WO2022065492A1 - Dispositif de fabrication de matériau d'électrode de batterie secondaire au lithium-ion, méthode de fabrication de matériau d'électrode de batterie secondaire au lithium-ion et méthode de régénération de matériau actif d'électrode positive usée - Google Patents

Dispositif de fabrication de matériau d'électrode de batterie secondaire au lithium-ion, méthode de fabrication de matériau d'électrode de batterie secondaire au lithium-ion et méthode de régénération de matériau actif d'électrode positive usée Download PDF

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WO2022065492A1
WO2022065492A1 PCT/JP2021/035412 JP2021035412W WO2022065492A1 WO 2022065492 A1 WO2022065492 A1 WO 2022065492A1 JP 2021035412 W JP2021035412 W JP 2021035412W WO 2022065492 A1 WO2022065492 A1 WO 2022065492A1
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WIPO (PCT)
Prior art keywords
electrode
lithium
ion secondary
secondary battery
lithium ion
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PCT/JP2021/035412
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English (en)
Japanese (ja)
Inventor
英明 堀江
祐一郎 横山
亮介 草野
峻 工藤
勇輔 中嶋
佑弥 田中
祐貴 猫橋
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Ａｐｂ株式会社
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Priority claimed from JP2020160934A external-priority patent/JP2022053995A/ja
Priority claimed from JP2020193627A external-priority patent/JP2022082205A/ja
Application filed by Ａｐｂ株式会社 filed Critical Ａｐｂ株式会社
Publication of WO2022065492A1 publication Critical patent/WO2022065492A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C11/00—Component parts, details or accessories not specifically provided for in groups B05C1/00 - B05C9/00
    • B05C11/10—Storage, supply or control of liquid or other fluent material; Recovery of excess liquid or other fluent material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C19/00—Apparatus specially adapted for applying particulate materials to surfaces
    • B05C19/06—Storage, supply or control of the application of particulate material; Recovery of excess particulate material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
    • B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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 disclosure relates to an electrode material manufacturing apparatus for a lithium ion secondary battery, a method for manufacturing an electrode material for a lithium ion secondary battery, and a method for regenerating a used positive electrode active material.
  • lithium-ion batteries have been used as power sources in various fields such as large stationary power sources, power sources for automobiles, and power sources for small electronic devices such as laptop personal computers and mobile phones.
  • a positive electrode active material layer containing a positive electrode active material, a binder resin and an electrolytic solution and a negative electrode active material layer containing a negative electrode active material, a binder resin and an electrolytic solution are laminated with a separator sandwiched between them. It is configured by being stored in a container (Patent Document 1).
  • the positive electrode active material constituting the lithium ion battery is, for example, in the form of particles, and is composed of a composite oxide of lithium and a transition metal, a transition metal oxide, a transition metal sulfide, a conductive polymer, and the like.
  • an electrode such as a lithium ion secondary battery
  • a pre-doping step of pre-doping the electrode material with lithium ions.
  • a carbon material such as activated carbon used as an electrode material is doped with lithium ions.
  • a carbon material is immersed in a doping tank filled with an electrolytic solution containing lithium ions to dope the carbon material with lithium ions.
  • a powder containing lithium is sprayed onto raw material particles made of a positive electrode active material raw material (electrode raw material).
  • a method for producing positive electrode active material particles in which a lithium thin film is formed on raw material particles has been proposed (Patent Document 2).
  • a coating step of coating an electrode material on the surface of a metal foil constituting a negative electrode plate vacuum vapor deposition, electron beam vapor deposition, sputtering, ion plating, CVD, and plasma CVD.
  • a manufacturing method including a film forming step of forming a lithium film on the surface of the electrode material formed in the coating step by any of the ion injection methods has been proposed (Patent Document 3).
  • the capacitor is left in a storage chamber controlled to a predetermined temperature (for example, room temperature) for a predetermined period (for example, 2 to 4 weeks).
  • the vapor-deposited lithium and the negative electrode active material are in electrical contact with each other, the vapor-deposited lithium is dissolved due to the potential difference between the negative electrode potential and the lithium potential, and the lithium ions are the negative electrode active material (amorphous carbon) of the negative electrode plate. ) Is supposed to be stored.
  • Patent Document 3 it takes more time than lithium spraying to form a lithium film on the surface of the negative electrode active material by sputtering or the like, and lithium ions are occluded in the negative electrode active material. Since it is necessary to leave the capacitor at room temperature for several weeks, it cannot be said that the reduction in manufacturing time is sufficient, and there is still room for improvement.
  • the present disclosure has been made in view of the above-mentioned circumstances, and the energy density is further increased by sufficiently introducing lithium sprayed onto the raw material particles of the positive electrode active material as lithium ions into the raw material particles.
  • Lithium-ion secondary battery electrode material manufacturing equipment, lithium-ion secondary battery electrode material manufacturing method which can improve battery performance, shorten manufacturing time, and further improve productivity. It is an object of the present invention to provide a method for regenerating an electrode material for a used lithium ion secondary battery.
  • the electrode material manufacturing apparatus for a lithium ion secondary battery has a layer forming portion for forming a lithium-containing material layer on the electrode raw material by spraying the molten lithium-containing material on the electrode raw material. It has a heat treatment unit for heating the electrode raw material on which the lithium-containing material layer is formed and introducing lithium contained in the lithium-containing material into the electrode raw material to obtain a positive electrode active material.
  • the layer formation in the layer forming portion may be performed in a dry air environment.
  • the heating temperature in the heat treatment section may be in the range of 400 ° C. or higher and 500 ° C. or lower.
  • the heating time in the heat treatment section may be in the range of 10 minutes or more and 1 hour or less.
  • the heat treatment in the layer forming portion may be performed in an inert gas atmosphere.
  • the electrode material manufacturing apparatus for a lithium ion secondary battery includes a supply device for supplying an electrode composition containing an electrode active material and a non-aqueous electrolytic solution, and the supply device supplied from the supply device. Further comprising a transport stage for transporting the electrode composition and a drive roll for driving the transport stage, the supply device includes a storage chamber for storing the electrode composition and the electrode composition stored in the storage chamber.
  • the rotary belt portion has a rotary belt portion for transporting an object and a supply port for supplying the electrode composition to the outside, and the rotary belt portion is an annular transport belt that rotates in one direction along the surface thereof, and the inside of the supply device.
  • the transport stage It has a supplied portion to which the electrode composition is supplied from the supply device, and the transport stage may be directly supported by the drive roll in the supplied portion.
  • the angle ⁇ formed by the first main surface of the rotating belt portion and the transport stage at the point closest to the second end portion may be 10 to 90 °.
  • the radius of the second end portion may be 1 to 25 mm.
  • the moving speed / moving speed of the transport stage may be 0.5 to 1.0.
  • the moving speed of the transfer stage may be 1 to 50 m / min.
  • the radius of the second end portion may be 0.02 to 5 times the radius of the drive roll.
  • a molten lithium-containing material is sprayed on the electrode raw material to form a lithium-containing material layer on the electrode raw material.
  • the layer forming step may be performed in a dry air environment.
  • the heating temperature in the heat treatment step may be in the range of 400 ° C. or higher and 500 ° C. or lower.
  • the heating time in the heat treatment step may be in the range of 10 minutes or more and 1 hour or less.
  • the heat treatment step may be performed in an inert gas atmosphere.
  • the electrode raw material may be a positive electrode active material raw material recovered from a used lithium ion battery.
  • the present disclosure is a method of manufacturing an electrode material for a lithium ion secondary battery using the above-mentioned electrode material manufacturing apparatus for a lithium ion secondary battery, in which the drive roll is driven to convey the transfer stage.
  • the electrode composition supply step of supplying the electrode composition onto the transport stage from the supply port, and the electrode composition supplied onto the transport stage in the gap between the transport stage and the supply device. It may have an electrode active material layer forming step of adjusting the thickness of the electrode composition by passing the electrode composition to obtain an electrode active material layer made of the electrode composition.
  • the electrode composition supplied on the transport stage is passed through a gap between the transport stage and the second end portion of the rotary belt portion. You may.
  • the energy density can be further increased and the battery performance can be improved, and the battery performance can be improved.
  • the time can be further shortened and the productivity can be further improved.
  • FIG. 1 is a schematic view showing an example of an electrode material manufacturing apparatus for a lithium ion secondary battery according to the first embodiment of the present disclosure.
  • FIG. 2 is a schematic cross-sectional view showing an example of the configuration of positive electrode active material particles manufactured by the electrode material manufacturing apparatus for a lithium ion secondary battery of the present disclosure.
  • FIG. 3 is a cross-sectional view schematically showing an example of an electrode material manufacturing apparatus for a lithium ion secondary battery according to the second embodiment of the present disclosure.
  • FIG. 4 is a partially enlarged view of the electrode material manufacturing apparatus for a lithium ion secondary battery shown in FIG.
  • FIG. 5 is a perspective view of a supply device constituting the electrode material manufacturing device for a lithium ion secondary battery shown in FIG. FIG.
  • FIG. 6 is a cross-sectional view schematically showing another example of the supply device.
  • FIG. 7 is a cross-sectional view schematically showing still another example of the supply device.
  • FIG. 8 is a perspective view schematically showing a modified example of the electrode material manufacturing apparatus for a lithium ion secondary battery according to the second embodiment.
  • FIG. 9 is a diagram schematically showing the configuration of the assembled battery according to the third embodiment of the present disclosure.
  • FIG. 10 is a diagram schematically showing the configuration of a battery cell according to the third embodiment.
  • FIG. 11 is a plan view of the frame-shaped member according to the third embodiment as viewed from the thickness direction.
  • FIG. 12 is a diagram illustrating the operation of the frame-shaped member according to the third embodiment.
  • FIG. 13 is an enlarged plan view of a main part of the frame-shaped member according to the fourth embodiment of the present disclosure as viewed from the thickness direction.
  • FIG. 14 is a diagram illustrating the operation of the frame-shaped member according to the fourth embodiment.
  • FIG. 15 is an enlarged plan view of a main part of the frame-shaped member according to the fifth embodiment of the present disclosure as viewed from the thickness direction.
  • FIG. 16 is a diagram illustrating the operation of the frame-shaped member according to the fifth embodiment.
  • the lithium ion battery is a concept including a lithium ion secondary battery.
  • FIG. 1 is a schematic view showing an example of an electrode material manufacturing apparatus for a lithium ion secondary battery according to the first embodiment of the present disclosure.
  • FIG. 2 is a schematic cross-sectional view showing an example of the configuration of positive electrode active material particles manufactured by an electrode material manufacturing apparatus for a lithium ion secondary battery.
  • the layer forming portion 1 for forming a lithium-containing material layer on the electrode raw material by spraying the molten lithium-containing material on the electrode raw material, and the lithium. It has a heat treatment unit 2 for heating an electrode raw material on which a contained material layer is formed and introducing lithium contained in the lithium-containing material into the electrode raw material to obtain a positive electrode active material.
  • the layer forming section 1 performs a layer forming step described later, and the heat treatment section 2 performs a heat treatment step described later.
  • the lithium ion secondary battery electrode material manufacturing apparatus is not limited to the layer forming unit 1 and the heat treatment unit 2 described above, and may have other configurations other than these configurations.
  • the lithium ion battery to which the positive electrode active material is applied is not particularly limited, and for example, a lithium ion battery having a liquid electrolyte, an all-solid-state battery having a solid electrolyte, a lithium ion battery having an electrode current collector and terminals made of resin, and the like. Can be mentioned. Of these, from the viewpoint of increasing the charging capacity, reducing the cost, and improving the safety, a lithium ion battery in which the electrode current collector and the terminal are made of resin is preferable.
  • the method for producing a positive electrode active material of the present embodiment includes a layer forming step and a heat treatment step.
  • the method for producing the positive electrode active material is not limited to the above steps, and may have other steps before and after each of the above steps.
  • the molten lithium-containing material 12 is sprayed on the electrode raw material 11 to form the lithium-containing material layer 13 on the electrode raw material 11.
  • the lithium-containing material 12 is sprayed onto the electrode raw material 11 while being melted (spraying step).
  • the present invention is not limited to this, and the lithium-containing material 12 may be melted (melting step), and then the melted lithium-containing material may be sprayed onto the electrode raw material 11 (spraying step).
  • the layer forming step is preferably carried out in a dry gas environment in order to suppress the reaction of active lithium with water.
  • a thermal spraying device 20 can be used as a method of spraying the molten lithium-containing material 12 onto the raw material particles of the electrode raw material 11.
  • the thermal spraying device 20 includes, for example, a lithium-containing powder supply unit 21, a heating gas supply unit 22, and a thermal spray nozzle 23.
  • a treatment room dry room
  • dry air having reduced humidity
  • the lithium-containing powder supply unit 21 constituting the thermal spraying device 20 supplies the lithium-containing powder to the thermal spray nozzle 23.
  • the heating gas supply unit 22 supplies the heating gas to the thermal spray nozzle 23.
  • the heating gas functions as a heat energy source for melting the lithium-containing powder and a carrier for injecting the melted lithium-containing powder.
  • an inert gas that does not react with lithium for example, a rare gas such as argon can be used.
  • the lithium-containing powder supplied from the lithium-containing powder supply unit 21 is mixed with the heating gas supplied from the heating gas supply unit 22 on the upstream side of the thermal spray nozzle 23 or in the thermal spray nozzle 23.
  • the lithium-containing powder is melted by the heating gas, becomes a sprayed liquid, and is sprayed onto the raw material particles of the electrode raw material 11.
  • a lithium-containing material layer 13 is formed on the surface of the raw material particles of the electrode raw material 11 (FIG. 2).
  • the electrode raw material 11 is formed on, for example, the electrode sheet 14 and contains raw material particles of the positive electrode active material.
  • the electrode raw material 11 may be made of raw material particles of the positive electrode active material, and in addition to the raw material particles of the positive electrode active material, a conductive auxiliary agent, an adhesive resin, and a solution-drying type known electrode binder (binding). It may contain one or more of the agent). Further, it may contain an electrolyte, a solvent or the like constituting a non-aqueous electrolytic solution used for manufacturing a lithium ion battery.
  • the electrode sheet 14 may be a positive electrode current collector or may be a base material other than the positive electrode current collector.
  • the positive electrode active material particles are not particularly limited as long as they can be used as the positive electrode active material of the lithium ion battery, and for example, a composite oxide of lithium and a transition metal ⁇ a composite oxide having one type of transition metal.
  • a composite oxide of lithium and a transition metal ⁇ a composite oxide having one type of transition metal LiCoO 2 , LiNiO 2 , LiAlMnO 4 , LiMnO 2 , LiMn 2 O 4 , etc.
  • composite oxides with two transition metal elements eg LiFeMnO 4 , LiNi 1-x Co x O 2 , LiMn 1-y Co) y O 2 , LiNi 1/3 Co 1/3 Al 1/3 O 2 and LiNi 0.8 Co 0.15 Al 0.05 O 2
  • the lithium-containing transition metal phosphate may be obtained by substituting a part of the transition metal site with another transition metal. Further, one selected from these compounds may be used alone, or two or more thereof may be used in combination.
  • the average particle size of the positive electrode active material particles is preferably 0.1 ⁇ m or more and 100 ⁇ m or less, more preferably 1 ⁇ m or more and 50 ⁇ m or less, and further preferably 2 ⁇ m or more and 20 ⁇ m or less from the viewpoint of the electrical characteristics of the lithium ion battery to be manufactured. preferable.
  • the volume average particle size of the positive electrode active material particles referred to here means the particle size (D v50 ) at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method (also referred to as the microtrack method).
  • the laser diffraction / scattering method is a method for obtaining a particle size distribution using scattered light obtained by irradiating particles with laser light.
  • a micro manufactured by Nikkiso Co., Ltd. A truck or the like can be used.
  • the electrode raw material 11 contains transition metal oxides containing no lithium, such as cobalt oxide, nickel oxide, nickel-cobalt oxide, nickel-cobalt-aluminum oxide, vanadium oxide, and transition metal sulfides (for example, MoS 2 and TiS). 2 ) may be used.
  • transition metal oxides containing no lithium such as cobalt oxide, nickel oxide, nickel-cobalt oxide, nickel-cobalt-aluminum oxide, vanadium oxide, and transition metal sulfides (for example, MoS 2 and TiS). 2 ) may be used.
  • the shape of the electrode raw material 11 used in the present embodiment is not particularly limited, and various shapes such as a spherical shape, a plate shape, a rod shape, a needle shape, and an indefinite shape can be applied.
  • the conductive auxiliary agent is not particularly limited, but is limited to metals [nickel, aluminum, stainless steel (SUS), silver, copper, titanium, etc.], carbon [graphite and carbon black (acetylene black, ketjen black, furnace black, channel black, etc.], Thermal lamp black, etc.)] etc. Further, one selected from these conductive aids may be used alone, or two or more thereof may be used in combination. Moreover, you may use these alloys or metal oxides. From the viewpoint of electrical stability, aluminum, stainless steel, carbon, silver, copper, titanium and mixtures thereof are preferable, silver, aluminum, stainless steel and carbon are more preferable, and carbon is more preferable. Further, these conductive auxiliaries may be those obtained by coating a conductive material (a metal one among the above-mentioned conductive auxiliaries materials) around a particle-based ceramic material or a resin material by plating or the like.
  • a conductive material a metal one among the above-mentioned conductive auxiliaries materials
  • the adhesive resin means a resin having adhesiveness (property of adhering by applying a slight pressure without using water, solvent, heat, etc.).
  • Those described as agents can be preferably used.
  • Binders for electrodes include starch, polyvinylidene fluoride (PVdF), polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), polyvinylpyrrolidone (PVP), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), and polyethylene.
  • PVdF polyvinylidene fluoride
  • PVA polyvinyl alcohol
  • CMC carboxymethyl cellulose
  • PVP polyvinylpyrrolidone
  • PTFE polytetrafluoroethylene
  • SBR styrene-butadiene rubber
  • PE polypropylene
  • PE polypropylene
  • lithium salts of inorganic acids such as LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 and LiClO 4 , LiN (CF 3 SO). 2
  • lithium salts of organic acids such as 2 , LiN (C 2 F 5 SO 2 ) 2 and LiC (CF 3 SO 2 ) 3 .
  • LiPF 6 is preferable from the viewpoint of battery output and charge / discharge cycle characteristics.
  • those used in known non-aqueous electrolytic solutions can be used, for example, lactone compounds, cyclic or chain carbonates other than the above, chain carboxylic acid esters, cyclic or chain ethers, phosphoric acid esters. , Ester compounds, amide compounds, sulfones, sulfolanes and the like, and mixtures thereof.
  • lithium-containing material 12 to be sprayed for example, a lithium metal powder coated with a phosphorus-containing compound or the like can be used.
  • Such lithium metal powder is extremely stable and easy to handle even in air, and can be melted to obtain lithium by heating at a temperature equal to or higher than the melting point temperature of lithium.
  • such lithium-containing powder is heated with a heating gas to enable lithium spraying on the electrode raw material 11.
  • the thermal spraying process includes the above-mentioned flame spraying, but the present invention is not limited to this, and may be arc spraying, plasma spraying, high-speed flame spraying, electromagnetically accelerated plasma spraying, laser spraying, or the like.
  • the electrode raw material 11 on which the lithium-containing material layer 13 is formed is heated, and lithium contained in the lithium-containing material layer 13 is introduced into the electrode raw material 11 to form positive electrode active material particles 16. do.
  • heat diffusion is used as a method of introducing lithium into the electrode raw material 11. That is, by heating the raw material particles of the electrode raw material 11 having the lithium-containing material layer 13 formed on the surface layer by the heating device 25, the lithium of the lithium-containing material layer 13 is applied to the entire inside (from the surface to the center) of the raw material particles. Heat diffuse. As a result, lithium ions are doped into the entire inside of the raw material particles of the electrode raw material 11 (FIG. 2).
  • lithium ions are coordinated between the crystal lattices of the composite oxide of lithium and the transition metal, and the lithium ion concentration distribution in the raw material particles of the electrode raw material 11 is changed from the initial state to the increased hypersaturated state. be able to.
  • the heating device 25 used in this heat treatment step is not particularly limited, but for example, an infrared heating furnace can be used.
  • the heating temperature is set to a temperature range in which lithium is easily diffused and does not scatter, for example, 400 ° C. or higher and 500 ° C. or lower. By setting the heating temperature to 400 ° C. or higher and 500 ° C. or lower, lithium ions can be doped in a more activated state.
  • the heating time is not particularly limited, but is preferably set to, for example, 10 minutes or more and 1 hour or less from the viewpoint of reliably doping lithium ions to the vicinity of the center of the raw material particles.
  • the heating time can be further extended (for example, depending on the specifications of the positive electrode active material layer containing the regenerated positive electrode active material obtained by reliably doping lithium ions (for example, the thickness and area of the layer)). 2 hours or more and 50 hours or less) may be used.
  • the positive electrode active material particles 16 in which lithium ions are coordinated between the crystal lattices of the composite oxide of lithium and the transition metal can be obtained.
  • the layer forming step to the heat treatment step for example, it is preferable to supply the electrode raw material 11 to a series of conveyors to continuously form the positive electrode active material particles 16, but the present invention is not limited to this and is intermittent by a batch method or the like.
  • the positive electrode active material particles 16 may be formed.
  • a forming step of forming a coating layer on the surface of the obtained positive electrode active material particles 16 may be provided.
  • the entire surface of the positive electrode active material particles 16 is covered with the coating layer, the volume change of the positive electrode is alleviated, and the expansion of the positive electrode can be suppressed.
  • Examples of the resin for coating the positive electrode active material constituting the coating layer include an ester compound (a11) of a monovalent aliphatic alcohol having 4 to 12 carbon atoms and (meth) acrylic acid, and (meth) acrylic acid (a12).
  • the compound (b2) having two or more radically polymerizable groups and the (meth) acrylic acid.
  • the content of the ester compound (a11) is not particularly limited, but is 20% by mass with respect to the total mass of the ester compound (a11) and the (meth) acrylic acid (a12) from the viewpoint of adhesion to the active material and the like. It is 98% by mass or less, preferably 40% by mass or more and 97% by mass or less, and more preferably 60% by mass or more and 95% by mass or less.
  • the coating layer may contain the above-mentioned conductive auxiliary agent, if necessary.
  • the lithium of the lithium-containing material layer formed on the surface of the raw material particles by spraying the lithium-containing material can be diffused to the inside of the raw material particles by heat treatment.
  • the positive electrode active material particles in which lithium ions are coordinated can be obtained in the entire interior from the surface to the center of the positive electrode active material particles, and the energy density of the positive electrode active material particles can be further increased to improve the battery performance. It will be possible.
  • the lithium-containing material layer can be formed in a short time as compared with sputtering or the like by spraying the molten lithium, and the lithium ions can be quickly diffused inside the positive electrode active material particles by the heat treatment. Therefore, it is possible to further shorten the production time of the positive electrode active material and further improve the productivity.
  • the used electrode material 11 in the above-described embodiment not only the unused electrode material but also the used electrode material (positive electrode active material) attached to the lithium ion battery can be used.
  • the used electrode material is the one from which the lithium ions existing in the crystal lattice of the composite oxide of lithium and the transition metal have escaped.
  • lithium ions are introduced into the raw material particles of the electrode material by heat treatment (annealing treatment), and the lithium ions are formed into crystal lattice defects of the composite oxide of lithium and the transition metal. It may be arranged.
  • Lithium ions are activated by replenishing the crystal lattice defects, which makes it possible to regenerate the used positive electrode active material. Therefore, the regenerated positive electrode active material can be easily obtained at low cost, and the recyclability of the positive electrode active material can be improved as compared with the conventional case.
  • the used electrode material When the used electrode material is used as the electrode raw material 11, it may further have a step of removing the coating layer on the surface of the positive electrode active material particles in advance. Further, after the electrode raw material 11 is subjected to a heat treatment step, a forming step of forming a coating layer on the surface of the positive electrode active material particles may be further provided.
  • a physical peeling method As a method for removing the coating layer of the used electrode material, either a physical peeling method or a chemical peeling method may be used.
  • the physical peeling method include a method of peeling with a brush or an abrasive.
  • the chemical stripping method include a method of dissolving and removing the coating layer using a solvent capable of dissolving the coating layer, and a method of decomposing and removing the coating layer using a reaction solution capable of decomposing the coating layer. Be done.
  • the electrodes used in a lithium-ion battery are provided with an active material layer containing an active material on a current collector, and a homogeneous active material layer is formed to exhibit stable battery performance.
  • This active material layer is manufactured by supplying a slurry-like electrode material in which the active material is dispersed in a liquid medium to a current collector, drying the particles, and then compacting the particles. However, the drying process is omitted to save energy.
  • a method for producing at low cost a method using granulated particles obtained by granulating active material particles and a binder is known (see Patent Document 4).
  • a current collector As a method for manufacturing a lithium ion battery capable of obtaining a homogeneous active material layer even with low-fluidity particles such as granulated particles obtained by granulating active material particles and binder, for example, a current collector is conveyed. Conveying means to supply, a supply unit that supplies granulated particles containing active material particles and binder to the surface of the current collector being transported, a squeegee that evens out the supplied granulated particles, and an arrangement on the upstream side of the squeegee.
  • Granulation is performed by a device including an adjusting unit for controlling the storage height of the granulated particles stored on the upstream side of the squeegee, and a rolling roll for rolling the leveled granulated particles to form an active material layer.
  • a method for rolling particles is disclosed (see Patent Document 5).
  • the base material is conveyed vertically downward and the base material is conveyed by a pair of press rolls. Is disclosed as a method for producing an electrode sheet by compacting the powder layer (see Patent Document 6).
  • the granulated particles are not stably supplied from the supply unit, and the surface of the active material is roughened, resulting in variations in the density of the active material layer, resulting in electrical characteristics. It was the cause of the variation and the decrease of the yield.
  • the electrode composition can be stably supplied, and an electrode active material layer having no surface roughness can be obtained. It is an object of the present invention to provide an electrode material manufacturing apparatus for an ion secondary battery and a method for manufacturing an electrode material for a lithium ion secondary battery using the manufacturing apparatus.
  • FIG. 3 is a cross-sectional view schematically showing an example of an electrode material manufacturing apparatus for a lithium ion secondary battery according to the second embodiment of the present disclosure.
  • the electrode material manufacturing apparatus 100 for a lithium ion secondary battery is supplied from a supply device 101 for supplying an electrode composition 150 containing an electrode active material and a non-aqueous electrolytic solution, and a supply device 101.
  • a transport stage 160 for transporting the electrode composition 150 and a drive roll 180 for driving the transport stage 160 are provided.
  • the drive roll 180 rotates clockwise and drives the transport stage 160 in the direction from the lower side of the paper surface to the right side of the paper surface (the direction indicated by the arrow A in FIG. 3).
  • FIG. 4 is a partially enlarged view of the electrode material manufacturing apparatus for a lithium ion secondary battery shown in FIG.
  • the moving direction of the rotary belt portion 120 is the direction indicated by the arrow B.
  • the moving direction of the rotating belt portion 120 is equal to the moving direction of the transport stage 160 (the direction indicated by the arrow A in FIG. 4) at the point facing the rotating belt portion 120 at the shortest distance d.
  • FIG. 5 is a perspective view of a supply device constituting the electrode material manufacturing device for a lithium ion secondary battery shown in FIG.
  • the supply device 101 includes a storage chamber 110 for storing the electrode composition 150, a rotary belt portion 120 for transporting the electrode composition 150 stored in the storage chamber 110, and an electrode composition. It has a supply port 130 for supplying 150 to the outside.
  • the rotary belt portion 120 faces the annular transport belt 121 that rotates in one direction along the surface thereof and the first main surface 120a and the first main surface 120a that come into contact with the electrode composition 150 inside the supply device 101. It has two main surfaces 120b, a first end portion 120c and a second end portion 120d constituting the rotation axis of the annular transfer belt 121.
  • the annular transfer belt 121 is the first of the rotary belt portions 120 forming a part of the supply port 130.
  • the two ends are moving in the direction toward the end 120d (the direction indicated by the arrow a in FIG. 3).
  • the annular transport belt 121 is directed toward the first end portion 120c of the rotary belt portion 120 (in FIG. 3). It is moving in the direction indicated by the arrow b). Therefore, the electrode composition 150 stored in the storage chamber 110 is conveyed to the supply port 130 by the annular transfer belt 121. Therefore, even when the fluidity of the electrode composition is low, the electrode composition can be stably supplied onto the transport stage.
  • the electrode composition 150 is supplied onto the transfer stage 160 through the supply port 130 of the supply device 101, and then passes between the second end portion 120d of the rotary belt portion 120 and the transfer stage 160 to have a predetermined thickness. It is adjusted to become the electrode active material layer 151.
  • the transport stage 160 has a supplied portion 160a to which the electrode composition 150 is supplied from the supply device 101.
  • the transport stage 160 is directly supported by the drive roll 180 in the supplied portion 160a.
  • the transfer stage 160a suppresses the positional deviation of the transfer stage 160 in the thickness direction (vertical direction) and is placed on the transfer stage 160. It is possible to suppress variations in the thickness of the supplied electrode composition 150.
  • the electrode composition is stably supplied onto the transport stage, and the supplied portion of the transport stage to which the electrode composition is supplied is driven by a drive roll. It is directly supported. Therefore, the electrode composition can be stably supplied on the transport stage in which the positional deviation in the thickness direction is suppressed, so that the electrode has no surface roughness even when the fluidity of the electrode composition is low. A composition layer can be obtained, which can contribute to improvement of electrical characteristics and product yield.
  • the fact that the transport stage is directly supported by the drive roll in the supplied portion means that a space is provided between the supplied portion of the transport stage and the drive roll to allow vibration of the supplied portion of the transport stage. Refers to the state where it is not.
  • the supplied portion 160a of the transport stage 160 is in close contact with the drive roll 180.
  • a space that allows vibration of the supplied portion 160a of the transport stage 160 between the supplied portion 160a of the transport stage 160 and the drive roll 180. is not formed.
  • the state in which the supplied portion 160a of the transport stage 160 is in close contact with the surface of the drive roll 180 is a state in which the supplied portion 160a of the transport stage 160 is directly supported by the drive roll 180.
  • the transfer stage is not directly supported by the drive rolls, for example, there is a case where the transfer stages are arranged across a plurality of drive rolls, such as a belt conveyor. In this case, the transport stage is provided with a portion that is not directly supported by the drive roll. In such a place, the position deviation in the thickness direction is likely to occur on the transport stage.
  • the transfer stage 160 is directly supported by the drive roll 180 at the point where the rotary belt portion 120 and the transfer stage 160 face each other at the shortest distance d.
  • the electrode composition 150 passes through a point where the rotating belt portion 120 and the transport stage 160 face each other at the shortest distance d, so that the electrode active material layer 151 has an adjusted thickness. That is, the thickness of the electrode active material layer 151 is determined by the shortest distance d between the rotating belt portion 120 and the transport stage 160. Therefore, when the transport stage 160 is directly supported by the drive roll 180 at the point where the rotary belt portion 120 and the transport stage 160 face each other at the shortest distance d, the shortest distance d between the rotary belt section 120 and the transport stage 160 becomes. It is stable and the variation in the thickness of the electrode active material layer 151 can be reduced.
  • a sheet-like base material that is in close contact with the transfer stage and the drive roll may be arranged between the transfer stage and the transfer roll. In this case, it can be said that the transfer stage is directly supported by the drive roll. In this way, even if another configuration is arranged between the transfer stage and the drive roll, if the transfer stage and the drive roll are in close contact with each other through this configuration, the transfer stage Is considered to be directly supported by the drive roll.
  • the surface roughness of the drive roll is not particularly limited, but it is preferable that the surface roughness Ra measured in accordance with JIS B 0601 is 2 ⁇ m or less.
  • the material constituting the drive roll is not particularly limited, and examples thereof include a high carbon chromium bearing steel material (SUJ2).
  • the drive roll may have a multi-layer structure.
  • An example of the case where the drive roll has a multi-layer structure includes a roll made of high carbon chrome bearing steel with a hard chrome plating (for example, a thickness of 30 to 80 ⁇ m) applied to the surface of the roll.
  • the second end portion 120d of the rotary belt portion 120 constitutes one side of the supply port 130, and the side facing the second end portion 120d is formed by the lower end portion 140a of the wall material 140.
  • the supply port 130 has a substantially rectangular shape, the second end portion 120d of the rotary belt portion 120 constitutes one of the long sides, and the lower end portion 140a of the wall material 140 constitutes the other long side.
  • the angle between the first main surface 120a of the rotary belt portion 120 and the transport stage 160 at the point closest to the second end portion 120d is preferably more than 0 ° and 90 ° or less, preferably 10 ° to 90 °. Is preferable.
  • the radius of the second end of the rotating belt portion is not particularly limited, but is preferably 0.02 to 5 times the radius of the drive roll.
  • the radius of the second end of the rotating belt portion is not particularly limited, but is preferably 1 to 25 mm.
  • the ratio of the moving speeds of the rotary belt and the transport stage facing each other is Although not particularly limited, it is preferably 0.5 to 1.0.
  • the moving speed of the annular transport belt may be appropriately set according to the fluidity of the electrode composition, but is preferably 0.5 to 50 m / min, for example.
  • the material constituting the annular transport belt is not particularly limited, but a material having a non-adhesive surface such as a fluororesin (hereinafter, also referred to as a non-adhesive material) is preferably mentioned.
  • a material having a non-adhesive surface such as a fluororesin (hereinafter, also referred to as a non-adhesive material) is preferably mentioned.
  • the material constituting the annular transfer belt is a non-adhesive material, the electrode composition is less likely to adhere to the surface of the annular transfer belt, and variations in the supply amount of the electrode composition are suppressed.
  • the means for rotating the annular conveyor belt is not particularly limited, and examples thereof include a method of rotating the rotation shaft using a rotating body such as a motor.
  • the material constituting the transport stage is not particularly limited, but a material that functions as a current collector such as a positive electrode current collector or a negative electrode current collector can be preferably used.
  • the transport stage functions as a current collector such as a positive electrode current collector or a negative electrode current collector
  • the electrode material for a lithium ion secondary battery is obtained in a state of being arranged on the current collector.
  • the combination of the current collector and the electrode material for the lithium ion secondary battery arranged on the current collector corresponds to the electrode for the lithium ion secondary battery.
  • the material constituting the positive electrode current collector examples include copper, aluminum, titanium, stainless steel, nickel, calcined carbon, conductive polymer, and conductive glass. Further, as the positive electrode current collector, a resin current collector composed of a conductive agent and a resin may be used.
  • the negative electrode current collector examples include copper, aluminum, titanium, stainless steel, nickel, and metal materials such as alloys thereof. Of these, copper is preferable from the viewpoint of weight reduction, corrosion resistance, and high conductivity.
  • the negative electrode current collector may be a current collector made of calcined carbon, a conductive polymer, conductive glass, or the like, or may be a resin current collector made of a conductive agent and a resin.
  • the resins constituting the resin collector include polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polycycloolefin (PCO), polyethylene terephthalate (PET), polyether nitrile (PEN), and polytetra. Fluoroethylene (PTFE), Styrene-butadiene rubber (SBR), Polyacrylonitrile (PAN), Polymethylacrylate (PMA), Polymethylmethacrylate (PMMA), Polyfluorinated vinylidene (PVdF), Epoxy resin, Silicone resin or mixtures thereof. And so on.
  • polyethylene (PE), polypropylene (PP), polymethylpentene (PMP) and polycycloolefin (PCO) are preferable, and polyethylene (PE), polypropylene (PP) and polymethylpentene are more preferable. (PMP).
  • the transfer stage does not function as a current collector such as a positive electrode current collector or a negative electrode current collector
  • the current collector is placed on the transfer stage or the electrode composition from the surface of the transfer stage. It is preferable to construct the transfer stage with a material that can be easily separated.
  • a material that does not function as a current collector is used as the transport stage, lithium ions are obtained by transferring the electrode active material layer obtained after the electrode active material layer forming step described later from the transport stage to the current collector.
  • Electrodes for secondary batteries can be manufactured.
  • Preferred examples of the material from which the electrode composition can be easily separated from the surface of the transport stage include fluororesin and a resin film having a surface subjected to a non-adhesive treatment such as a mold release treatment.
  • the electrode composition is supplied on the current collector arranged on the transfer stage. Therefore, the electrode active material layer is formed on the current collector.
  • the step of supplying the electrode composition onto the current collector arranged on the transport stage is also included in the electrode active material layer forming step described later. In this case, an electrode composed of a current collector and an electrode active material layer formed on the current collector can be formed on the transport stage.
  • the moving speed of the transport stage is not particularly limited, but is preferably 1 to 50 m / min.
  • the shape and size of the storage chamber are not particularly limited as long as they can store the electrode composition.
  • the inner wall of the storage chamber is preferably made of a non-adhesive material such as fluororesin. When the inner wall of the storage chamber is made of a non-adhesive material, the electrode composition can be stably discharged from the storage chamber. Further, the inner wall of the storage chamber may be a surface of a material (for example, metal) that is not a non-adhesive material coated with the non-adhesive material.
  • the shape of the supply port of the supply device is not particularly limited, but a substantially rectangular shape is preferable.
  • the substantially rectangular shape preferably has a short side length of 1 to 50 mm. Further, it is preferable that one of the long sides of the substantially rectangular shape is formed by the second end portion of the rotating belt portion.
  • the position where the supply port is provided may be the bottom surface of the supply device or the side surface.
  • FIG. 6 is a cross-sectional view schematically showing another example of the supply device.
  • the supply device 102 shown in FIG. 6 has a storage chamber 110, a rotary belt portion 120, and a supply port 130.
  • the moving direction of the annular conveyor belt 121 constituting the rotary belt portion 120 is the same as in FIGS. 3 and 5.
  • the position where the rotary belt portion is arranged is not particularly limited.
  • the rotary belt portion may be provided on the bottom surface inclined toward the supply port of the storage chamber, or may be provided on the side surface of the storage chamber.
  • FIG. 7 is a cross-sectional view schematically showing still another example of the supply device.
  • the supply device 103 shown in FIG. 7 has a storage chamber 110, a rotary belt portion 120, and a supply port 130, and the rotary belt portion 120 is arranged along a wall material 142 constituting a side surface of the storage chamber 110.
  • One side of the supply port 130 is formed by the second end portion 120d of the rotating belt portion 120, and the side facing the supply port 130 is formed by the lower end portion 141a of the wall material 141.
  • the annular transfer belt 121 constitutes one side of the supply port 130 on the first main surface 120a of the rotary belt portion 120 arranged on the surface facing the inside of the storage chamber 110 and in contact with the electrode composition.
  • the electrode composition 150 that is moving toward the second end portion 120d of the rotary belt portion 120 (in the direction indicated by the arrow a) and stored in the storage chamber 110 is conveyed to the supply port 130 by the annular transport belt 121. Ru. Therefore, even when the fluidity of the electrode composition is low, the electrode composition can be stably supplied to the outside.
  • the side surface of the storage chamber may be arranged perpendicular to the moving direction of the transport stage, and the side surface of the storage chamber 110 is inclined from the vertical direction. It may be arranged by.
  • the moving direction of the annular transport belt at the position facing the transport stage and the moving direction of the transport stage may be different.
  • FIG. 8 is a perspective view schematically showing a modified example of the electrode material manufacturing apparatus for a lithium ion secondary battery according to the second embodiment.
  • the electrode material manufacturing apparatus 200 for a lithium ion secondary battery shown in FIG. 8 includes a supply device 101 for supplying the electrode composition 150, a transfer stage 160 for transporting the electrode composition 150 supplied from the supply device 101, and a transfer stage.
  • the point that the drive roll 180 for driving the 160 is provided is the same as that of the electrode material manufacturing apparatus 100 for a lithium ion secondary battery shown in FIG.
  • the difference between the lithium ion secondary battery electrode material manufacturing device 200 and the lithium ion secondary battery electrode material manufacturing device 100 is that the supply device 101 is arranged.
  • the moving direction of the rotary belt portion 120 is the direction indicated by the arrow B.
  • the moving direction of the rotating belt portion is opposite to the moving direction of the transport stage 160 (the direction indicated by the arrow A in FIG. 8) at the point facing the rotating belt portion 120 at the shortest distance d.
  • the method for manufacturing an electrode material for a lithium ion secondary battery of the present disclosure is a method for manufacturing an electrode material for a lithium ion secondary battery using the electrode material manufacturing apparatus for a lithium ion secondary battery of the present disclosure, and is the above-mentioned drive roll.
  • the electrode composition supply step the electrode composition is supplied onto the transfer stage from the supply port while the drive roll is driven to transfer the transfer stage.
  • the electrode composition is stably supplied on the transport stage. Further, since the transfer stage is directly supported by the drive roll in the supplied portion of the transfer stage to which the electrode composition is supplied, it is possible to suppress the fluctuation of the thickness of the electrode composition supplied on the transfer stage. can.
  • the electrode composition may be supplied onto a current collector arranged on the transport stage.
  • the thickness of the electrode composition is adjusted by passing the electrode composition supplied on the transfer stage by the electrode composition supply step through the gap between the transfer stage and the supply device. Then, an electrode active material layer made of the electrode composition is obtained. Since the electrode composition supplied onto the transport stage by the electrode composition supply step has less density unevenness and high thickness uniformity, the electrode active material layer forming step has less surface roughness and density unevenness, and thickness. It is possible to form an electrode active material layer with low variation.
  • the length of the gap between the transport stage and the supply device can be appropriately adjusted according to the thickness of the electrode active material layer to be obtained, and is preferably 0.03 to 2 mm, for example.
  • the moving direction of the annular transfer belt and the transfer stage at the position facing the transfer stage is the same.
  • the transfer stage at the point where the electrode active material layer passes is moved by the drive roll. It is preferably directly supported.
  • the electrode composition used in the electrode composition supply step includes an electrode active material and a non-aqueous electrolyte solution.
  • the electrode active material may be a positive electrode active material or a negative electrode active material. Further, the electrode composition may contain a conductive auxiliary agent, if necessary.
  • the positive electrode active material examples include a composite oxide of lithium and a transition metal ⁇ composite oxide having one type of transition metal (LiCoO 2 , LiNiO 2 , LiAlMnO 4 , LiMnO 2 , LiMn2O 4 , etc.) and a transition metal element.
  • LiFeMnO 4 LiNi 1- x Co x O2, LiMn 1-y Coy O2 , LiNi 1/3 Co 1/3 Al 1/3 O 2 and LiNi 0.8 Co 0.15 Al 0.05 O 2
  • Examples thereof include metal sulfides (eg MoS 2 and TiS 2 ) and conductive polymers (eg polyaniline, polypyrrole, polythiophene, polyacetylene and poly-p-phenylene and polyvinylcarbazole), and two or more thereof may be used in combination.
  • the lithium-containing transition metal phosphate may be one in which a part of the transition metal site is replaced with another transition metal.
  • the volume average particle size of the positive electrode active material is preferably 0.01 to 100 ⁇ m, more preferably 0.1 to 35 ⁇ m, and even more preferably 2 to 30 ⁇ m from the viewpoint of the electrical characteristics of the battery. ..
  • Examples of the negative electrode active material include carbon-based materials [graphite, refractory carbon, amorphous carbon, fired resin (for example, phenol resin, furan resin, etc. baked and carbonized), cokes (for example, pitch coke, needle). Coke and petroleum coke etc.) and carbon fibers], silicon-based materials [silicon, silicon oxide (SiO x ), silicon-carbon composite (carbon particles whose surface is coated with silicon and / or silicon carbide, silicon particles or Silicon oxide particles whose surface is coated with carbon and / or silicon carbide, silicon carbide, etc.) and silicon alloys (silicon-aluminum alloys, silicon-lithium alloys, silicon-nickel alloys, silicon-iron alloys, silicon-titanium alloys, etc.
  • carbon-based materials graphite, refractory carbon, amorphous carbon, fired resin (for example, phenol resin, furan resin, etc. baked and carbonized), cokes (for example, pitch coke, needle). Coke and petroleum coke etc.)
  • conductive polymers eg, polyacetylene and polypyrrole, etc.
  • metals tin, aluminum, zirconium, titanium, etc.
  • metal oxides titanium oxides
  • metal alloys for example, lithium-tin alloys, lithium-aluminum alloys, lithium-aluminum-manganese alloys, etc.
  • carbon-based materials, silicon-based materials and mixtures thereof are preferable from the viewpoint of battery capacity and the like, graphite, non-graphitizable carbon and amorphous carbon are more preferable as carbon-based materials, and silicon-based materials are more preferable. , Silicon oxide and silicon-carbon composites are more preferred.
  • the volume average particle size of the negative electrode active material is preferably 0.01 to 100 ⁇ m, more preferably 0.1 to 20 ⁇ m, and even more preferably 2 to 10 ⁇ m from the viewpoint of the electrical characteristics of the battery.
  • the volume average particle size of the negative electrode active material means the particle size (Dv50) at an integrated value of 50% in the particle size distribution obtained by the microtrack method (laser diffraction / scattering method).
  • the microtrack method is a method for obtaining a particle size distribution by using scattered light obtained by irradiating particles with laser light.
  • a microtrack manufactured by Nikkiso Co., Ltd. can be used for measuring the volume average particle size.
  • the conductive auxiliary agent is selected from materials having conductivity. Specifically, metals [nickel, aluminum, stainless steel (SUS), silver, copper, titanium, etc.], carbon [graphite and carbon black (acetylene black, ketjen black, furnace black, channel black, thermal lamp black, etc.), etc.), etc. ], And a mixture thereof, etc., but is not limited thereto. These conductive auxiliaries may be used alone or in combination of two or more. Moreover, you may use these alloys or metal oxides. From the viewpoint of electrical stability, aluminum, stainless steel, carbon, silver, copper, titanium and mixtures thereof are preferable, silver, aluminum, stainless steel and carbon are more preferable, and carbon is more preferable. Further, these conductive auxiliaries may be those obtained by coating a conductive material (a metal one among the above-mentioned conductive auxiliaries materials) around a particle-based ceramic material or a resin material by plating or the like.
  • a conductive material a metal one among the above-mentioned
  • the average particle size of the conductive auxiliary agent is not particularly limited, but is preferably 0.01 to 10 ⁇ m, more preferably 0.02 to 5 ⁇ m, and 0, from the viewpoint of the electrical characteristics of the battery. It is more preferably 3.03 to 1 ⁇ m.
  • a "particle diameter" means the maximum distance L among the distances between arbitrary two points on the contour line of a conductive auxiliary agent.
  • the average particle size the average value of the particle size of the particles observed in several to several tens of fields using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The calculated value shall be adopted.
  • the shape (form) of the conductive auxiliary agent is not limited to the particle form, and may be a form other than the particle form, or may be a form practically used as a so-called filler-based conductive material such as carbon nanotubes.
  • the conductive auxiliary agent may be a conductive fiber whose shape is fibrous.
  • the conductive fibers include polyacrylonitrile (PAN) -based carbon fibers, pitch-based carbon fibers and other carbon fibers, conductive fibers in which highly conductive metals and graphite are uniformly dispersed in synthetic fibers, and stainless steel. Examples thereof include metal fibers obtained by fiberizing such metals, conductive fibers in which the surface of organic fibers is coated with metal, and conductive fibers in which the surface of organic fibers is coated with a resin containing a conductive substance. Among these conductive fibers, carbon fiber is preferable. Further, as the conductive fiber, a polypropylene resin kneaded with graphene is also preferable.
  • the conductive auxiliary agent is a conductive fiber, the average fiber diameter thereof is preferably 0.1 to 20 ⁇ m.
  • the electrode active material may be a coating active material in which at least a part of the surface thereof is coated with a coating layer containing a polymer compound.
  • a coating layer When the periphery of the electrode active material is covered with a coating layer, the volume change of the electrode active material layer is alleviated, and the expansion of the electrode can be suppressed.
  • the coated active material is referred to as a coated positive electrode active material, and the coated active material layer is also referred to as a coated positive electrode active material layer.
  • the coated active material when the negative electrode active material is used is referred to as a coated negative electrode active material, and the coated active material layer is also referred to as a coated negative electrode active material layer.
  • polymer compound constituting the coating layer those described in JP-A-2017-054703 as a resin for coating a non-aqueous secondary battery active material can be preferably used.
  • the electrode active material may be an electrode active material particle aggregate containing electrode active material particles, a conductive auxiliary agent and a pressure-sensitive adhesive.
  • the electrode active material particle aggregate is a kind of granulated particles obtained by granulating the electrode active material particles.
  • the electrode active material particle aggregate can be obtained, for example, with respect to the first mixing step of dry mixing the electrode active material particles and the conductive auxiliary agent to obtain a mixture and the mixture obtained in the first mixing step under stirring.
  • the pressure-sensitive adhesive exhibits adhesiveness to the surface of the electrode active material particles. Therefore, the electrode active material particles and the pressure-sensitive adhesive can be mixed and stirred to granulate the electrode active material particles, and an electrode active material particle aggregate can be obtained.
  • the adhesive has adhesiveness at room temperature and has the property of adhering to the adherend with a light pressure.
  • the pressure-sensitive adhesive is used in the form of a solution in which the pressure-sensitive adhesive is dissolved in a solvent in the method for producing electrode active material particle aggregates of the present disclosure.
  • the pressure-sensitive adhesive composition described in JP-A-2004-143420 and the acrylic pressure-sensitive adhesive composition described in JP-A-2000-239633 can be used, among which 2-ethylhexyl (2-ethylhexyl) can be used. It preferably contains a polymer containing at least one monomer selected from the group consisting of meta) acrylates, (meth) acrylic acids and butyl (meth) acrylates.
  • (meth) acrylic acid means acrylic acid and / or methacrylic acid
  • (meth) acrylate means acrylate and / or methacrylate.
  • the total weight of 2-ethylhexyl (meth) acrylate and (meth) acrylic acid in the constituent monomers of the copolymer is 10% by weight based on the total weight of the constituent monomers of the copolymer. The above is preferable. Further, the total weight of 2-ethylhexyl (meth) acrylate and (meth) acrylic acid in the constituent monomers of the copolymer is 65% by weight or less based on the total weight of the constituent monomers of the copolymer. Is preferable. When the total weight of 2-ethylhexyl (meth) acrylate and (meth) acrylic acid in the constituent monomers of the copolymer is in this range, the strength of the electrode active material particle aggregate is good, which is preferable.
  • a commercially available adhesive [Polythic series (manufactured by Sanyo Chemical Industries, Ltd.), etc.] may be used.
  • the pressure-sensitive adhesive is a solvent-drying type binder for known lithium ion battery electrodes (starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, polyvinylpyrrolidone, tetrafluoroethylene, styrene-butadiene rubber, polyethylene, polypropylene and styrene-butadiene). It is a different material from polymer etc.).
  • the electrode active material particle agglomerates obtained by the method for producing electrode active material particle agglomerates of the present disclosure the electrode active material particles and the conductive auxiliary agent are integrated with an adhesive, so that the electrode active material particle agglomerates are formed.
  • the solvent-drying type electrode binder is a material that dries and solidifies by volatilizing the solvent component to firmly fix the electrode active material particles and the electrode active material particles and the current collector, and the solid material thereof. The surface is not sticky.
  • the pressure-sensitive adhesive is a material having a property of having stickiness even when the solvent component is volatilized and dried.
  • the electrode active material particle agglomerates obtained by the method for producing the electrode active material particle agglomerates of the present disclosure preferably have a volume average particle diameter of 20 to 350 ⁇ m.
  • the volume average particle diameter is the particle diameter as an aggregate.
  • the volume average particle size of the electrode active material particle aggregate is the particle size at an integrated value of 50% in the particle size distribution on a volume basis obtained by the microtrack method and the laser diffraction / scattering method described in JISZ8825. It means Dv50).
  • the microtrack method is a method for obtaining a particle size distribution by using scattered light obtained by irradiating particles with laser light.
  • a microtrack manufactured by Nikkiso Co., Ltd. can be used for measuring the volume average particle size.
  • non-aqueous electrolyte solution a known non-aqueous electrolyte solution containing an electrolyte and a non-aqueous solvent used for manufacturing a lithium ion secondary battery can be used.
  • lithium salts of inorganic acids such as LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiN (FSO 2 ) 2 and LiClO 4 .
  • examples thereof include lithium salts of organic acids such as LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 and LiC (CF 3 SO 2 ) 3 , and LiN (FSO 2 ) 2 (also referred to as LiFSI). ) Or LiPF 6 .
  • non-aqueous solvent those used in known non-aqueous electrolytic solutions can be used, and for example, a lactone compound, a cyclic or chain carbonate ester, a chain carboxylic acid ester, a cyclic or chain ether, or a phosphoric acid ester can be used. , Ester compounds, amide compounds, sulfones, sulfolanes and the like, and mixtures thereof can be used.
  • lactone compound examples include a 5-membered ring ( ⁇ -butyrolactone and ⁇ -valerolactone, etc.) and a 6-membered ring lactone compound ( ⁇ -valerolactone, etc.).
  • Examples of the cyclic carbonic acid ester include propylene carbonate, ethylene carbonate and butylene carbonate.
  • Examples of the chain carbonate ester include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate, di-n-propyl carbonate and the like.
  • Examples of the chain carboxylic acid ester include methyl acetate, ethyl acetate, propyl acetate, methyl propionate and the like.
  • Examples of the cyclic ether include tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 1,4-dioxane and the like.
  • Examples of the chain ether include dimethoxymethane and 1,2-dimethoxyethane.
  • Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate, tripropyl phosphate, tributyl phosphate, tri (trifluoromethyl) phosphate, and tri (trichloromethyl) phosphate.
  • Examples of the nitrile compound include acetonitrile and the like.
  • Examples of the amide compound include DMF and the like.
  • Examples of the sulfone include dimethyl sulfone and diethyl sulfone.
  • One type of non-aqueous solvent may be used alone, or two or more types may be used in combination.
  • lactone compounds, cyclic carbonate esters, chain carbonate esters and phosphate esters are preferable from the viewpoint of battery output and charge / discharge cycle characteristics, and lactone compounds, cyclic carbonate esters and chains are more preferable.
  • a carbonic acid ester is particularly preferable, and a mixed solution of a cyclic carbonic acid ester and a chain carbonic acid ester is particularly preferable.
  • the most preferable is a mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DMC), or a mixed solution of ethylene carbonate (EC) and diethyl carbonate (DEC).
  • the coating active material may be produced, for example, by mixing a polymer compound, an electrode active material, and a conductive agent used if necessary, and when a conductive agent is used for the coating layer, the polymer compound and the conductive agent are mixed.
  • the coating material may be produced by mixing the coating material with the electrode active material, or may be produced by mixing the polymer compound, the conductive agent and the electrode active material.
  • the mixing order is not particularly limited, but after the electrode active material and the polymer compound are mixed, the conductive agent is further added and further mixed. Is preferable.
  • the above method at least a part of the surface of the electrode active material is covered with a coating layer containing a polymer compound and a conductive agent used if necessary.
  • the same conductive agent as the conductive auxiliary agent constituting the electrode composition can be preferably used.
  • the electrode composition may further contain a solution-drying type known electrode binder (carboxymethyl cellulose, SBR latex, polyvinylidene fluoride, etc.), an adhesive resin, or the like.
  • a solution-drying type known electrode binder carboxymethyl cellulose, SBR latex, polyvinylidene fluoride, etc.
  • an adhesive resin instead of a known electrode binder.
  • the electrode composition contains the above-mentioned solution-drying type known electrode binder, it is necessary to integrate the electrode composition by performing a drying step after the electrode active material layer forming step.
  • the electrode composition can be integrated with a slight pressure at room temperature without performing a drying step.
  • the electrode composition does not shrink or crack due to heating, which is preferable.
  • the electrode active material layer is maintained as a non-bound body even after undergoing the electrode active material layer forming step. ..
  • the electrode active material layer can be made thicker, and a high-capacity battery can be obtained, which is preferable.
  • the adhesive resin a small amount of an organic solvent is mixed with a polymer compound constituting the coating layer (such as the resin for coating a non-aqueous secondary battery active material described in Japanese Patent Application Laid-Open No. 2017-054703) and its glass transition. Those whose temperature is adjusted to room temperature or lower and those described as an adhesive in JP-A No.
  • the non-bound body means that the electrode active materials constituting the electrode composition are not bonded to each other, and means that the electrode active materials are fixed to each other irreversibly to the bonding. do.
  • the solution-drying type electrode binder is meant to be dried and solidified by volatilizing the solvent component to firmly bond and fix the active substances to each other.
  • the adhesive resin means a resin having adhesiveness (property of adhering by applying a slight pressure without using water, solvent, heat, etc.). Solution-drying electrode binders and adhesive resins are different materials.
  • the electrode composition is in a pendular state or a funicular state.
  • the ratio of the non-aqueous electrolyte solution in the electrode composition is not particularly limited, but in the case of a positive electrode, the proportion of the non-aqueous electrolyte solution is set to 0.5 to 0.5 for the entire electrode composition in order to bring it into a pendular state or a funicular state. It is desirable that the proportion of the non-aqueous electrolytic solution is 15% by weight, and in the case of the negative electrode, 0.5 to 25% by weight of the entire electrode composition.
  • a general lithium ion secondary battery is formed by stacking a plurality of battery cells.
  • the battery cell is, for example, an electrode composition in which a positive electrode composition layer and a negative electrode composition layer are laminated via a separator, and each electrode composition layer is arranged in an annular shape so as to surround the periphery of the electrode composition.
  • a frame-shaped member for sealing and an electrode current collector for covering the frame-shaped member from both sides in the thickness direction and collecting and extracting current are provided.
  • the positive electrode composition layer and the negative electrode composition layer contain electrode active material particles (see Patent Document 7).
  • the pressure inside the frame-shaped member may temporarily increase depending on the usage environment. For example, when discharged or overcharged with a large current, gas may be generated in the electrode composition and the pressure inside the frame-shaped member may increase. With such an increase in pressure, the battery cell may be damaged.
  • FIG. 9 is a diagram schematically showing the configuration of an assembled battery 600 modularized by combining the battery cells 301 according to the third embodiment of the present disclosure.
  • the assembled battery 600 is a so-called lithium ion secondary battery.
  • the assembled battery 600 is formed by stacking a plurality of flat plate-shaped battery cells 301 in the thickness direction.
  • the thickness direction of the battery cell 301 may be described simply as the thickness direction.
  • the assembled battery 600 has an outer layer film 601 provided so as to cover the periphery of the laminated battery cells 301.
  • a flexible insulating material can be used as the outer layer film 601.
  • the present invention is not limited to this, and for example, a laminated film may be used as the outer layer film 601.
  • a laminated film may be used as the outer layer film 601.
  • the assembled battery 600 is provided with current extraction units 602 at both ends of the battery cell 301 in the stacking direction. Current is supplied to various electric products through the current extraction unit 602.
  • FIG. 10 is a schematic configuration diagram of the battery cell 301.
  • the battery cell 301 includes an electrode composition 302, a frame-shaped member 303 that is annularly arranged so as to surround the outer periphery of the electrode composition 302 excluding both sides in the thickness direction, and a frame-shaped member 303.
  • a positive electrode current collector 304 and a negative electrode current collector 305 that close the opening 303a from both sides in the thickness direction are provided.
  • the battery cell 301 is formed, for example, in a rectangular shape when viewed from the thickness direction.
  • the electrode composition 302 is formed by laminating a positive electrode composition layer 306 containing positive electrode active material particles and a negative electrode composition layer 307 containing negative electrode active material particles via a separator 308. Then, the positive electrode current collector 304 is arranged so as to cover the positive electrode composition layer 306, and the negative electrode current collector 305 is arranged so as to cover the negative electrode composition layer 307.
  • An electrode for a lithium ion battery can be obtained by collecting and extracting the current of the battery cell 301 by the positive electrode current collector 304 and the negative electrode current collector 305 (hereinafter, also referred to as the respective pole current collectors 304 and 305).
  • each of the current collectors 304 and 305 is not particularly limited, but it is the same as the external shape of the frame-shaped member 303 in the plan view in the thickness direction, or is substantially similar to the external shape of the frame-shaped member 303, and is slightly smaller than the frame-shaped member. It is preferable that the shape is as small as possible.
  • the materials constituting the current collectors 304 and 305 include metal materials such as copper, aluminum, titanium, stainless steel, nickel and alloys thereof. Of these, copper is preferable from the viewpoint of weight reduction, corrosion resistance, and high conductivity.
  • the negative electrode current collector may be a current collector made of calcined carbon, a conductive polymer, conductive glass, or the like, or may be a resin current collector made of a conductive agent and a resin.
  • the resins constituting the resin collector include polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polycycloolefin (PCO), polyethylene terephthalate (PET), polyether nitrile (PEN), and polytetra.
  • PE polyethylene
  • PP polypropylene
  • PMP polymethylpentene
  • PCO polycycloolefin
  • PET polyethylene terephthalate
  • PEN polyether nitrile
  • PEN polytetra.
  • polyethylene (PE), polypropylene (PP), polymethylpentene (PMP) and polycycloolefin (PCO) are preferable, and polyethylene (PE), polypropylene (PP) and polymethylpentene are more preferable. (PMP).
  • the battery cell 301 has a configuration in which the electrolytic solution is sealed by sealing the outer periphery of the positive electrode composition layer 306 and the negative electrode composition layer 307 with the frame-shaped member 303.
  • the assembled battery 600 is configured by stacking the pole current collectors 305 of the battery cells 301 in the same direction and connecting the battery cells 301 in series.
  • the positive electrode collector 304 in one battery cell 301 and the negative electrode current collector 305 in another battery cell 301 adjacent to the battery cell 301 in the stacking direction are in mutual contact with each other.
  • a plurality of battery cells 301 are stacked, and each battery cell 301 is connected in series.
  • the current collector is formed by laminating the positive electrode current collector 304 and the negative electrode current collector 305.
  • a positive electrode is formed on one surface of the current collector and a negative electrode is formed on the other surface to form a bipolar (bipolar) type electrode, and the bipolar (bipolar) type electrode is laminated with a separator. It can also be expressed as a structure.
  • the assembled battery 600 includes a battery cell 301 in which a plurality of each battery cell 301 is stacked and connected in series, but the planar battery (cell unit) is physically connected to the planar battery (cell unit), although it is not electrically connected. It also includes multiple layers that are in contact with each other. Further, when used as a resin collector for a bipolar electrode having a positive electrode formed on one surface of the current collector and a negative electrode formed on the other surface, the assembled battery 600 is a current collector (resin collector for bipolar electrodes). ) Is formed on one surface and a negative electrode is formed on the other surface to form a bipolar electrode, and the bipolar electrode is laminated with a separator to form a laminated body (bipolar battery). good.
  • the assembled battery 600 includes a battery using a liquid material as an electrolyte and a battery using a solid material as an electrolyte (so-called all-solid-state battery). However, even when a solid material is used for the electrolyte, it is premised that the frame-shaped member 303 is used. Further, the assembled battery 600 includes a bipolar type battery in which an electrode is formed by applying a positive electrode active material, a negative electrode active material, or the like to a positive electrode current collector 304 or a negative electrode current collector 305 using a binder, respectively.
  • a bipolar type having a positive electrode active material or the like coated on one surface of a current collector using a binder and a negative electrode active material or the like coated on the opposite surface using a binder and having a negative electrode layer. Includes those that make up the electrodes.
  • the frame-shaped member 303 fixes the peripheral edge portion of the separator 308, and further seals the positive electrode composition layer 306 and the negative electrode composition layer 307.
  • the side on which the electrode composition 302 surrounded by the frame-shaped member 303 is arranged is referred to as the inside of the frame-shaped member 303, and is referred to as the inside of the frame-shaped member 303.
  • the outer peripheral side of the frame-shaped member 303 on the opposite side as the outside of the frame-shaped member 303.
  • FIG. 11 is a plan view of the frame-shaped member 303 as viewed from the thickness direction.
  • the frame-shaped member 303 forms an outer shell of the battery cell 301, and is formed in a rectangular frame shape (frame shape) when viewed from the thickness direction.
  • the frame-shaped member 303 is formed of, for example, an aramid resin.
  • the molding processing temperature of the frame-shaped member 303 is, for example, 120 ° C to 200 ° C. If this temperature range is exceeded, thermal decomposition will occur.
  • a fragile portion 309 is partially formed on the frame-shaped member 303.
  • the fragile portion 309 is formed on a part of the long side of the frame-shaped member 303.
  • the fragile portion 309 is vulnerable as compared with a portion of the frame-shaped member 303 other than the fragile portion 309 formed.
  • the fragile portion 309 has an outer recess 310a formed on the outside of one side of the frame-shaped member 303 and an inner recess 310b formed on the inside. These recesses 310a and 310b form a thin-walled portion 311 as compared to other parts of the frame-shaped member 303. This thin-walled portion 311 becomes a fragile portion 309.
  • the outer recess 310a and the inner recess 310b are formed, for example, in an arc shape when viewed from the thickness direction.
  • the shapes of the recesses 310a and 310b are not particularly limited.
  • the fragile portion 309 thinned by the recesses 310a and 310b may be formed.
  • the shapes of the recesses 310a and 310b may be triangular when viewed from the thickness direction.
  • the fragile portion 309 thinned in this way is more likely to melt than the portion of the frame-shaped member 303 other than the fragile portion 309.
  • the melting point of the fragile portion 309 is about 75 ° C to 90 ° C.
  • FIG. 12 is a diagram illustrating the operation of the frame-shaped member 303.
  • the frame-shaped member 303 is formed with a fragile portion 309. Therefore, as shown in FIG. 12, when the temperature of the battery cell 301 starts to rise abnormally, the fragile portion 309 melts and the opening portion 312 is formed. The inside and outside of the frame-shaped member 303 are communicated with each other through the opening 312. Since the melting point of the fragile portion 309 is, for example, about 75 ° C to 90 ° C, the inside and outside of the frame-shaped member 303 communicate with each other before the expansion of the battery cell 301 starts or the pressure inside the frame-shaped member 303 rises. Will be done.
  • the inside of the frame-shaped member 303 is depressurized through the fragile portion 309 (opening 312) in which the inside and outside are communicated. That is, the fragile portion 309 functions as a pressure release portion that communicates the inside and outside of the frame-shaped member 303 when the pressure inside the frame-shaped member 303 increases by a certain amount or more.
  • the battery cell 301 described above has a frame-shaped member 303 on which the fragile portion 309 is formed. Therefore, it is possible to suppress an increase in the pressure inside the frame-shaped member 303, and it is possible to reliably prevent damage to the battery cell 301.
  • the fragile portion 309 is formed by forming a thin portion 311 in the frame-shaped member 303 by the outer recess 310a and the inner recess 310b. By forming the thin-walled portion 311 in this way, the fragile portion 309 can be easily provided.
  • the present invention is not limited to this, and a thin portion having a thinner wall than other portions may be formed in a part of the frame-shaped member 303.
  • a thin-walled portion that is thinner in the thickness direction than other portions may be formed in a part of the frame-shaped member 303, and this thin-walled portion may be used as the fragile portion 309.
  • the separator 308 and the polar current collectors 304 and 305 may be formed of aramid resin. Even when the frame-shaped member 303 and the separator 308 and the pole collectors 304 and 305 are made of the same material, the fragile portion 309 is compared with the melting points of the separator 308 and the pole collectors 304 and 305. The melting point becomes lower. Therefore, the same effect as that of the third embodiment described above is obtained.
  • PVdF polyvinylidene fluoride
  • polytetrafluoroethylene polyethylene, polypropylene, polyamide, polyimide, polyamideimide, polyvinyl alcohol, polyacrylic acid, polyacrylic acid, methylpolyacrylic acid, ethyl polyacrylate, poly Hexyl acrylate, polymethacrylic acid, methylpolymethacrylate, ethyl polymethacrylate, hexylpolymethacrylate, vinyl acetate, polyvinylpyrrolidone, polyether, polyether sulfone, polyhexafluoropropylene, styrene butadiene rubber, carboxymethyl cellulose, etc. Can also be used. These materials may be used alone or in combination of two or more.
  • the battery cell 301 is composed of an electrode composition 302, a frame-shaped member 403 arranged in an annular shape so as to surround the outer periphery of the electrode composition 302 excluding both sides in the thickness direction, and a frame-shaped member 403.
  • the basic configuration of the positive electrode current collector 304 and the negative electrode current collector 305 that close the opening 403a from both sides in the thickness direction is the same as that of the third embodiment described above (the following third embodiment). But the same).
  • FIG. 13 is an enlarged plan view of a main part of the frame-shaped member 403 as viewed from the thickness direction.
  • the difference between the third embodiment and the fourth embodiment is the configuration of the fragile portion 309 formed in the frame-shaped member 303 of the third embodiment and the fourth embodiment. It is different from the configuration of the fragile portion 409 provided in the frame-shaped member 403. That is, the fragile portion 409 of the fourth embodiment is a low melting point portion 313 having a melting point lower than the melting point of a portion other than the fragile portion 409 in the frame-shaped member 403.
  • the low melting point portion 313 is formed of, for example, a material having a melting point of about 75 ° C. to 90 ° C.
  • the low melting point portion 313 may be formed separately from the frame-shaped member 403 and then assembled to the frame-shaped member 403. Further, the frame-shaped member 403 and the low melting point portion 313 may be integrally molded. When the frame-shaped member 403 and the low melting point portion 313 are integrally molded, various injection molding methods such as two-color molding, sandwich molding, and ultra-high-speed injection molding can be adopted.
  • a recess 314 is formed in a portion of the frame-shaped member 403 corresponding to the low melting point portion 313.
  • the low melting point portion 313 is formed with a convex portion 315 fitted into the concave portion 314.
  • the concave portion 314 and the convex portion 315 are formed by, for example, fitting a dovetail concave portion and a dovetail convex portion. As a result, the low melting point portion 313 (fragile portion 209) is surely prevented from falling off from the frame-shaped member 403.
  • the frame-shaped member 403 and the low melting point portion 313 are integrally molded by fitting the dovetail concave portion and the dovetail convex portion, an anchor effect is exhibited and the low melting point portion 313 from the frame-shaped member 403 is exhibited. Can be reliably prevented from peeling.
  • the low melting point portion 313 is formed with an opening 316 that penetrates in the thickness direction in most of the center when viewed from the thickness direction. By forming the opening 316, the outer wall thickness and the inner wall thickness of the low melting point portion 313 are reduced.
  • FIG. 14 is a diagram illustrating the operation of the frame-shaped member 403.
  • the frame-shaped member 403 is provided with a low melting point portion 313 (fragile portion 409). Therefore, as shown in FIG. 14, when the temperature of the battery cell 301 starts to rise abnormally, the low melting point portion 313 melts. Since the opening 316 is formed in the low melting point portion 313, the outer opening portion 317 and the inner opening portion 318 are formed when the low melting point portion 313 melts. The inside and outside of the frame-shaped member 403 are communicated with each other through these openings 316, 317, 318.
  • the melting point of the fragile portion 309 is, for example, about 75 ° C to 90 ° C
  • the inside and outside of the frame-shaped member 403 communicate with each other before the expansion of the battery cell 301 starts or the pressure inside the frame-shaped member 303 rises. Will be done. Therefore, the inside of the frame-shaped member 303 is depressurized through the fragile portion 409 (openings 316, 317, 318) in which the inside and outside are communicated. That is, the fragile portion 409 functions as a pressure release portion that communicates the inside and outside of the frame-shaped member 403 when the pressure inside the frame-shaped member 403 increases by a certain amount or more.
  • the same effect as that of the above-mentioned third embodiment is obtained. Further, by forming the opening 316 in the low melting point portion 313, the wall thickness in the inner and outer directions of the low melting point portion 313 can be reduced. As a result, when the temperature of the battery cell 301 rises abnormally, it becomes possible to easily form an opening (outer opening 317, inner opening 318). Therefore, it is possible to more reliably release the pressure inside the frame-shaped member 303.
  • the opening 316 is formed in the low melting point portion 313 .
  • the present invention is not limited to this, and the opening 316 may not be formed as long as the inside and outside of the frame-shaped member 403 can communicate with each other via the low melting point portion 313 when the temperature of the battery cell 301 rises abnormally.
  • FIG. 15 is an enlarged plan view of a main part of the frame-shaped member 503 as viewed from the thickness direction.
  • the frame-shaped member 503 is provided with a plug 319 instead of the fragile portions 309 and 409.
  • This point is different from the above-mentioned third and fourth embodiments. That is, an opening 321 that communicates the inside and outside of the frame-shaped member 503 is formed in a part of the long side of the frame-shaped member 503.
  • An engaging recess 322 is formed on the inner peripheral surface 321a of the opening 321.
  • the plug 319 is fitted so as to close such an opening 321.
  • the plug 319 is made of the same material as, for example, the frame-shaped member 503.
  • the plug 319 is integrally formed with an engaging convex portion 323 that is engaged with the engaging concave portion 322.
  • the strength of the engaging convex portion 323 is such that it is deformed or damaged when a certain external force is applied to the plug 319.
  • the plug 319 functions as a pressure relief portion that communicates the inside and outside of the frame-shaped member 503 when the pressure inside the frame-shaped member 503 rises by a certain amount or more. Therefore, according to the above-mentioned fifth embodiment, the same effects as those of the above-mentioned third and fourth embodiments are obtained.
  • the present invention is not limited to this, and it may be configured so that the inside and outside of the frame-shaped member 503 communicate with each other when the pressure inside the frame-shaped member 503 increases by a certain amount or more.
  • a film-like body that breaks when the pressure inside the frame-shaped member 503 rises by a certain amount or more may be provided in place of the plug 319. When the film state is damaged, the inside and outside of the frame-shaped member 503 are communicated with each other.
  • the present invention is not limited to this, and the fragile portions 309, 409 and the plug 319 may be formed or provided on a part of the frame-shaped members 303, 403, 503.
  • a fragile portion 309,409 may be formed on a part of the short side of the frame-shaped member 303, 403, 503, a plug 319 may be provided, or a fragile portion 309, 409 may be provided on a corner portion of the frame-shaped member 303, 403, 503. It may be formed or a plug 319 may be provided. Further, only one of the frame-shaped members 303, 403, 503 arranged around the positive electrode composition layer 306 or the frame-shaped members 303, 403, 503 arranged around the negative electrode composition layer 307. The fragile portions 309 and 409 may be formed or the plug 319 may be provided.
  • the electrode composition 302 is formed by laminating a positive electrode composition layer 306 containing positive electrode active material particles and a negative electrode composition layer 307 containing negative electrode active material particles via a separator 308.
  • the electrode composition 302 may be composed of one kind of electrode composition layer.
  • the case where the openings 303a and 403a of the frame-shaped members 303, 403 and 403 are closed by the respective current collectors 304 and 305 from both sides in the thickness direction has been described.
  • the present invention is not limited to this, and instead of the respective current collectors 304 and 305, a base material that simply closes the openings 303a and 403a of the frame-shaped members 303, 403 and 503 may be provided.
  • an electrode material manufacturing apparatus for a lithium ion secondary battery and a method for manufacturing an electrode material for a lithium ion secondary battery are particularly lithium ion used in a stationary storage battery, a hybrid vehicle, an electric vehicle, a mobile phone, a personal computer, and the like. It is useful as a manufacturing apparatus and manufacturing method for manufacturing battery electrodes. It is also extremely useful as a method for recycling lithium-ion batteries used in the above devices and the like.
  • the present-disclosed method for manufacturing an electrode material for a lithium ion secondary battery and a method for manufacturing an electrode material for a lithium ion secondary battery are bipolar secondary type used especially for a mobile phone, a personal computer, a hybrid vehicle and an electric vehicle. It is useful as a manufacturing apparatus and manufacturing method for manufacturing electrode materials for batteries and lithium ion secondary batteries.
  • the inside and outside of the frame-shaped member are communicated with each other, so that the pressure inside the frame-shaped member increases. It can be suppressed. Therefore, damage to the battery cell can be prevented.
  • the electrode composition is formed by laminating a positive electrode composition layer and a negative electrode composition layer via a separator.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Un dispositif de fabrication de matériau d'électrode de batterie secondaire au lithium-ion selon la présente invention comprend : une section de formation de couche (1) dans laquelle un matériau fondu contenant du lithium est pulvérisé sur une matière première d'électrode pour former une couche de matériau contenant du lithium sur la matière première d'électrode ; et une section de traitement thermique (2) dans laquelle la matière première d'électrode ayant la couche de matériau contenant du lithium formée sur celle-ci est chauffée, et le lithium contenu dans le matériau contenant du lithium est introduit dans la matière première d'électrode pour obtenir un matériau actif d'électrode positive.
PCT/JP2021/035412 2020-09-25 2021-09-27 Dispositif de fabrication de matériau d'électrode de batterie secondaire au lithium-ion, méthode de fabrication de matériau d'électrode de batterie secondaire au lithium-ion et méthode de régénération de matériau actif d'électrode positive usée WO2022065492A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2020160934A JP2022053995A (ja) 2020-09-25 2020-09-25 リチウムイオン二次電池用電極材製造装置及びリチウムイオン二次電池用電極材の製造方法
JP2020-160934 2020-09-25
JP2020-193627 2020-11-20
JP2020193627A JP2022082205A (ja) 2020-11-20 2020-11-20 正極活物質の製造方法及び使用済み正極活物質の再生方法

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JPH11317230A (ja) * 1998-02-10 1999-11-16 Samsung Display Devices Co Ltd リチウム二次電池用正極活物質及びその製造方法
JP2003331845A (ja) * 2002-05-13 2003-11-21 Samsung Sdi Co Ltd リチウム二次電池用正極活物質の製造方法
JP2008234843A (ja) * 2007-03-16 2008-10-02 Idemitsu Kosan Co Ltd 全固体二次電池用電極及び部材
JP2009117365A (ja) * 2007-11-07 2009-05-28 Korea Inst Of Science & Technology 電極活物質の製造方法及びその方法で製造された電極活物質を含むリチウム電池
JP2012209195A (ja) * 2011-03-30 2012-10-25 Tdk Corp 活物質の製造方法、電極及びリチウムイオン二次電池
JP5527670B2 (ja) * 2009-07-14 2014-06-18 川崎重工業株式会社 ファイバー電極を備える蓄電デバイス及びその製造方法
JP2015530721A (ja) * 2013-08-29 2015-10-15 エルジー・ケム・リミテッド リチウム遷移金属複合粒子、この製造方法、及びこれを含む正極活物質
JP2018028998A (ja) * 2016-08-16 2018-02-22 株式会社クラレ 炭素質材料の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11317230A (ja) * 1998-02-10 1999-11-16 Samsung Display Devices Co Ltd リチウム二次電池用正極活物質及びその製造方法
JP2003331845A (ja) * 2002-05-13 2003-11-21 Samsung Sdi Co Ltd リチウム二次電池用正極活物質の製造方法
JP2008234843A (ja) * 2007-03-16 2008-10-02 Idemitsu Kosan Co Ltd 全固体二次電池用電極及び部材
JP2009117365A (ja) * 2007-11-07 2009-05-28 Korea Inst Of Science & Technology 電極活物質の製造方法及びその方法で製造された電極活物質を含むリチウム電池
JP5527670B2 (ja) * 2009-07-14 2014-06-18 川崎重工業株式会社 ファイバー電極を備える蓄電デバイス及びその製造方法
JP2012209195A (ja) * 2011-03-30 2012-10-25 Tdk Corp 活物質の製造方法、電極及びリチウムイオン二次電池
JP2015530721A (ja) * 2013-08-29 2015-10-15 エルジー・ケム・リミテッド リチウム遷移金属複合粒子、この製造方法、及びこれを含む正極活物質
JP2018028998A (ja) * 2016-08-16 2018-02-22 株式会社クラレ 炭素質材料の製造方法

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