected from vinylene carbonate and vinylethylene carbonate are more preferable, and vinylene carbonate is further preferable. ..
  • the unsaturated cyclic carbonate can be used alone or in combination of two or more at any ratio.
  • the cyclic carbonate having a fluorine atom is not particularly limited as long as it has a cyclic carbonate structure and contains a fluorine atom.
  • Examples of the cyclic carbonate having a fluorine atom include a fluorinated product of a cyclic carbonate having an alkylene group having 2 or more and 6 or less carbon atoms and a derivative thereof, and for example, a fluorinated product of ethylene carbonate (fluoroethylene carbonate) and a derivative thereof, and a derivative thereof.
  • Examples thereof include ethylene carbonate having a fluorine group.
  • Examples of the derivative of the fluorinated product of ethylene carbonate include a fluorinated product of ethylene carbonate substituted with an alkyl group (for example, an alkyl group having 1 or more and 4 or less carbon atoms). Among these, fluoroethylene carbonate having 1 or more and 8 or less fluorine atoms and a derivative thereof are preferable.
  • Fluoroethylene carbonate having 1 or more and 8 or less fluorine atoms and its derivatives, and ethylene carbonate having a fluorine-containing group include monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, and 4-fluoro.
  • cyclic carbonate having a fluorine atom can be used alone or in combination of two or more in any ratio.
  • the content of the specific carbonate compound (total amount in the case of two or more kinds) in the total amount of the non-aqueous electrolyte solution is usually 0.001 to 10% by mass, preferably 0.01% by mass or more, and more preferably 0. .1% by mass or more, more preferably 0.5% by mass or more, preferably 8.0% by mass or less, more preferably 6.0% by mass or less, still more preferably 5.0% by mass or less. .. It is preferably 0.001 to 10% by mass, more preferably 0.001 to 8.0% by mass, still more preferably 0.001 to 6.0% by mass, and most preferably 0.001 to 5.0% by mass. be.
  • Mass ratio of the compound represented by the general formula (A) to a specific carbonate compound Mass ratio of the content of the specific carbonate compound (total amount in the case of two or more types) to the content of the compound represented by the general formula (A) (specific carbonate compound [g] / general formula (A)
  • the represented compound [g]) is usually 1 to 200. It is preferably 3 or more, more preferably 5 or more, preferably 100 or less, more preferably 70 or less, still more preferably 50 or less. It is preferably 1 to 100, more preferably 1 to 70, and even more preferably 1 to 50. When the mass ratio is within the above range, gas generation during initial conditioning can be significantly suppressed.
  • the mass ratio of the content of a specific carbonate compound (total amount in the case of two or more types) to the content of an electrolyte (preferably LiPF 6 ) (specific carbonate compound [g] / electrolyte [g] ) Is usually 0.001 to 0.8. It is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, and preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.35 or less. be. It is preferably 0.001 to 0.5, more preferably 0.001 to 0.4, and even more preferably 0.001 to 0.35.
  • R 7 to R 12 each independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or a substituent. It also shows a good alkoxy group having 1 to 12 carbon atoms.
  • n represents an integer of 1 to 5.
  • R 7 to R 12 are preferably a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent.
  • it is a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent or an alkoxy group having 1 to 12 carbon atoms which may have a substituent.
  • the hydrocarbon group has a substituent, the number of carbons contained in the substituent is not included in the number of carbon atoms of the hydrocarbon group as R 7 to R 12 .
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like.
  • Fluorine atoms are preferred from the perspective of having few electrochemical side reactions.
  • Specific examples of the unsubstituted hydrocarbon group and the alkoxy group include those exemplified by R 1 to R 6 of the general formula (A).
  • the compound represented by the general formula (B) is suitably localized on the electrode surface so that at least one of R 7 to R 12 is a hydrocarbon group having a carbon-carbon unsaturated bond and having 2 to 12 carbon atoms. It is preferable from the viewpoint that it tends to be converted.
  • hydrocarbon group having 2 to 12 carbon atoms having a carbon-carbon unsaturated bond examples include the above-mentioned alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, and 6 to 12 carbon atoms.
  • the alkenyl group having 2 to 12 carbon atoms or the alkynyl group having 2 to 12 carbon atoms has a tendency that the compound represented by the general formula (B) is more preferably localized on the electrode surface. It is preferable from the viewpoint of the above, and particularly preferably, it is an alkenyl group having 2 to 12 carbon atoms.
  • R 7 to R 12 may be the same or different, but it is preferable that at least two or more of them are the same in terms of easy compound synthesis, and it is further preferable that three or more of them are the same from the above-mentioned viewpoint. preferable.
  • Ra has an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl having 2 to 10 carbon atoms. Shows the group.
  • Halogen preferably fluorine
  • n is preferably an integer of 1 to 3, and more preferably 1 or 2.
  • n is in this range, the molecular size of the compound represented by the general formula (B) is appropriate, and it becomes easy to interact favorably with the electrode.
  • R 13 to R 14 each independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or a substituent. It also shows a good alkoxy group having 1 to 12 carbon atoms. k represents an integer of 3 to 6.
  • R 13 to R 14 are preferably a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent.
  • it is a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent or an alkoxy group having 1 to 12 carbon atoms which may have a substituent.
  • the hydrocarbon group has a substituent, the number of carbons contained in the substituent is not included in the number of carbon atoms of the hydrocarbon group as R 13 to R 14 .
  • R 13 to R 14 is a hydrocarbon group having a carbon-carbon unsaturated bond and having 2 to 12 carbon atoms, and the compound represented by the general formula (C) is suitable for the electrode surface. It is preferable from the viewpoint that it tends to be localized.
  • the hydrocarbon group having 2 to 12 carbon atoms having a carbon-carbon unsaturated bond include an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms, which will be described later.
  • an alkenyl group having 2 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms is preferable from the viewpoint that the compound represented by the general formula (C) tends to be more preferably localized on the electrode surface.
  • it is an alkenyl group having 2 to 12 carbon atoms.
  • R 13 to R 14 may be the same or different, but it is preferable that both are the same because the compound can be easily synthesized.
  • the general formula (B) is used as the halogen atom, the hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and the alkoxy group having 1 to 12 carbon atoms which may have a substituent. ) Is illustrated in R7 to R12 .
  • k is preferably 3 to 5, more preferably 3 or 4.
  • Examples of the compound represented by the general formula (B) or (C) preferably include the following compounds.
  • the content of the compound represented by the general formula (B) and / or (C) with respect to the total amount of the non-aqueous electrolyte solution according to the embodiment of the present invention is usually 0.001 to 10% by mass. It is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and preferably 8.0% by mass or less, more preferably 6.0% by mass. Below, it is more preferably 4.0% by mass or less, particularly preferably 3.0% by mass or less, particularly preferably 2.5% by mass or less, and most preferably 2.0% by mass or less. It is preferably 0.001 to 3.0% by mass, more preferably 0.001 to 2.5% by mass, and further preferably 0.001 to 2.0% by mass.
  • the non-aqueous electrolyte solution contains two or more compounds represented by the general formulas (B) and / or (C)
  • the total amount thereof is the compound represented by the general formulas (B) and / or (C).
  • the content is. If the content of the compound represented by the general formula (B) and / or (C) with respect to the total amount of the non-aqueous electrolyte solution is within the above range, the general formula (B) and / or (C) to the active material Concentration of the compound represented by (1) proceeds favorably, and it becomes possible to manufacture a battery in which the amount of gas generated during the initial conditioning is small.
  • the non-aqueous electrolytic solution according to the embodiment of the present invention can contain a compound represented by the following general formula (D).
  • R15 to R17 each independently represent a hydrocarbon group having 1 to 12 carbon atoms or a trialkylsilyl group which may have a heteroatom. Further, R 15 to R 17 may be bonded to each other to form a ring.
  • the number of carbon atoms contained in the substituent is not included in the number of carbon atoms of the hydrocarbon group as R 15 to R 17 . ..
  • the hydrocarbon group which may have a hetero atom may have a substituent containing a monovalent hetero atom which replaces the hydrogen atom of the hydrocarbon group, and may contain a carbon atom in the hydrocarbon group. It means that it may have a divalent substituent containing a hetero atom for substituting a group (methylene group or the like).
  • the hydrocarbon group having 1 to 12 carbon atoms is preferably a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 4 carbon atoms.
  • hydrocarbon group examples include those exemplified by R1 to R3 of the general formula ( A).
  • hetero atom examples include an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom and a halogen atom.
  • Ra has an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl having 2 to 10 carbon atoms. Shows the group.
  • Halogen preferably fluorine
  • trifluoromethyl group examples include an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom and the like.
  • a phosphorus atom or a nitrogen atom, particularly preferably a nitrogen atom, is preferable from the viewpoint of strengthening the interaction with the compound represented by the general formula (A).
  • the lone electron pair of the hetero atom may be coordinated to the boron atom.
  • trialkylsilyl group examples include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, and a tert-butyldimethylsilyl group.
  • a trimethylsilyl group and a triethylsilyl group are preferable from the viewpoint of having less steric hindrance and preferably interacting with the compound represented by the general formula (A).
  • R 15 to R 17 may be bonded to each other to form a ring.
  • R 15 to R 17 When R 15 to R 17 are bonded to each other to form a ring, two of R 15 to R 17 may be bonded to each other to form a ring, or all combinations of R 15 to R 17 may be used. They may be bonded to each other.
  • R 15 to R 17 according to the general formula (D) may be the same or different, but it is preferable that at least two or more of them are the same in that the compound can be easily synthesized, and all three are the same. Is more preferable from the above-mentioned viewpoint. Further, from the viewpoint that the compound represented by the general formula (D) easily interacts with the compound represented by the general formula (A) sterically, R 15 to R 17 are bonded to each other to form a ring. It is also preferable that R 15 to R 17 are bonded to each other via a hetero atom to form a ring.
  • the boron-containing cyclic compound in which all of R 15 to R 17 are bonded to each other via a hetero atom to form a ring is specifically a general formula (D).
  • ') Is a compound represented by.
  • R 18 to R 20 each independently represent an alkylene group having 1 to 12 carbon atoms which may have a substituent, and are preferably an alkylene group having 1 to 6 carbon atoms. Yes, and particularly preferably, it is an alkylene group having 2 to 4 carbon atoms. Specific examples thereof include those obtained by removing one hydrogen atom of the alkyl group exemplified in R 1 to R 6 to form an alkylene group. Examples thereof include methylene group, methylmethylene group, ethylmethylene group, dimethylmethylene group, diethylmethylene group, methylethylene group, dimethylene group (ethylene group), trimethylene group (propylene group) and tetramethylene group (butylene group). Specific examples of the substituent include a group exemplified by a monovalent substituent containing a heteroatom.
  • the lone electron pair of the heteroatom X may be coordinated to boron.
  • R 18 to R 20 according to the general formula (D') may be the same or different, but it is preferable that at least two or more of them are the same, because it is easy to synthesize the compound, and all three are the same. It is more preferable from the above-mentioned viewpoint.
  • Specific examples of the compound represented by the general formula (D) include compounds having the following structures.
  • triethanolamine borate and / or trimethylsilyl borate ester which are boron-containing cyclic compounds.
  • the compound represented by the general formula (D) may be used alone or in combination of two or more.
  • the content of the compound represented by the general formula (D) with respect to the total amount of the non-aqueous electrolytic solution according to the embodiment of the present invention is usually 0.001 to 10% by mass. It is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, still more preferably 2.0% by mass. Hereinafter, it is particularly preferably 1.5% by mass or less. It is preferably 0.001 to 3.0% by mass, more preferably 0.001 to 2.0% by mass, and further preferably 0.01 to 1.5% by mass.
  • the total amount thereof shall be the content of the compound represented by the general formula (D).
  • the content of the compound represented by the general formula (D) with respect to the total amount of the non-aqueous electrolyte solution is within the above range, the concentration of the compound in the active material proceeds favorably, and the battery with less gas generation during the initial conditioning is generated. Can be manufactured.
  • R 21 and R 22 each independently represent an alkylene group having 1 to 10 carbon atoms which may have a substituent.
  • m represents an integer of 0 or 1. When m is 0, the sulfur atom and the oxygen atom form a direct bond.
  • the R 22 is preferably an alkylene group having 1 to 5 carbon atoms which may have a substituent, and more preferably an alkylene group having 1 to 3 carbon atoms which may have a substituent. It is a methylene group which may preferably have a substituent. When the hydrocarbon group has a substituent, the number of carbons contained in the substituent is not included in the number of carbon atoms of the hydrocarbon group as R 21 to R 22 .
  • alkylene group examples include a methylene group, an ethylene group, an n-propylene group, a butylene group, a hexylene group and the like.
  • Ra represents an alkyl group having 1 to 12 carbon atoms, an alkylene group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
  • hydrocarbon group examples include those exemplified by R1 to R3 of the general formula ( A).
  • the content of the compound represented by the general formula (E) with respect to the total amount of the non-aqueous electrolytic solution according to the embodiment of the present invention is usually 0.001 to 10% by mass. It is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, still more preferably 2.0% by mass. Hereinafter, it is particularly preferably 1.5% by mass or less. It is preferably 0.001 to 3.0% by mass, more preferably 0.001 to 2.0% by mass, and particularly preferably 0.001 to 1.5% by mass.
  • the total amount thereof shall be the content of the compound represented by the general formula (E).
  • the content of the compound represented by the general formula (E) with respect to the total amount of the non-aqueous electrolyte solution is within the above range, the concentration of the compound in the active material proceeds favorably, and the battery with less gas generation during the initial conditioning is generated. Can be manufactured.
  • Non-aqueous electrolyte battery is a non-aqueous electrolyte battery including a positive electrode, a negative electrode, and a non-aqueous electrolyte solution, and the non-aqueous electrolyte solution is the above-described embodiment of the present invention.
  • This is a non-aqueous electrolyte solution.
  • a positive electrode having a positive electrode active material layer on at least a part of the current collector and the surface of the current collector and capable of storing and releasing metal ions, and at least one of the current collector and the surface of the current collector.
  • the negative electrode having a negative electrode active material layer in the portion and capable of storing and releasing metal ions, and the non-aqueous electrolytic solution containing an alkali metal salt and a non-aqueous solvent, as well as the compound represented by the above general formula (A). It is equipped with a non-aqueous electrolyte solution.
  • the non-aqueous electrolyte battery of the present embodiment has the same configuration as the conventionally known non-aqueous electrolyte battery except for the above-mentioned non-aqueous electrolyte battery.
  • the positive electrode and the negative electrode are laminated via a porous membrane (separator) impregnated with the above-mentioned non-aqueous electrolyte solution, and these have a form of being housed in a case (exterior body).
  • the shape of the non-aqueous electrolyte battery of the present embodiment is not particularly limited, and may be any of a cylindrical type, a square type, a laminated type, a coin type, a large size, etc., but the laminated type battery is particularly due to gas generation.
  • the laminated type is preferable because the influence of swelling is large.
  • Non-aqueous electrolyte solution As the non-aqueous electrolytic solution, the non-aqueous electrolytic solution according to the above-described embodiment of the present invention is used. It is also possible to mix and use another non-aqueous electrolytic solution with the above non-aqueous electrolytic solution as long as the gist of the present invention is not deviated.
  • the positive electrode has a current collector and a positive electrode active material on at least a part of the surface of the current collector. For other configurations, conventionally known ones can be adopted.
  • the positive electrode active material is not particularly limited as long as it can electrochemically store and release metal ions, but specifically, it contains lithium cobaltate or at least Ni and Co, and is a transition metal.
  • transition metal oxides in which 50 mol% or more are Ni and Co and those capable of storing and releasing lithium ions electrochemically are preferable.
  • transition metal oxides in which 60 mol% or more are Ni and Co are preferable. This is because Ni and Co have a redox potential suitable for use as a positive electrode material for a secondary battery and are suitable for high-capacity applications.
  • the mode of the transition metal oxide represented by the following composition formula (1) is preferable.
  • M represents at least one element selected from the group consisting of Mn, Co, Al, Mg, Zr, Fe, Ti and Er. From the viewpoint of increasing the capacity, the embodiment in which 0.40 ⁇ b1 ⁇ 0.98 is preferable, and the embodiment in which 0.50 ⁇ b1 ⁇ 0.98 is more preferable.
  • the aspect of the transition metal oxide represented by the following composition formula (2) is more preferable.
  • a2, b2, c2 and d2 are 0.90 ⁇ a2 ⁇ 1.10, 0.02 ⁇ b2 ⁇ 0.98, 0.01 ⁇ c2 ⁇ 0.50, 0.01 ⁇ .
  • M represents at least one element selected from the group consisting of Mn, Al, Mg, Zr, Fe, Ti and Er.
  • the composition formula (2) it is preferable to show a numerical value of 0.1 ⁇ d2 ⁇ 0.5.
  • Suitable specific examples include, for example, LiNi 0.85 Co 0.10 Al 0.05 O 2 , LiNi 0.80 Co 0.15 Al 0.05 O 2 , LiNi 0.5 Co 0.2 Mn 0. 3 O 2 , Li 1.05 Ni 0.50 Co 0.20 Mn 0.30 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 and the like can be mentioned.
  • the negative electrode has a current collector and a negative electrode active material on at least a part of the surface of the current collector. For other configurations, conventionally known ones can be adopted.
  • the negative electrode active material is not particularly limited as long as it can electrochemically occlude and release metal ions.
  • Specific examples include carbon-based materials, materials containing metal elements that can be alloyed with Li, materials containing semi-metal elements that can be alloyed with Li, lithium-containing metal composite oxide materials, and mixtures thereof. One of these may be used alone, or two or more thereof may be arbitrarily combined and used in combination.
  • the negative electrode active material containing is preferable, and the negative electrode active material containing a carbon-based material and a material containing a metal element that can be alloyed with Li and / or a material containing a semi-metal element that can be alloyed with Li is more preferable. Further, a negative electrode active material containing a material containing a metal element that can be alloyed with Li and / or a material containing a semi-metal element that can be alloyed with Li is more preferable.
  • carbon-based materials include natural graphite, artificial graphite, amorphous carbon, carbon-coated graphite, graphite-coated graphite, and resin-coated graphite. Of these, natural graphite is preferable.
  • Examples of natural graphite include scaly graphite, scaly graphite, and / or graphite particles obtained by subjecting these graphites to spheroidization or densification.
  • spherical or ellipsoidal graphite particles that have been subjected to a spheroidizing treatment are particularly preferable from the viewpoint of particle filling property or charge / discharge rate characteristics.
  • the average particle size (d50) of the graphite particles is usually 1 ⁇ m or more and 100 ⁇ m or less.
  • any conventionally known material can be used, but from the viewpoint of capacity and cycle life, for example, Sb, Si, etc. It is preferably a simple element selected from the group consisting of Sn, Al, As, and Zn, or an oxide, a nitride, or a carbide thereof, and a material containing a Si element is more preferable. Further, when the material containing a metal element that can be alloyed with Li and / or the material containing a metalloid element contains two or more kinds of elements, the material may be an alloy material composed of these alloys.
  • Si or Si-containing compounds are collectively referred to as Si compounds.
  • Si oxide (SiO x ) is preferable because it has a larger theoretical capacity than graphite, and amorphous Si or nano-sized Si crystals facilitate the entry and exit of alkaline ions such as lithium ions. , It is preferable in that a high capacity can be obtained.
  • This general formula SiO x is obtained by using silicon dioxide (SiO 2 ) and Si as raw materials, and the value of x is usually 0 ⁇ x ⁇ 2.
  • metallic Si hereinafter, may be referred to as Si
  • Si-containing compound is preferable in terms of increasing the capacity
  • Si or Si oxide is more preferable.
  • the average particle diameter (d50) of the particle is usually 0.01 ⁇ m or more and 10 ⁇ m from the viewpoint of cycle life. It is as follows.
  • the mixture of particles and graphite of a material containing a metal element that can be alloyed with Li used as a negative electrode active material and / or a material containing a semi-metal element that can be alloyed with Li is a metal that can be alloyed with Li.
  • It may be a mixture in which particles of a material containing an element and / or a material containing a semi-metal element that can be alloyed with Li and the above-mentioned graphite are mixed in the state of particles independent of each other, or a metal that can be alloyed with Li. It may be a composite in which a material containing an element and / or a material containing a semi-metal element that can be alloyed with Li exists on the surface or inside of graphite.
  • the content ratio of particles of the material containing a semi-metal element that can be alloyed is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, still more preferably. It is 2.0% by mass or more.
  • it is usually 99% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 25% by mass or less, still more preferably 20% by mass or less. It is particularly preferably 15% by mass or less, and most preferably 10% by mass or less. Within this range, it is possible to control side reactions on the surface of materials containing metal elements / metalloid elements that can be alloyed with Li such as Si, and it is possible to obtain sufficient capacity in non-aqueous electrolyte batteries. Because it becomes.
  • a separator is usually interposed between the positive electrode and the negative electrode to prevent a short circuit.
  • the non-aqueous electrolytic solution according to the embodiment of the present invention is usually used by impregnating this separator. Conventionally known separators can be used.
  • the reference electrolyte 1 was prepared by adding the mixture so as to be 2.0% by mass.
  • Compounds 1 to 20 were added to the reference electrolytic solution 1 at the contents shown in Table 1 below to prepare non-aqueous electrolytic solutions of Examples 1 to 16 and Comparative Examples 2 to 15. As the non-aqueous electrolytic solution of Comparative Example 1, the reference electrolytic solution 1 itself was used.
  • the “content (% by mass)" in the table is the content when the total amount of each non-aqueous electrolyte solution is 100% by mass.
  • the batteries manufactured in Examples 1 to 16 have a smaller initial gas amount than the batteries manufactured in Comparative Examples 1 to 15.
  • a non-aqueous electrolyte battery using a non-aqueous electrolyte solution containing a silicon compound having a trialkylsiloxy group but not corresponding to the compound represented by the formula (A) is an initial gas. It can be seen that the amount is increased as compared with Comparative Example 1. Further, in Comparative Example 8 using a non-aqueous electrolytic solution containing a silicon compound having neither a trialkylsiloxy group nor a carbon-carbon double bond, the initial gas amount was significantly increased as compared with Comparative Example 1. Recognize.
  • the silicon compound which does not correspond to the compound represented by the formula (A) does not effectively form an insulating film on the surface of the positive electrode active material and / or the negative electrode active material.
  • the compound represented by the formula (A), the compound represented by the formula (B), the compound represented by the formula (D), and the difluorophosphate anion By using the containing compound, the fluorosulfonic acid anion-containing compound, the oxalate anion-containing compound, or the sulfonylimide anion-containing compound in combination, an insulating film is more preferably formed on the surface of the positive electrode active material and / or the negative electrode active material, and the initial conditioning is performed.

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Abstract

La présente invention concerne une solution électrolytique non aqueuse caractérisée en ce qu'elle contient un électrolyte, un solvant non aqueux et un composé représenté par la formule générale (A). Dans le formule (A), R1 à R3 représentent chacun indépendamment un atome d'hydrogène ou un groupe hydrocarboné en C1-C12, et au moins l'un de R1 à R3 est un groupe hydrocarboné en C1-C12. R4 à R5 représentent chacun d'une manière indépendante un atome d'hydrogène ou un groupe hydrocarboné en C1-C5. R6 représente un atome d'hydrogène, un groupe hydrocarboné en C1-C12 ou un groupe alcoxy en C1-C12. L'un parmi R4 et R5 et R6 peut être lié l'un à l'autre et former un cycle.
PCT/JP2021/048103 2020-12-25 2021-12-24 Solution électrolytique non aqueuse et batterie à solution électrolytique non aqueuse WO2022138893A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019102459A (ja) * 2017-12-06 2019-06-24 セントラル硝子株式会社 非水電解液電池用電解液及びそれを用いた非水電解液電池
US20200388876A1 (en) * 2019-06-05 2020-12-10 Enevate Corporation Silicon-based energy storage devices with silicon containing electrolyte additives

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019102459A (ja) * 2017-12-06 2019-06-24 セントラル硝子株式会社 非水電解液電池用電解液及びそれを用いた非水電解液電池
US20200388876A1 (en) * 2019-06-05 2020-12-10 Enevate Corporation Silicon-based energy storage devices with silicon containing electrolyte additives

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