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WO2025028032A1 - Procédé de fabrication d'électrode et dispositif de fabrication d'électrode - Google Patents

Procédé de fabrication d'électrode et dispositif de fabrication d'électrode Download PDF

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Publication number
WO2025028032A1
WO2025028032A1 PCT/JP2024/021281 JP2024021281W WO2025028032A1 WO 2025028032 A1 WO2025028032 A1 WO 2025028032A1 JP 2024021281 W JP2024021281 W JP 2024021281W WO 2025028032 A1 WO2025028032 A1 WO 2025028032A1
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WIPO (PCT)
Prior art keywords
irradiation
workpiece
current collector
electrode
energetic
Prior art date
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Pending
Application number
PCT/JP2024/021281
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English (en)
Japanese (ja)
Inventor
康治 中島
茂樹 松本
信二 鈴木
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Ushio Denki KK
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Ushio Denki KK
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Publication date
Application filed by Ushio Denki KK filed Critical Ushio Denki KK
Publication of WO2025028032A1 publication Critical patent/WO2025028032A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/62—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method and device for manufacturing electrodes for secondary batteries.
  • electrodes for lithium ion secondary batteries generally have a structure in which an active material slurry is applied onto a current collector (for example, a metal foil such as aluminum foil, copper foil, or stainless steel foil).
  • a current collector for example, a metal foil such as aluminum foil, copper foil, or stainless steel foil.
  • active materials oxides and phosphate compounds of various metals such as lithium, nickel, cobalt, manganese, and iron are used for the positive electrode, and carbon-based materials such as graphite and hard carbon, and lithium titanate are used for the negative electrode.
  • These active material powders, a binder for binding them to the current collector, and a conductive assistant such as acetylene black for obtaining high conductivity are kneaded with a solvent to form an active material slurry.
  • lithium-ion secondary batteries are rapidly increasing in current, capacity, and speed. The obstacle to this is the contact resistance (interface resistance) between the current collector and the active material slurry. Therefore, it is necessary to reduce the contact resistance.
  • a factor that increases contact resistance is the metal oxide film that forms on the surface of the current collector; for aluminum or stainless steel foil current collectors, this corresponds to the passive layer, and for copper foil current collectors, this corresponds to the copper oxide film.
  • the passive layer also plays a role in preventing corrosion of the metal foil of the current collector by the electrolyte, so a certain thickness is required, but the thicker the layer, the greater the interfacial resistance, so there is a demand for it to be as thin as possible without causing metal corrosion. It is known that insufficient metal corrosion resistance significantly reduces the lifespan (number of charge/discharge cycles) of a secondary battery. For this reason, there is an optimum thickness for the passive layer or oxide film layer.
  • hydrophilization treatments include treatments that modify the surface by irradiating it with energy particles, such as vacuum ultraviolet light in the presence of oxygen or atmospheric pressure plasma (see, for example, Patent Document 1).
  • the present invention has been made in view of the above, and an object of the present invention is to suppress the progress of surface oxidation of a current collector caused by moisture in the atmosphere in which irradiation treatment with energetic particles is performed.
  • one aspect of the electrode manufacturing method is a method for manufacturing an electrode for a secondary battery, which includes an irradiation step in which an irradiation treatment is performed by irradiating at least one surface of a current collector workpiece constituting the electrode with energy particles, and a coating step in which a slurry containing an active material is applied to the surface of the workpiece that has been irradiated with the energy particles in the irradiation step, and in which the irradiation step is performed in a dry atmosphere that does not contain moisture.
  • the dry atmosphere may be an atmosphere having a dew point temperature of ⁇ 55° C. or less, or a relative humidity of 0.1% or less at room temperature. This makes it possible to form a dry atmosphere that does not contain moisture.
  • the energy particles in the irradiation step, may be irradiated to the same irradiated area of the workpiece multiple times for a predetermined irradiation time, and an irradiation pause time may be provided between each irradiation of the multiple irradiations of the energy particles and the next irradiation of the same irradiated area to pause the irradiation of the energy particles.
  • the irradiation of the energy particles to the same irradiated area is paused, so that the work can be cooled during that time.
  • the temperature rise of the work due to the irradiation process can be suppressed compared to the case where the energy particles are continuously irradiated to the same irradiated area for a predetermined irradiation time. Therefore, the increase in the resistance of the surface oxide film due to the increase in the thickness of the surface oxide film caused by the temperature rise of the work can be reduced, and the performance deterioration of the secondary battery can be reduced.
  • the shrinkage of the work due to the temperature difference between the active material slurry and the work can be reduced, so that the increase in the interface resistance due to the occurrence of wrinkles and peeling can be reduced.
  • the irradiation process can impart wettability to the surface of the work, by applying the active material slurry to the surface after the wettability is imparted, the adhesion with the active material slurry can be improved and the interface resistance can be reduced.
  • the irradiation pause time may be controlled so that the temperature of the workpiece after the temperature increase due to the irradiation of the energetic particles becomes equal to or lower than a predetermined temperature.
  • the specified temperature to, for example, a temperature at which shrinkage of the collector workpiece due to application of the active material slurry is unlikely to occur, or a temperature at which the thickness of the surface oxide film is unlikely to increase, it is possible to more reliably reduce the increase in interface resistance and the increase in resistance of the surface oxide film due to an increase in the temperature of the workpiece.
  • a plurality of types of radiation pause times having different time lengths may be set in the radiation step.
  • the temperature rise after each irradiation changes and the cooling conditions change, so that the temperature rise of the workpiece can be suppressed more efficiently than, for example, setting all irradiation pause times of the same length.
  • a longer radiation pause time may be set for each subsequent irradiation.
  • the temperature after irradiation with energetic particles becomes higher in later rounds due to residual heat, so by making the cooling time longer in later rounds, the temperature rise of the workpiece can be more efficiently suppressed.
  • the energetic particles may be photons having a wavelength of 200 nm or less, or plasma particles. This makes it possible to perform an irradiation process that can modify (make hydrophilic) the workpiece surface while suppressing a rise in the workpiece temperature, for example, by irradiating the workpiece with photons of vacuum ultraviolet light or atmospheric pressure plasma particles.
  • the slurry may contain the active material, a conductive assistant, and a binder, and when the sum of the compounding ratios of the active material, the conductive assistant, and the binder is 100 [%], the compounding ratio X [%] of the conductive assistant may be in the range of 0 ⁇ X ⁇ 5.
  • one aspect of the electrode manufacturing apparatus is an electrode manufacturing apparatus for manufacturing electrodes for secondary batteries, comprising an energy particle source that radiates energy particles, a movement mechanism that moves at least one of the energy particle source and a current collector workpiece that constitutes the electrode, a dry air supply mechanism that supplies dry air to at least the space around the workpiece, and a control unit that controls the energy particle source, the movement mechanism, and the dry air supply mechanism.
  • control unit controls the movement mechanism so that the irradiation area of the energy particle source moves along or relatively to the surface of the workpiece, controls the energy particle source to irradiate the same irradiated area of the workpiece with the energy particles for a predetermined irradiation time in multiple rounds, and controls the energy particle source to provide an irradiation pause time between each irradiation and the next irradiation of the multiple irradiations of the energy particles, during which the irradiation of the energy particles to the same irradiated area is paused, and controls the dry air supply mechanism so that the atmosphere of at least the space around the workpiece is maintained as a dry atmosphere that does not contain moisture.
  • the irradiation of the energy particles is paused during the irradiation pause time between each irradiation in multiple irradiations, and the workpiece can be cooled during that time.
  • This makes it possible to suppress the temperature rise of the workpiece due to irradiation, compared to when the same irradiated area is continuously irradiated with energy particles for a specified irradiation time.
  • it is possible to reduce the increase in resistance of the surface oxide film due to the increase in the thickness of the surface oxide film caused by the temperature rise of the workpiece, and to reduce performance deterioration of the secondary battery.
  • At least the space around the workpiece can be maintained in a dry atmosphere, which can prevent moisture in the atmosphere from being adsorbed onto the workpiece during irradiation processing or when irradiation is paused.
  • a dry atmosphere which can prevent moisture in the atmosphere from being adsorbed onto the workpiece during irradiation processing or when irradiation is paused.
  • the electrode manufacturing apparatus may include a drying chamber that houses the energetic particle source, the workpiece, and the moving mechanism, the dry air supply mechanism supplies dry air into the drying chamber, and the control unit controls the dry air supply mechanism so that the atmosphere in the drying chamber is maintained as a dry atmosphere that does not contain moisture.
  • the atmosphere in the drying chamber can be maintained as a dry atmosphere that does not contain moisture, so that the space around the workpiece can be more reliably maintained as a dry atmosphere.
  • one aspect of the electrode manufacturing apparatus is an electrode manufacturing apparatus for manufacturing electrodes for secondary batteries, comprising a plurality of energy particle sources that radiate energy particles, a conveying mechanism that conveys a collector workpiece that constitutes the electrode, a dry air supply mechanism that supplies dry air to at least the space surrounding the workpiece, and a control unit that controls the plurality of energy particle sources, the conveying mechanism, and the dry air supply mechanism.
  • the multiple energy particle sources are arranged at a predetermined interval along the longitudinal direction of the workpiece, and the transport mechanism is configured to transport the workpiece in sequence to the irradiation positions of the energy particles of each of the energy particle sources, and the control unit controls the transport mechanism to a transport speed that can irradiate the energy particles to the same irradiated area of the workpiece during a divided irradiation time obtained by dividing a predetermined irradiation time required for processing into the same number of divided irradiation times as the number of energy particle sources at each irradiation position, and controls the transport mechanism to a transport speed that can form an irradiation pause time in which the irradiation is paused on the same irradiated area in the predetermined interval section, and controls the dry air supply mechanism so that the atmosphere of at least the space around the workpiece is maintained as a dry atmosphere that does not contain moisture.
  • the workpiece is transported at a transport speed that creates radiation pauses in sections at predetermined intervals, so the workpiece can be cooled in these sections.
  • This makes it possible to suppress the temperature rise of the workpiece due to radiation, compared to when the same irradiated area is continuously irradiated with energy particles for a predetermined irradiation time.
  • it is possible to reduce the increase in resistance of the surface oxide film due to the increase in thickness of the surface oxide film caused by the temperature rise of the workpiece, and to reduce performance deterioration of the secondary battery.
  • At least the space around the workpiece can be maintained in a dry atmosphere, which can prevent moisture in the atmosphere from being adsorbed onto the workpiece during irradiation processing or when irradiation is paused.
  • a dry atmosphere which can prevent moisture in the atmosphere from being adsorbed onto the workpiece during irradiation processing or when irradiation is paused.
  • the above electrode manufacturing apparatus is provided with a drying chamber that houses the energy particle source, the workpiece, and the conveying mechanism, and the dry air supply mechanism supplies dry air into the drying chamber, and the control unit controls the dry air supply mechanism so that the atmosphere in the drying chamber is maintained as a dry atmosphere that does not contain moisture.
  • the atmosphere in the drying chamber can be maintained as a dry atmosphere that does not contain moisture, so that the space around the workpiece can be more reliably maintained as a dry atmosphere.
  • the predetermined interval may be configured as a plurality of intervals having different lengths. According to this configuration, it is possible to set multiple types of irradiation pause times with different lengths depending on the length of the interval while keeping the transport speed constant.
  • the multiple types of spacing may be configured such that the spacing between the energy particle sources arranged downstream in the transport direction is longer than the spacing between the energy particle sources arranged upstream.
  • the dry atmosphere is an atmosphere having a dew point temperature of ⁇ 55° C. or less, or a relative humidity of 0.1% or less at room temperature.
  • the energetic particle source may be an ultraviolet light radiation source that radiates photons having a wavelength of 200 nm or less, or a plasma radiation source that radiates atmospheric pressure plasma particles.
  • the workpiece surface can be hydrophilized while suppressing an increase in the workpiece temperature.
  • the electrode manufacturing apparatus may further include a coating mechanism that coats a slurry containing an active material on the surface of the workpiece after the surface has been irradiated with the energetic particles. According to this configuration, the active material slurry can be applied to the surface of the workpiece after the irradiation treatment (after the surface modification) in which the temperature rise is suppressed.
  • the present invention can suppress the progression of surface oxidation of the current collector caused by moisture in the atmosphere in which the irradiation treatment is performed.
  • FIG. 1 is a schematic diagram showing a basic configuration of a lithium-ion secondary battery 30 according to a first embodiment.
  • 3A to 3C are diagrams illustrating an example of a process for manufacturing an electrode of a lithium ion secondary battery 30.
  • FIG. 2 is a diagram showing an example of a schematic configuration of an electrode manufacturing apparatus 1 used in an irradiation step and a coating step.
  • 1 is a diagram showing an example of the positional relationship between an irradiation area of an energetic particle source 11 and a current collector workpiece 40.
  • FIG. 4 is a flowchart showing an electrode manufacturing control process according to the first embodiment.
  • FIG. 4 is a flowchart showing an electrode manufacturing control process according to the first embodiment.
  • FIG. 13 is a diagram showing a change in temperature of a current collector workpiece when the current collector workpiece is continuously irradiated with vacuum ultraviolet light for an irradiation time required for surface modification.
  • FIG. 13 is a diagram showing a temperature change of a current-collector workpiece when irradiation with vacuum ultraviolet light for an irradiation time required for surface modification is performed by the irradiation method according to the first embodiment.
  • FIG. 2 is a diagram showing an example of a schematic configuration of an electrode manufacturing apparatus 2 used in an irradiation step and a coating step.
  • 1 is a diagram showing an example of the positional relationship between an irradiation area of an energetic particle source 22 and a current collector workpiece 60.
  • FIG. 13 is a flowchart showing an electrode manufacturing control process according to a second embodiment.
  • FIG. 13 is a diagram showing a change in temperature of a current collector workpiece.
  • FIG. 13 is a diagram showing the rated capacity of a secondary battery cell after charging and discharging in the case where the compounding ratio X of the conductive additive 36 in the active material slurry 50 is 2%.
  • FIG. 13 is a diagram showing the rated capacity of a secondary battery cell after charging and discharging in the case where the compounding ratio X of the conductive additive 36 in the active material slurry 50 is 5%.
  • FIG. 13 is a diagram showing a schematic configuration of an electrode manufacturing apparatus 1A according to a modified example.
  • FIG. 1 is a schematic diagram showing the basic configuration of a lithium-ion secondary battery 30.
  • a lithium ion secondary battery 30 includes a negative electrode 31, a separator 32, a positive electrode 33, and an electrolyte solution .
  • the negative electrode 31 and the positive electrode 33 are disposed facing each other with a separator 32 for preventing short circuits therebetween, and an electrolyte 34 fills the space between the negative electrode 31 and the separator 32 and the space between the positive electrode 33 and the separator 32 .
  • the negative electrode 31 has a negative electrode current collector 31a and a negative electrode active material layer 31b provided on the surface of the negative electrode current collector 31a facing the positive electrode 33
  • the positive electrode 33 has a positive electrode current collector 33a and a positive electrode active material layer 33b provided on the surface of the positive electrode current collector 33a facing the negative electrode 31.
  • the negative electrode current collector 31a is made of a metal foil such as a copper foil or a stainless steel foil.
  • the negative electrode active material layer 31b is configured to contain, for example, a carbon-based material such as graphite or hard carbon, an active material such as lithium titanate, a conductive assistant such as acetylene black, and the like.
  • the positive electrode current collector 33a is made of a metal foil such as an aluminum foil or a stainless steel foil.
  • the positive electrode active material layer 33b is configured to contain active materials such as oxides of various metals such as lithium, nickel, cobalt, manganese, and iron, and phosphate compounds, as well as conductive assistants.
  • the electrolyte 34 is formed by dissolving an electrolyte salt such as LiPF6 or LiBF4 in a mixed solvent of a cyclic carbonate ester and a chain carbonate ester, for example.
  • the negative electrode active material layer 31b and the positive electrode active material layer 33b are formed by applying an active material slurry to the negative electrode current collector 31a and the positive electrode current collector 33a, respectively.
  • the active material layer is composed of active material 35, conductive additive 36, binder 37, and voids 38.
  • the positive electrode active material layer 33b also contains active material 35c that has cracked due to compression.
  • the drying and compression process involves drying the current collector after coating with the active material slurry in a thermostatic chamber or the like, and then pressing the active material slurry onto the current collector using a roll press or the like after drying. This reduces the interface resistance and adjusts the density of the slurry. In recent years, semi-solid electrodes that do not require drying have appeared, and compression may be performed without drying. For this reason, the drying process is appropriately selected depending on the structure and type of the battery. [Electrode manufacturing method] Next, a method for manufacturing the electrodes of the lithium ion secondary battery 30 will be described.
  • FIG. 2 is a diagram showing an example of a process for manufacturing an electrode of the lithium ion secondary battery 30.
  • a work 40 (hereinafter referred to as "current collector work 40") of the negative electrode current collector 31a or the positive electrode current collector 33a is prepared.
  • a drying chamber 17 is prepared.
  • the current collector work 40 has a long strip shape, which is wound up in a roll by a reel. This roll-shaped current collector work 40 is transported by a guide roller (not shown) from an upstream feed reel through the irradiation area and coating area of the energetic particle source 11 and the coating mechanism 12 to a downstream take-up reel.
  • the arrow in FIG. 2 indicates the transport direction.
  • the irradiation area is the area of the irradiation position where the energy particle source 11 irradiates the surface of the current collector workpiece 40 with energy particles
  • the application area is the area of the application position where the application mechanism 12 applies the active material slurry 50 to the surface of the current collector workpiece 40.
  • the drying chamber 17 is airtight, and contains the collector workpiece 40, the feed reel, the guide roller, the take-up reel, the energy particle source 11, the coating mechanism 12, and the dry air supply mechanism 16.
  • Preparation of the drying chamber 17 means supplying dry air into the drying chamber 17 using the dry air supply mechanism 16 to make the atmosphere in the drying chamber 17 dry, for example, with a dew point temperature of -55°C or less, and maintaining this state.
  • a dry atmosphere with a dew point temperature of -55°C or less is equivalent to a dry atmosphere with a relative humidity of 0.1% or less at room temperature.
  • the Japanese Industrial Standards (JISZ8703) define "room temperature" as a range of 20°C ⁇ 15°C (5 to 35°C).
  • an irradiation treatment (surface modification treatment) is performed in which energy particles are irradiated from the energy particle source 11 onto at least one surface of the current-collector workpiece 40 transported by the guide rollers.
  • This irradiation treatment is performed in the above-mentioned dry atmosphere in the drying chamber 17.
  • the surface of the current-collector workpiece 40 to which the active material slurry 50 is to be applied (hereinafter referred to as the "applied surface") is modified.
  • the surface modification is a modification that makes the coating surface of the current-collector workpiece 40 hydrophilic (imparts wettability) to reduce the contact resistance (interface resistance) between the coating surface and the active material slurry 50 .
  • the energetic particle source corresponds to, for example, an ultraviolet light radiation source that radiates photons with a wavelength of 200 nm or less, a plasma radiation source that radiates plasma particles, and the like.
  • the process of irradiating energy particles such as vacuum ultraviolet light or atmospheric pressure plasma causes a temperature rise in the current collector workpiece 40, so if it is performed continuously for a long period of time, the temperature rise in the current collector workpiece 40 will cause the current collector workpiece 40 to thermally expand. Furthermore, the current collector workpiece 40 will expand unevenly due to temperature variations within the irradiated surface. This temperature rise is even more pronounced for current collector workpieces 40 with carbon coating on the surface, as the light absorption rate increases. Furthermore, strong light emission is produced when plasma is generated, and this is even more pronounced in atmospheric pressure plasma irradiation processing in which both plasma and light are incident on the workpiece.
  • energy particles such as vacuum ultraviolet light or atmospheric pressure plasma
  • the current collector workpiece 40 cools rapidly after application and shrinks because the active material slurry 50 is at room temperature, which is lower than the temperature of the current collector workpiece 40, and this shrinkage occurs unevenly due to the above-mentioned variations. This causes the active material slurry 50 to wrinkle or partially peel off, increasing the interface resistance and causing performance degradation.
  • the irradiation treatment of energetic particles in the presence of oxygen is accompanied by an oxidation reaction that generates active oxygen and makes the current collector surface hydrophilic
  • the oxidation will progress into the inside of the current collector workpiece 40 and the surface oxide film will increase more than necessary. This will increase the resistance of the oxide film and cause performance degradation of the secondary battery. Therefore, in the irradiation process of S11 described above, in order to suppress a rise in temperature of the current collector workpiece 40, the irradiation of the energy particles for the irradiation time required for surface modification (hydrophilization) of the irradiated area of the coated surface of the current collector workpiece 40 is divided into multiple irradiations.
  • this irradiation method irradiates the same irradiated area with energy particles each time using split irradiation times that are the required irradiation time divided into the same number of irradiations.
  • this method provides an irradiation pause time between each irradiation, during which the irradiation of energy particles is paused. In other words, this method does not irradiate the same irradiated area with energy particles continuously for the required irradiation time, but rather irradiates the area in multiple times with irradiation pause times in between.
  • the divided irradiation time is, for example, 2 seconds, which is "6 seconds/3 times". Note that this configuration is not limited, and the divided irradiation time can be set to different time lengths such as 3 seconds, 2 seconds, and 1 second, as long as it is divided into 3 times.
  • the irradiation pause time is set so that the temperature of the current collector workpiece 40 after the temperature rise due to the irradiation of the energetic particles is equal to or lower than a predetermined temperature.
  • the irradiation pause time is set to 4 seconds after the first irradiation and 6 seconds after the second irradiation.
  • the irradiation pause time is set to an appropriate time based on the temperature measurement results after irradiation in, for example, a test run.
  • the irradiation method of the present invention in the irradiation process in S11 above will be referred to as a "fractionated irradiation method.”
  • the reason why the irradiation treatment by the divided irradiation method is carried out in the above-mentioned dry atmosphere is that when moisture is present in the atmosphere in which the irradiation treatment is carried out, the moisture is decomposed by energy particles such as vacuum ultraviolet light or atmospheric pressure plasma, and oxidatively active hydroxyl radicals are generated.
  • oxidation by oxygen radicals generated from oxygen in the atmosphere is compounded by oxidation by hydroxyl radicals generated from moisture, causing the surface oxidation of the current collector workpiece 40 to proceed more than necessary, resulting in a problem.
  • the moisture adsorbed to the surface of the current collector workpiece 40 is the largest contributor to this reaction. That is, most of the hydroxyl radicals generated in the space collide with other gas molecules before reaching the surface of the current collector workpiece 40 and are deactivated, but the hydroxyl radicals originating from the moisture adsorbed to the surface immediately react with the surface of the current collector workpiece 40, causing an oxidation reaction. This oxidation reaction increases the thickness of the surface oxide film.
  • a coating process is performed in which active material slurry 50 is applied to the surface to be coated of current-collector workpiece 40 after irradiation treatment (surface modification) by coating mechanism 12.
  • This coating process is also performed in the above-mentioned dry atmosphere.
  • a die coater, a comma coater, a reverse roll coater, a gravure coater, etc. can be used as the coating mechanism 12.
  • the current collector workpiece 40 after being coated with the active material slurry 50 is taken up by a take-up reel. Also, after the active material slurry 50 is applied, the current collector workpiece 40 may be primarily dried and then wound up on a take-up reel.
  • S13 which is a drying step
  • the current collector workpiece 40 wound around the take-up reel is transported into the thermostatic chamber 14, and the current collector workpiece 40 is dried in the thermostatic chamber 14.
  • the current collector workpiece 40 is dried in the thermostatic chamber 14 for several days.
  • the drying step S13 is not performed and the process proceeds to the next compression step S14.
  • the active material slurry 50 applied to the current collector workpiece 40 is compressed by a roll press type compression mechanism 15.
  • the roll press type is a compression method in which the current collector workpiece 40 is poured between two rotating rollers and compressed into a linear shape.
  • FIG. 3 is a diagram showing an example of a schematic configuration of an electrode manufacturing apparatus 1 used in the irradiation step S11 and the coating step S12.
  • the electrode manufacturing apparatus 1 includes a transport mechanism 10 that transports the current collector workpiece 40, energy particle sources 11a, 11b, and 11c that radiate energy particles, and a coating mechanism 12 that coats the surface-modified current collector workpiece 40 with an active material slurry 50.
  • the apparatus includes a dry air supply mechanism 16, a drying chamber 17, and a control unit 13 that controls the operations of the transport mechanism 10, the energy particle sources 11a to 11c, the coating mechanism 12, and the dry air supply mechanism 16.
  • the arrows in FIG. 3 indicate the transport direction of the current collector workpiece 40.
  • the energetic particle sources 11a to 11c will be simply referred to as "energetic particle source 11" when there is no need to distinguish between them.
  • the transport mechanism 10 includes a feed reel 10a, a plurality of guide rollers 10b, and a take-up reel 10c.
  • the feed reel 10a is a reel for feeding the long, strip-shaped current collector workpiece 40 wound around the feed reel 10a to the guide rollers 10b.
  • the guide rollers 10b are rollers for transporting the current collector workpiece 40 wound around the feed reel 10a, in this order, to the irradiation areas of the energetic particle sources 11a to 11c, the coating area of the coating mechanism 12, and then to the take-up reel 10c.
  • the take-up reel 10 c is a reel that winds up the current collector workpiece 40 after the active material slurry 50 has been applied by the application mechanism 12 .
  • the conveying mechanism 10 may also be equipped with a tension control mechanism that adjusts the tension applied to the current collector workpiece 40.
  • the tension control mechanism may be, for example, a dancer roll type automatic tension control device.
  • the conveying mechanism 10 may also be equipped with a position adjustment mechanism that adjusts the widthwise position of the current collector workpiece 40.
  • the position adjustment mechanism may be, for example, an EPC (edge position control) that combines an edge inspection device and a position correction device.
  • the energy particle sources 11a to 11c are arranged at a predetermined interval along the longitudinal direction of the current collector workpiece 40. Specifically, as shown in FIG. 3, the energy particle source 11a is arranged at a position closest to the feed reel 10a (upstream side), and the energy particle source 11b is arranged at a distance L1 from the energy particle source 11a. Moreover, the energy particle source 11c is arranged at a distance L2 (L1 ⁇ L2) from the energy particle source 11b.
  • the energetic particle source 11 can be composed of an ultraviolet light radiation source that emits photons with a wavelength of 200 nm or less, or a plasma radiation source that emits plasma particles.
  • the energetic particle sources 11a to 11c can be, for example, xenon excimer lamps that emit vacuum ultraviolet light with a central wavelength of 172 nm.
  • the energetic particle sources 11a to 11c can be, for example, atmospheric pressure plasma devices that emit atmospheric pressure plasma particles.
  • the energetic particle sources 11a to 11c are ultraviolet radiation sources that emit vacuum ultraviolet light.
  • the number of energetic particle sources 11 is not limited to three, namely energetic particle sources 11a to 11c, but may be two or four or more depending on the type of radiation source and the number of times the same region is irradiated.
  • the coating mechanism 12 is a mechanism that coats the active material slurry 50 on the coating surface after the surface modification of the current-collector workpiece 40.
  • the coating mechanism 12 can be, for example, a die coater.
  • the dry air supply mechanism 16 supplies dry air into the drying chamber 17 and circulates the dry air within the chamber.
  • the drying chamber 17 houses the conveying mechanism 10, the energy particle sources 11a-11c, the coating mechanism 12, the control unit 13, and the dry air supply mechanism 16.
  • the drying chamber 17 is configured to seal off areas that cannot be entered by workers. In other words, it is isolated from the area (space) where workers are present.
  • control unit 13 and the dry air supply mechanism 16 are housed within the drying chamber 17, but this configuration is not limited to this.
  • the control unit 13 may be placed outside the room as long as signal lines are connected to each particle source and each mechanism.
  • the main body of the dry air supply mechanism 16 may be placed outside the room as long as the dry air supply port and the mechanism for adjusting the wind direction are inside the room.
  • the configuration is not limited to isolating it from the space where the worker is present, and the entire mechanism, including the space where the worker is present, may be housed within the drying chamber 17.
  • the control unit 13 includes a processor that controls the entire electrode manufacturing apparatus 1 based on a control program, and a ROM (Read Only Memory) that stores the control program, setting data, etc.
  • the control unit 13 includes a RAM (Random Access Memory) for storing data read from the ROM and calculation results required in the calculation process of the processor, and an I/F (interface) that mediates input and output of data to and from an external device. These are connected to each other so that data can be transmitted and received by a bus, which is a signal line for transferring data.
  • the control unit 13 is electrically connected to the transport mechanism 10, the energetic particle sources 11a to 11c, the coating mechanism 12, and the dry air supply mechanism 16 via the I/F, and controls the operations of these mechanisms.
  • control unit 13 controls the rotation speed of each reel and each roller of the transport mechanism 10 (the transport speed of the current collector workpiece 40), the irradiation intensity and irradiation time of the energy particles from the energy particle source 11, the coating thickness of the coating mechanism 12, etc.
  • control unit 13 controls the supply and circulation operation of the dry air supply mechanism 16, and controls the atmosphere in the drying chamber 17 to be equal to or lower than a target dew point temperature.
  • the control unit 13 also controls the operations of these mechanisms.
  • FIG. 4 is a diagram showing an example of the positional relationship between an irradiation area of the vacuum ultraviolet light from the energetic particle source and a current collector workpiece 40.
  • the irradiation areas 110a, 110b, and 110c of the energetic particle sources 11a, 11b, and 11c are each linear (rectangular) ranges that include the entire area of the collector workpiece 40 in the short direction.
  • the interval L1 between the energy particle source 11a and the energy particle source 11b is set as the interval between the point directly below 111a of the energy particle source 11a and the point directly below 111b of the energy particle source 11b.
  • the interval L2 between the energy particle source 11b and the energy particle source 11c is set as the interval between the point directly below 111b of the energy particle source 11b and the point directly below 111c of the energy particle source 11c.
  • 4 indicates the conveying direction of the current-collector workpiece 40
  • T1 indicates the radiation pause time in the section between the energetic particle sources 11a and 11b
  • T2 indicates the radiation pause time in the section between the energetic particle sources 11b and 11c.
  • the transport speed of the current collector workpiece 40 is controlled to a constant speed, and the irradiation pause times T1 and T2 are determined by the lengths of the intervals L1 and L2. In other words, the sections of the irradiation pause times T1 and T2 become irradiation pause sections.
  • the irradiation pause times T1 and T2 can also be changed by changing the transport speed.
  • the irradiation pause times are set to the time when the temperature of the current collector workpiece 40 after rising becomes equal to or lower than a predetermined temperature.
  • This predetermined temperature is a temperature at which wrinkles or peeling do not occur on the current collector workpiece 40 even if the active material slurry 50 is continuously applied without cooling by a cooling device after the irradiation process of the energy particles (vacuum ultraviolet light) by the energy particle sources 11a to 11c is completed.
  • the temperature is set to a temperature at which oxidation of the applied surface of the current collector workpiece 40 due to the irradiation of the energy particles does not progress to the inside of the current collector, causing the surface oxide film to increase more than necessary.
  • the allowable temperature for preventing wrinkles and peeling varies depending on the characteristics of the active material slurry 50 and the material of the current collector workpiece 40.
  • the temperature as low as possible below the vaporization temperature of the solvent added when kneading the active material slurry 50, and for example, in the case of water-soluble solvent, it is desirable to set the temperature below 60 [°C].
  • the irradiation energy intensity (irradiation energy value) and intervals L1 and L2 of the energetic particle sources 11a to 11c are set so that the intensity can be regarded as substantially non-irradiation at the positions of the midpoints Lc1 and Lc2 of the irradiation pause section in Fig. 4. For example, they are set so as to be 1/20 or less of the energy value at the directly below points 111a and 111b. That is, in a configuration in which a plurality of energetic particle sources are arranged for irradiation, it is assumed that depending on the lengths of the intervals L1 and L2, light leakage or the like may occur even during the irradiation pause section, and the irradiation energy value will not become zero.
  • FIG. 5 is a flowchart showing the electrode manufacturing control process.
  • the processor of the control unit 13 starts a control program stored in a predetermined area of the ROM, and executes an electrode manufacturing control process shown in the flowchart of FIG. 5 in accordance with the program.
  • the electrode manufacturing control process is executed in the processor, as shown in FIG. 5, the process first proceeds to step S100.
  • step S100 setting information that has been input by the user and stored in the ROM in advance is obtained, and then the process proceeds to step S102.
  • the setting information includes information such as the irradiation intensity (energy intensity) of the vacuum ultraviolet light from the energetic particle source 11, the irradiation area, the irradiation time and the number of irradiations, the coating thickness of the active material slurry 50 from the coating mechanism 12, and the target dew point temperature of the dry air supply mechanism 16.
  • the number of irradiations is the same as the number of energetic particle sources.
  • step S102 based on the setting information acquired in step S100, the conveying speed of the conveying mechanism 10 for the current collector workpiece 40, the irradiation intensity of the energy particle source 11, and the discharge amount of the active material slurry 50 of the coating mechanism 12 are set. In addition, the target dew point temperature of the dry air supply mechanism 16, etc. are set. Then, the process proceeds to step S104.
  • the divided irradiation times are calculated by "irradiation time/number of irradiations (three times in the example of FIG. 3)".
  • the conveying speed is set to a speed that allows irradiation of the divided irradiation times to the same irradiated area based on the divided irradiation times and the irradiated area. That is, the conveying speed is set to a speed at which the surface portion of the current collector workpiece 40 that has passed the irradiated area is in a state of being irradiated for the divided irradiation times.
  • the discharge amount of the active material slurry 50 from the coating mechanism 12 is determined to an appropriate discharge amount based on the coating thickness and the conveying speed.
  • the target dew point temperature is set to, for example, -55°C.
  • step S104 the operation of the dry air supply mechanism 16 is controlled to supply dry air into the drying chamber 17 and circulate the supplied dry air to make the atmosphere in the drying chamber 17 a dry atmosphere with a dew point temperature of ⁇ 55° C. Then, the process proceeds to step S106.
  • the control unit 13 causes the dry air supply mechanism 16 to continue operating so as to maintain the dew point temperature at ⁇ 55° C.
  • step S106 the operation control of each mechanism and each particle source is started, and then the process proceeds to step S108. Specifically, the control unit 13 controls the reels and rollers of the transport mechanism 10 so as to transport the current-collector workpiece 40 at a set transport speed.
  • control unit 13 controls the energetic particle sources 11a to 11c to radiate energy particles at a set irradiation intensity. As a result, the energetic particle sources 11a to 11c radiate vacuum ultraviolet light at the set irradiation intensity.
  • the control unit 13 also controls the energetic particle sources 11a to 11c to continue radiating vacuum ultraviolet light until the irradiation process (surface modification process) on the coating surface of the current-collector workpiece 40 is entirely completed.
  • the timing of starting irradiation may be controlled so that the energy particle source 11 starts emitting vacuum ultraviolet light in response to detection by a sensor or the like that the current collector workpiece 40 has reached the irradiation area.
  • the control unit 13 sets the amount of active material slurry 50 to be discharged by the application mechanism 12 .
  • the current collector workpiece 40 is first sent from the feed reel 10a to the most upstream guide roller 10b.
  • the tip of the current collector workpiece 40 is first transported via the multiple guide rollers 10b to the irradiation area below the energy particle source 11a (the irradiation position of the irradiation region 110a).
  • the tip of the current collector workpiece 40 enters the irradiation area 110a, in the example of Figure 3, the top surface of the tip (surface to be coated) within the irradiation area 110a is irradiated with vacuum ultraviolet light.
  • the current collector workpiece 40 is transported at the set transport speed, and the part of the top surface of the tip that first passes through the irradiation area 110a (hereinafter referred to as the "first irradiated part”) is irradiated with vacuum ultraviolet light for the divided irradiation time.
  • the first irradiated part becomes in a state where its temperature is higher than before irradiation.
  • the section from when the first irradiated portion of the current collector workpiece 40 leaves the irradiation area 110a until it reaches just before the irradiation area 110b of the energy particle source 11b is an irradiation pause section in which vacuum ultraviolet light is not irradiated.
  • the time during which the first irradiated portion is transported through this irradiation pause section is the irradiation pause time T1, and during the irradiation pause time T1, the first irradiated portion is cooled.
  • the first irradiated portion When the first irradiated portion subsequently passes the irradiation position of the lower irradiation area 110b of the energy particle source 11b, the first irradiated portion is in a state in which it has been irradiated twice with vacuum ultraviolet light in the divided irradiation time. As a result, the first irradiated portion is in a state in which its temperature has increased compared to before the second irradiation.
  • the section from when the first irradiated portion leaves the irradiation area 110b until it reaches just before the irradiation area 110c of the energy particle source 11c is the second irradiation pause section where vacuum ultraviolet light is not irradiated.
  • the time during which the first irradiated portion is transported through this irradiation pause section is the irradiation pause time T2, and during the irradiation pause time T2, the first irradiated portion is cooled.
  • the length of section L2 is set so that irradiation pause time T2 is longer than irradiation pause time T1, and in the second irradiation pause section, the first irradiated portion is cooled for a time longer than irradiation pause time T1. This is because the temperature after the first irradiation and after cooling during irradiation pause time T1 is higher than the initial temperature of the first irradiated portion before the first irradiation, and the temperature of the current collector workpiece 40 is higher after the second irradiation than after the first irradiation.
  • the first irradiated portion passes through the irradiation region 110c below the energy particle source 11c, the first irradiated portion is in a state in which the vacuum ultraviolet light has been irradiated three times in the divided irradiation time. That is, the first irradiated portion is in a state equivalent to the state in which the vacuum ultraviolet light has been continuously irradiated in the set irradiation time.
  • the section until the first irradiated portion reaches the coating area of the coating mechanism 12 also becomes an irradiation pause section, and the first irradiated portion whose temperature has increased due to the third irradiation is cooled.
  • the coating mechanism 12 detects by a sensor (not shown) that the first irradiated portion has reached the coating area, it discharges the active material slurry 50 at a set discharge rate onto the first irradiated portion moving at a set transport speed. This causes the active material slurry 50 to be coated onto the first irradiated portion. This coating process is also performed in a dry atmosphere.
  • the series of irradiation, cooling and coating operations described above are sequentially performed on other portions subsequent to the first irradiated portion on the upper surface of the current-collector workpiece 40.
  • the portion of the current-collector workpiece 40 after being coated with the active material slurry 50 is sequentially taken up by the take-up reel 10c.
  • step S108 it is determined whether the entire current collector workpiece 40 has been wound around the take-up reel 10c, thereby determining whether the process is complete. If it is determined that the process is complete (Yes), the process proceeds to step S110, and if it is determined that the process is not complete (No), the determination process is repeated until the process is complete.
  • step S110 the operation of each mechanism and each particle source of the electrode manufacturing apparatus 1 is stopped, and the series of processes is terminated.
  • the irradiation process of energetic particles onto the collector workpiece 40 of the negative electrode collector 31a or the positive electrode collector 33a constituting the electrode is performed in a dry atmosphere having a dew point temperature of ⁇ 55° C. or lower, which is substantially free of moisture.
  • the drying chamber 17 is configured to be isolated from the space where the worker is present. This makes it possible to prevent the drying state from being hindered by the worker's breath or moisture released from the skin. As a result, it becomes easier to maintain a dry atmosphere at the target dew point temperature. Also, since the amount of dry air supplied can be reduced compared to when the drying chamber 17 is configured to accommodate the entire space including the space where the worker is present, production costs can be reduced.
  • the same irradiated area of the current collector workpiece 40 is irradiated with energy particles for a predetermined irradiation time (irradiation time required for hydrophilization) in multiple separate rounds.
  • irradiation time required for hydrophilization irradiation time required for hydrophilization
  • an irradiation pause time is provided between each irradiation and the next irradiation to pause the irradiation.
  • the irradiation of the energy particles to the same irradiated area of the current collector work 40 is paused, so that the same irradiated area can be cooled during that time.
  • the temperature rise of the current collector work 40 due to the irradiation process can be suppressed compared to the case where the same irradiated area is continuously irradiated with energy particles for a predetermined irradiation time.
  • the increase in the resistance of the surface oxide film due to the increase in the film thickness of the surface oxide film caused by the temperature rise of the current collector work 40 can be reduced, and the performance deterioration of the secondary battery can be reduced.
  • the active material slurry 50 is applied continuously after the irradiation process, a sudden temperature drop due to the application of the active material slurry 50 can be prevented, and the occurrence of shrinkage of the current collector work 40 can be reduced.
  • the specified irradiation time is set to the irradiation time required to hydrophilize the coated surface of the current collector workpiece 40, so the coated surface of the current collector workpiece 40 can be hydrophilized.
  • the transport mechanism 10 can be shared, reducing equipment costs.
  • the irradiation pause times T1 and T2 are set so that the temperature of the current collector workpiece 40 after it has risen due to irradiation with energetic particles (vacuum ultraviolet photons) is equal to or lower than a predetermined temperature.
  • this predetermined temperature is set to a temperature that prevents or reduces the shrinkage of the current collector workpiece 40 and the increase in the surface oxide film. This makes it possible to more reliably prevent or reduce the shrinkage of the current collector workpiece 40 and the increase in the surface oxide film.
  • the irradiation pause time T2 is set to a time longer than the irradiation pause time T1. Since the temperature of the current collector workpiece 40 becomes higher after the second irradiation than after the first irradiation, the rest period of the subsequent irradiations is lengthened accordingly, so that the temperature of the current collector workpiece 40 after multiple irradiations can be more reliably lowered to a predetermined temperature or lower.
  • the energetic particle sources 11a to 11c are arranged along the longitudinal direction of the current collector workpiece 40 with a distance L1 between the energetic particle sources 11a and 11b.
  • the energetic particle sources 11b and 11c are arranged with a distance L2 longer than the distance L1.
  • the transport speed of the transport mechanism 10 is controlled to a constant speed, and the irradiation pause times T1 and T2 are set to different lengths of time depending on the lengths of the distances L1 and L2. With this configuration, the desired irradiation pause time can be set while keeping the conveying speed constant, making it easier to control the irradiation time and reducing the occurrence of uneven application of the active material slurry 50.
  • Figure 6 shows the temperature change of the current collector workpiece when the vacuum ultraviolet light is continuously irradiated for the irradiation time required for surface modification.
  • Figure 7 shows the temperature change of the current collector workpiece when the vacuum ultraviolet light is irradiated for the irradiation time required for surface modification using the divided irradiation method according to the first embodiment.
  • the current collector workpiece used in measuring the temperature changes in Figures 6 and 7 is an aluminum foil workpiece, and the amount of irradiation required for surface modification is 1000 [mJ/ cm2 ] or more.
  • the illuminance (irradiation energy intensity) of the vacuum ultraviolet light from the energy particle source (vacuum ultraviolet light source) used in this example is 170 [mW/ cm2 ], and the irradiation time required for surface modification is 6 seconds or more.
  • the temperature change was measured when the current collector workpiece was continuously irradiated with vacuum ultraviolet light of 170 [mW/cm 2 ] for 6 seconds, 13 seconds, and 25 seconds.
  • a 4-second irradiation rest period was provided after the first irradiation
  • a 6-second irradiation rest period was provided after the second irradiation.
  • the temperature change of the current collector workpiece was measured. As shown by the solid line in FIG. 7, the temperature after the third irradiation of the collector workpiece is about 43° C., which is about 32° C. lower than the temperature of about 75° C. achieved when the irradiation was performed continuously for 6 seconds without dividing the temperature.
  • Each irradiation pause time may be set to the same time, but instead of setting them to the same time as in this embodiment, the degree of cooling can be strengthened by making the pause times longer toward the end.
  • the thickness of the surface oxide film was measured before and after the aluminum foil current collector workpiece was irradiated with vacuum ultraviolet light.
  • the thickness before the irradiation process was 5.4 nm, and the thickness after three separate irradiations of 2 seconds each, with a 4-second rest period after the first and a 6-second rest period after the second, was 5.7 nm.
  • the thickness after six consecutive seconds of irradiation was 6.2 nm.
  • the temperature reached was 43 [°C] and the thickness increase was only 0.3 [nm], which was slight.
  • the temperature reached was 75 [°C] and the thickness increase was significant at 0.8 [nm]. From this, it can be seen that the progression of the surface oxide film in the depth direction can be suppressed by providing an irradiation pause time.
  • the split irradiation process was not performed in a dry atmosphere with a dew point temperature of -55 [°C] or less as in the first embodiment, and the result is in a state where an oxidation reaction due to moisture in the atmosphere also occurs. Therefore, further improvement is expected by performing the split irradiation process in a dry atmosphere with a dew point temperature of -55 [°C] or less as in the first embodiment.
  • the more power is input to shorten the processing time the greater the temperature difference tends to be between continuous irradiation and divided irradiation with irradiation rest periods, and the divided irradiation method of the present invention is a method suitable for short-time processing at high power.
  • FIG. 8A is a diagram showing a schematic configuration example of an electrode manufacturing apparatus 2 used in the irradiation step and the coating step in the second embodiment. As shown in FIG.
  • the electrode manufacturing apparatus 2 includes a base 20, a movable table 21, an energy particle source 22 that emits energy particles, a coating mechanism 23, a control unit 24, a dry air supply mechanism 26, and a drying chamber 27.
  • the base 20 supports the moving stage 21 so as to be movable in the direction of the arrow in FIG. 8A, and includes a moving mechanism (not shown) for moving the moving stage 21 in the direction of the arrow.
  • the moving table 21 includes a catcher (not shown) for fixing the current collector workpiece 60, and is moved on the base 20 by a moving mechanism in the direction of the arrow in FIG. 8(A).
  • the current collector workpiece 60 is made of the same material as the current collector workpiece 40 of the first embodiment, and is a workpiece that is shorter than the current collector workpiece 40. In other words, the current collector workpiece 60 does not have a length sufficient to be wound around a reel for processing.
  • the energetic particle source 22 is a particle source similar to the energetic particle source 11 of the first embodiment. In the following description, the energetic particle source 22 is an atmospheric pressure plasma radiation source that emits atmospheric pressure plasma particles.
  • the coating mechanism 23 is a device that coats the surface to be coated of the current-collector workpiece 60 after irradiation treatment (surface modification) with the active material slurry 50, similar to the coating mechanism 12 of the first embodiment.
  • the drying chamber 27 is configured to be airtight, similar to the first embodiment described above.
  • the drying chamber 27 houses the base 20, the moving table 21, the energy particle source 22, the coating mechanism 23, the control unit 24, and the dry air supply mechanism 26. Also, similar to the first embodiment described above, the drying chamber 27 is configured to seal off areas that workers cannot enter. In other words, it is isolated from the area (space) where workers are present.
  • the control unit 24 like the control unit 13 of the first embodiment, includes a processor, a ROM, a RAM, an I/F, and a bus that interconnects these components so that data can be exchanged.
  • the device is provided with a timer for determining the lapse of divided irradiation times and irradiation rest times, a first counter for counting the number of irradiations, and a second counter for counting the number of surface modification treatments.
  • the control unit 24 is electrically connected to the moving mechanism of the base 20, the energetic particle source 22, the coating mechanism 23, and the dry air supply mechanism 26 via the I/F, and controls the operations of these mechanisms.
  • control unit 24 controls the movement of the moving mechanism (movement of the current collector workpiece 60), the irradiation intensity of the atmospheric pressure plasma of the energetic particle source 22, the irradiation time, the on/off of the irradiation, the coating thickness of the coating mechanism 23, etc. In addition, it controls the supply and circulation of dry air by the dry air supply mechanism 26, and controls the atmosphere in the drying chamber 27 to be equal to or lower than the target dew point temperature.
  • FIG. 8B is a diagram showing an example of the positional relationship between the irradiation area of the energetic particle source 22 and the current collector workpiece 60.
  • the irradiation area 220 of the energetic particle source 22 is a linear range that includes the entire area in the short direction of the collector workpiece 60, as shown in the dashed rectangle in FIG. 8(B). Note that the irradiation area 220 of the atmospheric pressure plasma of the energetic particle source 22 is narrower than the irradiation areas 110a to 110c of the vacuum ultraviolet light of the energetic particle source 11 of the first embodiment.
  • the current collector workpiece 60 can be moved in the direction of the arrow in Fig. 8(B) by a moving mechanism.
  • the width of the irradiation area 220 in the short side direction is shorter than the length of the current collector workpiece 60. Therefore, in the second embodiment, the surface to be coated of the current collector workpiece 60 is divided into a plurality of parts based on the width of the irradiation area 220, and the current collector workpiece 60 is moved by the moving mechanism to sequentially perform divided irradiation processing on each divided area.
  • FIG. 9 is a flowchart showing an electrode manufacturing control process according to the second embodiment.
  • the processor of the control unit 24 starts a control program stored in a predetermined area of the ROM, and executes an electrode manufacturing control process shown in the flowchart of FIG. 9 in accordance with the program.
  • the electrode manufacturing control process is executed in the processor, as shown in FIG. 9, the process first proceeds to step S200.
  • step S200 setting information that has been input by the user and stored in the ROM in advance is obtained, and then the process proceeds to step S202.
  • the setting information includes information such as the irradiation energy intensity of the atmospheric pressure plasma from the energetic particle source 22, the irradiation area, the irradiation time and the number of irradiations, the number of treatments of the surface modification treatment, and the coating thickness of the active material slurry 50 from the coating mechanism 12.
  • the setting information includes information such as the target dew point temperature in the drying chamber 27.
  • the number of times of the divided irradiation process is set based on, for example, the irradiation area and the length of the current collector workpiece 60 .
  • step S202 the irradiation intensity of the atmospheric pressure plasma from the energetic particle source 22 and the discharge amount of the active material slurry 50 from the coating mechanism 23 are set based on the setting information acquired in step S200. Then, the process proceeds to step S203.
  • the divided irradiation time is calculated by "irradiation time/number of irradiations.” For example, when the irradiation time is 70 seconds and the number of irradiations is 10, the divided irradiation time is 7 seconds.
  • the amount of active material slurry 50 discharged by coating mechanism 23 is determined to be an appropriate amount based on the coating thickness and the moving speed of current collector workpiece 60 by the moving mechanism.
  • the radiation pause time is set so that the temperature after the increase due to radiation is kept at or below a predetermined temperature.
  • the target dew point temperature is set to, for example, ⁇ 55° C.
  • the operation of the dry air supply mechanism 26 is controlled to supply dry air into the drying chamber 27 and circulate the supplied dry air to make the atmosphere in the drying chamber 27 a dry atmosphere with a dew point temperature of ⁇ 55° C.
  • the process proceeds to step S204.
  • the control unit 24 causes the dry air supply mechanism 26 to continue operating so as to maintain the dew point temperature at ⁇ 55° C.
  • the moving mechanism is controlled to move the current-collector workpiece 60 to an initial position for irradiation with the energetic particles.
  • step S206 the energetic particle source 22 is caused to start irradiating the irradiated region of the current-collector workpiece 60 located at the irradiation position of the irradiation region 220 with atmospheric pressure plasma, and the timer is started to measure the divided irradiation time. Then, the process proceeds to step S208.
  • step S208 it is determined whether or not the divided irradiation time has elapsed based on the value of the timer, and if it is determined that the divided irradiation time has elapsed (Yes), the process proceeds to step S210. On the other hand, if it is determined that the divided irradiation time has not elapsed (No), the process continues the irradiation of atmospheric pressure plasma and repeats the determination process until the divided irradiation time has elapsed.
  • the process stops the irradiation of atmospheric pressure plasma from the energetic particle source 22. The process also resets the timer, and starts measuring the next irradiation pause time using the timer. Then, the process proceeds to step S212.
  • step S212 it is determined whether the irradiation pause time has elapsed based on the timer value. If it is determined that the irradiation pause time has elapsed (Yes), the timer is reset and the process proceeds to step S214. If it is determined that the irradiation pause time has not elapsed (No), the determination process is repeated until the irradiation pause time has elapsed.
  • step S214 it is determined whether or not the set number of irradiations for the same irradiated area of the current collector workpiece 60 has been completed based on the count value of the first counter. If it is determined that the irradiation has been completed (Yes), the first counter is reset and the process proceeds to step S216, and if it is determined that the irradiation has not been completed (No), 1 is added to the count value of the first counter and the process proceeds to step S206.
  • step S216 it is determined whether or not the divided irradiation process for the set number of processes is completed based on the count value of the second counter. If it is determined that the divided irradiation process is completed (Yes), the second counter is reset and the process proceeds to step S218, and if it is determined that the divided irradiation process is not completed (No), 1 is added to the count value of the second counter and the process proceeds to step S222.
  • the moving mechanism is controlled to move the current-collector workpiece 60 to the coating position of the coating mechanism 23. After that, the process proceeds to step S220.
  • step S220 the coating mechanism 23 applies the active material slurry 50 to the current-collector workpiece 60 after the surface modification. Specifically, the moving mechanism moves the current collector workpiece 60 at a set speed, and the coating mechanism 23 discharges the active material slurry 50 at a set discharge rate onto the surface to be coated of the current collector workpiece 60 moving at the set speed.
  • step S216 if it is determined in step S216 that the divided irradiation processes for the set number of times have not been completed and the process proceeds to step S222, the moving mechanism is controlled to move the next irradiated area of the current-collector workpiece 60 to the irradiation position of the energetic particle source 22. In addition, the timer is reset, and the process proceeds to step S206.
  • the irradiation process of energetic particles onto the collector workpiece 60 of the negative electrode collector 31a or the positive electrode collector 33a constituting the electrode is performed in a dry atmosphere having a dew point temperature of ⁇ 55° C. or lower, which is substantially free of moisture.
  • the drying chamber 27 is configured to be isolated from the space where the worker is present. This makes it possible to prevent the drying state from being hindered by the worker's breath or moisture released from the skin. As a result, it becomes easier to maintain a dry atmosphere at the target dew point temperature. Furthermore, the amount of dry air supplied can be reduced compared to when the drying chamber 27 is configured to accommodate the entire space including the space where the worker is present, thereby reducing production costs.
  • the same irradiated area of the current collector workpiece 40 is irradiated with energy particles for a predetermined irradiation time (irradiation time required for hydrophilization) in multiple separate rounds.
  • irradiation time required for hydrophilization irradiation time required for hydrophilization
  • an irradiation pause time is provided between each irradiation and the next irradiation to pause the irradiation.
  • the irradiation of the energy particles to the same irradiated area of the current collector work 60 is paused, so that the same irradiated area can be cooled during that time.
  • the temperature rise of the current collector work 60 due to the irradiation process can be suppressed compared to the case where the same irradiated area is continuously irradiated with energy particles for a predetermined irradiation time.
  • the increase in the resistance of the surface oxide film due to the increase in the film thickness of the surface oxide film caused by the temperature rise of the current collector work 60 can be reduced, and the performance deterioration of the secondary battery can be reduced.
  • the active material slurry 50 is applied continuously after the irradiation process, the occurrence of contraction of the current collector work 60 due to the sudden temperature drop caused by the application of the active material slurry 50 can be reduced. As a result, it is possible to prevent or reduce the occurrence of wrinkles or partial peeling of the applied active material slurry 50, and therefore the increase in the interface resistance can be reduced.
  • the specified exposure time is set to the exposure time required to hydrophilize the coated surface of the current collector workpiece 60, so the coated surface of the current collector workpiece 60 can be hydrophilized. This makes it possible to impart wettability to the coated surface, and by applying the active material slurry 50 to the coated surface after the wettability has been imparted, the adhesion with the active material slurry 50 can be improved and the interface resistance can be reduced.
  • the irradiation pause time is set so that the temperature of the current collector workpiece 60 after it has risen due to irradiation with energetic particles (atmospheric pressure plasma particles) is equal to or lower than a predetermined temperature.
  • This predetermined temperature is set to a temperature that prevents or reduces the shrinkage of the current collector workpiece 60 and the increase in the surface oxide film. This makes it possible to more reliably prevent or reduce the shrinkage of the current collector workpiece 60 and the increase in the surface oxide film.
  • the irradiation pause time is set to two different lengths and alternately repeated between these two lengths, which makes it easier to control the temperature to a predetermined temperature or lower and makes the temperature rise more gradual than when the same length of irradiation pause time is set between each irradiation and the next irradiation.
  • FIG. 10 is a diagram showing the temperature change of the current collector workpiece when the atmospheric pressure plasma particles are continuously irradiated for the irradiation time required for surface modification and when the divided irradiation method of the present invention is used.
  • the horizontal axis is time (seconds) and the vertical axis is the temperature (°C) of the current collector workpiece.
  • the current collector workpiece used in the experiment was made of aluminum foil, and the amount of irradiation required for surface modification was 1000 [mJ/ cm2 ] or more.
  • the irradiation energy intensity of the atmospheric pressure plasma particles from the energetic particle source (atmospheric pressure plasma radiation source) used in this example was about 14.5 [mW/ cm2 ], and the irradiation time required for surface modification was 70 seconds or more.
  • the temperature change was measured when the surface treatment was carried out using a single energy particle source (plasma radiation source).
  • the temperature change was measured when atmospheric pressure plasma particles of approximately 14.5 [mW/ cm2 ] were continuously irradiated to the same irradiated area of the collector workpiece for approximately 300 seconds.
  • the measurement results at the time position where atmospheric pressure plasma particles were continuously irradiated for 70 seconds reveal that the temperature of the current collector workpiece reached approximately 90° C.
  • the temperature change was measured when the same irradiated area of the current collector workpiece was irradiated with atmospheric pressure plasma particles of approximately 14.5 [mW/ cm2 ] for 70 seconds using the divided irradiation method of the present invention.
  • 70 seconds was divided into 10 parts, and irradiation was performed in 10 parts with each part being 7 seconds long.
  • the temperature change was measured after each odd-numbered irradiation with a 16-second rest period and after the 2nd, 4th, 6th, and 8th even-numbered irradiation with a 12-second rest period.
  • the temperature reaches approximately 70 [°C], which is a reduction in temperature of approximately 20 [°C] compared to approximately 90 [°C] achieved when irradiating continuously for 70 seconds without division.
  • the third embodiment differs from the first and second embodiments in that the range of the compounding ratio of the conductive assistant in the active material slurry (hereinafter simply referred to as "slurry") is set to a specific range.
  • slurry the range of the compounding ratio of the conductive assistant in the active material slurry
  • the present inventors have found that the effect of reducing the interfacial resistance by the hydrophilic treatment (surface modification treatment) on the battery performance is remarkable when the electrical resistance of the slurry itself is relatively high, that is, when the compounding ratio of the conductive additive is relatively low and when the density of the slurry is relatively low. In such a state, the electrical resistance of the slurry itself becomes large, and when the resistance of the interface is added to this, it exceeds the allowable resistance of the entire electrode for maintaining the performance of the secondary battery.
  • the density increases, the slurry becomes denser, the contact of the conductive additive becomes closer, and the resistance value of the slurry decreases.
  • excessive compression makes it difficult for lithium ions and other ions to move within the slurry film, which in turn reduces battery performance, so the density cannot be increased unnecessarily. It is required to keep the density below a level that ensures sufficient movement of lithium ions and other ions.
  • the interface resistance will not exceed the allowable value even if it is high.
  • attempts to reduce the interface resistance value are effective solutions for improving battery performance.
  • the compounding ratio X [%] of the conductive additive 36 when the sum of the compounding ratio V [%] of the active material 35 in the active material slurry 50, the compounding ratio X [%] of the conductive additive 36, and the compounding ratio Y [%] of the binder 37 in the active material slurry 50 is 100 [%], the compounding ratio X [%] of the conductive additive 36 is in the range of 0 ⁇ X ⁇ 5.
  • the active material slurry 50 will be simply referred to as "slurry 50.”
  • Figure 11 shows the rated capacity measured when a secondary battery cell was assembled using a collector coated with a slurry 50 in which the compounding ratio X of the conductive additive 36 was 2% and the charge/discharge cycle was repeated multiple times.
  • Figure 12 shows the rated capacity measured when a secondary battery cell was assembled using a collector coated with a slurry 50 in which the compounding ratio X of the conductive additive 36 was 5% and the charge/discharge cycle was repeated multiple times.
  • untreated indicates the measurement result when the irradiation treatment by the divided irradiation method of the present invention was not performed.
  • AP indicates the measurement result when the irradiation treatment by the divided irradiation method of the present invention was performed with atmospheric pressure plasma
  • VUV indicates the measurement result when the irradiation treatment by the divided irradiation method of the present invention was performed with vacuum ultraviolet light.
  • the charge/discharge rate was changed to 0.2 [C (Capacity)] (twice) ⁇ 1 [C] (twice) ⁇ 2 [C] (twice) ⁇ 0.2 [C] (twice) for a total of eight times, and the rated capacity at the completion of each charge/discharge was measured.
  • the "two times" in parentheses refers to a total of two times, consisting of one full charge at each charge/discharge rate and one full discharge after charging.
  • the 1 C represents the current value when the battery goes from a fully charged state to a fully discharged state in 1 hour. In other words, the higher the number, the larger the current that can be output.
  • the 2 C represents the current value when the battery goes from a fully charged state to a fully discharged state in 30 minutes
  • the 0.2 C represents the current value when the battery goes from a fully charged state to a fully discharged state in 5 hours. For example, if the capacity of the secondary battery is 20 Ah, the current value at 1 C is 20 A, the current value at 2 C is 40 A, and the current value at 0.2 C is 4 A.
  • a slurry 50 was used in which the compounding ratio X [%] of the conductive additive was 2 [%] when the sum of the compounding ratio V [%] of the active material 35, the compounding ratio X [%] of the conductive additive 36, and the compounding ratio Y [%] of the binder 37 was 100 [%].
  • a slurry 50 was used in which the compounding ratio X of the conductive additive 36 was set to 5% instead of 2% in FIG. 11. The amount of the active material 35 was reduced to compensate for the increase in the conductive additive 36.
  • the compounding ratio X [%] of the conductive additive 36 is in the range of 0 ⁇ X ⁇ 5.
  • the effect of improving the capacity and charge/discharge ability of the battery can be further enhanced compared to the case where the irradiation is outside the above range.
  • FIG. 13 is a diagram showing a schematic configuration of an electrode manufacturing apparatus 1A according to a modified example. As shown in FIG. 13, the electrode manufacturing apparatus 1A has a configuration in which the transport mechanism 10 in the electrode manufacturing apparatus 1 of the first embodiment is replaced with a transport mechanism 10A.
  • the transport mechanism 10A includes a feed reel 10a, a plurality of guide rollers 10b, a take-up reel 10c, and a plurality of bypass rollers 10d.
  • the multiple detour rollers 10d form a detour route 101 that forms an irradiation pause section of irradiation pause time T1 between the energetic particle sources 11a and 11b, and a detour route 102 that forms an irradiation pause section of irradiation pause time T2 between the energetic particle sources 11b and 11c.
  • the detours 101 and 102 each form a detour that detours the current collector workpiece 40 in a generally U-shaped manner in a side view toward the lower side of the regular transport path, and the length of the detour (the length of the workpiece that is detouring) corresponds to the intervals L1 and L2 in the first embodiment described above.
  • the lengths of the detours 101 and 102 are configured to be the same, so the irradiation pause time is the same for both, but this is not limited to this configuration, and the lengths of the detours may be configured to be different lengths instead of being equal.
  • the irradiation pause time can be adjusted only by the length of the detour, so it is possible to change only the irradiation pause time without changing the interval between the energy particle sources and the transport speed of the current collector workpiece 40.
  • the current collector work 60 is moved by the moving mechanism, but the present invention is not limited to this configuration.
  • the current collector work 60 may be fixed and the energy particle source 22 and the application mechanism 23 may be moved.
  • the current collector work 60 and the energy particle source 22 and the application mechanism 23 may both be movable, and moved relative to each other.
  • the irradiation process is performed for multiple irradiated areas of the current collector workpiece 60 using multiple split irradiation times with an irradiation pause time between each irradiated area, but this is not the only possible configuration.
  • another irradiated area may be irradiated for the split irradiation time until the irradiation pause time has elapsed. This allows irradiation processing to be performed on multiple irradiated areas while waiting for the irradiation pause time to elapse, thereby improving the efficiency of the split irradiation process.
  • the coating mechanism 12 or 23 is configured to be housed inside the drying chamber 17 or 27, but this is not the only possible configuration, and the coating mechanism 12 or 23 may be located outside the drying chamber 17 or 27. It is difficult to make the drying chamber 17 airtight, but for example, the portion of the transport mechanism 10 involved in the irradiation process may be housed inside the drying chamber 17, and the portion involved in the coating process may not be housed inside the drying chamber 17. Alternatively, the current collector workpiece 40 after the irradiation process (surface modification process) may be temporarily wound up on a take-up reel inside the drying chamber 17, and a separate coating process may be performed outside the drying chamber 17.

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

Abstract

La présente invention supprime la progression de l'oxydation de surface d'un collecteur de courant provoquée par l'humidité dans l'atmosphère dans laquelle un traitement d'irradiation utilisant des particules d'énergie est réalisé.　Ce procédé de fabrication d'électrode pour une batterie secondaire comprend une étape d'irradiation pour effectuer un traitement d'irradiation par irradiation, avec des particules d'énergie, d'au moins une face d'une pièce de collecteur de courant 40 qui comprend une électrode; et une étape de revêtement pour appliquer une barbotine de matériau actif 50 sur la face de la pièce de collecteur de courant 40, qui a été soumise au traitement d'irradiation avec les particules d'énergie pendant l'étape d'irradiation, le traitement d'irradiation étant effectué dans une atmosphère sèche qui est une atmosphère ne contenant pas d'humidité.
PCT/JP2024/021281 2023-07-28 2024-06-12 Procédé de fabrication d'électrode et dispositif de fabrication d'électrode Pending WO2025028032A1 (fr)

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JP2023123173A JP2025019523A (ja) 2023-07-28 2023-07-28 電極製造方法および電極製造装置
JP2023-123173 2023-07-28

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005026349A (ja) * 2003-06-30 2005-01-27 Tdk Corp 電気化学キャパシタ用電極の製造方法及び電気化学キャパシタの製造方法
JP2013188945A (ja) * 2012-03-14 2013-09-26 Toray Ind Inc 積層シート
WO2015025650A1 (fr) * 2013-08-22 2015-02-26 Ｎｅｃエナジーデバイス株式会社 Électrode négative, procédé permettant de produire cette dernière, et batterie
US20190237758A1 (en) * 2018-02-01 2019-08-01 GM Global Technology Operations LLC Plasma pretreatment on current collectors for thin film lithium metallization
US20220328803A1 (en) * 2021-04-09 2022-10-13 Applied Materials, Inc. Pretreatment and post-treatment of electrode surfaces
KR20230020196A (ko) * 2021-08-03 2023-02-10 주식회사 엘지에너지솔루션 대기압 플라즈마 모듈을 포함하는 전극 집전체 세정 장치 및 이를 통해 세정된 전극 집전체

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005026349A (ja) * 2003-06-30 2005-01-27 Tdk Corp 電気化学キャパシタ用電極の製造方法及び電気化学キャパシタの製造方法
JP2013188945A (ja) * 2012-03-14 2013-09-26 Toray Ind Inc 積層シート
WO2015025650A1 (fr) * 2013-08-22 2015-02-26 Ｎｅｃエナジーデバイス株式会社 Électrode négative, procédé permettant de produire cette dernière, et batterie
US20190237758A1 (en) * 2018-02-01 2019-08-01 GM Global Technology Operations LLC Plasma pretreatment on current collectors for thin film lithium metallization
US20220328803A1 (en) * 2021-04-09 2022-10-13 Applied Materials, Inc. Pretreatment and post-treatment of electrode surfaces
KR20230020196A (ko) * 2021-08-03 2023-02-10 주식회사 엘지에너지솔루션 대기압 플라즈마 모듈을 포함하는 전극 집전체 세정 장치 및 이를 통해 세정된 전극 집전체

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