WO2020116574A1 - Solution électrolytique et dispositif électrochimique - Google Patents

Solution électrolytique et dispositif électrochimique Download PDF

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WO2020116574A1
WO2020116574A1 PCT/JP2019/047661 JP2019047661W WO2020116574A1 WO 2020116574 A1 WO2020116574 A1 WO 2020116574A1 JP 2019047661 W JP2019047661 W JP 2019047661W WO 2020116574 A1 WO2020116574 A1 WO 2020116574A1
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ppm
mass
electrolytic solution
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negative electrode
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PCT/JP2019/047661
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English (en)
Japanese (ja)
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薫平 山田
馨 今野
中村　真也
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日立化成株式会社
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Priority to JP2020560016A priority Critical patent/JP7380589B2/ja
Priority to KR1020217020256A priority patent/KR20210094065A/ko
Priority to CN201980091221.5A priority patent/CN113396493A/zh
Publication of WO2020116574A1 publication Critical patent/WO2020116574A1/fr

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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
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/64—Liquid electrolytes characterised by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 electrolytic solution and an electrochemical device.
  • Patent Document 1 discloses an electrolyte solution for a non-aqueous electrolyte battery containing a specific siloxane compound in order to improve cycle characteristics and internal resistance characteristics.
  • the present invention has an object to provide an electrolytic solution capable of improving the performance of an electrochemical device.
  • the present invention provides an electrolytic solution which exhibits a peak in at least one chemical shift range of ⁇ 180 ppm or more and ⁇ 150 ppm or less, and more than ⁇ 150 ppm and ⁇ 130 ppm or less in measurement by 19 F-NMR. provide.
  • the electrolytic solution may further show a peak within a range of a chemical shift of more than ⁇ 130 ppm and not more than ⁇ 110 ppm as measured by 19 F-NMR.
  • the present invention provides an electrochemical device including a positive electrode, a negative electrode, and the electrolytic solution described above.
  • the negative electrode preferably contains a carbon material.
  • the carbon material preferably contains graphite.
  • the negative electrode preferably further contains a material containing at least one element selected from the group consisting of silicon and tin.
  • the electrochemical device may be a non-aqueous electrolyte secondary battery or a capacitor.
  • an electrolytic solution capable of improving the performance of an electrochemical device.
  • FIG. 1 is a perspective view showing a non-aqueous electrolyte secondary battery as an electrochemical device according to an embodiment.
  • FIG. 2 is an exploded perspective view showing an electrode group of the secondary battery shown in FIG. 1.
  • 19 is a spectrum obtained by 19 F-NMR measurement, (a) is a spectrum for the electrolytic solution of Example 1, and (b) is a spectrum for the electrolytic solution of Example 2.
  • 9 is a spectrum obtained by 19 F-NMR measurement for the electrolytic solution of Comparative Example 2.
  • 19 is a spectrum obtained by 19 F-NMR measurement, (a) is a spectrum for the electrolytic solution of Example 3, and (b) is a spectrum for the electrolytic solution of Example 4.
  • FIG. 1 is a perspective view showing an electrochemical device according to one embodiment.
  • the electrochemical device is a non-aqueous electrolyte secondary battery.
  • the non-aqueous electrolyte secondary battery 1 includes an electrode group 2 including a positive electrode, a negative electrode, and a separator, and a bag-shaped battery exterior body 3 that houses the electrode group 2.
  • a positive electrode current collecting tab 4 and a negative electrode current collecting tab 5 are provided on the positive electrode and the negative electrode, respectively.
  • the positive electrode current collecting tab 4 and the negative electrode current collecting tab 5 project from the inside of the battery case 3 to the outside so that the positive electrode and the negative electrode can be electrically connected to the outside of the non-aqueous electrolyte secondary battery 1, respectively. ..
  • the non-aqueous electrolyte secondary battery 1 may be a battery (coin type, cylindrical type, laminated type, etc.) having a shape other than the so-called “laminate type” as described above.
  • the battery outer casing 3 may be a container formed of, for example, a laminated film.
  • the laminated film may be, for example, a laminated film in which a resin film such as a polyethylene terephthalate (PET) film, a metal foil such as aluminum, copper and stainless steel, and a sealant layer such as polypropylene are laminated in this order.
  • PET polyethylene terephthalate
  • metal foil such as aluminum, copper and stainless steel
  • a sealant layer such as polypropylene
  • FIG. 2 is an exploded perspective view showing an embodiment of the electrode group 2 in the non-aqueous electrolyte secondary battery 1 shown in FIG.
  • the electrode group 2 includes a positive electrode 6, a separator 7, and a negative electrode 8 in this order.
  • the positive electrode 6 and the negative electrode 8 are arranged such that the surfaces on the positive electrode mixture layer 10 side and the negative electrode mixture layer 12 side face the separator 7, respectively.
  • the positive electrode 6 includes a positive electrode current collector 9 and a positive electrode mixture layer 10 provided on the positive electrode current collector 9.
  • the positive electrode current collector 9 is provided with the positive electrode current collector tab 4.
  • the positive electrode current collector 9 is made of, for example, aluminum, titanium, stainless steel, nickel, baked carbon, conductive polymer, conductive glass, or the like.
  • the positive electrode current collector 9 may be one in which the surface of aluminum, copper, or the like is treated with carbon, nickel, titanium, silver, or the like for the purpose of improving adhesiveness, conductivity, and oxidation resistance.
  • the thickness of the positive electrode current collector 9 is, for example, 1 to 50 ⁇ m in terms of electrode strength and energy density.
  • the positive electrode material mixture layer 10 contains a positive electrode active material, a conductive agent, and a binder.
  • the thickness of the positive electrode mixture layer 10 is, for example, 20 to 200 ⁇ m.
  • the positive electrode active material may be, for example, lithium oxide.
  • the positive electrode active material may be, for example, a lithium phosphate.
  • the lithium phosphate include lithium manganese phosphate (LiMnPO 4 ), lithium iron phosphate (LiFePO 4 ), lithium cobalt phosphate (LiCoPO 4 ), and lithium vanadium phosphate (Li 3 V 2 (PO 4 ). 3 ).
  • the content of the positive electrode active material may be 80% by mass or more, or 85% by mass or more, and 99% by mass or less, based on the total amount of the positive electrode mixture layer.
  • the conductive agent may be carbon black such as acetylene black or Ketjen black, or carbon material such as graphite, graphene or carbon nanotube.
  • the content of the conductive agent may be, for example, 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more, and 50% by mass or less, 30% by mass, based on the total amount of the positive electrode mixture layer. Or less, or 15% by mass or less.
  • binder examples include resins such as polyethylene, polypropylene, polyethylene terephthalate, polymethylmethacrylate, polyimide, aromatic polyamide, cellulose and nitrocellulose; SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), fluororubber.
  • resins such as polyethylene, polypropylene, polyethylene terephthalate, polymethylmethacrylate, polyimide, aromatic polyamide, cellulose and nitrocellulose
  • SBR styrene-butadiene rubber
  • NBR acrylonitrile-butadiene rubber
  • fluororubber examples include fluororubber.
  • a fluorine-containing resin a resin having a nitrile group-containing monomer as a monomer unit, a polymer composition having an alkali metal ion (for example, lithium ion) ion conductivity, and the like.
  • the content of the binder may be, for example, 0.1% by mass or more, 1% by mass or more, or 1.5% by mass or more, based on the total amount of the positive electrode mixture layer, 30% by mass or less, 20% by mass. % Or less, or 10% by mass or less.
  • the separator 7 is not particularly limited as long as it electrically insulates between the positive electrode 6 and the negative electrode 8 while allowing ions to pass therethrough and has resistance to the oxidizing property on the positive electrode 6 side and the reducing property on the negative electrode 8 side. Not done.
  • Examples of the material (material) of the separator 7 include resins and inorganic materials.
  • the separator 7 is preferably a porous sheet or a non-woven fabric formed of polyolefin such as polyethylene or polypropylene from the viewpoint of being stable with respect to the electrolytic solution and excellent in liquid retaining property.
  • the inorganic substance examples include oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate.
  • the separator 7 may be, for example, a thin film substrate such as a nonwoven fabric, a woven fabric, or a microporous film to which a fibrous or particulate inorganic substance is attached.
  • the negative electrode 8 includes a negative electrode current collector 11 and a negative electrode mixture layer 12 provided on the negative electrode current collector 11.
  • the negative electrode current collector 11 is provided with a negative electrode current collector tab 5.
  • the negative electrode current collector 11 is made of copper, stainless steel, nickel, aluminum, titanium, baked carbon, conductive polymer, conductive glass, aluminum-cadmium alloy, or the like.
  • the negative electrode current collector 11 may be one in which the surface of copper, aluminum, or the like is treated with carbon, nickel, titanium, silver, or the like for the purpose of improving adhesion, conductivity, and reduction resistance.
  • the thickness of the negative electrode current collector 11 is, for example, 1 to 50 ⁇ m from the viewpoint of electrode strength and energy density.
  • the negative electrode mixture layer 12 contains, for example, a negative electrode active material and a binder.
  • the negative electrode active material is not particularly limited as long as it can absorb and release lithium ions.
  • the negative electrode active material include carbon materials, metal composite oxides, oxides or nitrides of Group IV elements such as tin, germanium, and silicon, simple substances of lithium, lithium alloys such as lithium aluminum alloys, Sn, Si, and the like. And a metal capable of forming an alloy with lithium.
  • the negative electrode active material is preferably at least one selected from the group consisting of carbon materials and metal composite oxides.
  • the negative electrode active material may be one type of these alone or a mixture of two or more types.
  • the shape of the negative electrode active material may be, for example, a particle shape.
  • the carbon material amorphous carbon material, natural graphite, composite carbon material obtained by forming a film of amorphous carbon material on natural graphite, artificial graphite (resin raw material such as epoxy resin, phenol resin, or petroleum, coal, etc. Obtained by firing a pitch-based raw material obtained from the above).
  • the metal composite oxide preferably contains one or both of titanium and lithium, and more preferably contains lithium.
  • the negative electrode active material may further contain a material containing at least one element selected from the group consisting of silicon and tin.
  • the material containing at least one element selected from the group consisting of silicon and tin may be a simple substance of silicon or tin, or a compound containing at least one element selected from the group consisting of silicon and tin.
  • the compound may be an alloy containing at least one element selected from the group consisting of silicon and tin. For example, in addition to silicon and tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver. , An alloy containing at least one selected from the group consisting of titanium, germanium, bismuth, antimony and chromium.
  • the compound containing at least one element selected from the group consisting of silicon and tin may be an oxide, a nitride, or a carbide, and specifically, for example, silicon oxide such as SiO, SiO 2 , and LiSiO.
  • silicon oxide such as SiO, SiO 2 , and LiSiO.
  • a silicon nitride such as Si 3 N 4 or Si 2 N 2 O, a silicon carbide such as SiC, a tin oxide such as SnO, SnO 2 or LiSnO.
  • the negative electrode mixture layer 12 preferably contains a carbon material as the negative electrode active material, more preferably contains graphite, and further preferably contains a carbon material and silicon and tin. It contains a mixture with a material containing at least one element selected from the group consisting of, and particularly preferably contains a mixture of graphite and silicon oxide.
  • the content of the material (silicon oxide) containing at least one element selected from the group consisting of silicon and tin in the mixture is 1% by mass or more, or 3% by mass or more, based on the total amount of the mixture. Well, it may be 30 mass% or less.
  • the content of the negative electrode active material may be 80% by mass or more, or 85% by mass or more, and 99% by mass or less, based on the total amount of the negative electrode mixture layer.
  • the binder and the content thereof may be the same as the binder and the content thereof in the positive electrode mixture layer described above.
  • the negative electrode mixture layer 12 may further contain a thickener to adjust the viscosity.
  • the thickener is not particularly limited, but may be carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, salts thereof, or the like.
  • the thickener may be one of these alone or a mixture of two or more thereof.
  • the content thereof is not particularly limited.
  • the content of the thickener may be 0.1% by mass or more, and preferably 0.2% by mass or more, based on the total amount of the negative electrode mixture layer, from the viewpoint of coatability of the negative electrode mixture layer. , And more preferably 0.5% by mass or more.
  • the content of the thickener may be 5% by mass or less, preferably 3% by mass, based on the total amount of the negative electrode mixture layer, from the viewpoint of suppressing a decrease in battery capacity or an increase in resistance between the negative electrode active materials. % Or less, and more preferably 2% by mass or less.
  • the electrolytic solution contains at least one chemical shift of ⁇ 180 ppm to ⁇ 150 ppm and ⁇ 150 ppm to ⁇ 130 ppm in 19 F-NMR (fluorine 19 nuclear magnetic resonance) measurement. A peak is shown within the range.
  • the electrolytic solution may show a peak in any range of ⁇ 180 ppm or more and ⁇ 150 ppm or less, and chemical shift of more than ⁇ 150 ppm and ⁇ 130 ppm or less.
  • the electrolytic solution may show peaks in two ranges of chemical shifts of -180 ppm or more and -150 ppm or less, and -150 ppm or more and -130 ppm or less, respectively.
  • the 19 F-NMR measurement of the electrolytic solution is performed under the following conditions.
  • Measuring device Avance neo made by Bruker Japan Measurement method: Single pulse method Observation nucleus: 19 F Spectral width: 90 kHz Pulse width: 15 ⁇ s (90° pulse) Pulse repetition time: 1 s
  • Reference substance C 6 H 5 CF 3 (external standard: ⁇ 63.9 ppm) Temperature: 23 °C Sample rotation speed: 20Hz
  • the electrolytic solution shows a peak (peak A) within the range of chemical shift of ⁇ 180 ppm or more and ⁇ 150 ppm or less. Even if the range of the chemical shift in which the peak A exists is ⁇ 175 ppm or more and ⁇ 155 ppm or less, ⁇ 170 ppm or more and ⁇ 158 ppm or less, ⁇ 168 ppm or more and ⁇ 160 ppm or less, ⁇ 165 ppm or more and ⁇ 160 ppm or less, or ⁇ 163 ppm or more and ⁇ 161 ppm or less.
  • the peak A may be a peak group consisting of a plurality of peaks existing in the range of chemical shift of ⁇ 180 ppm or more and ⁇ 150 ppm or less.
  • the electrolytic solution exhibits a peak (peak B) within the range of the chemical shift of more than ⁇ 150 ppm and less than ⁇ 130 ppm.
  • the range of the chemical shift in which peak B exists is -145 ppm or more and -130 ppm or less, -143 ppm or more and -133 ppm or less, -140 ppm or more and -130 ppm or less, -140 ppm or more and -133 ppm or less, -140 ppm or more and -135 ppm or less, or -138 ppm or more. It may be -133 ppm or less.
  • the peak B may be a peak group composed of a plurality of peaks existing within the range of the chemical shift of more than -150 ppm and less than -130 ppm.
  • each of the above-mentioned peaks is derived from the compound represented by the following formula (1) contained in the electrolytic solution. That is, in one embodiment, the electrolytic solution contains a compound represented by the following formula (1).
  • R 1 to R 3 each independently represents an alkyl group or a fluorine atom
  • R 4 represents an alkylene group
  • R 5 represents an organic group containing a sulfur atom or a nitrogen atom
  • R 1 to R At least one of 3 is a fluorine atom.
  • R 1 to R 3 are alkyl groups
  • the alkyl groups may have 1 or more carbon atoms and 3 or less carbon atoms.
  • R 1 to R 3 may be a methyl group, an ethyl group, or a propyl group, and may be linear or branched.
  • At least one of R 1 to R 3 is a fluorine atom.
  • any one of R 1 to R 3 is a fluorine atom, that is, when the electrolytic solution contains a compound represented by the following formula (2), the electrolytic solution has the peak A mentioned above in 19 F-NMR measurement.
  • R 2 and R 3 each independently represent an alkyl group
  • R 4 represents an alkylene group
  • R 5 represents an organic group containing a sulfur atom or a nitrogen atom.
  • the electrolytic solution contains a compound represented by the following formula (3) or (4) In that case, the electrolytic solution exhibits the peak B described above in the 19 F-NMR measurement.
  • R 3 represents an alkyl group
  • R 4 represents an alkylene group
  • R 5 represents an organic group containing a sulfur atom or a nitrogen atom.
  • R 4 represents an alkylene group
  • R 5 represents an organic group containing a sulfur atom or a nitrogen atom.
  • the carbon number of the alkylene group represented by R 4 in the above formulas (1) to (4) may be 1 or more or 2 or more, and 5 or less or 4 or less.
  • the alkylene group represented by R 4 may be a methylene group, an ethylene group, a propylene group, a butylene group, or a pentylene group, and may be linear or branched.
  • R 5 in the above formulas (1) to (4) may be an organic group containing a sulfur atom.
  • R 5 When R 5 is an organic group containing a sulfur atom, R 5 may be a group represented by the following formula (5) in one embodiment.
  • R 6 represents an alkyl group.
  • the alkyl group may be the same as the alkyl group represented by R 1 to R 3 described above. * Indicates a bond (same below).
  • R 5 When R 5 is an organic group containing a sulfur atom, R 5 may be a group represented by the following formula (6) in another embodiment.
  • R 7 represents an alkyl group.
  • the alkyl group may be the same as the alkyl group represented by R 1 to R 3 described above.
  • R 5 When R 5 is an organic group containing a sulfur atom, R 5 may be a group represented by the following formula (7) in another embodiment.
  • R 8 represents an alkyl group.
  • the alkyl group may be the same as the alkyl group represented by R 1 to R 3 described above.
  • R 5 may be an organic group containing a nitrogen atom in another embodiment.
  • R 5 When R 5 is an organic group containing a nitrogen atom, R 5 may be a group represented by the following formula (8) in one embodiment.
  • R 9 and R 10 each independently represent a hydrogen atom or an alkyl group.
  • the alkyl group may be the same as the alkyl group represented by R 1 to R 3 described above.
  • the number of silicon atoms in one molecule of the compound represented by formula (1) is one. That is, in one embodiment, the organic group represented by R 5 does not include a silicon atom.
  • the content of the compound represented by the formula (1) is preferably 0.001% by mass or more and 0.005% by mass or more, based on the total amount of the electrolytic solution, from the viewpoint of further improving the performance of the electrochemical device. 0.01 mass% or more, 0.05 mass% or more, 0.1 mass% or more, 0.3 mass% or more, or 0.5 mass% or more, and preferably 10 mass% or less, 7 mass% % Or less, 5% by mass or less, 3% by mass or less, 2% by mass or less, 1.5% by mass or less, or 1% by mass or less.
  • the electrolytic solution may further show a peak (peak C) within the range of the chemical shift of more than ⁇ 130 ppm and not more than ⁇ 110 ppm in addition to the above-mentioned peak A and peak B.
  • the range of chemical shift in which peak C exists may be ⁇ 128 ppm or more and ⁇ 115 ppm or less, ⁇ 126 ppm or more and ⁇ 120 ppm or less, ⁇ 125 ppm or more and ⁇ 122 ppm or less, or ⁇ 123 ppm or more and ⁇ 120 ppm or less.
  • the peak C may be a peak group composed of a plurality of peaks existing within the range of the chemical shift of more than -130 ppm and less than -110 ppm.
  • peak C is derived from the fluorine-containing cyclic carbonate that may be contained in the electrolytic solution. That is, in one embodiment, the electrolytic solution may contain a fluorine-containing cyclic carbonate.
  • Fluorine-containing cyclic carbonate is a cyclic carbonic acid ester containing a fluorine atom in the molecule.
  • the fluorine-containing cyclic carbonate is a cyclic carbonic acid ester containing a fluoro group.
  • the fluorine-containing cyclic carbonate is not particularly limited as long as it is a cyclic carbonic acid ester containing a fluoro group.
  • fluoro-1,3-dioxolan-2-one fluoroethylene carbonate; FEC
  • FEC fluoroethylene carbonate
  • 1,2 It may be difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2-trifluoroethylene carbonate, 1,1,2,2-tetrafluoroethylene carbonate and the like.
  • the fluorine-containing cyclic carbonate is preferably 4-fluoro-1,3-dioxolan-2-one (fluoroethylene carbonate; FEC).
  • the content of the fluorine-containing cyclic carbonate is preferably 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% based on the total amount of the electrolytic solution, from the viewpoint of further improving the performance of the electrochemical device. As described above, the content is 0.05 mass% or more, or 0.1 mass% or more, and 5 mass% or less, 3 mass% or less, 2 mass% or less, or 1 mass% or less.
  • the total content of the compound represented by formula (1) and the content of the fluorine-containing cyclic carbonate is From the viewpoint of further improving the performance of the electrochemical device, based on the total amount of the electrolytic solution, preferably 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.1 mass% or more, Or 0.5 mass% or more, preferably 10 mass% or less, 7 mass% or less, 5 mass% or less, 3 mass% or less, 2 mass% or less, 1.5 mass% or less, or 1 mass% or less Is.
  • the electrolytic solution may further contain an electrolyte salt, a non-aqueous solvent, and an additive in addition to the compound represented by the formula (1) and the fluorine-containing cyclic carbonate.
  • the electrolyte salt may be, for example, a lithium salt.
  • the lithium salt is, for example, LiPF 6 , LiBF 4 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiCH 3 SO 3 , CF 3 SO 2 OLi, LiN(SO 2 F) 2 (Li[FSI], lithium bis. Fluorosulfonylimide), LiN(SO 2 CF 3 ) 2 (Li[TFSI], lithium bistrifluoromethanesulfonylimide), and at least one selected from the group consisting of LiN(SO 2 CF 2 CF 3 ) 2 Good.
  • the lithium salt preferably contains LiPF 6 from the viewpoint of further excellent solubility in a non-aqueous solvent described later and performance of the electrochemical device.
  • the concentration of the electrolyte salt is preferably 0.5 mol/L or more, more preferably 0.7 mol/L or more, and further preferably 0.8 mol/L or more, based on the total amount of the non-aqueous solvent. Further, it is preferably 1.5 mol/L or less, more preferably 1.3 mol/L or less, still more preferably 1.2 mol/L or less.
  • non-aqueous solvent examples include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ⁇ -butyl lactone, acetonitrile, 1,2-dimethoxyethane, dimethoxymethane, tetrahydrofuran, dioxolane, methylene chloride and methyl acetate. May be
  • the non-aqueous solvent may be one of these alone or a mixture of two or more thereof, and preferably a mixture of two or more thereof.
  • the additive is a compound other than the compound represented by the above formula (1) and a fluorine-containing cyclic carbonate, such as a cyclic carbonate having a carbon-carbon double bond, a nitrile compound, and a cyclic sulfonate compound.
  • a fluorine-containing cyclic carbonate such as a cyclic carbonate having a carbon-carbon double bond, a nitrile compound, and a cyclic sulfonate compound.
  • the content of the additive may be, for example, 0.001% by mass or more and 5% by mass or less based on the total amount of the electrolytic solution.
  • a cyclic carbonate having a carbon-carbon double bond is a cyclic carbonic acid ester having a carbon-carbon double bond.
  • the two carbons constituting the ring may form a double bond.
  • the cyclic carbonate may be vinylene carbonate, vinylene carbonate, methylvinylene carbonate, dimethylvinylene carbonate (4,5-dimethylvinylene carbonate), ethylvinylene carbonate (4,5-diethylvinylene carbonate), diethylvinylene carbonate, etc. From the viewpoint of being able to further improve the performance of the chemical device, vinylene carbonate is preferable.
  • a nitrile compound is a compound having at least one cyano group (nitrile group).
  • the nitrile compound may have, for example, one, two or three cyano groups.
  • the nitrile compound having one cyano group may be, for example, butyronitrile, valeronitrile, n-heptanenitrile or the like.
  • the nitrile compound having two cyano groups may be, for example, succinonitrile, glutarnitrile, adiponitrile, pimelonitrile, suberonitrile and the like.
  • the nitrile compound having three cyano groups may be, for example, 1,2,3-propanetricarbonitrile, 1,3,5-pentanetricarbonitrile and the like.
  • the nitrile compound has two or more cyano groups and excludes carbon atoms in the cyano group from the viewpoint that a stable film is formed on the positive electrode or the negative electrode and the expansion of the battery due to the decomposition of the electrolytic solution can be suppressed.
  • Compounds having 2 or more carbon atoms are preferred.
  • the nitrile compound is more preferably a compound having two or three cyano groups and having two or more carbon atoms excluding carbon atoms in the cyano group.
  • the nitrile compound is more preferably succinonitrile, glutarnitrile, adiponitrile, pimelonitrile, suberonitrile, 1,2,3-propanetricarbonitrile, or 1,3,5-pentanetricarbonitrile, which is suitable for electrochemical devices. From the viewpoint that the performance can be further improved, succinonitrile is particularly preferable.
  • the cyclic sulfonic acid ester compound is a compound having a ring containing one or two —OSO 2 — groups.
  • the cyclic sulfonic acid ester compound is, for example, 1,3-propane sultone, 1-propene-1,3-sultone, 1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone, 1,3-propene.
  • It may be a monosulfonic acid ester such as sultone, a methylenemethane disulfonic acid ester, a disulfonic acid ester such as ethylene methanedisulfonic acid ester, and the like, from the viewpoint of further improving the performance of the electrochemical device, preferably 1, It is 3-propane sultone or 1-propene-1,3-sultone.
  • the manufacturing method of the non-aqueous electrolyte secondary battery 1 includes a first step of obtaining the positive electrode 6, a second step of obtaining the negative electrode 8, and a third step of accommodating the electrode group 2 in the battery outer casing 3.
  • the material used for the positive electrode mixture layer 10 is dispersed in a dispersion medium using a kneader, a disperser or the like to obtain a positive electrode mixture in a slurry state, and then this positive electrode mixture is treated by a doctor blade method,
  • the positive electrode current collector 9 is coated with a dipping method, a spray method, or the like, and then the dispersion medium is volatilized to obtain the positive electrode 6.
  • a compression molding step using a roll press may be provided, if necessary.
  • the positive electrode mixture layer 10 may be formed as a positive electrode mixture layer having a multi-layer structure by performing the above-described steps from the application of the positive electrode mixture to the volatilization of the dispersion medium a plurality of times.
  • the dispersion medium may be water, 1-methyl-2-pyrrolidone (hereinafter, also referred to as NMP), or the like.
  • the second step may be the same as the above-mentioned first step, and the method of forming the negative electrode mixture layer 12 on the negative electrode current collector 11 may be the same method as the above-mentioned first step. ..
  • the separator 7 is sandwiched between the produced positive electrode 6 and negative electrode 8 to form the electrode group 2.
  • the electrode group 2 is housed in the battery case 3.
  • the electrolytic solution is injected into the battery exterior body 3.
  • the electrolytic solution can be prepared, for example, by first dissolving an electrolyte salt in a solvent and then dissolving other materials.
  • the electrochemical device may be a capacitor.
  • the capacitor may include an electrode group including a positive electrode, a negative electrode, and a separator, and a bag-shaped battery exterior body that houses the electrode group.
  • the details of each component of the capacitor may be the same as those of the non-aqueous electrolyte secondary battery 1.
  • Example 1 [Preparation of electrolyte]
  • a mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate containing 1 mol/L of LiPF 6 1% by mass of vinylene carbonate (VC) was added to the total amount of the mixed solution, and a compound A represented by the following formula (9). 1% by mass (based on the total amount of the electrolytic solution) was added to prepare an electrolytic solution.
  • VC vinylene carbonate
  • Example 2 [Preparation of electrolyte] An electrolytic solution was prepared in the same manner as in Example 1 except that 1% by mass of the compound B represented by the following formula (10) in Example 1 was added (based on the total amount of the electrolytic solution).
  • Example 1 [Preparation of electrolyte] Example 1 Example 1 was repeated except that Compound A was not used and 4-fluoro-1,3-dioxolan-2-one (fluoroethylene carbonate; FEC) was added in an amount of 1% by mass (on the basis of the total amount of the electrolytic solution). An electrolytic solution was prepared in the same manner as in.
  • FEC fluoroethylene carbonate
  • Example 3 [Preparation of electrolyte] An electrolytic solution was prepared in the same manner as in Example 1 except that 1% by mass (based on the total amount of electrolytic solution) of compound C represented by the following formula (11) was added in place of compound A.
  • Example 4 [Preparation of electrolyte] An electrolytic solution was prepared in the same manner as in Example 1 except that 1% by mass of the compound D represented by the following formula (12) was added in place of the compound A (based on the total amount of the electrolytic solution).
  • Example 5 [Preparation of electrolyte] An electrolytic solution was prepared in the same manner as in Example 1 except that the content of the compound A was changed to 0.5% by mass and FEC was added at 0.5% by mass (all based on the total amount of the electrolytic solution). Prepared.
  • Example 6 Preparation of electrolyte
  • An electrolytic solution was prepared in the same manner as in Example 3 except that the content of the compound C was changed to 0.5% by mass and FEC was added at 0.5% by mass (all based on the total amount of the electrolytic solution). Prepared.
  • Example 7 [Preparation of electrolyte] An electrolytic solution was prepared in the same manner as in Example 4, except that the content of the compound D was changed to 0.5% by mass and FEC was added at 0.5% by mass (all based on the total amount of the electrolytic solution). Prepared.
  • NMP as a dispersion medium was added to the obtained mixture, and the mixture was kneaded to prepare a slurry-like positive electrode mixture.
  • a predetermined amount of this positive electrode mixture was uniformly and uniformly applied to an aluminum foil having a thickness of 20 ⁇ m as a positive electrode current collector. Then, the dispersion medium was volatilized and then pressed to consolidate it to a density of 3.6 g/cm 3 to obtain a positive electrode.
  • the lithium ion secondary batteries of Examples 1 and 2 to which the electrolytic solution having a peak within the chemical shift range of ⁇ 180 ppm to ⁇ 150 ppm was applied were The discharge capacity ratio at the 200th cycle was higher than that of the lithium ion secondary batteries of Comparative Examples 1 and 2 to which the electrolytic solution showing no peak in the range was applied. Therefore, the lithium ion secondary batteries of Examples 1 and 2 show excellent performance (cycle characteristics).
  • Non-aqueous electrolyte secondary battery electrochemical device
  • 6 Positive electrode
  • 7 Separator
  • 8 Negative electrode

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Abstract

La présente invention concerne une solution électrolytique qui, selon un aspect, présente un pic dans la plage d'un déplacement chimique de -180 ppm à -150 ppm et/ou d'un déplacement chimique de plus de -150 ppm à -130 ppm ou moins, telle que déterminée par la mesure de la RMN du 19F (fluor 19).
PCT/JP2019/047661 2018-12-05 2019-12-05 Solution électrolytique et dispositif électrochimique WO2020116574A1 (fr)

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EP3054521B1 (fr) * 2013-10-04 2021-06-16 Asahi Kasei Kabushiki Kaisha Électrolyte et batterie secondaire lithium-ion
JP2015213014A (ja) * 2014-05-02 2015-11-26 ソニー株式会社 電池、電池パック、バッテリモジュール、電子機器、電動車両、蓄電装置および電力システム

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JP2004171981A (ja) * 2002-11-21 2004-06-17 Mitsui Chemicals Inc 非水電解液およびそれを用いた二次電池
JP2015092470A (ja) * 2013-10-04 2015-05-14 旭化成株式会社 電解液及びリチウムイオン二次電池
JP2015141824A (ja) * 2014-01-29 2015-08-03 旭化成株式会社 非水電解液二次電池
JP2016186910A (ja) * 2015-03-27 2016-10-27 旭化成株式会社 電解液及びリチウムイオン二次電池
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JP7415947B2 (ja) 2018-12-05 2024-01-17 株式会社レゾナック 電解液及び電気化学デバイス
JP7415946B2 (ja) 2018-12-05 2024-01-17 株式会社レゾナック 電解液及び電気化学デバイス

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