WO2024075484A1 - Procédé d'application de poudre, procédé de production de batterie secondaire, procédé de production de batterie entièrement solide, batterie secondaire et batterie entièrement solide - Google Patents

Procédé d'application de poudre, procédé de production de batterie secondaire, procédé de production de batterie entièrement solide, batterie secondaire et batterie entièrement solide Download PDF

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WO2024075484A1
WO2024075484A1 PCT/JP2023/033496 JP2023033496W WO2024075484A1 WO 2024075484 A1 WO2024075484 A1 WO 2024075484A1 JP 2023033496 W JP2023033496 W JP 2023033496W WO 2024075484 A1 WO2024075484 A1 WO 2024075484A1
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powder
electrode
roll
solid
applying
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PCT/JP2023/033496
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English (en)
Japanese (ja)
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正文 松永
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エムテックスマート株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
    • B05D1/06—Applying particulate materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M4/04—Processes of manufacture in general
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a powder coating method, a method for manufacturing a secondary battery, a method for manufacturing an all-solid-state battery, a secondary battery, and an all-solid-state battery.
  • electrodes for secondary batteries such as lithium-ion batteries (LIBs) have often used resin-based binders with a solid content of less than a few percent by weight.
  • Fluorine-based binders such as polyvinylidene fluoride (PVDF) have been widely used, especially for the positive electrode, due to their heat resistance, solvent resistance, and durability.
  • a composite slurry is made from active material particles, conductive additives, binders, and solvents, which is then applied to a current collector such as aluminum foil, copper foil, or stainless steel foil and dried to form the electrode.
  • a composite slurry is made from active material particles, electrolyte particles or fibers, conductive additives, binders, and solvents, which is then applied to a current collector and dried to form the electrode.
  • electrodes for secondary batteries such as LIBs were formed by creating a slurry from active material, binder, conductive additive, and a solvent to dissolve the binder, which was then coated on a moving current collector using a die head and dried. Increasing the coating speed led to huge drying ovens, sometimes reaching a total length of over 100 m.
  • the general power and heat sources for drying ovens are sources of carbon dioxide emissions, and while this can contribute to carbon neutrality (CN) in electric vehicles, it is counterproductive from the perspective of life cycle assessment (LCA).
  • the objective of the present invention is to contribute to carbon neutrality by converting the manufacturing method of electrodes and batteries, particularly slurry-type, for existing secondary batteries and next-generation secondary batteries in general, particularly all-solid-state batteries, into a dry method or a method equivalent thereto. Another important goal is to reduce the cost per unit watt-hour in terms of manufacturing costs. To achieve this, it is necessary to further pursue resource conservation, energy conservation, and space conservation. It is also necessary to make the total productivity of the products, such as electrode formation and battery cells, at least equivalent to that of conventional methods. To achieve this, the solvents required for electrode and electrolyte materials must be handled in a small, sealed or nearly sealed space in the limited space of the upstream process, the process must be completed, and the solvent must be recovered.
  • the dry electrode formation method using powders that does not use solvents when forming electrodes can be ideal because it requires only pressing with a press and can form electrodes with short heating and pressing as necessary, and the installation area is small, and especially when the binder is a thermoplastic resin such as a polymeric fluorine-based resin, there is no need for heating time for crosslinking reaction.
  • the inventor has already proposed a powder coating method and film formation method that are also suitable for LIB electrode formation prior to this information.
  • the following major challenges are unavoidable and high hurdles.
  • the binder which is the resin content of LIB electrode powder
  • the binder is less than a few percent of the total solids by weight, and especially recently, due to performance improvements, it is less than 1%, which is too large a gap compared to powders for powder coating. Therefore, it was almost impossible to manufacture powders that are close to the ideal spherical shape. For this reason, it was difficult to make the particle size distribution of powder particles uniform for each lot.
  • a general volumetric feeder could not be applied to the formation of LIB electrodes, which requires coating weight per unit centimeter area and coating film uniformity. Also, if the resin content is small, it was not possible to apply data for conventional production lines in which the powder is electrostatically charged and electrostatically coated on an earthed object. Even if such powder was transported using a method for adjusting the thickness of the powder supplied by a doctor blade, such as an electric screw-type auger feeder or a volumetric feeder using an electric table, it was not possible to make the coating weight per unit area constant, for example, the electrode weight per unit area equivalent to a film thickness of 60 to 100 ⁇ 2.5 micrometers.
  • powder particles become an air-powder mixture with a large amount of gas, as typified by cedar pollen and PM2.5 of about 30 micrometers, they behave like aerosols, floating in the air and being affected by the flow of gas. Even if the powder particles of general electrostatic powder coating, which have an average particle size of about 20 to 80 micrometers and are rich in resin, were electrostatically charged, they could not be electrostatically attached to the target object in a high-speed airflow. Even if powder is electrostatically charged and sprayed on an object moving at a speed of several tens of meters per minute or more, for example, 60 meters per minute or more, it is not possible to adhere more than 50% of the powder.
  • the electrode composite particles for LIBs and solid-state batteries which have a low binder content, become unstable in charging, making it even more difficult to apply them to the target object.
  • the line speed for slurry coating to form LIB electrodes is high, at over 60 meters per minute, so high-speed powder coating formation using powder instead of slurry was far removed from industry common sense.
  • Cited Document 1 proposes a method for producing an electrode for a lithium ion battery using a pair of press rolls, the method including a step of applying a binder coating liquid to a substrate, a step of supplying powder containing an electrode active material from a hopper and adjusting it with a squeegee to control the basis weight of the powder and removing the powder supplied outside the electrode width.
  • the cited document 2 discloses a powder coating method invented by the present inventor and discloses its industrial applicability in the formation of electrodes for secondary batteries such as LIBs. In both of the methods described in the above documents, there are many difficult factors to apply a fixed amount of powder, unlike liquids.
  • the coating weight per unit time can be made constant simply by keeping the viscosity, pressure, and nozzle diameter constant. If the temperature of the liquid can be kept constant and the density can be kept constant, the coating weight can be made constant by pumping with a volumetric pump, making it easy to manage. For solutions and emulsions, the coating weight per short period of time, for example, per millisecond, can be made constant by keeping the temperature constant and the above measures constant.
  • the electrode slurry is made up of active material particles, conductive additives, binders or binder solutions and solvents, and in the case of solid-state batteries, electrolytes.
  • the dispersion state is different at the time of discharge, it will cause a fatal defect. Therefore, the longer the distance and time from stable mixing and dispersion to application, the higher the risk. This is because at the manufacturing speed of LIBs at 60 meters per minute, it takes only one second to travel one meter. In other words, if poorly dispersed electrode slurry is applied in just one millisecond, one millimeter will be defective. Therefore, in the present invention, the electrode composite powder is produced in advance with a compact device in which the mixing and dispersion is adequately controlled in milliseconds.
  • the mixing and dispersion device may be a static mixer or the like, and although not particularly limited, an OHR mixer that utilizes centrifugal force and centripetal force to finely disperse, or a dynamic mixer that rotates at high speed to mix and disperse, etc., are even better because they can mix and disperse uniformly and instantly in milliseconds.
  • the average particle diameter of the composite powder should be larger than the particle diameter of the active material. In other words, it should be about 5 micrometers or more. If you want to increase the powder particle diameter, in the present invention, you can create a slurry of small-diameter powder and at least a solvent to create large-diameter powder particles in which multiple powders are aggregated.
  • the electrode can be formed by applying it to an object such as a current collector with a powder coating device and pressing it. Therefore, even if it is a powder slurry, the composite ratio is stable regardless of the composite powder particle diameter, so a powder slurry consisting of a poor solvent for the binder of the composite powder, especially a low-boiling point solvent, or a solvent containing a poor solvent, can be created.
  • the poor solvent may be liquefied carbon dioxide gas obtained by liquefying the recovered carbon dioxide gas or a supercritical fluid thereof.
  • the powder slurry is applied to the target object using a die coater or spray coating device, and the poor solvent is evaporated in a short time of seconds to form an electrode powder layer, which is then pressed to form an electrode.
  • the evaporated solvent can be recovered using a small recovery device. If necessary, a small amount of binder solution, binder nanoparticles, or short fibers limited to a few percent or less of the solid content of the electrode may be added to the powder slurry.
  • the solvent can be evaporated in a short time of seconds, so the solvent recovery device can be made small, and electrodes can be formed using only a roll press, which has a much greater advantage than the conventional slurry method.
  • the electrode composite slurry is first granulated into powder while recovering the solvent in a compact device upstream of the electrode production line.
  • the upstream includes the process of producing electrode active materials, electrolytes, etc., and is because the composite powder can be produced by consolidating electrode powder for several or several tens of electrode production lines in a relatively small facility.
  • electrolyte materials can be added and mixed.
  • active material particles and electrolyte core-shell particles can be created, and conductive additives, binders, and solvents can be added to make a composite slurry, which can then be granulated.
  • the dispersed composite slurry can be granulated using centrifugal granulation methods such as high-speed rotating disks and bells, which are in the category of spray dryers, and the granulation process can be performed while causing electrostatic repulsion to prevent blocking between particles during granulation.
  • Powder particles with little binder tend to crumble during the handling process, and each part of the mixture is likely to fall off. If the particles are not charged, as in Reference 1, the powder will partially crumble with a slight mechanical impact and become fine powder, which will fly away and float, and will be affected by wind currents with typical aerosol fluid behavior. Such fine powder is difficult to attach and fix to the target object. The effect of the binder applied to the target object at the beginning cannot be expected for such fine powder. Due to the nature of special powders for secondary batteries, it is difficult to keep the powder coating weight per unit area constant. In anticipation of this, Reference 2 devise a method for stabilizing the coating weight per unit area of the final substrate.
  • the powder will be affected by the flow speed and volume of the gas flow (e.g. compressed gas) that transports it, and the powder that collides with the target object will bounce back along with the gas, resulting in extremely poor coating efficiency. Furthermore, if the air-powder mixture is not uniformly fluidized and dispersed, the agglomerated powder transported by a fixed-volume feeder or the like will be applied as is. Furthermore, as mentioned above, even small mechanical vibrations can cause part of the powder layer to fall off and scatter, and become suspended in the high-speed moving gas flow, making it impossible to solve problems with workability and quality.
  • the gas flow e.g. compressed gas
  • active material particles and electrolyte particles may be mixed in advance in a dry state to form a core-shell structure, or the mixture may be thin-film laminated in a single device.
  • the conductive assistant and binder solution may be thin-film laminated in separate devices, or the composite may be made into a slurry and a small amount may be thin-film laminated between the core-shell layers to form a uniformly mixed electrode layer.
  • the core-shell particles may be mixed with the conductive assistant and binder to form a composite powder.
  • the composite powder for electrodes may be made into a slurry with a solvent as described above.
  • the small particle size granulated powder may be made into a slurry and granulated multiple times to gradually increase the granulated particle size and granulate to the desired particle size to form a powder.
  • a LIB electrode composite powder an all-solid-state battery electrode composite powder, or an all-solid-state battery composite powder consisting of a core shell
  • each material other than the binder has a low electrical resistance and is difficult to charge.
  • conductive assistant protrusions such as carbon fibers present on the surface of the powder particles, they act as antennas for the charged powder particles, and tend to be more prone to discharge.
  • the present invention has been made to solve the above-mentioned problems, and is as follows: 1. To stabilize the supply amount even for powder whose flow (fuldize) in the air-powder mixture is unstable. 2. Shorten the process from powder supply to coating and eliminate piping and other flow paths as much as possible. 3. Even powders with low electrostatic charging efficiency can be easily attached to objects after charging. 4. Even if the object is moving at high speed, for example 60 meters per minute or more, the structure should be designed to be less susceptible to wind when applying powder. 5. The next process, pressing or hot pressing, allows for high-performance pressing to form electrodes. To solve the above problems. Therefore, in the present invention, we have focused on the following: 1. Stabilize the amount of powder sucked or sprayed. 2.
  • the powder is applied to the object by adsorbing, transferring, and releasing it using a porous hollow roll or porous belt. 3. When the direction of powder movement in the gas-powder mixture has stabilized, the excess gas is discharged. 4. The structure must be designed to prevent disturbances when the powder is applied to the target object (especially the coating part of the coating device). 5. To provide a coating method that enables the formation of multiple rows of electrodes using multiple rolls with short face lengths to achieve high precision with a line pressure of up to about 50 kN/cm.
  • the bulk density per square centimeter is made constant in order to make the coating weight per unit area of the powder constant before supply.
  • the powder on the porous object is sucked from the opposite side of the porous object, the powder layer is leveled to the desired thickness with a squeegee or the like to make the bulk density constant, and then it is configured to be transported.
  • the ejector pump is operated at high pressure in a pulsed manner in milliseconds, and even powder that is difficult to flow on a porous plate is forcibly adsorbed with pulse negative pressure and pushed downstream with a high pressure pulse flow, for example 0.3 MPa or more.
  • the powder is adsorbed to a porous hollow roll or porous belt with negative pressure, moved with a constant bulk density, and the powder is released at the desired location and applied to the target object.
  • the structure is designed so that the wind flow generated by the object moving at high speed does not affect the coating device and the object.
  • the powder transport is of the powder adsorption roll type or adsorption belt type, the roll or belt is also partially enclosed at the coating position, making the whole of it the coating device, and the structure of the coating device is not affected by external factors.
  • the coating device has an exhaust port for excess gas at least downstream of the coating device, and is designed to exhaust excess gas that affects powder adhesion.
  • the small amount of powder discharged together with the excess gas in the coating device is always the same under the same conditions, so it adheres to the target at approximately the same ratio. Therefore, the amount of powder per unit area on the target adheres at the same ratio as the amount of powder supplied. 4.
  • the electrode is designed to be compatible with wide-width objects, and an electrode powder layer with multiple electrode patterns is formed around the periphery of the uncoated area, allowing the electrode to be pressed with a roll with high press accuracy and a short face length in a later process.
  • the linear pressure of the press roll is required to be as high as about 10 kN/cm to 50 kN/cm depending on the lamination process.
  • the present invention is not limited to one application and one pressing, but multiple powder applications and multiple pressings or temporary pressings can be performed. Of the multiple pressings, only the final pressing needs to be performed with a high linear pressure. In addition, multiple pressings may be performed by temporarily pressing the entire electrode powder layer of a wide current collector with a single roll with a long face length.
  • the electrodes on the pre-pressed current collector are slit, and then heated as necessary with a high-performance roll having a short surface length and pressed at high linear pressure for each electrode width. Therefore, it is possible to form multiple stripe electrodes with narrow electrode widths.
  • the method for producing a secondary battery such as a LIB can be used to form electrodes for secondary batteries in general, electrodes for next-generation secondary batteries such as all-solid-state batteries and air batteries, electrodes for capacitors including electric double-layer capacitors, and further, by combining a dry method and a wet method, electrodes for fuel cells and water electrolysis, and microporous layers for gas diffusion layers can be formed. Furthermore, the method can be suitably applied to the fields of powder coating and powder adhesion for general metal flat plates, long plates, nonwoven fabrics, films, etc. Furthermore, each layer of a next-generation solar cell power generation layer can be formed by applying nano-sized or submicron fine powder that does not require a binder directly or in powder slurry form. Therefore, the present invention is as follows.
  • the present invention provides a method for applying powder to a moving grounded object, comprising the steps of: filling a porous object with powder; stabilizing the weight of powder sucked in per second when sucking the powder and moving it downstream; sucking the powder through a suction port and transporting it as an air-powder mixture to a nozzle that communicates with a flow path by a pressure difference; discharging excess gas from the air-powder mixture to the outside midway through the flow path to increase the powder density per volume in the downstream flow path; connecting the nozzle to a powder application device, the inside of which is an opening facing the moving object and which is made of a structure with a space through which the powder flow moves; electrostatically charging the powder from the time of suction until it adheres to the object; and applying the powder to a moving object that is in contact with or close to the opening of the powder application device, which is grounded.
  • the present invention provides a method for manufacturing a secondary battery or an all-solid-state battery, which includes the steps of: filling a porous body with electrode powder; stabilizing the weight of the powder sucked in per second when sucking the powder and moving it downstream; sucking the powder through a suction port and transporting it as an air-powder mixture to a nozzle that communicates with a flow path by a pressure difference; discharging excess gas from the air-powder mixture to the outside midway through the flow path to increase the powder density per volume in the downstream flow path; connecting the nozzle to a powder coating device, which has an opening on the side facing the moving object, and has a structure with a space through which the powder flow moves inside the powder coating device, and electrostatically charging the powder between the time of suction and the time of attachment to the object; attaching the powder to an earthed object that is in contact with or in close proximity to the opening of the powder coating device to form a powder electrode layer; and pressing the powder electrode layer with a roll to form an electrode.
  • the present invention provides a method for manufacturing a secondary battery or an all-solid-state battery, characterized in that the method for stabilizing the suction weight of powder per second during suction of the powder is performed by operating an ejector pump with a compressed gas of 0.3 MPa or more and a pulse opening and closing of 10 cycles or more per second when sucking and pumping the powder on the porous body with the ejector pump.
  • the method of the present invention for stabilizing the suction weight of powder per second during suction of the powder provides a method for manufacturing a secondary battery or an all-solid-state battery, characterized in that when sucking powder with a constant bulk density into a recess of a porous object, negative pressure is applied to the porous surface opposite the recess, and the powder is volumetrically filled into the recess to make the bulk density of the powder in the recess constant, thereby stabilizing the bulk density of the powder in the recess per volume.
  • the present invention provides a method for manufacturing a secondary battery or an all-solid-state battery, characterized in that the position of the flow path for discharging excess gas from the gas-powder mixture is upstream of the point where the cross-sectional area of the flow path is reduced to 1/4 or less, and the powder density of the downstream flow path with the smaller cross-sectional area is increased to move the powder.
  • the present invention provides a method for manufacturing a secondary battery or an all-solid-state battery, characterized in that at least one corona electrode or elongated electrode is arranged in a shape corresponding to a wide area in the space inside the powder coating device of the present invention, the powder is charged, at least both sides and the wall of the upstream part of the space are made of a material that electrostatically repels the charged powder, and the wall is structured to block the flow of external wind with the object moving in contact with or close to the object side end of the wall, at least the walls on both sides in the moving direction of the object regulate the flow of the powder flow to cause the powder to adhere to the object, the space is extended downstream, the powder that does not adhere to the object is electrostatically repelled or recharged by the corona electrode located downstream, increasing the chance of it adhering to the object as it moves downstream, and at least the excess gas inside the coating device is discharged from the most downstream exhaust port of the powder device.
  • the present invention provides a method for manufacturing a secondary battery or an all-solid-state battery, characterized in that a plurality of partitions are provided on the inside of both side walls of the coating device, and a single or multiple nozzles are provided between the partitions, and the partitions form a plurality of stripe-shaped powder electrode layers and uncoated areas in the width direction perpendicular to the target object.
  • the present invention provides a method for manufacturing a secondary battery, which is characterized by a step of vacuum-sucking the powder scattered in the electrode uncoated area between the powder layer electrodes in the moving direction of the object along the width of the electrodes and discharging it to the outside, and further vacuum-sucking the powder other than the electrode pattern on the object perpendicular to the electrodes in the moving direction of the object to form the electrode uncoated area, thereby forming the powder uncoated area and the powder electrode pattern layer.
  • the present invention provides a method for manufacturing a secondary battery or an all-solid-state battery, characterized in that the electrode is formed by stacking powder on an object and pressing with a roll multiple times, and at least in the final press, the object and the powder layer are heated to a temperature equal to or higher than the softening point of the binder contained in the electrode powder, and pressed with a linear pressure of 10 kN/cm or more to form an electrode.
  • the present invention provides a method for manufacturing a secondary battery or an all-solid-state battery, characterized in that in the roll press process for laminating the current collector, negative electrode layer, electrolyte layer, positive electrode layer, and current collector, which is a subsequent process for forming the electrodes, the roll temperature or powder temperature is heated to a temperature equal to or higher than the softening point of the binder or electrolyte polymer contained in the electrode powder, and pressed with a linear pressure of 10 kN/cm to 50 kN/cm.
  • the present invention provides a method for producing a secondary battery or an all-solid-state battery, characterized in that the electrode powder is a powder granulated from at least one selected from among active material particles for electrodes, electrolyte particles or fibers, binders, electrolyte polymers, conductive assistants, and core-shell particles obtained by dry granulation of active material particles and electrolytes.
  • the present invention provides a method for manufacturing a secondary battery or an all-solid-state battery, which is characterized in that, before applying electrode powder to the current collector of the object of the present invention, a dispersant is added to a conductive assistant consisting of carbon nanotubes or carbon nanofibers, and then a binder solution or a slurry consisting of binder fine particles having an average particle size of 0.1 micrometers or less and a poor solvent is selected and added to the current collector, and the liquid having a solid content of 1.5% or less is applied to a wet thickness of 15 micrometers or less.
  • the present invention provides a method for applying powder to an object by sucking in the powder supply position of a porous hollow roll rotating in the moving direction of the object, depositing and stacking the powder on the outer periphery of the roll, and releasing the powder at the application position to the object, by creating a negative pressure inside the roll at the powder loading position to suck in the powder and deposit the powder on the surface of the roll to form a powder layer and stabilize the bulk density of the powder layer, providing an electrostatic charging means between the roll and the object to charge the powder, releasing the powder from inside the roll at least at the closest position to the roll of the object by compressed gas, earthing the powder on the surface of the roll and depositing it on the moving object, and providing an enclosure means with an exhaust port for excess gas between the roll and the object to prevent the influence of wind from the outside and the outflow of the powder to the outside of the application device.
  • the present invention provides a powder application method characterized in that a hollow roll into which the powder is filled has at least one porous recessed shape, the powder is filled into the recessed portion while being sucked from the hollow side of the roll, and in an application device located close to the object, the powder in the recessed portion is sprayed from the hollow side by positive pressure gas to apply it to the object.
  • the present invention provides a method for manufacturing a secondary battery or an all-solid-state battery, characterized in that the powder is applied to an object by sucking the powder at a supply position of the electrode powder of a porous hollow roll rotating in the moving direction of the object, depositing and stacking the powder on the outer periphery of the roll, and releasing the powder at a coating position for the object, by applying the powder to the object by applying a negative pressure inside the roll at the powder loading position to suck the powder and deposit the powder on the surface of the roll to form a powder layer and stabilizing the bulk density of the powder layer, providing an electrostatic charging means between the roll and the object to charge the powder, at least at the closest position of the object to the roll, releasing the powder from inside the roll with compressed gas, and depositing the powder on the surface of the roll to the moving object while being grounded, and applying the powder to the object, and providing an enclosure means with an exhaust port for excess gas between the roll and the object as a coating device to prevent the influence of wind from the outside and the outflow
  • the present invention provides a method for applying powder to an object by applying a powder on a porous belt that rotates in the direction of movement of the object, comprising the steps of: applying negative pressure to the opposite side of the belt at a powder supply position to suck in the powder and deposit the powder on at least the belt surface; charging the powder between the belt and the object with an electrostatic charging means; detaching and earthing the powder on the belt at an application position for the object to deposit the powder on the moving object; and providing an enclosure with an exhaust port for excess gas between the belt and the object at the application position to prevent the effect of wind from outside and the outflow of powder to the outside as an application device, thereby applying powder to the object.
  • the present invention provides a method for manufacturing a secondary battery or an all-solid-state battery by applying an electrode powder on a porous belt that rotates in the moving direction of the object to the object to form an electrode, comprising the steps of: applying a negative pressure to the opposite side of the belt at the powder supply position to suck in the powder and attach it to at least the belt surface; charging the powder between the belt and the object with an electrostatic charging means; removing and earthing the powder on the belt at the application position to the object to attach the powder to the moving object; and providing an enclosure with an outlet for excess gas between the belt and the object at the application position as an application device to prevent the influence of wind from the outside and the outflow of the powder to the outside, thereby applying the electrode powder to the object to form an electrode.
  • the composite material for electrodes of secondary batteries and all-solid-state batteries of the present invention can be made into particles by mixing at least active material particles for electrodes, inorganic electrolyte particles, inorganic electrolyte fibers, inorganic fine particles, binders, electrolyte polymers, and conductive assistants.
  • the particles can be made into particles by mixing multiple materials and granulating them, or by coating the core particles with a liquid such as a slurry or solution containing a single or different materials to encapsulate them.
  • the active material particles can be dry-coated with electrolyte particles to make particles with the active material particles as the core and the electrolyte as the shell.
  • a milling method or mechanochemical method in which multiple fine particles, such as nanoparticles, are mixed and made into particles can also be used.
  • these particles will be referred to as composite particles or mixed particles hereinafter.
  • PVDF polyvinylidene fluoride
  • NMP normal methylpyrrolidone
  • DMF dimethylpyrrolidone
  • the binder is foamed with gas in advance to increase its volume and expand the bonding area. Therefore, a binder with elasticity has the effect of filling the voids between active material particles together with fine active material particles and conductive assistant.
  • polyethylene oxide (PEO) which is used as an electrolyte polymer
  • PEO polyethylene oxide
  • PTFE polyethylene oxide
  • PVDF polyethylene styrene
  • the active material and electrolyte particles granulated by this method can be handled and applied as powder.
  • application can be performed with high precision by using Patent No. 6328104 and Patent No. 6481154, which the inventor invented and holds the rights to.
  • a film When applying as a powder, a film can be formed by pressing after application, or by heating to a temperature above the softening point of the binder and pressing after laminating the electrolyte layer and counter electrode.
  • the powder can be made more fluid by using a matrix of high molecular weight PVDF, PTFE and PEO or by mixing them together, and further mixing them with ceramic fine particles.
  • Oxide-based electrolyte particles and sulfide-based electrolyte particles can be used alone or mixed with the binder or electrolyte polymer.
  • a poor solvent, recovered liquefied carbon dioxide gas or its supercritical fluid is added to make a slurry, which is then sprayed onto a heated object, allowing instantaneous dry coating that is denser than powder coating, and the desired coating film can be obtained.
  • sulfide-based electrolytes such as argyrodite-based electrolytes
  • argyrodite-based electrolytes have good ionic conductivity, but require a dehumidified atmosphere with a dew point of -50°C or even -70°C or lower, or the filling of an inert gas such as argon gas, which tends to increase the size of the equipment. Therefore, in this invention, not only can the compact device apply powder and press or heat press, but also the DRY on WET method, which enhances the adhesion of the powder, can be used.
  • a conductive assistant such as carbon nanotubes, a dispersant that has an anchoring effect on the target object, binder fine particles or short fibers with a low solid content, and a slurry made of a solvent mainly composed of a poor solvent for the binder are applied, and then the powder is applied and heat pressed to create a dry electrode layer with high adhesion to the interface with the target object.
  • conventional electrodes for secondary batteries and all-solid-state batteries were formed by mixing a mixture of materials selected from at least electrode active material particles, inorganic electrolyte particles, inorganic electrolyte fibers, inorganic fine particles, fluorine-based binders, polymeric ion-conductive electrolyte polymers, and conductive assistants with a high-boiling point solvent such as NMP that can dissolve PVDF, etc., to form a slurry, which was then applied to objects such as current collectors.
  • a high-boiling point solvent such as NMP that can dissolve PVDF, etc.
  • a selected mixed material from the above-mentioned electrode materials for secondary batteries, etc. is handled as a particulate powder, which is applied to an object such as a current collector, and then heated to above the softening point of the thermoplastic or electrolyte polymer, or above the melting point if possible, and pressed to form an electrode.
  • powders that are not smooth and suitable for powder fluidity such as binders and electrolyte polymers, for example polymers such as PEO, can be mixed with other hard polymers, such as PTFE or inorganic fine particles, and handled as polymer particles.
  • the inorganic fine particles can be oxide-based electrolyte particles, sulfide-based particles, or fibers. A mixture of these is also acceptable.
  • 1-2 is a schematic cross-sectional side view of a powder coating unit for coating an object with electrode powder according to an embodiment of the present invention.
  • 2-1 A schematic cross-sectional plan view of multiple powder nozzles, an electrostatic electrode, and a gas or powder flow outlet according to an embodiment of the present invention.
  • 2-2 A schematic cross-sectional plan view of an embodiment of the present invention in which multiple partition sections are provided in parallel in the direction of movement of the target object in the application section.
  • 2-3 A schematic cross-sectional side view of a powder application section according to a practical embodiment of the present invention.
  • 1 is a schematic cross-sectional side view of a powder coating unit according to an embodiment of the present invention, showing how powder is applied to an object moving below the powder coating unit.
  • FIG. 1 is a schematic cross-sectional side view of an embodiment of the present invention in which an electrode liquid, for example a slurry, is applied to an object and then powder coating is performed thereon.
  • the bottom surface of the powder coating unit according to the embodiment of the present invention is a rotating body.
  • the rotating body can have a porous surface, and compressed gas can be added to the coating unit to fill the powder.
  • the bottom surface of the powder coating unit according to the embodiment of the present invention is a circulating belt, and the belt is porous so that compressed gas can be added to fluodize the powder.
  • FIG. 1 is a schematic cross-sectional view showing the supply of powder to a porous roll and the application of the powder to an object by separation of the powder within a coating device according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing the supply of powder to a porous belt, the separation of the powder within a coating device, and the coating of the powder onto an object in an embodiment of the present invention.
  • powder is applied onto an object 1 through a suction port 3 of a powder pump 4 such as an ejector pump.
  • the gas is sucked in through the flow passage 5 and is forced out into the flow passage 5.
  • the flow passage 5 may be a pipe or tube with an inner diameter of about 6 mm to 12 mm, such as a metal pipe, rubber, ceramics, or plastic.
  • the flow passage 7 beyond the flow passage 5 can be narrowed to enrich the powder density of the powder fluid. By enriching the powder ratio and smoothly moving the powder into the narrow tube, mainly excess gas can be discharged to the outside from the outlets 6, 6'.
  • the outlets 6, 6' are connected to a mini cyclone (not shown) or the like, and the powder mixed in the surplus gas can be collected and reused.
  • the tube with a narrow inner diameter can also be a tube made of PTFE or PFA with an inner diameter of about 4 mm to 2 mm. It can be 1 mm or 5 mm.
  • the tube can be made of a material that is easily charged with binders, electrolyte polymers, etc.
  • the powder is a polyamide-based powder such as nylon
  • the inner surface of the tube should be PTFE, and efficient frictional charging can be achieved by earthing the outer surface of the tube.
  • the positive electrode binder of a secondary battery is notably mostly fluorine-based, and the active material is hard and easy to scrape the inner surface of the tube, but in order to ignore contamination due to wear on the inner surface of the tube, a fluorine-based tube with good slipperiness of powder such as PTFE or PFA is selected, and the powder can be ionized by ionizing the gas in the atmosphere with a corona electrode and ionizing the powder that comes into contact with it.
  • the negative electrode is good for ionizing air (mainly oxygen), and the positive electrode is good for charging nitrogen.
  • the present invention provides exhaust ports 6, 6' that allow excess gas to escape from the middle of the flow path, and the powder from the nozzle 8 can be made powder-rich.
  • the exhaust can be evenly released around the entire circumference outside the tube, and the excess gas can also be released from one or more exhaust ports 6, 6'. If an exhaust means is provided immediately before narrowing the inner diameter of the flow path tube, the exhaust of excess gas becomes more effective. If the inner diameter of the tube suddenly changes from a large diameter to a small diameter, the powder fluid containing a large amount of compressed gas cannot flow into the small diameter tube and flows back to the ejector pump side.
  • the tube should be gradually tapered to ensure a smooth flow.
  • the powder is ejected from the nozzle 8, charged by electrostatic electrodes 11, 11', 11'' arranged in the powder coating section 16, flows out from the end 15 of the powder coating section 16, and adheres to the object 12 moving close to the end 15.
  • the nozzle 8 may be angled toward the object 12 so that the powder collides with it and adheres to it.
  • the electrostatic charge may already be charged in the flow path upstream of the nozzle or on the object 1 upstream of that.
  • the object 12 may be placed via a conductive object such as a metal roll, and the end 15 and the object may be at a level where they are almost in contact, which may be about 0.5 to 3 mm. Therefore, even if the object moves at high speed, the wind flow that affects the adhesion of the powder can be prevented by a wall or the like and can be ignored. Furthermore, the powder is charged, and therefore the powder can be efficiently attached to the object in the powder coating section 16.
  • the unattached powder and air flow move downstream, including the bottom 14, so the excess air flow and the powder that did not adhere to the object 12 are discharged by suction from the discharge port 10, and the powder is recovered and reused.
  • the powder is ejected from the nozzle 8, moves along the walls 9, 9' on both sides, and is charged by the electrostatic discharge section, and the excess gas and powder that does not adhere to the object are sucked in and discharged from the discharge port 10.
  • the number of nozzles It can be one or more.
  • the distance between the walls but if you want to form the electrodes in a narrow stripe shape, it is better to set it to about 5 to 30 mm per nozzle. If you want to have electrodes with a wide width, you can install the desired number of powder coating sections in parallel.
  • the powder coating section longer in the direction of movement of the object and keep the contact time of the powder longer, so that the powder can be attached more efficiently.
  • the moving speed of the object is 60 m per minute, a length of 0.5 to 1 m or more is good. In this way, the contact time between the object and the powder will be 0.5 to 1 second or more.
  • the particle size of the powder is large and the specific gravity is heavy, the bottom can be made porous and gas can be added to move it while it flows. The discharged powder can be sucked up and collected using a cyclone device (not shown) and reused.
  • powder is ejected from the nozzles 28, 28', 28'', and moves while being restricted in the lateral direction by the walls 29, 29', becomes charged at the electrostatic discharge parts 21, 21', and adheres to the object moving above it (not shown).
  • Static electricity is generated by an electrostatic generator (not shown) and is connected to an electrostatic cable 22 made of a conductor with resistance covered with an insulating material.
  • sparks may occur when the metal foil of the object comes into contact with it, so a material with resistance that does not allow the current to flow suddenly and does not spark should be selected.
  • a thin corona pin is suitable for the discharge point, and the discharge current is at the microampere level, for example, 50 microamperes, and the voltage is adjusted to a range of about 20,000 to 700,000 volts.
  • polypropylene or other materials to which charged powder does not easily adhere due to electrostatic repulsion should be selected for the walls 29, 29' and the bottom 26 of the powder coating part.
  • the desired number of nozzles can be selected from, for example, 1 to 100.
  • the nozzles can enter the powder coating part, and the walls can be processed to make them into nozzles.
  • partitions 25, 25' can be provided between walls 29, 29' for the desired number of nozzles.
  • the main purpose of the partitions is to regulate the widthwise flow of powder downstream between the wide walls and move it into a laminar flow.
  • the partitions can regulate the flow of powder in the direction of movement of the object.
  • the tip in particular should be as thin as possible so that the partitions do not become a shadow and inhibit the powder from adhering to the object (not shown).
  • the end of the partition 25 is located away from the wall end 209 so as not to interfere with adhesion to the target object.
  • the bottom 24 is made porous and can be made into a powder fluidized bed by introducing compressed gas from the outside. Therefore, the powder that is sprayed out from the nozzle 28 and settles at the bottom can be moved while being fluidized. Excess gas and powder that does not adhere to the target object (not shown) can be sucked in from the discharge port 20 and transported to a cyclone (not shown) for recovery and reuse.
  • powder is sprayed from the nozzle 38 of the powder application section located above the moving object 32, charged by the electrostatic discharge section 31, and falls or adheres to the object 32 in a directional manner to form a powder layer 102. Excess gas from the sprayed air-powder mixture and powder that does not adhere to the object are sucked in from the discharge port 30, allowing the powder to be collected.
  • the position of the discharge port 30 is not limited. With this positional relationship, there is also no need to provide a special compressed gas-based filling function at the bottom 34 for powder fluidization.
  • the powder layer 202 applied to the object 42 is moved to the pressing means 45, 45' and pressed.
  • the pressing means may be heated, for example, a roll-type pressing means having an induction heating function.
  • the roll pressing means may be a line press in the roll width direction. Since the pressing only needs to fix the powder until the next process, heating and pre-pressing to raise the binder above its softening point are sufficient. Therefore, when there is a small amount of binder, etc., the powder surface before pressing can be prevented from moving by evaporating it at 200°C or less or in a vacuum until the final heating and pressing process, or the object can be temporarily fixed by applying a viscous monomer or liquid plasticizer that is not a problem if it remains.
  • a liquid is applied to a moving object 52 by a liquid application device to form a liquid coating layer 350.
  • electrode powder is applied by a powder application device 310 to form a powder coating layer 302.
  • the liquid may be a slurry for electrodes. It is desirable that the liquid easily penetrates into the gaps of the powder layer to be applied in the next process, is easily wetted, and evaporates instantly by heat or vacuum. In addition, in order to form a dense interface with the target object, it is desirable that the particle size of the electrode composite particles is smaller than the particle size of the powder.
  • a liquid can be applied on the powder coating layer in the form of a thin film of a slurry or the like having a smaller average composite particle size or made of electrolyte particles using a liquid application device (not shown).
  • the purpose is to improve the smoothness of the electrode or to form fine irregularities to improve the surface area. Therefore, a more uniform surface can be formed by applying the slurry or the like on the powder layer after hot pressing.
  • the air-powder mixture is ejected from an ejection port 68, charged by an electrostatic discharge section 61, and adheres to an object 62. Excess air and powder that does not adhere to the object are sucked through an exhaust port 60, and the collected powder can be reused.
  • This method uses a roll 64 instead of the bottom of the powder coating device. The roll 64 can be rotated.
  • FIG. 7 is a diagram showing the configuration of a powder coating device for coating a moving object 72 with powder.
  • Powder is ejected from a powder ejection port 78 and adheres to the object. Excess gas and powder that has not adhered to the object are sucked from an exhaust port, and the collected powder can be reused.
  • the bottom of the powder coating device is a belt 74 that moves in the direction of movement of the object.
  • the belt may be porous, for example a screen belt with fine openings, and pressurized gas may be applied to the belt 74 outside the coating device to form a full die structure at the bottom of the powder coating device to prevent the powder from accumulating at the bottom. Excess gas used in full die can be sucked out from the exhaust port.
  • the roll is a hollow roll 84, and the hollow roll 84 is made porous, so that the inside 830 of the porous part of the hollow roll 84 can be made negative pressure at the position of the powder supplying device 802, and the powder can be attached to the surface of the roll.
  • the gap between the rolls can be adjusted with a squeegee 801 to obtain a desired powder layer thickness with a stable bulk density. If the thickness of the lithium iron phosphate electrode powder after pressing is about 150 micrometers and the true specific gravity is about 2.3, the bulk density of the powder before supply is 0.8 to 0.9, so the powder layer thickness is about three times as thick, 450 micrometers.
  • Such low bulk density powder falls when moved by a rotating body or the like, so it is necessary to further increase the bulk density by sucking it with a vacuum from the other side on a porous body.
  • the powder layer with increased bulk density is moved to powder coating device 810, and since the roll can be structured so that compressed gas is fed from inside the roll at least closest to the object 82 or at a desired position, a positive pressure 820 is created inside the hollow space, causing the powder on the roll to be released and coated from below onto the object 82 moving above coating device 810.
  • the powder is charged and earthed by static electricity generator 81, and adheres to the moving object to form a powder layer. If the gas used to spray the powder can be given directionality, it becomes surplus gas after coating and can be discharged from the exhaust port 80.
  • Discharge may also be by suction.
  • the coating device 810 can also prevent the flow of gas generated by the movement of the target object 82 outside the device. Therefore, the coating device 810 and the target object 82 can be close to each other by a few millimeters or less. At least the upstream side of the coating device can be in contact with each other. The small amount of powder discharged together with the excess gas during suction can be recovered and reused. The powder flow inside the coating device 810 is not affected by the wind flow outside the device, so a powder layer can be efficiently formed on the object 82 moving at high speed.
  • a desired number of combinations of powder coating device 810, roll 84, and powder supply device 802 can be installed in the direction of movement of the object and stacked.
  • Powder of the same type can be stacked, or different types of powder can be stacked.
  • the charge/discharge performance can be improved by increasing the amount of electrolyte as the ratio of active material to electrolyte increases with distance from the current collector and applying at an angle.
  • a groove of the electrode width can be formed around the porous hollow roll, and a recess can be formed on the cross section of the roll.
  • the desired number of recesses can be formed and the powder can be adsorbed and filled in the porous parts in the same way, it is also possible to fill a large amount of powder depending on the shape of the recesses and apply the powder to the object in a thick film.
  • the hollow roll 84 and the application device 802 can be reversed to move the object 82 moving under the application device with the opening facing downward, with the powder adsorbed to the porous roll or grooves at the top of the roll, and the powder can be released at the bottom and applied to the object.
  • the powder can be released and applied to the object in either direction.
  • the speed of the object and the rotation speed of the outer periphery of the hollow roll can be made constant, and the coating weight per unit area can be made constant by following the speed of the object moving roll-to-roll.
  • a powder layer with a stable bulk density can be formed on the surface of a porous belt 94 that rotates in synchronization with the moving direction of the object by supplying powder 900 by a powder supplying device 902 at a desired position and applying negative pressure to the opposite side of the belt.
  • a powder layer of a desired thickness can be formed on the belt by adjusting the gap with a squeegee 910.
  • the powder supplying device 902 may be an auger feeder or the like, and the powder may be fluidized in a fluidized bed to adhere to the belt, or the powder may be sprayed to adhere. Therefore, the means of supply and adhesion are not limited.
  • the powder layer moves together with the belt 94 and enters the powder coating device 901.
  • compressed gas is discharged from the opposite side of the belt, and the powder on the belt 94 is separated, and the charged powder is grounded by static electricity generating devices 91, 91' and applied to the moving object to form a powder layer.
  • a plurality of compressed gas ejection devices 920, 920' may be arranged in the belt moving direction to separate the powder on the belt and make it adhere to the object, or the powder may be ejected in a pulsed manner to coat the object with multiple layers of powder. If the compressed gas used to eject the powder can be given directionality, it becomes surplus gas and can be discharged from the exhaust port 90. Discharge can also be achieved by creating negative pressure and sucking.
  • the coating device 910 also serves to prevent wind currents caused by the movement of the target object 92 outside the device. For this reason, this can be achieved by coating the target object with at least contact between the upstream part of the coating device 910 and the target object or by keeping the distance between the upstream part and the target object within a few millimeters.
  • a desired number of combinations of powder coating devices 910, belts 94, and powder supply devices 902 can be installed in the direction of movement of the object and stacked.
  • the powder can be the same type, or different types of powder can be stacked.
  • the ratio of active material to electrolyte can be increased as the amount of electrolyte increases with distance from the current collector, and gradient coating can be used to improve charge/discharge performance. At least temporary pressing can be repeated for each layer.
  • the surface opposite to the porous belt on the powder supply side is subjected to negative pressure and suction, so that the bulk density of the powder layer can be made constant.
  • the side of the target object 92 is open, and an excess gas exhaust port 90 is provided downstream of the coating device 910 that encloses the powder layer moving on the belt 94, and the excess gas is exhausted through the exhaust port 90, so that the powder can be prevented from scattering to places other than the desired place on the target object.
  • the small amount of powder discharged from the exhaust port can be sucked up and collected using a mini cyclone or similar device for reuse.
  • the gist of the present invention is to make a powder of composite particles of a composite material for secondary battery electrodes, which includes an all-solid-state battery electrode, and apply the mixture to an object such as a current collector while preventing the powder from agglomerating into a desired ratio, and then heat it as necessary in a short press to form an electrode.
  • an object such as a current collector
  • a surfactant, a dispersant, etc. can be selected and mixed with a resin such as a binder with a small amount of anchor effect dissolved or dispersed in a solvent that evaporates in a later process and applied.
  • a powder of fine particles smaller than the average particle size of the powder of the active material, etc. can be mixed.
  • a slurry of the electrode material in which the binder has been dissolved or swollen can be applied.
  • the solvent or a plasticizer that can evaporate in a later process can be applied in a small amount to the surface of the powder layer to fix the powder layer until the pressing process.
  • the powder-coated surface that comes into contact with the electrolyte layer can be provided with a micron-level fine uneven surface to increase the surface area and improve adhesion with the electrolyte layer, so fine powder can be applied to at least one side of the electrode layer and electrolyte layer.
  • the present invention allows the formation of electrodes for secondary batteries. It is even possible to form electrodes for all-solid-state batteries and semi-solid-state batteries.
  • the manufacturing method for secondary batteries such as LIBs can be used to form electrodes for secondary batteries in general, electrodes for next-generation secondary batteries such as all-solid-state batteries and air batteries, for example, electrodes for capacitors including electric double-layer capacitors, and further, by using the dry method and the wet method alone or in combination, to form electrodes for fuel cells and water electrolysis, and microporous layers for gas diffusion layers.
  • it can be suitably applied to the coating and adhesion of powder to general metal flat plates, long plates, nonwoven fabrics, films, etc.
  • the use of nano-sized or submicron fine powders can further expand the field of application, and it can be used to form each layer of next-generation solar cells, for example.

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Abstract

[Problème] Une électrode d'une batterie secondaire telle que LIB et une électrode d'une batterie entièrement solide ont été formées par : préparation d'une suspension fibreuse à l'aide d'un matériau actif, d'un liant, d'un polymère d'électrolyte, de particules d'électrolyte inorganique, de fibres d'électrolyte inorganique, d'un assistant conducteur et d'un solvant qui dissout le liant et similaire ; application de la suspension fibreuse à un objet tel qu'un collecteur ; et séchage et pressage de la suspension fibreuse sur celui-ci. En particulier, étant donné que le polymère pour l'électrode positive est un liant à base de fluor tel que le fluorure de vinylidène, un solvant organique qui dissout le polymère présente un point d'ébullition élevé, et un four de séchage associé est un grand dispositif supérieur à 100 m et nécessite une grande zone d'installation. Par conséquent, un dispositif de récupération du solvant est de grande taille et consomme une grande quantité d'énergie, et même une batterie pour voitures de batterie a entraîné des problèmes importants en termes d'émissions de CO2 sur la base de LCA. [Solution] En changeant instantanément une suspension fibreuse, qui est obtenue par mélange uniforme de matériaux de mélange d'électrode, en une poudre par un dispositif dédié, les particules de poudre ont les mêmes proportions de matériaux indépendamment des diamètres des particules. Par application de la poudre directement sur un objet, ou par application d'une suspension fibreuse de poudre principalement composée de la poudre et d'un solvant présentant un point d'ébullition bas sur un objet et volatilisation et récupération du solvant dans une courte période, une couche de poudre plus dense est formée. Selon la présente invention, une électrode peut être formée en effectuant uniquement une compression de rouleau.
PCT/JP2023/033496 2022-10-05 2023-09-14 Procédé d'application de poudre, procédé de production de batterie secondaire, procédé de production de batterie entièrement solide, batterie secondaire et batterie entièrement solide WO2024075484A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016077982A (ja) * 2014-10-18 2016-05-16 エムテックスマート株式会社 粉粒体の塗布方法
JP2016182579A (ja) * 2015-03-26 2016-10-20 富士ゼロックス株式会社 粉体塗装装置、及び粉体塗装方法
JP2018192380A (ja) * 2017-05-12 2018-12-06 新日鉄住金エンジニアリング株式会社 静電粉体塗装装置
JP2020129495A (ja) * 2019-02-08 2020-08-27 エムテックスマート株式会社 全固体電池の製造方法
JP2021087905A (ja) * 2019-12-02 2021-06-10 エムテックスマート株式会社 粉粒体の塗布または成膜方法

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JP2016182579A (ja) * 2015-03-26 2016-10-20 富士ゼロックス株式会社 粉体塗装装置、及び粉体塗装方法
JP2018192380A (ja) * 2017-05-12 2018-12-06 新日鉄住金エンジニアリング株式会社 静電粉体塗装装置
JP2020129495A (ja) * 2019-02-08 2020-08-27 エムテックスマート株式会社 全固体電池の製造方法
JP2021087905A (ja) * 2019-12-02 2021-06-10 エムテックスマート株式会社 粉粒体の塗布または成膜方法

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