WO2019117101A1 - Solution électrolytique pour batteries à électrolyte non aqueux, et batterie à électrolyte non aqueux l'utilisant - Google Patents

Solution électrolytique pour batteries à électrolyte non aqueux, et batterie à électrolyte non aqueux l'utilisant Download PDF

Info

Publication number
WO2019117101A1
WO2019117101A1 PCT/JP2018/045365 JP2018045365W WO2019117101A1 WO 2019117101 A1 WO2019117101 A1 WO 2019117101A1 JP 2018045365 W JP2018045365 W JP 2018045365W WO 2019117101 A1 WO2019117101 A1 WO 2019117101A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
substituted
carbonate
atom
general formula
Prior art date
Application number
PCT/JP2018/045365
Other languages
English (en)
Japanese (ja)
Inventor
幹弘 高橋
孝敬 森中
益隆 新免
渉 河端
誠 久保
克将 森
亮太 江▲崎▼
貴寛 谷川
Original Assignee
セントラル硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2018219853A external-priority patent/JP7116312B2/ja
Priority claimed from JP2018219846A external-priority patent/JP7116311B2/ja
Application filed by セントラル硝子株式会社 filed Critical セントラル硝子株式会社
Priority to US16/771,109 priority Critical patent/US20200335823A1/en
Priority to KR1020207018055A priority patent/KR102498193B1/ko
Priority to EP18889822.5A priority patent/EP3726636B1/fr
Priority to CN201880079898.2A priority patent/CN111527636B/zh
Publication of WO2019117101A1 publication Critical patent/WO2019117101A1/fr

Links

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
    • H01M10/056—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrolyte for a non-aqueous electrolyte battery and a non-aqueous electrolyte battery using the same.
  • the battery which is an electrochemical device
  • information related equipment, communication equipment that is, storage systems for small-sized, high energy density applications such as personal computers, video cameras, digital cameras, mobile phones, and smartphones, electric vehicles, hybrid vehicles
  • storage systems for large-sized and power applications such as fuel cell vehicle auxiliary power supplies and electric power storage have attracted attention.
  • a non-aqueous electrolyte secondary battery including a lithium ion battery which has a high energy density and a high voltage, and is actively researched and developed at present.
  • optimization of various battery components including active materials of positive and negative electrodes has been studied as a means for improving the durability and battery characteristics of non-aqueous electrolyte batteries.
  • non-aqueous electrolytes examples include lithium carbonate hexafluorophosphate (hereinafter referred to as LiPF 6 ) as a solute in solvents such as cyclic carbonates, linear carbonates, and esters.
  • Non-aqueous electrolytes in which a fluorine-containing electrolyte such as lithium bis (fluorosulfonyl imide) (hereinafter LiFSI) or lithium tetrafluoroborate (hereinafter LiBF 4 ) is dissolved are used to obtain high voltage and high capacity batteries. It is often used because it is suitable.
  • non-aqueous electrolyte batteries using such non-aqueous electrolyte are not always satisfactory in battery characteristics including cycle characteristics and output characteristics.
  • the negative electrode and lithium cation, or the negative electrode and the electrolyte solvent react, and lithium oxide, lithium carbonate, alkyl carbonate on the negative electrode surface Form a coating containing lithium as a main component.
  • the film on the surface of the electrode is called Solid Electrolyte Interface (SEI), and its properties greatly affect the battery performance, such as suppressing the reductive decomposition of the solvent and suppressing the deterioration of the battery performance.
  • SEI Solid Electrolyte Interface
  • SEI Solid Electrolyte Interface
  • a film of a decomposition product is also formed on the positive electrode surface, which also plays an important role such as suppressing the oxidative decomposition of the solvent and suppressing the gas generation inside the battery.
  • Patent Document 1 vinylene carbonate (hereinafter referred to as VC) is used as an additive for forming an effective SEI which significantly improves the durability of a battery.
  • Patent Documents 2 and 3 use a silicon compound having an unsaturated bond, or Patent Document 4 uses a silicon compound containing both an unsaturated bond and a halogen to exhibit cycle characteristics and low temperature characteristics. It is disclosed that an excellent battery can be obtained.
  • Patent Document 5 discloses that the use of a trialkoxyvinylsilane exerts an effect of suppressing battery swelling in a lithium secondary battery having 4.2 V or more and less than 4.35 V.
  • Patent Document 6 discloses that a battery having excellent low temperature output characteristics even at a temperature of not more than ° C and having excellent cycle characteristics at a high temperature of not less than 50 ° C can be obtained.
  • Patent Document 7 discloses an improvement in high-temperature storage characteristics at 70 ° C. or higher and an effect of reducing the amount of gas generated during high-temperature storage, as an electrolyte for non-aqueous electrolyte batteries
  • Electrolyte containing a silane compound containing a group having a carbon-carbon unsaturated bond (II) at least one kind of cyclic sulfonic acid compound and cyclic sulfuric acid ester compound, (III) non-aqueous organic solvent, (IV) solute A liquid is disclosed.
  • Patent Document 8 discloses sulfonic acid ester compounds in which a cyclic sulfone group is bonded to a sulfonic acid ester group in order to improve high temperature characteristics and life characteristics (cycle characteristics) of a lithium battery. It is disclosed to be contained in an electrolytic solution as an additive.
  • Patent Document 9 discloses a lithium ion secondary battery using LiNiO 2 as a positive electrode.
  • Nickel oxide has high theoretical capacity but low thermal stability at the time of charge, and initially cobalt oxide, manganese oxide, iron phosphate and the like have been mainly used as a positive electrode active material.
  • Patent Document 10 discloses a positive electrode in which a part of nickel is replaced with manganese, cobalt or the like.
  • Ni-rich positive electrode in which the nickel ratio is increased, nickel, cobalt, and manganese based ones having a ratio of "3 to 1 to 1" or “8 to 1 to 1", and manganese being replaced by aluminum
  • Nickel, cobalt, and aluminum ratio “8.5 to 1.0 to 0.5”, “8.8 to 0.9 to 0.3”, “9.0 to 0.5 to 0.5”, etc.
  • LiPF 6 synthesis of concentrate used in the nonaqueous electrolyte battery electrolyte solution is disclosed, for example, in Patent Document 11.
  • An electrolytic solution containing a silicon compound having an unsaturated bond is certainly excellent in terms of durability (cycle characteristics, high-temperature storage characteristics), but a Ni-rich positive electrode (specifically, in a metal contained in a positive electrode active material)
  • a Ni-rich positive electrode specifically, in a metal contained in a positive electrode active material
  • the eluted Ni precipitates on the negative electrode, which may cause a short circuit of the battery and is a very dangerous situation. Therefore, it is strongly desired to prevent the elution of Ni from the positive electrode.
  • the inventors of the present invention have well-balanced effects of improving the high-temperature storage characteristics of lithium batteries and reducing the amount of gas generated during high-temperature storage, with an electrolyte containing a durability improver as described in Patent Document 7
  • a durability improver as described in Patent Document 7
  • 1,3-propane sultone, 1,3-propene sultone, 1,3,2-dioxathiolane 2,2-dioxide, methylene methane disulfonate and their derivatives which are used as a durability improver
  • the decomposition may progress during storage at a high temperature of 50 ° C. or more in the liquid state. The solution of this problem is also strongly desired.
  • the present invention provides an electrolytic solution containing a silicon compound having an unsaturated bond, in which the elution of Ni from the Ni-rich positive electrode into the electrolytic solution is reduced without impairing the capacity retention rate after cycling, and the electrolytic solution.
  • An object of the present invention is to provide a non-aqueous electrolyte battery provided with a positive electrode having a high Ni content.
  • this invention makes it a subject to provide the non-aqueous electrolyte battery provided with the electrolyte solution for non-aqueous electrolyte batteries in which high-temperature storage stability (high-temperature storage characteristic) was improved, and the said electrolyte solution.
  • R 1 's each independently represent a group having a carbon-carbon unsaturated bond.
  • R 2 is each independently a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an allyl group having 3 to 10 carbon atoms, an alkynyl having 2 to 10 carbon atoms Group selected from the group consisting of a group having 6 to 15 carbon atoms, an aryloxy group having 3 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, and an aryloxy group having 6 to 15 carbon atoms These groups may have a fluorine atom and / or an oxygen atom.
  • having a fluorine atom specifically refers to one in which a hydrogen atom in the above group is substituted by a fluorine atom.
  • having an oxygen atom specifically includes a group in which “—O—” (ether bond) intervenes between carbon atoms of the above group. a is 2 to 4; ] [In general formula (2), R 3 is an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an aryloxy group.
  • the alkyl group of the above R 3 is preferably a methyl group, a trifluoromethyl group, an ethyl group, a pentafluoroethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group,
  • the alkenyl group is preferably ethenyl group
  • the aryl group may be a phenyl group, a methylphenyl group, a dimethylphenyl group, a tert-butylphenyl group, a tert-amylphenyl group, a biphenyl group or a naphthyl group (even if the hydrogen atom of each aromatic ring is substituted by a fluorine atom Good) is preferable
  • the aryloxy group is a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, a tert-butylphenoxy group, a
  • R 3 is particularly preferably a methyl group, a trifluoromethyl group, an ethyl group, an ethenyl group or a phenyl group.
  • R 4 is an alkoxy group or an aryloxy group
  • R 5 is OLi (note that O is oxygen and Li is lithium).
  • the alkoxy group of the above R 4 is a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, a 2,2-dimethylpropoxy group, a 3-methylbutoxy group, 1- Methyl butoxy, 1-ethylpropoxy, 1,1-dimethylpropoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 1,1,1-trifluoro Preferred is isopropoxy group, 1,1,1,3,3,3-hexafluoroisopropoxy group or cyclohexyloxy group,
  • the aryloxy group is preferably a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, a fluorophenoxy group, a tert-butylphenoxy group, a tert-amylphenoxy group, a biphenoxy group or a naphthoxy
  • R 4 an ethoxy group is particularly preferable as R 4 from the viewpoint of the balance between the capacity retention rate after cycling and the inhibitory effect on Ni elution and the stability of the compound.
  • R 6 is an aryl group, an alkoxy group, or an aryloxy group.
  • the aryl group of R 6 is a phenyl group, a methylphenyl group, a dimethylphenyl group, a tert-butylphenyl group, a tert-amylphenyl group, a biphenyl group, or a naphthyl group (the hydrogen atom of each aromatic ring is a fluorine atom (Optionally substituted) is preferred,
  • the alkoxy group is a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, a 2,2-dimethylpropoxy group, a 3-methylbutoxy group, a 1-methylbutoxy group, 1 -Ethylpropoxy group, 1,1-dimethylpropoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 1,1,1-trifluoroisopropoxy group, 1 1,1,
  • R 6 is particularly preferably a phenyl group or a phenoxy group from the viewpoint of the balance between the capacity retention rate after cycling and the inhibitory effect on Ni elution and the stability of the compound.
  • X is an oxygen atom or a methylene group which may be substituted by a halogen atom
  • Y is a phosphorus atom or a sulfur atom.
  • n is 0 when Y is a phosphorus atom, and 1 when it is a sulfur atom.
  • R 7 and R 8 are each independently a halogen atom, an alkyl group which may be substituted by a halogen atom, an alkenyl group, or an aryl group.
  • the halogen atom of R 7 and R 8 is preferably a fluorine atom
  • the alkyl group which may be substituted by a halogen atom is preferably methyl group, trifluoromethyl group, ethyl group, pentafluoroethyl group, propyl group, butyl group, pentyl group or hexyl group
  • the alkenyl group which may be substituted by a halogen atom is preferably ethenyl group
  • the aryl group which may be substituted by a halogen atom is a phenyl group, a methylphenyl group, a dimethylphenyl group, a tert-butylphenyl group, a tert-amylphenyl group, a biphenyl group or a naphthyl group (a hydrogen atom of each aromatic ring Is preferably substituted by a fluor
  • R 7 and R 8 each represent a fluorine atom, a methyl group, a trifluoromethyl group, an ethyl group, an ethenyl group, or a phenyl from the viewpoint of the balance between the capacity retention rate after cycling and the Ni elution suppression effect and the compound stability.
  • Groups and fluorophenyl groups are particularly preferred.
  • the above (III) and (IV) be present in the above-mentioned predetermined concentration in the electrolytic solution.
  • the electrolytic solution containing the above (III) is applied to a battery provided with a Ni-rich positive electrode, the elution of Ni from the Ni-rich positive electrode into the electrolytic solution is reduced. Ru.
  • R 1 in the general formula (1) is preferably ethenyl.
  • the alkyl group of R 2 is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, and tert.
  • the alkoxy group is a methoxy group, an ethoxy group, a butoxy group, a tert-butoxy group, a propoxy group, an isopropoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, 1 And 1,1,1-trifluoroisopropoxy and 1,1,1,3,3,3-hexafluoroisopropoxy are preferred.
  • the allyl group is preferably a 2-propenyl group
  • the alkynyl group is preferably an ethynyl group
  • the aryl group is preferably selected from a phenyl group, a methylphenyl group, a tert-butylphenyl group, and a tert-amylphenyl group (a hydrogen atom of each aromatic ring may be substituted with a fluorine atom)
  • the allyloxy group is preferably a 2-propenyloxy group
  • the alkynyloxy group is preferably a propargyloxy group
  • the aryloxy group is preferably selected from a phenoxy group, a methylphenoxy group, a tert-butylphenoxy group, and a tert-amylphenoxy group (a hydrogen atom of each aromatic ring may be substituted with a fluorine atom).
  • (III) is preferably at least one selected from the group consisting of the following compounds (1-1) to (1-28), and among them, (1-1), (1-2) ), (1-3), (1-4), (1-6), (1-7), (1-8), (1-10), (1-12), (1-15), At least one selected from the group consisting of (1-22), (1-23), (1-24), (1-25), (1-26), (1-27), and (1-28)
  • the species is more preferable in terms of easiness of synthesis and stability of the compound.
  • the silicon compound (1) which is the component (III) can be produced by various methods. For example, as described in Patent Document 13 and Non-Patent Documents 2 and 3, a silicon compound having a silanol group or a hydrolyzable group is reacted with a carbon-carbon unsaturated bond-containing organometallic reagent to form a silicon compound. It can be produced by a method of producing a carbon-carbon unsaturated bond-containing silicon compound in which the OH group or hydrolyzable group of the silanol group is substituted with a carbon-carbon unsaturated bond group.
  • the second aspect of the present invention is (I) non-aqueous organic solvent, (II) an ionic salt, a solute, (III) at least one additive selected from the group consisting of compounds represented by the general formula (1) (hereinafter sometimes referred to as "silicon compound (1)"), and (IV) A non-aqueous electrolyte comprising at least one additive selected from the group consisting of compounds represented by the general formula (6) (hereinafter sometimes referred to as "cyclic sulfur compound (6)”)
  • X is an oxygen atom or a methylene group which may be substituted by a halogen atom
  • Y is a phosphorus atom or a sulfur atom.
  • n is 0 when Y is a phosphorus atom, and 1 when it is a sulfur atom.
  • R 3 and R 4 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by a halogen atom, or a cycloalkyl group having 5 to 20 carbon atoms which may be substituted by a halogen atom;
  • a C2-C20 alkenyl group which may be substituted by a halogen atom, a C2-C20 alkynyl group which may be substituted by a halogen atom, a C6-C40 carbon atom which may be substituted by a halogen atom
  • a cycloalkoxy group having 5 to 20 carbon atoms an alkenyloxy group having 2 to 20 carbon atoms which may be substituted by a halogen atom, or a halogen atom.
  • Y is a sulfur atom, R 4 is absent.
  • R 5 and R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by a halogen atom, or a carbon number 2 to 20 which may be substituted by a halogen atom Alkenyl group, an alkynyl group having 2 to 20 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, carbon which may be substituted for a halogen atom
  • the cycloalkyl group is a cycloalkyl group having a number of 5 to 20, an aryl group having a carbon number of 6 to 40 which may be substituted with a halogen atom, or a heteroaryl group having a carbon number of 2 to 40 which may be substituted for a halogen atom.
  • R 1 in the general formula (1) is preferably ethenyl.
  • the alkyl group of R 2 is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, and tert.
  • the alkoxy group is a methoxy group, an ethoxy group, a butoxy group, a tert-butoxy group, a propoxy group, an isopropoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, 1 And 1,1,1-trifluoroisopropoxy and 1,1,1,3,3,3-hexafluoroisopropoxy are preferred.
  • the allyl group is preferably a 2-propenyl group
  • the alkynyl group is preferably an ethynyl group
  • the aryl group is preferably selected from a phenyl group, a methylphenyl group, a tert-butylphenyl group, and a tert-amylphenyl group (a hydrogen atom of each aromatic ring may be substituted with a fluorine atom)
  • the allyloxy group is preferably a 2-propenyloxy group
  • the alkynyloxy group is preferably a propargyloxy group
  • the aryloxy group is preferably selected from a phenoxy group, a methylphenoxy group, a tert-butylphenoxy group, and a tert-amylphenoxy group (a hydrogen atom of each aromatic ring May be substituted by a fluorine atom).
  • a in the above general formula (1) is 3 or 4 from the viewpoint of better
  • (III) is preferably at least one selected from the group consisting of the above compounds (1-1) to (1-28), and among them, (1-1), (1-2) ), (1-3), (1-4), (1-6), (1-7), (1-9), (1-10), (1-12), (1-15), At least one selected from the group consisting of (1-22), (1-23), (1-24), (1-25), (1-26), (1-27), and (1-28)
  • the species is more preferable in terms of easiness of synthesis and stability of the compound.
  • the silicon compound (1) which is the component (III) can be produced by various methods (see Patent Document 13, Non-patent Documents 2, 3 and the like).
  • R 3 and R 4 in the above general formula (6) are each independently a fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group , N-hexyl group, trifluoromethyl group, trifluoroethyl group, ethenyl group, 2-propenyl group, 2-propynyl group, phenyl group, naphthyl group, pentafluorophenyl group, methoxy group, ethoxy group, n-propoxy group , Isopropoxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, trifluoromethoxy group, trifluoroethoxy group, ethenyl oxy group, 2-propenyloxy group, 2-propynyloxy group Group,
  • R 5 and R 6 each independently represent a hydrogen atom, 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 or a tetrafluoroethyl group It is preferable to select from a group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a pyrrolyl group, and a pyridinyl group, and it is independently selected from a hydrogen atom and a fluorine atom that the synthesis is easy and the stability is high. Particularly preferred from the viewpoint of
  • (IV) is preferably at least one selected from the compounds represented by the following compounds (6-1) to (6-40), and among them, (6-1), 6-2), (6-3), (6-5), (6-7), (6-8), (6-9), (6-11), (6-12), (6- 6) 14), (6-16), (6-19), (6-20), (6-21), (6-22), (6-23), (6-24), (6-25) , (6-27), (6-28), (6-29), (6-31), (6-32), (6-34), (6-38), (6-39) and At least one member selected from the group consisting of 6-40) is more preferable in terms of the ease of synthesis and the height of the high temperature storage characteristics.
  • the cyclic sulfur compound (6) which is the component (IV) can be produced by various methods.
  • the compound of the above formula (6-1) is subjected to hydration reaction of 2,5-dihydrothiophene-1,1-dioxide 3-hydroxytetrahydrothiophene-1,1-dioxide is obtained which can be obtained by reaction with methanesulfonyl chloride in the presence of triethanolamine.
  • the other cyclic sulfur compounds can also be obtained by the same process by changing the corresponding raw materials.
  • the first aspect of the present invention by containing a silicon compound having a specific structure as the component (III) and a specific compound as the component (IV) in a specific concentration in the electrolyte for a non-aqueous electrolyte battery, It is possible to reduce the elution of Ni from the Ni-rich positive electrode into the electrolytic solution without losing the capacity retention rate after cycling.
  • the electrolyte for a non-aqueous electrolyte battery contains a silicon compound having a specific structure as the component (III) and a cyclic sulfur compound having a specific structure as the component (IV).
  • the high temperature storage stability can be improved.
  • the type of nonaqueous organic solvent used in the electrolyte for nonaqueous electrolyte batteries is not particularly limited, and any nonaqueous organic solvent can be used.
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • methyl propyl carbonate ethyl propyl carbonate
  • Methyl butyl carbonate 2,2,2-trifluoroethyl methyl carbonate
  • 2,2,2-trifluoroethyl ethyl carbonate 2,2,2-trifluoroethyl propyl carbonate
  • the non-aqueous organic solvent is preferably at least one member selected from the group consisting of cyclic carbonates and chain carbonates, from the viewpoint of excellent cycle characteristics at high temperatures. Moreover, it is preferable at the point which is excellent in the input-output characteristic in low temperature that the said non-aqueous organic solvent is at least 1 sort (s) chosen from the group which consists of ester.
  • the cyclic carbonate include EC, PC, butylene carbonate, and FEC. Among them, at least one selected from the group consisting of EC, PC, and FEC is preferable.
  • linear carbonates are EMC, DMC, DEC, methyl propyl carbonate, ethyl propyl carbonate, 2,2,2-trifluoroethyl methyl carbonate, 2,2,2-trifluoro ethyl ethyl carbonate, 1,1, 1,3,3,3-hexafluoro-1-propylmethyl carbonate and 1,1,1,3,3,3-hexafluoro-1-propylethyl carbonate etc., among which EMC, DMC, DEC, And at least one selected from the group consisting of methyl propyl carbonate and methyl propyl carbonate.
  • ester examples include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, and ethyl 2-fluoropropionate.
  • the non-aqueous electrolyte battery electrolyte of the first embodiment can also contain a polymer, and is generally referred to as a polymer solid electrolyte.
  • Polymer solid electrolytes also include those containing non-aqueous organic solvents as plasticizers.
  • the polymer is not particularly limited as long as it is an aprotic polymer capable of dissolving the solute and the additive.
  • 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 can be mentioned.
  • an aprotic non-aqueous organic solvent is preferable among the above non-aqueous organic solvents.
  • (II) Solute for example, at least one cation selected from the group consisting of alkali metal ions and alkaline earth metal ions, and hexafluorophosphate anion, tetrafluoroborate anion, trifluoromethanesulfonate anion, fluorosulfone Acid anion, bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, (trifluoromethane sulfonyl) (fluorosulfonyl) imide anion, bis (difluorophosphonyl) imide anion, (difluorophosphonyl) (fluorosulfonyl) An ionic salt comprising an imido anion, and at least one anion pair selected from the group consisting of (difluorophosphonyl) (trifluoromethanesulfonyl) imide anions Is preferred.
  • the cation of the ionic salt which is the above solute is lithium, sodium, potassium or magnesium
  • the anion is hexafluorophosphate anion, tetrafluoroborate anion, trifluoromethanesulfonate anion, bis (trifluoromethanesulfonyl) imide
  • the concentration of these solutes is not particularly limited, but the lower limit is 0.5 mol / L or more, preferably 0.7 mol / L or more, more preferably 0.9 mol / L or more, and the upper limit is 2.5 mol / L or less, preferably 2.2 mol / L or less, more preferably 2.0 mol / L or less.
  • the ion conductivity will be lowered to lower the cycle characteristics and output characteristics of the non-aqueous electrolyte battery, while if it exceeds 2.5 mol / L, the electrolyte of the non-aqueous electrolyte battery
  • the increase in viscosity may also lower the ion conductivity, which may lower the cycle characteristics and output characteristics of the non-aqueous electrolyte battery.
  • solutes may be used alone or in combination of two or more.
  • Component (III) As the component (III), as described above, the silicon compound represented by the general formula (1) is used.
  • the concentration of (III) is preferably 0.01% by mass or more and 2.00% by mass or less based on 100% by mass of the total amount of (I) to (IV). If it is 0.01 mass% or more, the effect of improving the characteristics of the non-aqueous electrolyte battery is easily obtained, while if it is 2.00 mass% or less, good durability without significantly increasing the amount of Ni elution It is easy to demonstrate the improvement effect. More preferably, it is 0.04 mass% or more and 1.00 mass% or less, and still more preferably in the range of 0.08 mass% or more and 0.50 mass% or less.
  • the concentration of (IV) is 0.01% by mass or more and 5.00% by mass or less based on 100% by mass of the total amount of (I) to (IV). If it is less than 0.01% by mass, the effect of reducing the elution of Ni from the Ni-rich positive electrode into the electrolytic solution can not be sufficiently obtained, while if it exceeds 5.00% by mass, the effect of improving the durability is extremely high. There is a fear that the capacity may decrease, and there is a concern that the positive electrode current collector aluminum may be eluted. More preferably, it is 0.10 mass% or more and 2.50 mass% or less, and still more preferably in the range of 0.50 mass% or more and 1.50 mass% or less.
  • Additives generally used in the electrolyte for a non-aqueous electrolyte battery of the first embodiment may be further added at an arbitrary ratio as long as the gist of the present invention is not impaired.
  • Specific examples include cyclohexylbenzene, cyclohexylfluorobenzene, fluorobenzene (hereinafter sometimes referred to as FB), biphenyl, difluoroanisole, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, 2-fluorobiphenyl , Vinylene carbonate, dimethylvinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, methyl propargyl carbonate, ethyl propargyl carbonate, dipropargyl carbonate, maleic anhydride, succinic anhydride, propane sultone, 1,3-propane sultone (hereinafter PS May be described), butane sulf
  • R 9 is a hydrocarbon group having 2 to 5 carbon atoms, and may have a branched structure when the carbon number is 3 or more.
  • the hydrocarbon group may contain a halogen atom, a hetero atom or an oxygen atom.
  • the content of the ionic salt mentioned as the solute in the electrolytic solution is smaller than 0.5 mol / L which is the lower limit of the suitable concentration of the solute, the negative electrode film forming effect as “other additive” And positive electrode protection effect.
  • the content in the electrolytic solution is preferably 0.01% by mass or more and 5.00% by mass or less.
  • Examples of the ionic salt in this case include lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, sodium fluorosulfonate, potassium fluorosulfonate, magnesium fluorosulfonate, Bis (trifluoromethanesulfonyl) imide lithium, bis (trifluoromethanesulfonyl) imide sodium, bis (trifluoromethanesulfonyl) imide potassium, bis (trifluoromethanesulfonyl) imide magnesium, bis (fluorosulfonyl) imide lithium, bis (fluorosulfonyl) imide Sodium, Bis (fluorosulfonyl) imide potassium, Bis (fluorosulfonyl) imide Magne Lithium, (trifluoromethanesulfonyl) (fluorosulfonyl
  • non-aqueous electrolyte battery called a polymer battery
  • electrolytic solution pseudo-solidified with a gelling agent or a cross-linked polymer.
  • a nonaqueous electrolyte battery according to a first embodiment of the present invention comprises at least (a) the above-described electrolyte for a non-aqueous electrolyte battery, (a) a positive electrode, (c) a negative electrode, and including. Furthermore, it is preferable to include (d) a separator, an exterior body, and the like.
  • the positive electrode contains one or more oxides containing at least nickel as a positive electrode active material, and the nickel content in the metal contained in the positive electrode active material is 30 to 100% by mass. Even with such a Ni-rich positive electrode, the use of the above-mentioned electrolytic solution can reduce the elution of Ni into the electrolytic solution without impairing the capacity retention rate after cycling.
  • the positive electrode active material constituting (i) the positive electrode is not particularly limited as long as it is various materials capable of charge and discharge.
  • the positive electrode active material constituting (i) the positive electrode is not particularly limited as long as it is various materials capable of charge and discharge.
  • (A) Lithium transition metal complex oxide As a lithium transition metal complex oxide containing a positive electrode active material (A) nickel or nickel and one or more metals selected from the group consisting of manganese, cobalt, and aluminum and having a layered structure, for example, lithium -Nickel composite oxide, lithium-nickel-cobalt composite oxide, lithium-nickel-manganese composite oxide, lithium-nickel-manganese-cobalt composite oxide, etc. may be mentioned.
  • transition metal atoms which are main components of these lithium transition metal complex oxides, may be Al, Ti, V, Cr, Fe, Cu, Zn, Mg, Ga, Zr, Si, B, Ba, Y, Sn Those substituted with other elements such as.
  • lithium-nickel composite oxide aluminum oxide is coated on a part of the particle surface of lithium nickelate or LiNiO 2 particle powder to which different elements such as LiNiO 2 , Mg, Zr, Al, Ti etc. are added May be used.
  • the lithium-nickel-cobalt composite oxide and the composite oxide in which part of nickel-cobalt is substituted with Al or the like are represented by the general formula [1-1].
  • M 1 is at least one element selected from the group consisting of Al, Fe, Mg, Zr, Ti, and B, a is 0.9 ⁇ a ⁇ 1.2, and b is And c satisfy the conditions of 0.1 ⁇ b ⁇ 0.3 and 0 ⁇ c ⁇ 0.1.
  • These can be prepared, for example, according to the manufacturing method etc. which are described in Unexamined-Japanese-Patent No. 2009-137834 grade
  • lithium-nickel-manganese composite oxides examples include LiNi 0.5 Mn 0.5 O 2 and the like.
  • lithium-nickel-manganese-cobalt composite oxide examples include a lithium-containing composite oxide represented by the general formula [1-2].
  • M 2 is at least one element selected from the group consisting of Al, Fe, Mg, Zr, Ti, B, and Sn, and d is 0.9 ⁇ d ⁇ 1.2.
  • a lithium-nickel-manganese-cobalt composite oxide contains manganese in a range represented by the general formula [1-2] in order to enhance the structural stability and improve the safety at high temperature in a lithium secondary battery
  • one further containing cobalt in the range represented by the general formula [1-2] is more preferable.
  • Li [Ni 1/3 Mn 1/3 Co 1/3] O 2 Li [Ni 0.45 Mn 0.35 Co 0.2] O 2
  • Li [Ni 0.5 Mn 0.3 Co 0.2 ] O 2 Li [Ni 0.6 Mn 0.2 Co 0.2 ] O 2
  • Li [Ni 0.49 Mn 0.3 Co 0.2 Zr 0.01 ] O 2 Li [Ni 0.49 Mn 0.3 Co 0.2 Mg 0.01 ] O 2 etc. It can be mentioned.
  • M 3 may contain Ni, and may further contain at least one metal element selected from the group consisting of Co, Fe, Mg, Cr, Cu, Al and Ti.
  • j is 1.05 ⁇ j ⁇ 1.15, and k is 0 ⁇ k ⁇ 0.20.
  • LiMn 1.9 Ni 0.1 O 4 , LiMn 1.5 Ni 0.5 O 4 and the like can be mentioned.
  • (C) olivine lithium phosphate) examples include those represented by the general formula [1-4].
  • M 4 contains Ni, and is at least one selected from Co, Mn, Cu, Zn, Nb, Mg, Al, Ti, W, Zr and Cd, and n is other than that , 0 ⁇ n ⁇ 1.
  • LiNiPO 4 and the like.
  • Examples of the nickel-containing lithium-exclusive layered transition metal oxide having a positive electrode active material (D) layered rock salt type structure include those represented by the general formula [1-5].
  • x is a number satisfying 0 ⁇ x ⁇ 1
  • M 5 is at least one or more metal elements having an average oxidation number of 3 +
  • M 6 is an average oxidation It is at least one metal element whose number is 4 + .
  • M 5 is preferably one metal element selected from trivalent Mn, Ni, Co, Fe, V, and Cr, but is equivalent to divalent and tetravalent
  • the average oxidation number may be trivalent with a metal of In the formula [1-5]
  • M 6 is preferably at least one metal element selected from Mn, Zr, and Ti. Incidentally, either M 5 or M 6 necessarily contains nickel.
  • the positive electrode active material (D) represented by this general formula [1-5] expresses high capacity by high voltage charge of 4.4 V (Li basis) or more (for example, US Pat. No. 7, , 135, 252).
  • These positive electrode active materials can be prepared, for example, according to the manufacturing method described in JP-A-2008-270201, WO2013 / 118661, JP-A-2013-030284 and the like.
  • the positive electrode active material contains at least one selected from the above (A) to (D) as a main component, contains at least one oxide containing at least nickel, and is contained in the metal contained in the positive electrode active material.
  • the nickel content may be 30 to 100% by mass, and examples of other elements include transition element chalcogenides such as FeS 2 , TiS 2 , TiO 2 , V 2 O 5 , MoO 3 , MoS 2 and the like.
  • conductive polymers such as polyacetylene, polyparaphenylene, polyaniline and polypyrrole, activated carbon, polymers generating radicals, carbon materials and the like can be mentioned.
  • the positive electrode has a positive electrode current collector.
  • the positive electrode current collector for example, aluminum, stainless steel, nickel, titanium or an alloy thereof can be used.
  • a positive electrode active material layer is formed on at least one surface of a positive electrode current collector.
  • the positive electrode active material layer is made of, for example, the above-described positive electrode active material, a binder, and, as needed, a conductive agent.
  • a binder polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, styrene butadiene rubber (SBR), carboxymethylcellulose, methylcellulose, cellulose acetate phthalate, hydroxypropyl methylcellulose, polyvinyl alcohol Etc.
  • the conductive agent for example, carbon materials such as acetylene black, ketjen black, furnace black, carbon fiber, graphite (particulate graphite and flake graphite), fluorinated graphite and the like can be used.
  • carbon materials such as acetylene black, ketjen black, furnace black, carbon fiber, graphite (particulate graphite and flake graphite), fluorinated graphite and the like can be used.
  • acetylene black or ketjen black having low crystallinity is preferably used.
  • the negative electrode material is not particularly limited, but in the case of a lithium battery or lithium ion battery, lithium metal, an alloy or intermetallic compound of lithium metal and another metal, various carbon materials (such as artificial graphite and natural graphite), metal Oxides, metal nitrides, tin (single), tin compounds, silicon (single), silicon compounds, activated carbon, conductive polymers and the like are used.
  • Examples of the carbon material include graphitizable carbon, non-graphitizable carbon (hard carbon) having a spacing of 0.32 nm or more on the (002) plane, and graphite having a spacing of 0.34 nm or less on the (002) plane.
  • cokes include pitch coke, needle coke, and petroleum coke.
  • the organic polymer compound fired body is a product obtained by firing and carbonizing a phenol resin, furan resin or the like at an appropriate temperature.
  • the carbon material is preferable because a change in crystal structure accompanying storage and release of lithium is very small, so that high energy density and excellent cycle characteristics can be obtained.
  • the shape of the carbon material may be fibrous, spherical, granular or scaly. Amorphous carbon or a graphite material coated with amorphous carbon on the surface is more preferable because the reactivity between the material surface and the electrolytic solution is lowered.
  • the negative electrode preferably contains at least one negative electrode active material.
  • a lithium ion secondary battery in which the cation in the non-aqueous electrolytic solution is mainly lithium
  • (c) as a negative electrode active material constituting the negative electrode lithium ions can be doped and de-doped
  • G An oxide of one or more metals selected from Si, Sn, Al, (H) Si, one or more metals selected from Si, Sn, Al, an alloy containing these metals, or an alloy of these metals or alloys with lithium And (I) those containing at least one selected from lithium titanium oxides.
  • These negative electrode active materials can be used alone or in combination of two or more
  • (E) Carbon material in which the d value of the lattice plane (002 plane) in X-ray diffraction is 0.340 nm or less As a carbon material whose d value of the lattice plane (002 plane) in the negative electrode active material (E) X-ray diffraction is 0.340 nm or less, for example, pyrolytic carbons, cokes (for example, pitch coke, needle coke, petroleum coke, etc.) Graphites, organic polymer compound fired bodies (for example, those obtained by firing and carbonizing a phenol resin, furan resin and the like at an appropriate temperature), carbon fibers, activated carbon and the like may be mentioned, and these may be graphitized.
  • the carbon material is a graphite having a (002) plane spacing (d 002) of 0.340 nm or less measured by X-ray diffraction method, and a true density of 1.70 g / cm 3 or more, or a graphite thereof Highly crystalline carbon materials having similar properties are preferred.
  • Examples of carbon materials in which the d value of the lattice plane (002 plane) in the negative electrode active material (F) X-ray diffraction exceeds 0.340 nm include amorphous carbon, which is heat treated at a high temperature of 2000 ° C. or higher Is also a carbon material with almost no change in the stacking order.
  • amorphous carbon which is heat treated at a high temperature of 2000 ° C. or higher Is also a carbon material with almost no change in the stacking order.
  • non-graphitizable carbon (hard carbon), mesocarbon microbeads (MCMB) calcined at 1500 ° C. or less, mesophased Bitch carbon fiber (MCF), etc. are exemplified.
  • Carbotron (registered trademark) P and the like manufactured by Kureha Co., Ltd. is a typical example.
  • the oxide of one or more metals selected from the negative electrode active material (G) Si, Sn, and Al include, for example, silicon oxide, tin oxide, and the like which can be doped and de-doped with lithium ions.
  • SiO x or the like having a structure in which ultrafine particles of Si are dispersed in SiO 2 .
  • this material When this material is used as a negative electrode active material, charging / discharging is smoothly performed because Si reacting with Li is ultrafine particles, while the SiO x particles having the above structure have a small surface area, so the negative electrode active material layer
  • the coating properties when forming a composition (paste) for forming a metal, and the adhesion of the negative electrode mixture layer to the current collector are also good.
  • SiO x has a large volume change due to charge and discharge, high capacity and good charge and discharge cycle characteristics can be achieved by using SiO x and the graphite of the above-mentioned negative electrode active material (E) in combination with the negative electrode active material at a specific ratio. And both.
  • the negative electrode active material (H) As a metal selected from one or more metals selected from Si, Sn, Al or an alloy containing these metals or an alloy of these metals or alloys and lithium, for example, a metal such as silicon, tin, aluminum, a silicon alloy And tin alloys, aluminum alloys and the like, and materials in which such metals and alloys are alloyed with lithium during charge and discharge can also be used.
  • Specific preferred examples thereof include simple metals such as silicon (Si) and tin (Sn) described in, for example, WO 2004/100293, JP-A 2008-016424, etc. And compounds containing the metal, alloys containing tin (Sn) and cobalt (Co) in the metal, and the like.
  • Si silicon
  • Sn tin
  • Co cobalt
  • the said metal is used for an electrode, high charge capacity can be expressed, and since expansion and contraction of the volume accompanying charge and discharge are comparatively small, it is preferable.
  • these metals are used as the negative electrode of a lithium ion secondary battery, they are known to exhibit high charge capacity because they are alloyed with Li during charge, and this point is also preferable.
  • a negative electrode active material formed of silicon pillars of submicron diameter, a negative electrode active material formed of fibers composed of silicon, or the like described in WO 2004/042851 or WO 2007/083155 may be used. .
  • Examples of the negative electrode active material (I) lithium titanium oxide include lithium titanate having a spinel structure and lithium titanate having a ramsdellite structure.
  • Examples of lithium titanate having a spinel structure include Li 4 + ⁇ Ti 5 O 12 ( ⁇ changes within the range of 0 ⁇ ⁇ ⁇ 3 by charge and discharge reaction).
  • As the lithium titanate having a ramsdellite structure for example, Li (the beta vary in the range of 0 ⁇ ⁇ ⁇ 3 by charge and discharge reactions) 2 + ⁇ Ti 3 O 7 and the like.
  • These negative electrode active materials can be prepared, for example, according to the production method described in JP-A-2007-18883, JP-A-2009-176752, and the like.
  • a sodium ion secondary battery in which the cation in the non-aqueous electrolytic solution is mainly sodium hard carbon or an oxide such as TiO 2 , V 2 O 5 , MoO 3 or the like is used as the negative electrode active material.
  • a sodium-containing transition metal complex oxide such as NaFeO 2 , NaCrO 2 , NaNiO 2 , NaMnO 2 , NaCoO 2 as a positive electrode active material
  • a mixture of a plurality of transition metals such as Fe, Cr, Ni, Mn, Co, etc.
  • transition metals of their sodium-containing transition metal complex oxides and some of the transition metals of their sodium-containing transition metal complex oxides are other than the other transition metals
  • Phosphoric acid compounds of transition metals such as Na 2 FeP 2 O 7 and NaCo 3 (PO 4 ) 2 P 2 O 7
  • sulfides such as TiS 2 and FeS 2
  • Conducting polymers such as phenylene, polyaniline and polypyrrole, activated carbon, polymers generating radicals, carbon materials, etc. are used
  • the negative electrode has a negative electrode current collector.
  • the negative electrode current collector for example, copper, stainless steel, nickel, titanium or an alloy thereof can be used.
  • a negative electrode active material layer is formed on at least one surface of a negative electrode current collector.
  • the negative electrode active material layer is made of, for example, the above-described negative electrode active material, a binder, and, as needed, a conductive agent.
  • a binder polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, styrene butadiene rubber (SBR), carboxymethylcellulose, methylcellulose, cellulose acetate phthalate, hydroxypropyl methylcellulose, polyvinyl alcohol Etc.
  • the conductive agent for example, carbon materials such as acetylene black, ketjen black, furnace black, carbon fiber, graphite (particulate graphite and flake graphite), fluorinated graphite and the like can be used.
  • the electrode is obtained, for example, by dispersing and kneading an active material, a binder and, if necessary, a conductive agent in a predetermined amount in a solvent such as N-methyl-2-pyrrolidone (NMP) or water.
  • NMP N-methyl-2-pyrrolidone
  • the paste can be applied to a current collector and dried to form an active material layer.
  • the obtained electrode is preferably compressed by a method such as a roll press to adjust to an electrode of appropriate density.
  • the above non-aqueous electrolyte battery can be provided with (d) a separator.
  • separators for preventing contact between (i) the positive electrode and (ii) the negative electrode non-woven fabric or porous sheet made of polyolefin such as polypropylene and polyethylene, cellulose, paper or glass fiber is used. It is preferable that these films be micro-porous so that the electrolyte can penetrate and the ions can easily permeate.
  • a polyolefin separator the film which electrically insulates the positive electrode and negative electrodes, such as microporous polymer films, such as a porous polyolefin film, for example, and can permeate
  • porous polyolefin film for example, a porous polyethylene film alone, or a porous polyethylene film and a porous polypropylene film may be laminated and used as a multilayer film. Moreover, the film etc. which compounded the porous polyethylene film and the polypropylene film are mentioned.
  • a metal can such as a coin type, a cylindrical type, or a square type, or a laminate outer package can be used.
  • the metal can material include a steel plate plated with nickel, a stainless steel plate, a stainless steel plate plated with nickel, aluminum or an alloy thereof, nickel, titanium and the like.
  • the laminate outer package for example, an aluminum laminate film, a laminate film made of SUS, a polypropylene coated with silica, a laminate film such as polyethylene, and the like can be used.
  • the configuration of the non-aqueous electrolyte battery according to the first embodiment is not particularly limited.
  • the electrode element in which the positive electrode and the negative electrode are disposed facing each other, and the non-aqueous electrolyte are included in the outer package.
  • the configuration can be made.
  • the shape of the non-aqueous electrolyte battery is not particularly limited, but an electrochemical device having a coin shape, a cylindrical shape, a square shape, an aluminum laminate sheet type, or the like can be assembled from the above-described elements.
  • Second Embodiment 1 Electrolyte Solution for Nonaqueous Electrolyte Battery Electrolyte Solution for Nonaqueous Electrolyte Battery According to Second Embodiment of the Present Invention (I) non-aqueous organic solvent, (II) an ionic salt, a solute, (III) at least one additive selected from the group consisting of compounds represented by the above general formula (1), and (IV) at least one additive selected from the group consisting of compounds represented by the above general formula (6).
  • Nonaqueous Organic Solvent As the nonaqueous organic solvent, the same nonaqueous organic solvent as that of the first embodiment is preferably used. The category is different from the non-aqueous solvent, but an ionic liquid can also be used.
  • the non-aqueous organic solvent is preferably at least one selected from the group consisting of cyclic carbonates and chain carbonates, from the viewpoint of excellent cycle characteristics at high temperatures, and from the group consisting of esters It is preferable at the point which is excellent in the input-output characteristic in low temperature as it is at least 1 sort (s) chosen.
  • Specific examples of the cyclic carbonate, linear carbonate, and ester are the same as in the first embodiment.
  • solute As the solute, the same solute (ionic salt) as in the first embodiment can be suitably used. The concentration of the solute is also the same as in the first embodiment.
  • the silicon compound represented by the general formula (1) is used.
  • the concentration of (III) with respect to the total amount 100 mass% of (I) to (IV) is the same as that of the first embodiment, and a particularly preferable concentration range is 0.08 mass% or more, 0 .75 mass% or less.
  • Component (IV) in the second embodiment, as the component (IV), as described above, at least one additive selected from the group consisting of compounds represented by General Formula (6) is used.
  • the concentration of (IV) with respect to the total amount 100 mass% of (I) to (IV) is the same as that of the first embodiment, and the more preferable concentration range is 0.10 mass% or more; It is 00 mass% or less, and a more preferable concentration range is 0.30 mass% or more and 2.00 mass% or less.
  • additive components may be further added to the electrolyte solution for a non-aqueous electrolyte battery of the second embodiment at an arbitrary ratio.
  • Specific examples include cyclohexylbenzene, cyclohexylfluorobenzene, fluorobenzene (hereinafter sometimes referred to as FB), biphenyl, difluoroanisole, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, 2-fluorobiphenyl , Vinylene carbonate, dimethylvinylene carbonate, vinyl ethylene carbonate, FEC, trans-difluoroethylene carbonate, methyl propargyl carbonate, ethyl propargyl carbonate, dipropargyl carbonate, maleic anhydride, succinic anhydride, methyl methanesulfonate, 1,6-di Isocyanatohe
  • the content of the ionic salt mentioned as the solute in the electrolytic solution is smaller than 0.5 mol / L which is the lower limit of the suitable concentration of the solute, the negative electrode film forming effect as “other additive” And positive electrode protection effect.
  • the content in the electrolytic solution is preferably 0.01% by mass or more and 5.00% by mass.
  • Examples of the ionic salt in this case include lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, lithium fluorosulfonate (hereinafter referred to as LiSO 3 F) Sodium fluorosulfonate, potassium fluorosulfonate, magnesium fluorosulfonate, lithium bis (trifluoromethanesulfonyl) imide, sodium bis (trifluoromethanesulfonyl) imide, potassium bis (trifluoromethanesulfonyl) imide, bis (trifluoromethanesulfonyl) ) Imidomagnesium, bis (fluorosulfonyl) imide lithium, bis (fluorosulfonyl) imide sodium, bis (ful (Sulfonyl) imide potassium, bis (fluorosulfonyl) imide magnesium, (
  • alkali metal salts other than the above-mentioned solutes may be used as an additive.
  • carboxylates such as lithium acrylate, sodium acrylate, lithium methacrylate, sodium methacrylate and the like, lithium methyl sulfate, sodium methyl sulfate, lithium ethyl sulfate, sulfuric acid ester salts such as sodium methyl sulfate and the like can be mentioned. .
  • the polymer may be contained, and the electrolyte for non-aqueous electrolyte battery may be gelled as in the case of a non-aqueous electrolyte battery called a polymer battery. It is also possible to use it as a pseudosolid by using a crosslinking agent or a crosslinking polymer.
  • concentration range is 0.01 to 1.0% by mass in the electrolytic solution and is a range smaller than the concentration of the component (IV).
  • a nonaqueous electrolyte battery according to a second embodiment of the present invention comprises at least (a) the above-mentioned electrolyte for a non-aqueous electrolyte battery, (a) a positive electrode, and (c) lithium metal And a negative electrode having at least one selected from the group consisting of a negative electrode material capable of inserting and extracting lithium, sodium, potassium, or magnesium. Furthermore, it is preferable to include (d) a separator, an exterior body, and the like. Since the above-mentioned electrolytic solution is excellent in high-temperature storage stability (high-temperature storage characteristic), the durability of the battery can be improved.
  • the positive electrode preferably contains at least one oxide and / or polyanion compound as a positive electrode active material.
  • the positive electrode active material constituting (i) the positive electrode is not particularly limited as long as it is various materials capable of charge and discharge.
  • (A) lithium transition metal complex oxide having at least one metal of nickel, manganese, cobalt and having a layered structure (B) lithium manganese complex oxide having a spinel structure, (C) The lithium-containing olivine-type phosphate and the lithium-containing layered transition metal oxide having a layered rock salt-type structure (D) include at least one of them.
  • (A) Lithium transition metal complex oxide As a lithium transition metal complex oxide containing a positive electrode active material (A) at least one or more metals of nickel, manganese, and cobalt and having a layered structure, for example, lithium-cobalt complex oxide, lithium-nickel complex oxide , Lithium-nickel-cobalt composite oxide, lithium-nickel-cobalt-aluminum composite oxide, lithium-cobalt-manganese composite oxide, lithium-nickel-manganese composite oxide, lithium-nickel-manganese-cobalt composite oxide Etc.
  • transition metal atoms which are main components of these lithium transition metal complex oxides, may be Al, Ti, V, Cr, Fe, Cu, Zn, Mg, Ga, Zr, Si, B, Ba, Y, Sn Those substituted with other elements such as.
  • lithium-cobalt complex oxide and lithium-nickel complex oxide include lithium cobaltate (LiCo 0.98 Mg 0.01 Zr 0.01 O) to which LiCoO 2 , LiNiO 2 or different elements such as Mg, Zr, Al, Ti, etc. are added.
  • LiCo 0.98 Mg 0.01 Al 0.01 O 2 LiCo 0.975 Mg 0.01 Zr 0.005 Al 0.01 O 2 and the like
  • lithium cobaltate having a rare earth compound fixed to the surface described in WO 2014/034043 may be used .
  • a part of the particle surface of LiCoO 2 powder may be coated with aluminum oxide.
  • lithium-nickel-cobalt composite oxide and the lithium-nickel-cobalt-aluminum composite oxide include the composite oxide represented by the above general formula [1-1], and specific examples thereof are the first embodiment. It is the same as illustrated.
  • lithium-cobalt-manganese composite oxide examples include LiNi 0.5 Mn 0.5 O 2 and LiCo 0.5 Mn 0.5 O 2 .
  • lithium-nickel-manganese-cobalt composite oxide examples include the composite oxide represented by the above general formula [1-2], and specific examples thereof are the same as those exemplified in the first embodiment.
  • the lithium-nickel-manganese-cobalt composite oxide also improves the structural stability and the safety at high temperatures in the lithium secondary battery, and in the second embodiment, manganese is also represented by the general formula [1-2] Those which are contained in the range shown in are preferable, and in particular, those further containing cobalt in the range shown in the general formula [1-2] are more preferable in order to enhance the high rate characteristics of the lithium ion secondary battery.
  • (B) Lithium manganese complex oxide having spinel structure As a lithium manganese complex oxide which has a positive electrode active material (B) spinel structure, the spinel type lithium manganese complex oxide shown by said general formula [1-3] is mentioned, for example.
  • M 3 may be at least one metal element selected from the group consisting of Ni, Co, Fe, Mg, Cr, Cu, Al and Ti. Specific examples thereof include LiMnO 2 , LiMn 2 O 4 , LiMn 1.95 Al 0.05 O 4 , LiMn 1.9 Al 0.1 O 4 , LiMn 1.9 Ni 0.1 O 4 , LiMn 1.5 Ni 0.5 O 4 and the like.
  • (C) Lithium-containing olivine-type phosphate examples include those represented by the above general formula [1-4].
  • M 4 may be at least one selected from Co, Ni, Mn, Cu, Zn, Nb, Mg, Al, Ti, W, Zr and Cd. Specific examples include, LiFePO 4, LiCoPO 4, LiNiPO 4, LiMnPO 4, and among them LiFePO 4 and / or LiMnPO 4 are preferred.
  • lithium-rich layered transition metal oxide having a positive electrode active material (D) layered rock salt structure examples include those represented by the above general formula [1-5]. However, in the first embodiment, either M 5 or M 6 necessarily includes nickel, but in the second embodiment, M 5 or M 6 may not necessarily include nickel. Specific examples of the lithium excess layered transition metal oxide are the same as those exemplified in the first embodiment.
  • At least one selected from the above (A) to (D) may be contained as a main component, and as other substances contained, for example, FeS 2 , TiS 2 , TiO 2 , V Transition element chalcogenides such as 2 O 5 , MoO 3 and MoS 2 or conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole, activated carbon, polymers generating radicals, carbon materials, etc. may be mentioned.
  • the positive electrode has a positive electrode current collector and a positive electrode active material layer formed on at least one surface of the positive electrode current collector.
  • the configurations of the electrostatic current collector and the positive electrode active material layer are the same as those of the first embodiment, and thus the description thereof is omitted here.
  • the configuration of the non-aqueous electrolyte battery according to the second embodiment is also not particularly limited, and, for example, as in the first embodiment, an electrode element in which a positive electrode and a negative electrode are disposed opposite to each other, and non-aqueous electrolysis
  • the liquid may be contained in the outer package.
  • the shape of the non-aqueous electrolyte battery is not particularly limited, but an electrochemical device having a coin shape, a cylindrical shape, a square shape, an aluminum laminate sheet type, or the like can be assembled from the above-described elements.
  • a non-aqueous electrolyte battery using the non-aqueous electrolyte according to the first embodiment was produced and performance evaluation was performed.
  • NCM 811 positive electrode Mix 9% by mass of LiNi 0.8 Mn 0.1 Co 0.1 O 2 powder, 4.5% by mass of polyvinylidene fluoride (hereinafter PVDF) as a binder, and 4.5% by mass of acetylene black as a conductive material, and further N-methyl.
  • PVDF polyvinylidene fluoride
  • acetylene black as a conductive material
  • NMP -2-Pyrrolidone
  • NCA positive electrode 5.0 mass% of PVDF as a binder, 6.0 mass% of acetylene black as a conductive material are mixed with 89.0 mass% of LiNi 0.87 Co 0.10 Al 0.03 O 2 powder, NMP is further added, and a positive electrode mixture paste Was produced. This paste was applied to both sides of an aluminum foil (A1085), dried and pressurized, and then punched into 4 ⁇ 5 cm to obtain an NCA positive electrode for test.
  • the silicon compound having a substituent having an unsaturated bond represented by the above general formula (1) can be produced by various methods.
  • the production method is not limited.
  • ethynyltrichlorosilane, diethynyldichlorosilane, and triethynyl can be reacted by reacting silicon tetrachloride and ethynyl Grignard reagent in tetrahydrofuran at an internal temperature of 40 ° C. or less.
  • a chlorosilane, tetraethynylsilane (1-15) is obtained.
  • it is possible to separately produce these silicon compounds by performing distillation under reduced pressure at an internal temperature of 100 ° C. or less after adjusting the amount of ethynyl Grignard reagent to be used for reaction.
  • Compound (1-5) is reacted with diethynyldichlorosilane in the presence of 2 equivalents of methanol in the presence of a base such as triethylamine, and compound (1-17) is reacted with 2 equivalents of allyl Grignard reagent to give a compound 1-19) was obtained by reacting 2 equivalents of sodium acetylide.
  • Compounds (1-25), (1-26) and (1-27) are reacted with diethynyldichlorosilane in the presence of a base in the presence of a base after reacting one equivalent of the corresponding alcohol or an organolithium reagent, It was obtained by reacting potassium fluoride.
  • compounds (1-9) and (1-20) were obtained by reacting ethynyltrichlorosilane as a raw material and reacting 3 equivalents of propargyl alcohol or sodium acetylide.
  • Compound (1-12) reacts phenyltrichlorosilane with 3 equivalents of ethynyl Grignard reagent
  • compound (1-18) reacts phenyltrichlorosilane with an equal number of moles of ethynyl Grignard reagent after reacting 2 equivalents of sodium It was obtained by reacting acetylide.
  • Compound (1-24) was obtained by reacting trichloromethylsilane with 3 equivalents of ethynyl Grignard reagent.
  • methanesulfonyl fluoride can be obtained by fluorinating methanesulfonyl chloride manufactured by Aldrich, benzenesulfonyl chloride manufactured by Tokyo Chemical Industry Co., Ltd., phenyl dichlorophosphate, and phenyldichlorophosphine oxide manufactured by Wako Pure Chemical Industries, Ltd. with potassium fluoride.
  • compound (2-4) benzenesulfonyl fluoride
  • compound (2-2) benzenesulfonyl fluoride
  • phenyl difluorophosphate hereinafter, as There were obtained “compound (4-1)”, phenyldifluorophosphine oxide (hereinafter sometimes described as “compound (4-2)”).
  • compound (2-3) trifluoromethanesulfonyl fluoride
  • compound (3-1) lithium ethyl fluorophosphate was obtained by reacting lithium difluorophosphate with ethanol.
  • LiPF 6 solution (DMC, EMC)
  • the synthesis of the LiPF 6 concentrate was performed. That is, after phosphorus trichloride, lithium chloride and chlorine are reacted in carbonate ester (DMC or EMC) to synthesize lithium hexachloride phosphate, fluorination is carried out by introducing hydrogen fluoride there, A DMC solution containing LiPF 6 and hydrogen chloride and unreacted hydrogen fluoride, and an EMC solution were obtained, respectively. This was concentrated under reduced pressure to obtain a LiPF 6 concentrate from which almost all hydrogen chloride and most of the hydrogen fluoride were removed.
  • DMC carbonate ester
  • each carbonate is added to adjust the concentration to 30.0% by mass to reduce the viscosity, and then 10% by mass of dehydrated ion exchange resin is added to 100 g of each concentrate.
  • the purification process was performed.
  • a 30.0% by weight of LiPF 6 / DMC solution, LiPF 6 / EMC solution 30.0 mass% was obtained.
  • Nonaqueous Electrolyte According to Examples and Comparative Examples
  • the silicon compound (1-1) corresponding to 0.25 mass% was added to the reference electrolyte solution 1 and dissolved by stirring for 1 hour. This was designated as non-aqueous electrolyte 1- (1-1) -0.25- (0).
  • a silicon compound (1-1) corresponding to 0.25 mass% and LiSO 3 F corresponding to 0.02 mass% were added to the reference electrolyte solution 1 and dissolved by stirring for 1 hour. The resultant was used as a non-aqueous electrolyte 1- (1-1) -0.25-LiSO3F-0.02.
  • the component (III), the component (IV), and other solutes or added components are added to the reference electrolyte 1 so as to have the concentrations shown in Table 3 and stirred. Each non-aqueous electrolyte was obtained by dissolving.
  • LiPO 2 F 2 means lithium difluorophosphate
  • LTFOP means lithium tetrafluorooxalatophosphate
  • LDFBOP means lithium difluorobis (oxalato) phosphate
  • LDFOB is difluorooxalato Means lithium borate
  • LiFSI means bis (fluorosulfonyl) imide lithium
  • LTFFSI means (trifluoromethanesulfonyl) (fluorosulfonyl) imide lithium
  • LDFPI means bis (difluorophosphonyl) imide lithium .
  • the component (III), the component (IV), and other solutes or added components are added to the reference electrolyte 2 so as to have the concentrations shown in Table 5 and stirred. Each non-aqueous electrolyte was obtained by dissolving.
  • NCM 811 / Graphite After welding the terminal to the above NCM 811 positive electrode in argon atmosphere with dew point-50 ° C or less, sandwich both sides with two polyethylene separators (5 x 6 cm) and further The negative electrode active material surface was pinched
  • the assembled battery described above had a capacity of 73 mAh, which was standardized by the weight of the positive electrode active material.
  • the battery was placed in a 25 ° C. constant temperature bath and connected to a charge / discharge device in that state.
  • the battery was charged to 4.2 V at a charge rate of 0.2 C (current value that fully charges in 5 hours).
  • discharge was performed to 3.0 V at a discharge rate of 0.2C. This was defined as one cycle of charge and discharge, and a total of three cycles of charge and discharge were performed to stabilize the battery.
  • Capacity retention rate [%] (discharge capacity after 400 cycles / discharge capacity at first cycle) ⁇ 100
  • Ni elution amount measurement After 400 cycles, the battery was disassembled in an atmosphere not exposed environment, and the negative electrode was taken out. The collected negative electrode was washed with dimethyl carbonate, and then the active material layer on the current collector was scraped off and collected. The recovered active material layer was added to a 14.0 mass% high-purity nitric acid aqueous solution and heated at 150 ° C. for 2 hours. The amount of the Ni component [ ⁇ g / g] contained in the active material layer was measured with an inductively coupled plasma emission spectrophotometer (ICPS-7510 manufactured by Shimadzu Corp.) using an aqueous solution in which the entire amount of the residue was dissolved in ultrapure water.
  • ICPS-7510 inductively coupled plasma emission spectrophotometer
  • Ni component / negative electrode active material layer was determined. Similarly, only the test negative electrode (a test negative electrode before being incorporated into a battery) obtained in the above [Production of Graphite Negative Electrode] was similarly washed with dimethyl carbonate, and then the active material layer on the current collector was scraped off and collected. The amount of Ni component contained in the negative electrode active material layer was measured with an inductively coupled plasma emission spectrometry after the same process as described above for the collected active material layer, and the detection lower limit of less than 1.0 ⁇ g / g ( Since it was Ni component / negative electrode active material layer), it can be said that all Ni components quantified from the negative electrode active material layer taken out from the battery after 400 cycles were eluted from the positive electrode active material.
  • Tables 6 and 7 show the evaluation results of the NCM811 / graphite electrode configuration battery.
  • Comparative Examples 1-9, 1-10, and Examples 1-13 to 1-17 after 400 cycles, the capacity retention ratio of the Comparative Example 1-9 using the electrolytic solution not containing the component (III), Ni elution It showed as a relative value when quantity was made into 100 each.
  • the amount of LiSO 3 F is adjusted to 0. 0. 0.
  • the amount of LiSO 3 F was up to 2.40% by mass, the improvement of the capacity retention rate was observed together with the suppression of the Ni elution amount (Examples 1-1 to 1-5, Comparative Example 1-1).
  • the concentration of the silicon compound having an unsaturated bond represented by General Formula (1) is 0.01 to 2.00.
  • Examples 1-13 to 1-17 which are% by mass are likely to exhibit a good durability improvement effect without significantly increasing the amount of Ni elution.
  • Examples 1-14 to 1-16 having the same concentration of 0.04 to 1.00% by mass are more likely to exert the above-mentioned effects, and the examples having the same concentration of 0.08 to 0.50% by mass.
  • Examples 1-15 to 1-16 are particularly easy to exhibit the effects described above.
  • the amount of addition of LiSO 3 F (the amount of addition of the component (IV)) is fixed to 1.00% by mass which is in the particularly preferable range of 0.50 to 1.50% by mass. It is carried out.
  • the addition amount of the silicon compound having an unsaturated bond represented by the general formula (1) is particularly preferably in the range of 0.08 to 0.50 mass%. The experiment is performed by fixing to 25% by mass.
  • Comparative Examples 1-11 to 1-20 and Examples 1-18 to 1-27 show the evaluation results when the type of the silicon compound having an unsaturated bond represented by the general formula (1) is changed. In either case, as compared to the system without addition of LiSO 3 F, towards the system plus LiSO 3 F 1.00% by weight, the capacity maintenance rate of improvement and Ni elution of inhibition was confirmed clearly.
  • the above-mentioned assembled battery had a capacity of 70 mAh, which was standardized by the weight of the positive electrode active material.
  • the battery was placed in a 25 ° C. constant temperature bath and connected to a charge / discharge device in that state.
  • the battery was charged to 4.1 V at a charge rate of 0.2 C (current value that fully charges in 5 hours).
  • discharge was performed at a discharge rate of 0.2 C to 2.7 V. This was defined as one cycle of charge and discharge, and a total of three cycles of charge and discharge were performed to stabilize the battery.
  • the evaluation results are shown in Tables 8 and 9.
  • the values of the capacity retention rate and the elution amount of Ni of Examples 2-1 to 2-18 are the values of the retention rates of the capacity and the elution amount of Ni of Comparative Examples 2-1 to 2-18, respectively. It is a relative value.
  • the component (III), the component (IV), and the other solutes or the additive components are added to the reference electrolyte 1 or the reference electrolyte 2.
  • the respective non-aqueous electrolytes were obtained by adding so as to give the concentrations shown in 10 to 13 and stirring and dissolving.
  • the aluminum laminate type batteries according to Examples 3-1 to 3-12 are fabricated by the same procedure as Example 1-1 except that the non-aqueous electrolyte described in Table 18 is used, and the same evaluation is performed. went. The results are shown in Table 19. In addition, about the Example of Table 19, it showed as a relative value when the capacity
  • lithium fluorosulfonate as the component (IV)
  • the compounds (2-1) to (2- (2) to (2- (2)) were used as the component (IV) as compared to Example 3-12 using the compound (3-1) as the component (IV).
  • Examples 3-1 to 3-11 using (4-1) to (4-2) and (5-1) to (5-4) show the capacity retention ratio and Ni after 400 cycles. It was confirmed that the evaluation result of one or both of the elution amounts is more excellent.
  • the component (III) and the component (IV) are added to the reference electrolyte 1 so as to have the concentrations shown in Table 20, stirred and dissolved. By doing this, each non-aqueous electrolyte was obtained.
  • Example 21 In the same manner as in Example 1-1 except that the non-aqueous electrolyte described in Table 20 was used, production of an aluminum laminate type battery according to Examples 4-1 to 4-28 and Comparative Example 4-1 And made a similar assessment. The results are shown in Table 21. In addition, regarding the example of Table 21 and the comparative example, it is shown as a relative value when the capacity retention ratio after 400 cycles of Comparative Example 4-1 is 100.
  • a non-aqueous electrolyte battery using the non-aqueous electrolyte according to the second embodiment was manufactured, and performance evaluation was performed.
  • NCM 811 positive electrode Mix 9% by mass of LiNi 0.8 Mn 0.1 Co 0.1 O 2 powder, 4.5% by mass of polyvinylidene fluoride (hereinafter PVDF) as a binder, and 4.5% by mass of acetylene black as a conductive material, and further N-methyl.
  • PVDF polyvinylidene fluoride
  • acetylene black as a conductive material
  • NMP -2-Pyrrolidone
  • LiPF 6 solution Preparation of LiPF 6 solution
  • EC, FEC, EMC, and DMC were mixed at a volume ratio of 2: 1: 3: 4, respectively. Thereafter, while maintaining the internal temperature at 40 ° C. or less, LiPF 6 was added in an amount to give a concentration of 1.0 M, and was completely dissolved by stirring to obtain a LiPF 6 solution.
  • the component (III), the component (IV), and other solutes or added components are added to the LiPF 6 solution to a concentration shown in Table 24, and dissolved by stirring. By doing this, each non-aqueous electrolyte was obtained.
  • a terminal is welded to the above NCM 811 positive electrode in an argon atmosphere with a dew point of -50 ° C. or less, and then both sides are sandwiched between two polyethylene separators (5 ⁇ 6 cm), and further the terminal is welded in advance. Two sheets were inserted so that the negative electrode active material surface faced the positive electrode active material surface. And after putting them in the bag of the aluminum laminate in which the opening part of one side was left, after vacuum-injecting non-aqueous electrolyte, the opening part is sealed with heat, The aluminum laminate which concerns on an Example and a comparative example Type batteries were made. The non-aqueous electrolytes described in Tables 1 to 3 were used. In addition, the non-aqueous electrolyte used the new thing (The thing which did not evaluate above "50 degreeC storage stability of electrolyte solution").
  • the above-described assembled battery had a capacity of 75 mAh, which was specified by weight of the positive electrode active material.
  • the battery was placed in a 25 ° C. constant temperature bath and connected to a charge / discharge device in that state.
  • the battery was charged to 4.2 V at a charge rate of 0.2 C (current value that fully charges in 5 hours).
  • discharge was performed to 3.0 V at a discharge rate of 0.2C. This was defined as one cycle of charge and discharge, and a total of three cycles of charge and discharge were performed to stabilize the battery.
  • Tables 25 and 26 show the evaluation results (APHA) of the storage stability of the above electrolyte solution at 50 ° C. and the measurement results of the recovery capacity of a cell manufactured using an electrolyte solution having the same composition.
  • the recovery capacity is defined as the cyclic sulfur compound (6), PRS, or the cyclic sulfur compound (6), with the value of cells (for example, Comparative Examples 5-1, 5-3, 5-5, etc.) using an electrolytic solution containing no cyclic sulfur compound being 100 respectively.
  • the relative values of cells using an electrolyte containing MMDS are shown.
  • MMDS The stability of MMDS is lower than that of PRS, and when 1% by mass of MMDS is added to silicon compounds (1-1), (1-12) and (1-24), the increase in APHA over PRS addition increases Were observed (Comparative Examples 8-1 and 8-2, Comparative Examples 10-1 and 10-2, and Comparative Examples 12-1 and 12-2).
  • cyclic sulfur compounds (6-1), (6-5), (6-11), (6-19), (6-22), (6-38) may be used.
  • the recovery capacity could be improved without a significant increase in APHA (Examples 8-1 to 8-2, Examples 10-1 to 10-2, Examples 12-1 to 12-2).
  • Table 27 shows the results (APHA) and measurement results of recovery capacity of cells produced using electrolytes of the same composition. The recovery capacity was shown as a relative value when the value of the cell using the electrolyte solution which does not contain other components is set to 100, respectively.
  • LiSO 3 F, LDFOB, LiPO 2 F 2 , and LDFBOP was added, further improvement of the recovery capacity could be achieved without significantly affecting APHA.

Landscapes

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

Abstract

La présente invention concerne une solution électrolytique pour batteries à électrolyte non aqueux qui contient (I) un solvant organique non aqueux, (II) un soluté qui est un sel ionique, (III) au moins un additif qui est choisi dans le groupe constitué par les composés représentés par la formule générale (1), et (IV) un additif qui a une structure spécifique. Grâce à l'utilisation combinée du composant (III) et du composant (IV), des effets tels que la réduction de la dissolution de Ni de l'électrode positive riche en Ni dans la solution électrolytique et l'amélioration de la stabilité du stockage de la solution électrolytique à des températures élevées peuvent être obtenus sans détériorer le taux de rétention de capacité après cycles.
PCT/JP2018/045365 2017-12-12 2018-12-10 Solution électrolytique pour batteries à électrolyte non aqueux, et batterie à électrolyte non aqueux l'utilisant WO2019117101A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US16/771,109 US20200335823A1 (en) 2017-12-12 2018-12-10 Electrolyte Solution for Nonaqueous Electrolyte Batteries and Nonaqueous Electrolyte Battery Using Same
KR1020207018055A KR102498193B1 (ko) 2017-12-12 2018-12-10 비수전해액 전지용 전해액 및 그것을 이용한 비수전해액 전지
EP18889822.5A EP3726636B1 (fr) 2017-12-12 2018-12-10 Solution électrolytique pour batteries à électrolyte non aqueux, et batterie à électrolyte non aqueux l'utilisant
CN201880079898.2A CN111527636B (zh) 2017-12-12 2018-12-10 非水电解液电池用电解液和使用其的非水电解液电池

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2017-237455 2017-12-12
JP2017237455 2017-12-12
JP2018-219853 2018-11-26
JP2018219853A JP7116312B2 (ja) 2018-11-26 2018-11-26 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
JP2018-219846 2018-11-26
JP2018219846A JP7116311B2 (ja) 2017-12-12 2018-11-26 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

Publications (1)

Publication Number Publication Date
WO2019117101A1 true WO2019117101A1 (fr) 2019-06-20

Family

ID=66820342

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/045365 WO2019117101A1 (fr) 2017-12-12 2018-12-10 Solution électrolytique pour batteries à électrolyte non aqueux, et batterie à électrolyte non aqueux l'utilisant

Country Status (1)

Country Link
WO (1) WO2019117101A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020246521A1 (fr) * 2019-06-05 2020-12-10 セントラル硝子株式会社 Solution électrolytique non aqueuse
WO2021006302A1 (fr) * 2019-07-08 2021-01-14 セントラル硝子株式会社 Solution électrolytique non aqueuse et batterie à électrolyte non aqueux la comprenant
WO2021006238A1 (fr) * 2019-07-09 2021-01-14 セントラル硝子株式会社 Électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
CN113036212A (zh) * 2021-03-05 2021-06-25 星恒电源股份有限公司 一种具有高倍率性能的非水电解液及钠离子电池
CN113054254A (zh) * 2019-12-27 2021-06-29 丰田自动车株式会社 非水电解液、非水电解液二次电池和非水电解液二次电池的制造方法
CN113471514A (zh) * 2020-03-31 2021-10-01 宁德新能源科技有限公司 一种电化学装置及包括其的电子装置
CN114188607A (zh) * 2021-12-20 2022-03-15 珠海市赛纬电子材料股份有限公司 添加剂及使用该添加剂的电解液和锂离子电池
WO2022092136A1 (fr) * 2020-10-30 2022-05-05 パナソニックＩｐマネジメント株式会社 Batterie secondaire à électrolyte non aqueux
CN114552014A (zh) * 2022-02-25 2022-05-27 惠州锂威新能源科技有限公司 一种电解液及含有该电解液的电化学装置
CN116435601A (zh) * 2023-06-14 2023-07-14 广州天赐高新材料股份有限公司 一种电解液及其应用
CN116848688A (zh) * 2023-02-20 2023-10-03 宁德时代新能源科技股份有限公司 非水电解质溶液及其锂二次电池和用电装置
JP7551221B2 (ja) 2021-03-23 2024-09-17 エルジー・ケム・リミテッド 化合物、これを含む非水電解液およびリチウム二次電池

Citations (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS497812B1 (fr) 1970-11-09 1974-02-22
JPS5845955B2 (ja) 1978-12-28 1983-10-13 住友化学工業株式会社 加熱転写体の改良方法
JPS6051537B2 (ja) 1981-06-29 1985-11-14 日本鋼管株式会社 ホ−ロ−性に優れたアルミキルド冷延鋼板の製造法
JPH0696769A (ja) 1992-09-11 1994-04-08 Matsushita Electric Ind Co Ltd 非水電解質リチウム二次電池用正極
JPH0845545A (ja) 1994-04-22 1996-02-16 Saft (Soc Accumulateurs Fixes Traction) Sa 炭素アノードを有するリチウム蓄電池
JPH10139784A (ja) 1996-11-06 1998-05-26 Kanegafuchi Chem Ind Co Ltd ビニルシリル基含有ケイ素化合物の製造方法
JP2002141110A (ja) * 2000-11-01 2002-05-17 Matsushita Electric Ind Co Ltd 非水系電池用電解液およびこれを用いた二次電池
JP2002151077A (ja) 2000-11-14 2002-05-24 Toda Kogyo Corp 非水電解質二次電池用正極活物質及びその製造法
JP2004039510A (ja) 2002-07-05 2004-02-05 Denso Corp 非水電解液及び該電解液を用いた非水電解液二次電池
WO2004042851A2 (fr) 2002-11-05 2004-05-21 Imperial College Innovations Limited Anode en silicium structure
WO2004100293A1 (fr) 2003-05-09 2004-11-18 Sony Corporation Matiere active negative et son procede de production, accumulateur a electrolyte non aqueux utilisant ladite matiere
WO2005104289A1 (fr) * 2004-04-19 2005-11-03 Bridgestone Corporation Solution électrolytique non aqueuse pour batterie et batterie électrolytique non aqueuse utilisant ladite solution
US7135252B2 (en) 2000-06-22 2006-11-14 Uchicago Argonne Llc Lithium metal oxide electrodes for lithium cells and batteries
JP2007018883A (ja) 2005-07-07 2007-01-25 Toshiba Corp 負極活物質、非水電解質電池及び電池パック
WO2007083155A1 (fr) 2006-01-23 2007-07-26 Nexeon Ltd Procédé de fabrication de fibres composées de silicium ou d'un matériau à base de silicium et utilisations de celles-ci dans des accumulateurs au lithium rechargeables
JP2008016424A (ja) 2006-06-05 2008-01-24 Sony Corp 電解質およびこれを用いた電池、並びに電解質の製造方法
JP2008270201A (ja) 2007-03-27 2008-11-06 Univ Kanagawa リチウムイオン電池用正極材料
JP2009137834A (ja) 2007-11-12 2009-06-25 Toda Kogyo Corp 非水電解液二次電池用Ｌｉ−Ｎｉ系複合酸化物粒子粉末及びその製造方法、並びに非水電解質二次電池
WO2010113583A1 (fr) 2009-03-31 2010-10-07 日鉱金属株式会社 Matériau actif d'électrode positive pour batterie lithium ion
JP5072379B2 (ja) 2007-01-26 2012-11-14 株式会社デンソー 非水電解液及び該電解液を用いた二次電池
JP2012230897A (ja) * 2011-04-13 2012-11-22 Mitsubishi Chemicals Corp フルオロスルホン酸リチウム、非水系電解液、及び非水系電解液二次電池
JP2013030284A (ja) 2011-07-26 2013-02-07 Mitsubishi Chemicals Corp 非水系電解液電池
WO2013118661A1 (fr) 2012-02-06 2013-08-15 日本電気株式会社 Batterie au lithium-ion et procédé pour sa fabrication
WO2014034043A1 (fr) 2012-08-27 2014-03-06 三洋電機株式会社 Batterie rechargeable à électrolyte non aqueux
JP5668684B2 (ja) 2009-08-04 2015-02-12 和光純薬工業株式会社 環状スルホン酸エステルの製造方法及びその中間体
JP2016035820A (ja) * 2014-08-01 2016-03-17 セントラル硝子株式会社 非水電解液電池用電解液、及びこれを用いた非水電解液電池
JP2016157679A (ja) 2015-02-19 2016-09-01 セントラル硝子株式会社 非水電解液電池用電解液、及びこれを用いた非水電解液電池
WO2017138452A1 (fr) 2016-02-08 2017-08-17 セントラル硝子株式会社 Électrolyte pour batterie à électrolyte non aqueux, et batterie à électrolyte non aqueux mettant en œuvre celui-ci
US20170271715A1 (en) 2016-03-18 2017-09-21 Samsung Sdi Co., Ltd. Organic electrolytic solution and lithium battery using the same
WO2018016195A1 (fr) * 2016-07-19 2018-01-25 住友精化株式会社 Additif pour solutions électrolytiques non aqueuses, solution électrolytique non aqueuse et dispositif de stockage d'électricité

Patent Citations (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS497812B1 (fr) 1970-11-09 1974-02-22
JPS5845955B2 (ja) 1978-12-28 1983-10-13 住友化学工業株式会社 加熱転写体の改良方法
JPS6051537B2 (ja) 1981-06-29 1985-11-14 日本鋼管株式会社 ホ−ロ−性に優れたアルミキルド冷延鋼板の製造法
JPH0696769A (ja) 1992-09-11 1994-04-08 Matsushita Electric Ind Co Ltd 非水電解質リチウム二次電池用正極
JPH0845545A (ja) 1994-04-22 1996-02-16 Saft (Soc Accumulateurs Fixes Traction) Sa 炭素アノードを有するリチウム蓄電池
JPH10139784A (ja) 1996-11-06 1998-05-26 Kanegafuchi Chem Ind Co Ltd ビニルシリル基含有ケイ素化合物の製造方法
US7135252B2 (en) 2000-06-22 2006-11-14 Uchicago Argonne Llc Lithium metal oxide electrodes for lithium cells and batteries
JP2002141110A (ja) * 2000-11-01 2002-05-17 Matsushita Electric Ind Co Ltd 非水系電池用電解液およびこれを用いた二次電池
JP2002151077A (ja) 2000-11-14 2002-05-24 Toda Kogyo Corp 非水電解質二次電池用正極活物質及びその製造法
JP2004039510A (ja) 2002-07-05 2004-02-05 Denso Corp 非水電解液及び該電解液を用いた非水電解液二次電池
WO2004042851A2 (fr) 2002-11-05 2004-05-21 Imperial College Innovations Limited Anode en silicium structure
WO2004100293A1 (fr) 2003-05-09 2004-11-18 Sony Corporation Matiere active negative et son procede de production, accumulateur a electrolyte non aqueux utilisant ladite matiere
WO2005104289A1 (fr) * 2004-04-19 2005-11-03 Bridgestone Corporation Solution électrolytique non aqueuse pour batterie et batterie électrolytique non aqueuse utilisant ladite solution
JP2007018883A (ja) 2005-07-07 2007-01-25 Toshiba Corp 負極活物質、非水電解質電池及び電池パック
JP2009176752A (ja) 2005-07-07 2009-08-06 Toshiba Corp 負極活物質及びその製造方法、非水電解質電池及び電池パック
WO2007083155A1 (fr) 2006-01-23 2007-07-26 Nexeon Ltd Procédé de fabrication de fibres composées de silicium ou d'un matériau à base de silicium et utilisations de celles-ci dans des accumulateurs au lithium rechargeables
JP2008016424A (ja) 2006-06-05 2008-01-24 Sony Corp 電解質およびこれを用いた電池、並びに電解質の製造方法
JP5072379B2 (ja) 2007-01-26 2012-11-14 株式会社デンソー 非水電解液及び該電解液を用いた二次電池
JP2008270201A (ja) 2007-03-27 2008-11-06 Univ Kanagawa リチウムイオン電池用正極材料
JP2009137834A (ja) 2007-11-12 2009-06-25 Toda Kogyo Corp 非水電解液二次電池用Ｌｉ−Ｎｉ系複合酸化物粒子粉末及びその製造方法、並びに非水電解質二次電池
WO2010113583A1 (fr) 2009-03-31 2010-10-07 日鉱金属株式会社 Matériau actif d'électrode positive pour batterie lithium ion
JP5668684B2 (ja) 2009-08-04 2015-02-12 和光純薬工業株式会社 環状スルホン酸エステルの製造方法及びその中間体
JP2012230897A (ja) * 2011-04-13 2012-11-22 Mitsubishi Chemicals Corp フルオロスルホン酸リチウム、非水系電解液、及び非水系電解液二次電池
JP2013030284A (ja) 2011-07-26 2013-02-07 Mitsubishi Chemicals Corp 非水系電解液電池
WO2013118661A1 (fr) 2012-02-06 2013-08-15 日本電気株式会社 Batterie au lithium-ion et procédé pour sa fabrication
WO2014034043A1 (fr) 2012-08-27 2014-03-06 三洋電機株式会社 Batterie rechargeable à électrolyte non aqueux
JP2016035820A (ja) * 2014-08-01 2016-03-17 セントラル硝子株式会社 非水電解液電池用電解液、及びこれを用いた非水電解液電池
JP2016157679A (ja) 2015-02-19 2016-09-01 セントラル硝子株式会社 非水電解液電池用電解液、及びこれを用いた非水電解液電池
WO2017138452A1 (fr) 2016-02-08 2017-08-17 セントラル硝子株式会社 Électrolyte pour batterie à électrolyte non aqueux, et batterie à électrolyte non aqueux mettant en œuvre celui-ci
US20170271715A1 (en) 2016-03-18 2017-09-21 Samsung Sdi Co., Ltd. Organic electrolytic solution and lithium battery using the same
WO2018016195A1 (fr) * 2016-07-19 2018-01-25 住友精化株式会社 Additif pour solutions électrolytiques non aqueuses, solution électrolytique non aqueuse et dispositif de stockage d'électricité

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMICKE ZVESTI, vol. 18, 1954, pages 21 - 7
JOURNAL OF ORGANIC CHEMISTRY, vol. 22, 1957, pages 1200 - 2
ROVNANIK PRVEL: "Z. Anorg. Chem.", vol. 632, 2006, WILEY-VCH VERLAG CMBH & CO. KGAA, article "Syntheses of Phosphoryl Chloro- and Bromofluorodies and Crystal Structures of POFC12 and POF2CI", pages: 1356
See also references of EP3726636A4 *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020246521A1 (fr) * 2019-06-05 2020-12-10 セントラル硝子株式会社 Solution électrolytique non aqueuse
CN114097123B (zh) * 2019-07-08 2024-09-06 中央硝子株式会社 非水电解液、及使用其的非水电解液电池
WO2021006302A1 (fr) * 2019-07-08 2021-01-14 セントラル硝子株式会社 Solution électrolytique non aqueuse et batterie à électrolyte non aqueux la comprenant
CN114097123A (zh) * 2019-07-08 2022-02-25 中央硝子株式会社 非水电解液、及使用其的非水电解液电池
WO2021006238A1 (fr) * 2019-07-09 2021-01-14 セントラル硝子株式会社 Électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
CN114128006A (zh) * 2019-07-09 2022-03-01 中央硝子株式会社 非水系电解液、和非水系电解液二次电池
CN113054254A (zh) * 2019-12-27 2021-06-29 丰田自动车株式会社 非水电解液、非水电解液二次电池和非水电解液二次电池的制造方法
CN113471514A (zh) * 2020-03-31 2021-10-01 宁德新能源科技有限公司 一种电化学装置及包括其的电子装置
WO2022092136A1 (fr) * 2020-10-30 2022-05-05 パナソニックＩｐマネジメント株式会社 Batterie secondaire à électrolyte non aqueux
CN113036212A (zh) * 2021-03-05 2021-06-25 星恒电源股份有限公司 一种具有高倍率性能的非水电解液及钠离子电池
JP7551221B2 (ja) 2021-03-23 2024-09-17 エルジー・ケム・リミテッド 化合物、これを含む非水電解液およびリチウム二次電池
CN114188607A (zh) * 2021-12-20 2022-03-15 珠海市赛纬电子材料股份有限公司 添加剂及使用该添加剂的电解液和锂离子电池
CN114188607B (zh) * 2021-12-20 2022-09-06 珠海市赛纬电子材料股份有限公司 添加剂及使用该添加剂的电解液和锂离子电池
CN114552014A (zh) * 2022-02-25 2022-05-27 惠州锂威新能源科技有限公司 一种电解液及含有该电解液的电化学装置
CN116848688A (zh) * 2023-02-20 2023-10-03 宁德时代新能源科技股份有限公司 非水电解质溶液及其锂二次电池和用电装置
CN116435601A (zh) * 2023-06-14 2023-07-14 广州天赐高新材料股份有限公司 一种电解液及其应用
CN116435601B (zh) * 2023-06-14 2024-03-22 广州天赐高新材料股份有限公司 一种电解液及其应用

Similar Documents

Publication Publication Date Title
CN111527636B (zh) 非水电解液电池用电解液和使用其的非水电解液电池
JP7116314B2 (ja) 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
JP7116311B2 (ja) 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
US11230564B2 (en) Method for producing phosphoryl imide salt, method for producing nonaqueous electrolyte solution containing said salt, and method for producing nonaqueous secondary battery
US11177507B2 (en) Electrolyte for lithium secondary battery and lithium secondary battery including the same
WO2019117101A1 (fr) Solution électrolytique pour batteries à électrolyte non aqueux, et batterie à électrolyte non aqueux l'utilisant
US10454139B2 (en) Electrolytic solution for nonaqueous electrolytic solution secondary batteries and nonaqueous electrolytic solution secondary battery
WO2019111983A1 (fr) Solution électrolytique pour batteries à électrolyte non aqueux, et batterie à électrolyte non aqueux dans laquelle elle est utilisée
WO2016117280A1 (fr) Solution électrolytique non aqueuse et cellule à solution électrolyte non aqueuse utilisant ladite solution
JP2019102451A (ja) 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
JP7116312B2 (ja) 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
WO2020246522A1 (fr) Solution électrolytique non aqueuse et batterie à électrolyte non aqueux
US20220278371A1 (en) Nonaqueous electrolyte solution and nonaqueous electrolyte battery using the same
WO2019111958A1 (fr) Solution électrolytique pour batterie à électrolyte non aqueux, et batterie à électrolyte non aqueux mettant en œuvre celui-ci
JP2019169238A (ja) 非水電解液用カチオン、非水電解液、それを用いた蓄電デバイス、及びそれに用いるホスホニウム塩
JP2022042755A (ja) 非水電解液、及びこれを用いた非水電解液電池
KR101797273B1 (ko) 전해질 및 이를 포함하는 이차 전지
US20220231337A1 (en) Nonaqueous Electrolytic Solution

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18889822

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20207018055

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2018889822

Country of ref document: EP

Effective date: 20200713