WO2016098371A1 - Procédé de production de groupe de particules de composé métallique, groupe de particules de composé métallique, et électrode pour dispositif de stockage d'électricité contenant un groupe de particules de composé métallique - Google Patents

Procédé de production de groupe de particules de composé métallique, groupe de particules de composé métallique, et électrode pour dispositif de stockage d'électricité contenant un groupe de particules de composé métallique Download PDF

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WO2016098371A1
WO2016098371A1 PCT/JP2015/065203 JP2015065203W WO2016098371A1 WO 2016098371 A1 WO2016098371 A1 WO 2016098371A1 JP 2015065203 W JP2015065203 W JP 2015065203W WO 2016098371 A1 WO2016098371 A1 WO 2016098371A1
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Prior art keywords
metal compound
particle group
compound particle
particles
carbon
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PCT/JP2015/065203
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English (en)
Japanese (ja)
Inventor
洋宇 花輪
啓裕 湊
覚 爪田
修一 石本
勝彦 直井
和子 直井
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日本ケミコン株式会社
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Priority claimed from JP2015074270A external-priority patent/JP6363550B2/ja
Application filed by 日本ケミコン株式会社 filed Critical 日本ケミコン株式会社
Priority to EP15869580.9A priority Critical patent/EP3236481B1/fr
Priority to CN201580067141.8A priority patent/CN107004519B/zh
Priority to US15/535,626 priority patent/US10505187B2/en
Priority to CN201910653797.8A priority patent/CN110335763B/zh
Priority to KR1020177010364A priority patent/KR102438519B1/ko
Publication of WO2016098371A1 publication Critical patent/WO2016098371A1/fr
Priority to US16/454,018 priority patent/US11398626B2/en

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to a method for producing a metal compound particle group used for an electrode of an electricity storage device, a metal compound particle group, and an electrode using the same.
  • Electrodes using metal compound particles include lithium ion secondary batteries using metal compound particles for the positive electrode and negative electrode, and materials that can reversibly adsorb / desorb lithium ions on the positive electrode and activated carbon on the positive electrode (graphene and metal compounds) Etc.) is used for power storage devices such as lithium ion capacitors. These power storage devices are used as power sources for information devices such as mobile phones and laptop computers, and for regenerative energy applications such as in-vehicle. In particular, high rate characteristics are required for in-vehicle applications.
  • a kind of carbon material selected from carbon nanotubes, graphene, and carbon black having an average dispersed particle size of 0.2 ⁇ m or less on the surface of a specific lithium-containing composite oxide Is known, but the charge / discharge characteristics at a high rate are still unsatisfactory.
  • an object of the present invention is to provide a method for producing a metal compound particle group used for an electrode of an electricity storage device with improved rate characteristics, a metal compound particle group, and an electrode using the metal compound particle group.
  • a manufacturing method of the present invention is a manufacturing method of a metal compound particle group used for an electrode of an electricity storage device, wherein a metal compound particle precursor and a carbon source are combined to form a first composite.
  • a step of removing the carbon to obtain a metal compound particle group by heat-treating the second composite material in an oxygen atmosphere.
  • the metal compound particles are bonded to a three-dimensional network structure by heat treatment in the step of obtaining the metal compound particle group.
  • the heat treatment temperature in the step of obtaining the second composite material is 600 to 950 ° C.
  • the heat treatment time for obtaining the second composite material is 1 to 20 minutes.
  • the method further comprises a preheating step of heat-treating the first composite material in a non-oxidizing atmosphere at 200 to 500 ° C. before the step of obtaining the second composite material.
  • the heat treatment temperature in the step of obtaining the metal compound particle group is 350 to 800 ° C.
  • the heat treatment temperature in the step of obtaining the metal compound particle group is set to be equal to or higher than the heat treatment temperature in the preheating step.
  • the process of obtaining the metal compound particle group is characterized in that the remaining amount of carbon is less than 5% by weight of the metal compound particle group.
  • the step of obtaining the first composite material is a process in which a mechanochemical reaction is performed by applying shear stress and centrifugal force to a solution containing a material source of metal compound particles and a carbon source in a rotating reaction vessel. It is characterized by.
  • the material source of the metal compound particles is a titanium source and a lithium source
  • the precursor of the metal compound particles is a lithium titanate precursor.
  • the titanium source contained in the solution is titanium alkoxide, and the solution further contains a reaction inhibitor that forms a complex with the titanium alkoxide.
  • the step of obtaining the first composite material is characterized in that a process including spray drying a solution containing a material source of metal compound particles and a carbon source. Further, the solution is obtained by adding a material source of metal compound particles after adding a carbon source to a solvent.
  • the step of obtaining the first composite material is characterized in that the solution containing the material source of the metal compound particles and the carbon source is agitated.
  • the carbon source is a polymer.
  • the material source of the metal compound particles is characterized in that the average particle diameter is 500 nm or less.
  • the second composite material is characterized in that the mixing ratio of the metal compound particles and carbon is 95: 5 to 30:70 by weight.
  • the present invention is a metal compound particle group used for an electrode of an electricity storage device, and is characterized in that it is a metal compound particle group in which nano-sized metal compound particles are bonded to a three-dimensional network structure.
  • the porosity in the cross section of the metal compound particle group is 7 to 50%. Further, in the differential pore volume converted from the pore distribution measured by the nitrogen gas adsorption measurement method for the metal compound particle group consisting of the metal compound particles having an average particle diameter of 100 nm or less, the fine pore volume in the range of 10 to 40 nm.
  • the differential pore volume in the pore diameter is characterized by having a value of 0.01 cm 3 / g or more. Further, in the differential pore volume converted from the pore distribution measured by the nitrogen gas adsorption measurement method for the metal compound particle group composed of the metal compound particles having an average particle diameter of more than 100 nm, a fine pore volume in the range of 20 to 40 nm is obtained.
  • the differential pore volume in the pore diameter is characterized by having a value of 0.0005 cm 3 / g or more.
  • the metal compound particle group is characterized in that the remaining amount of carbon is less than 5% by weight of the metal compound particle group.
  • the metal compound particles contained in the metal compound particle group are characterized in that the average particle diameter of primary particles thereof is 5 to 100 nm.
  • the metal compound particles are lithium titanate.
  • it can also be set as the electrode for electrical storage devices containing these metal compound particle groups and a binder.
  • the carbon is removed by heat treatment in an oxygen atmosphere, and the portions of the carbon that existed before the heating are voids.
  • the heat treatment causes the metal compound particles to react and bond to each other, and the void derived from carbon and the bond between the metal compound particles combine to form a three-dimensional network structure of the metal compound particles. Since this metal compound particle group has an appropriate gap, it is impregnated with the electrolytic solution when the power storage device is configured, and the ions in the electrolytic solution move smoothly in the electrode. It is considered that the movement of the electrode becomes faster, and the resistance of the electrode is lowered by the synergistic action of both, and the rate characteristic can be improved.
  • the rate characteristics of the electrode for the electricity storage device can be improved.
  • (A) is a conceptual diagram which shows the 2nd composite material of this invention
  • (b) is a conceptual diagram which shows the metal compound particle group of this invention.
  • (A) is the STEM photograph of the cross section of the metal compound particle group which concerns on the lithium titanate of this invention
  • (b) is the STEM photograph of the cross section of the conventional metal compound particle group.
  • FIG. 1 A) is the STEM photograph of the cross section of the metal compound particle group which concerns on the lithium titanate of this invention
  • (b) is the STEM photograph of the cross section of the conventional metal compound particle group. It is a STEM photograph of the section of the metal compound particle group concerning lithium cobaltate of the present invention.
  • (A) is the figure which image-analyzed the STEM photograph of the cross section of the metal compound particle group of this invention
  • (b) is the figure which image-analyzed the STEM photograph of the cross section of the conventional metal compound particle group. It is a SEM photograph of the surface of the metal compound particle group of the present invention.
  • the metal compound particle group of the present invention is mainly used for an electrode of an electricity storage device, and the metal compound particle constituting the metal compound particle group includes a positive electrode of an electricity storage device such as a lithium ion secondary battery or a lithium ion capacitor. It is a material that can operate as an active material or a negative electrode active material.
  • the metal compound particle is an oxide or oxyacid salt containing lithium, and is represented by Li ⁇ M ⁇ Y ⁇ .
  • M Co, Ni, Mn, Ti, Si, Sn, Al, Zn, or Mg
  • Y O
  • M Fe, Mn, V, Co, or Ni
  • Y PO 4 , SiO 4 , BO 3 , or P 2 O 7
  • M ′ Fe, Co, Mn, V, Ti, or Ni. is there.
  • lithium manganate, lithium iron phosphate, lithium titanate, lithium cobaltate, lithium vanadium phosphate, and lithium manganese manganese phosphate can be used.
  • the manufacturing method of the metal compound particle group used for the electrode of the electricity storage device according to the present invention includes the following steps.
  • Step of obtaining a first composite material by compounding a precursor of metal compound particles and a carbon source (2) Generating metal compound particles by heat-treating the first composite material in a non-oxidizing atmosphere And a step of obtaining a second composite material in which the metal compound particles and carbon are composited. (3) The second composite material is heat-treated in an oxygen atmosphere to remove carbon and to form a metal compound particle group.
  • Step of obtaining the first composite material In the step of obtaining the first composite material, the precursor of the metal compound particles and the carbon source are combined to obtain the first composite material.
  • the precursor of the metal compound particles refers to a substance before the metal compound particles are generated by the heat treatment process.
  • M ⁇ Y ⁇ or a constituent compound thereof each range of M ⁇ Y ⁇ is the same as that of the metal compound particle, and further includes a material obtained by adding a lithium source to M ⁇ Y ⁇ or the constituent compound. .
  • the material source of the metal compound particles may be a powder or a state dissolved in a solution.
  • Fe sources such as iron (II) acetate, iron (II) nitrate, iron (II) chloride, iron (II) sulfate, phosphoric acid, ammonium dihydrogen phosphate, phosphoric acid
  • a precursor of metal compound particles is generated using a phosphoric acid source such as diammonium hydrogen and a carboxylic acid such as citric acid, malic acid, and malonic acid as a material source.
  • a precursor of metal compound particles is generated using a titanium source such as titanium alkoxide, or a lithium source such as lithium acetate, lithium nitrate, lithium carbonate, or lithium hydroxide as a material source.
  • lithium cobaltate for example, lithium source such as lithium hydroxide monohydrate, lithium acetate, lithium carbonate, lithium nitrate, and cobalt acetate, cobalt nitrate, cobalt sulfate, cobalt sulfate (II) tetrahydrate, A precursor of metal compound particles is generated using a cobalt source such as cobalt chloride as a material source.
  • a cobalt source such as cobalt chloride as a material source.
  • the carbon source of the present invention means carbon itself (powder) or a material that can be converted to carbon by heat treatment.
  • carbon (powder) any carbon material having electrical conductivity can be used without particular limitation.
  • carbon black such as ketjen black, acetylene black, channel black, fullerene, carbon nanotube, carbon nanofiber, amorphous carbon, carbon fiber, natural graphite, artificial graphite, graphitized ketjen black, mesoporous carbon, gas phase method Carbon fiber etc.
  • a carbon material having a nano-sized particle size is preferable.
  • the material that can be converted to carbon by heat treatment is an organic substance that is deposited on the surface of the precursor of the metal compound particles, and is converted into carbon in the subsequent heat treatment step.
  • organic substances include polyhydric alcohols (such as ethylene glycol), polymers (such as polyvinyl alcohol, polyethylene glycol, and polyvinylpyrrolidone), sugars (such as glucose), and amino acids (such as glutamic acid).
  • the material source of these metal compound particles and the carbon source are combined to obtain a first composite material.
  • the composite material is a dissolved or powdered material source as the material source of the metal compound particles, and carbon.
  • the source is a composite material using carbon (powder) or a substance that can be converted to carbon by heat treatment.
  • Examples of a method of combining the material source of the metal compound particles and the carbon source include the following.
  • (A) Mechanochemical treatment As the mechanochemical treatment, a solution is obtained by adding at least one material source of metal compound particles and carbon powder to a solvent and dissolving the material source in the solvent.
  • any liquid that does not adversely affect the reaction can be used without particular limitation, and water, methanol, ethanol, isopropyl alcohol, and the like can be preferably used. Two or more solvents may be mixed and used.
  • the material source includes metal alkoxide M (OR) x.
  • reaction inhibitor can also be added to a solution as needed.
  • Substances that can form complexes with metal alkoxides include acetic acid, citric acid, succinic acid, formic acid, lactic acid, tartaric acid, fumaric acid, succinic acid, propionic acid, amino acids such as repric acid, and aminopolyesters such as EDTA.
  • Examples include complexing agents represented by amino alcohols such as carboxylic acid and triethanolamine.
  • a shear stress and a centrifugal force are applied to the solution to bond the precursor of the metal compound particles to the surface of the carbon powder by a mechanochemical reaction.
  • a process of applying shear stress and centrifugal force to the solution is performed.
  • the outer cylinder and the inner cylinder described in FIG. 1 of JP-A-2007-160151 are used.
  • a reactor comprising a concentric cylinder, having a through-hole on the side surface of the inner cylinder that can be swung, and a slat plate disposed at the opening of the outer cylinder is preferably used.
  • the distance between the inner cylinder outer wall surface and the outer cylinder inner wall surface is preferably 5 mm or less, and more preferably 2.5 mm or less.
  • the centrifugal force required to produce on the thin film is 1500 N (kgms -2) or more, preferably 70000N (kgms -2) or more.
  • any liquid that does not adversely affect the reaction can be used without particular limitation, and water, methanol, ethanol, isopropyl alcohol, and the like can be preferably used. Two or more solvents may be mixed and used.
  • metal alkoxide M (OR) x is preferable.
  • the material source of metal compound particles and carbon powder are added to the solvent, and the solution is prepared by stirring as necessary.
  • carbon powder is dispersed in a solvent, and then a material source of metal compound particles is dispersed.
  • a dispersion method it is preferable to highly disperse carbon powder in a solvent by ultracentrifugation (treatment of applying shear stress and centrifugal force to powder in a solution), bead mill, homogenizer, or the like.
  • a solution obtained by dissolving metal alkoxide as a material source of metal compound particles in a solvent in which the carbon powder is dispersed is spray-dried on a substrate, and the metal alkoxide is oxidized to be a precursor of metal compound particles. And the precursor and carbon powder are combined to obtain a first composite material. If necessary, a material source of metal compound particles may be further added to the composite material to form the first composite material.
  • the spray drying process is performed at a temperature at which the carbon powder is not burned out at a pressure of about 0.1 MPa.
  • a precursor of metal compound particles having an average primary particle diameter in the range of 5 to 300 nm is obtained by spray drying.
  • (C) Stirring treatment As the stirring treatment, at least one powder as a material source of metal compound particles and a material that can be converted to carbon by heat treatment as a carbon source are added to a solvent, the solution is stirred, and the metal compound is stirred.
  • a first composite material is obtained in which a material that can be carbon is deposited on the surface of a material source of particles.
  • the powder serving as the material source is preferably pulverized in advance to form nano-level fine particles.
  • a material source of metal compound particles may be added to a solvent to which a polymer has been added in advance, and the solution may be stirred.
  • the polymer may be adjusted to be in the range of 0.05 to 5 when the weight of the powder that is the material source of the metal compound particles is 1.
  • the average secondary particle diameter of the fine particles is 500 nm or less, preferably 100 nm or less, whereby a metal compound particle group having a small particle diameter can be obtained.
  • water, methanol, ethanol, and isopropyl alcohol can be used suitably as a solvent.
  • Step of obtaining the second composite material In the step of obtaining the second composite material, the first composite material is heat-treated in a non-oxidizing atmosphere to produce metal compound particles, and the metal compound particles A second composite material in which carbon and carbon are combined is obtained.
  • the non-oxidizing atmosphere is used to suppress the loss of the carbon source, and examples of the non-oxidizing atmosphere include an inert atmosphere and a saturated steam atmosphere.
  • the first composite material in which the precursor of the metal compound particles and the carbon source are combined is subjected to heat treatment in a non-oxidizing atmosphere such as nitrogen or argon atmosphere in a vacuum.
  • a non-oxidizing atmosphere such as nitrogen or argon atmosphere in a vacuum.
  • the precursor of the metal compound particles grows by this heat treatment, and the metal compound particles are generated in a state of being complexed with the carbon source.
  • the carbon source is present in a state where it is difficult to burn out and is combined with the metal compound particles, and a second composite material in which the metal compound particles and carbon are combined is obtained. As shown in the conceptual diagram of FIG.
  • the second composite material is a composite material in which metal compound particles (for example, lithium titanate: LTO) are supported on carbon (for example, carbon nanofiber: CNF). It is considered that LTO is dispersed and present as nano-sized particles on CNF.
  • metal compound particles for example, lithium titanate: LTO
  • CNF carbon nanofiber
  • the precursor of the metal compound particles on the surface of the carbon powder is converted in the non-oxidizing atmosphere by the heat treatment in the non-oxidizing atmosphere. It reacts during the heat treatment, grows on the surface of the carbon powder and lattice-joins, and the carbon powder and the metal compound particles are integrated.
  • the material that can be converted into carbon by heat treatment is used as the carbon source contained in the first composite material
  • the material is carbonized on the surface of the precursor of the metal compound particles by the heat treatment in the non-oxidizing atmosphere.
  • carbon is generated, and a second composite material in which the carbon and metal compound particles grown by heat treatment are combined is generated.
  • “carbon” contained in the second composite material indicates carbon powder or carbon produced by heat treatment.
  • the temperature is maintained in the range of 600 to 950 ° C. for 1 to 20 minutes in order to prevent the carbon source from being burned out.
  • the metal compound particles are lithium titanate
  • heat treatment in a nitrogen atmosphere is particularly preferable as an inert atmosphere, and the metal compound particles are doped with nitrogen to increase the conductivity of the metal compound particles, and as a result, rapid charge / discharge characteristics are improved.
  • the temperature is maintained in the range of 110 to 300 ° C. for 1 to 8 hours in order to prevent the carbon source from being burned out. Within this range, good metal compound particles can be obtained, and good capacity and rate characteristics can be obtained.
  • the metal compound particles are lithium cobalt oxide
  • the heat treatment temperature is less than 110 ° C. because the formation of lithium cobalt oxide is not sufficient, and if the heat treatment temperature exceeds 300 ° C., the carbon source is burned out. Since lithium cobaltate aggregates, it is not preferable.
  • the average particle diameter of the primary particles of the metal compound particles obtained in the step of obtaining the second composite material preferably includes a range of 5 to 300 nm.
  • the obtained second composite material preferably has a weight ratio of metal compound particles to carbon in the range of 95: 5 to 30:70, and by making such a range, the finally obtained metal The porosity of the compound particle group can be increased.
  • what is necessary is just to adjust the mixing ratio of the material source of a metal compound particle, and a carbon source previously in order to set it as such a range.
  • the first composite material is held at a temperature range of 200 to 500 ° C. for 1 to 300 minutes.
  • a non-oxidizing atmosphere is desirable.
  • the carbon source is less than 300 ° C. at which the carbon source does not burn, it may be performed in an oxygen atmosphere.
  • impurities present in the first composite material can be removed, and a state in which the precursor of the metal compound particles is uniformly attached to the carbon source can be obtained. it can.
  • Step of obtaining metal compound particle group In the step of obtaining metal compound particle group, the second composite material is heat-treated in an oxygen atmosphere to remove carbon and obtain the metal compound particle group.
  • the second composite material in which the nano-sized metal compound particles and carbon are combined is subjected to heat treatment in an oxygen atmosphere.
  • the carbon is burned off and removed, and the portions of carbon that existed before heating become voids.
  • the metal compound particles react and bond with each other by this heat treatment.
  • the voids derived from carbon and the bonds between the metal compound particles combine to form a three-dimensional network structure of the metal compound particles as shown in the conceptual diagram of FIG. Since this metal compound particle group has an appropriate gap, it is impregnated with the electrolytic solution when the power storage device is configured, and the ions in the electrolytic solution move smoothly in the electrode.
  • the temperature is maintained in the range of 350 to 800 ° C., preferably 400 to 600 ° C. for 0.25 to 24 hours in order to remove carbon and to bond metal compound particles to each other. It is preferable to hold it, more preferably 0.5 to 10 hours.
  • the temperature is lower than 350 ° C., the carbon contained in the second composite material is not sufficiently removed, and when the temperature exceeds 800 ° C., the aggregation of the metal compound particles proceeds and the voids of the metal compound particle group decrease.
  • the average particle diameter of the primary particles of the metal compound particles is maintained at 5 to 300 nm, and the particles from the average particle diameter of the primary particles of the metal compound particles before the heat treatment Growth is suppressed.
  • the heat treatment temperature be equal to or higher than the temperature of the preheating step.
  • the oxygen atmosphere a mixed atmosphere with nitrogen or the like may be used, and an atmosphere in which oxygen is present at 15% or more, such as in the air, is preferable.
  • the amount of oxygen decreases due to the disappearance of carbon, so that oxygen may be appropriately supplied into the heat treatment furnace.
  • the porosity in the cross section of the metal compound particle group is preferably in the range of 7 to 50%.
  • the porosity is less than 7%, the area of the metal compound particles in contact with the electrolytic solution is small, which affects the movement of ions in the electrolytic solution.
  • the porosity exceeds 50%, the bond between the metal compound particles becomes rough and it becomes difficult to form a three-dimensional network structure.
  • the metal compound particles have particles whose primary particles have an average particle diameter in the range of 5 to 300 nm, and since these are fine particles in such a range, a large number of nano-sized pores in the metal compound particle group can be obtained.
  • the area of the metal compound particles in contact with the electrolytic solution is increased, and the movement of ions in the electrolytic solution becomes smooth.
  • the pores of this metal compound particle group are measured, there are many fine pores. In particular, it contains many fine pores of 40 nm or less.
  • the difference in the pore diameter in the range of 10 to 40 nm in the difference pore volume converted from the pore distribution measured by the nitrogen gas adsorption measurement method for the metal compound particle group having an average primary particle size of 100 nm or less, the difference in the pore diameter in the range of 10 to 40 nm.
  • the pore volume has a value of 0.01 cm 3 / g or more, in particular, a value of 0.02 cm 3 / g or more, and the area of the metal compound particles in contact with the electrolytic solution is increased. The larger the area of the metal compound particles in contact with the electrolytic solution, the better the rate characteristics when used for the electrode.
  • the pore diameter in the range of 20 to 40 nm in the differential pore volume converted from the pore distribution measured by the nitrogen gas adsorption measurement method for the metal compound particle group having an average primary particle diameter of more than 100 nm, the pore diameter in the range of 20 to 40 nm.
  • the differential pore volume in the sample has a value of 0.0005 cm 3 / g or more, and the area of the metal compound particles in contact with the electrolytic solution increases, and as the area of the metal compound particles in contact with the electrolytic solution increases as described above. The rate characteristics when used for an electrode are improved.
  • the amount of carbon remaining in the obtained metal compound particle group is preferably less than 5% by weight based on the metal compound particle group.
  • the amount is preferably less than 1% by weight.
  • the metal compound particle group thus obtained is used for an electrode of an electricity storage device.
  • the metal compound particle group is formed by kneading and molding a predetermined solvent and binder and, if necessary, conductive carbon such as carbon black, acetylene black, ketjen black, and graphite as a conductive aid.
  • Electrode This electrode is impregnated with an electrolytic solution and stored in a predetermined container to form an electricity storage device.
  • Example 1 20 g of carbon nanofibers and 245 g of tetraisopropoxy titanium were added to 1300 g of isopropyl alcohol, and tetraisopropoxy titanium was dissolved in isopropyl alcohol.
  • the weight ratio of titanium alkoxide and carbon nanofibers was selected so that the weight ratio of lithium titanate to carbon nanofibers in the second composite material was about 8: 2.
  • the obtained liquid was introduced into the inner cylinder of the reactor, which was composed of a concentric cylinder of an outer cylinder and an inner cylinder, a through hole was provided on the side surface of the inner cylinder, and a shed plate was arranged at the opening of the outer cylinder.
  • the carbon nanofibers were highly dispersed in the liquid by rotating the inner cylinder for 300 seconds so that a centrifugal force of 35000 kgms- 2 was applied to the liquid.
  • the obtained carbon nanofiber carrying the lithium titanate precursor was subjected to preliminary heat treatment in nitrogen at 400 ° C. for 30 minutes, and then heat treated in nitrogen at 900 ° C. for 3 minutes to obtain an average particle size of primary particles.
  • a second composite material in which nanoparticles of lithium titanate having a diameter of 5 to 20 nm were supported in a highly dispersed state on carbon nanofibers was obtained.
  • 100 g of the obtained second composite material was subjected to a heat treatment at 500 ° C. for 6 hours to burn off the carbon nanofibers and bind lithium titanate particles to form a lithium titanate particle having a three-dimensional network structure A group was obtained.
  • Example 2 In Example 1, the weight ratio of lithium titanate to carbon nanofibers in the second composite material was selected to be about 8: 2, whereas in the metal compound particle group of Example 2, the second compound material A lithium titanate particle group was obtained in the same manner as in Example 1 except that the weight ratio of lithium titanate to carbon nanofiber in the composite material was selected to be about 7: 3.
  • Example 5 First, 20 g of ketjen black, 202 g of Co (CH 3 COO) 2 .4H 2 O, and 3243 g of H 2 O were mixed and introduced into the inner cylinder of the reactor. It was swirled for 5 minutes at a rotational speed of 50 m / s. To the mixed solution after the first mechanochemical treatment, 3300 g of LiHO.H 2 O (65 g containing) aqueous solution was added and swirled at a rotational speed of 50 m / s for 5 minutes. Mechanochemical treatment was performed. In this mechanochemical treatment, a centrifugal force of 66000 N (kgms ⁇ 2 ) is applied. The first and second mechanochemical treatments correspond to a step of obtaining a first composite material by supporting a precursor of a metal compound by mechanochemical treatment on a carbon source.
  • the obtained solution is rapidly heated to 250 ° C. in an oxidizing atmosphere such as the air and baked by holding for 1 hour.
  • H 2 O, a precursor prepared by firing, and H 2 O 2 are added to the autoclave, and the mixture is held in saturated steam at 250 ° C. for 6 hours to perform hydrothermal synthesis to perform lithium cobalt oxide (LiCoO 2 And 100 g of a second composite material of ketjen black.
  • the pressure at this time is 39.2 atmospheres.
  • This hydrothermal synthesis is a process in which the first composite material is heat-treated in a non-oxidizing atmosphere to generate metal compound particles and obtain a second composite material in which the metal compound particles and carbon are combined. Correspond.
  • FIG. 3 is a graph showing the relationship between the rate and the capacity retention rate for the capacitors of Examples 1 and 2 and Conventional Example 1 obtained.
  • FIG. 4 is a graph showing the relationship between the rate and the capacity retention rate for the capacitors of Example 5 and Conventional Example 2 obtained.
  • the capacitors of Examples 1, 2, and 5 can obtain good rate characteristics even at high rates.
  • such an excellent rate characteristic was obtained even when the electrode did not contain conductive carbon serving as a conductive auxiliary agent.
  • the characteristics of the metal compound particle group of the present invention But there is.
  • FIG. 5A is a bright field STEM photograph showing a cross section of the lithium titanate particle group of Example 1
  • FIG. 5B is a bright field showing a cross section of the lithium titanate particle group of Conventional Example 1.
  • It is a visual field STEM photograph. 6 is a bright-field STEM photograph showing a cross section of the lithium cobalt oxide particle group of Example 5.
  • FIG. 5 (a) it can be seen that there are many voids in the cross section of the lithium titanate particle group including the center of the particle group (in the cross section, the lithium titanate particles show gray, Indicates black). Further, in FIG.
  • the cross section of the lithium cobalt oxide particle group has many voids including the center of the particle group as in Example 1.
  • the lithium titanate particle group of Conventional Example 1 there are almost no voids and are slightly seen in the vicinity of the outer periphery of the particle group.
  • FIG. 7 is a bright-field STEM photograph of a cross-section in which the lithium titanate particles of Example 1 and Conventional Example 1 are further enlarged.
  • FIG. 8 is a bright field STEM photograph of a cross-section obtained by further enlarging the lithium cobalt oxide particle group of Example 3.
  • the grain boundary between the particles is hardly visible (gray indicates particles).
  • Particles are bonded to form a three-dimensional network structure.
  • the particle diameter of the primary particle of a lithium titanate particle is mainly 100 nm or less.
  • the contour between the particles is visible, and it can be seen that the grain boundary exists.
  • the particle diameter is mainly 200 nm or more.
  • Example 5 the void states of the lithium titanate particle group and the lithium cobaltate particle group obtained in Example 1, Example 5 and Conventional Example 1 are confirmed.
  • the area of the voids in the cross section of the lithium titanate particle group shown in FIG. 5 was analyzed by image processing. As shown in FIG. 9, image processing was performed using white in the lithium titanate particle group as the lithium titanate particle and gray as the void, and the area ratio occupied by the void in the lithium titanate particle group was calculated.
  • the porosity of the lithium titanate particle group obtained in Example 1 of FIG. 9A was 22%. Further, the void area in the cross section of the lithium cobalt oxide particle group shown in FIG. 6 was also analyzed by image processing in the same manner as in Example 1. As a result, the porosity of the lithium cobaltate particles obtained in Example 5 of FIG. 6 was 9.9%. On the other hand, the porosity of the lithium titanate particle group obtained in Conventional Example 1 in FIG. 9B was 4%. Thus, it turns out that the lithium titanate particle group of Example 1 and Example 5 and the lithium cobaltate particle group have a high porosity.
  • FIG. 10 is a 100,000 times SEM photograph showing the surface of the obtained lithium titanate group.
  • FIG. 10 shows that the surface of the lithium titanate group is also a fine particle group at the nano level.
  • a nitrogen gas adsorption measuring method is used as a measuring method. Specifically, nitrogen gas is introduced into the metal oxide particle surface and pores formed in the interior communicating with the metal oxide particle surface, and the adsorption amount of the nitrogen gas is determined. Next, the pressure of nitrogen gas to be introduced is gradually increased, and the adsorption amount of nitrogen gas with respect to each equilibrium pressure is plotted to obtain an adsorption isotherm.
  • 11 and 12 are differential pore volume distributions in which the horizontal axis represents the pore diameter and the vertical axis represents the increase in pore volume between measurement points, and FIG. 11 illustrates Examples 1 and 2 and the conventional example. 1 shows a lithium titanate particle group of 1 and FIG. 12 shows a lithium cobaltate particle group of Example 5 and Conventional Example 2.
  • FIG. 11 illustrates Examples 1 and 2 and the conventional example. 1 shows a lithium titanate particle group of 1 and FIG. 12 shows a lithium cobaltate particle group of Example 5 and Conventional Example 2.
  • FIG. 1 shows a lithium titanate particle group of 1
  • FIG. 12 shows a lithium cobaltate particle group of Example 5 and Conventional Example 2.
  • the lithium titanate particles of Examples 1 and 2 have a larger differential pore volume than the lithium titanate particles of Conventional Example 1. Since the differential pore volume is large in such a small pore diameter range (100 nm), it can be seen that the electrolytic solution penetrates into the lithium titanate particle group and the area of the lithium titanate particles in contact with the electrolytic solution is large.
  • the differential pore volume at a pore diameter in the range of 10 to 40 nm has a value of 0.01 cm 3 / g or more, and further a value of 0.02 cm 3 / g or more is obtained.
  • the lithium cobaltate particle group of Example 5 has a larger differential pore volume than the lithium cobaltate particle group of Conventional Example 2. It can be seen that since the differential pore volume is large in such a small pore diameter range (100 nm), the electrolytic solution penetrates into the lithium cobalt oxide particle group and the area of the lithium cobalt oxide particles in contact with the electrolytic solution is large. In particular, the differential pore volume at a pore diameter in the range of 20 to 40 nm has a value of 0.0005 cm 3 / g or more.
  • the difference in the differential pore volume between the lithium titanate particle group of Examples 1 and 2 and the lithium cobaltate particle group of Example 5 is that the average primary particle diameter of the lithium titanate particle group of Examples 1 and 2 is 100 nm. This is considered to be due to the fact that the average primary particle diameter of the lithium cobaltate particle group of Example 5 exceeds 100 nm. In any case, the differential pore volume is larger than when the carbon is not used.
  • Example 1-1 In Example 1, 100 g of the second composite material was heat-treated at 500 ° C. for 6 hours, whereas in the metal compound particle group of Example 1-1, 100 g of the second composite material was added at 350 ° C. A lithium titanate particle group was obtained in the same manner as in Example 1 except that heat treatment was performed for 3 hours.
  • Example 1-2 In Example 1, 100 g of the second composite material was heat-treated at 500 ° C. for 6 hours, whereas in the metal compound particle group of Example 1-2, 100 g of the second composite material was added at 300 ° C. A lithium titanate particle group was obtained in the same manner as in Example 1 except that heat treatment was performed for 1 hour.
  • the residual carbon content of the obtained lithium titanate particle groups of Example 1, Example 1-1, and Example 1-2 was measured. Note that TG-DTA measurement (differential thermal-thermogravimetric simultaneous measurement) is used. Table 1 shows the results of a 60 ° C. standing test of these examples. In addition, the standing test condition was that each capacitor was charged for 30 minutes while being charged at 2.8 V, and then left in an atmosphere at 60 ° C. for 1500 hours. It is the value which computed the discharge capacity at the time of charging / discharging this capacitor again as a ratio of the discharge capacity before a test. As shown in Table 1, the residual amount of carbon is preferably less than 5% by weight, and in particular, Example 1 in which the residual amount of carbon was 1% by weight or less gave good results.
  • the conductivity of the metal compound particle group of the present invention will be confirmed.
  • the conductivity of the particle group is high.
  • FIG. 13 using the metal compound particle group of Example 1 and the metal compound particle group obtained by pulverizing the metal compound particle group obtained in Example 1 for 1 minute with a ball mill as Reference Example 1, The result of producing a sheet and measuring the conductivity of this electrode is shown.
  • an appropriate amount of isopropyl alcohol was mixed with a mixture of the lithium titanate particles of Example 1 and Reference Example 1 and polytetrafluoroethylene (PTFE) as a binder in a weight ratio of 10: 1. Then, an electrode sheet having a thickness of 150 to 180 ⁇ m was produced by a roll press. The produced electrode sheet was sandwiched between stainless steel meshes to form a working electrode, a lithium foil was used as a counter electrode through a separator, and a 1M LiBF 4 propylene carbonate solution was used as an electrolyte. As measurement conditions, charging was performed at a current of about 0.05 C, and the impedance of the electrode sheet was measured in a timely manner. The utilization factor (SOC) of the lithium titanate particle group was calculated from the time required for full charge.
  • SOC utilization factor
  • the electrode sheet of Example 1 shows good conductivity regardless of the utilization rate.
  • the reference example 1 obtained by pulverizing the lithium titanate particle group of Example 1 it can be seen that the conductivity is lowered. This is presumably because the three-dimensional network structure of the lithium titanate particle group is partially broken by pulverization, thereby reducing the electron path between the particles and increasing the resistance. That is, the lithium titanate particle group of Example 1 indicates that a three-dimensional network structure in which the particles are bonded to each other is formed.
  • Example 3 A solution obtained by adding 20 g of ketjen black to 1200 g of isopropyl alcohol was dispersed by ultracentrifugation, and then 247 g of tetraisopropoxytitanium was added and dissolved to obtain a solution.
  • the weight ratio of titanium alkoxide to ketjen black was selected so that the weight ratio of lithium titanate to ketjen black in the second composite material was about 8: 2.
  • the obtained solution is introduced into a spray drying apparatus (ADL-311: manufactured by Yamato Scientific Co., Ltd.) and spray-dried (pressure: 0.1 Mpa, temperature 150 ° C.) on the substrate to obtain a dried product.
  • ADL-311 manufactured by Yamato Scientific Co., Ltd.
  • This dried product was added to 200 g of water in which 52 g of lithium acetate was dissolved, stirred and dried to obtain a mixture.
  • This mixture is a first composite material in which a precursor of metal compound particles generated by oxidizing metal alkoxide and a carbon powder are combined.
  • the obtained second composite material was subjected to a heat treatment at 500 ° C. in the atmosphere for 6 hours to burn off the carbon nanofibers and bind lithium titanate to form a three-dimensional network structure lithium titanate Particle groups were obtained.
  • the average particle diameter of the primary particles of the metal compound particles of the obtained particle group was 5 to 100 nm. Further, the residual amount of carbon in this metal compound particle group was measured and found to be 1% by weight or less.
  • Example 4 87 g of nano-sized (average particle diameter 5-20 nm) titanium oxide (TiO 2 ), 87 g of polyvinyl alcohol and 60 g of lithium acetate were added to 800 g of water. A first composite material in which polyvinyl alcohol was deposited on the surface of the precursor of metal compound particles obtained by drying this solution was obtained.
  • the obtained first composite material was subjected to preliminary heat treatment in nitrogen at 400 ° C. for 30 minutes, and then heat treated in nitrogen at 900 ° C. for 3 minutes to form 5 to 20 nm lithium titanate nanoparticles. Obtained a second composite material supported in a highly dispersed state on carbon derived from polyvinyl alcohol. In this second composite material, the weight ratio of lithium titanate particles to carbon was about 9: 1.
  • 100 g of the obtained second composite material is subjected to a heat treatment in the atmosphere at 500 ° C. for 6 hours to burn off carbon and bind lithium titanate to form a three-dimensional network lithium titanate particle group Got.
  • the average particle diameter of the primary particles of the metal compound particles of the obtained particle group was 5 to 100 nm. Further, the residual amount of carbon in this metal compound particle group was measured and found to be 1% by weight or less.
  • FIG. 14 shows the relationship between the charge / discharge current and the capacity retention rate for the obtained half cells of Examples 3 and 4 and Conventional Example 1.
  • the half cells of Examples 3 and 4 can obtain good rate characteristics even at a high rate.
  • the pore distribution of the obtained lithium titanate particle group of Example 4 was measured.
  • a nitrogen gas adsorption measuring method is used as a measuring method. The measurement conditions are the same as those shown in FIGS. 11 and 12, and the difference pore volume distribution obtained is shown in FIG.
  • the lithium titanate particle group of Example 4 has a large differential pore volume as in Examples 1 and 2. Since the differential pore volume is large in such a small pore diameter range (100 nm), it can be seen that the electrolytic solution penetrates into the lithium titanate particle group and the area of the lithium titanate particles in contact with the electrolytic solution is large. In particular, the differential pore volume at a pore diameter in the range of 10 to 40 nm has a value of 0.01 cm 3 / g or more, and the value also exceeds 0.03 cm 3 / g. In addition, when the pore volume distribution was similarly obtained for the lithium titanate particle group of Example 3, it was found that the differential pore volume was large as in Examples 1 and 2 (not shown). In particular, the differential pore volume at a pore diameter in the range of 10 to 40 nm had a value of 0.01 cm 3 / g or more, and the value also exceeded 0.02 cm 3 / g.

Abstract

La présente invention vise à proposer : un procédé de production de groupe de particules de composé métallique qui possède des caractéristiques de taux améliorées et est utilisé pour des électrodes de dispositifs de stockage d'électricité ; un groupe de particules de composé métallique ; et une électrode qui utilise ledit groupe de particules de composé métallique. La présente invention porte également sur un procédé de production de groupe de particules de composé métallique qui est utilisé pour des électrodes de dispositifs de stockage d'électricité, qui est caractérisé en ce qu'il comprend : une étape pour l'obtention d'une première matière composite par complexation d'un précurseur pour des particules de composé métallique et d'une source de carbone ; une étape pour l'obtention d'une seconde matière composite, les particules de composé métallique et le carbone étant complexés, en produisant les particules de composé métallique par soumission de la première matière composite à un traitement thermique dans une atmosphère non oxydante ; et une étape pour l'obtention d'un groupe de particules de composé métallique, les particules de composé métallique étant liées dans une structure de réseau à trois dimensions, par élimination de carbone par soumission de la seconde matière composite à un traitement thermique dans une atmosphère d'oxygène.
PCT/JP2015/065203 2014-12-16 2015-05-27 Procédé de production de groupe de particules de composé métallique, groupe de particules de composé métallique, et électrode pour dispositif de stockage d'électricité contenant un groupe de particules de composé métallique WO2016098371A1 (fr)

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EP15869580.9A EP3236481B1 (fr) 2014-12-16 2015-05-27 Procédé de production de groupe de particules de composé métallique, groupe de particules de composé métallique, et électrode pour dispositif de stockage d'électricité contenant un groupe de particules de composé métallique
CN201580067141.8A CN107004519B (zh) 2014-12-16 2015-05-27 金属化合物粒子群的制造方法及蓄电装置用电极的制造方法
US15/535,626 US10505187B2 (en) 2014-12-16 2015-05-27 Method of producing metal compound particle group, metal compound particle group, and electricity storage device electrode containing metal compound particle group
CN201910653797.8A CN110335763B (zh) 2014-12-16 2015-05-27 金属化合物粒子群及蓄电装置用电极
KR1020177010364A KR102438519B1 (ko) 2014-12-16 2015-05-27 금속 화합물 입자군의 제조 방법, 금속 화합물 입자군 및 금속 화합물 입자군을 포함하는 축전 디바이스용 전극
US16/454,018 US11398626B2 (en) 2014-12-16 2019-06-26 Method of producing metal compound particle group, metal compound particle group, and electricity storage device electrode containing metal compound particle group

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