WO2019016903A1 - Solution électrolytique non aqueuse et dispositif de stockage d'électricité comprenant ladite solution - Google Patents

Solution électrolytique non aqueuse et dispositif de stockage d'électricité comprenant ladite solution Download PDF

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WO2019016903A1
WO2019016903A1 PCT/JP2017/026151 JP2017026151W WO2019016903A1 WO 2019016903 A1 WO2019016903 A1 WO 2019016903A1 JP 2017026151 W JP2017026151 W JP 2017026151W WO 2019016903 A1 WO2019016903 A1 WO 2019016903A1
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group
carbon atoms
dioxolan
lithium
oxo
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PCT/JP2017/026151
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English (en)
Japanese (ja)
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圭 島本
宏行 瀬戸口
洋輔 佐藤
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宇部興産株式会社
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    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous electrolyte capable of improving electrochemical characteristics in a wide temperature range, and an electricity storage device using the same.
  • storage devices particularly lithium secondary batteries
  • PHEVs plug-in hybrid electric vehicles
  • BEVs battery electric vehicles
  • lithium secondary battery Due to the long travel distance of cars, they can be used in a wide temperature range from very hot areas in the tropics to extremely cold areas. Therefore, particularly these storage devices for vehicles are required to have no deterioration in electrochemical characteristics even when used in a wide temperature range from high temperature to low temperature.
  • the term lithium secondary battery is used as a concept including so-called lithium ion secondary battery.
  • a lithium secondary battery is mainly composed of a positive electrode and a negative electrode containing a material capable of absorbing and desorbing lithium ions, a lithium salt, and a non-aqueous electrolytic solution composed of a non-aqueous solvent, and ethylene carbonate (EC And carbonates such as propylene carbonate (PC) are used.
  • EC And carbonates such as propylene carbonate (PC)
  • a negative electrode of a lithium secondary battery metal lithium, a metal compound capable of inserting and extracting lithium ions (a single metal, a metal oxide, an alloy with lithium, etc.) and a carbon material are known.
  • lithium secondary batteries using carbon materials capable of absorbing and desorbing lithium ions, such as coke, artificial graphite and natural graphite have been widely put to practical use.
  • a lithium secondary battery using a highly crystallized carbon material such as natural graphite or artificial graphite as a negative electrode material is a decomposed product generated by reduction decomposition of the solvent in the non-aqueous electrolyte on the surface of the negative electrode during charging. It has been found that gas deposits on the negative electrode surface and results in a decrease in cycling characteristics as it inhibits the desired electrochemical response of the cell. In addition, when the decomposition product of the non-aqueous solvent is accumulated, it is not possible to smoothly insert and extract lithium ions to the negative electrode, and the electrochemical characteristics in the case of using in a wide temperature range are easily deteriorated.
  • lithium secondary batteries using lithium metal or an alloy thereof, a metal simple substance such as tin or silicon, or a metal oxide as a negative electrode material have a high initial capacity, but pulverization proceeds during use as an electricity storage device. It is known that the reductive decomposition of the non-aqueous solvent occurs in an accelerated manner and the battery performance such as the battery capacity and the cycle characteristics is greatly reduced compared to the negative electrode of the carbon material. In addition, when pulverization of these negative electrode materials and decomposition products of non-aqueous solvent are accumulated, absorption and release of lithium ions to the negative electrode can not be performed smoothly, and the electrochemical characteristics are easily deteriorated when used in a wide temperature range. Become.
  • the positive electrode material and the non-aqueous electrolyte are used when the non-aqueous solvent in the non-aqueous electrolyte is charged.
  • decomposition products and gases generated by partial oxidation decomposition locally are deposited on the negative electrode surface to inhibit the desired electrochemical reaction of the battery, so the electricity when used also in a wide temperature range It has been found to cause a decrease in chemical properties.
  • the battery performance has been lowered by the movement of lithium ions being inhibited or the battery being swollen by decomposition products and gas when the non-aqueous electrolyte is decomposed on the positive electrode and the negative electrode.
  • multifunctionalization of electronic devices equipped with lithium secondary batteries is in progress and power consumption is increasing. Therefore, the capacity of lithium secondary batteries is increasing, the density of the electrodes is increased, and the useless space volume in the batteries is reduced, and the volume occupied by the non-aqueous electrolyte in the batteries is small. It has become. Therefore, with the decomposition of a small amount of non-aqueous electrolyte, the electrochemical characteristics are likely to deteriorate when used in a wide temperature range.
  • Patent Document 1 discloses an electrolyte solution for a secondary battery containing an electrolyte salt and an electrolyte solvent, wherein the electrolyte solution contains a compound in which a cyclic carbonate group and a sulfonate group are linked via an alkylene group. There is. Patent Document 1 describes 1,3-dioxolane-2-onylmethyl allyl sulfonate as one of the compounds described above, and by adding to the electrolytic solution, the discharge capacity retention ratio after cycling of the battery is improved. It is supposed to be.
  • the present invention provides a non-aqueous electrolyte capable of improving the electrochemical properties in a wide temperature range, a storage device using the same, and a novel (2-oxo-1,3-dioxolan-4-yl) oxy compound
  • the purpose is
  • Patent Document 1 does not at all describe or suggest the effect of improving the low temperature discharge characteristics after high temperature storage.
  • cycle characteristics under high temperature, low temperature discharge characteristics after high temperature storage, etc. The fact is that no sufficient effect has been obtained for the problem of improving the electrochemical characteristics in a wide temperature range of. Therefore, the present inventors have intensively studied to solve the above problems, and by containing a specific compound in a non-aqueous electrolyte in which an electrolyte salt is dissolved in a non-aqueous solvent, a wide temperature range can be obtained.
  • the inventors have found that the electrochemical characteristics of a storage device, in particular, the lithium battery can be improved, and the present invention has been completed.
  • the present invention provides the following (1), (2) and (3).
  • R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3.
  • R 4 represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, It represents an aryl group having 6 to 12 carbon atoms or an alkoxycarbonyl group having 2 to 6 carbon atoms.
  • R 5 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or 7 to 13 carbon atoms It represents an aralkyl group, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • R 6 and R 7 each independently represent a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms.
  • n is 3
  • at least one hydrogen atom of the alkyl group, the aralkyl group, the aryl group, the alkoxycarbonyl group, the alkoxy group, and the aryloxy group may be substituted by a halogen atom.
  • a power storage device comprising a positive electrode, a negative electrode, and a non-aqueous electrolytic solution in which an electrolyte salt is dissolved in a non-aqueous solvent, wherein the non-aqueous electrolytic solution is the non-aqueous electrolytic solution according to (1) Power storage device characterized by.
  • R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3.
  • R 5 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or 7 to 13 carbon atoms It represents an aralkyl group, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • R 6 and R 7 each independently represent a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms.
  • R 9 represents a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or 7 to 13 carbon atoms in which at least one hydrogen atom is substituted by a halogen atom And an aralkyl group, an aryl group having 6 to 12 carbon atoms, or an alkoxycarbonyl group having 2 to 6 carbon atoms.
  • n is 3
  • at least one hydrogen atom of the alkyl group, the aralkyl group, the aryl group, the alkoxycarbonyl group, the alkoxy group, and the aryloxy group may be substituted by a halogen atom.
  • a non-aqueous electrolyte capable of improving the electrochemical characteristics of a storage device over a wide temperature range, particularly the low temperature discharge characteristics after high temperature charge storage, a storage device such as a lithium secondary battery using the same, and a novel (2-oxo-1,3-dioxolan-4-yl) oxy compounds can be provided.
  • the present invention relates to a non-aqueous electrolytic solution and an electricity storage device using the same.
  • the non-aqueous electrolytic solution of the present invention is a non-aqueous electrolytic solution in which an electrolyte salt is dissolved in a non-aqueous solvent, and is represented by the general formula (I) in the non-aqueous electrolytic solution (2-oxo-1, It is characterized by containing a 3-dioxolan-4-yl) oxy compound.
  • the compound used in the present invention is a cyclic carbonate in which a polar group is directly bonded to a ring without an alkylene group as described in the general formula (I). Therefore, the decomposition is more electrochemical than that of 1,3-dioxolane-2-onylmethyl allyl sulfonate, which is a compound in which the cyclic carbonate group described in Patent Document 1 and a sulfonate group as a polar group are linked via an alkylene group. Forming a dense and heat-resistant film on the positive electrode and the negative electrode. Therefore, it is considered that the electrochemical characteristics in a wide temperature range such as the low temperature discharge characteristics after high temperature charge storage can be improved.
  • the compound contained in the non-aqueous electrolytic solution of the present invention is a (2-oxo-1,3-dioxolan-4-yl) oxy compound represented by the following general formula (I).
  • R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3.
  • R 4 represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, It represents an aryl group having 6 to 12 carbon atoms or an alkoxycarbonyl group having 2 to 6 carbon atoms.
  • R 5 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or 7 to 13 carbon atoms It represents an aralkyl group, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • R 6 and R 7 each independently represent a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms.
  • n is 3
  • at least one hydrogen atom of the alkyl group, the aralkyl group, the aryl group, the alkoxycarbonyl group, the alkoxy group, and the aryloxy group may be substituted by a halogen atom.
  • R 1 include halogen atoms such as hydrogen atom, fluorine atom, chlorine atom and bromine atom; methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group and n-hexyl group And straight-chain alkyl groups such as isopropyl group, sec-butyl group, 2-pentyl group, 3-pentyl group, tert-butyl group, tert-amyl group and the like branched alkyl groups; fluoromethyl group, difluoromethyl group Group, trifluoromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 3,3-difluoropropyl group Halogenated alkyl groups such as 3,3,3-trifluoropropyl, 2,2,3,3
  • R 1 hydrogen atom, fluorine atom, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, sec-butyl group, 2 -Pentyl group, tert-butyl group, tert-amyl group, trifluoromethyl group, 2-fluoroethyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group, vinyl group, 1-propen-1-yl group, 2-propene -1-yl group, 1-propen-2-yl group, ethynyl group, 2-propynyl group, 2-butynyl group, benzyl group, 4-methylbenzyl group, phenyl group, 4-methylphenyl group, acetyloxy group, Propionyloxy group, fluorosulfonyloxy group
  • R 2 and R 3 independently include halogen atoms such as hydrogen atom, fluorine atom, chlorine atom and bromine atom; methyl group, ethyl group, n-propyl group, n-butyl group, n- Straight-chain alkyl groups such as pentyl group and n-hexyl group; branched alkyl groups such as isopropyl group, sec-butyl group, 2-pentyl group, pentan-3-yl group, tert-butyl group and tert-amyl group Alkyl group; fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3-chloro Propyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3-t
  • each of R 2 and R 3 independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a sec-butyl group, or tert.
  • -Butyl group or trifluoromethyl group is preferable, and a hydrogen atom, a fluorine atom or a methyl group is more preferable.
  • R 4 include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl; isopropyl and sec-butyl; Branched alkyl groups such as 2-pentyl group, 3-pentyl group, tert-butyl group, tert-amyl group; fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2, Halogenated alkyl groups such as 2,3,3,3-pentafluoropropyl group; cycloamides such as cyclopropyl group, cyclobutyl group, cyclopentyl group
  • Aralkyl group phenyl group, 2-methyl Aryl groups such as hexyl group, 3-methylphenyl group, 4-methylphenyl group, 4-tert-butylphenyl group; 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-trifluoromethyl Phenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 4-fluoro-2-trifluoromethylphenyl group, 4-fluoro-3-trifluoromethylphenyl group, 2,6-difluorophenyl group Halogenated aryl groups such as 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, perfluorophenyl and the like; methoxycarbonyl group, ethoxycarbonyl group And the like.
  • 2-methyl Aryl groups such as hexyl group, 3-
  • R 4 methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, fluoromethyl group, chloromethyl group, trifluoromethyl group, 2-fluoroethyl group, cyclopropyl group , Cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, vinyl group, 1-propen-1-yl group, ethynyl group, 2-propynyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4 -Methylphenyl group, 4-fluorophenyl group, 4-trifluoromethylphenyl group, methoxycarbonyl group, or ethoxycarbonyl group is preferable, and methyl group, ethyl group, isopropyl group, trifluoromethyl group, cyclopropyl group, cyclohex
  • R 5 include halogen atoms such as fluorine atom, chlorine atom and bromine atom; straight lines such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group and n-hexyl group -Chain alkyl groups; branched alkyl groups such as isopropyl, sec-butyl, 2-pentyl and 3-pentyl; fluoromethyl, chloromethyl, trifluoromethyl and 2,2,2- Halogenated alkyl groups such as trifluoroethyl group and 1,1,2,2,3,3,4,4,4-nonafluorobutyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group Cycloalkyl groups such as hexyl group; alkenyl groups such as vinyl group, 1-propen-1-yl group, 2-propyl
  • R 6 and R 7 are each independently a halogen atom such as fluorine atom, chlorine atom or bromine atom; methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentoxy group, straight-chain alkoxy groups such as n-hexyloxy group; branched alkoxy such as isopropoxy group, sec-butoxy group, 2-pentoxy group, pentan-3-yloxy group, tert-butoxy group, tert-amyloxy group and the like Group: 2-fluoroethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 3,3-difluoropropoxy group, 3,3 Halogen such as 3, 3-trifluoropropoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group
  • R 6 and R 7 each independently represent a fluorine atom, chlorine atom, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, isopropoxy group, sec-butoxy group, tert-butoxy group Group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, phenoxy Group, 2-methyl phenoxy group, 3-methyl phenoxy group, 4-methyl phenoxy group, 2-fluoro phenoxy group 4- fluoro phenoxy group, or 4- trifluoromethyl phenoxy group is preferable, and a fluorine atom, a methoxy group, an ethoxy group , 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy or phenoxy is more preferred.
  • E15, F1 to F3, F5 to F7, F9 to F11, and G1 to G3 are preferably at least one member selected from the group consisting of A1, A2, A4, A7, A8, A16 to A18.
  • Dioxolan-4-yl sulfolofluoridate (structural formula C1), 2-oxo-1,3-dioxolan-4-yl methanesulfonate (structural formula C2), 2-oxo 1,3-dioxolan-4-yl trifluoromethanesulfonate (structural formula C7), 2-oxo-1,3-dioxolan-4-yl ethene sulfonate (structural formula C9), methyl (2-oxo-1,3-dioxolane 4-yl) sulfate (structural formula C17), 5-fluoro-2-oxo-1,3-dioxolan-4-yl methanesulfonate (structural formula C18), 5-methyl-2-oxo-1,3-dioxolane -4-yl methanesulfonate (structural formula C19), 2-oxo-1,3-dioxolane-4,5
  • particularly preferred compounds are 2-oxo-1,3-dioxolan-4-yl acetate (structural formula A1), 2-oxo-1,3-dioxolan-4-yl 2,2,2-triacetate Fluoroacetate (Structural formula A4), 2-oxo-1,3-dioxolan-4-yl acrylate (Structural formula A7), 2-oxo-1,3-dioxolan-4-yl methacrylate (Structural formula A8), bis ( 2-oxo-1,3-dioxolan-4-yl) oxalate (structural formula B1), 2-oxo-1,3-dioxolan-4-yl sulfolofluoridate (structural formula C1), 2-oxo-1, 3-Dioxolan-4-yl methanesulfonate (structural formula C2), 2-oxo-1,3-dioxolan-4
  • the (2-oxo-1,3-dioxolan-4-yl) oxy derivative compound of the present invention can be synthesized by the following two methods, but is not limited to these methods.
  • A Method by the reaction of an alkyl halide and a potassium salt of carboxylic acid
  • the above compound is obtained by reacting an alkyl halide and a potassium salt of carboxylic acid in a solvent by the method described in Chemische Berichte, 1970, 112 , 148. Can.
  • the above-mentioned compound can be obtained by reacting an alkyl halide and silver sulfonate in a solvent by the method described in Synthesis, 1971, 150.
  • the content of the (2-oxo-1,3-dioxolan-4-yl) oxy compound represented by the above general formula (I) contained in the non-aqueous electrolytic solution is not particularly limited.
  • the content is preferably 0.01 to 10% by mass in the water electrolyte. If the content is 10% by mass or less, there is little possibility that the film is excessively formed on the electrode and the low temperature characteristics are deteriorated, and if it is 0.01% by mass or more, the formation of the film is sufficient and a wide temperature
  • the above range is preferable because the improvement effect of the electrochemical characteristics in the range is enhanced.
  • the content is more preferably 0.05% by mass or more in the non-aqueous electrolyte, and still more preferably 0.1% by mass or more. Moreover, 5 mass% or less is more preferable, and, as for the upper limit, 3 mass% or less is still more preferable.
  • the (2-oxo-1,3-dioxolan-4-yl) oxy compound represented by the above general formula (I) is described in the following non-aqueous solvent, electrolyte salt, and others.
  • the combination of additives produces a unique effect that the electrochemical properties are synergistically improved over a wide temperature range.
  • Non-aqueous solvent As a non-aqueous solvent used for the non-aqueous electrolyte solution of this invention, 1 type (s) or 2 or more types selected from the group which consists of cyclic carbonate, chain
  • a chain ester more preferably to include a chain carbonate, and further to include both a cyclic carbonate and a chain ester.
  • both cyclic carbonate and linear carbonate are preferably included.
  • the term "linear ester" is used as a concept including linear carbonate and linear carboxylic acid ester.
  • the cyclic carbonates include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 4-fluoro-1,3-dioxolan-2-one (FEC), trans or Cis-4,5-difluoro-1,3-dioxolan-2-one (hereinafter collectively referred to as “DFEC”), vinylene carbonate (VC), vinyl ethylene carbonate (VEC), and 4-ethynyl-1 And 3-dioxolan-2-one (EEC), and ethylene carbonate (EC), propylene carbonate (PC), 4-fluoro-1,3-dioxolan-2-one (EC), and the like.
  • FEC vinylene carbonate
  • VC vinylene carbonate
  • VC 4-ethynyl-1,3-dioxolane
  • One or more members selected from the group consisting of 2-one is more preferred.
  • cyclic carbonates having an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond or a fluorine atom
  • the electrochemical characteristics in a high temperature environment are further improved. It is more preferable to include both a cyclic carbonate containing an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond and a cyclic carbonate having a fluorine atom.
  • VC, VEC, or EEC is preferable as a cyclic carbonate having an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond
  • FEC or DFEC is preferable as a cyclic carbonate having a fluorine atom.
  • the content of the cyclic carbonate having an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond is preferably 0.07% by volume or more, more preferably 0.2% by volume, relative to the total volume of the non-aqueous solvent.
  • the upper limit is preferably 7% by volume or less, more preferably 4% by volume or less, and still more preferably 2.5% by volume or less. It is preferable that the content is in the above range, since the electrochemical characteristics in a wider temperature range can be increased without impairing the Li ion permeability.
  • the content of the cyclic carbonate having a fluorine atom is preferably 0.07% by volume or more, more preferably 4% by volume or more, still more preferably 6% by volume or more, based on the total volume of the non-aqueous solvent.
  • the upper limit is preferably 35% by volume or less, more preferably 25% by volume or less, and further 15% by volume or less. It is preferable that the content is in the above range, since the electrochemical characteristics in a wider temperature range can be improved without deteriorating the Li ion permeability.
  • the non-aqueous solvent contains both cyclic carbonate having unsaturated bond such as carbon-carbon double bond or carbon-carbon triple bond and cyclic carbonate having fluorine atom
  • carbon relative to the content of cyclic carbonate having fluorine atom The content of cyclic carbonate having an unsaturated bond such as a carbon double bond or a carbon-carbon triple bond is preferably 0.2% by volume or more, more preferably 3% by volume or more, still more preferably 7% by volume or more
  • the upper limit thereof is preferably 40% by volume or less, more preferably 30% by volume or less, and further preferably 15% by volume or less. It is particularly preferable that the content is in the above range, since the electrochemical characteristics in a wider temperature range can be improved without impairing the Li ion permeability.
  • the non-aqueous solvent contains both ethylene carbonate and a cyclic carbonate having unsaturated bonds such as carbon-carbon double bonds or carbon-carbon triple bonds
  • the electrical properties over a wide temperature range of the film formed on the electrode The content of a cyclic carbonate having an unsaturated bond such as ethylene carbonate and a carbon-carbon double bond or a carbon-carbon triple bond is preferable with respect to the total volume of the non-aqueous solvent, since the chemical properties can be improved. Is 3% by volume or more, more preferably 5% by volume or more, still more preferably 7% by volume or more, and the upper limit thereof is preferably 45% by volume or less, more preferably 35% by volume or less, still more preferably 25% by volume % Or less.
  • These solvents may be used alone or in combination of two or more, since the effect of improving the electrochemical characteristics in a high temperature environment is further improved, which is preferable, and a combination of three or more is used. It is particularly preferred to Preferred combinations of these cyclic carbonates include EC and PC, EC and VC, PC and VC, VC and FEC, EC and FEC, PC and FEC, FEC and DFEC, EC and DFEC, PC and DFEC, VC and DFEC , VEC and DFEC, VC and EEC, EC and EEC, EC and PC and VC, EC and PC and FEC, EC and VC and FEC, EC and VC and VEC, EC and VC and EEC, EC and EEC and FEC, PC And VC and FEC, EC and VC and DFEC, PC and VC and DFEC, EC, PC and VC and FEC, or EC and PC and VC and DFEC, etc.
  • ⁇ Chain ester> As the chain ester, one or more asymmetric chains selected from the group consisting of methyl ethyl carbonate (MEC), methyl propyl carbonate (MPC), methyl isopropyl carbonate (MIPC), methyl butyl carbonate and ethyl propyl carbonate Carbonates; one or more symmetrical linear carbonates selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate and dibutyl carbonate; methyl pivalate, ethyl pivalate, pivalate 1 or 2 or more chain
  • MEC methyl ethy
  • dimethyl carbonate DMC
  • MEC methyl ethyl carbonate
  • MPC methyl propyl carbonate
  • MIPC methyl isopropyl carbonate
  • EA methyl butyl carbonate
  • a linear carbonate having a methyl group is preferable, and in particular, a linear carbonate having a methyl group is preferable.
  • chain ester in which at least one hydrogen atom is substituted by a fluorine atom is included.
  • chained esters in which at least one hydrogen atom is substituted with a fluorine atom include: 2,2-difluoroethyl acetate (DFEA), 2,2,2-trifluoroethyl acetate (TFEA), 2,2 -Difluoroethyl propionate, 2,2,2-trifluoroethyl propionate, methyl 2,2-difluoropropionate, methyl 2,2,2-trifluoropropionate, methyl (2,2-difluoroethyl) 1) At least one member selected from the group consisting of carbonate (MDFEC), methyl (2,2,2- trifluoroethyl) carbonate (MTFEC), and ethyl (2,2,2- trifluoroethyl) carbonate (ETF
  • TFEA 2,2,2-trifluoroethyl acetate
  • MDFEC 2,2-difluoroethyl carbonate
  • MDFEC methyl (2, 2, 2- trifluoroethyl) carbonate
  • EDFEC ethyl (2, 2, 2- trifluoroethyl) carbonate
  • a linear carbonate when using a linear carbonate, it is preferable to use 2 or more types. Furthermore, it is more preferable that both symmetrical linear carbonate and asymmetric linear carbonate are contained, and it is further preferable that the content of symmetrical linear carbonate is larger than that of asymmetric linear carbonate.
  • the content of the linear ester is not particularly limited, but is preferably in the range of 60 to 90% by volume with respect to the total volume of the non-aqueous solvent.
  • the content is 60% by volume or more, the viscosity of the non-aqueous electrolyte does not become too high, and when it is 90% by volume or less, the electrical conductivity of the non-aqueous electrolyte decreases and the electrochemical characteristics in a wide temperature range Since it is less likely to decrease, the above range is preferable.
  • the symmetrical linear carbonate comprises dimethyl carbonate.
  • the asymmetric linear carbonate has a methyl group, and methyl ethyl carbonate (MEC) is particularly preferable. In the above case, the electrochemical characteristics in a wider temperature range are improved, which is preferable.
  • the ratio of cyclic carbonate to linear ester is preferably 10/90 to 45/55, and more preferably 15/85 to 40/60, from the viewpoint of improving the electrochemical properties at high temperatures. Is more preferable, and 20/80 to 35/65 is even more preferable.
  • nonaqueous solvents In the present invention, other nonaqueous solvents can be added in addition to the above-mentioned nonaqueous solvents.
  • Other nonaqueous solvents include cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, etc., chains such as 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, etc.
  • the content of the other non-aqueous solvent is usually 1% by volume or more, preferably 2% by volume or more, and usually 40% by volume or less, preferably 30% by volume or less, based on the total volume of the non-aqueous solvent Preferably it is 20 volume% or less.
  • additives In order to improve the electrochemical properties over a wider temperature range, it is preferable to further add other additives to the non-aqueous electrolyte.
  • specific examples of the other additives include the following compounds (A) to (I).
  • nitriles selected from the group consisting of acetonitrile, propionitrile, succinonitrile, glutaronitrile, adiponitrile, pimeronitrile, suberonitrile, and sebaconitrile.
  • (F) One or more cyclic acetal compounds selected from the group consisting of 1,3-dioxolane, 1,3-dioxane, and 1,3,5-trioxane.
  • Linear carboxylic acid anhydrides such as acetic anhydride and propionic anhydride, succinic anhydride, maleic anhydride, 3-allyl succinic anhydride, glutaric anhydride, itaconic anhydride, and 3-sulfo-propionic anhydride Or one or more cyclic acid anhydrides selected from the group consisting of
  • cyclic phosphazene compounds selected from the group consisting of methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, and ethoxyheptafluorocyclotetraphosphazene.
  • nitriles one or more selected from the group consisting of succinonitrile, glutaronitrile, adiponitrile, and pimeronitrile are more preferable.
  • aromatic compounds one or two selected from biphenyl, terphenyl (o-, m-, p-form), fluorobenzene, cyclohexylbenzene, tert-butylbenzene, and tert-amylbenzene The above is more preferable, and one or more selected from the group consisting of biphenyl, o-terphenyl, fluorobenzene, cyclohexylbenzene and tert-amylbenzene are more preferable.
  • isocyanate compounds (C) one or more selected from hexamethylene diisocyanate, octamethylene diisocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate are more preferable.
  • the content of the compounds (A) to (C) is preferably 0.01 to 7% by mass in the non-aqueous electrolyte. In this range, the coating is sufficiently formed without becoming too thick, and the electrochemical properties in a wider temperature range are enhanced.
  • the content is more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and the upper limit thereof is 5% by mass or less in the non-aqueous electrolyte. Is more preferable, and 3% by mass or less is more preferable.
  • cyclic or chain-like S O group-containing compounds selected from (D) triple bond-containing compounds, (E) sultones, cyclic sulfites, sulfonic acid esters, and vinyl sulfones (however, triple bond-containing compounds, and the aforementioned general compounds) (F) cyclic acetal compounds, (G) phosphorus-containing compounds, (H) cyclic acid anhydrides, or (I) cyclic phosphazene compounds, which do not include specific compounds represented by any of the formulas It is preferable because the electrochemical properties in the temperature range are improved.
  • 2-propynyl methyl carbonate, 2-propynyl methacrylate, 2-propynyl methanesulfonic acid, 2-propynyl vinyl sulfonate, 2-propynyl 2- (methanesulfonyloxy) propionate One or two or more selected from (2-propynyl) ogitalate, methyl 2-propynyl oxyallate, ethyl 2-propynyl oxygenate, and 2-butyne-1,4-diyl dimethanesulfonate are preferable, and methanesulfonic acid 2-propynyl is preferred.
  • 1-type selected from the group consisting of vinylpropanoic acid 2-propynyl, 2- (methanesulfonyloxy) propionic acid 2-propynyl, di (2-propynyl) oxolate, and 2-butyne-1,4-diyl dimethanesulfonate Or two or more Preferred.
  • (E) Of the cyclic or chain-like S O group-containing compounds, 1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone, 2,2-dioxide-1,2-oxathiolane-4 One or more selected from the group consisting of -yl acetate, ethylene sulfate, pentafluorophenyl methanesulfonate and divinyl sulfone are more preferable.
  • the cyclic acetal compound (F) 1,3-dioxolane or 1,3-dioxane is preferable, and 1,3-dioxane is more preferable.
  • (G) As the phosphorus-containing compound, tris (2,2,2-trifluoroethyl) phosphate, tris (1,1,1,3,3,3-hexafluoropropan-2-yl) phosphate, methyl 2- (Dimethylphosphoryl) acetate, ethyl 2- (dimethylphosphoryl) acetate, methyl 2- (diethylphosphoryl) acetate, ethyl 2- (diethylphosphoryl) acetate, 2-propynyl 2- (dimethylphosphoryl) acetate, 2-propynyl 2 -(Diethylphosphoryl) acetate, methyl 2- (dimethoxyphosphoryl) acetate, ethyl 2- (dimethoxyphosphoryl) acetate, methyl 2- (diethoxyphosphoryl) acetate, ethyl 2- (diethoxyphosphoryl) acetate, 2-propynyl 2- (Dimet Preferred is cyphosphoryl) acetate or 2-propyny
  • the cyclic phosphazene compound is preferably a cyclic phosphazene compound such as methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene or phenoxypentafluorocyclotriphosphazene, and is preferably methoxypentafluorocyclotriphosphazene or ethoxypentafluorocyclo Triphosphazene is more preferred.
  • the content of the compounds (D) to (I) is preferably 0.001 to 5% by mass in the non-aqueous electrolyte. In this range, the coating is sufficiently formed without becoming too thick, and the electrochemical properties in a wider temperature range are enhanced.
  • the content is more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and the upper limit thereof is 3% by mass or less in the non-aqueous electrolytic solution. Is more preferable, and 2% by mass or less is more preferable.
  • LiFSI lithium bis (fluo
  • lithium salt selected from the group consisting of LiBOB, LiDFOB, LiTFOP, LiDFOP, LiPO 2 F 2 , LiTFMSB, LMS, LES, LFES, FSO 3 Li, and LiFSI, LiDFOP, LiPO It is more preferable to include a lithium salt selected from the group consisting of 2 F 2 , LES, and LiFSI.
  • the total content of the lithium salt in the non-aqueous solvent is preferably 0.001 M or more and 0.5 M or less. Within this range, the effect of improving the electrochemical characteristics in a wide temperature range is further exhibited. Preferably it is 0.01 M or more, More preferably, it is 0.03 M or more, More preferably, it is 0.04 M or more. The upper limit thereof is preferably 0.4 M or less, more preferably 0.2 M or less.
  • M represents mol / L.
  • lithium salt As an electrolyte salt used for this invention, the following lithium salt is mentioned suitably.
  • inorganic lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 , LiPO 2 F 2 , LiN (SO 2 F) 2 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2, LiCF 3 SO 3, LiC (SO 2 CF 3) 3, LiPF 4 (CF 3) 2, LiPF 3 (C 2 F 5) 3, LiPF 3 (CF 3) 3, LiPF 3 (iso-C 3 F 7 ) 3 , lithium salts containing a linear fluorinated alkyl group such as LiPF 5 (iso-C 3 F 7 ), (CF 2 ) 2 (SO 2 ) 2 NLi, (CF 2 ) 3 (SO 2 )
  • LiPF 6 LiBF 4, LiPO 2 F 2, LiN (SO 2 F) 2, LiN (SO 2 CF 3) 2, and LiN (SO 2 C 2 F 5 ) 1 kind or 2 selected from 2
  • the species is more preferable, and LiPF 6 is more preferable.
  • the concentration of the electrolyte salt is preferably 0.3 M or more, more preferably 0.7 M or more, and still more preferably 1.1 M or more, in the non-aqueous electrolyte.
  • the upper limit thereof is preferably 2.5 M or less, more preferably 2.0 M or less, and still more preferably 1.6 M or less.
  • preferable combinations of these electrolyte salts include LiPF 6 and at least one lithium selected from LiBF 4 , LiN (SO 2 CF 3 ) 2 , and LiN (SO 2 F) 2 [LiFSI]. It is preferred that the salt be contained in the non-aqueous electrolyte.
  • the proportion of lithium salt other than LiPF 6 in the non-aqueous solvent is 0.001 M or more, the effect of improving the electrochemical characteristics in a wide temperature range is easily exhibited, and if it is 1.0 M or less, the wide temperature range It is preferable because there is little concern that the improvement effect of the electrochemical characteristics in
  • the content of lithium salt other than LiPF 6 is preferably 0.01 M or more, more preferably 0.03 M or more, still more preferably 0.04 M or more, and the upper limit thereof is preferably 0.8 M or less, more preferably It is 0.6 M or less, more preferably 0.4 M or less.
  • the non-aqueous electrolytic solution of the present invention can be obtained, for example, by mixing the above-mentioned non-aqueous solvent, adding to the above-mentioned electrolytic salt and the above-mentioned non-aqueous electrolytic solution, It can be obtained by adding a 3-dioxolan-4-yl) oxy compound. Under the present circumstances, it is preferable to refine
  • the non-aqueous electrolyte solution of the present invention can be used in the following first to fourth electricity storage devices, and as the non-aqueous electrolyte, not only liquid ones but also gelled ones can be used. Furthermore, the non-aqueous electrolytic solution of the present invention can also be used for solid polymer electrolytes. Above all, it is preferable to use as a first storage battery device (that is, for lithium battery) or a fourth storage battery device (that is, for lithium ion capacitor) that uses lithium salt for electrolyte salt. It is more preferable to use for lithium secondary batteries.
  • the lithium battery which is the first electricity storage device, is a general term for lithium primary batteries and lithium secondary batteries, and the term lithium secondary battery is used as a concept including so-called lithium ion secondary batteries.
  • the lithium battery of the present invention comprises a positive electrode, a negative electrode, and the non-aqueous electrolytic solution in which an electrolyte salt is dissolved in a non-aqueous solvent.
  • the constituent members such as the positive electrode and the negative electrode other than the non-aqueous electrolyte can be used without particular limitation.
  • a positive electrode active material of a positive electrode for a lithium secondary battery a composite metal oxide with lithium containing one or more selected from the group consisting of cobalt, manganese, and nickel is used. These positive electrode active materials can be used singly or in combination of two or more.
  • lithium composite metal oxides for example, LiCoO 2 , LiCo 1 -x M x O 2 (where M is Sn, Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn, and One or more elements selected from Cu, 0.001 ⁇ x ⁇ 0.05), LiMn 2 O 4 , LiNiO 2 , LiCo 1-x Ni x O 2 (0.01 ⁇ x ⁇ 1), LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 0.5 Mn 0.3 Co 0.2 O 2 , LiNi 0.8 Mn 0.1 Co 0.1 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , LiNi 1/2 Mn 3/2 O 4 , solid solution of Li 2 MnO 3 and LiMO 2 (M is a transition metal such as Co, Ni, Mn, Fe, etc.), and LiNi consisting of 1/2 Mn 3/2 O 4 More 1 or more are suitably exemplified chosen, or two or more is more preferable. Further, LiM
  • the electrochemical characteristics are likely to be degraded in a high temperature environment due to a reaction with an electrolyte during charge, but in the lithium secondary battery according to the present invention The deterioration of these electrochemical properties can be suppressed.
  • the non-aqueous solvent is generally decomposed on the surface of the positive electrode by the catalytic action of Ni, and the resistance of the battery tends to increase.
  • the electrochemical characteristics in a high temperature environment tend to be deteriorated, but the lithium secondary battery according to the present invention is preferable because the deterioration of these electrochemical characteristics can be suppressed.
  • the above effect is remarkable when the positive electrode active material in which the ratio of the atomic concentration of Ni to the atomic concentration of all transition metal elements in the positive electrode active material exceeds 10 atomic% is preferable, and 20 atomic% or more is more preferable. And 30 atomic% or more is particularly preferable.
  • LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 0.5 Mn 0.3 Co 0.2 O 2 , LiNi 0.8 Mn 0.1 Co 0.1 O 2 , One or more selected from the group consisting of LiNi 1/2 Mn 3/2 O 4 and LiNi 0.8 Co 0.15 Al 0.05 O 2 is preferably mentioned.
  • a lithium-containing olivine-type phosphate can also be used as the positive electrode active material.
  • a lithium-containing olivine-type phosphate containing one or more selected from the group consisting of iron, cobalt, nickel and manganese include one or more selected from LiFePO 4 , LiCoPO 4 , LiNiPO 4 , LiMnPO 4 , and LiFe 1-x Mn x PO 4 (0.1 ⁇ x ⁇ 0.9).
  • lithium-containing olivine-type phosphates may be substituted with other elements, and some of iron, cobalt, nickel and manganese may be replaced with Co, Mn, Ni, Mg, Al, B, Ti, V, Nb Alternatively, it may be substituted with one or more elements selected from Cu, Zn, Mo, Ca, Sr, W, and Zr, or may be coated with a compound or carbon material containing these other elements. Among these, LiFePO 4 or LiMnPO 4 is preferred.
  • the lithium-containing olivine-type phosphate can also be used, for example, as a mixture with the above-mentioned positive electrode active material.
  • the lithium-containing olivine-type phosphate forms a stable phosphoric acid (PO 4 ) structure and is excellent in thermal stability at the time of charging, so that it can improve the electrochemical characteristics in a wide temperature range.
  • the positive electrode for lithium primary battery CuO, Cu 2 O, Ag 2 O, Ag 2 CrO 4, CuS, CuSO 4, TiO 2, TiS 2, SiO 2, SnO, V 2 O 5, V 6 O 12 , VO x , Nb 2 O 5 , Bi 2 O 3 , Bi 2 Pb 2 O 5 , Sb 2 O 3 , CrO 3 , Cr 2 O 3 , MoO 3 , WO 3 , SeO 2 , MnO 2 , Mn 2 O 3 Oxides or chalcogen compounds of one or more metal elements such as Fe 2 O 3 , FeO, Fe 3 O 4 , Ni 2 O 3 , NiO, CoO 3 , CoO etc., sulfur such as SO 2 , SOCl 2 etc. compounds of the general formula (CF x) fluorocarbon (graphite fluoride) represented by n, and the like. Among these, MnO 2 , V 2 O 5 , fluorinated graphite and the like are preferable.
  • the conductive agent of the positive electrode is not particularly limited as long as it is an electron conductive material which does not cause a chemical change.
  • graphite such as natural graphite (scalate graphite etc.), artificial graphite etc., carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black or thermal black etc. may be mentioned.
  • graphite and carbon black may be appropriately mixed and used.
  • the amount of the conductive agent added to the positive electrode mixture is preferably 1 to 10% by mass, and more preferably 2 to 5% by mass.
  • the positive electrode includes the above-mentioned positive electrode active material as a conductive agent such as acetylene black and carbon black, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), copolymer of styrene and butadiene (SBR), acrylonitrile and butadiene Mixed with a binder such as copolymer (NBR), carboxymethyl cellulose (CMC), ethylene propylene diene terpolymer, etc., added with a high boiling point solvent such as 1-methyl-2-pyrrolidone and kneaded to prepare a positive electrode mixture Then, the positive electrode mixture is applied to an aluminum foil of a current collector, a stainless steel lath plate, etc., dried and pressure-molded, and then under a vacuum at a temperature of about 50 ° C.
  • a conductive agent such as acetylene black and carbon black, polytetrafluoroethylene (PTFE), polyvinylidene flu
  • the density of the part except the collector of the positive electrode is usually at 1.5 g / cm 3 or more, for further increasing the capacity of the battery, it is preferably 2 g / cm 3 or more, more preferably, 3 g / cm 3 It is the above, More preferably, it is 3.6 g / cm 3 or more. The upper limit thereof is preferably 4 g / cm 3 or less.
  • a highly crystalline carbon material such as artificial graphite or natural graphite in the ability to absorb and release lithium ions
  • the lattice spacing (d 002 ) of the lattice plane ( 002 ) is 0.
  • the upper limit of the peak intensity ratio I (110) / I (004) is preferably 0.5 or less, and 0. 0. 3 or less is more preferable.
  • the highly crystalline carbon material (core material) is coated with a carbon material having a lower crystallinity than the core material, because the electrochemical characteristics in a wide temperature range are further improved.
  • the crystallinity of the coated carbon material can be confirmed by transmission electron microscopy (TEM).
  • TEM transmission electron microscopy
  • the use of a highly crystalline carbon material generally tends to react with the non-aqueous electrolyte during charging and to lower the electrochemical properties at low or high temperatures by increasing the interfacial resistance, but the lithium according to the present invention
  • the secondary battery has good electrochemical characteristics in a wide temperature range.
  • metal compounds capable of inserting and extracting lithium ions as the negative electrode active material include Si, Ge, Sn, Pb, P, Sb, Bi, Al, Ga, In, Ti, Mn, Fe, Co, Ni, Examples thereof include compounds containing at least one metal element such as Cu, Zn, Ag, Mg, Sr, or Ba. These metal compounds may be used in any form such as an alloy, an oxide, a nitride, a sulfide, a boride, an alloy with lithium, or any of an alloy, an oxide, an alloy with an oxide or lithium. It is preferable because it can increase the capacity. Among them, one containing at least one element selected from the group consisting of Si, Ge and Sn is preferable, and one containing at least one element selected from Si and Sn is more preferable because the capacity of the battery can be increased.
  • the negative electrode is kneaded using the same conductive agent, binder and high boiling point solvent as in the preparation of the above positive electrode to form a negative electrode mixture, and this negative electrode mixture is then applied to copper foil of the current collector and the like. After drying and pressure molding, it can be manufactured by heat treatment at a temperature of about 50 ° C. to 250 ° C. for about 2 hours under vacuum.
  • the density of the part excluding the current collector of the negative electrode is usually 1.1 g / cm 3 or more, and is preferably 1.5 g / cm 3 or more, more preferably 1.7 g to further increase the capacity of the battery. / cm 3 or more, the upper limit is preferably 2 g / cm 3 or less.
  • lithium metal or a lithium alloy is mentioned as a negative electrode active material for lithium primary batteries.
  • the structure of the lithium battery is not particularly limited, and a coin battery, a cylindrical battery, a prismatic battery, a laminate battery or the like having a single layer or multilayer separator can be applied.
  • the battery separator is not particularly limited, but a microporous film, woven fabric, non-woven fabric, etc. of a single layer or laminated layer of polyolefin such as polypropylene, polyethylene, ethylene-propylene copolymer, etc. can be used.
  • a laminate of polyolefin a laminate of polyethylene and polypropylene is preferable, and a three-layer structure of polypropylene / polyethylene / polypropylene is more preferable.
  • the thickness of the separator is preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more, still more preferably 4 ⁇ m or more, and the upper limit thereof is 30 ⁇ m or less, preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less.
  • the lithium secondary battery according to the present invention is excellent in electrochemical characteristics in a wide temperature range even when the charge termination voltage is 4.2 V or more, particularly 4.3 V or more, and further, the characteristics are excellent even at 4.4 V or more is there.
  • the discharge termination voltage can be usually 2.8 V or more, and further 2.5 V or more, but the lithium secondary battery in the present invention can be 2.0 V or more.
  • the current value is not particularly limited, it is usually used in the range of 0.1 to 30C.
  • the lithium battery in the present invention can be charged and discharged at -40 to 100 ° C, preferably -10 to 80 ° C.
  • a method of providing a safety valve on the battery cover or making a notch in a member such as a battery can or a gasket can also be adopted.
  • a current blocking mechanism that senses the internal pressure of the battery and cuts off the current can be provided on the battery cover.
  • the second electricity storage device of the present invention is an electricity storage device that contains the non-aqueous electrolyte solution of the present invention and stores energy using the electric double layer capacity at the interface between the electrolyte solution and the electrode.
  • One example of the present invention is an electric double layer capacitor.
  • the most typical electrode active material used for this storage device is activated carbon.
  • the bilayer capacity increases approximately in proportion to the surface area.
  • the third electricity storage device of the present invention is an electricity storage device that includes the non-aqueous electrolyte solution of the present invention and stores energy using the electrode doping / dedoping reaction.
  • the electrode active material used in the electricity storage device include metal oxides such as ruthenium oxide, iridium oxide, tungsten oxide, molybdenum oxide and copper oxide, and ⁇ -conjugated polymers such as polyacene and polythiophene derivatives. Capacitors using these electrode active materials can store energy associated with electrode doping / de-doping reactions.
  • a fourth electricity storage device of the present invention is an electricity storage device that includes the non-aqueous electrolyte solution of the present invention and stores energy using intercalation of lithium ions to a carbon material such as graphite which is a negative electrode. It is called a lithium ion capacitor (LIC).
  • the positive electrode include those using an electric double layer between an activated carbon electrode and an electrolytic solution, and those using a doping / dedoping reaction of a ⁇ -conjugated polymer electrode.
  • the electrolyte includes lithium salts such as at least LiPF 6.
  • the (2-oxo-1,3-dioxolan-4-yl) oxy derivative compound which is a novel compound of the present invention is represented by the following general formula (II).
  • R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3.
  • R 5 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or 7 to 13 carbon atoms It represents an aralkyl group, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • R 6 and R 7 each independently represent a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms.
  • R 9 represents a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or 7 to 13 carbon atoms in which at least one hydrogen atom is substituted by a halogen atom And an aralkyl group, an aryl group having 6 to 12 carbon atoms, or an alkoxycarbonyl group having 2 to 6 carbon atoms.
  • n is 3
  • at least one hydrogen atom of the alkyl group, the aralkyl group, the aryl group, the alkoxycarbonyl group, the alkoxy group, and the aryloxy group may be substituted by a halogen atom.
  • R 8 include halogen atoms such as hydrogen atom, fluorine atom, chlorine atom and bromine atom; methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and the like Straight-chain alkyl groups of: branched alkyl groups such as isopropyl group, sec-butyl group, 2-pentyl group, 3-pentyl group, tert-butyl group, tert-amyl group, etc .; fluoromethyl group, difluoromethyl group , Trifluoromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 3,3-difluoropropyl group And halogenated alkyl groups such as 3,3,3-trifluoropropyl
  • R 9 is a fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group Halogenated alkyl groups such as 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group; cyclopropyl group, Cycloalkyl groups such as cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl; ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 4-heptynyl, 1-methyl-2-propynyl, Alkynyl groups such as 1,1-dimethyl-2-propynyl group, 1-methyl-3-butynyl group, 1-methyl
  • fluoromethyl group trifluoromethyl group, 2-fluoroethyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, ethynyl group, 2-propynyl group, phenyl group, 2-methyl group A phenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-fluorophenyl group, 4-trifluoromethylphenyl group, methoxycarbonyl group or ethoxycarbonyl group is preferable, and a trifluoromethyl group, cyclopropyl group, cyclohexyl A group, ethynyl group, phenyl group, 4-fluorophenyl group, 4-trifluorophenyl group, methoxycarbonyl group or ethoxycarbonyl group is more preferable.
  • Specific compounds represented by the general formula (II) are the same as described and preferred in the specific compounds of the general formula (I) except for compounds having a structural formula of A1 to A3, A7 to A8, or A20. It is.
  • the filtrate is concentrated under reduced pressure, diethyl ether is added to the residue, and filtration is performed to obtain 2.00 g (yield 44%) of the target 2-oxo-1,3-dioxolan-4-yl methanesulfonate as a white solid.
  • the obtained 2-oxo-1,3-dioxolan-4-yl methanesulfonate was subjected to measurement of 1 H-NMR spectrum to confirm its structure. The results are shown below.
  • Synthesis Example 4 [Synthesis of 2-oxo-1,3-dioxolan-4-yl 2,2,2-trifluoroacetate (Structural Formula A4)]
  • silver methanesulfonate is changed to silver trifluoroacetate, and in the same manner as in the synthesis example 3, the target 2-oxo-1,3-dioxolan-4-yl 2,2,2-trifluoroacetate was obtained as a colorless oil.
  • the 1 H-NMR spectrum of the obtained 2-oxo-1,3-dioxolan-4-yl 2,2,2-trifluoroacetate was measured to confirm its structure. The results are shown below.
  • Synthesis Example 5 Synthesis of 2-oxo-1,3-dioxolan-4-yl ethene sulfonate (structural formula C9)]
  • the target 2-oxo-1,3-dioxolan-4-yl ethene sulfonate was obtained as a white solid.
  • the obtained 2-oxo-1,3-dioxolan-4-yl ethene sulfonate was subjected to measurement of 1 H-NMR spectrum to confirm its structure. The results are shown below.
  • the target dimethyl (2-oxo-1,3-dioxolan-4-yl) is obtained by isolating the residue by silica gel column chromatography (eluent: n-hexane / ethyl acetate (1: 1 to 1: 4)). 0.72 g (50% yield) of phosphate was obtained as an oil.
  • the obtained dimethyl (2-oxo-1,3-dioxolan-4-yl) phosphate was subjected to measurement of 1 H-NMR spectrum to confirm its structure. The results are shown below.
  • Synthesis Example 7 Synthesis of Diethyl (2-oxo-1,3-dioxolan-4-yl) phosphate (Structural Formula E11)]
  • dimethyl phosphate was changed to diethyl phosphate, and in the same manner as in Synthesis Example 6, the target diethyl (2-oxo-1,3-dioxolan-4-yl) phosphate was obtained as a white solid.
  • the obtained diethyl (2-oxo-1,3-dioxolan-4-yl) phosphate was subjected to measurement of 1 H-NMR spectrum to confirm its structure. The results are shown below.
  • Examples 1 to 24 and Comparative Examples 1 to 2 [Fabrication of lithium ion secondary battery] LiNi 0.33 Mn 0.33 Co 0.34 O 2 94% by mass, acetylene black (conductive agent) 3% by mass are mixed, and 3% by mass of polyvinylidene fluoride (binding agent) in advance is 1-methyl-2- The mixture was added to a solution dissolved in pyrrolidone and mixed to prepare a positive electrode mixture paste. The positive electrode material mixture paste was applied to one side of an aluminum foil (current collector), dried and pressurized, and cut into a predetermined size to prepare a strip-shaped positive electrode sheet. The density of the portion of the positive electrode excluding the current collector was 3.6 g / cm 3 .
  • a negative electrode mixture paste was prepared by adding 5% by mass to a solution in which 1% by mass was dissolved in 1-methyl-2-pyrrolidone and mixing.
  • the negative electrode material mixture paste was applied to one side of a copper foil (current collector), dried and pressurized, and cut into a predetermined size to prepare a negative electrode sheet.
  • the density of the part except the current collector of the negative electrode was 1.5 g / cm 3 .
  • the peak intensity I of the (110) plane of the graphite crystal and the ratio of the peak intensity I (004) of the (004) plane [I (110) / I (004) ) was 0.1.
  • the obtained positive electrode sheet, microporous polyethylene film separator, and negative electrode sheet were laminated in this order, and the non-aqueous electrolytic solution of the composition shown in Table 1 and Table 2 was added to prepare a laminate type battery.
  • Discharge capacity maintenance rate after high temperature cycle Using the battery fabricated by the above method, the battery is charged to a final voltage of 4.25 V for 3 hours at a constant current of 1 C and a constant voltage in a thermostatic chamber at 55 ° C., and then a discharge voltage of 3.0 V under a constant current of 1 C The discharging up to 1 cycle was repeated until this reached 300 cycles. And the discharge capacity maintenance factor after a cycle was calculated
  • required by the following formula. Discharge capacity retention rate (%) (discharge capacity at 300th cycle / discharge capacity at 1st cycle) ⁇ 100
  • Example 25 and Comparative Example 3 A positive electrode sheet was produced using lithium nickel manganate (LiNi 1/2 Mn 3/2 O 4 , positive electrode active material) in place of the positive electrode active material used in Example 1 and Comparative Example 1. 94% by mass of LiNi 1/2 Mn 3/2 O 4 coated with amorphous carbon and 3% by mass of acetylene black (conductive agent) are mixed, and 3% by mass of polyvinylidene fluoride (binding agent) is mixed in advance. The solution was added to a solution dissolved in methyl-2-pyrrolidone and mixed to prepare a positive electrode mixture paste.
  • lithium nickel manganate LiNi 1/2 Mn 3/2 O 4 coated with amorphous carbon and 3% by mass of acetylene black (conductive agent)
  • conductive agent 3% by mass of polyvinylidene fluoride (binding agent) is mixed in advance.
  • the solution was added to a solution dissolved in methyl-2-pyrrolidone and mixed to prepare a positive electrode mixture paste.
  • This positive electrode material mixture paste was applied on one side of an aluminum foil (current collector), dried, pressurized and cut into a predetermined size to prepare a positive electrode sheet, and the charge termination voltage at the time of battery evaluation.
  • a laminate type battery was produced in the same manner as in Example 4 and Comparative Example 1 except that the discharge termination voltage was set to 2.7 V, and the battery evaluation was performed. The results are shown in Table 4.
  • Examples 26, 27 and Comparative Example 4 A negative electrode sheet was produced using lithium titanate (Li 4 Ti 5 O 12 , a negative electrode active material) in place of the negative electrode active material used in Example 4 and Comparative Example 1. 80% by mass of lithium titanate and 15% by mass of acetylene black (conductive agent) are mixed, and 5% by mass of polyvinylidene fluoride (binder) is added to a solution previously dissolved in 1-methyl-2-pyrrolidone The mixture was mixed to prepare a negative electrode mixture paste. The negative electrode material mixture paste was applied to one side of a copper foil (current collector), dried, pressurized and cut into a predetermined size to prepare a negative electrode sheet, and the charge termination voltage at the time of battery evaluation.
  • lithium titanate Li 4 Ti 5 O 12
  • a negative electrode active material a negative electrode active material
  • Example 5 In the same manner as in Example 1 and Comparative Example 1, except that the voltage of the discharge was 2.8 V and the discharge end voltage was 1.2 V, and the composition of the non-aqueous electrolyte was changed to a predetermined one, a laminate type battery was produced. The battery was evaluated. The results are shown in Table 5.
  • Example 25 and Comparative Example 3 the same applies to the case where lithium titanate is used for the negative electrode and the case where lithium titanate is used for the negative electrode from the comparison of Examples 26 to 27 and Comparative Example 4 Effect is seen. Therefore, it is clear that the effect of the present invention is not dependent on a specific positive electrode or negative electrode.
  • non-aqueous electrolyte of the present invention also has the effect of improving the discharge characteristics of the lithium primary battery in a wide temperature range.
  • the non-aqueous electrolytic solution of the present invention By using the non-aqueous electrolytic solution of the present invention, it is possible to obtain an electricity storage device having excellent electrochemical characteristics in a wide temperature range.
  • the electric storage devices when used as a non-aqueous electrolyte for storage devices such as lithium secondary batteries mounted in hybrid electric vehicles, plug-in hybrid electric vehicles, battery electric vehicles, etc., the electric storage devices whose electrochemical characteristics are unlikely to deteriorate over a wide temperature range You can get
  • the novel compounds of the present invention due to their special structures, are generally used as materials for electrolyte applications, heat resistant applications, etc. in the fields of general chemistry, in particular in the fields of organic chemistry, electrochemistry, biochemistry and polymer chemistry. Are useful as intermediate materials such as electronic materials and polymer materials, or as battery materials.

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Abstract

L'invention concerne : une solution électrolytique non aqueuse capable de présenter des caractéristiques électrochimiques améliorées dans une large plage de températures, qui renferme un sel d'électrolyte dissous dans un solvant non aqueux, et qui est caractérisée en ce qu'elle contient un composé (2-oxo-1,3-dioxolan-4-yl)oxy représenté par la formule générale (I) ; un dispositif de stockage d'électricité ; et un nouveau composé (2-oxo-1,3-dioxolan-4-yl)oxy. (Dans la formule, R1 représente un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe cycloalkyle, un groupe alcényle, un groupe alcynyle, un groupe aralkyle, un groupe aryle, -OC(=O)-R4, -OS(=O)2-R5, ou -OP(=O)(-R6)-R7. . R2 et R3 représentent chacun indépendamment un atome d'hydrogène, un atome d'halogène ou un groupe alkyle, et n représente un nombre entier de 1 à 3. R4 représente un groupe alkyle, un groupe cycloalkyle, un groupe alcényle, un groupe alcynyle, un groupe aralkyle, un groupe aryle ou un groupe alcoxycarbonyle. R5 représente un atome d'halogène, un groupe alkyle, un groupe cycloalkyle, un groupe alcényle, un groupe alcynyle, un groupe aralkyle, un groupe aryle ou un groupe alcoxy. R6 et R7 représentent chacun indépendamment un atome d'halogène, un groupe alcoxy ou un groupe aryloxy. Dans le cas où n est égal à 1, L1 représente -C(=O)-R4, -S(=O)2-R5 ou -P(=O)(-R6)-R7. Dans le cas où n est égal à 2, L1 représente -C(=O)C(=O)-, -S(=O)2-, ou -P(=O)(-R6)-. Dans le cas où n est égal à 3, L1 représente -P(=O)(-)2.)
PCT/JP2017/026151 2017-07-19 2017-07-19 Solution électrolytique non aqueuse et dispositif de stockage d'électricité comprenant ladite solution WO2019016903A1 (fr)

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CN111725563A (zh) * 2019-03-18 2020-09-29 诺莱特电池材料(苏州)有限公司 一种锂离子电池非水电解液及锂离子电池
CN111883839A (zh) * 2020-08-03 2020-11-03 远景动力技术(江苏)有限公司 高压电解液及基于其的锂离子电池
WO2023016412A1 (fr) * 2021-08-09 2023-02-16 深圳新宙邦科技股份有限公司 Solution électrolytique non aqueuse et batterie
CN116315083A (zh) * 2021-12-20 2023-06-23 张家港市国泰华荣化工新材料有限公司 一种非水电解液及含有该非水电解液的锂离子电池
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

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CN111725563A (zh) * 2019-03-18 2020-09-29 诺莱特电池材料(苏州)有限公司 一种锂离子电池非水电解液及锂离子电池
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CN111883839A (zh) * 2020-08-03 2020-11-03 远景动力技术(江苏)有限公司 高压电解液及基于其的锂离子电池
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CN116315083B (zh) * 2021-12-20 2024-03-01 张家港市国泰华荣化工新材料有限公司 一种非水电解液及含有该非水电解液的锂离子电池
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

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